DE2112825B2 - Bromide-free, aqueous, photographic developer or activator solution for lith development - Google Patents

Description

The photographic developer or activator, the formates and acetates, can be used. This solution of the invention has the advantage over the corresponding developer compounds can either alone or the known solutions that they can be kept longer in any combination with each other and in, especially in the air of any desired level of development effective and a higher one Development capacity 5 centration can be used. It has a suitable concentration, especially in the current widespread use, within the range from 0.05 to 0.50, the automatic, machine development at preferably from 0.10 to 0.30 mol of developer-increased temperatures of about 43 ° C. Simultaneously binding per liter of developer solution,
it provides images with a high maximum density . The cysteine used in the photographic developer or (Dmax) better tint, good sharpness and activator solution of the invention, with good edge development, is L-cysteine (/ J-mercaptoalanine ). As

Compared to that from the above-mentioned USA.-Pa- is explained in more detail below, the term includes tentschrift 2 902 367 known developer solution, "cysteine" not only has the amino acid itself, but the developer or activator solution of the invention also includes its hydrohalides. Suitable concentrate periods The advantage that, under comparable conditions, the amount of cysteine is from about 0.1 to about 0.9 g, voreine Has a service life that, in the case of the machine, is about 0.5 g of cysteine per liter of developer len development at a temperature of 43 ° C min- or activator solution.

is at least twice as long as the useful life of the developer or activator solution of the invention

known developer solution and that its developer contains no bromides as a development retarder.

treatment capacity is much greater than that of the 20 instead of the bromide development retarder

known developer solution (cf. Tables I, III according to the invention organic anti-fogging agents

uno IV of Examples 1, 3 and 4 below). turns. Usable organic antifoggants

This also applies to those from the above are known, for example, from M e s, “The Theory of

German Offenlegungsschrift 1 572 143 known the Photographic Process ", 3rd edition, pp. 344 to 346

Developer solution containing a combination of ascorbin-25 (1966).

acid and dissociated sulfite, which they against According to a preferred embodiment of the

Protecting air oxidation in peel development can use invention as organic antifoggants

target. The developer or activator solution of the Er benzimidazoles or indazoles can be used. Ge

However, even with the substantial height dimension of a further preferred embodiment of the

ren temperature of 43 ^c C carried out machine 30 invention can be used as organic antifoggants

A significantly higher level of utility nitrobenzimidazole and nitroindazole can be used

lasts longer than the well-known developer solution, whereby the. Examples of organic antifoggants used in

this effect in the case of the developer or activator solution of the invention mentioned in the aforementioned German open

application document, which can be carried out at 27 "C, are 5-nitrobenzimidazole,

The development of the shell is even more evident 35 5-nitroindazole and 6-nitrobenzimidazole nitrate.

occurs. In addition, the developer or activator The concentration of the organic anti-fog

Solution of the invention a higher developing capacity is preferably within the range of

acted on than the 0.1 to 2.0 g in the German disclosure mentioned, preferably at about 0.8 g per liter of

developer solution described in writing. developer or activator solution for rapid removal

In the case of the development in the developer or activator solution 40 (in a development device with

the invention usable monoaldehyde bisulfite continuous transport and high absorption capacity

it is preferably an alkali metal or speed) at high temperature. About half of this

a short-chain hydrocarbyl, especially a short amount, is sufficient for development in the shell

chain aliphatic monoaldehyde bisulfite. Such normal temperature (20 ⁰ C). Preferred used

Monoaldehyde bisulfites are, for example, from the 45 organic antifoggants are the nitro-substituted

U.S. Patents 2,313,523 and 2 S43,483 ask for organic antifoggants,

knows. Specific examples of monoaldehyde bisulfites, optimal results are obtained using the

which is advantageous in the photographic developer pH of the developer or activator solution

or activator solution of the invention is used, invention holds between about 10 and 11.2. At the ma-

Sodium formaldehyde bisulphite can be used, but can also provide optimal results

lium formaldehyde bisulfite, sodium acetaldehyde bisulfite obtained if the temperature of the developer

and sodium isobutyraldehyde bisulfite. A special or activator solutions between about 32 and about

Preferred monoaldehyde bisulfite is sodium form-54 ° C, preferably at about 43 ° C. When developing

aldehyde bisulfite. The monoaldehyde bisulfite is purposely wound in the shell, the temperature can be within

moderately in an amount within the range 55 of the range of about 15 to about 27 ^° C.

0.05 to 1.0 mol, preferably in an amount of the developer and activator solution of the invention

0.3 moles of monoaldehyde bisulfite per liter of developer can be used either in shell development processes or

or activator solution used. preferably in an automatic development

In the developer or activator solution of the device, for example in high-temperature rapid

invention is used as a developer compound except for hydrochi-60 winding tapes, whereby the

non itself also a derivative of hydroquinone, such as high-contrast photographic recording material

Chlorohydroquinone, bromohydroquinone, 9,3-dichloro-

hydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromo-wraps, or during any other contihydroquinone, 1,4-Dihydroxy-2-acetophenone-2,5-thin movement, whereby it is through at least one

methylhydroquinone, 2,5-diethylhydroquinone, 2,5-di- 65 developer solution is transported through, as with

p-phenethylhydroquinone, 2,5-dibenzoyl \ minohydro- for example in the USA patents 3,025,779,

quinone and 2,5-diacetaminohydroquinone are useful. 3 078 024.3 122 086.3 149 551.3 156 173 and 3 224 356

It can also be the esters of these compounds, e.g. B. described. The continuous development of the band

can be described as a development in one direction nete synthetic polymers are z. B. from the USA.

will. The expression »development in a Rieh patent specification 3,142,568, 3,193,386, 3,062,674,

tung «is to be understood to mean that the photographic 3,220,844, 3,287,289 and 3,411,911 are known. Special

The water-insoluble poly-

movement, this general movement um- 5 merisate of alkyl acrylates and methacrylates,

but also holds up and down movements, acrylic acid, sulfoalkyl acrylates or methacrylates,

the one adjustment z. B. to the roller and the Ent- those that have crosslinking centers that the

winder- hzw. Allow activator solution. Cure easier and those that are recurring

The activator solution of the invention may have sulfobetain units in the form of the same as those used in the Canadian

a working solution or in concentrated form as see patent 774 054 are described.

Liquid within the solubility limits of the die in the presence of the developer or activator

applied chemicals are produced. Appropriate solution of the invention developed high contrast

Concentrations are obtained when diluting with recording materials and other layers

Water in a ratio of 1: 3 can be applied to a wide variety of substrates.

Which can be obtained with the developer solution of the invention. Examples of typical substrates are

wrapped high-contrast emulsion of the lith type can be those made of cellulose nitrate, cellulose ester, polyvinyl

not washed or acetal, polystyrene, polyethylene terephthalate and poly-

be washed. In the latter case, the soluble carbonate or resinous materials as well

Salts by quenching and setting made from glass, paper and metal. Preferably a

Leaching removed or the emulsion can be a flexible support, in particular a support

Coagulation wash, for example after the one made of paper, used that is partially acylated or with

USA patents 2,618,556, 2,614,928, 2,565,418, barium oxide and / or an aliphatic polymer

3,241,969 and 2,489,341, sat, in particular a polymer of an x-olefin

be subjected. with 2 to 10 carbon atoms, such as polyethylene and

Which are coated with the developer or activator solution of the ethylene-butene copolymers

Emulsions developed in accordance with the invention can be mixed with.

mix sensitizers, for example with reducing compounds, sulfur, selenium οάζτ tellurium solution of the invention developed in the presence of the developer or activator compounds, gold, platinum or palladium erbindun- recording materials of the lith type can be antigenic or Combinations of these, sensitized s> a. 30 have static or electrically conductive layers. Suitable processes are, for example, from the USA. B. soluble salts, such as chlorides and nitrates, are known from patents 1,623,499, 3,297,447, 2,399,083 and vaporized metal layers, ionic polymers, such as 3,297,446. she z. In U.S. Patents 2,861,056 and

The high-contrast emulsions of the lith type and 3,206,312 are described, or insoluble inorganic

others with the developer or activator solution of the 35 niche salts, as z. B. U.S. Patent

Curable layers that can be developed in accordance with the invention may be described, may have 3,428,451,

with various organic and inorganic You can use plasticizers and lubricants, for example

Hardeners, either alone or in combination, both pol) alcohols, e.g. B. glycerine and diols of in

for example with aldehydes and aldehyde precursors of the type described in the USA patent 2,960,404,

compounds, ketones, carboxylic and carbon fatty acids or esters, such as those found in the

Acid derivatives, sulfonate esters, sulfonyl halides U.S. Patents 2,588,765 and 3,121,060

and vinyl sulfonic ethers, reactive halogens are prescribed, and silicone resins contain like them

bonds, epoxy compounds, aziridines, reac- for example in British patent specification > 15 061

tion capable olefins, isocyanates, carbodiimides are described. You can also use surfactants

Hardeners with mixed functions and polymeric 45 agents contain, for example, saponin, anionic

Hardeners such as oxidized polysaccharides e.g. B. Di compounds, e.g. B. that in the U.S. Patent

aldehyde starch and oxyguar gum. 2 600 831 described alkylarylsulfonates, ampho-

The usable high-contrast emulsions and tere compounds, as they are, for. B. U.S. Patent Recording Materials of the lith type can be written 3 133 816, as well as water-soluble Colloids, alone or in combination, as 50 borrowed adducts of glycidol and an alkylphenol, Contain auxiliaries or binders and various such as, for example, in the British patent Have layers. Examples of suitable hydro- 1 022 878 are described. You can also use Mattiephile Materials are contained in naturally occurring substances, e. B. starch, titanium dioxide, zinc mende substances such as proteins, e.g. B. gelatin, Ge oxide, silicon dioxide and polymer beads in the latin derivatives, cellulose derivatives, polysaccharides, such as 55 United States patents 2,992,101 and 2,701,245 be-dextran, Gum arabic, as well as synthetic poly-written type. You can also use brighteners, mere substances, e.g. B. water-soluble polyvinyl such as stilbene, triazine, oxazole and coumarin brighteners Compounds such as poly (vinyl pyrrolidone) and acrylic contain. Lightening that is soluble in water can also be used! amide polymers. can be used, for example the one in the German

The high contrast emulsions and other 60 patents 972 067 and in the USA patents

Layers of the usable high-contrast recording 2,933,390 described brighteners, or brighteners

tion materials of the lith type can also alone dispersions, such as. B. in the German patent

or in combination with hydrophilic, for water font 1150 274, in the USA.-Patent 3 406 07 (

permeable colloids other synthetic polymers and in French patent 1 530 244 be

Contain compounds, e.g. B. in latex form dispersed 65 are written.

Gated vinyl compounds and in particular those that de with the developer or activator solution

which photographs the dimensional stability of the invention developable photosensitive silver halo

see recording materials improve. Suitable emulsion layer of a multilayer photogra

Phic recording material of the lith type can be obtained by adding spectral sensitizing dyes additionally be sensitized. Such an additional spectral sensitization can, for example can be achieved by the fact that the emulsion with a solution of a sensitizing dye in treated with an organic solvent or that the dye is added in the form of a dispersion, as described in British Patent 1154,781. To get the best results you can the dye can be added to the emulsion either in the last stage or in a higher stage.

Sensitizing dyes that are used to sensitize Such emulsions are suitable, for example, in U.S. Patents 2,526,632, 2,503,776, 2,493,748 and 3,384,486. Examples of usable spectral sensitizers are the cyanines, Merocyanine, (trinuclear or quadricycle) complex Merocyanine, (trinuclear or quadricycle) complex Cyanines, holopolar cyanines, styryls, hemicyanines, e.g. B. Enaminhemicyanine, Oxonole and Hemioxonols.

The sensitizing dyes of the cyanine classes can have basic nuclei such as thiazolines, oxazolines, Pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles. These cores can too Contain alkyl, alkylene, hydroxyalkylene, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups, and they can be unsubstituted or by halogen, phenyl, alkyl, haloalkyl, cyano or Carbocyclic or heterocyclic ring systems substituted by alkoxy groups have been condensed off. the Dyes can be symmetrical or unsymmetrical, and they can be on the methine or polymethine chain Have alkyl, phenyl, enamine or heterocyclic substituents.

The merocyanine dyes can contain both the above-mentioned basic nuclei and acidic nuclei, such as B. thiohydantoins, rhodanines, oxazolidendiones, thiazolidendiones, barbituric acids, thiazolines and malononitrile. These acidic nuclei can be replaced by alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, Hydroxyalkyl, alkoxyalkyl, alkylamino groups or heterocyclic rings may be substituted. It If desired, combinations of these dyes can also be used. They can also be supersensitizing Additives that do not absorb visible light can be used. Examples are Ascorbic acid derivatives, azaindenes, cadmium salts and organic sulfonic acids, such as are found, for. B. U.S. Patents 2,933,390 and 2,937,089.

The high-contrast lith recording materials and other layers that can be developed in the developer or activator solution of the invention can also contain light-absorbing substances and filter dyes, such as those used, for. See U.S. Patents 3,253,921; 2,274,782; 2,527,583 and 2,956,879. If desired, the dyes can also be stained, as is described, for example, in US Pat. No. 3,282,699.
ίο The invention is explained in more detail by the following examples, in which preferred embodiments are described.

example 1
is

Strips of a high-contrast, lith-type chlorobromide emulsion were sensitometrically exposed using an optical step wedge with a density gradation of 0.1. The individual strips were developed in one of the following developer solutions A, B, C and D in a conventional developer device at a temperature of 43 ^° C.

Developer A

Developer without cysteine and sodium formaldehyde bisulphite.

Hydroquinone 33.0 g

5-nitrobenzimidazole nitrate 1.1 g

Triethylene glycol 60.0 ml

Sodium bicarbonate 70.0 g

Potassium hydroxide 47.0 g

Sodium sulfite 8.0 g

Trisodium phosphate (· 12 H ₂ O) 16.0 g

Aminoethanol 4.0 g

Water for topping up to pH
set to 10.6 1.01

Developer B (According to U.S. Patent 2,902,367)

Developer A + 40 g sodium formaldehyde bisulfite.

Developer C (according to the invention)

Developer A + 40 g sodium formaldehyde bisulfite + 0.3 g cysteine.

Developer D

Developer A + 0.3 g cysteine.
The results obtained in developing the exposed emulsion layers are summarized in Table I below

Table I.

developer Relative
sensitivity
log E ¹ ) 7th Effective contrast
(Contrast in
slope area) DmIn Dmax Service life
of solution ² ) A.
B.
C.
D. 0.00
-0.05
+0.05
0.00 5.5
4.5
5.0
4.0 3.7
4.0
4.0
1.8 0.04
0.05
0.04
0.11 5.2
4.7
5.7
5.2 ^ lh
IStd.
2 hours.
<^ 1 hour

>) Based on the sensitivity 0 of the comparison developer.

*) 3.791, 43 ° C was circulated in a rapid development device (a solution life of 1 hour eni

speaks of 12 levels in a normal temperature processor when using 3,791 developer

will).

9 10

The data given above show that sodium formaldehyde bisulfite 50 g

the developer B, which did not contain any cysteine, a g. Sodium carbonate (monohydrate) ... 60 g

wrestle loss of sensitivity, a sizable potassium carbonate (anhydrous) 60 g

Loss of maximum density (D _max ) revealed and also sodium phosphate

exhibited a short service life. The both Na-5 (tribasic crystal) 21.5 g

triumformaldehyde bisulphite and cysteine-containing sodium sulphite (anhydrous) ".". '. "" 1θ'δ g

Developer (Developer C) provided a sensitive 6-nitrobenzimidazole nitrate 1.125 g

increase, a considerable increase in Dmax, _ν ,,. «

and the useful life of the solution was twice that of hydroquinone ii g

long. ₁₀ L-Cystem (free base) 0.43 g

A developer solution similar to that of the developing triethylene glycol 50.6 g

ler A, which, however, also contained 0.3 g of cysteine (ent-2-aminoethanol 10 g

Curler D) resulted in a significant decrease in the water for topping up to 1.0 liter

Contrast in the toe area and an undesirable one

Increase in haze. 15 high-contrast chlorobromide emulsion layers from

Example 2 Lith-type were made with a 0.10 optical step wedge

exposed sensitometrically and in a conventional

This example illustrates the excellent capacitance winding device at a speed of

did the developer or activator solution of the invention 75 cm / min, developed at 43 ° C. Regarding the

A developer solution of the following 20 capacity was obtained. Test results are in the following

Composition prepared: summarized in Table II.

Tabel

Exhaustion rate ¹ ) logarithm
the relative
Sensitivity ² ) y Dmax D min quality
of the line negative Freshly made
32 6 m ² 5.90
5.85
5.90
5.85 6.0
5.0
6.0
6.5 3.9
3.7
3.6
3.5 0.07
0.07
0.06
0.05 outstanding
outstanding
excellent
excellent 65 2 m ² 97.8 m ²

·) Per 18.91 container.

-) Based on a value set at 4.0 for a standard film, measured at an overall density of 1.8 on the H and D curve.

Example 3

A developer solution A was prepared which was identical to the developer solution prepared in Example 2. The same developer solution B was then prepared, except that the cysteine was omitted. Strips of a high-contrast chlorobromide emulsion of the lith type were exposed to an optical 0.1 step wedge and developed in the developer solutions in a tray ^{at 43 ° C. in order to simulate machine development conditions.} The results of the sensitometric investigations are summarized in Table III below.

Table III

developer logarithm
the relative
Sensitivity ¹ ) y Dmax Danish A.
B. 5.95
5.60 7.0
6.1 4.20
3.35 0.04
0.04

*) Based on a value set at 4.0 for a Standard film, measured at an overall density of 1.8 on the H and D curve.

Example 4

This example contrasts the exceptional capacity of a developer solution of the invention a known developing solution when used in a shell developing process The lith developers were made as follows:

Developer A (with cysteine and sodium formaldehyde bisulfite)

Sodium formaldehyde bisulfite 40 g / l

sodium

(Monohydrate, granulated) 60 g / l

Potassium carbonate (anhydrous) 60 g / l

tribasic crystalline sodium phosphate 30 g / l

Sodium sulfite (anhydrous) 4 g / l

5-nitrobenzimidazole 0.26 g / l

5-nitroindazole 0.04 g / l

Boric acid 3 g / l

Hydroquinone 20 g / l

L-cysteine (free base,

/? - mercaptoalanine) 0.33 g / l

2,5-dithiobiurea

(H ₂ NCSNHNHCSNh ₂ ) 0.10 g / l

Water to make up to 1.01

Developer B (well-known developer of the "Litfa" type)

Sodium formaldehyde bisulfite 70 g / l

Hydroquinone 15 g / l

Sodium carbonate (monohydrate) 75 g / l

Potassium bromide 3 g / l

Water to top up to 11

Developer C
(well-known developer for copying lines)

Sodium formaldehyde bisulfite 50 g / l

Hydroquinone 15 g / l

Sodium carbonate (monohydrate) ... 20 g / l

Potassium bromide 0.1 g / l

Water to top up to 11

Test exposures with line reflection originals were carried out in a copy camera Use of incident radiation of 12800 Lux to generate line negatives a high contrast lith-type chlorobromide emulsion. The results of the capacity studies are summarized in Table IV below, while the results of the sensitometric studies are summarized in Table V below.

Table IV

Ent
winder Development time
(Minutes) tempera
door
° C capacity
(20.3 x 25.4 cm
large strips per
18.9 liters) A.
B.
C. 1*)
2 _^3/4 *)
³ U *)
IV ₂ **) 21.1
21.1
21.1 100
32
16

*) With stirring.
**) Without stirring.

Table V

Used
developer Properties of the
developed image
Quality of the line negative Image tint A.
B.
C. excellent that
Copies showed
fine and coarse
Lines on
pretty good that
Copies showed
some fine and
all rough
Lines on
excellent that
Copies pointed like this
probably fine as well
rough lines black
Brown
black
Brown

45

Example 5

A suitable activator solution of the invention provided, in the case of high-contrast emulsions of the lith type, containing an incorporated developer compound, developed images of excellent quality, In comparison with known developer solutions containing reducing agents, these activator solutions showed excellent storage and exhaustion properties. Since no If problems existed, the activator solutions of the invention could be made at higher pH values which shortened the development time in the desired sense. Also, these solutions could can be used at higher temperatures with little deterioration on storage entered

An example of an activator solution of the invention usable at high temperature in an automatic developing machine is shown below.
A solution was prepared that contained:

Sodium formaldehyde bisulfite 40.0 g

Sodium carbonate 60.0 g

Potassium carbonate 60.0 g

Sodium phosphate 30.0 g

5-nitrobenzimidazole 1.2 g

5-nitroindazole 0.45 g

L-cysteine 0.8 g

2,5-dithiobiurea 0.05 g

Water to fill up to pH value

about 11.8 1.01

The activator solution was used in a conventional developing device for developing a high contrast silver chlorobromide recording material of the lith type with an incorporated hydroquinone developing agent. Development was carried out at 43 ° C at a speed of 90 cm / min. The activator solution was used to develop film strips, the typical negatives with at least. 85 ° / ₀ containing the exposed area. Very good results were obtained with the activator solution of the invention even after 92.9 m ^{2 of} film strips had been developed in only 18.9 1 of activator solution. The sensitometric results obtained after developing various amounts of film strips are summarized in the table below.

Exhaustion
35 speed Relative
Sensation
opportunity ¹ ) ßm ".r D _m i " quality Fresh manufactured .. 0 3.8 0.05 excellent ₄₀ 18.6 m ² 0 3.6 0.05 excellent * 37.2 m ² -0.05 3.5 0.05 excellent 55.8 m ² -0.05 3.6 0.05 excellent 74.4 m ² -0.10 3.4 0.05 excellent 93.0 m ² -0.10 3.4 0.05 very good

^l ) Based on the sensitivity 0 of the freshly prepared developer.

The results obtained illustrate the excellent exhaustion properties of the activator of the invention. The exhaustion properties were achieved with very little change in sensitivity and only a minimal change in Dmax-

Example 6

An activator solution of the invention for developing a lith emulsion with incorporated Developer compound in bowls at room temperature was established as follows:

Sodium formaldehyde bisulfite 20.00 g

Sodium carbonate (monohydrate) ... 30.00 g

Potassium carbonate (anhydrous) 30.00 g

tribasic sodium phosphate 15.00 g

5-nitrobenzimidazole 0.14 g

5-nitroindazole .. 0.14 g

L-cysteine 0.40 g

2,5-dithiobiurea 0.10 g

Water to make up to pH adjusted to 11.4 1.01

Strips of an exposed lith recording material which contained a high-contrast chlorobromide emulsion with a norbornene-hydroquinone developer compound were developed for 30 seconds at 20 ^° C. in flat dishes which contained the above-mentioned solution. Images of an excellent

good quality and density. When performing a comparative experiment using of a corresponding activator, in which, however, the cysteine had been omitted, images with a lower density and a poorer line quality.

Claims (3)

sulfite ions or patent claims derived from aldehyde bisulfite complexes: in addition to hydroquinone as a developer compound, ascorbic acid and possibly a dissociated one 1. Bromide-free, aqueous photographic de-sulphite, such as sodium formaldehyde bisulphite, contain,
Developer or activator solution for lith development The previously known photographic developer development containing hydroquinone as development solutions for lith development have the disadvantage, however, that they contain relatively little developer and one monoaldehyde bisulphite , thereby having winding capacity and already after which indicates that it also contains cysteine development relatively less recording. io lith-type materials are exhausted. You need to 2. Developer or activator solution can then be discarded or regenerated after application. Furthermore is Spruch 1, characterized in that their useful life is relatively short. this Cysteine in a concentration within the occurs especially when the conreiches from 0.000826 to 0.00743 moles (0.1 to 0.9 g) of high density lith-type recording materials, per liter of solution. 15 as is common today, a rapid development at high 3. Developer or activator solution according to temperatures (43 ° C) in automatic development claim 2, characterized in that they are subjected to the devices v / earth. Although you can Cysteine at a concentration of 0.003 mol per using the previously known Lith-Ent-liter Solution contains. winder under normal time and temperature conditions 20 good, high-contrast images can be generated with automatic, machine-based rapid development at 43 ^° C., however, the known lith developers do not meet the requirements placed on them in terms of their useful life and development capacity. The invention relates to a bromide-free, aqueous, 25 The same applies to the activator solutions for photographic developer or activator solution Lith development used for developing for the lith development, the hydroquinone as de-when the developer compound in the light developer, contain an organic antifoggant and a sensitive recording material itself Contains monoaldehyde bisulphite. (see French patent specification 1,479,090). Of the- In the photographic production of line 3 ° -like activator solutions, it is true that raster images are used for a longer period of time, as they are less of the autoxidation-unnamed lith type due to the lack of high-contrast photographic emulsions of the so-developer compound. These are subject to development during development, but because of their ratio emulsions of the lith type, the development-wise low development capacity also grow to centers autocatalytically with a very high development rate, in particular with the automatic, winding speed with the formation of a extremely machine development at 43 ^r C, as it is today for high contrast. Many extremely high contrast photographic recordings are used to develop such lithographic plates and films. The purpose of the invention is therefore to provide an improved called lith developers differ in respect of 40 bromide-free, aqueous photographic developers or. lent their composition very much to indicate from the activator solution for the lith development, usual black and white developers. To some extent, especially the one that is often used today To produce high contrast and sharp lines, machine development at high temperature has one namely, it has proven to be useful as a development longer service life and higher development solution To use lith developer, which essentially has 45 capacity without affecting the quality of the borrowed from hydroquinone, an alkali, an alkali-developed image suffers. metal bromide and a small amount of sulfite It has now been found that this task with ions exist. Due to the small amount of sulfite a developer or activator solution of the entrance ions will be the developer solution for a brief mentioned type that can be dissolved in addition Period stabilized. All 50 commercially available still contain cysteine, which together with the others Lith developers will use the ingredients required for stabilization to have a synergistic effect on the Such sulfite ions are generated by having properties of the developer or activator solution Aldehyde sulfite, e.g. B. sodium formaldehyde bisulfite exercised. which acts as a sulfite ion buffer. Such the invention is based on a bromide-free, aqueous Developer solutions are generally separated into two photographic developer and activator solutions Containers kept as, for example, a solution for the lith development, the hydroquinone the sodium formaldehyde bisulfite at a high level as a developing agent, an organic AntipH value dissociated and not only contains the desired fogging agent and a monoaldehyde bisulfite, Sulphite ion, but also an equimolar amount form and is characterized by the fact that it is also aldehyde, which reacts with the hydroquinone, where 60 contains cysteine. by the developability of the lith developer. According to a preferred embodiment, the contains lers is affected. Developer or activator solution of the invention that From US Pat. No. 2,902,367 and the German Cysteine in a concentration within the range Offenlegungsschrift 1 572 143 are already bro- ches from 0.000826 to 0.00743 mol (0.1 to 0.9 g) per amide-free, aqueous, photographic developer or 65 liter solution. Activator solutions for lith development are known, according to a further preferred embodiment In addition to hydroquinone as a developer compound, it contains the cysteine in a concentration of small amount of from dissociation of a form- 0.003 moles per liter of solution.