DE2403645A1 - PHOTOGRAPHIC DEVELOPER MASS - Google Patents

Description

PATENTANWALT e

DR. E. WIEGAND DIPL-ING. \ ΑΛ ΝΙΕΜ & .ΝΝ DR. M. KÖHLER DIPL-ING. C. GERNHARDT

MDNCHEN HAMBURG

TELEPHONE: 555476 TELEGRAMS: CARPATENT

8000 MÖNCHEN 2, MATHILDENSTRASSE12

January 25, 1974

W 41 899/74 - Ko / DE

Fuji Photo PiIm Co., Ltd., Minami Ashigara-sbi, Kanagawa / Japan

Photographic developer material

The invention relates to a photographic developer composition for obtaining high-contrast images, especially one useful in the graphic arts field.

According to the invention there is provided a photographic processing composition which (1) a dihydroxybenzene as a developing agent, (2) 5 to 30 g / l of free sulfite ions and (3) a bipyridinium salt compound of formula

(CH = CH)

2X

contains, in which IL and R _{2 are} ^an alkyl group, whereby R ₁ and R _{2 can} also form a ring, η denotes the number O or 1 and Σ denotes an anion. The developer composition is valuable for obtaining high contrast images.

In the graphic arts field, photographic materials of high contrast are generally used and a developer for photographic education used in reproductions of line images and halftone images. A developer with the property for the infectious development of an exposed photographic material of high contrast is called infectious Designated developer.

The infectious developers basically comprise an alkaline solution containing a dibydroxybenzene developing agent and are characterized by a low concentration of sulfite ions, as described in The Journal of the Franklin Institute , Volume 239, pages 221-230, 1945 and Photographic Processing Chemistry by Mason , the Focal Press Co., 1966, pp. 163-165.

The reason the sulfite ion concentration in the infectious developer is kept low is because of this in that the high contrast photographic material can be developed infectiously. In general if the sulfite ion concentration in the developer is 5 g or less, in particular 3 g or less, stated as sulfite, per 1 l of the developer, although it is known that the stability of the developer with such low sulfite ion concentration is not sufficient. It should therefore be pointed out that the appearance infectious development and stability are opposed to each other.

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One object of the invention is photographic Developer masses of improved stability and highly accelerated developability that are free from damage to halftone image quality and are useful in the graphic arts field are.

Another object of the invention is to provide methods for photographic processing with stability of the developer is improved and the development sensitivity is accelerated without the Halftone image quality which are useful in the graphic arts field is deteriorated.

In the context of the invention, after extensive investigations, it was found that photographic design Curlers containing the following components (1), (2) and (3) are the objects of the present invention can fulfill in the manner described above:

(1) a dihydroxybenzene developing agent,

(2) 5 to 30 g / l of free sulfite ions and

(3) a connection of the IOrmel.

N.

(GH = CH)

2X

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wherein R ^ and R _{2 are} a lower aliphatic hydrocarbon group, where R ₁ and R _{2 can} also be combined and can form a ring, η is the number O or 1 and X is an anion.

Suitable lower aliphatic hydrocarbon groups for R ₁ and R ₂ in the above formula I are preferably alkyl groups, more preferably alkyl groups having 1 to 5 carbon atoms.

If R ₁ and R _{2 form} a closed ring with the two nitrogen atoms, the ring formed represents an unsaturated or saturated 6- to 8-membered ring, to which an aromatic ring, for example a benzene ring, can also be fused.

Suitable anions for X include halogens, p-toluenesulfonate, Citrates, hydrochlorides, sulfates and the like.

The compounds corresponding to the above general formula are bipyridinium salts, which are referred to as "Weitz radicals", for which reference is made to E. Weitz, Angew. Chem. _T Volume 66, page 658, 1954. Illustrative examples of this are the following compounds:

Connection 1

2 B

Connection 2

2 B

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Connection 3

2 B

Connection 4

2CH ₃ -

Connection 5

NC ₂ H ₅ 2CÄ,

Connection 6

N-C ₃ H ₇ 2Br

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Connection 7

CH ₃ N> CH = CH- / VN-

-CH;

-so,

Connection 8

C ₂ H ₅ -

n / \ Vch = ch-V N-

-C ₂ H

2Π5

2CH ₃

SO ₃

Connection 9

2CH ₃ -

SO ₃

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Connection 10

2Br

Connection 11

2NO ₃

The compounds 1 to 9 are known compounds and, for example, in Tetrahedron , Volume 24, page 2697 (1968), ibid., Volume 24, page 5433 (1968), ibid., Volume 24, page 6453 (1968), J. Hetero- Cyclic Chero. , Volume 7, page 719 (1970), ibid., Volume 7, page 401 (1970), ibid., Volume 8, page 29 (1970), J. Chem. Soc , (C), page 1643 (1969) and like described. The other compounds can be easily prepared according to the methods as given in the literature.

The preparations of the compounds described above are explained below in the context of examples.

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Production example 1 (connection 10)

7 g of α, α'-dipyridyl and 25 g of o-xylene bromide were added to 50 ml of dimethylformamide and refluxed in an oil bath for 3 hours. The one after cooling down obtained crystals were filtered off and recrystallized from ethanol to give 14 g of needle-like crystals (Melting point 350 ^ C and above) were obtained.

Elemental analysis (C.gH .. gH

Preparation example 2 (compound 11)

8 g of compound 1 were dissolved in 100 ml of water and stirred at room temperature. To the obtained solution, a solution of 7 g of silver nitrate dissolved in 100 ml of water was gradually added dropwise. After the addition was completed, the formed silver bromide was filtered off and the mother liquid was concentrated under reduced pressure. The crystals obtained were recrystallized from ethanol and gave 4 g of colorless needle-like crystals (decomposition point 215 ^° C.).

•
m * ber .: , 43 51, 38 * 51 , 81 3, 87 1 ° 3 , 67 6, 95 6th

Elementarana Iy s e (C ₁₂ H ₁₂ N ₄ O ₆ ) found . j Uer 76 46, 54 % 46, 92 C. 3, 90 # 3, 18th H 17, $ 90> 18 N

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It is also already known to use bipyridinium salts from Weitz radical type to photographic emulsions from Add Mthotyp, as in the British patent specification 946 476 stated. The end. However, this patent shows that if a bipyridinium salt to a Silver halide emulsion is added, the emulsion is desensitized - and it is evident from this patent specification neither a hint nor a suggestion to use the bipyridinium salt as a high contrast developer composition to add. Despite this point of view, it was found within the scope of the invention after extensive investigations that that the addition of the bipyridinium salt to a developer composition of high contrast is an extreme acceleration the development results. This finding cannot be expected from the prior art, so that it It can be seen that the present invention is in contrast to the prior art.

On the other hand, however, it is known that bipyri'dinium salts accelerate the development effect of hydroquinone hyperadditively, as described by JF Williams, Phot. May be. Eng " , Volume 15, page 213 (1971). In this case, the bipyridinium salts act as a hyperadditive developer, such as phenidone or metol. In addition, it is also known that quaternary nitrogen compounds, such as quaternary ammonium salts or pyridinium salts, markedly accelerate the development effect of hydroquinone, as stated by LFA Mason Photographic Processing Chemistry , pp. 41-42 (1966), Focal Press Co. However, if phenidone, üfetol or a quaternary salt compound are added to a high contrast developer, it is impossible to obtain a high contrast image of stable and uniform quality.

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However, the bipyridinium salts are according to the invention completely different from all common development accelerators, such as quaternary ammonium salt compounds or from all common hyperadditive developers, such as phenidone or metol, and if they are used for development according to the invention, the development is not adversely affected in any way, but extremely accelerated, and a high contrast image of high quality can be obtained with them. This could in no way be foreseen from the prior art.

In addition, it could not be foreseen in any way from the prior art that the use of a developer containing 5 g or more of sulfite ions, the formation of images of high contrast due to the presence of the bipyridinium salt in the developer.

Illustrative examples of bipyridinium salts which can be used according to the invention are given above and in particular compounds 2 and 3 are particularly preferred since they relate to the other materials the line and halftone image quality and the development acceleration effect tower above.

According to the invention, it is advantageous to use the bipyridiniunr salt in a range from 1 χ 10 '^ to 1 χ 10 mol, preferably 1 × 10 "* to 1 × 10" ** moles per 1 liter of developer to use.

According to the invention, the photographic processing composition is for obtaining high contrast images basically from the above compounds and a dihydroxybenzene compound (developing agent) and a sulfite and the developing solution formed consists of an alkaline solution containing 5 to

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Contains 30 g / l of free sulfite ions.

The dihydroxybenzene compounds used as the developing agent can be selected as desired from those known in the photographic art such as those disclosed in U.S. Patents 3,573,914, 3,615,524 and 3,625,689. Examples of dihydroxybenzenes as developing agents are as follows: p-dihydroxybenzenes such as hydroquinones such as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone and the like. Of these dihydroxybenzenes, hydroquinone is particularly preferred in practice.

These developing agents can be used alone or as mixtures can be used by two or more. The amount of the developing agent used is 5 to 50 g, preferably 10 to 30 g, per 1 liter of the developer.

As is known in the art, the developer must necessarily be alkaline and stronger in use its pH must preferably be a value of pH 8 or more, in particular pH 9 to 11. That's why kind and The amount of the alkaline agent used is not particularly limited.

Another characteristic feature of the developer composition according to the invention for obtaining images. of high contrast lies in the fact that the concentration of free sulfite ions in the developer composition during use is high. The developer compositions according to the invention therefore differ fundamentally from the other conventional ones Developer compounds that have a low concentration have free sulfite ions in that the former have the bipyridinium compound corresponding to the above given general formula and the concentration of free sulfite ions in the former is high.

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As sulphite ions, in order to keep the content of the free sulphite ion concentration in the developer high, Alkali sulfites as commonly used in the art such as sodium sulfite, potassium sulfite and Potassium metabisulfite, can be used.

The developing compositions according to the invention may contain the following components in addition to those listed above contain absolutely necessary elements. These components can be used herein prior to the preparation of the developer solution for use or during the preparation of the developing solution for use or can also be incorporated during development.

With regard to such components, the sulfite ion buffer will first be described. The sulfite ion buffer is used in an amount effective to maintain a sufficient concentration of sulfite ions in the developer and illustrative examples are, for example, aldehyde-alkali bisulfite adducts, such as formaldehyde-sodium bisulfite adducts, Ketone-alkali bisulfite adducts, such as acetone-sodium bisulfite adducts, carbonyl bisulfite-amine condensation products such as sodium bis (2-hydroxyethyl) aminomethanesulfonate and the same. The amount of the sulfite ion buffer to be used is from 0 to 130 g, preferably 60 g or less for every 1 liter of the developer.

As additional components, the present compositions can also be a water-soluble acid, for example Acetic acid, boric acid, an alkali e.g. sodium carbonate, sodium hydroxide, a pH buffering agent e.g. Salts and development control agents such as alkali halides such as potassium bromide. Some of the alkaline agents not only make the developer alkaline but also act as a pH buffer and as a development control agent. The developer can

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also an antioxidant such as ascorbic acid, an organic antifoggant such as benzotriazole or i-phenyl-5-mercaptotetrazole, a water softener such as ethylenediaminetetraacetic acid or nitrilotriacetic acid, an organic solvent such as a polyalkylene oxide compound, an amine compound and triethylene glycol, dimethylformamide, methyl alcohol, cellosolve and like included.

The photographic processing compositions according to the invention can be in any form. It all that is necessary is that the developing composition has the above three components when using the same contains. For example, the three components can be dissolved separately to form individual solutions or on the other hand, these three components can be used beforehand to form a powder or liquid Preparations are mixed. Also, the three components can be mixed and powdered into two or more or liquid preparations can be divided or the components can be used to form a concentrated liquid Preparation can be mixed and concentrated. The preparations prepared in this way can be in water or diluted with water when using the same or can also be used directly as a developer (solution in use) can be used without dissolving or diluting.

Of course, when using the developer compositions according to the invention, if the concentration of the respective components in the developer changes, all components that are not in the corresponding Quantities are available to be supplemented to achieve the desired concentration.

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The high contrast photographic materials, which can be treated with the processing compositions according to the invention include photographic silver halide ions, as described, for example, in U.S. Patents 2,656,271, 2,271,291, 3,000,736, 2,496,940 and 2,497,917. Illustrative examples of silver halides are e.g. silver chloride, silver bromochloride, Silver bromoiodochloride and the like. the Objects of the invention can be achieved particularly advantageously if silver halide compositions are used, which 50 mol # or more, preferably 75 mol # or more of silver chloride.

The silver halide emulsion can be used as a dispersant contain one or more hydrophilic colloidal substances as described in U.S. Patents 3,600,174 and 3,625,689, for example gelatin, gelatin derivatives such as phthalated gelatin or malonated Gelatin, cellulose derivatives such as hydroxyethyl cellulose or carboxymethyl cellulose, soluble starches such as dextrin or alkali starch, hydrophilic high molecular substances such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide or polystyrene sulfonic acid.

The silver halide emulsion may further contain a water-insoluble high molecular substance corresponding to U.S. Patents 3,294,540 and 3,615,836, such as polyalkyl acrylates, polymethacrylate, or polyacrylic acid, or interpolymers of alkyl acrylates and acrylic acid as well as plasticizers such as glycerine or trimethanol propane.

The emulsions used to make such sensitive materials can be in any of the following Manner in the manufacture of the same or in their application. For example, they can using known methods, for example using sodium thiosulfate, alkylthiourea and / or gold compounds such as complex salts of monovalent

409831/0848

.- 15 -

Gold and thiocyanic acid or using mixtures such compounds are chemically sensitized. Furthermore, the emulsions can contain heavy metal compounds, for example, compounds of platinum, palladium, iridium, rhodium or cadmium. The emulsions can be orthochromatic or panchromatic by adding color sensitizers such as cyanine dyes or meroeyanine dyes. Farther the emulsions can also use line or halftone improvers, such as polyalkylene oxides and amine compounds according to DS patents 3,288,612, 3 615 527 and 3 345 175, as well as sodium benzene thiosulphate, Benzotriazole and 1,3,3a, 7-tetrazaindene derivatives accordingly U.S. Patents 3,190,752, 3,375,114, and 3,333,959. In addition, the emulsions using hardeners such as formaldehyde, dimethylolurea, 2,4-dichloro-6-hydroxy-1,3,5-triazine according to US Pat. No. 3,325,287 and mucochloric acid be hardened or can contain surface-active agents such as saponin as coating aids. The emulsions Development improvers such as 3-pyrazolidone derivatives can also be used or contain pyrazolone derivatives. Farther The emulsions can contain development accelerators such as quaternary ammonium salts and cationic surfactants Funds included. The carrier for the photosensitive materials which can be used in the present invention is not limited. Thus, glass, cellulose acetate, polystyrene, polycarbonate and polyethylene terephthalate films can be used and papers including artificial papers and waterproof papers can be used as supports. Suitable Examples of the foregoing materials are shown in U.S. Patents 3,294,540, 3,615,836, and 3,600,174 and 3,625,689.

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■ In the development process according to the invention the development is effectively accelerated without any harm to the development and thereby can Extremely high contrast images can be obtained. Thus, halftone images from photo engraving negatives, which by developing a photographic material which has been subjected to point image exposure by a screen was produced, no areas of an intermediate density range, what as a seam or edge around the point images is designated so that the obtained images are quite excellent. aside from that the time necessary for development can be shortened in the method according to the invention and continues to be, if the developing time is lengthened, the quality of the line and halftone dot images will not be greatly increased decreased. As a result, infectious development can occur within a wide range of development times can be carried out with practically uniform photographic qualities. In addition, the Stability of the developer composition improved remarkably according to the invention, so that the developer composition in an automatic developing machine for several weeks without any noticeable deterioration can be.

The following examples serve to further illustrate the invention. Palis is not otherwise specified, all parts, percentages, ratios and the like are by weight.

example 1

A silver halide emulsion containing 75 mol- # silver chloride, 0.2 mol-56 silver iodide and the remainder silver bromide containing, was using gold sensitization of KAuCl ^ and sulfur sensitization using

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was subjected to sodium thiosulfate and was then with 3-carboxymethyl-5- (2- (3-ethylthiazolinylidene) ethylidene ) -rhodamine optically sensitized and a polyoxyethylene nonylphenyl ether, containing 50 ethylene oxide groups per mole, and a development accelerator of the formula

^X N - CH ₂ CH ₂ CH ₂ CH - NHCONH C ₂ H ₅ ^ - I

CH ₃

were added and mucochloric acid was further added. The resulting mixture was mixed with a polybutyl methacrylate polymer and then drawn on a base film to form a lithotype film. Then, the film using an exposure wedge and a magenta contact screen with 150 lines was sensitometrically exposed and the film was developed in each of the following four developer at a temperature of 27 C using ^6.

Developer A:

solution I: 50 cm ² distilled water 30 cm ³ Triethylene glycol 45 g Formaldehyde-ITa triumbis sulfite adduct 2.0 g Sodium Ulfit 16 g Hydroquinone 125 cm ⁵ distilled water too

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Solution II:

distilled water sodium carbonate (1 H ₂ O)

Sodium hydroxide boric acid sodium bromide distilled water too

When Developer A was used, Solution I was added to 750 cm of water and then it became dilute solution I was added to solution II to produce 1 liter of developer solution.

Developer B:

100 cm S. cm 30th G 5 S. 5 S. 2, 5 125

20 g of sodium sulfite was used and the other ingredients were the same as those of Developer A and the pH of Developer B was the same as that of Developer A.

Developer C:

To the developer B, 100 mg of 5-nitroindazole was added.

Developer D:

To the developer B, 100 mg of the compound of the invention was added.

The relative values obtained after developing for 90 seconds with the above developers A to D, respectively Sensitivity is shown in the table below. Further, the time it takes for each developer B to D is required to have the same sensitivity as that used during 90 seconds of development with the

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same developer A and the halftone image quality obtained during development as well reproduced in the table.

required time to

Ent
wick
ler Sodium-
sulfite
(g / l) additive Develop
selection
rend 90
Seconds
relative Achievement of the same
Sensitivity like that
with the development
Developer A during
Reached 90 seconds Halftone image
quality Sensation Develop
lungs time 9 A. 2.0 - 1.00 90 sec. 2 B. 20.0 - -0.40 300 sec. 7th C. 20.0 5 nitro
indazole -0.90 400 sec. 9 D. 20.0 Connect
application no. 1.10
3 85 sec.

The sensitivity of each of the above developers B to D is relative in terms of logarithmic sensitivity corresponding to a sensitivity (1.00) for developer A after developing therewith for 90 seconds reproduced.

The halftone image quality is represented using numerical gradations from 1 to 10, where 1 means an extremely poor halftone image and 10 means an extremely good halftone image. The number .1 is a halftone image quality after development with a common metolhydroquinone developer (e.g. Kodak D-72) and the gradations within the range of 8 or more usable developers.

These developers were allowed to stand in the air for 60 hours to be deteriorated by air oxidation then the same treatments were carried out. The results obtained are shown in the following table

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given.
development
during 90
Seconds
Develop- relative.
ler sensitive 0.50 required time to reach
the same feeling
like that of the Ent
development with fresh development
ler A for 90 seconds
was enough
Development halftone image
time quality 3 A. -0.40 150 sec. 2 B. -0.90 300 sec. 7th C. 1.10 400 sec. 9 D. 85 sec.

The sensitivity of the respective developers A to D is relatively corresponding as logarithmic sensitivity a sensitivity (1.00) for fresh (i.e. prior to deterioration of air oxidation) Developer A. Development thus reproduced for 90 seconds.

The table above shows the following: Developer A can Produce images of good halftone quality. On the other hand, when using Developer A after leaving it to stand in the air the deterioration in sensitivity and halftone image quality are considerable. In terms of Developer B did not noticeably deteriorate with the lapse of time, but the sensitivity and are the halftone image quality is extremely poor. With respect to Developer C, there was no noticeable deterioration with the lapse of time but the halftone image quality is poor and the drop in sensitivity is very great. In contrast, it is apparent that the developer D of the Invention surpasses the other developers in that the halftone image quality is good and after the expiry of the Time does not deteriorate.

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Example 2

As described using the same motion picture from the lithotype in Example 1, a wedge exposure for sensitometry through a Magentakontaktsieb of 150 lines was photographed and then the film using In each case develops the following five developer at a temperature of 27 ⁰ C.

Developer E;

solution I distilled water triethylene glycol

Formaldehyde-sodium bisulfite adduct

Potassium sulfite hydroquinone added to distilled water

solution II distilled water potassium carbonate potassium hydroxide Glacial acetic acid potassium bromide to distilled water

When Developer E was used, Solution I was added to 750 ml of water and then it became so dilute solution I was added to solution II to produce 1 liter of developer solution.

Developer F:.

50 ml 30th ml 45 G 2 G 16 G 125 ml 100 ml 40 G 4th G 2 ml 2 G 125 ml

10 g · Potassium sulfite was used and the other components were the same as those of Developer E and the pH of Developer F was the same as that of Developer E.

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Developer G:

100 mg of compound no. 1 according to the invention were added to developer F.

Developer H;

100 mg of compound no. 4 according to the invention were added to developer F.

Developer I:

100 mg of compound no. 8 according to the invention were added to developer F.

The relative values obtained after developing for 90 seconds with the above developers E to I, respectively Sensitivity is shown in the table below. Further, those required for each of the developers F, G, H, and I are required Time to achieve the same sensitivity as that used during development for 90 seconds The image quality obtained from developer E and the image quality obtained during development are also shown in the table.

necessary time development to achieve the same sensitivity during 90

Development of potassium seconds like that of wick sulfite relative emp- development with Entler (g / l) additional sensitivity winder E during

90 seconds received

Development halftone imaging time quality E 2.0 - 1.00 90 sec. 9 F 10.0 - -0.10 250 sec. 2 G 10.0 connection 1.05 85 sec. 9

number 1

H 10.0 connection 1.00 90 sec. 9

No. 4

I 10.0 connection 1.00 90 sec. 9

No. 8

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The sensitivity for the respective developers P to I is relative as logarithmic sensitivity corresponding to a sensitivity (1.00) for developer E after developing therewith for 90 seconds reproduced.

The meaning of the halftone image quality is the same as in Example 1.

These developers were left to stand in the air for 60 hours to be deteriorated by air oxidation and then the same treatments were carried out. The results obtained are in the following table reproduced.

time required to achieve the same sensitivity as the development time obtained by developing with fresh developer E for 90 seconds, halftone image quality

150 sec. 3

250 sec. 2

85 sec. 9

90 sec. 9

90 sec. 9

The sensitivity for the respective developers E to I is relatively corresponding as logarithmic sensitivity a sensitivity (1.00) to fresh (i.e., prior to being affected by air oxidation) developer E thus reproduced for 90 seconds after development.

The developers of the invention significantly outperform other developers in terms of halftone image quality is good and does not deteriorate after a period of time.

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Ent
wick
ler development
during 90
Seconds
relative
Sensitive
speed E. 0.50 P. -0.10 G 1.05 H 1.00 I. 1.00

Example 3

A lithotype photographic material comprising 86 Mo 1% silver chloride, 0.2 mol following components at a temperature of 27 ⁰ C developed.

Developer J:

Sodium carbonate (1-HpO) 60 g

Hydroquinone 18 g

Sodium sulfite 30 g

Compound No. 2 100 mg

Sodium bromide 3 g

Water to 11

Developer J is excellent as there is no noticeable one Deterioration in sensitivity and halftone image quality occurred with the passage of time.

The invention has been described above on the basis of preferred embodiments, without being limited thereto be.

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Claims (18)

Claims ¹ -1/4 photographic developer composition, characterized by a content of dihydroxybenzene developing agent, 5 to 30 g / l of free sulfite ions and a bipyridinium salt compound. 2. developer composition according to claim 1, characterized in that the bipyridinium salt compound is the following has general formula (CH = CH) 2X where R ₁ and R ₂ each represent an alkyl group and R ₁ and R ₂ can form a ring, η is the number 0 or 1 and X represents an anion. 3. developer composition according to claim 2, characterized in that the bipyridinium salt compound from the Group of the following compounds is selected 2Br 2Br 409831/0848 2Br -CH, 2CH ₅ SO ₃ C ₂ H ₅ N, N-C ₂ H ₅ C ₃ H ₇ C ₃ E ₇ 2Br CH ₃ W XS-CH = CH-V ^ N CH ₃ 0 \ / Φ 2CH ₃ - -SO ₃ 409831/0848 C ₂ Hs- 2CH ₃ - -CzHs SO ₃ C ₂ H ₅ 2CH ₃ SO ₃ 2Br and or 2NO ₃ 409831/0848 4. developer composition according to claim 1 to 3, characterized in that the bipyridinium salt is present in such an amount that 1 χ 10 "* ^ to 1 χ 10"" ² moles per liter of developer solution are supplied. 5. Entwieklermasse according to claim 4, characterized in that the bipyridinium salt is present in an amount such that χ 1 10 ~ ⁴ are supplied to 1 χ 1CT ⁵ moles per liter of developer solution. 6. Entwieklermasse according to claim 1 to 5, characterized characterized in that the dihydroxybenzene developing agent from hydroquinone, chlorohydroquinone, bromohydroquinone, Isopropyl hydroquinone, tolu hydroquinone, methyl hydroquinone, 2,3-dichlorohydroquinone or 2,5-dimethy! Hydroquinone. 7. Entwieklermasse according to claim 6, characterized in that that the dihydroxybenzene developing agent consists of hydroquinone. 8. Entwieklermasse according to claim 6, characterized in that the dihydroxybenzene developing agent Has mixture of 2 or more p-dihydroxybenzenes. 9. Entwieklermasse according to claim 1 to 8, characterized in that the dihydroxybenzene developing agent is present in such an amount that 5 to 50 g per liter of developer solution are supplied. 10. Entwieklermasse according to claim 9, characterized in that the dinydroxybenzene developing agent in in an amount such that 10 to 30 g per liter Developer solution to be delivered- 11. Entwieklermasse according to claim 1 to 10, characterized in that the developer solution produced therefrom is alkaline. 12. Entwieklermasse according to claim 11, characterized in that the developer solution has a pH of 8 or above. 409831/084 8 13. developer composition according to claim 1 to 12, characterized in that the sulfite consists of sodium sulfate, Potassium sulfite or potassium metabisulfite consists. 14. developer composition according to claim 1 to 13, characterized in that it is a sulfite ion buffer contains. 15. developer composition according to claim 14 »characterized in that that the sulfite ion buffer from an aldehyde-alkali bisulfite adduct, a ketone-alkali bisulfite adduct and / or a carbonyl bisulfite amine condensation product. 16. developer composition according to claim 14 »characterized in that the sulfite ion buffer in such There is an amount that 0 to 130 g per liter of developer solution are delivered. 17. developer composition according to claim 1 to 16, characterized characterized in that it contains at least one of the following agents: a water-soluble acid, an alkali, a pH buffering agent and includes means for regulating the development. 18. developer composition according to claim 1 to 17 »characterized in that it contains at least one of the following Agents: an antioxidant, an organic antifoggant, a water softener and an organic Contains solvent. 409831/0848