DE2245287A1 - DEVELOPMENT OF PHOTOGRAPHICAL MATERIALS AT INCREASED TEMPERATURE - Google Patents

Description

AGi ¹ A-GEVAERT AKTIENGESELLSCHAFT LEVERKUSEN

Development of photographic materials at elevated temperatures.

Priority: Great Britain, September 17, 1971 Note no. 43 518/71

The present invention relates to the development of exposed, radiation-sensitive silver halide materials at elevated temperature.

In the normal processing of exposed photographic materials, the development at ambient temperature (about 2O ⁰ C) is carried out and requires a relatively long time of several minutes. There is therefore a desire to increase the speed of processing, which can be done by carrying out development and other processing at elevated temperatures. Rapid development of photographic materials occurs at temperatures above 30 ^° C. and preferably between 35 and 4-5 ^° C.

If the processing of exposed silver halide materials is carried out at an elevated temperature, ie above 30 ^° C., these materials have the tendency to show increased fog; in general, the other sensitometric properties are also impaired.

It is known to cause the formation and growth of fog in silver halide photographic materials Anti-skid agents or stabilizers, e.g. heterocyclic mercapto compounds such as i-phenyl-5-mercaptotetrazole and azaindenes, especially tetra- or penta-azaindenes, especially those represented by hydroxy or amino groups

GV. 565/1024

309812/1183 * '

are substituted, e.g. 5-methyl-7-hydroxy-s-triazolo | [1,5-a] pyrimidine. The latter are used to stabilize the emulsion against the formation and growth of fog, if the photographic materials are stored after use. The connections only have a relatively weak one Effect to prevent fogging when the photographic materials are used immediately after manufacture will. In contrast, i-phenyl-5-inercapto-tetrazole shows one high fog-reducing influence immediately after the preparation of the photographic emulsions. That is why the Emulsion generally uses both compounds together.

However, the extra haze created by processing at elevated temperatures can be caused by the ordinary Anti-fog agents or stabilizers are not sufficiently reduced.

It has now been found that Nitri! Compounds of the group that consists of (a) benzene compounds that carry at least 2 cyano groups on the benzene nucleus, of (b) ^ -ficient heterocycles, e.g. pyridine, quinoline, isoquinoline, etc., which have at least one cyano group on the heterocyclic ring and (c) from compounds containing at least one cyano group on an olefin group and correspond to the following formula:

NC.

^V C = CHR _O

in which:

R ^ a cyano group or a «r-deficient heterocycle and Ro an aryl group, a substituted aryl group, a Heterocycle, e.g. euryl, thienyl, indolyl, indolinyl, Benzimidazolyl, etc. or a substituted heterocycle, a beneficial effect on the sensitometric properties, i.e., fog and / or sensitivity and / or gradation of photosensitive silver halide emulsions which are after the exposure to be processed at elevated temperature. . They generally reduce that additionally formed Veil, without the emulsion sensitivity in a

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to influence assess extent; in some cases there is even an increase in emulsion sensitivity. Other connections give rise to an increase in the sensitivity and / or the gradation without any noticeable influence on the haze to show.

As known to those skilled in organic chemistry, and how to by A.Albert "Heterocyclic Chemistry", pages J4 and 39, University of London, The Athlone Press, 1959., ir-deficient heterocycles are completely unsaturated heterocycles, the nitrogen as the only hetero element and somewhere are deficient in it electrons, especially heterocycles, derived from carbocyclic, aromatic ring systems in which one or more = CH groups are replaced by = N groups have been.

Thus, the present invention provides a Verfahren'zur production photοgraphischer images before, which comprises developing an exposed photographic material at a temperature above 30 ⁰ C, which comprises a support and at least one silver halide photographic emulsion, wherein the development in the presence of at least one above defined nitrile compound is carried out.

The nitrile compounds for use in the present invention are . Particularly useful in photographic silver halide materials, those against the formation and growth of veils by means of azaind compounds are stabilized as described above. Therefore, the present invention also provides photosensitive ones Silver halide materials containing an azaindene stabilizer, particularly 5-methyl-7-hydroxy-s-triazole i., 5 ~ a3 pyrimidine and an ITi tri! compound as defined above.

Following are representative examples of nitrile compounds which one for use according to the present invention as particularly found suitable. Wherever it appears necessary, references are given for the preparation of the compounds:

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CN

3. NC - ^ - is, (Collect.Czech.Chem.Commun. 35, ^ "" T (1970) CN

CN

N 5.

I Il

I-CN

N 6. ^

0 7. OpN- ^ 3 .- ^ X-CH = C (CN) ₂

⁸ · ^S \ -CH = C (CN) J-Am.Chem.Soc. 21, 29 ^ 9

ii

N \

ί-CH = C (CN)

CH = C (CN) ₀

10. t ^^^ ^N CH-CH _Z

ι

309812/1163

H
N
11. r- ^ Y N-CH = O (GN) ₂

N
12. H ₅ C ₆ -HC = C- ^ \ Yakugaku Zasshi 8 ° ,, 188 (1969)

CRF

JN

13. H0 - ^> .- CH = C (CN) ₂ Chem. Ber. ££, 485 (1962)

14. (H ₃ C) ₂ N - ^^ - CH = C (CN) ₂ Ann. £ 21.69 (1955)

15. H ₃ CO - ^^ .- CH = C (CN) ₂ J.Am.Chem.Soc. £ 0.2828 (1928)

OCH ₅

Connection 7 is made as follows; A mixture of 43.4 g (0.2 mol) 5- (p-nitrophenyl) -2 ~ furaldehyde (SlD.Pr.Chem.Fak. SVST (Slov.Vys.Sk.Techn.), 1967 , 35), 13.2 g (0.2 mol) of malodinitrile, 0.5 g of ammonium acetate and 0.5 g of acetamide in 150 ml of acetic acid are refluxed for 2 hours. The precipitate formed is filtered off with suction and recrystallized with ethylene glycol monomethyl ether. Yield: 32 g (60 %) . Melting point: 222 to 223 ° C.

Compound 9 is prepared as follows: A mixture of 29 g (0.2 mol) indole-J-carbonaldehyde (Org. Syn.Coll., Volume 4, 539), 13.2 g (0.2 mol) malodinitrile, 0 , 5 g of ammonium acetate and 0.5 g of acetamide in 80 ml of acetic acid is refluxed for one hour. The precipitate formed is filtered off with suction and recrystallized with ethylene glycol monomethyl ether / water (2: 1).
Yield: 26 g (67%), melting point: 229 to 23O ⁰ C.

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Compound 10 is prepared as follows: A solution of 13.3 g (0.1 mol) of 2-methylindoline, 14.8 g (0.1 mol) of ethyl orthoformate and 6.6 g (0.1 mol) of malodinitrile in 150 ml Ethylene glycol monomethyl ether is refluxed for 30 minutes. The reaction mixture is poured into water, the precipitate is suction filtered and, after washing with water, recrystallized with methanol. Yield: 11 g (52 %) . Melting point: 155 ° C.

Connection 11 is established as follows:

A suspension of 29.2 g (0.2 mol) of benzimidazole-2-carboxaldehyde (Chem. Ber. ^ 8, 1330 (1965)), 13.2 g (0.2 mol) of malodinitrile, 0.5 g of ammonium acetate and 0.5 g of acetamide in 200 ml of acetic acid is refluxed with stirring for 2 hours. The precipitate formed is filtered off and boiled with ethylene glycol monomethyl ether. The filtrate is poured into water and the precipitate is suction filtered and washed with ither. Yield: 6 g (15 %). ' Melting point: over 260 ⁰ C.

Connection 16 is established as follows:

A mixture of 39.2 g (0.2 mol) of 3-methoxy-4- / 9-hydroxyethoxybenzaldehyde according to the preparation below, 13.2 g (0.2 mol) of malodinitrile, 0.5 g of ammonium acetate and 0.5 f? Acetamide in 80 ml of acetic acid is refluxed for 2 hours.

The precipitate formed is filtered off with suction and washed with toluene recrystallized.

Yield: 21.5 g (44 %) . Melting point: 148 ° C.

The 3-methoxy-4- ^ 5-hydroxyethoxybenzaldehyde is prepared as follows :

A mixture of 76 g (0.5 mol) of 3-methoxy-4-hydroxybenzaldehyde, 80.5 g (1 mol) of 2-chloroethanol and 106 g (1 mol) of sodium carbonate in 500 ml of dimethylformamide is refluxed for one hour while stirring . The mixture is concentrated by evaporation and the residue is recrystallized from benzene. Yield: 67 g (69 %) . Melting point: 98 ⁰ C.

309812/1183

While the nitrile compounds produced according to the present invention can be used in each of the water-permeable colloid layers of the photographic material which are in water-permeable Are related to the silver halide emulsion layer, e.g. a gelatin protective layer, an intermediate layer, a filter layer, etc. can be present, it has to be proved particularly useful, the Mtrilverbindungen in the Include silver halide emulsion itself.

The production of silver halide emulsions comprises three separate operations:

(1) emulsifying and digesting or ripening the silver halide,

(2) removing water-soluble salts from the emulsion, usually by washing, and

(3) Second digestion or post-ripening (chemical ripening) for Obtaining increased sensitivity.

The inventive compounds are the emulsion in a added to any stage of their manufacturing process, but preferably immediately before their application to a suitable one Underlay, such as paper, glass or PiIm, e.g. made of cellulose triacetate or polyethylene terephthalate.

The compounds to be used according to the invention can be used in alüai Types of photosensitive material used to be processed after exposure at elevated temperature. Various photosensitive silver salts can be used as photosensitive salts, such as silver bromide, Silver iodide and silver chloride, as well as mixed silver halides, such as silver chlorobromide or silver bromide iodide. they are particularly valuable to remove the haze during high-speed processing at elevated temperature of medium or high-sensitivity, image-producing Silver halide emulsions in which the silver halide is predominantly silver bromide, e.g. silver bromoiodide emulsions, whose iodide content is less than 10 mol $ to improve.

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The silver halides are found in the usual hydrophilic colloids, such as gelatin, casein, zein, polyvinyl alcohol, carboxymethyl cellulose, alginic acid, etc., of which the gelatin is preferred has dispersed.

The silver halide emulsions for processing at elevated Temperature after exposure are generally silver halide emulsions with a low content of a hydrophilic colloid, e.g. gelatin. The ratio of the hydrophilic colloid, in particular from gelatin, to silver halide, expressed as silver nitrate, is generally between 0.2 and 0.6.

^: The amount of the compounds of the above general formula to be used can accordingly vary between wide limits. The optimum amount of a specific compound to be selected in each individual case is best determined in each case by trial and error. The optimum amount in the silver halide emulsion is mostly in the range between 1 and 1000 mg per mole of silver halide.

The light-sensitive emulsions in question can be sensitized both chemically and optically.

The emulsions are chemically sensitized in any way, e.g. by maturing with naturally active gelatine or with small amounts of sulfur-containing compounds, such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc. The emulsions can also be sensitized with reducing agents such as tin compounds according to the British Patent 789 823 described method, or even with small amounts of certain precious metal compounds, such as e.g. gold, piatina, palladium, iridium, ruthenium and rhodium compounds take place as described by R. Koslowsky, Z.wiss.Phot. 46, 67-72 (1951). Representative noble metal compounds are ammonium chloropalladati potassium chlorine oplatinate, potassium chloroaurate, and potassium aurithiocyanate.

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The emulsions can of course also be mixed with a mixture of the above chemical sensitizers can be chemically sensitized.

The emulsions can further contain compounds which sensitize the emulsion by accelerating development, for example alkylene oxide polymers. These alkylene oxide polymers may be of various types, for example, polyethylene glycol having a molecular weight of 1500 or more, alkylene oxide condensation products or polymerizates as described in the American patent specifications 1970578, 2240472, 2423549, 2441389, 2 531 and 2,533,990 and in British Patent Specifications 920 637, 940 051 945 340 991 608 and 1 015 023. These development accelerating compounds can developer solution of silver halide present ₀ Other development accelerating compounds are onium and Polyonium compounds preferably of the ammonium in the phosphonium - and sulphonium types.

The emulsions can be spectrally sensitized, for example by means of the usual methine dyes such as neutrocyanine, basic or acidic carbocyanines, bhodacyanines, hemicyanines, Styryl dyes, oxonol dyes and the like. Such spectral sensitizing dyes are available from F.M. Hamer in "The Cyanine Dyes and Related Compounds" (1954).

The general emulsion stabilizers or anti-fog agents can be added to the silver halide emulsions or the developer solution. Known anti-fogging agents or stabilizers are, for example, sulphine and selenium acids or their salts, aliphatic, aromatic or heterocyclic mercapto compounds or disulfides, for example benzothiazoline-2-thione and i-phenyl-5-niercaptotetrazole, which may contain sulfo groups or carboxyl groups, nitroindazthole, nitrobenzene. Nitrobenzimidazole, mercury compounds, for example those described in Belgian patents 524 121, 677 337 ₅ 707 386 and 709 195, and the azaindenes already mentioned, in particular those. Tetra- or penta-azaindenes and

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especially those substituted by hydroxy or amino groups as described by Birr in Z.Wiss.Phot. 47, 2-58 (1952) has been described.

Other additives, e.g. hardeners such as formaldehyde, mucochlorine and mucobromic acid, dialdehydes, etc., wetting agents, e.g. the fluorinated surfactants of the German patent application No. P 1 961 638, plasticizers, matting agents, e.g. polymethyl methacrylate and silica particles, color couplers, mask-forming compounds, light-shielding dyes, etc. may be in the silver halide emulsion or in another Layer of the photosensitive material according to the invention to be present.

The following examples illustrate the invention.

example 1

A ready-to-cast silver bromoiodide X-ray emulsion contains per kg an amount of silver halide, the 19Og silver nitrate corresponds to, 74 g gelatin, 545 mg 5-methyl-7-hydroxy-s ~ triazolo [1,5-a] pyrimidine, 6.5 mg i-phenyl-5-mercaptotetrazole and 0.45 Mercury cyanide.

The above emulsion is divided into several aliquots and for each of these parts one of the nitrile compounds that listed in the table below, in the given Amount added.

The emulsion parts are on a polyethylene terephthalate carrier applied and dried.

After exposure through a continuous wedge with a constant 0.15, the emulsions are in an automatic 90 second developing machine processed. The development happens within 23 seconds at 35 ° C in the Agfa-Gevaert tanning developer for automatic processing G 138, the Contains hydroquinone and 1-phenyl-3-pyrazolidinone as a developing agent and glutaraldehyde as a hardener.

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The sensitometrisehen results, 'which have been obtained with the fresh materials, and with material, the relative prior to exposure and processing for 5 days at 45 ⁰ C and .70% moisture were stored, are listed in the table below. The values given for the sensitivity are relative values, measured at density 1 above the haze; the sensitivity of the fresh material which does not contain a nitrobenzene compound has been given a value of 100. '

Tabel

mg nitrile fresh material gamma Sensation
opportunity stored material gamma Sensation
opportunity binding per
kg of emulsion veil 1.52 100 veil 1.32 112 - 0.21 1.47 91 0.27 1.24 107 10 mg of
Connection 3 0.17 1.53 98 0.21 1.55 117 100 mg of
Connection 5 0.20 1.54 102 0.22 1.58 120 10 mg of
Connection 6 0.20 1.52 89 0.23 1.16 81 10 mg of
Connection 9 0.18 1.55 85 0.22 1.21 87 10 mg of
Connection 10 0.17 1.61 • 89 0.20 1.55 86 100 mg of
Connection 10 0.19 1.42 86 0.23 1.19 102 10 mg of
Connection 15 0.19 1.46 86 0.22 1.27 105 100 mg of
Connection 13 0.19 1.48 91 0.21 1.29 98 10 mg of
Compound 14- 0.18 1.65 87 0.21 1.91 120 100 mg of
Connection 14 0.19 0.27

The above results show that the inventive Compounds in silver halide photographic materials which are processed at elevated temperature cause fogging Reduce. Some compounds have a beneficial effect on gradation (compound 14) and sensitivity (Compounds 3, 6 and 14) after storage.

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Example 2

Example 1 is repeated with the difference that nitrile

connections according to the following table can be used. It gets the following sensitometric results achieved.

Tabel

mg of nitrile compound per kg of emulsion

stored material

veil

gamma

sensitivity

100 mg of compound 11

0.16 0.15

0.84

100

182

The above results show the beneficial influence of Compound 11 on both haze and gradation and sensitivity of the material processed at elevated temperature after being stored at 45 ° C and 70% relative humidity for 5 days.

GV.565

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Claims (9)

Patent claims: A process for the production of photographic images, wherein a photographic material that is exposed from a support and at least consists of a silver halide photographic emulsion and developed at a temperature of about 30 ⁰ C, characterized in that the development in the presence of at least one nitrile compound of the following kind is carried out; (a) Benzene compounds which contain at least 2 cyano groups in the benzene nucleus (b) heterocyclic compounds with a ^ -Electron deficit the at least one cyano group in the heterocyclic Ring included (c.) eC -cyano-substituted olefinic compounds of the following Formula:. NC ^ C = CHRp where mean: R ^ is a cyano group or a heterocyclic group with a ^ pelectron deficit and
R2 is an aryl group or a heterocyclic group. 2. The method according to claim 1, characterized in that a silver halide emulsion containing the nitrile compound is used. 3. The method according to claim 2, characterized in that the nitrile compound in an amount of 1 mg - 1000 mg / per mol Silver halide is included. 4. The method according to claim 1, characterized in that an emulsion is used as a stabilizer in addition contains an azaind compound. 5. The method according to claim 4, characterized in that the azaindene compound is 5-methyl-7-hydroxy-s-triazolo / 1,5-a / pyrimidine is included. GV 565 309812/1163 6. Light-sensitive photographic material comprising a support and at least one photographic silver halide emulsion, characterized in that the emulsion as a stabilizer. an azaindene compound and additionally a nitrile compound according to claim 1 contains. 7. Silver halide photographic light sensitive material according to claim 6, characterized in that the nitrile compound is present in the silver halide emulsion in an amount comprised between 1 mg and 1000 mg per mole of silver halide. Photosensitive material according to claim 7, characterized in that that in the emulsion the ratio of gelatin to silver halide based on silver nitrate is 0.2-0.6. 9. Photosensitive material according to claim 6, characterized in that that as azaindene compound 5-methyl-7-hydroxys-triazolo / T, 5-§7pyrimidine is included. GV 565 - 309812/1163