US3567454A

US3567454A - Light-sensitive materials

Info

Publication number: US3567454A
Application number: US684622A
Authority: US
Inventors: Jozef Frans Willems; Robrecht Julius Thiers; Adam Marcel Schouwenaars
Original assignee: Agfa Gevaert NV
Current assignee: Agfa Gevaert NV
Priority date: 1966-12-12
Filing date: 1967-11-21
Publication date: 1971-03-02
Anticipated expiration: 1988-03-02
Also published as: DE1597501A1; GB1173609A; BE707386A

Abstract

PHOTOGRAPHIC MATERIALS COMPRISING A SUPPORT AND AT LEAST ONE LAYER OF LIGHT-SENSITIVE SILVER HALIDE EMULSION CONTAINING A WATER-SOLUBLE MERCURY(II) COMPOUND HAVING ONE OF THE FOLLOWING FOMRULAE:

(M-O3S-X1-S)2-HG AND M-O3S-X2-S-HG-Y

WHEREIN: X1 IS A BIVALENT ORGANIC RADICAL, X2 STANDS FOR AN ALIPHATIC OR AROMATIC BIVALENT GROUP, M REPRESENTS HYDROGEN, ALKALI METAL, ALKALINE EARTH METAL, AMMONIUM, GUANIDINE OR AN ORGANIC AMIND, AND Y STANDS FOR AN ALIPHATIC, ALICYCLIC, AROMATIC OR HETEROCYCLIC RADICAL, SAID RADICALS INCLUDING THE SUBSTITUTED DERIVATIVES THEREOF ARE DESCRIBED. THE PHOTOGRAPHIC MATERIAL HAS IMPROVED STABILITY AND FOGGING CHARACTERISTICS.

Description

United States Patent Ofice 3,567,454 Patented Mar. 2, 1971 3,567,454 LIGHT-SENSITIVE MATERIALS Jozef Frans Willems, Wilrijk, Robrecht Julius Thiers, Brasschaat, and Adam Marcel Schouwenaars, Edegem, Belgium, assiguors to Gevaert-Agfa N.V., Mortsel, Belgium No Drawing. Filed Nov. 21, 1967, Ser. No. 684,622

Claims priority, application Great Britain, Dec. 12, 1966,

55,445/ 66 Int. Cl. G03c 1/34 US. Cl. 96-109 7 Claims ABSTRACT OF THE DISCLOSURE Photographic materials comprising a support and at least one layer of light-sensitive silver halide emulsion containing a water-soluble mercury(II) compound having one of the following formulae:

wherein:

X is a bivalent organic radical,

X stands for an aliphatic or aromatic bivalent group,

M represents hydrogen, alkali metal, alkaline earth metal,

ammonium, guanidine or an organic amine, and

Y stands for an aliphatic, alicyclic, aromatic or heterocyclic radical, said radicals including the substituted derivatives thereof are described. The photographic material has improved stability and fogging characteristics.

This invention relates to improved light-sensitive silver halide emulsions.

Light-sensitive silver halide emulsions are in general characterised by their sensitivity, gradation and fog.

As is well-known, sensitivity, gradation and fog are determined by the way in which the silver halide emulsion is prepared and by the use of special chemical ingredients elfecting a desired improvement or reuslt. Addenda to the emulsion, which are of particular importance for the stability of the light-sensitive characteristics of a silver halide emulsion are the so-called stabilizers.

Stabilizers or antifoggants protect the light-sensitive silver halide emulsions against spontaneous formation and growth of fog known as chemical fog during prolonged storage or storage at high temperatures and humidities or during development to maximum contrast and speed. Indeed, the fog increases with the degree and temperature of development, and, in constant development circumstances, with the time the light-sensitive emulsion is stored and with the temperature and the relative humidity of the atmosphere wherein the emulsion is stored. It is evident that a light-sensitive emulsion should be obtained which is as stable as possible at high temperature and high relative humidity for instance in view of its use in tropical countries.

It is known to protect light-sensitive silver halide emulsions against the growth of chemical fog during storage by addition of stabilizers of the triazolopyrimidine type (azaindolizines). Heterocyclic thioxo and mercapto compounds too have been proposed for this purpose but show the disadvantage of impairing the sensitivity and gradation. The same disadvantageous influence on the sensitivity occurs with the known mercury compounds such as simple anorganic mercury salts, addition complexes of mercury with amines, organic mercury salts and heterocyclic mercury compounds. Indeed, these compounds, when used in the concentration necessary for obtaining a sufficient antifogging action, have a considerable desensitizing effect.

It is also known that emulsions stabilised with compounds of the triazolopyrimidine type still show a tendency to fog formation in extreme storage circumstances i.e. at very high temperatures and humidities and in extreme development circumstances e.g. rapid processing at elevated temperatures. The addition to these emulsions of the above known mercury compounds reduces the fogging tendency but, as mentioned above, at the cost of a reduction of the sensitivity.

It has now been found that mercury(II) compounds corresponding to one of the following general Formulae I and II X, represents a bivalent organic radical e.g. an aliphatic, aromatic or heterocyclic bivalent radical such as alkylene including substituted alkylene, arylene including substituted aralkylene and a bivalent radical comprising a heterocyclic nucleus including a substituted heterocyclic nucleus,

X stands for an aliphatic or aromatic bivalent group such as alkylene including substituted alkylene, arylene including substituted arylene, and aralkylene including substituted aralkylene,

M represents hydrogen, an alkali metal or alkaline earth metal, ammonium, guanidine, an organic amine, etc., and

Y stands for an organic aliphatic, alicyclic, aromatic or heterocyclic radical said radicals including the substituted alkyl, aryl including substituted aryl and a heterocyclic nucleus including a substituted heterocyclic nucleus,

are particularly good stabilizers and antifoggants for photographic light-sensitive silver halide emulsions without causing an appreciable desenitization of the light sensitive silver halide emulsion material.

Moreover, it has been found that these mercury(II) compounds are very suitable for use in combination with stabilizers of the triazolopyrimidine type, particularly in extreme storage and development circumstances in order to reduce the fogging tendency of the light-sensitive emulsion without giving rise to an appreciable desensitization thereof.

The high-water-solubility, obtained by the presence of the sulphonic acid group in the mercury(II) compounds of the above general formula guarantees a homogeneous distribution of the stabilizer in the emulsion.

The following is a non-limitative list of particularly suitable mercury(II) compounds for use as stabilizers for photographic light-sensitive silver halide emulsions according to the present invention:

The watersoluble mercury(II) mercaptides of use according to the present invention can be prepared by allowing to react a mercury (II) salt such as mercury(II) acetate or mercury(II) chloride with the corresponding mercapto compound. The said mercury(II) mercaptides can also be obtained in a very pure form by reaction of mercury(II) oxide with the corresponding mercapto compound.

The mercury(II) compounds corresponding to the above general Formula II can be prepared by allowing to react the corresponding organo-mercury salts such as the chlorides, bromides or acetates or the corresponding organomercury hydroxides with the sulphonated mercaptans.

The following preparations illustrate more particularly how the mercury(II) compounds are prepared.

PREPARATION l.COMPOUND 1 (a) To a solution of 10.75 g. (0.05 mole) of the guanidine salt of 3-mercapto-propane sulphonic acid in 55 ccs. of water a solution of 7.95 g. (0.025 mole) of mercury(II) acetate in 35 ccs. of water was added. The water was distilled off under reduced pressure and the mercury(II) mercaptide formed was recrystallized from methanol.

.(b) To a solution of 43 g. (0.2 mole) of the guanidine salt of 3-mercapto-propane sulphonic acid in 500 ccs. of water, 21.6 g. (0.1 mole) of yellow mercury(II) oxide 4 were added with vigorous stirring. After evaporation of the water the residue was washed with acetone.

PREPARATION 2COMPOUND 3 To a solution of 13.15 g. (0.05 mole) of the guanidine salt of o-sulpho-benzyl mercaptan in 300 ccs. of water a solution of 7.95 g. (0.025 mole) of mercury(II) acetate in 50 ccs. of water was added. A white precipitate formed, which was filtered by suction and washed with alcohol.

PREPARATION 3.COMPOUND 4 To a solution of 12.8 g. (0.05 mole) of the guanidine salt of Z-mercapto-4-methyl-4-sulpho-pentane in 400 ccs. of water a solution of 7.95 g. (0.025 mole) of mercury(II) acetate in 50 ccs. of water was added. After evaporation of the water the residue was digested with methanol and dried.

PREPARATION 4.-COMPOUND 5 To a solution of 7.7 g. (0.03 mole) of S-(m-sulphophenyl)-triazoline-3-thione in ccs. of water a solu tion of 4.78 g. (0.015 mole) of mercury(II) acetate in 25 ccs. of water was added. The precipitate formed was filtered by suction and washed with water and ethanol. The mercury(II) mercaptide formed is soluble in diluted sodium hydroxide.

PREPARATION 5.COMPOUND 7 (a) 79 g. of mercury(II) acetate, 15.5 g. of allyl alcohol and 150 ccs. of methanol were refluxed for 5 min. The excess of methanol and the acetic acid formed were distilled oiT under reduced pressure. The product obtained (32 g.) had an oxygen content of 18.76% (calculated: 18.4%).

(b) 3.48 g. of the product obtained in ,(a) were treated with an aqueous solution of 2.15 g. of the guanidine salt of 3-mercapto-propane sulphonic acid. The water was distilled 01f under reduced pressure and the residue purified with ethanol.

PREPARATION 6.COMPOUND 8 A solution of 10 g. of allylurea in ccs. of methanol, 31.9 g. of mercury(II) acetate and 6 ccs. of acetic acid were refluxed for 6 hours. The excess of methanol and the acetic acid formed were distilled off under reduced pressure.

To the residue an aqueous solution of 21.5 g. of the guanidine salt of 3-mercapto-propane sulphonic acid was added with vigorous stirring. The mercury(II) compound formed was purified with ethanol.

PREPARATION 7.-COMPOUND 12 (a) To a solution of 13.5 g. of mercury(II) chloride in 200 ccs. of water a solution of 6 g. of sodium hydroxide in 25 ccs. of water was added. The precipitate formed was filtered 01f by suction and washed with water until no chloride ions could be indicated anymore.

The product was suspended in 50 ccs. of water and then an aqueous solution of 22 g. of salicylic acid was added with stirring. After some hours the suspension formed was concentrated by evaporation and the resi due digested with ethanol.

(b) 4.3 g. of the compound obtained according to (a) were treated with an aqueous solution of 1.8 g. of the sodium salt of 3-mercapto-propane sulphonic acid. After having concentrated the solution by evaporation the residue was purified with ethanol.

As compared with the known mercury compounds used as stabilizers the mercury(II) compounds according to the present invention when used in the appropriate concentration do not cause or only to a slight extent a decrease in sensitivity.

The antifoggants according to the present invention are particularly suitable for use in combination with cornpounds which sensitize the emulsion by development ac celeration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in United States Pat. 2,531,832 and 2,533,990, in United Kingdom Pat. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. 648,710 and onium derivatives of amino-N-oxides as described in US patent application Ser. No. 573,801, filed Aug. 22, 1966, and now pending.

The stabilizers according to the inventions can also be used in combination with other known stabilizers for instance with heterocyclic nitrogen containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2- tetrazoline-S-thione and, as said above, preferably with compounds of the hydroxytriazolopyrimidine type (azaindolizines).

The stabilizers according to the present invention may be incorporated into any type of light-sensitive material comprising a silver halide emulsion layer e.g. a spectrally sensitized or non-sensitized emulsion layer, X-ray emulsion layer, and an emulsion layer sensitive to infra-red radiation. They may be incorporated into high-speed negative materials as well as into rather low speed positive materials. Various silver salts may be used as lightsensitive salt e.g. silver bromide, silver iodide, silver chloride, or mixed silver halides e.g. silver chloro-bromoide or silver bromo-iodide.

The silver halides are dispersed in the common hydrophilic colloids such as gelatin, casein, zein, polyvinyl alcohol, carboxymethylcellulose, alginic acid, etc., gelatin being however favoured.

The stabilizing agents are generally incorporated into the silver halide emulsion layer of the light-sensitive material; they may be added to the emulsion during no mat ter what step of emulsion preparation; however, they are preferably added to the photographic emulsion after the chemical ripening and just before coating of the emulsion. The addenda according to the present invention are incorporated into the photographic emulsions accord ing to the methods well known in emulsion preparation. For instance they can be added to the emulsion in the form of a solution or of a dispersion according to the methods applied for incorporating colour couplers in the emulsion. Instead of incorporating the compounds of the invention into the emulsion layer they can also be incorporated into a water-permeable layer e.g. a gelatin covering layer or intermediate layer.

The amount of mercury(II) compound employed in the light-sensitive silver halide material depends on the particular type of emulsion and the desired effect and can vary within very wide limits. The optimum amount of mercury(II) compound to be added can be determined for each particular emulsion in a very simple way by application of the usual tests. Usually said compounds are employed in a ratio of about 0.1 mg. to about 30 mg. per mole of silver halide.

The light-sensitive emulsions may be chemically as well as optically sensitized. They may be chemically sensitized by eifecting the ripening in the presence of small amounts of sulphur containing compounds such as allylthiocyanate, allyl thiourea, sodium thiosulphate, etc. The emulsions may also be sensitized by means of reductors for instance tin compounds as described in our French patent specification 1,146,955 and in our Belgian patent specification 568,687, imino-aminomethane sulphinic acid compounds as described in our British patent specification 789,823 and small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium.

Other addenda such as hardening agents, wetting agents, plasticizers, colour couplers, developing agents and optical sensitizers can be incorporated into the emulsion in the usual way.

The following examples illustrate the present invention.

Example 1 A high sensitive gelatino silver bromoiodide emulsion (:4.5 mole percent of iodide) is divided into six aliquot portions A, B, C, D, E and F.

To emulsion portion B is added per mole of silver halide 1.2 l0 millimole (3 mg.) of mercury (II) cyanide, to emulsion portion C 0.6 10- millimole (3.8 mg.) of compound 1, to emulsion portion D 1.2 10- millimole (7.5 mg.) of compound 1, to emulsion portion E 2.0 10- millimole (10 mg.) of compound 7 and to emulsion portion F l.2 10- millimole (6.6 mg.) of compound 8. The six emulsions are then coated on a subbed cellulose triacetate support and dried whereupon the six materials thus obtained are stored for 5 days in an atmosphere of 57 C. and 34% of relatively humidity.

The stored materials as well as six identical freshly prepared materials are exposed and developed for 5 minutes at 20 C. in a developing bath with the following composition:

Water-800 ccs.

p-Monomethylaminophenol sulphate-15 g.

Sodium sulphite (anhydrous)50 g.

Hydroquinone--6 g.

Sodium carbonate (anhydrous)-32 g.

Potassium bromide-2 g.

Water up to1000 ccs.

After the treatment in a stop bath, rinsing and fixing of the materials the following sensitometric results are obtained.

TABLE Freshly prepared materials Stored materials Relative Relative Gradaspeed Gradaspeed Material Fog tion (percent) Fog tion (percent) A gelatino silverbromoiodide emulsion (0.35 mole percent of iodide) comprising per mole of silver halide 400 mg. of 5 methyl 7 hydroxy-s-triazolo [LS-a]- pyrimidine and '5 mg. of 1-phenyl-2-tetrazoline 5-thione as stabilizers, 200 mg. of development accelerator corresponding to the formula:

wherein x has a value of about and 2 g. of saponin as coating aid, is divided into 4 aliquot portions.

To three of these emulsion portions is added an amount of compound 1 as listed in the table below.

The four emulsions are coated on both sides of a cellulose triacetate support, which has been provided on both sides with a subbing layer, in such a way that per sq. m. an amount of silver halide equivalent to 36 g. of silver nitrate (both sides taken together) is present.

The emulsion layers are then overcoated with a gelatin antistress layer.

The four materials A, B, C and D obtained are then stored for 36 hours in an atmosphere of 57 C. and 34% of relative humidity.

Thereupon the said four materials as well as four identical freshly prepared materials are exposed to X-rays with an X-ray radiation source of 80 kv. and developed for 8 min. at 20 C. in a common X-ray developer having the following composition:

Water-800 ccs.

p-Monomethylaminophenol hemisulphate-4 g. Hydroquinne-10 g.

Anhydrous sodium sulphite65 g.

Anhydrous sodium carbonate-45 g. Potassium bromide g.

Water up to-1000 ccs.

The results obtained are listed in the following table.

TABLE Amount of Freshly prepared stabilizer materials Fog per mole produced of silver Relative in stored Material halide, mg. Fog sensitivity materials None 0. O8 100 0. 36 3 0. 08 112 0. 2a 6 0.08 112 0. O. 05 100 0. 04

Example 3 A gelatino silverbromoiodide emulsion as described in Example 2 is divided into 4 aliquot portions.

To three of these emulsion portions is added an amount of mercury(II) compound as listed in the table below.

The four emulsions are then coated as described in Example 2 on a cellulose triacetate support and the resulting materials A, B, C and D are further treated as described in Example 2 with the difference, however, that the development now takes place at 26 C.

The results obtained are listed in the following table.

TABLE Fog produced on development Amount of mercury (11) for 8 min. at 26 0.

mercaptide per mole of silver halide Material Example 4 TABLE Freshly prepared A mount of materials mercury(II) Fog mercaptide per Relative produced mole of silver Gradaspeed in stored Material halide Fog tion (percent) materials A None 0. 11 2. 32 100 0.32 B 2.5 mg. of 0. 11 2.10 99 0.16

, compound 1. C 2.9 mg. of 0. l1 2. 25 99 0. 14

compound 3. D 2.8 mg. 0.12 2. 21 100 0.1.4

compound 4. E 2.3 mg. of 0. 12 2. 23 102 O. 14

compound 7. F 2.3 mg. of 0.11 2. 99 0. 14

compound 8. G 2.3 mg. of 0.11 2. 21 99 0. 14

compound 10. H 2.3 mg. of 0.12 2. 24 102 0.14

compound 12.

We claim: e e

1. Photographic material comprising a support and at ll lliiiiiilll llll lllll l l llllllllll lillllllllll i llllillll till least one light-sensitive silver halide emulsion layer comprising in said emulsion layer or in at least one waterpermeable layer coated at the same side of the support as the said emulsion layer at least one water-soluble mercury(II) compound corresponding to one of the general Formulae I and II:

[MOSS-XIS]Q H and MOtSX2SHgY I II 10 wherein:

X is a bivalent organic radical, X stands for an aliphatic or aromatic bivalent group, M represents hydrogen, alkali metal, alkaline earth metal, 15 ammonium, guanidine or an organic amine, and

Y stands for an aliphatic, alicyclic, aromatic or heterocyclic radical, said radicals including the substituted derivatives thereof,

said mercury(II) compound being present in an amount 20 sufficient to improve the stability or fogging characteristics of said material without appreciable desensitization thereof.

2. Photographic material according to claim 1, wherein said mercury(II) compound corresponds to the for- 25 mula:

wherein X stands for alkylene including substituted alkylene, arylene including substituted arylene, aralkylene including substituted aralkylene or a bivalent group conprisin a heterocyclic nucleus including a substituted heterocyclic nucleus, and M represents hydrogen, alkali metal, alkaline earth metal, ammonium, guanidine or an organic amine.

3. Photographic material according to claim 1, wherein said mercury(II) compound corresponds to the formula:

X stands for alkylene including substituted alkylene,

arylene including substituted arylene, or aralkylene including substituted aralkylene,

Y stands for alkyl including substitute dalkyl, aryl including substituted aryl or a heterocyclic nucleus including a substituted heterocyclic nucleus, and

M stands for hydrogen, alkali metal, alkaline earth metal,

ammonium, guanidine or an organic amine.

4. Photographic material according to claim 1, wherein said mercury(II) compound is present in an amount of from 0.1 mg. to 30 mg. per mole of silver halide.

5. Photographic light-sensitive silver halide material according to claim 1, wherein said material also includes a stabilizer of the hydroxytriazolopyrimidine type.

6. Photographic light-sensitive silver haldie material according to claim 1, wherein said material also includes a development accelerator of the polyoxyalkylene type.

7. Photographic light-sensitive silver halide material according to claim 1, wherein said emulsion is a gelatino silver halide emulsion.

References Cited UNITED STATES PATENTS 2,728,663 12/1955 Allen et al. 96109 2,728,665 12/1955 Leubner et al. 96l09 2,728,666 12/1955 Carroll et al. 96l09 2,728,667 12/1955 Knott et a1. 96l09 2,732,302 1/1956 Knott et al. 96l09 3,432,304 3/1969 Saleck et al 96l09 FOREIGN PATENTS 537,023 2/1957 Canada 96l09 WILLEAM D. MARTIN, Primary Examiner 5 R. M. sPEER Assistarfi EXamin er