DE1772404A1 - Photographic developer - Google Patents

Description

Dr. Ing. E. BERKENFELD · Piping. ⁰ H *. BER'K ^ N? BflO) _y Patent Attorneys, Cologne Attachment file number

to enter the name d. Ann, _{phllip A> Hunt Chemlcal Corp} ,

Photographic developer

The invention relates to the treatment of photographic silver halide layers such as, for example, the treatment of silver halide containing gelatin layers which are applied to films or paper. In particular, the invention relates to the treatment of such applied layers a bath containing a compound from the class of quaternary ammonium bisulfites, ammonium sulfites and pyrosulfites as a preservative contains. The best economic applicability of the invention is in developing photographic gelatin layers, if the invention is not limited thereto either.

The invention includes the use of said chemical

(a)
Compounds in / ready-to-use photographic developer solutions, (b) in liquid developer concentrates, ie liquid mixtures which are intended to be diluted with water to make ready-to-use solutions, (c) in liquid replenishment solutions for developers that are more concentrated solutions than ready-to-use solutions and are intended for this purpose are to be added to ready-to-use solutions, which are at least partially exhausted, in order to give them the required concentration again, (d) in ready-to-use combined fixing developers, the so-called "monobaths", in which both developing and fixing take place and (e) in monobath concentrates,

^{H 91/1} 109SU / 0806

which, for example, should be diluted with water to make them ready for use To give fixing developer solutions.

It is customary to use preservatives in photographic processing baths, particularly in photographic developer solutions to be used, for example, to prevent the oxidation of the developer components. The usual so far Preservatives used were alkali sulfites, alkali bisulfites, hydroxyalkylamines-sulfur dioxide addition products ^ and ascorbic acid and its isomers. The alkali sulfites and / or alkali bisulfites are effective preservatives, however, have limited solubility in water. Developer containing high proportions of hydroxyalkylamine ^ -Schwefeldioxyäadditionsprodukte contain tend to show a high viscosity and are therefore difficult to pour, to pour off exactly.

with
measure and light and smooth like thinners like water

to mix.

In addition, in some developers containing such known preservatives, there is a tendency for the preservatives to react with other bath ingredients, so that the developer solutions are not particularly stable. In particular, there is a tendency for a reaction between these known preservatives and known gelatin hardeners, namely aldehydes and dialdehydes,

According to the invention, preservatives are provided for photographic silver halide having any of the drawbacks mentioned and, therefore, the highly stable liquid concentrates and ready to use solutions of all types

1098 U / 0806 -2-

which do not tend to react with other components of the developer and which have a sufficiently low viscosity to be poured accurately and easily, and to be smooth and easy to use with thinners such as water mix.

According to the invention, all these disadvantages are overcome by that quaternary ammonium bisulfites, sulfites and pyrosulfites are used as preservatives.

The quaternary ammonium bisulfites, sulfites and pyrosulfites according to the invention have the following general structural formulas:

R-,

L ^R 4

Bisulfite ^ + 1-

Sulfite*
+1

_ 2

Pyrosulfitef

. -1

HSO ..

-2

• «• 2 * ^S 2 ° 5 ■ ·

1098U / 0806

-3-

in which the radicals R ₁ , R ₀ , R, and Rj, for alkyl radicals with

■ J. Cm. ^ / · ■

1-4 carbon atoms, hydroxyalkyl radicals HO (CH ₂ J _n , where η is 2, 3 or 4, benzyl and phenyl radicals are.

The following compounds are specific examples of quaternary ammonium bislulfites, sulfites and pyrosulfites, the Suitable preservatives in developers for photographic silver halide layers are:

(1) Tetramethylammonium bisulfite (CH ₃ ) u N HSO ₃

(2) Tetramethylammonium sulfite βσΗ, Κ nL SO,

(3) tetramethylammonium pyrosulfite _{(J (CH 3} ) ^ N ^ S _{2 Oj-}

(4) Tetraethylammonium bisulfite (CH ₃ CH ₂ ) ^ N HSO ₃

(5) Tetraethylammonium sulfite [(CH ₃ CH ₂ ) ^ N] ₂ S0 ₃

(6) Tetraethylammonium pyrosulfite ^ H ₃ CH ₂ ) 2, N] ₃ S ₂ O ^

(7) N, N, N-Tris (2-hydroxyethyl) -N-methylammonium bisulfite

CH ₃
(HIGH ₂ CH ₂ ) ₃ N HSO ₃

(8) N, N-bis (2-hydroxyethyl) -N, N-dimethylammonium bisulfite

(HIGH ₂ CH ₂ ) ₂ N HSO ₃

CH ₃

(9) N, N, N-Tris (ethyl) -N-methyl-ammonium bisulfite

CH ₃
(C ₀ H ₁ ,), N HSO,

(lo) Ν, Ν, Ν-Tris-methyl-N-phenyl-ammonium bisulfite

C ₆ H ₅

(CH,), N HSO,
3 3 3

109814/0806

(11) NjNjN-Trls-methyl-N-benzylammonium bisulfite

G ₆ H ₅ CH ₂
(CH _x ), N HSO,

^ (12) N _i N _i Na? Ris- / methyl-N- (2-hydroxyethyl) ammonium bisulfite

HIGH ^ CH,

27 * 2

[ (CH ₃ ) ₃ N

(13) Ν, Ν, Ν, Ν-Tetra (2-hydroxyethyl) ammonium bisulfite) J ₁ N HSO ₃

The compounds listed in Examples 7-13 can

* ■ ■

(not only in the form of their bisulfites, but also as fyrosulfite 'or sulfites are used without the scope of the invention ,/ to leave· -

Said compounds can be prepared by introducing gas "shaped or liquid sulfur dioxide are produced in a solution of the corresponding quaternary ammonium hydroxide / For example, if the compound to be prepared Its Tetramethylammoniumpyrqsulfit, a solution is presented by Tötramethylammoniumhydroxyd. If the compound to be produced is NjNjN-Tris (2-hydroxyethyl) -N-methylammonium pyrosulfite, a solution of Η, Ν, Ν-Tris (2-hydroxyäthyI) -N-methylammonium hydroxide is used,

Quaternary ammonium bisulfites, sulfites and pyrosulfites der mentioned type are already known. For further illustration However, the following is a method of manufacturing

1098 U / 0806 -5-

of tetramethylammonium pyrosulfite.

A solution of 1 mole of tetramethylammonium hydroxide in methanol i.e. «Ine 24% solution of tetramethylammoniurahydroxyd in Methanol is placed in a glass reaction flask with a gas distribution device, i.e. one at the bottom of the Qe * vessel attached gas inlet ring, a stirrer and a Thermometer provided 1st. While stirring, gaseous sulfur dioxide is transferred through the gas distribution device at the bottom of the reaction vessel into the methanolic solution of tetraraethyl

ammonium hydroxide initiated. The reaction is carried out at atmospheric pressure. If the temperature does not rise above 60 °, it is good to do so because the reaction vessels are cooled. The reaction can be carried out using any ratio of sulfur dioxide to quaternary ammonium hydroxide ^!

be, for example, a thousandth part of SohwefelCiöw *

I part quaternary es Auenottiuiehydroxyifbia iu

holding niases varied

The following equation represents one possible response: ι

2 (ΟΗ ₅ ) ₄ Ν OH 4 2SO ₂ - * I (0H ₃ > ₄ nI ₂ S ₃ O ₅ * H _g 0

To isolate the Tetramethylammoniumpyrosulfit is the LOE sungsmittelsystem removed, for example by heating the flask in a water bath at low temperatures such as -60 ⁰ 5o C and applying a vacuum to the piston which is sufficient to achieve a good Verdampfungsgesohwindigkeit. The tetramethylammonium pyrosulfite then crystallizes out.

ÜASPECTEQ, -β-L.

1098U / 0806

Tetramethylammonium pyrosulfite can be dissolved in water to form tetramethylammonium bisulfite. The following equation illustrates this reaction: [(CH ₃ ) !, N] ₂ S ₂ O ₅ + H ₂ O -> 2 (CH ₃ ) JjN HSO ₃

bi.

When tetramethylammonium pyKHsulfite in an aqueous alkaline Solution is dissolved, it converts to the sulfite = tetramethylammonium sulfite.

The method described is only an exemplary one Production method. Any other suitable manufacturing method can be used.

Serving as preservatives according to the invention Quaternary ammonium bisulfites, sulfites and pyrosulfites have the same properties as those of photographic developers stabilizing effect, i.e. the same anti-oxidation effect as is usually achieved by alkali metal sulfites, bisulfites, hydroxyalkylamine-sulfur oxide addition products, ascorbic acid and its isomers. The inventive new preservatives are used according to the invention for the production of stable photographic developers, namely ready-to-use solutions and liquid concentrates that are resistant to oxidation. These developers contain substances active as photographic developers, customary alkali buffer systems such as, for example, quaternaries Ammonium hydroxides, alkali metal carbonates, tetraborates, metaborates, hydroxides, hydroxyalkylamines or mixtures thereof Links.

109814/0806

The invention accordingly encompasses the use of these as preservatives new compounds in photographic processing solutions, in which they are used in combination with all known Types of alkalis and alkaline buffer systems are effective as preservatives.

The invention includes the use of these preservatives together with all known developers, in particular developers for silver halide, which are known to the person skilled in the art. Some examples of photographic developers which are useful alone or in combination with those according to the invention Preservatives to be used in ready-to-use baths, concentrates and monobaths are: hydroquinone, chlorohydroquinone, Bromohydroquinone, p-phenylenediamine and its derivatives, N-monomethyl-p-aminophenol sulfate, l-phenyl-3-pyrazolidone and its derivatives including ^, ^ - dimethyl-1-phenyl-J-pyrazolidone. Other developers can be used without departing from the scope of the invention. Developers formulated in this way can use the contain known additives for photographic developers,

ψ namely retarders such as alkali chlorides, alkali bromides, alkali iodides; Antifoggants such as benzotriazole, 5-methylbenztriazole, 6-nitrobenzimidazole, l-phenyl-5-mercaptotetrazole, 2-anthraquinone sulfonic acid; such as formaldehyde and glutaraldehyde and their bisulfite adducts.

It should be mentioned that these treatment mixtures and in particular

-8- 1098 1 4/0806

the developer mixes which are effective as developers are not limited to use on gelatin layers. You can just as well, for example, for treatment of gelatin layers containing silver halide, which are still gelatin extenders such as carboxymethylated Soy protein or succinic acid esterified hydroxyethyl cellulose contained in place of part of the gelatin in the photographic emulsion layer.

It has been found that by using combinations of the components mentioned, namely the % substances effective as developers, the new compounds as preservatives, alkaline buffer systems and possibly. Retarders, antifoggants, tea-forming agents, silver halide solvents, solubilizers and gelatin hardening agents, high quality photographic developers and fixing developers excellent in stability have been obtained.

It has been found that when using the preservatives according to the invention, quaternary ammonium bisulfites, sulfites g and pyrosulfite developers and pixel developers can be manufactured which are packaged in highly concentrated liquid form and can be stored. This fact is the result of the high solubility of quaternary ammonium bisulfites, sulfites and pyrosulfites in water compared to the lesser Solubility of the usual alkali metal sulfites or bisulfites and other known preservatives.

Quaternary ammonium bisulphites, ammonium sulphites and pyrosulphites result in a higher solubility of the developer system, ie a higher solubility of the preservative system

1098U / 0806 -9-

and developer ingredients, hardeners and / or antifoggants and / orfeelat images etc.

The concentrates of the developer and pixel developer according to Invention made using quaternary ammonium bisulfites, sulfites and pyrosulfites produced as preservatives have a low degree of viscosity, which in particular contributes to effortless mixing and in contrast to known concentrates of developers and fixers stands, the as preservatives Hydroayalkylamin-sulfur dioxide addition products contain. These known solutions are considerably more viscous. For example, a developer concentrate has, in addition to corresponding Amounts of a developer and a buffer an alkanolamine-sulfur dioxide addition product contains as a preservative in an amount of 25 g per 50 ml of concentrate, one Viscosity of 525o centipoise at room temperature. This fact makes the production of ready-to-use developer baths difficult extraordinary.

The new preservatives according to the invention are well compatible with the other constituents of the developer mixtures, ie they are inert towards them. It is particularly when using quaternary ammonium bisulphites, sulfites and pyrosulfites that a particularly stable developer concentrate and / or a ready-to-use solution is achieved when these compounds are combined with known gelatin hardeners, namely aldehydes and dialdehydes.

It has already been mentioned that the new preservatives according to the invention are effective with aldehydes and dialdehydes

10 9814/0806 " ^l0 "

as a gel hardener for making a particularly stable developer concentrate and / or a ready-to-use developer solution can be combined. For the inventive Aldehydes which are suitable for the purpose and listed as examples are formaldehyde, glyoxal, glutaraldehyde and succinic dialdehyde. Maleindialdehyde, its derivatives and bisulfite addition products.

The following examples illustrate the examples according to the invention Use of quaternary ammonium bisulfites and sulfites and pyrosulfites in a variety of developer mixes different system types. These developers contain the compounds according to the invention in different proportions, in which they act as preservatives for these developers.

example 1

Mix the following ingredients:

Water 700 ml

Tetramethylammonium bisulfite (55 # solution,

55 g per loo cnr of the aqueous solution 2o, o g

Hydroquinone (developer component) 4, o g

l-phenyl-3-pyrazolidone (developer component) o, 125g

^{Boric Acid} I (Alkaline Buffer) ²⁰ ' ⁰ *

Potassium hydroxide (90 %)) 18.6 g

Ethylenediamine tetraacetic acid (chelating agent) 1.0 g potassium bromide (retarder) 0.2 g

After thorough mixing of the said components so much water has been added that looo ml solution Ber get * ¹ were.

-11- 1098U / 0806

The solution prepared according to Example 1 is an excellent ' drew ready-to-use developer for both film and paper. Looking at Eastman-Kodak Plus-X Pan film, a film with a silver halide gelatin emulsion layer only for 2 minutes at 20 ° C. with the developer according to example 1, excellent results are obtained.

Eastman Kodak Kodabromide F-2 paper, one with silver bromide containing photographic gelatin-coated paper, was fe with the developer according to Example 1 60 seconds at 20 ° C treated. Excellent results are obtained. Both the film and the paper will be in an acidic Rapid fixation bath fixed for 3 minutes at 20 ° C and washed for 15 minutes at 20 ° C and then dried in the usual way. The developer solution according to Example 1 can be packaged in any conventional manner.

Example 2

Water 700 ml

Tetramethylammonium pyrosulfite 22, ο g

Hydroquinone 5, ο g

iJ-methyl-1-phenyl-3-pyrazolidone 0.125 g

Potassium carbonate (monohydrate) 2o, o g

Potassium bromide 0.2 g

Potassium hydroxide 4.4 g

Water to looo ml

The developer produced in this way is extremely stable and buffered. Plus-X Pan-Film and Kodabromide F-2 paper are treated with this developer for 2 minutes at 20 ° C and then fixed and washed as described in Example 1.

1098U / 0806

β Example 3 1772404 ' water Ethylenediaminetetraacetic acid 7oo ml Tetramethylammonium bisulfite (55th year solution) 2nd Floor Hydroquinone . 13.4 g 1-phenyl-3-pyrazolidone 3.0 g l-phenyl-5-mercapto-tetrazole l, o g 2-methylaminoethanol o, o2 g Water on 16.7g looo ml

This mixture is used to make photographic printing paper, the Kodabromide F-2 is similar, developed effectively at 20 ° C and 1 minute development time. Bas fixing and washing is carried out as in Example 1 described.

Example 4

Water 600 ml

Ethylenediaminetetraacetic acid l, o g

Tetramethylammonium bisulfite (55 # solution) 58, ο g

Hydroquinone 2α, ο g -

Glutaraldehyde (5o %) 8, ο g

It-methyl-1-phenyl-S-pyrazolidone 2, o g

Benzotriazole 0.5o g

6-nitrobenzimidazole 0.2 o g

Boric acid 28, ο g

Potassium bromide 8, ο g

Potassium hydroxide (9o %) 31.ο g

Water to 1500 ml

-13-

1098U / 0806

it

This stable, hardening device develops both double-sided and single-sided coated X-ray film at 32 ° C within 7o seconds. The developed X-ray film is in a standardized, acidic ammonium thiosulfate containing rapid fixing bath, as used for the automatic treatment of X-ray film, for 35 seconds fixed and then washed at 32 ° C for 60 seconds and dried.

Example 5

Water 700 ml

Ethylenediaminetetraacetic acid l, o g

Tetramethylammonium bisulfite (55% solution) 15.0 g Hydroquinone Ί, ο g

* l-methyl-l-phenyl-3-pyrazolidone l, o g

Potassium carbonate 15, ο g

Potassium bromide 0.25 g

5-methylbenzotriazole 0.05 g of water to 100 ml

With the aid of the developer prepared in Example 5, Plus-X Pan-Pilm is developed in 5 minutes at 20 ° C. to a gamma value of 0.82. Kodabromide P-2 paper is developed within 2 minutes at 20 ° C. Both materials are fixed in a rapid fixing bath for 3 minutes and washed under running water for 15 minutes at 20 ° C and then dried in the usual way.

1098U / 0806

1772404 ml 6oo S. 2, o G 3o, o G Ιο, 0 G 2.5 G 5o, o G 0, oil G Ιο, 0 ml looo

4S

Example 6

Water ethylenediaminetetraacetic acid

Tetramethylanimonium bisulfite (55 # solution)

Hydroquinone l-phenyl-3-pyrazolidone sodium thiosulfate (anhydrous) l-phenyl-5-mereapto-tetrazole sodium hydroxide Water on

With the help of the fixing developer described (monobath) the complete development and fixation of a Plus-X Pan-Film-like film within 8 minutes at 20 ° C performed. After the treatment, the film is washed for 5 minutes at 20 ° C. and dried. It'll be an excellent one Maintain image quality.

Example 7

Water 700 ml

Tetramethylammonium bisulfite (55% solution) lo, o g "

Hydroquinone 3> above

1-phenyl-3-pyrazolidone 0.5 g

Tetramethylararaonium hydroxide (24 # solution) 12.5 g

Water to looo ml.

With the help of this bath, 35mm film such as Plus-X Pan-Film is processed within 10 minutes at 20 ° C up to a gamma value of 0.65 developed. Fixing, washing and drying are carried out in the usual way.

-15-. 10 98U / 0806

The chemical nature of the quaternary ammonium sulfityerblndungers allows the formulation of packaged finished developers or pixel developers in the usual high concentration Shape.

The following examples demonstrate this additional advantage of the invention:.

Example 8

Part A.

Tetramethylammonium bisulfite (55 $ solution) * Ιο, ο g

Hydroquinone 5> above

iJ-methyl-1-phenyl-3-pyrazolidone'0, 125 g

Water to ^ o ml

Viscosity 17.5 centipoise at 20 ° C.

part B

V / ater 20 ml.

Potassium carbonate 2o, o g

Potassium bromide ο, 2 g

ψ Potassium Hydroxide ^ »^ G

Water to ¹ io ml.

The two concentrates, A and B are combined and diluted to 1 liter with tap water. The result is a developer which develops film and paper with the same result as described in Example 2.

Example 9

Tetramethylammonium bisulfite (55 £ solution) 13, ^ c Hydroquinone 3, ο r,

109 8 U / 0806 BQD ORIGINAL -Ιό-

l-phenyl-5-mereapto-tetrazole O

l-phenyl-3-pyrazolidone l, o g

Water to 3o, o ml

part B

α-methylaminoethanol 16.7 g

Ethylenediaminetetraacetic acid 2 _{3 above}

Water to 3o, o ml

The concentrates A and B produced in this way are combined and mixed with tap water to 100 ml. To form a ready-to-use solution diluted. When Kodabromide F-2 paper is treated, sensitometric results similar to those obtained in Example 3 are obtained Results are the same.

Example Io

Part A

Tetramethylammonium bisulfite (55 # solution) 58, ο g

Hydroquinone 2o, o g

Glutaraldehyde (5o / »solution) 8, ο g

Benzotriazole 0.5 g

Water to 8o.0 ml

part B

V / ater 4o ₃ o ml

Ethylenediaminetetraacetic acid l, o g

Boric acid 28, ο g

Potassium bromide 8, ο g

Potassium hydroxide (9o / 5lp; e solution) 31, ο g

'// ater to 8o, o ml

BATH ORIGINAL

1 Ü 9; j 1 UI (j 8 0 6

Tell C

Methylcellosolve "15, ο ml

Jj-methyl-1-phenyl-3-pyrazolidone 2, o g

6-nitrobenzimidazole 0.2 g

By combining part A, part B and part C and diluting with tap water to 1500 ml, a developer is obtained with which X-ray film can be treated as described in Example 4

can.

Other examples of ready-to-use developer solutions are:

™ Example 1 1

Water Joo ml

N, N, N-tris (methyl) -N- (2-hydroxyethyl) it -ammoniumbisulf

(58 double solution) 25, ο g

Hydroquinone 4, ο g

l-phenyl-3-pyrazolidone o, 125 g

Boric acid 2o, o g

Ethylenediaminetetraacetic acid "l, o g

Potassium bromide 0.2 g

Potassium hydroxide 18.2 g

Water to looo ml.

With the help of the developer described , Plus-X-Film is developed within 2 minutes at 20 ° C. It is then fixed, washed and dried in the usual way.

Example 12

V / ater 7oo ml

II-methyl-N, N, N-trir> (2-hydroxyethyl) ammonium sulfite

(51 Zige solution).,., ..... ·. · ²⁵ »° S

Hydroquinone .... ^{J |} > ° S

i-Phenyl-3-pyrazolldon BAD ORIGINAL o, 125 S.

109 8 U / 080 6 -18-

Boric acid; Ethylenediaminetetraessic acid Potassium bromide Potassium hydroxide Water on

ι / / C.HUH

2o, o g

ο , 2 g 18.4 g looo ml

With the help of the developer produced in this way, Plus-X becomes Pan-Pilm Developed within 2 minutes at 20 ° C. The development is followed by the usual fixing, washing and drying.

Example 13

Tetrstethylammonium bisulfite (38 # solution) Hydroquinone l-phenyl-3-pyrazolidone potassium carbonate Potassium bromide potassium hydroxide water

25, above

_S og 5

ο, 125 g

2o, o g ο, 2 g 0.8 g

looo ml.

With the help of the ^s he Lösnng is Plus-X Pan-Pilm developed within 2 minuter at a temperature of 2ooc. Then it is fixed, washed and dried in the usual way.

To achieve the photographic results obtained in the previous examples Property ^ to illustrate was the greatest part the data characteristic of the development are summarized in the following tables in which various common Developer mixtures as examples for conventional photochemistry were listed. The parameters measured do not necessarily show the corresponding advantages of the different ones Formulations. These parameters can be changed if desired Change in the special formulations.

1098U / 0806

BAD ORlGINAL-19-

Examples of the photographic effect on kodabromide P-2

paper

Developer developer developer Density Contrast Relative permanent temper. Base + veil speed

digk. at density l, oo

D-72 (l: : 2> 6o Sec. 20 ° C 0.00 l, 5o 5 , 0 Ex. I. 6o -Il 20 ° C O, OO 1.48 6th ,8th Il 2 12o Il 20 ° C 0.00 2, Io 11 , 0 Il 3 6o ti 20 ° C O, OO l, 3o 6th , 5 It 5 12o Il 20 ° C O, OO 1.23 H ,8th

(Developer D-72 is a developer from Pa. Eastman Kodak, the sodium sulfite, hydroquinone, N-monomethyl-p-aminophenol sulfate (Metol), sodium carbonate and potassium bromide. A vol part of the developer D-72 is mixed with 2 parts by volume of water).

Examples of the photographic effect on Plus-X Pan-Hollfilm

Developer developer developer Density Contrast Relative Duration Temper. Base + veil speed

digk. at a density of 5o above Schleiei

D-76 1 7th Min. 20 ° C o, ll o, 76 85, o D-76 2 Io Min. 2O ⁰ C 0.11 0.88 115, o Ex. 5 2 Min. 20 ° C o, lo o, 76 7o, o Ex. 6th 2 Min. 20 ° C o, lo o, 96 95, o Ex. 7th 5 Min. 20 ° C o, lo o, 82 13o, o Ex. 11 8th Min. 20 ° C 0.07 o, i »7 26, o Ex. 12th Io Min. 20 ° C 0.22 0.65 7o, o Ex. 13th 2 Min. 20 ° C o, lo o, 72 60.0 Beiso. 2 Min 20 ° C o, o9 o, 72 5o, o Ex. 2 Min. 2O ⁰ C ο, ΐΊ 0.85 Ιΐο, ο

109HU / U806

-2c

(Developer D-76 is a developer from Pa. Eastman Kodak, which has essentially the same ingredients in different Contains proportions like D-72 with the exception that sodium carbonate has been replaced by borax.)

Examples of the photographic effect on Eastman Kodak

Blue fire x-ray film

Developer Development Density Contrast Relative Duration Temper. Base + veil speed

at a density of 0.5o above Basis + Schlel

I er_

D-19 5 min. 2o ° C o, 23 2,4o 24, ο Ex. Jl 7o sec. 32 ° C o, 23 2.49 25.0

(Developer D-19 is a developer from Eastman Kodak, the hydroquinone, sodium carbonate, sodium hydroxide, Metoi and Contains sodium sulfite.)

Claims

-21-

10 98U / 0806

Claims (1)

Claims 1. Photographic developer for gelatin and silver halide-containing photographic emulsion layers, thereby characterized in that it contains a developer component and a quaternary ammonium bisulfite as a preservative, sulfite or pyrosulfite of the formulas ^Rlx \ ~ .ESO ₃ , \ ^R 2 ^R 3 y / ^R 3 V ^R 4 SO, «Ind ^S 2 ° 5 J 2 contains, in which the radicals R ₁ , R ₂ , R, and R ^ are alkyl radicals with 1-4 carbon atoms, hydroxyalkyl radicals with 2 - k carbon atoms, benzyl and phenyl radicals. 2. Photographic developer according to claim 1, characterized in that N, N, N-tris (2-hydroxyethyl) -N-methylammonium bisulfite, Ν, Ν-bis (2-hydroxyethyl) -NN-dimethylammonium bisulfite, N _f N, N-tris-ethyl-N-methylammonium bisulfite, Ν, Ν, Ν-trismethyl-N-benzylaminonium bisulfite, NjlIjN-trismethyl-H-phenylammonium bisulfite, Ν, Ν, Ν-tris methyl-N- (2-hydroxyethyl) ammonium bisulfite, N, N, N, N-Tetra (2-hydroxyethylammonium bisulfite or the sulfites or pyrosulfites of these Αηιιηοηΐμηινβ ^ indungen, tetramethylammonium biaulfite, tetramethylammonium sulfite, tetramethylammonium pyrosulfite, tetraethylammonium bisulfite, tetraethylammonium bisulfite, tetraethylammonium 10 9 8 14/0806 BATH ORIGINAL -22- äthylammoniumpyrosulfit is present. 3. Photographic developer according to claim 1 or 2, characterized in that the developer component is dihydroxybenzene is present. 4. The method according to any one of claims 1-3, characterized in, that a combination of dihydroybenzene and 3-pyrazolidone is present as the developer component. 5. A photographic developer according to any one of claims ^ j 1 - 'J, characterized in that the developer components are a mixture of hydroquinone and a compound of the class 1-phenyl-3-pyrazolidone, i} -methyl-1-phenyl-3-pyrazolidone and 4,4-dimethyl-1-phenyl-3-pyrazolidone is present. 6. Photographic developer according to one of claims 1-5, characterized in that as developer components at least 2 compounds of the group: hydroquinone, chlorohydroquinone, Bromhydroehinone, p-phenylenediamine and its derivatives, N-monomethyl-p-aminophenol sulfate and l-phenyl-3-pyrazolidone and its derivatives are present. 7. Photographic developer according to one of claims 1-6, characterized in that the developer component a substituted p-phenylenediamine is present as a color developer. 8. A photographic developer according to any one of claims 1-7, characterized in that it is a silver halide solvent contains. 1098U / 0806 -23- 9. Photographic developer according to any one of claims 1-8, characterized in that it is used as a gelatin hardener contains an aldehyde or dialdehyde. 10. A photographic developer according to any one of the claims 1 - 9j characterized in that it has a buffer system Contains base of alkali compounds. 11. A photographic developer according to any one of the claims 1 - Io, characterized in that it is in the form of a liquid Concentrate with a high content of preservatives. 12. A photographic developer according to any one of claims 1-11, characterized in that the preservative Is tetramethylammonium bisulfite. 13 · A photographic developer according to any of claims 1 - Io, characterized in that it is in the form of a loading ψ operating finished developer bath. lU. Process for the treatment of photographic emulsion layers containing silver halide and gelatin, characterized in that the treatment is carried out with a bath according to one of Claims 1-13 which contains, as preservative, a compound from the class of quaternary ammonium bisulphites, ammonium sulphites and pyrosulphites of the formulas 1098U / 0806 -24- HSO ₃ , SO- and J 2 ^S 2 ° 5. contains, in which R ^, R ₂ , R, and Ru are alkyl radicals with one to four carbon atoms, hydroxyalkyl radicals with 2 - H carbon atoms, benzyl and phenyl radicals. 15. The method according to claim lk _t, characterized in that the bath is a developer bath and contains an effective developer component in addition to the preservative. 16. The method according to claim Ik or 15, characterized in that the bath is prepared by diluting a liquid aqueous concentrate with a high proportion of developer component and preservative according to any one of claims 1-13, with water. 1098U / 0806