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Publication numberUS3801330 A
Publication typeGrant
Publication dateApr 2, 1974
Filing dateDec 20, 1971
Priority dateDec 21, 1970
Also published asDE2162714A1
Publication numberUS 3801330 A, US 3801330A, US-A-3801330, US3801330 A, US3801330A
InventorsE Brinckman, R Ceulemans, F Heugebaert
Original AssigneeAgfa Gevaert Nv
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic silver halide recording material
US 3801330 A
Abstract  available in
Images(8)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent m1 Brinckman et al.

[ 1 PHOTOGRAPHIC SILVER HALIDE RECORDING MATERIAL [75] Inventors: Eric Maria Brinckman, Mortsel;

Frans Clement Heugebaert, Kontich; Renaat Andreas Ceulemans, Deurne, all of Belgium [73] Assignee: AGFA-Gevaert N.V., Mortsel,

Belgium [22] Filed: Dec. 20, 1971 [21] Appl. No.: 210,120

[30] Foreign Application Priority Data Dec. 21, 1970 Great Britain. 60633/70 [52] US. Cl. 96/66 T, 96/48 HD, 96/61 R,

96/95, 96/1 14.1 [51] Int. Cl. G03c 5/30, G030 1/06, G030 1/02 [58] Field of Search 96/95, 114.1, 66 T, 48 HD,

[56] References Cited UNITED STATES PATENTS 3,301,678 l/l967 Humphlett et al. 96/61 R [111 3,801,330 [4 1 Apr. 2, 1974 3,312,550 4/1967 Stewart et al. 96/66 T 3,348,945 10/1967 Mader et al. 96/95 3,506,444 4/1970 Haist et a1 913/61 R 3,535,115 10/1970 Weber 96/61 R 3,565,619 2/1971 Johnson 96/95 3,617,289 11/1971 Ohkubo et a1. 96/1 14.1 3,666,477 5/1972 Goffe 96/ll4.l

OTHER PUBLICATIONS Def. Pub. T870,007, Bredoux, Jan. 6, 1970 (pub. date) Primary ExaminerNorman G. Torchin Assistant Examiner-M. F. Kelley Attorney, Agent, or Firm-William J. Daniel [5 7 ABSTRACT 14 Claims, No Drawings PHOTOGRAPHIC SILVER HALIDE RECORDING MATERIAL This invention relates to an improved process for, the production of photographic images by means of a dry processing.

In the United Kingdom Patent Specification 930,572 filed Apr. 8, 1960 by Kodak Co. a process for the production of silver images has been described wherein a photographic silver halide emulsion layer containing an alkaline substance and a pyrazolidin-3-one silver halide developing agent is image-wise exposed to electromagnetic radiation in order to form a latent image whereupon said image is developed by subjecting the exposed material to heat.

As described in the United Kingdom Patent Specification 1,001,702 filed Oct. 12, 1961 by Gevaert Photo- Producten N.V. the heat-development of silver halide materials containing pyrazolidin-3-one can proceed in the absence of alkaline substances and in the presence of a substance or substances liberating water while the pH of the recording layer is kept at 7 or less.

The main problem associated with the application of said processes lies in the dry post-exposure stabilization of the visible image, since without effective stabilization an overall illumination of the developed material will bring about an undesirable background colouration.

For the post-exposure stabilization ofheatdevelopable alkali-containing silver halide materials mercaptans such as thiosalicylic acid and 1-phenyl5- mercaptotetrazole have been proposed. These mercaptans appear to react with the residual silver halide and form a much less light-sensitive silver salt than the original silver halide.

In practice, however, said mercaptansproved to having a desensitizing action on the silverhalide and to react therewith already in the coating stage to such a considerable extent, that in fact little stabilizing agent was left for effecting the post-exposure stabilization.

According to the present invention photosensitive silver halide recording materials are used in a dry pro cessing comprising a heat-development of a latent silver image by means of a reducing agent suited for the heat development of photoexposed silver halide whereupon the produced silver images are stabilized'by means of a heterocyclic sulphur compound correspondingto the following general'formula or the mutemeric thiol structure thereof: I

: C=S Z I wherein:

X represents sulphur or a -NR- group, wherein R represents hydrogen, a saturated or unsaturated aliphatic group, e.g. an alkyl group, preferably a C,-C alkyl group, a hydroxyalkyl group e.g. fl-hydroxyethyl, an ally] group or an aromatic group such as a phenyl group, and Z represents the necessary carbon atoms to close a 5-or 6-membered nucleus, e.g. -(CH -(CH -CH=CH- or oE oH oH- Y Particularly suited stabilizing agents are those having the structural formulae mentioned in the following Table.

TABLE 1. H Can be prepared, e.g. according to /N\ Ber. 5 (1872), 240. H20 C=S Hz NH i Can be prepared, e.g. according to I Ber. 22 (1889), 1354.

H("J W=SH HC-N 31.? w" S Can be prepared, e.g according to the French patent specification 1,094,167 HaC-HC (3:5 filed March 2, 1954 by Ruhrch'emie H, NH

4.2 in 1 Prepared as descrTbed heretnafter.

H2O C=S 1 l H2 ---NH 7 Prepared according Am. J. Chem.

1 a2 (1954) 59. HzC C=S Hz -NH ii.-- W i A Prepared according was. 24 (1891) H2 NH 7"? Prepared according to Ann. 607 (1957) /N\ 73-91. H20 C=S Hi /NH C H:

To 40 g (0.4 mole) of N-allylethylenediamine, prepared as described in .I. Am. Chem. Soc. 67 (1945) 158 l and 80 ml of methylcellosolve 36.5 g (0.48 mole) of carbon disulphide were added dropwise with stirring at 50C. A white precipitate formed. On boiling the reaction mixture is dissolved while hydrogensulphide evolved. The solution was cooled at C and the precipitate filtered with suction. Yield 50.9 g. Melting point 8788C.

These stabilizing agents may be used as separate compounds or in admixture. They may be used in the photosensitive layer containing the silver halide or in an adjacent layer from which they can come in effective contact with the silver halide during the coating or heat-development step.

Preferred developing agents for reducing exposed silver halide with the aid of heat are pyrazolidin-3-one derivatives that have reducing properties. Other developing agents suited for the purpose are, e.g., aromatic polyhydroxy compounds and their reducing derivatives such as hydroquinone, pyrogallol, resorcinol, 2,3-dihydroxy-naphthalene and pyrocatechol, aromatic hydroxy-amino compounds and their reducing derivatives such as p-aminophenol hydrochloride, p-methylaminophenol sulphate, p-hydroxyphenylglycin and 8- hydroxyl ,2,3 ,4-tetrahydroquinoline; aromatic polyamino compounds and their reducing derivatives such as p-phenylene-diamine and 4,4-diaminodiphenylamine; 3-aminopyrazoline derivatives that have reducing properties such as l-phenyl-3- aminopyrazoline.

Pyrazolidin-3-one developing agents that are particularly suited for use according to the present invention correspond to the following general formula:

wherein: MM

R represents an aryl group including a substituted aryl group e.g. phenyl, a-naphthyl or ,B-napthyl including substituted aryl e.g. substituted by alkyl such as methyl, aralkyl such as benzyl, alkoxy such as methoxy, amino, dialkylamino, halogen such as bromine and chlorine, hydroxyalkyl, hydroxy or acetamido, or a heterocyclic group, R represents hydrogen or an acyl group e.g. an acetyl group,

each of R R and R (equal or different) represents hydrogen, an alkyl group including a substituted alkyl group, or an aryl group including a substituted aryl group, and

R represents hydrogen, an alkyl group preferably comprising at most 4 C-atoms, an alkoxy group preferably comprising at most 4 C-atoms, an aralkoxy group, an aryloxy group, or an aryl group including a substituted aryl group.

For example R can be benzothiazolyl or an aryl group of the benzene or the naphthalene series, either substituted or not. The R R R and R are preferably hydrogen atoms or alkyl groups containing from 1 to 4 carbon atoms or aryl groups such as phenyl or naphthyl, either substituted or not.

Together with the pyrazolidin-S-one developing agent, which is the primary developing agent, an auxiliary developing agent may be used. In that connection reference is made to ascorbic acid, hydroquinone, py-

rogallol, 2,3-dihydroxy-naphthalene, p-phenylenediamine, p-aminophenol, monomethyl-paminophenolflr H SO 8-hydroxy-l,2,3,4-tetrahydroquinoline and a 2- 18. l-0-chlorophenyl-4-methyl-4-ethyl-pyrazolidin- 3-one l9. l-m-acetamidophenyl-4,4-diethyl-pyrazolidin- 3-one 20. l-p-chlorophenyl-4-methyl-4-ethyl-pyrazolidin- 3-one 2l l-p-acetamidophenyl-4,4-diethyl-pyrazolidin-3-one 22. 1-(p-B-hydroxyethylphenyl )-4,4-dimethylpyrazolidin-3-one 23. l-p-hydroxyphenyl-4,4-dim ethyl-pyrazolidin-B-one 24. l-p-methoxyphenyl-4 ,4-diethyl-pyrazolidin-3 -one 25. 1-p-tolyl-4,4-diethylpyrazolidin-3-one 26. 1-(7-hydroxy-2-naphthly)-4-methyl-4-npropylpyrazolidin-3 -one 27. l-p-diphenyl-4,4-dimethylpyrazolidin-3-one 28. l-(p-B-hydroxyethylphenyl )-pyrazolidin-3-one 29 l-0-tolyl-pyrazolidin-3-one 30. 1-o-tolyl-4,4-dimethyl-pyrazolidin-3-one 3 l l-( 2 '-benzothiazolyl )-pyrazolidin-3 -one 3 2. l-phenyl-4,4-dihydroxymethyl-pyrazolidin-3 -one 33 l-phenyl-4,4-dimethyl-S-methoxy-pyrazolidin- 3 -one 34. l-phenyl-4,4-dimethyl-S-ethoxy-pyrazolidin-3-one 3 5 l-phenyl-4,4-dimethyl-5 -n-propoxy'-pyrazoliding i l-phenyl-4,4-dimethyl-5isopropoxy-pyrazoliding i l-phenyl-4,4-dimethyl-5-benzyloxy-pyrazolidinis? l-phenyl-4,4-dimethyl-5-phenoxy-pyrazolidin- 33i l-phenyl 4-methyl-4-hydroxymethyl-pyrazolidinis? l-phenyl-4-ethyl-4-hydroxymethyl-pyrazolidingit li l-(p-tolyl )-4,4-dimethyl-5 -methoxy-pyrazolidin- -one . 42. 1-(p-tolyl)-4,4-dimethyl-5-ethoxy-pyrazolidin- 3-one 43. l-(p-tolyl)-4,4-dimethyl-5-n-propoxy-pyrazolidin- 3-one 44. 1-(p-tolyl-4,4-dimethyl-5-isopropoxy-pyrazolidin- 3-one 45. l-(p-tolyl)-4,4-dimethyl-5-n-butoxy-pyrazolidin- 3-one 46. 1-(p-tolyl)-4,4-dimethyl-5-benzyloxy-pyrazolidin- 3-one.

The l-aryl-pyrazolidin-B-one compounds of use according to the present invention can be prepared according to techniques known in the art, e.g. as described in the United States Patent Specifications 3,330,839 of Jozef Frans Willems, Albert Lucien Foot and Raymond Albert Roosen, issued July 1 1, 1967 and US Pat. No. 2,772,982 of Vincent C. Vesce, issued Dec. 4, 1956.

The silver halide emulsion layers suited for heat development by means of a pyrazolidin-3-one developing agent may contain an alkaline substance as described in'the United Kingdom Patent Specification 930,572 mentioned above, but have not to contain such substance to yield a photographic silver image as described in the United Kingdom Patent Specification 1,001,702 mentioned above.

When a pyrazolidin-3-one is used in alkaline medium in combination with, e.g. hydroquinone as an auxiliary developing agent, less of the pyrazolidin-S-one is necessary to maintain high development activity and thus silver images can be produced with a minimum of heat energy.

An alkaline substance may be advantageous for accelerating the development of the latent image and such substance is therefore either present in the silver halide emulsion layer or in an adjacent layer from which on heating it can penetrate into the silver halide emulsion layer containing the pyrazolidin-3-one developing agent.

The alkaline substances, which may be employed in the sensitive materials together with the developing agents, include inorganic substances that when dissolved in water can yield a pH above 7 such as sodium hydroxide, sodium carbonate, sodium metaborate, sodium sulphite and organic alkaline substances such as aliphatic amines, e.g. ethanolamine and ethylenediamine or heterocyclic amines, e.g. morpholine and quaternary ammonium bases.

Since alkaline substances yield images with a fairly strong optical density but are disadvantageous with regard to the keepability of the recording material a compromise has to be found in the use of substances liberating alkali on heating. In that respect are particularly mentioned sodium formate, sodium acetate, ammonium acetate, sodium benzoate, tetramethylguanidine, aminoquanidine hydrogen carbonate, trichloroacetic acid guanidine salt (see the French patent of Addition 93,748 filed Jan. 24, 1968 by Kodak-Pathe), 4-amino- 2,6-dimethyl-pyrimidine and an addition complex compound of diethylamine and 2,2'-bis(4-hydroxy-2,3,5,6- tetrachlorophenyl)-propane.

Additional ingredients, which may be present in the light-sensitive silver halide emulsion layer or in a layer wherefrom they can come in effective contact with the silver halide, are substances having a plurality of aliphatic ether and/or hydroxyl groups such as are present in polymers containing oxyalkylene e.g. oxyethylene groups, and aliphatic polyols of which glycerol and the non-reducing oligosaccharides, e.g. sucrose and raffinose, are particularly useful for enhancing the development activity.

In order to improve the developability of the lightsensitive material it may contain likewise a compound or compounds liberating water on heating, e.g. salts that contain a high amount of crystal water and can easily set free a certain amount thereof as e.g. sodium carbonate-lO-water or that contain a high amount of water in adsorbed or absorbed state as present, e.g., in a clathrate structure, or simply contain water associated with a hygroscopic compound, e.g. glycerol or polyethylene glycols.

In the presence of an alkaline substance effecting in the recording layer a pH of at least 8, l5'to 60 of pyrazolidin-3-one developing agent per mole of silver halide yield upon heating of the information-wise exposed recording material a high density silver image. When in the alkaline medium an auxiliary developing agent such as an ascorbic acid developing agent or hydroquinone is present together with a saccharide, as little as 5 g of pyrazolidin-3-one per mole of silver halide are sufficient.

In the absence of a pH-increasing compound but in the presence of (a) compound(s) liberating water on heating the recording layer having a pH of 7 or less preferably contains from 0.1 mole to 2 moles of pyrazolidin-3-one developing agent per mole of silver halide.

The auxiliary developing agents such as those containing ascorbic acid may be used in amounts of 30-100 g per mole of silver halide and the aromatic polyhydroxy developing agents such as hydroquinone in the range of 15 to g per mole of silver halide.

The saccharides and polymeric oxyalkylene compounds may be used in amounts ranging from 30 to 600 g per mole of silver halide.

The post-exposure stabilizing agent of the above general formulae (1) or (ll) is preferably used in a range of molar ratios of 1:2 to 2:1 with respect to the silver ha] ide.

Any kind of photosensitive silver halide may be used in a recording material according to the present invention, but for reason of light-sensitive and development speed preference is given to silver bromide and silver chlorobromide emulsions.

The photosensitive coating composition may be applied to a paper support or film support. It may be advantageous to use a paper base having a thin foil of aluminium laminated thereto in order to have a better heat conductance in the heat-development step.

The heat-development of the silver halide recording materials may proceed in the range of to 200C. Application of heat may be carried out in different ways, e.g. by contact with a hot substance or body such as a hot plate or rollers, by high-frequency electric field heating, Joule effect heating, or by means of a hot gas stream.

The development may also proceed by infra-red radiation absorbed by suitable substances present in heatconductive contact with the silver halide. In that case the silver halide emulsion layer is used, e.g., in combination with a carbon-black-containing layer from which it is separated by means of a heat-conductive white pigment layer containing, e.g., zinc oxide or titanium dioxide. The exposure to infrared radiation is then carried out preferably through the rearside of the recording material.

The following examples illustrate the present invention. The amounts are expressed in parts by weight, unless otherwise indicated.

EXAMPLE 1 A photographic paper support of 90 glsq.m was coated at a coverage of 75 g per sq.m with a following mixture for forming a heat-developable photosensitive silver 6 aqueous gelatin solution 200 g polyoxyethylene glycol (average molecular weight: 30 g 200) imidazolidin-Z-thione as a post-exposure stabilizing l6 g agent ethanol 240 g lphenyl-pyrazolidin-3-one l g 4 aqueous formaldehyde solution l0 ml aqueous saponinc solution 3 ml a gelatino-silver chlorobromide emulsion (50 mole 500 g percent bromide) containing 0.45 mole of silver halide per kg (average particle size of silver halide grains: 0.4 nm) The pH of the coating mixture was 5.8

After drying the photosensitive layer was exposed through a microfilm halftone print in a commercial microfilm enlarging copying apparatus, and developed by heating it for 5 sec. at 140C in contact with a hot plate.

The obtained image had a maximum optical density of 0.62 and a minimum optical density of 0.10. It showed no background colouration after a several days exposure to daylight.

EXAMPLE 2 A photographic paper support of 90 g/sq.m was coated at a coverage of 100 g per sq.m with a following mixture for forming a heat-developable photosensitive silver halide recording layer:

6 aqueous gelatin solution 200 g glycerol 20 g I-methyl-2-mercapto-imidazole as a post-exposure 17 g stabilizing agent ethanol 240 G l-phenyl-pyraz0lidin3-onc l0 g 4 aqueous formaldehyde solution l0 ml l2 aqueous saponine solution 3 ml a gelatino-silver chloride emulsion contaning 75 g of 300 g silver chloride per kg (average particle size of silver halide grains 0.3 nm) The pH of the coating mixture was 4.9.

After drying the photosensitive layer was exposed in contact with a transparent halftone original. The development proceeded by heating the image-wise exposed material for 7 sec. at 130C by conveying it between a pair of hot rollers. The obtained image had a maximum density of 0.93 and a minimum density of 0.08 and proved to be stable under overall daylight exposure for several weeks.

EXAMPLES 3-6 Similar results were obtained after having replaced the l-phenyl-pyrazolidin-3-one from the recording layer in example 2 by the same amount of:

l-phenyl-4-methyl-4-hydroxymethyl-pyrazolidin- 3-0ne l-phenyl-4-ethyl-4-hydroxymethyl-pyrazolidin-3-one l-phenyl-4,4-dihydroxymethyl-pyrazolidin-3-one, or

1-phenyl-4-methyl-pyrazolidin-3-one.

EXAM PLE 7 A photographic paper support of 90 g/sq.m was coated at a coverage of g per sq.m with a following mixture for forming a heat-developable photosensitive silver halide recording layer:

6 aqueous gelatin solution 200 g polyoxyethylene glyeol(average molecular weight: 30 g 200) imidazolidin-Z-thionc as a post-exposure stabilizing l6 g agent ethanol 240 g l-phcnyl-pyrazolidin-3-one 10 g 4 aqueous formaldehyde solution 10 ml l2 aqueous saponine solution 3 ml trichloroacetic acid guanidine salt 40 g a gelatinosilver chlorobromide emulsion (50 mole 500 g percent bromide) containing 0.45 mole of silver halide per kg (average particle size of silver halide grains 0.4 nm) The pH of the coating mixture was 5.9.

EXAMPLE 8 A photographic paper support of g/sq.m was coated at a coverage of 132 g per sq.m with a following mixture for forming a heat-developable photosensitive silver halide recording layer:

6 aqueous gelatin solution 220 ml fi-methyl-tetrahydro-l,3-thiazine-2-thione 20 g ethanol 240 ml l-phenyI-pyrazolidin-3-0nc 10 g 4 aqueous formaldehyde solution 10 ml 12 aqueous saponine solution 3 ml a gelatino-silvcr chloro-bromide emulsion (50 mole 300 g bromide) containing 0.55 mole of silver halide per kg (average particle size of silver halide grains: 0.4 nm) 25 aqueous ethanolamine solution The pH of the coating mixture was 8.0

l0 ml After drying the photosensitive material was exposed through a transparent halftone original and developed by heating the image-wise exposed material for 5 sec at 135C in contact with a hot plate.

The obtained image had a maximum density of 0.91 and a minimum density of 0.09. It proved to be stable under normal daylight conditions.

EXAMPLE 9 A photographic paper support of 90 g/sq.m was coated at a coverage of g per sq.m with a following mixture for forming a heat-developable photosensitive silver halide recording layer:

6 aqueous gelatin solution 204 g polyoxyethylcne glycol (average molecular weight 30 g 200) imidazolidin-Z-thione 16 g ethanol 240 g P-methylaminophenol sulphate 12 g sodium acetate-B-water 40 g 4 aqueous formaldehyde solution 12 aqueous saponine solution 10ml 3m1 The dispersion obtained was adjusted to a pH of 8 by addition of 1N sodium hydroxide whereupon 340 g of a mixed galatino-silver chlorobromoiodide emulsion (approximately 55/42.5/2.5 percent) were added containing 0.49 mole of silver halide per kg (the silver halide grains sizing 0.4 nm on the average).

After drying, the photosensitive material was exposed through a transparent halftone original and developed by heating said material for 5 sec at 140C in contact with a hot plate. A visible image was obtained with a maximum density of 0.54 and a minimum density of 0.10. It proved to be stable under normal daylight conditions.

EXAMPLES l4 EXAMPLE A photographic paper support of 90 g/sq.m was coated at a coverage of 125 g per sq.m with the following mixture for forming a heat-developable photosensitive silver halide recording layer:

6 aqueous gelatin solution 350 g polyoxyethylene glycol (molecular weight: ca. 200) 18 g imidazoline-Z-thione 9.7 g ethanol 80 g l-phenyl-pyrazolidin-3-one 8 g 2-hydrazino-6-sulpho-benzothiazole 18 g 4 aqueous formaldehyde solution 10 ml 3 ml 12 aqueous saponine solution a gelatino-silver chlorobromide emulsion (50 mole 210 g percent bromide) containing 0.52 mole of silver halide per kg (average particle size of silver halide grains 0.4 nm) The pH of the coating mixture was 5.5.

After drying, the photosensitive material was exposed through a transparent halftone original and developed by heating said material for 2 sec at 140C in contact with a hot plate. The obtained greyish-blue image had a maximum density of 0.85 and a minimum density of 0.15. it proved to be stable under normal daylight conditions.

When the 2-hydrazino-6-sulpho-benzothiazole was omitted, the colour of the image was greyish-brown and the maximum density had a lower value.

We claim:

1. In a photosensitive heat-developable recording material comprising a support bearing at least one recording layer containing photosensitive silver halide, a reducing agent for heat-developing exposed silver halide and including a post-exposure stabilizing agent which is in effective contact with the silver halide during heat-development, the improvement wherein said stabilizing agent corresponds to the following general formula or the tautomeric thiol form thereof:

wherein:

X represents sulphur or a -NR- group, wherein R represents hydrogen or a C -C alkyl, allyl, a B-hydroxyethyl, or phenyl group, and

Z represents -(CH -(CH -CH=CH- or said recording layer having a pH not higher than 7 and said stabilizing agent is present in an amount having a molar ratio of 0.5-2:l relative to said photosensitive silver halide.

2. A photosensitive material according to claim 1, wherein the silver halide is dispersed in gelatin as binding agent.

3. A photosensitive material according to claim 1, wherein as developing agent a pyrazolidin-3-one developing agent is used, which corresponds to the following general formula:

wherein:

R represents an aryl group or a heterocyclic group,

R represents hydrogen or an acyl group,

each of R R and R represents hydrogen, an alkyl group or an aryl group and may be similar or different, and

R represents hydrogen, an alkyl group, an alkoxy group, an aralkoxy group, an aryloxy group or an aryl group.

4. A photosensitive material according to claim 1, wherein the silver halide is used in combination with a compound liberating water on heating.

5. A photosensitive material according to claim 1, wherein the silver halide is used in combination with a hygroscopic compound.

6. A photosensitive material according to claim 1, wherein the silver halide is used in combination with a polymer containing oxyalkylene groups.

7. A photosensitive material according to claim 1, wherein the silver halide is used in combination with a polyol.

8. A photosensitive material according to claim 1, wherein an alkaline compound is present in an adjacent layer to said recording layer from which it can penetrate into the recording layer so that during development the pH of the recording layer is raised above 7.

9. A photosensitive material according to claim 8, wherein said alkaline compound is sodium formate, sodium acetate, ammonium acetate, sodium benzoate, tetramethylguanidine, aminoguanidine hydrogen carbonate, trichloroacetic acid guanidine salt, 4-amino- 2,6-dimethyl-pyrimidine, or an addition complex compound of diethylamine and 2,2-bis(4-hydroxy-2,3,5,6- tetrachlorophenyl)-propane.

10. A photosensitive material according to claim 3, wherein the pyrazolidin-3-one developing agent is used in conjunction with a minor amount of an auxiliary developing agent.

11. A photosensitive material according to claim 10, wherein 2-hydrazino-benzothiazole is said auxiliary developing agent.

12. A photosensitive material according to claim 1, wherein the stabilizing agent is present in the layer containing the silver halide.

13. A photosensitive material according to claim 1, wherein the stabilizing agent is present in a layer adjacent to the silver halide containing layer.

14. A process for the production of silver images, which comprises information-wise exposing to electromagnetic radiation a photosensitive recording material comprising a support bearing at least one recording layer containing photosensitive silver halide, a reducing agent for heat-developing exposed silver halide and including in effective contact with the silver halide during heat-development, a post-exposure stabilizing agent corresponding to the following general formula or the tautomeric thiol form thereof:

wherein:

X represents sulphur or a -NR- group, wherein R represents hydrogen or a C,-C alkyl, allyl, a B-hydroxyethyl, or phenyl group, and

Z represents -(CH -(Cl-l -CH=CH- or more stable to light than silver halide.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,801,330 Dated April 2 1974 Inventods) Eric Marla BRINCKMAN et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 10, Claim 1, approximately line 15, after "or",

-CH CH CH, I

insert 2 Signed and sealed this 17th day of September 197 ($EAL) Attest:

C. MARSHALL DANN McCOY M. GIBSON JR. Attesting Officer Commissloner of Patents USCOMM-DC GO376-P69 Q U S GOVERNMENY PRINTING OFFICE I909 0"366-33A FORM 90-1050 (10-69)

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4036650 *Aug 26, 1975Jul 19, 1977Canon Kabushiki KaishaHeat developable photosensitive material containing compounds of sulfur
US4138265 *Jun 27, 1977Feb 6, 1979Eastman Kodak CompanyAntifoggants in certain photographic and photothermographic materials that include silver salts of 3-amino-1,2,4-mercaptotriazole
US4168980 *Aug 19, 1977Sep 25, 1979Eastman Kodak CompanyHeat developable photographic material and process
US4237213 *Oct 3, 1978Dec 2, 1980Canon Kabushiki KaishaImage forming method
US4273844 *Aug 9, 1978Jun 16, 1981Canon Kabushiki KaishaHeat-developable photosensitive member for forming electrostatic printing masters
US4336316 *Oct 20, 1978Jun 22, 1982Fuji Photo Film Co., Ltd.Image forming method
US4678735 *Sep 10, 1985Jul 7, 1987Fuji Photo Film Co., Ltd.Heat developable light-sensitive material with development inhibitor releaser
US4859580 *Mar 29, 1988Aug 22, 1989Fuji Photo Film Co., Ltd.Heat developable photosensitive material
US5491050 *Feb 9, 1994Feb 13, 1996Eastman Kodak CompanyMethod of processing originating photographic elements containing tabular silver chloride grains bounded by (100) faces
US5635328 *Aug 16, 1994Jun 3, 1997Konica CorporationLight-sensitive lithographic printing plate utilizing o-quinone diazide light-sensitive layer containing cyclic clathrate compound
US6037115 *Jul 10, 1997Mar 14, 2000Eastman Kodak CompanyPhotothermographic and thermographic films containing low levels of formate to prevent fog
US6514682Jun 20, 2001Feb 4, 2003Eastman Kodak CompanySpeed addendum for photographic emulsions
EP1271233A1 *Jun 10, 2002Jan 2, 2003Eastman Kodak CompanyA speed addendum for photographic emulsions
Classifications
U.S. Classification430/353, 430/599, 430/611, 430/566, 430/617, 430/602, 430/354
International ClassificationG03C1/43, C07D233/42, G03C1/34
Cooperative ClassificationG03C1/43, C07D233/42, G03C1/346
European ClassificationG03C1/34S, G03C1/43, C07D233/42