DE2032078A1 - Stabilization of photographic material - Google Patents

Description

AQTA- OI V AERT AQ

iÄVBRKtWEN 25 June 1170

Stabilization of Photographic Hatorial

Priority: Great Britain, Thu 3 Jul 19 © 9. Note Mr. 3k k} 2/6 $ Gevaert-Agfa N »V ·, Hortsel, Belgium ·

The invention relates to the stabilization of photographic material, the light-sensitive Silver halide emulsions, and in particular the Reduction of fogging in photographic material without a noticeable Cause desensitization.

It is known that light-sensitive material having gelatin-silver halide emulsion layers is exposed to fogging · Fogging in general and chemical fogging in particular can be seen as the formation of a uniform silver precipitate when developing and depends on a whole range of circumstances and factors, in particular on the type of emulsions, their a Age, their storage conditions, the development conditions, etc. Under certain developmental conditions tend to form very veil when the storage time and the temperature and relative humidity the air in which the emulsions are stored is extended or increased.

All stabilizers or anti-egg agents known additives eu photographic Material protect the light-sensitive silver halide emulsions against the formation and expansion of fog, especially with highly sensitive emulsions and with emulsions that operate at high temperatures and moisture must be stored, as in the case of tropical Countries"

Be has now ftfundtn _f do · * Vorbindungen, the anions of acetylene dicarboxylic Ii ο away, an advantageous schleiorverhtitende effect on ^ photosensitive Silberhalosonideinulsionon have without a bemerkohs- "erte Deseneibilieierung cause the photosensitive material · This Vorbindungen include Ac 0 ty lendi carboxylic acid selbet , so v / ie * ^B1

009885/1502

GV.396. ORjQiNAi INSPECTED

easily the aerosol derivatives of acetylenedicarboxylic acid, for example • in mono- or dialkali metal salt, oin mono- or ifcaeeoniuaaalz . aono- or diorganic ammonium salt such as, for example, monoanilinium salt, dianilinium salt, di-α-chloroanilinium salt, di-p-methoxyaniliniurasalzr Di-p-toluidium salt, di-m- and -p-sulfoanilinium salt, di (diethylammonium) - «Alz, di (triethylammonium) 3 salt, dipyridinium as, etc. as well as mono- or Diesters of acetylenedicarboxylic acid, provided they dissociate easily and so that anions of acetylenedicarboxylic acid can be supplied, such as, for example, the dibenzohydryl ester.

'The anti-fogging agents to be used according to the invention or Stabilizers are generally incorporated into the silver halide emulsion layer of the light-sensitive material. The manner, P 'in which the compounds used according to the invention are emulsions added is irrelevant, 'and the addition can be made in the case of a any step of the emulsion preparation take place; you can before or be added after the optical sensitization, preferably immediately before the application of the emulsion to a suitable carrier, v / ie for example paper, glass or film.

Instead of the compounds according to the invention in the emulsion layer they can also be introduced into another layer of the photographic Material are introduced, for example in a gelatin-containing Protective layer or intermediate layer in vaseerdurnhlSeelg «r R *» 7.i «luine to said emulsion layer, or in one of the processing baths for said photographic material.

The anti-fogging agents according to the invention can be used for any type of light-sensitive silver halide aeratorial, as well as for partially sensitized or non-sensitized silver halide material, for a diffusion transfer process for the production of Material used for silver images and for a radiographic silver halide material. They can be used for highly sensitive negative material as well as for low-sensitivity positive material. " Various silver salts can be used as photosensitive salt are, for example, silver bromide, silver iodide, silver chloride or mixed silver halides, v / ie for example silver chlorobromide or Silver bromoiodide.

OV. 396 009 885/150 2

The silver halides are like in the common hydrophilic colloids Gelatin, casein, zein, polyvinyl alcohol, carboxymethyl cellulose, alginic acid, etc. are dispersed, although gelatin is preferred.

- "" ■■■ '■ "" ■. ·

The amount used in the silver clogenide photosensitive material of anti-seal agent depends on the type of emulsion and the desired effect and can vary within very wide limits is best determined on a trial basis for each individual type of emulsion In general, the most suitable concentration is between 0.2 millinoles and 30 millimoles of anti-fog agent per mole of silver halide *

The light-sensitive emulsions can be chemically as well as optically sensitized.They can be chemically sensitized by ripening in the presence of small amounts of sulfur-containing compounds, such as allyl thiocyanate, allyl thiourea, sodium thiosulfate, etc. The emulsions can also be sensitized by means of reductors, for example tin compounds as described in British Patent No. ? & 9 823, as well as small amounts of precious metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium *

Other additives such as hardeners, wetting agents, plasticizers, color couplers, developing agents and optical sensitizers can be used in be introduced into the emulsion in the usual way *

The anti-corrosion agents according to the invention are particularly suitable for use in conjunction with compounds that sensitize the emulsion by accelerating development, such as Alkylene Oxide Polymers * These alkylene oxide polymers can be different Be kind. Various derivatives of alkylene oxides can be used to sensitize the silver halide emulsions, for example Alkylene oxide condensation products such as those described in U.S. Patents Nos. 2,531,832 and 2,533,990 in British Patents, among others No. * 920 63? - 9 ^ 0 051 - 9 ^ 5 3 ^ 0 and 991 6Ο8 and in Belgian patent specification No. 6 ^ 8 710. Other connections that the Sensitize emulsion by accelerating the development and to Use in conjunction with those to be used according to the invention

_n " _lQfi 009885/150 2

. , anti-smear agents are suitable, oind the Oniunderivat® from Araino- H-oxides vegetables Description in the Belgian patent specification No. 686 520

The stabilizers according to the invention can also be used in combination. other known stabilizers can be used, for example with * heterocyclic! nitrogen-containing thioxo compounds, such as benzothiazoline-2-thione and 1-methyl-4X-tetrazoline-5-thione, with mercury compounds vie. those described in Belgian patents Nos. 52 ** 121 - 677 337 - 707 335 and 709 195 and with compounds of the hydroxytriazol-pyrimitlin type (hydroxyazaindolizines) such as, for example, 5-ethyl-7-hydroxy-s-triazole £ i, 5 -a] jpyrimidine «

^ The invention is illustrated by the following examples.

Example 1

A conventional photographic gelatin silver bromoiodide emulsion (h _t 3 mol % iodide), which contains an amount of silver halide corresponding to 50 g of silver nitrate per kilogram, is divided into two parts A and B. The emulsion part B is acetyl dicarboxylic acid diammonium salt in a concentration of 1 mmol per kg of the emulsion added, while no anti-fogging agent is added to emulsion part A The emulsions are then applied to a conventional carrier and dried

• The sensitivity, gradation and haze values of the produced V materials A and B are determined shortly after preparation and after a 5-day incubation at 57 ^e C and 3 ** % relative humidity. coincide with a density of 0.1 above the veil * The fresh material A receives the value 100; The development takes place at 20 ° C for 5 minutes in a developer solution with the following composition:

water 800 cm3 p-monoracthyl arainopheriol sulfate 1, , 5 g anhydrous sodium sulfite 50 _ β Hydroquinone 6th G anhydrous sodium carbonate 32 G Potassium bromide 2 ε Water to prepare 1000 cm3

QV.396 009885/1502

> ■ veil Frischraat erial > veil gradation -
Sensation
opportunity material 0.10
O, 18 gradation Sensation
opportunity 0.96
0.19 1.3 *
1.35 63
Cn 1.85
1.77 100
85 Incubation material A.
B.

From these results it clearly follows that the acetylenedicarboxylic acid diararaonium salt has a beneficial anti-glare effect Acetylenedicarboxylic acid diacimonium salt is an equally advantageous: veil preventive effect observed ',

Example 2 Example 1 is repeated with the intorechiod that emulsion B is now 2 nlfol Acetylenedicarboxylic acid dianiliniiifliap.lz per kg of the emulsion contains

The results obtained are shown in the table below · The The words given for the sensitivity are relative values that start with match a density of 0.1 above the haze; the value 100 is given to the fresh material that does not contain any anti-haze agent according to the Invention contains *

Tabel veil Fragrant material ^; Sensation
opportunity Incubation material gradation Sensation
opportunity material 4 ¹⁰
0.15 gradation 100
61 veil 1.3 *
1.29 63
80 1.85
1.77 0.96
0.22 A.
B.

The above results show that the dianilinium salt of acetylenedicarboxylic acid has a beneficial anti-lock effect and does not cause desensitization.

BAD ORJGiNAL,

00988671502

jeiapiel 3 . *

Example 1 is repeated with the difference that Emuleion B now contains 1 aMol AoetylenedicarboneHüifo-di-p ^ oluiJiniuDeal * Jo kg of the Eaulsion «

t) The results obtained are listed in the table below The values given for the sensitivity are relative values that are marked with match a density of 0.1 above the haze; the value 100 is given to the fresh material »which is not an anti-haze agent according to the Invention contains

material veil 4th Friechmat eri al Is
opportunity
• veil Incubation material Sensation
opportunity 0.12
0.16 gradation 100
114 1.02
0.20 gradation 104
71 A.
B. 1.52
1.45 0.78
1.1 « example

This example shows that derivatives of acetylenedicarboxylic acid ^ which are not dissociate easily and do not give acetylenedicarboxylic acid anions, are unsuitable as anti-sluggish agents because they are completely inert and do not prevent fogging.

An emulsion as described in Example 1 is divided into four parts A, B, C and D divided * The emulsion ingredients B, C and D are added per kg: 2 amol acetylenedicarboxylic acid dinethyl ester, 2 amol acetylenedicarboxylic acid diisopropyl ester or * 2 mmoles acetylenedicarboxylic acid dibenzohydryl ester, during the Eraulsion part A no achleiorwitirieeo receives remedies

The emulsions are then applied to a film base and dried *

The values of the materials in the '/., B ₁ C and D formed veil' are bestirnt relative humidity just after the preparation and after an incubation 5tlgigon boi -57 ^e C and 34%. The development is carried out as described in Example 1. The results are listed in the table below.

009885/1502

material Veil in] A. , 0.07 B. 0.08 C. O, O8 D. 0.06

Veil in stored material.

0.68 0.63 0.60 0.16

These results show that only dibenzohydryl esters have an anti-skid effect, since they provide acetylenedicarboxylic acid anions can, while the Dimethyleetcr and Diisopropylester completely inert are.

The dibenzohydryl ester of acetylenedicarboxylic acid was prepared as follows.

2 g p-toluenesulfonic acid monohydrate, 500 ml of anhydrous benzene ^s added. That Benno! It is distilled off until the p-toluenesulfonic acid is drained. Then 36.0 g (0.2 mol) of benzohydryl alcohol and 11.4 g (0.1 mol) of acetylenedicarboxylic acid were added and the reaction mixture was refluxed for 16 hours, during which the azeotropic mixture of water and alcohol was distilled off. The mixture was evaporated and the dibenzohydryl ether of acetylenedicarboxylic acid obtained is recrystallized from η-hexane. Yield: 2k g (53 %) . Melting point: 79 ° C ·; -

GV.396

009885/1502

Claims (1)

Claim © ^ "■ '. A method to prevent the wear and tear in photograpaiechep Silberhalogenid ^ tericl, that a carrier usfaeet ', Ä®r old water-permeable colloid layers, which optionally contain silver halide, is coated, characterized in that @@ dloHl ttrial "AchbäurÄäßiger Bellehtoag im üegmmBäßiger Bellehtoag # -Anloa «n 2. The method nsch claim 1, characterized in that the processing gokmnseictmet takes place in the presence of a development accelerator of the polyoxyalkylene type '. . P 3 * Photographic material, the qinen carrier and raindeetens one . Comprises silver halide efflulsion layer, is it? EBtÜeJfHieeMdifc and / or in at least one on the same side as the carrier Emulsion layer applied \; ascer-permeable layer a Contains compound that supplies acetyl dicarboaric acid anions k. Photographic material according to Claim 3, characterized in that the compound is acetylenedicarboxylic acid or a readily dissociative derivative of the acetylenedicarboxylic acid 5 · Photographic material according to claim%, characterized in that that the easily dissociating acetylenedicarboxylic acid derivative . Mono- or dialkaline metal cccls, a honey or diasmonium salt or a mono- or diorganic AaiQoniumsas the Acetylenclicarbonshure is 6. Photographic material according to claim h, characterized in that the easily dissociating acetylenedicarboxylic acid derivative is a readily dissociating mono- or diester of acetylenedicarboxylic acid. 7 · A photographic material according to claim 6, characterized in that _t the £ eter a mono- or Dibenzohydrylester of-Acetylendicarbonsöure is · _{αν # 396} 009885/1502 8. Photographic material according to claim 5 »characterized in that öaa diorganic ammonium salt is the dianilinium salt which is acetylenedicarboxylic acid. , » 9. Photographer's material according to one of Claims 4 to 8, characterized in that it is the acetylenedicarboxylic acid or contains the easily dissociative derivative of the light-sensitive silver halide emulsion layer in an amount between 0.2 and 30 millimoles per mole of silver halide. . ·. 10. Photographic material according to any one of claims 3 to 3 9, characterized in that the material is a development accelerator of the polyoxyalkylene type. 11. Photographic material according to any one of claims 3 to 9, characterized in that the emulsion layer is a gelatin-silver halide emulsion layer. GV.396 009885/1502