DE1170777B - Stabilized photographic material - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school KJ .: G 03 c

German class: 57 b-8/02

Number: 1 170 777

File number: A 42031IX a / 57 b

Filing date: January 5, 1963

Opening day: May 21, 1964

The invention relates to the stabilization of photographic materials, the at least one with an alkylene oxide polymerization product containing sensitized halogen silver layer.

It is known that the general sensitivity of photographic silver halide emulsions is reduced by alkylene oxide derivatives, for example Äthylenoxydpolymerisationsprodukte, can be increased. Next to These polyalkylene oxide sensitizers have strong fogging Another unpleasant property that severely limits their usability, especially in the case of highly sensitive halogen silver emulsions. Halogen silver emulsions sensitized with polyalkylene oxide have a strong tendency to reduce the Sensitivity during storage. This decrease is considerable and can be an aperture or two be.

In order to counteract these deficiencies, it is already known to use these polyalkylene oxide derivatives together with to use certain stabilizers, as such the fogging depressants z. B. certain organic mercury compounds should be used.

Furthermore, certain compounds from the series of the tetrazaindenes, tetrazaindoles, pentaaziindenes, Urazoles and parabanic acid and derivatives of melonic acid and cyameluric acid as well as phenols and bisphenols became known for this purpose.

These additives have the disadvantage that they partly reduce the fog and partly the decrease in sensitivity of the _{photographic material sensitized with 3U} polyalkylene oxide derivatives during storage, but never completely eliminate both deficiencies.

It has now been found that Ortho-Hydioxybenzyliden- or benzylamino derivatives of the general formulas

OH

> - CH = N - X - R

and

OH

^ - CHo - NH - X - R

, 7

Stabilized photographic material

Applicant:

Agfa Aktiengesellschaft,

Leverkusen, Kaiser-Wilhelm-Allee 24

Named as inventor:
Dr. Wolfgang Müller-Bardorff, Cologne,
Dr. Wilhelm Saleck,:

Schildgen (Bergisch Gladbach),
Dr. Hans Ulrich, Leverkusen

Not only prevent the sensitivity achieved by halogen silver emulsions during storage, but also bring about an additional gain in sensitivity. In the general formulas, X is an alkylene or arylene group and R is an - OSO ₃ H group - or a sulfonic acid or carboxylic acid group or salts thereof. The benzene ring of the general formulas and the substituent X can in turn be substituted again. Examples of possible substituents are: halogen, hydroxyl, alkyl, alkoxy, sulfonic acid or carboxyl.

There are therefore a variety of suitable radicals available, through which different properties of connections, such as B. their water solubility can be influenced.

Suitable compounds are e.g. B .:

40

45

the haze and the decrease in the effects of the addition of polyalkylene oxide sensitizers and a basic stabilizer z. B. of the type of the azaindolizine

OH

I _{- CH 2} - NH - (CHj) ₃ - COOH

OH

CH = N - CH ₂ - COOK

CH ₂ - NH - CH ₂ - COOH

409 590/392

IV

OH

XIV OH

Ο _ \ - CH, - NH - CH ₂ - COOH Br-

■ CH, - NH - CH, - COOH

Cl

OH XV

ίο HOOC

OH

-CH = N-CH-

-COOK

-CH, - NH- <

COOH

VI
H ₃ CO

VII

OH

- I - CH ₂ - NH - CH ₂ - COOH

OH

CH = NH CH ₂ CH. O SO ₃ K

VIII

OH

CH .-- NH-CH ₁ CH, OSO ₁ H

IX

OH

HO

- CH = N - CH, - COOK

X
H ₃ C-

XI
tert. C ₄ H ₉

XII

OH

OH

OH

CH = N-CH (CH ₂ ) ₂ COOK

COOK

CH = N CH (CH ₂ ) ₂ COOK COOK

CH = N CH (CH ₂ ) ₂ COOK COOK

XIII
C ₄ H ₉ -O - '

OH

·, - CH ₂ - NH - CH, - COOH The abovementioned compounds are largely described in the literature, e.g. B. in P. P feiffer, J. pr. (2), p. 159 (1941); Fraehnhel - Conrat, J. biol., 174, p. 827 (1948); Bergmann, Ensl in, J erras, B., 58, p. 1038. The azomethine compounds can be prepared by allowing 1 mol of optionally substituted aldehyde to act on 1 mol of alkali metal salt of an amino acid in aqueous solution. The hydrogenation of the azomethine compounds can easily be carried out in aqueous solution with the aid of a Raney nickel catalyst.

The invention applies to all photographic silver halide emulsions applicable. The halogen silver can consist of chlorine, bromine, iodine silver or mixtures thereof exist; however, silver bromide emulsions are preferred. These emulsions can additionally sensitized, for example with sulfur compounds such as sodium sulfite, thiourea derivatives or alkali rhodanides, as well as noble metal sensitizers such as gold salts. In addition, you can they are visually sensitized, e.g. B. by cyanine, meiocyanine dyes and the like.

Organic mercapto compounds, quaternary benzothiazoles, triazoles, tetrazaindolizines and the like can be added as basic stabilizers.
Another advantage of the photographic material according to the invention is that hydrophobic or hydrophilic color couplers can be incorporated into the emulsions. The compounds according to the invention can also be used in photographic materials in which colored photographic images are produced by the color development process.

The condensation products of alkylene oxides, preferably ethylene oxide, can be used as polyalkylene oxides be used among themselves or with aliphatic alcohols, acids and amines or phenols. Those polyethylene oxides which contain quaternary nitrogen groups are also suitable. It will those products which have a molecular weight of at least 1500 are preferred. The applicable The amount depends on the halogen silver content of the emulsion and varies between 0.01 and 1 g per 1 kg of emulsion. The optimal amount must be determined empirically for each emulsion.

The addition of the orthohydroxybenzyl- or -benzylidene-amino compounds to be used according to the invention takes place preferably before chemical ripening. Some of the compounds dissolve in organic compounds Solvents, partly in water, partly in water containing a little alkali or acid.

The compounds are used in concentrations of 0.1 to 1 g per 1 kg of emulsion (preferably 0.35 g / kg) used. The optimal amount to be added depends on the constitution of the

applying compound and the type of emulsion. You can do this without difficulty through a few attempts be determined. The compounds can also be added to the finished photographic layer in the bath process incorporate.

The mode of action of the photographic material according to the invention is illustrated by the following examples shown without limiting the invention.

For example

One now treats the three samples A, B and C, as indicated in Example 1, the photographic material produced in this way can five months: store, subjecting a Teil'des material 3 days a Heizschranktemperatur of 6O ⁰ C and exposed to light and then developed this material and, for comparison, the corresponding samples stored at normal temperature.

A highly sensitive bromine-iodine-silver-gelatin emulsion, which contains 4 g of silver iodide and whose silver halide content per liter corresponds to 50 g of silver, For chemical ripening, the usual ripening additives are added (35 to 40 mg / 1 KBr and a gold rhodanide solution). This emulsion is divided into three parts A, B and C.

Part A is tested as a comparison sample without any further additives.

Part B is mixed with 300 mg / l of compound I.

Part C is admixed with 600 mg / l of compound I.

After all three samples A, B and C digestion until maximum sensitivity is reached they are panchromatically sensitized with an azaindolizine as a stabilizer as well as with 200 mg / 1 of a polyethylene oxide (molecular weight greater than 1500) and added to one of the usual film materials drawn.

After 5 months of storage, some of these photographic materials thus prepared become Stored for 3 days at 60 ° C in a heating cabinet and for comparison against the corresponding samples, stored at normal temperature, exposed and developed.

The result can be seen in Table 1:

Table 1 Attempt a
Normal storage
Heating cabinet sensitivity gamma veil Attempt B
Normal storage
Heating cabinet Type
-1.5 ° Din 0.55
0.55 0.22
0.28 Attempt C
Normal storage
Heating cabinet Type
same type 0.55
0.55 0.28
0.31 Type
+ 1.5 ° Din 0.50
0.50 0.25
0.29

40

45

Regarding the sensitivity, it should be pointed out that an increase in sensitivity of 3 ° Din corresponds to an increase of one f-stop.

Example 2

A highly sensitive bromine-iodine-silver emulsion, as described in Example 1, is divided into three parts A, B and C.

Part A is tested as a comparison sample without any further additives.

Part B is admixed with 300 mg / l of compound IV.

Part C is admixed with 600 mg / l of compound IV.

The result shows Table 2: ... s veil Table 2 gamma 0.23
0.23 sensitivity ■ 1
0.5
0.5 0.22
0.25 Attempt a
Normal storage
Heating cabinet Type
-1.5 ° Din 0.5
0.5 0.24
0.29 Attempt B
Normal storage
Heating cabinet Type,
+ 1.5 ° Din 0.5
0.5 ■ Attempt C
Normal storage
Heating cabinet ..... Type
'± 0 ° Din

From this table it can be seen that the optimal amount of the addition of the compound IV (experiment B) must be determined in each case.

Example 3

A highly sensitive bromine-iodine-silver emulsion described in Example 1 is divided into 3 parts A, B and C.

Part A is ripened as a comparison sample without any further additives.

Part B is mixed with 300 mg / l of compound VIII.

Part C is admixed with 600 mg / l of compound VIII.

All three samples A, B and C are now treated as indicated in Example 1, but it is left as it is The photographic material produced is stored for 5 months and a part of the material is subjected to 3 days long a heating cabinet temperature of 60 ° C. This material is then exposed and developed and also, for comparison, the corresponding samples that were stored at normal temperature.

Table 3 summarizes the result:

^ÖU table 3 sensitivity gamma veil Type
-1.5 ° Din 0.55
0.55 0.20
0.43 55 Part A
Normal storage
Heating cabinet Type
± 0 ° Din 0.55
0.5 0.20
0.25 part B
Normal storage
^5o heating cabinet Type
± 0 ° Din 0.55
0.5 0.26
0.33 Part C.
Normal storage
Heating cabinet

65

Claims (5)

Patent claims: 1. Photographic material containing in at least one layer an alkylene oxide polymerization contains product and a basic stabilizer, characterized in that the Material additionally ortho-hydroxybenzylidene or -benzylamino derivatives of the general formulas OH CH = N-X-R and II OH - CH ₂ -NH-X-R \ ■ /
\ y contains, where X is an alkylene or arylene group and R is an O - SO ₃ H radical, a sulfonic acid or carboxylic acid group or their salts. 2. Photographic material according to claim 1, characterized in that it is used as polyalkylene oxides Condensation products of alkylene oxides with aliphatic alcohols, acids, amines and / or phenols with a molecular weight of at least 1500. 3. Photographic material according to claims 1 and 2, characterized in that it contains compounds of the azaindolizine type as a basic stabilizer. 4. Photographic material according to claims 1 to 3, characterized in that the photographic emulsion in addition to the polyalkylene oxides mentioned, noble metal salts and / or Contains sulfur compounds. 5. Photographic material according to claims 1 to 4, characterized in that it a stabilizer of the formula OH Cl-. -CHo-NH-CH ₂ -COOH Cl contains. 4M 590/392 5.64 © Bundesdruckerei Berlin