US3772022A

US3772022A - Developing composition for use with photographic materials for the graphic arts

Info

Publication number: US3772022A
Application number: US00239978A
Authority: US
Inventors: E Okutsu; Y Iijima; H Iwano
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1971-03-31
Filing date: 1972-03-31
Publication date: 1973-11-13
Anticipated expiration: 1990-11-13
Also published as: DE2215714A1; IT952467B; FR2132371A1; JPS519613B1; GB1346028A; FR2132371B1

Abstract

A developing agent for use in photographic materials for the graphic arts, containing an infectious developing agent and acetonitrile, malonitrile or derivatives thereof is disclosed. These nitrile compounds have improved storage stability and prevent air-oxidation.

Description

United States atem 1 Okutsu et al.

[451 Nov. 13, 1973 DEVELOPING COMPOSITION FOR USE WITH PHOTOGRAPHIC MATERIALS FOR THE GRAPHIC ARTS Inventors: Eiichi Okutsu; Yoo Iijima; Haruhiko Iwano, all of Kanagawa, Japan Fuji Photo Film Co. Ltd., Kanagawa, Japan Filed: Mar. 31, 1972 Appl. No.: 239,978

Assignee:

Foreign Application Priority Data Mar. 31, 1971 Japan 46/19515 US. Cl 96/66 R, 96/66.3, 96/665 Int. Cl G03c 5/30 Field of Search 96/66, 66.3, 66.5,

Primary Examiner-Norman G. Torchin Assistant Examiner-M. F. Kelley Attorney-Richard C. Sughrue et al.

[5 7] ABSTRACT A developing agent for use in photographic materials for the graphic arts, containing an infectious developing agent and acetonitrile, malonitrile or derivatives thereof is disclosed. These nitrile compounds have improved storage stability and prevent air-oxidation.

14 Claims, No Drawings DEVELOPING COMPOSITION FOR USE WITH PI-IOTOGRAPHIC MATERIALS FOR THE GRAPHIC ARTS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photographic developer for developing a photographic material for the graphic arts. Particularly, it relates to a developer composition prepared by incorporating acetonitrile, malonitrile or their derivatives into an infectious developing agent, for use with a high contrast photographic negative for the graphic arts. Air-oxidation of an infectious developing agent is prevented and an improvement in stability of the developer is obtained.

2. Description of the Prior Art Photographic line and halftone reproductions are carried out by imagewise exposing a high-contrast or litho-type silver halide photographic element through a cross-screen or contract screen and then developing it with a developer, whereby continuous tone images are converted into photographic line and halftone (dot) images.

It is most desirable that the line and dot images be composed of only a maximum density portion and a background having a minimum density. However, since a high-contrast photographic element has the property of forming an intermediate density portion besides a maximum density portion and background, a portion of intermediate density which is termed fringe is always formed around the dot images. The formation of fringe is not desirable for graphic arts because it deteriorates the dot qualities.

As well known in the art, the fringe can be removed by using a so-called infectious developer which essentially contains a dihydroxybenzene type developing agent and a small amount of sulfite ion. In a conventional developer, a dihydroxybenzene type developing agent, for example, hydroquinone is converted into quinone during development and the resulting quinone reacts with sodium bisulfite to yield sodium hydroquinone monosulfonate. However, sodium hydroquinone monosulfonate is less reductive than hydroquinone due to its low electrode potential and is essentially incapable of acting as a developing agent. Accordingly, development does not proceed rapidly, resulting in the formation of a fringe.

In contrast to this, in case of an infectious developing agent, the concentration of free sulfite ions is kept low, since sodium sulfite is added in a small amount andit reacts with a compound having carbonyl groups, such as paraformaldehyde, incorporated in the infectious developing agent, in accordance with the following equation:

CH O Na SO H O CH ONaI-ISO NaOI-I For this reason, it becomes difficult for quinone derived from hydroquinone in a development process to react with sulfurous acid to produce hydroquinonemonosulfonic acid, thereby the concentration of quinone is increased. The thus produced quinone and the original hydroquinone give rise to a disporportionation reaction and produce semiquinone. Semiquinone reduces silver halide and itself is converted to quinone due to its high developing activity. Yule describes in J. Frank. lnst., 239, page 221(1945) that rapid developing is brought about by a repetition of this procedure,

poor stability as compared to common black and white photographic developers, and the life of the infectious developer is short. Consequently, when infectious developers are continuously used, images having a low contrast and a high fringe are obtained because the development is not carried out rapidly. Accordingly, it has been proposed to add an antioxidant other than sulfite to improve the storage stability. In this attempt, it is already known to add ascorbic acid into an infectious developing solution (see Great Britian Patent No. 928,390).

Ascorbic acid is, however, poor in stability and hence tends to be decomposed. Particularly, ascorbic acid is readily decomposed when metal ions such as iron ions or copper ions are present, and this leads to the poor stability of the developing solution. Further, ascorbic acid has the disadvantages that the progress of the development is slowed to a certain extent and that the dot quality is reduced when it is added in an large amount.

An object of this invention is to provide a photographic developer for a high-contrast photographic element useful for the graphic arts having an excellent preservative property unaccompanied by adverse influences on dot qualities.

Another object of the invention is to provide an infectious developer which is easily controlled before and during development.

Still another object of the invention is to provide an infectious developer in which the amount of replenishment during development is reduced.

A further object of the invention is to provide a photographic development process for the graphic arts capable of forming line and dot images having good qualities by using an infectious developer stable for a long period of time.

SUMMARY OF THE INVENTION In order to accomplish these objects various investigations have been made and it has been found that addition of at least one kind of nitrile compound of the formula:

R1 RZ C (CHI)BCN .ai in which R R R and n are defined hereinafter increases remarkably the storage stability of a developing solution without exerting any adverse influence on the dot quality.

DETAILED DESCRIPTION OF THE INVENTION In the above formula, R R and R which can be same or different, represents a hydrogen atom, alkyl group with not more than four carbon atoms, a halogen-substituted alkyl group with not more than four carbon atoms, an alkoxy group with not more than four carbon atoms, COOM in which M represents a hydrogen atom or a water-soluble cation, COR in which R represents an alkyl group with not more than four carbon atoms, CONR'R" in which R and R" represent a hydrogen atom or an alkyl group with not more than four carbon atoms or CN, and n represents or an integer of from 1 to 3.

Representative compounds which can be used in the present invention are shown in the following Table, but the invention is not limited to those.

TABLE Compound l lov R R R; n l H H H 0 2 CN H H 0 3 COOH H H 0 4 OCH, H H 0 5 H H H l 6 CN H H 1 7 COONa H H l 8 OCH H H l 9 H H H 2 10 CN H H 2 ll COOH H H 2 12 H H H 3 13 CN H H 3 l4- COONa H H 3 15 CH; H H 3 16 CN CH H 0 17 CN CH H 1 l8 COCH H H 0 l9 CONH H H 0 20 CH Cl H H 0 2l CONHCH, H H 0 These compounds are all known compounds and are commerically available. However, application of the compounds of the present invention to photographic developing solutions has not been known yet, and particularly it has not been known yet to improve the stability ofa developing solution for use in a photographic material for the graphic arts by addition of the compounds of the present invention to such a developing solution.

As a result of investigations on various compounds, it has been discovered that the compounds of the above formula improve the stability of a developing solution for use in a photographic material for the graphic arts. The reason why addition of these compounds improve the stability when added to a developer for the graphic arts is not yet understood. But, these compounds give an excellent stability and dot quality, compared to heretofore known compounds such as ascorbic acid or excess amounts of sodium sulfite. Particularly, a slowing of developing speed or the formation of a fringe which often accompanys the use of the hitherto known compounds is not at all observed with the compounds of the present invention.

The developing agent for use in a photographic material for the graphic arts can be a general infectious developing agent.

An infectious developer, in use, is basically composed of a dihydroxybenzene (developing agent), an alkali, a small amount of sulfite and, if necessary, a sulfite ion buffer. The infectious developer of the invention further contains the aforesaid compound.

Dihydroxybenzenes are known in the art and can be easily selected by one skilled in the art. Typical examples of these compounds are hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, 2, S-dimethylhydroquinone, etc. In developing agents, hydroquinone can be practically used. These developing agents are used singly or in combination. A suitable amount of the developing agent to be added ranges from about 5 to 50g,

preferably about 10 to 30g, per one liter of the developer.

A sulfite ion buffer can be used in such an amount that the concentration of sulfite is maintained at a low level in the developer. Examples of such buffers are an aldehyde-alkali metal hydrogen sulfite addition product such as formalin-sodium hydrogen sulfite, a ketonealkali metal hydrogen sulfite addition product such as acetone-sodium hydrogen sulfite addition product, and a carbonylbisulfite-amine condensation product such as sodium bis(Z-hydroxyethyl)aminomethane sulfonate. The sulfite ion buffer is not limited to the above examples and each ingredient of the addition product or condensation product may be added to the developer. The amount of the sulfite ion buffer which is added can range from about 13 to g., preferably 30 to 60g. per one liter of the developer.

An alkali is added to adjust the developer to an alkaline condition, preferably to a pH higher than 8, more preferably to a pH of 9 to l 1. Accordingly, the addition amount and kind of additive can be freely selected and is not limited to the above examples.

The infectious developing agent in addition may contain, a pH buffering agent such as alkanolamines, water soluble acids (e.g., acetic acid or boric acid), a water-soluble alkalis (e.g., sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydroxide) and salts. Yet further, in some cases the infectious developing agent may contain organic antifogging agents (e.g., benzotriazole, l'phenyl-S- mercaptotetrazole or nitroindazole), lithographic development inhibiting agents and oragnic solvents (e.g., triethyleneglycol, dimethylformamide, methylalcohol, or cellosolve) in an amount of not more than 300 ml per 1 liter of the developing solution.

As described above, a characteristic of the infectious developing solution is that the concentration of free sulfite ions is low. For this purpose, a sulfite ion buffer solution such as formaldehyde-sodium bisulfite adduct is generally employed. In general, the concentration of free sulfite ions is controlled by addition of an alkali metal sulfite such as sodium sulfite in an amount of not more than 5 g per 1 liter of developing solution as well as sulfite ion buffer solution. Addition of sulfite in an amount of not more than 3 g per l liter of developing solution is generally employed, and this improves slightly the stability of the developing solution, although the dot quality is reduced more or less. As described above, however, this degree of stability is not satisfactory. On the other hand, the compounds of the present invention improve markedly the poor stability of the infectious developing solution which does not contain alkali metal sulfites other than a sulfite ion buffer solution such as formaldehyde-sodium sulfite adduct, and further improve outstandingly the stability infectious developing solution which contains an alkali metal sulfite in an amount of not more than 5 g per 1 liter of developing solution in addition to a sulfite ion buffer agent.

One compound of the present invention or mixtures of two or more compounds of the present invention can be employed, if desired. The amount of the compounds of the present invention added to a developing solution varies according to the composition of the developing solution and the kind of the compounds of the present invention used, but generally the amount added is in the range of from 0.1 to 40 g per l liter of developing solution, more preferably from 0.15 g to g per 1 liter of developing solution.

When developing agents are processed prior to use so tht they may be readily used as a developing solulion on mixing with water or dissolving in water, that is, when they are in the form of a liquid or a powdered developing composition, it is effective to incorporate the compounds of the present invention into the developing preparation. When liquid preparations are used, it is particularly effective to add the compounds of the present invention since they improve markedly the stability of liquid preparations. A representative liquid preparation generally comprises two liquid compositions, that is, a composition which contains the developing agent and a composition which contains the alkali agent. In this case, the compounds of the present invention may be incorporated into any of these compositions, but is particularly effective to add them to the composition which contains the developing agent. Using the approach, a liquid developing agent having excellent stability, and an infectious developing solution prepared on dilution, having a quite excellent stability, can be obtained. Alternatively, in the course of development of the photographic materials for printing or after development, the compounds of the present invention may be added to improve the stability of the developing solution.

The developing agents of the present invention are also suitable for high temperature development (i.e., a developing temperature 27C or higher) using an automatic developing apparatus.

Light-sensitive materials for the graphic arts, which can be used in the present invention, include conventional silver halide emulsions (e.g., silver chloride emulsions, silver chlorobromide emulsions, and silver chloroiodobromide emulsions). Particularly, silver chlorobromide emulsions or silver chloroiodobromide emulsions, containing not less than about 50 mole of silver chloride, more preferably from about 70 to about 95 mole of silver chloride, are suitable for the present invention. As silver halide dispersing agents employed in these light-sensitive materials, there may be used hydrophilic colloidal substances such as gelatin or gelatin derivatives (e.g., gelatin, phthalyl gelatin, malonyl gelatin); cellulose derivatives such as hydroxyethylcellulose or carboxymethylcellulose; water-soluble starchs such as dextrin or alkali starch; hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide or polystylenesulfonic acid. These light-sensitive materials further may contain hydrophobic polymers such as polyacrylates, and gelatin plasticizers such as glycerin and trimethanol-propane.

The emulsions employed in these light-sensitive materials can be sensitized on manufacture or by application in accordance with various methods. For example, they may be chemically sensitized according to methods well known in the art, for example, with sodium thiosulfate, alkylthiourea, gold compounds such as complex of monovalent gold and thiocyanic acid, or

6 mixtures thereof. The emulslons further may contain heavy metals such as platinum, palladium, iridium, rhodium or cadmium. In addition, the emulsions may be panchromatically or orthochromatically sensitized with color sensitizers such as cyanine dyes or merocyanine dyes. Further, the emulsions may contain dot quality improving agents such as polyalkyleneoxides and amine compounds (as disclosed in U.S. Pat. No. 3,288,612, German Specification OLS 1,932,882, U.S. Pat. No. 3,345,175) and sodium benzenethiosulfate, benzenetriazole and 1, 3, 3a, 7-tetrazaindene derivatives (as disclosed in U.S. Pat. No. 3,375,114 and U.S. Pat. No. 3,333,959). The emulsions may be hardened with hardeners such as formaldehyde, resorcylaldehyde dimethylol urea, 2, 4-dichloro-6-hydroxy-l, 3, 5- triazine (see U.S. Pat. No. 3,325,287) or mucochloric acid, and they may contain surface active agents such as saponin in order to facilitate application. The emulsions may contain development progress improving agents such as 3-pyrazolidone derivatives or pyrazolone derivatives. Further, the emulsions may contain development accelerating agents such as quaternary ammonium salts or cation surface-active agents. The supports which are coated with the compounds of the present invention can be varied widely, and glass, cellulose acetate, polystyrene, polycarbonate, polyethyleneterephthalate and the like can be used.

All parts and percents set forth herein are by weight unless otherwise indicated.

EXAMPLE 1 After photographing an exposure wedge for sensitometry, through a 150-line magenta contact screen, using a commerical lithographic film comprising a film support having coated thereon a silver chlorobromoiodide emulsion (70 mol% AgCl, 0.2 mol% Agl) sensitized with gold and sulfur, spectrally sensitized with 3- carboxymethyl-S 2-( 3-ethylthiazolinilidene) ethylidene) rhodamine, and containing polyoxyethylenenonylphenyl ether having 50 ethyleneoxide groups, muccochloric acid and polybutylmethacrylate, development was conducted at 20C using four kinds of developing solutions having the following compositions:

Developing Solution A Sodium Carbonate (monohydrate)50 g Formaldehyde-Sodium Bisulfite Adduct45 g Potassium Bromide-2 g Hydroquinone18 g Sodium Sulfite-2 g Water to makel liter Developing Solution B Developing Solution B was prepared by adding 10 g of Compound-1 of the present invention to Developing Solution A.

Developing Solution C Developing Solution C was prepared by adding additionally 3 g of sodium sulfite to Developing Solution A. Developing Solution D Developing Solution D was prepared by adding 1.0 g of ascorbic acid to Developing Solution A.

The results obtained are shown in Table l.

The development time is expressed as the time required to reach the sensitivity obtained when development was conducted for 2 minutes using Developing Solution A, this sensitivity being set at 100. The dot quality was graded as a, b, c, each representing good, fairly good" and bad, respectively. The aerated sensitivity was obtained by placing 500 ml of developing solution in a cm X cm developing bath and contacting such with air for 5 hours to determine deterioration.

As can be seen from the results contained in Table 1, Developing Solution A with no additive shows a great decrease in sensitivity when aerated. Developing Solution C containing 3.0 g of sodium sulfite added shows a smaller decrease in sensitivity than Developing Solution A does, but it is greatly deteriorated and the dot quality of the fresh solution is poor. The hitherto TABLE 2 Develop- Amount merit Sensitivity Developing added time Dot solution Additive (g., l.) (min) quality Fresh Aerated F Compound-2.

known Developing Solution D containing 1.0 g of L- ascorbic acid shows almost the same decrease in sensitivity as Developing Solution C when aerated, but this is not completely satisfactory. On the other hand, Developing Solution B containing 10 g of Compound-1 of the present invention shows the smallest decrease in sensitivity when aerated, and no decrease in the dot quality was observed at all.

EXAMPLE 2 as described in Japanese application 23 ,465/65, mucochloric acid, polybutylmethacrylate prepared by emulsion polymerization as described in Japanese application 5,331/70 and pentaerythritol. The mixture was then coated on a film base to manufacture the desired lithographic film.

An exposure wedge for sensitometry was photographed through a ISO-line magenta contact screen, using this lithographic film. The film was then treated at 20C with the two kinds of developing solutions having following compositions.

Developing Solution E Solution 1 Distilled Water55 ml Triethylene Glycolml Formaldehyde-Sodium Bisulfite Adductg Hydroquinonel6 g Distilled was added to make the total volume 125 The developing solution containing Compound-2 shows a smaller decrease in sensitivity, compared to the developing solution which did not contain Compound- 2.

EXAMPLE 3 After photographing an exposure wedge for sensitometry through a ISO-line magenta contact screen, using a commerical lithographic film, development was conducted at 20C, using developing solutions of the following compositions:

Developing Solution G Sodium Carbonate (monohydrate)55 g Formaldehyde-Sodium Bisulfite Adduct-6O g Potassium Bromide-2 g Boric Acid-3 g Hydroquinone18 g Sodium Sulfite2 g Water to makel liter The Developing Solutions H, I, J, K, L, M were prepared by adding the Compound-Ii, -4, -5, -6, -1 1, -l3 of the present invention, respectively, to Developing Solution G.

The results obtained are shown Table 3.

TABLE 3 Additive Developeom- Amount merit Sensitivity Developing pound added time Dot solution number (gJL) (min) quality Fresh Aerated 2% a 100 38 3 4. 0 2% a 100 75 4 3. 0 2% a 100 5 5. 0 2% a 1.00 90 6 3. 5 2% a 100 85 11 2. 0 2% a 100 13 2. O 2% a 100 As can be seen the developing solutions containing the compounds of the present invention do not cause a reduction in the dot quality, show only a small decrease in sensitivity when aerated, and have an excellent stability.

EXAMPLE 4 Each of two 25 liter portions of a Developing Solution E as described in Example 2 was placed in two developing apparatus for engraving. 200 sheets of a halfcut lithographic film were processed in each, with 70 ml of a supplementary solution of the following composition being added for each sheet of the half-cut lithographic film. Supplementary Solution Solution 1 Distilled Water45 ml Triethylene Glycol-40 ml Formaldehyde-Sodium Bisulfite Adduct-45 g Hydroquinonel 8 g Distilled Water to make-125 ml Solution 2 Distilled Water-9O ml Sodium Carbonate (monohydrate)-3O g Sodium Hydroxide-5 g Potassium Bromide-2 g Distilled Water to make-125 ml The supplementary solution was prepared by adding Solution 1 and Solution 2, in order, to 750 ml of water. To one of the automatic developing apparatus was added 20 g of Compound-9 of the present invention, and both apparatus were allowed to stand for 64 hours. Then, lithographic films were developed in each automatic development apparatus. No decrease in sensitivity was observed in the automatic developing apparatus to which the compound of the present invention had been added. On the other hand, a great decrease in sensitivity was observed in the automatic developing apparatus to which no compound of the present invention had been added.

EXAMPLE 5 Development was conducted at 29.5C, using Developing Solutions G, I, J, K, L, and M as described in Example 3, are using the automatic developing apparatus. The results obtained are shown in Table 4.

TABLE 4 The aerated solution in Table 4 comprises a developing solution which has been allowed to stand at room temperature for 64 hours in an automatic developing apparatus. From the results it can be seen that no deterioration of the dot quality occurs and a remarkably excellent stability is obtained with the developing solutions containing Compound-3, -4, -5, -6, -11 or -l3 of the present invention.

What is claimed is:

1. An infectious developing composition for a high contrast photographic material having a silver chloride content of not less than 50 mol for the graphic arts, comprising a dihydroxybenzene developing agent, sulfite ion in an amount up to 5g/liter, and at least one compound having the following formula:

wherein R R and R which may be the same or different, each represents a hydrogen atom, an alkyl group with not more than four carbon atoms, a halogensubstituted alkyl group with not more than four carbon atoms, an alkoxy group with not more than four carbon atoms, a COOM group in which M represents a hydrogen atom or a water-soluble cation, a COR group in which R represents an alkyl group with not more than 4 carbon atoms, a CONRR" group in which R and R each represents a hydrogen atom or an alkyl group with not more than four carbon atoms or CN, and n represents 0 or an integer of from 1 to 3.

2. The developing composition of claim 1, wherein said composition additionally contains an aldehydealkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.

3. The developing composition of claim 2, wherein said composition contains formaldehyde-sodium bisulfite adduct.

4. The developing composition of claim 1, wherein said dihydroxy developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, or 2, S-dimethylhydroquinone.

5. The developing composition of claim 4, wherein said dihydroxy-benzene developing agent is hydroquinone.

6. The developing composition of claim 1, wherein said compound is present at a level of from 0.1 g to g per liter of developing solution and wherein said dihydroxy developing agent is present at a level ranging from 5 to g per liter of developing solution.

7. The developing composition of claim 1, wherein R, is a hydrogen atom, a ,carboxyl group, or a cyano group, and wherein R and R are hydrogen atoms.

8. A method for forming photographic images for the graphic arts which comprises exposing imagewise a high contrast photographic element having a silver chloride content not less than 50%, and developing said exposed element in a developer composition comprising a dihydroxybenzene developing agent, sulfite ion in an amount up to 5g/liter and at least one compound having the formula:

wherein R R and R which may be the same or different, each represents a hydrogen atom, an alkyl group with not more than four carbon atoms, a halogen-substituted alkyl group with not more than four carbon atoms, an alkoxy group with not more than four carbon atoms, a COOM group in which M represents a hydrogen atom or a water-soluble cation, a COR group in which R represents an alkyl group with not more than four carbon atoms, a CONR'R" group in which R and R each represents a hydrogen atom or an alkyl group with not more than four carbon atoms or CN, and n represents 0 or an integer of from 1 to 3.

9. The method of claim 8, wherein said composition additionally contains an aldehyde-alkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.

13. The method of claim 8, wherein said compound is present at a level of from 0.1 g to 40 g per liter of developing solution and wherein said dihydroxy developing agent is present at a level ranging from 5 to 50 g per liter of developing solution.

14. The method of claim 8, wherein R is a hydrogen atom, a carboxyl group, or a cyano group, and wherein R and R are hydrogen atoms.

Claims

2. The developing composition of claim 1, wherein said composition additionally contains an aldehyde-alkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
3. The developing composition of claim 2, wherein said composition contains formaldehyde-sodium bisulfite adduct.
4. The developing composition of claim 1, wherein said dihydroxy developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, or 2, 5-dimethylhydroquinone.
5. The developing composition of claim 4, wherein said dihydroxy-benzene developing agent is hydroquinone.
6. The developing composition of claim 1, wherein said compound is present at a level of from 0.1 g to 40 g per liter of developing solution and wherein said dihydroxy developing agent is present at a level ranging from 5 to 50 g per liter of developing solution.
7. The developing composition of claim 1, wherein R1 is a hydrogen atom, a carboxyl group, or a cyano group, and wherein R2 and R3 are hydrogen atoms.
8. A method for forming photographic images for the graphic arts which comprises exposing imagewise a high contrast photographic element having a silver chloride content not less than 50%, and developing said exposed element in a developer composition comprising a dihydroxybenzene developing agent, sulfite ion in an amount up to 5g/liter and at least one compound having the formula:
9. The method of claim 8, wherein said composition additionally contains an aldehyde-alkali metal bisulfite adduct, a ketone-alkali metal bisulfite adduct or a combination thereof.
10. The method of claim 9, wherein said composition contains formaldehyde-sodium bisulfite adduct.
11. The method of claim 8, wherein said dihydroxy developing agent is hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2, 3-dichlorohydroquinone, or 2, 5-dimethylhydroquinone.
12. The method of claim 11, wherein said dihydroxy-benzene developing agent is hydroquinone.
13. The method of claim 8, wherein said compound is present at a level of from 0.1 g to 40 g per liter of developing solution and wherein said dihydroxy developing agent is present at a level ranging from 5 to 50 g per liter of developing solution.
14. The method of claim 8, wherein R1 is a hydrogen atom, a carboxyl group, or a cyano group, and wherein R2 and R3 are hydrogen atoms.