DE1447645A1 - Photographic developer - Google Patents

Description

PATENT LAWYERS 7 STUTTGART I

PATENT LAWYERS 7 STUTTGART

DR.-ING. WOLFF, BARTELS, DR. BRANDES O / 49 Lange Strasse 51

TELEPHONE 296310

TELEPHONE: 296310 and 297295 TELEPHONE: 0722312

Reg.Hr. 119 352

Eastman Kodak Company, 343 State Street, Rochester Sew York State, United States of America

Photographer! Rather a developer

The invention relates to a photographic developer which, but keeps the pH constant, uses a buffering compound contains.

It is known that the developing activity of a photograph! The developer depends heavily on the alkalinity of the developer solution being affected. The various known developer compounds a usually develop their optimal development activity at different pH values. Farther the speed at which the photographic developer develops also depends on the stability of the pH of the solution. In order to achieve a consistently good development, it is therefore necessary to adjust the pH value of the Keep the developer solution as constant as possible. Also is

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it is usually beneficial to work at high pH levels, in order to achieve a satisfactory development

to achieve. To achieve these goals it is known to add buffering compounds to the developer solution.

However, the known buffering compounds, which are effective at pH values of 9-13, have disadvantages. To f the most famous, buffering compounds include phosphates. The phosphate ions present in the developer solution when phosphate buffers are used have the disadvantage, for example, that they form calcium phosphate precipitates if calcium ions are present in the developer or if other compounds containing calcium are present in the developer solution. Other buffering compounds, such as, for example, the guanidines, the phenols and the amino acids, either have insufficient developer qualities or are too expensive.

It has now surprisingly been found that water-soluble, Silver halide non-reducing sulfonamides are excellent as buffering compounds in photographic applications Suitable for developers. It has been shown that these sulfonamides are not only excellent in developing solutions

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but also at high pH values work, no precipitation and continue to be cheap are.

Accordingly, the invention relates to a photograph Developer that contains a buffering compound to keep the pH constant · The developer is thereby gekennaeichnet that it is a water-soluble, silver halide non-reducing sulfonamide as a buffering compound contains »

In a special way, the photographic Developer of the invention a sulfonamide of the following formula:

R - SOo - HH - C (R ₁ ) - HH- SO «l R ₅ ,

^{2 1} IB-I ^d * n-1 ^ά

where mean:
a and η 1 and 2 \

R is an alkyl or aryl group

a · Alkylengruppeι

R _{2 is} a hydrogen atom »an alkyl or

Aryl group when η »1 or a Alkyl or aryl group when η is * 2.

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Advantageously, R consists of an alkyl group with 1 to 5 carbon atoms, for example a methyl, ethyl, n-propyl, laoliut '/ I- ", fS" -hydroxyethyl group, etc. this preferably consists of a monoeyoic aryl group of the besisol series, for example a phenyl, o, ε or p-iolyl, p-carboxyphenyl or p-sulfophenyl group.

R. can for example be a methylene or Ätliylen'gruppe be.

JS? For Rp Iwimen stand for the same alkyl or aryl groups that were mentioned in the ji context "for R»

A particular advantage of the sulfonamides described is that they not only have excellent buffering properties besiiiseFi, special-n also additionally ^ the density of the developed increase photographic material and or the

sensitivity
effective -lii * wi «^^ igeg« s «tet ^« M ^ e ^ 4 ^ can increase »

For example, the following sulfonamides have been shown to be beneficial

9 0 9 8 0 7/0 9 8 7

1. CH, - SO ₂ - NIL, - methanesulfonamide

, - SO ₂

^V 2

2. CH, - SOp - KH - CpH ₁ - - N-ethyl methane

- ^ sulfonamid

3. C ₂ H ₅ - SO ₂ - NH - CH ₃ - N-methylethane-

aulfonamide

4. HO-C- f >> - SO ₂ - NH ₂

p-carboxybenzenesulfonamide

5.HO ₅ S - ^ A- SO ₂ -

p-sulfofcenzenesulfonumiii

6. CH ₅ - SO ₂ - NH - HH - SO ₂ - ₅

K- (Me fchansulfonamido) methanesulfonamide

7. CH, - SO ₀ - NH - C ₀ H, - NH - GO ₀ - OH,

1,2-bis (methansulf onamifio) aethane

8. CH ₅ - SO ₂ - IiH - C ₂ H ₄ OH

N- (!! - Hydroxyethyl) methanesulfonamide.

Many of the compounds covered by general formula 1 are known per se. These compounds can be prepared, for example, by the method as described by Field and co-workers in J. Am »Chem. Soe. 75 »934- (1953). Thereafter, the production of τοπ sulfonaaidaib can be done, for example, as follows;

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tf-ethylmethanesulfonamide of the formula CpH ₅ -HH-SO ₂ -CHs was prepared from methanesulfonyl chloride and ethylamine. For this purpose, 100 g of methanesulfonyl chloride were added to 500 ml of benzene in a 1 liter round-bottom flask which was equipped with a dropping funnel, condenser and stirrer. The mixture was cooled to 0 ° 0 using an ice bath. Then 78 g of ethylamine was added dropwise from the dropping funnel * while the temperature was maintained below ⁰ C 1G. After all of the ethylamine had been added, the reaction mixture was warmed to room temperature. The mixture was then filtered to remove the precipitated ethylamine hydrochloride. The benzene was then evaporated (using a Rinco evaporator). The liquid residue was then distilled at a pressure of 11 mm using a water pump and a Vigreaux column. The over at φ 144-149 ⁰ C parliamentary groups

tion consisted of N-ethyl methanesulfonamide. The refractive index of the compound was 25 ⁰ C at 1.4900.

Hach the described. The most varied of procedures can be used Compounds that have a structural formula of the given formula I have, are produced. For example, K - (^ - Hydroxyäthyl) methanesulfonamia after the procedure described can be prepared if instead of ethylamine ^ aminoethanol is used. In

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p-carboxybenzenesulfonamide, for example, can be used in the same way by reacting p-cyanobenzenesulfonyl chloride with Ammonia and hydrolysis of the p-cyanobenzene sulfonamide obtained getting produced. The p-cyanobenzenesulfonyl chloride can be obtained by reacting cyanobenzene with sulfochloride will hold.

The water-soluble beschrielienen sulfonamides are especially suitable as buffering compounds for EntwickTerlösungen, the _t 0 at pH values of 9 - Own 13.0. The developer compounds which are used together with the buffering compounds of the invention can consist of all known jrf black and white or color developer compounds, such as phenylenediamines such as K-alkylphenylenediamines and N-alkyltoluenediamines, as well as p-aminophenols such as p Aminophenol, N-methyl-p-aminophenol, etc., hydroquinone, 3-pyrazolidones, eg 1-phenyl-3-pyrazolidone, etc. Normally, the developer compounds which contain an amino group are used in P.orm dee Hydrochlorides or Sulfa ^ Ctes.

The described water-soluble, non-reducing silver halide sulfoamides can be added to the developer solutions in different concentrations, whereby

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the most favorable concentration of course depends on the particular developer compound used and the other additives; loriaally, about 0.1 Ms about 200 g sulfonamide per developer solution have proven to be suitable, with consentrations of 1 to about 100 g being preferred. per liter Entwicklerwlösung used warden "For developers, various additives may be added. such as Bntwicklungsverzögerer (such as Caliumbromid) training preventing of Piekken Yerbindungen such as -Alkalimetallsulfide, complexing agents, such as! ethylenediaminetetraacetic or the tetrasodium salt of 1,3 Diaffiiiio- »2-propanol tetraacetic acid and the like.

The following Examples® are intended to illustrate the invention in more detail. In Example 1 below, a multi-layered color film as described in US Pat. No. 2,772,163 was exposed in an intensity scale sensitometer (ilyj> 1 b KodakJ %% and then exposed for 5 minutes at 20 ^° C. in customary developers containing customary known buffering compounds. Furthermore, film strips which were exposed and developed in the same way were developed in the same developer, but instead of the known buffering compounds, water-soluble sulfonamide buffers were added to the developer *

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example 1

The materials used to develop dee fairphotograph! ▼ The developers used had the following composition:

Common color developer according to the inventor

water

Benzyl alcohol

Ethylenediaminetetraacetic acid Na ₉ SO,

1 liter 0 1 liter 6th ml 1 6th ml 4th 11 4th G 5 G 11 5 G 40 G 0 G 2.86 G 0 G 0 G 40 G 0.25 S. , 25 G 1.4 G , 4 G 1 1.3 G , 3 G 1 1.57 .57

Ha ^ P0j.12H ₉ 0

ÄtKylSndiamine

H-Ethyimethanesulfonamiß KBr

Citrazinic _{acid ώ}

Color developer pH at 23.9 C

4-Amino-N-ethyl-E (betaine thans \ ilfonamideaäthyl) ~ m-toluidinseaquiaulfat-monohydrate.

In the developer according to the invention, the buffer Ha ^ PO-, 12HgO and the development accelerator ethylenediasin were replaced by H-ethyl methanesulfonamide. The densities of blue IL _11x *, which are a measure of the yellow dye yields, dl "critical bind for this type of fila and development" were 3.90 for a film that was developed with the usual color developer and 3.90 for the film that was developed with the developer According to the invention, 3.95% was developed. In addition to the somewhat higher oil dye yield, the use of N-Ethylmsthansulfonaaides brings the

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- ίο -

Part of the goal is that a sehlammbil & uRg in the developer is avoided. The reason for this is that the phosphate ion leads to the formation of insoluble calcium phosphates when hard water is used, while the calcium salt of the sulfonamide is soluble. The buffer capacities of the phosphate and the U-ethyl methanesulfonainide are compared in Table 1 below. The buffer capacity is defined as dJU where dA is a differential dpi
the addition of the acid to the developer, while dpH represents the

represents the change in pH that occurs during this process.

buffer

Table 1

Developer in g / liter of buffer capacity solution ity at

pH 11.6

»4 2

40 0.008 80 0.013 120 0.018 10 0.007 20th 0.012 40 0.020

N-Ethylmetliansulfonamid ft

Since the phosphate ion is one of the best buffer ions in this represents the pH range, it follows from Table 1 that the Sulfonamide is also of excellent quality which is at least equal to the quality of the phosphate ion.

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Example 2

In this example developers are compared with one another, the once ale buffering compound sodium carbonate and the other ISethaneulfonamidj ^ contained "

Usual developer after winder of the invention

Water benzyl alcohol HaBr HaCl

1 liter ml 1 liter 10.0 G 12.64 G 12.64 ml G 0.417 G 0.417 G 0.730 G 0.730 G 2.08 G 2.08 G 4.17 G 4.17 G 2.08 G 2.08 G 0 G 40 G 22.52 G 0 7.92 0 10.0

Color developer CD-3 hydroxylamine sulfate Methaneulfonamide HaoCO ^

Hatriumseequiearbonat pH at 21.1 ⁰ C

Color photographic material such as it is described in U.S. Patent 2,772,163 is developed after exposure in a Kodak Type 1b sensitometer The sensitivity of the material developed in the developer of the invention was about 4 times the sensitivity of the material developed in the usual developer. That 4 fold increase in sensitivity has the advantage that only a quarter of the exposure time is required is to achieve the same densities using the developer of the invention as when using it of the usual developer. When using the developer according to the invention, no major fogging was found »

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As a result, the one used in the present invention increases Buffer oils effective sensitivity of the photographiechen Materials camouflages approximately two full blind values, without a normal carbonate buffer in comparison increased fogging occurs

When using the photographic battery winder according to the invention in the context of a color photographic process, the color-forming compounds can be arranged in the photographic emulsions, as for example in a photographic material, && b Xn US Pat. No. 2,772,163, color-forming compounds, dia % ν $ Particularly advantageous results when they are incorporated in photographic emulsions are described, for example, in US Pat. No. 2,860,976. The buffering compounds of the invention described can, however, also be used in the context of color photographic processes in which the color couplers are sugeactured to the developers. Couplers used in color developers are described, for example, in U.S. Patent 3,068,097.

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Claims (5)

- 13 claims 1. PhotograpixiBeher developer who is responsible for keeping constant of the pB value contains a buffering connection, thereby marked that it is used as a buffering connection a horizontal, non-reducing silver halide Contains sulfonamide. 2. A photographic developer according to claim 1, characterized characterized »that he is a sulfonamide of the following Formula contains R - SO ₉ - SH - (R ₁ ) NH - SO ₉ - H ₉ where mean} m and η 1 and 2 $ R is an alkyl or aryl group j H- an alkylene group} R _{2 is} a hydrogen atom, an alkyl or 'Aryl group when η * is 1 or a Alkyl or aryl group when η = 2 iet. 3. Photographiicher ittwickler according to claim 1 and 2 »thereby characterized as being a sulfonamide of the following ? or »el contains: Ä- SO ₂ HH - H ₂ 909807/0887 -H- in which meanι R 'is an alkyl or aryl group and Hydrogen atom, an alkyl or an ar ^ l group ,. 4. Phot © graphic developer according to claim 1 and 2, characterized in that it contains a sulfonamide of the following formula? E - SO ^ - KH - NH - SOo - '2 2 "2 where H and Rg are alkyl or aryl groups own* 5. Photographisöher developer naoh claims 1 and 2, characterized in that it contains a sulfonaiaid of the following formula % R - SO ₂ ~ HH - I ₁ - HH - SO ₂ in which 1st interpret * E _{1 is} an alkylene group and H and Sg alkyl or aryl groups, 909807/0887