US3817753A - Development of photographic material - Google Patents

Abstract

IODONIUM COMPOUNDS HAVING THE FORMULAE

(PHENYL)2-I(+) X(-) AND DIBENZIODOLIUM X(-)

WHEREIN THE AROMATIC NUCLEI CAN BE SUBSTITUTED AND X REPRESENTS AN ANION UTILIZED IN A PHOTOGRAPHIC SILVER HALIDE EMULSION. INCREASE THE RATE OF DEVELOPMENT OF A DEVELOPER COMBINATION COMPRISING HYDROQUINONE AND POLYOXYALKYLENE COMPOUNDS, EXTEND THE DEVELOPMENT LATITUDE IN WHICH SCREEN PRINTS OF GOOD QUALITY CAN BE PRODUCED WITHIN NORMAL DEVELOPING TIMES, AND DO NOT FOG THE PHOTOGRAPHIC SILVER HALIDE EMULSION.

Description

States Patent i 3,817,753 DEVELOPMENT OF PHOTOGRAPHIC MATERIAL Jozef Frans Willems, Wilrijk-Antwerp, and Joseph Louis de Munck, Heide-Kalmthout, Belgium, assignors to Agfa-Gevaert, Mortsel, Belgium No Drawing. Continuation of abandoned application Ser. No. 573,797, Aug. 22, 1966. This application Sept. 30,

1971, Ser. No. 185,351 Glaimsipriority, application Great Britain, Oct. 7, 1965, 42,591/65 Int. Cl. (20%: 1/06, 1/34, 5/30 mete- 7 aims ABSTRACT OF THE DISCLOSURE Iodonium compounds having the formulae This is a continuation of application Ser. No. 573,797, filed Aug. 22', 1966, now abandoned.

This invention relates to a development process and to combinations of substances influencing the development, used in this development process.

It is known that the development of continuous tone images by means of a hydroquinone-p-N-methyl-aminophenol developer is accelerated under the influence of polyoxyalkylene compounds having a molecular weight preferably above 1500. When, however, such polyoxyalkylene cgmpounds are used in combination with a hydroquinone-formaldehyde bisulphite developer, as is k-nown'from the German Patent Application 1,141,531, filed Jan;. .24, 1962 by Perutz Photowerke G.m.b.H., an increase of gradationtogether with a desensitisation is obtainedr-The latter combination is found to be very suitable for the development of light-sensitive materials for use in the graphic art on account of the very contrasty development obtained therewith.

It is also known that the development retardation caused when using the combination of polyoxyalkylene compounds with the above-mentioned type of developer can be neutralized andthat the initial rate of development can beraised by using quaternary ammonium salts in conjunction with the above combination. However, quaternary ammonium salts especially in high concennations have the disadvantage of fogging a light-sensitive silver halide material.

It has beenfound now that iodonium compounds and frnore particularly iodonium compounds according to the following structural formulae:

wnereinz V C- represents an anion e.'g. a halogen anion, a nitrate anion, a bisulphate anion, or a bendotriazolium anion,

ice

and wherein the aromatic nuclei of said compounds may be substituted e.g. with an alkyl radical, a halogen atom, an alkoxy radical, a cyano radical, an acyl radical, or an acylamino radical,

considerably increase the initial rate of development of a developer combination comprising hydroquinone and polyoxyalkylene compounds, extend the development latitude in which screen prints of good quality can be produced, within normal developing times, preferably not longer than 3 minutes, and do not fog the photographic silver halide emulsion.

These compounds influencing the development are preferably added to the composition of the light-sensitive silver halide emulsions in dissolved form in water or a mixture of water and water-miscible organic solvents, which do not impair the photographic characteristics of the emulsion.

However, these compounds can. also be incorporated into the emulsion by imbibition by treating it with a solution containing these products or by diifusion from an adjacent water-permeable layer comprising these compounds.

The compounds infiuencing the development according to the present invention can be added to the light-sensitive silver halide emulsion during different preparation steps of the light-sensitive material. For example they can be incorporated therein by a separate addition or they can be added as a mixture with one or more ingredients used in the formation of the silver halide grains, during the physical or chemical ripening or during another step preceding the coating of the emulsion.

The compounds according to the above general formulae are preferably used in combination with watersoluble polyoxyalkylene compounds i.e. alkylene oxide condensation products as described e.g. in the US. Patent Specifications 1,970,578 by Conrad Schoeller and Max WittWer, issued Aug. 21, 1934, 2,240,472 by Donald R. Swan, issued Apr. 29, 1941, 2,423,549 by Ralph K. Blake, William A. Stanton, Ferdinand Schulze, issued July 8, 1947, 2,441,389 by Ralph K. Blake, issued May 11, 1948, 2,531,832 by William A. Stanton, issued Nov. 28, 1950, 2,533,990 by Ralph K. Blake, issued Dec. 12, 1950, and the British Patent Specifications 920,637, filed May 7, 1959, 940,051, filed Nov. 1, 1961, 945,340, filed Oct. 23, 1961 by Gevaert Photo-Producten N.V., 991,608, filed June 14, 1961 by Kodak and the Belgian Patent Specification 648,710, filed June 2, 1964 by Gevaert Photo-Producten NV. and the British Pat. No. 1,107,022, corresponding to US. Pat. No. 3,573,913.

The alkylene oxide condensation products together with the compounds influencing the development as described above can be added to the composition of the silver halide emulsion or to a Water-permeable layer, which together with the emulsion layer forms part of'a waterpermeable element. v,

The alkylene oxide condensationproduetsand/or the compounds according to theabovengeneralformulae can also be added to the developing bath.

The compounds influencing the development 'are preferably added to the emulsion after thechemical ripening and just before the coating of the emulsion. I

The optimum amount" of alkylene oxide condensation product and iodonium compoundaccording'J-to the. above formulae depends on the very compound, on the nature of the colloid binder of the silver halide grains and on the kind of silver halide in the emulsion. In general, however, the above alkylene oxide condensation prod nets are added to the light-sensitive material in an amount of mg. to 10 g. per mole of silver halide. When incorporated into the developer they are used in amounts ranging from 0.1 g. to 10 g. per litre of developer.

The amount of iodonium derivative incorporated into the light-sensitive material preferably ranges between mg. and g. per mole of silver halide. When added to the developing bath, the derivative is used preferably in an amount varying between 0.1 g. to 20 g. per litre.

The development acceleration and the increase of dot definition and of the development latitude obtained with the products according to the present invention can be combined with a chemical sensitisation by using in com bination with the above-mentioned condensation products chemical sensitising agents such as sulphur-containing compounds, e.g. allyl isothiocyanate, allyl thiourea or sodium thiosulphate, reducing agents such as the tin compounds described in the Belgian Patent Specifications 4'93,- 464, filed Jan. 24, 1950 and 568,687, filed June 18, 1958, by Gevaert Photo-Producten N.V., the imino-amino methane sulphinic acid compounds described in the British Patent Specification 789,823, filed Apr. 29, 1955 by Gevaert Photo-Producten N.V., or precious metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium compounds. The sensitising action also manifests itself, of course, when combining the abovementioned condensation products with the sensitising compounds present by nature in gelatin.

The compounds influencing the development according to the present invention can also be used in combination with stabilising agents for silver halide emulsions, such as mercury compounds and the compounds described in the Belgian Patent Specifications 571,916 and 571,917, filed Oct. 10, 1958 by Gevaert Photo-Producten N.V., and in combination with sensitising and stabilising cadmium salts in the light-sensitive material as well as in the developer.

Other water-soluble compounds, which also accelerate the development, such as those described, e.g. in the British Patent Specification 954,205, filed June 30, 1960 by Gevaert Photo-Producten N.V. can be applied together with the condensation products according to the present invention in a developing bath as well as in the light-sensitive material.

4 general formula can be used as fo g-inhibiting compounds in the light sensitive material:

each of R and R represents a hydrogen atom, analkyl,

an aralkyl, or an aryl radical, and

R represents a hydrogen atom, an alkyl, a

alkoxycarbonyl group.

carboxy, or an Such compounds can be prepared starting from' 'l mole of fl-ketoester or an a-ethoxymethylene-p-ketoester with 1 mole of a suitable 3-amino-1, 2,4-triazole. By way of example of such derivatives 5methyl-7-hydroxy-s-triazolo (1,5-a)-pyrimidine can be mentioned.

Other agents such as hardening agents, Wetting agents, plasticisers, developing agents, and optical sensitising agents can be incorporated into the emulsion in the usual way.

The combination of products influencing the development according to the present invention can preferably be used in the development of silver chloride and silver bromochloride emulsions with a hydroquinoneformalde hyde-bisulphide developer, but it can also be used advantageously in the development of other emulsion types in combination with other developers. 1

The following example illustrates the invention.

EXAMPLE After ripening of a green-sensitised silver chlorobromide emulsion mole percent of bromide) containing S-methyl 7 hydroXy-s-triazolo-(1,5-a)-pyrimidine and cadmium chloride the compounds listed in the following Table 1 are added thereto. After the addition of the usual TABLE 1 Development time (in min.)

Mg. of ingredients per mole of silver halide Dot definition Fog Speed 1 Fog Speed 7 Fogv Speed :7

1 1.8 2 3 0.01 84 13 0.01 7.9 0.01 8.3 2 100 mg. of compound 1 .au fl .-f 2. 5 1. 5 1 0. 01 35 12. 5 0. 01 58 12 0. 01 84 14.5

100 of com ound 1 an 0 m 0 com- 3 pouxi d 2 p g 2 1 1.5 0.01 47 11.8 0.01 80 18.2 0.01' 87 12.3 1 1.8 2 3 0.01 84 12.7 0.01 100 9.1 0.01 100 8.1 2 100 mg. of compound 8 2. 5 1. 5 1 0. 01 18 8. 3 0. 01 38 8.7 0.01 76 14 3 100 mg. of compound 3 and 100 m of compound 2 2. 3 1 1 0. 01 29 8. 2 0. 01 50 11.3 0. 01 84 25 1 1.8 2 3 0.01 84 12.5 0.01 100, 9. 5 0.01 100 8.4 2 mg. of compound -.f 2.5 1. 5 1 0.01 35 10 0. 01 58 13. 2 0.01 87 i 13. 5

10 of com oun 4 an 0 m 0 comv 3 1 po i igdfi ..P -5 1.6 1 1 0.01 66 11.7 0.01 84 15.5 0.01 ,87 10.9 1 4 2 2 0.01 22 6.3 0.01 66 12.2 0.01 ,100 I. 9.7 2 110 mg. of compound (iizufiufgb f 4 4 1. 5 0. 01 0. 01 7. 5 0. 01 33' 11. 8

m of com oun an m 0 com- 3 pour id 2 -2 4 2 1.5 0.01 18 10.6 0.01 54 11.3 0.01 81 12.4 4 160 mg. ofcompoundd6.. .9. '1 4 1 0. 01 0. 01 34 8 0.01 71 10. 3

. f on 6 an m 0 com- 5 160 mg 0 comp n g 4 1 1 0.01 32 10.8 0.01 62 11.8 0.01 84 11 pound 2 Together with the above-mentioned condensation products, derivatives of tetra-azaindenes having the following wetting agent, of 25% by weight of polyethyl acrylatef as 75 a plasticiser calculated on the weight of gelatin, and of hardening agent such as formaldehyde and glyoxal the emulsion samples are coated in the same Way on a cellulose triacetate support and dried. The latex-plasticiser consists in a latex of 20% by weight of poly(ethyl acrylate) prepared according to known techniques by emulsion polymerisation in the presence of 3% by weight calculated on the monomer of the sodium salt of poly(ethylene-oxyoctylphenol) sulphonic acid wherein three ethylene-oxy units are present, 1% by weight of the sodium salt of the sulphuric acid ester of dodecyl alcohol and 2% of the condensation product of oleic acid and methyl taurine.

All of the samples are exposed in the same way through a grey wedge and a glass screen to a light source with a colour temperature of 3700 K. and developed at 19 C. in a bath comprising:

G. Sodium bisulphite 1.5 Hydroquinone 17 Formaldehyde bisulphite 60 Anhydrous sodium carbonate 60 Anhydrous sodium bicarbonate 15 Potassium bromide 1 Water to 1000 ml.

The dot definition is judged visually by comparison to standard materials, which in decreasing value of dot definition quality are defined with the numbers 1, 2, 3 and 4.

For judging the speed the light-sensitive materials are exposed through a grey wedge (with constant 0.01).

The speed, measured at a density 3 above fog, is on a percentage basis as compared with the speed attained after a development time of 3.5 minutes using an emulsion containing no development-influencing compound.

Compound I: is a polycondensation product of 1 mole of maleic anhydride and 1 mole of polyethylene glycol having an average molecular weight of 2000 prepared in an analogous way to preparation 3 of the British Patent Specification 920,637 filed May 7, 1959 by Gevaert Photo- Producten N.V.

Compound 2: is a compound used according to the present invention having the following structural formula:

Compound 3: is a polyoxyethylene polymer according to the following structural fomiulaz wherein x is approximately 135.

Compound 4: is a polyoxyethylene polymer prepared according to preparation 7 of the U.K. Pat. No. 1,107,022, corresponding to US. Pat. No. 3,573,913.

Compound 5: is a compound used according to the present invention having the following structural formula:

Compound 6: is a polyoxyethylene polymer prepared according to preparation 3 of the U.K. Pat. No. 1,107,022, corresponding to U.'S. Pat. No. 3,573,913.

United Kingdom Pat. No. 1,107,022 is assigned to Gevaert Photo-Producten, N.V., and describes the preparation of various polymeric materials, particularly polyoxyethylene polymers useful in photographic emulsions.

We claim:

1. Process for developing a photographic element containing a light-sensitive silver halide layer, said layer comprising a member of the group consisting of a silver cholride and a silver bromochloride emulsion, said process comprising exposing said photographic element, and developing said photographic element with an alkaline solution, a polyoxyalkylene polymer and an iodonium com- 6 pound corresponding to one of the following structural formulae:

/I* xand i X- Al \1+ wherein:

X- is an anion selected from the group consisting of halogen, nitrate, bisulfate, and benzotriazoline, and Ar is a phenyl radical.

2. Process according to claim 1, wherein the development is carried out with a hydroquinone-formaldehydebisulphite developer.

3. Process according to claim 1, wherein the iodonium derivative is present in the light-sensitive material in a range of 10 mg. to 20 g. per mole of silver halide.

4. Process according to claim 2, wherein the polyoxyalkylene polymer is present in the light-sensitive material in an amount ranging from mg. to 10 g. per mole of silver halide.

5. Process according to claim 1, wherein the iodonium derivative is present in a developing bath is an amount varying from 0.1 to 20 g. per litre of developer solution.

6. A photographic light-sensitive silver halide element comprising a member of the group consisting of a silver chloride and a silver bromochloride emulsion, and containing an iodonium compound and a polyoxyalkylene polymer, said iodonium compound corresponding to one of the following structural formulae:

wherein: each of R, and R' represents a hydrogen atom, an alkyl,

aralkyl or aryl radical, and

R' represents a hydrogen atom, an alkyl, a carboxy, or

an alkoxycarbonyl group.

References Cited UNITED STATES PATENTS 2,105,274 1/ 1938 Steigmann 96-95 2,848,330 8/1958 Chechak 96-107 3,294,540 12/1966 Gotfe 96 -107 3,518,085

6/1970 Milton 96 -107 QTHER REFERENCES C. Abstr.: vol. 53, 16775c-d.

RONALD H. SMITH, Primary Examiner M. F. KELLEY, Assistant Examiner US. Cl. X.R. 96-66.4, 95, 109

UNITED STATES PATENT OFFICE CERTIFlCATE OF CORRECTION PATENT NO. 3, 817, 753

DATED I June 18, 1974 INVENTOR S 1 Jozef Frans WILLEMS ET AL It is certified that error appears in the above-identified patent aid that said Letters Patent are hereby corrected as shown below:

Column 1, in the heading, in the inventors names, "Jozef Frans Willems, Wilrijk-Antwerp" should read Jozef Frans Willems, Wilrijk-Antwerpen Column 1, line 71, "bendotriazolium anion" should read benzotriazolium anion Column 4, line 29, "bisulphide" should read bisulphite Column 5, line 72, claim 1, "cholride" should read chloride Column 6, line 43, claim 7, "claim 5" should read claim 6 Signed and Scaled this fourth Day of Mayl976' [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN (nmmissimu'r ufPatrnIs and Trademarks Arresting Ojficer