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US3617280A - Photopolymerization of ethylenically unsaturated organic compounds - Google Patents

Photopolymerization of ethylenically unsaturated organic compounds Download PDF

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US3617280A
US3617280A US818381A US3617280DA US3617280A US 3617280 A US3617280 A US 3617280A US 818381 A US818381 A US 818381A US 3617280D A US3617280D A US 3617280DA US 3617280 A US3617280 A US 3617280A
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process according
ethylenically unsaturated
unsaturated organic
carbon atoms
light
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Harald Huckstadt
Wilhelm Saleck
August Randolph
Erwin Ranz
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • SILVER BROMIDE EMULSION SENSITIZED WITH 1,4,TRIAZINES A number of methods have previously been described for increasing the'sensitivity of photographic silver halide emulsions. The incorporation of certain colored compounds or dyes in the emulsions increases the optical range of sensitivity, and for this reason such dyes are commonly referred to as optical or spectral sensitizing dyes. It is also well known to increase the sensitivity of photographic emulsions by addition of sulfur compounds capable of reacting with silver salts to form silver sulfide, or by addition of reducing agents (compounds of these types are also naturally present in gelatin), or with salts of gold or other noble metals, or with combinations of two or more of the'aforementioned compounds generally known as chemical sensitizers.
  • Such chemical sensitizers are believed to react with the silver halide to form, on the surface of the silver halide, minute amounts of silver sulfide or of silver or of other noble metals, and these processes are capable of increasing the sensitivity of emulsions by very large factors.
  • the process of chemical sensitization reaches a definite limit beyond which further addition of sensitizer, or of further digestion with the sensitizer present, merely increases the fog of the photographic emulsion leaving the sensitivity constant or even decreasing it.
  • sensitivity it is intended to refer to the sensitivity of photographic emulsions through the whole spectrum.
  • spectral sensitivity it is intended to refer to the sensitivity of the photographic emulsion to light ofa certain range of the spectmm.
  • R represents hydrogen or an alkyl group containing up to carbon atoms preferably methyl
  • R stands for (1) hydrogen, (2) a linear or branched alkyl group containing up to 12 carbon atoms, preferably up to 5 carbon atoms, which alkyl radicals may be substituted with phenyl, hydroxyl, cyano, carboxyl, esterified carboxyl or alkoxy groups, (3) aryl, especially a radical of the phenyl series which may be substituted, (4) acyl, especially acyl derived from aliphatic carboxylic acids preferably having up to 5 carbon atoms, (5) carbamoyl in which the amide group may be substituted with alkyl having preferably up to 5 carbon atoms, aralkyl such as benzyl, or aryl especially phenyl, or (6) an amino group in which the hydrogen atoms may be substituted with alkyl groups, preferably alkyl having up to 5 carbon atoms, aryl, especially phenyl, or acyl, especially those of the type mentioned above; the amino group may in addition be substitute
  • nitrogen-atom of the morpholine ring is capable of forming simple salts or quaternary ammonium salts, these may, of course, also be used in the process according to the invention.
  • Suitable quaternary groups are alkyl groups containing up to 12 carbon atoms, preferably up to 5 carbon atoms, which may be substituted, e.g. with phenyl groups as in benzyl or phenyl ethyl groups.
  • any anions may occur in these compounds, e.g. halides, perchlorates and the like.
  • the nitrogen atom of the morpholine ring cannot be quatemized if the basic properties of the nitrogen are suppressed by electro negative substituents. This occurs, e.g. when R isphenyl, carbamoyl or acyl.
  • 1,4-Thiazanes substituted on the nitrogen atom are prepared from the corresponding unsubstituted thiazane which is reacted according to known processes with a suitable halogenated compound with the addition of acid binding agents.
  • the other compounds given above can be obtained by reacting unsubstituted thiazane with acid chlorides or with isocyanates.
  • N-Amino-1,4-thiazane can be prepared by introducing a nitroso group into thiazane followed by reduction.
  • the acid salts and quaternary salts are prepared by known methods.
  • Emulsification and physical ripening which is also called Ostwald ripening
  • the sensitizers of the present invention can be added to the emulsion before, during or after the chemical ripening or they can be added immediately prior to the casting.
  • the particular quantity of the sensitizers of the invention used in a given emulsion can vary, depending upon the effects desired, silver content of the emulsion, the silver halide composition etc. Generally they are added in amounts of 3 mg. to 20 g. preferably 3 mg. to 6 g. per mol of silver halide. The compounds are also effective when they are added to the developer solution in which case they are preferably used in similar quantities per liter of the aqueous developer bath.
  • the sensitizers can be dissolved in water or a solvent miscible with water or a mixture of water and water-miscible solvents, and added in this form to the emulsion.
  • the solvent is not critical and should be selected so that it should have no harmful effect to the photographic properties of the silver halide emulsion.
  • the optimum amount for any sensitizer of the present invention can be determined for any particular emulsion by running a series of comparison tests in which the quantity of the sensitizer is varied over a given range. Exposure of the emulsion containing the sensitizer in a manner well known and measuring of the sensitivity in conventional apparatuses will reveal most advantageous concentrations. Such technique is well understood by those skilled in the art.
  • the thiomorpholine derivatives of the invention are used in silver bromide emulsions wh ich may contain a small amount of silver iodide of up to 10 mol percent.
  • the photographic emulsion in which the sensitizers according to the invention are used can be chemically sensitized by any of the known procedures. They can be sensitized, for example, with sulfur compounds as referred to, e.g. in the book The Theory of the Photographic Process" by Mees (1954) pp. 149-161.
  • the emulsions can also be chemically sensitized with salts of noble metal such as gold, ruthenium, rhodium, palladium, iridium and platinum, used in amounts below that which produce any substantial fog.
  • noble metal such as gold, ruthenium, rhodium, palladium, iridium and platinum
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate, potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and the like.
  • the emulsions can be sensitized with reducing agents, stannous salts or polyamines and the like.
  • the emulsions can also be optically sensitized with cyanine, merocyanine or rhodacyanine dyes.
  • the emulsions may also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonoles and the like. Sensitizers of this type have been described in the work by F. M. Hamer (The Cyanine Dyes n R te Q g g qg 111? my ,7 W w,
  • the emulsions can be stabilized with any of the known stabilizers, e.g. homopolar or salt-type compounds of mercury with aromatic or heterocyclic compounds (for example mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • suitable stabilizers include azaindenes, especially tetraor pentaazaindenes, in particular those which are substituted with hydroxyl or amino groups. Such compounds have been described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
  • the silver halide emulsion layers may contain any suitable film-forming and water-permeable colloid as binding agent, such as gelatin but the gelatin can be replaced partially with products like alginic acid and derivatives thereof such as salts, preferably with alkali metals, esters with lower aliphatic alcohols or amides.
  • the gelatin can also be partially replaced with polyvinyl alcohol, polyvinyl pyrrolidone, starch, carboxymethyl cellulose and the like.
  • the emulsions may be hardened in the usual manner, for example, with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
  • formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
  • the compounds according to the invention are effective for both black-white emulsions and for color photographic emulsions which contain color couplers.
  • EXAMPLE 1 600 mg. of saponin as wetting agent, 200 mg. of 4-hydroxy- 6-methyl-1,3,3a,7-tetraazaindene as stabilizer and 10 ml. of a 10% aqueous solution of formaldehyde are added to a silver iodobromide gelatin emulsion which contains 60 g. of silver per liter in the form of silver halide which has a silver iodide content of 6 mols percent.
  • the emulsion was divided into three equal samples and the following substances were added per liter of emulsion to the individual samples:
  • Sample A Comparison sample without additive
  • Sample B 300 mg. of compound 1
  • Sample C 600 mg. of compound II]
  • the casting solutions are applied onto a support of cellulose triacetate, exposed in a sensitometer customarily employed in the art behind a grey step wedge and developed for 10 minutes in a developer of the following composition:
  • An increase by 3 represents a sensitivity gain of one shutter stop or double sensitivity.
  • EXAMPLE 2 A silver iodobromide gelatin emulsion containing 4.5 5 mol percent silver iodide which has been ripened to optimum sensitivity with gold and sulfur compounds in known manner is sensitized by the addition of 45 mg. of the following sensitizing dye per kg. of emulsion:
  • ingredients are added per kg. of emulsion: g. of 1-(3'-sulfo-4'-phenoxy)-phenyl-3-heptadecyl-pyrazolone as magenta coupler; 250 mg. of 1,3,3a,7- tetraaza-4-hydroxy-6-methyl indene as stabilizer; ml. of a 5% aqueous solution of saponin as wetting agent; 2.5 ml.
  • the emulsion was divided into 7 equal samples and the following substances were added per kg. of emulsion to the individual samples:
  • Sample A Comparison sample without additive
  • Sample B 1.0 g. of compound I
  • Sample C 3.0 g. of compound I-II
  • Sample D 1.0 g. of compound XII
  • Sample E 1.0 g. of compound IV
  • Sample F 0.3 g. of compound XI
  • Sample G 1.0 g. of compound XIV
  • the samples are applied onto a support of cellulose acetate and dried. They are then exposed behind a step wedge and processed in the usual manner. Processing is carried out as follows:
  • the color developer has the following composition:
  • the color density of the magenta layers was determined with a Macbeth Quanta Log, Model TD- 102 densitometer, a green color filter being interposed in the path of the beam of measuring light.
  • An increase by 3 here also represents double sensitivity or a sensitivity increase of one shutter stop.
  • EXAMPLE 3 The thiomorpholine compounds of the invention are also effective when applied in color developers, as illustrated by the following Example. Each of the following substances is added to a color developer in an amount of l g. per liter:
  • Sample A Comparison sample without additive
  • Sample B compound I
  • Sample C compound 11
  • Sample D compound XV (0.5 g. per liter).
  • the color developer has the following composition: Diethyl-p-pheny1enediamine sulfate 2.75 g., hydroxylamine sulfate 1.2 g., sodium sulfite anhydrous 2.0 g., sodium hexametaphosphate 2.0 g., potassium carbonate anhydrous 75.0 g., potassium bromide 2.0 g., make up to 1 liter with water.
  • a conventional commercial color photographic multilayer material having on a support'a red-sensitive silver bromide emulsion layer with a cyan coupler, a green-sensitive emulsion layer with a magenta coupler and a blue-sensitive emulsion layer containing a yellow coupler, is exposed behind a step wedge and processed in the usual manner.
  • the color densities of the individual layers of the multilayer material are measured with a Macbeth Quanta Log, Model TD 102" densitometer, the appropriate color filter" being interposed in each case into the path of the beam.
  • An increase by 3 again denotes a sensitivity increase of one shutter stop or double the sensitivity.
  • R stands for hydrogen or alkyl containing up to 5 carbon atoms
  • R represents (1) hydrogen, (2) a linear or branched alkyl group containing up to 12 carbon atoms, (3) a radical of the phenyl series, (4) an aliphatic carboxylic acyl group having up to five carbon atoms, (5) a carbamoyl group, or (6) an amino group. 7.
  • the emulsion of claim 6 containing additionally up to 10 mol percent of silver iodide based on the silver bromide.
  • R represents alkyl, substituted with phenyl, hydroxyl, cyano, carboxyl or alkoxy.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A process for the photopolymerization of ethylenically unsaturated organic compounds, is disclosed, which comprises irradiating with actinic light a composition comprising a photopolymerizable ethylenically unsaturated organic compound and as a photopolymerization initiator a compound containing at least one diazosulfone group, said compound corresponding to one of the formulas: X-SO2-N N-Y and X''-SO2-N N-Z-N N-SO2

Description

D United States Patent 1 3,617,280
[72] Inventors Harald Huckstadt, Cologne, Stammheim; [50] Field of Search 96/66.3, Wilhelm Saleck, Schild gen; 107 August Randolph, Leverkusen; Erwin Ranz, Leverkusen, all of Germany [21] Appl. No. 818,381 [22] Filed Apr. 22, 1969 [56] References Cited [45] Patented Nov. 2, 1971 [73] Assignee 'AGFA-Gevaert Aktiengesellschalt, UNITED STATES PATENTS Leverkusen, Germany 3,062,646 11/1962 Dann et a1 96/107 3,471,296 10/1969 Huckstadt et al 96/107 Primary Examiner- Norman G. Torchin Assistant Examiner-Richard E. Fichter [54] SILVER BROMIDE EMULSION Attorneys-Connolly and Hutz SENSITIZED WITH 1,4,TRIAZINES 10 Claims, N0 Drawings [52] US. Cl 96/66.3, ABSTRACT: The present invention relates to a process for 107 increasing the sensitivity of photographic silver bromide [51] Int. Cl Go3c 5/30, emulsions by developing the emulsions in the presence of 1/28 thiomorpholine compounds.
SILVER BROMIDE EMULSION SENSITIZED WITH 1,4,TRIAZINES A number of methods have previously been described for increasing the'sensitivity of photographic silver halide emulsions. The incorporation of certain colored compounds or dyes in the emulsions increases the optical range of sensitivity, and for this reason such dyes are commonly referred to as optical or spectral sensitizing dyes. It is also well known to increase the sensitivity of photographic emulsions by addition of sulfur compounds capable of reacting with silver salts to form silver sulfide, or by addition of reducing agents (compounds of these types are also naturally present in gelatin), or with salts of gold or other noble metals, or with combinations of two or more of the'aforementioned compounds generally known as chemical sensitizers. Such chemical sensitizers are believed to react with the silver halide to form, on the surface of the silver halide, minute amounts of silver sulfide or of silver or of other noble metals, and these processes are capable of increasing the sensitivity of emulsions by very large factors. The process of chemical sensitization, however, reaches a definite limit beyond which further addition of sensitizer, or of further digestion with the sensitizer present, merely increases the fog of the photographic emulsion leaving the sensitivity constant or even decreasing it.
Other chemical sensitizers are higher polyethyleneglycols having a molecular weight of at least 1500. Lower polyethyleneglycols have no or only very small effect on the sensitivity of silver halide emulsions. While the higher polyethyleneglycols have a considerable or remarkable sensitization effect, the utility of such compounds is limited by the fact that they cause marked increases in the fog levels of silver halide emulsions. It is known that the fog level increase cannot sufficiently be controlled by the addition of antifoggants to the emulsion.
It is among the objects of the present invention to increase the general sensitivity or speed of silver halide emulsion layers. A further object is to provide photographic silver halide emulsions and emulsion layers having an increased general sensitivity without concomitant increase in fog level. Other objects will be apparent from the following descrip tion of the invention.
By the term general sensitivity it is intended to refer to the sensitivity of photographic emulsions through the whole spectrum. By the term spectral sensitivity it is intended to refer to the sensitivity of the photographic emulsion to light ofa certain range of the spectmm.
It is the object of the invention to find new chemical sensitizers which do not have the above disadvantages and by means of which it is possible to increase the sensitivity of photographic silver halide emulsions without causing unwanted fog formation.
It has now been found that the sensitivity of silver bromide emulsions can be considerably increased without concomitant increase in fogging if the development of the exposed emulsion layers is performed in the presence of 1,4-thiazanes-of the following formula:
in which R represents hydrogen or an alkyl group containing up to carbon atoms preferably methyl; and
R stands for (1) hydrogen, (2) a linear or branched alkyl group containing up to 12 carbon atoms, preferably up to 5 carbon atoms, which alkyl radicals may be substituted with phenyl, hydroxyl, cyano, carboxyl, esterified carboxyl or alkoxy groups, (3) aryl, especially a radical of the phenyl series which may be substituted, (4) acyl, especially acyl derived from aliphatic carboxylic acids preferably having up to 5 carbon atoms, (5) carbamoyl in which the amide group may be substituted with alkyl having preferably up to 5 carbon atoms, aralkyl such as benzyl, or aryl especially phenyl, or (6) an amino group in which the hydrogen atoms may be substituted with alkyl groups, preferably alkyl having up to 5 carbon atoms, aryl, especially phenyl, or acyl, especially those of the type mentioned above; the amino group may in addition be substituted with carbamoyl groups which may in turn be alkylated orphenylated.
If the nitrogen-atom of the morpholine ringis capable of forming simple salts or quaternary ammonium salts, these may, of course, also be used in the process according to the invention. Suitable quaternary groups are alkyl groups containing up to 12 carbon atoms, preferably up to 5 carbon atoms, which may be substituted, e.g. with phenyl groups as in benzyl or phenyl ethyl groups.
Any anions may occur in these compounds, e.g. halides, perchlorates and the like. As is well known, the nitrogen atom of the morpholine ring cannot be quatemized if the basic properties of the nitrogen are suppressed by electro negative substituents. This occurs, e.g. when R isphenyl, carbamoyl or acyl. W
Particular utility is exhibited by thefollowing compounds:
F JLNHQ N- H -CHa s N-NH-ii-NHQ The substances for use according to the invention are prepared from thiomorpholine in known manner. The preparation of thiomorpholine has been described in J. Chem. Soc. 1920, pp. 761-308; J. Am. Chem. Soc. 76 (1954), pp. 1187-1188; US. Patent 2,761,860; DAS 1,104,513. The preparation of C-substituted 1,4-thiazanes are described in J. Am. Chem. Soc. 76 (1954), pp. 2902-2906.
1,4-Thiazanes substituted on the nitrogen atom are prepared from the corresponding unsubstituted thiazane which is reacted according to known processes with a suitable halogenated compound with the addition of acid binding agents. The other compounds given above can be obtained by reacting unsubstituted thiazane with acid chlorides or with isocyanates.
N-Amino-1,4-thiazane can be prepared by introducing a nitroso group into thiazane followed by reduction.
The acid salts and quaternary salts are prepared by known methods.
The preparation of photographic silver halide emulsions.
includes 3 separate steps:
(1) Emulsification and physical ripening which is also called Ostwald ripening;
(2) the freeing of the emulsion of excess water soluble salts, usually by washing with water and drying, and
(3) the after ripening which is also called chemical ripening to obtain increased emulsion speed or general sensitivity.
The sensitizers of the present invention can be added to the emulsion before, during or after the chemical ripening or they can be added immediately prior to the casting.
The particular quantity of the sensitizers of the invention used in a given emulsion can vary, depending upon the effects desired, silver content of the emulsion, the silver halide composition etc. Generally they are added in amounts of 3 mg. to 20 g. preferably 3 mg. to 6 g. per mol of silver halide. The compounds are also effective when they are added to the developer solution in which case they are preferably used in similar quantities per liter of the aqueous developer bath.
The sensitizers can be dissolved in water or a solvent miscible with water or a mixture of water and water-miscible solvents, and added in this form to the emulsion. The solvent is not critical and should be selected so that it should have no harmful effect to the photographic properties of the silver halide emulsion.
The optimum amount for any sensitizer of the present invention can be determined for any particular emulsion by running a series of comparison tests in which the quantity of the sensitizer is varied over a given range. Exposure of the emulsion containing the sensitizer in a manner well known and measuring of the sensitivity in conventional apparatuses will reveal most advantageous concentrations. Such technique is well understood by those skilled in the art.
The thiomorpholine derivatives of the invention are used in silver bromide emulsions wh ich may contain a small amount of silver iodide of up to 10 mol percent.
The photographic emulsion in which the sensitizers according to the invention are used, can be chemically sensitized by any of the known procedures. They can be sensitized, for example, with sulfur compounds as referred to, e.g. in the book The Theory of the Photographic Process" by Mees (1954) pp. 149-161.
The emulsions can also be chemically sensitized with salts of noble metal such as gold, ruthenium, rhodium, palladium, iridium and platinum, used in amounts below that which produce any substantial fog. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and the like. The emulsions can be sensitized with reducing agents, stannous salts or polyamines and the like. The emulsions can also be optically sensitized with cyanine, merocyanine or rhodacyanine dyes.
The emulsions may also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonoles and the like. Sensitizers of this type have been described in the work by F. M. Hamer (The Cyanine Dyes n R te Q g g qg 111? my ,7 W w,
The emulsions can be stabilized with any of the known stabilizers, e.g. homopolar or salt-type compounds of mercury with aromatic or heterocyclic compounds (for example mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds. Other suitable stabilizers include azaindenes, especially tetraor pentaazaindenes, in particular those which are substituted with hydroxyl or amino groups. Such compounds have been described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
The silver halide emulsion layers may contain any suitable film-forming and water-permeable colloid as binding agent, such as gelatin but the gelatin can be replaced partially with products like alginic acid and derivatives thereof such as salts, preferably with alkali metals, esters with lower aliphatic alcohols or amides. The gelatin can also be partially replaced with polyvinyl alcohol, polyvinyl pyrrolidone, starch, carboxymethyl cellulose and the like.
The emulsions may be hardened in the usual manner, for example, with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
The compounds according to the invention are effective for both black-white emulsions and for color photographic emulsions which contain color couplers.
EXAMPLE 1 600 mg. of saponin as wetting agent, 200 mg. of 4-hydroxy- 6-methyl-1,3,3a,7-tetraazaindene as stabilizer and 10 ml. of a 10% aqueous solution of formaldehyde are added to a silver iodobromide gelatin emulsion which contains 60 g. of silver per liter in the form of silver halide which has a silver iodide content of 6 mols percent.
The emulsion was divided into three equal samples and the following substances were added per liter of emulsion to the individual samples:
Sample A: Comparison sample without additive Sample B: 300 mg. of compound 1 Sample C: 600 mg. of compound II] The casting solutions are applied onto a support of cellulose triacetate, exposed in a sensitometer customarily employed in the art behind a grey step wedge and developed for 10 minutes in a developer of the following composition:
Sodium sulfite anhydrous 70.0 g. borax 7.0 g. hydroquinone 3.5 g. p-monomethyl-aminophenol 3.5 g. sodium citrate 7.0 g. potassium bromide 0.4 g.
make up to 1 liter with water The results of the sensitometric test are given in the following table:
An increase by 3 represents a sensitivity gain of one shutter stop or double sensitivity.
EXAMPLE 2 A silver iodobromide gelatin emulsion containing 4.5 5 mol percent silver iodide which has been ripened to optimum sensitivity with gold and sulfur compounds in known manner is sensitized by the addition of 45 mg. of the following sensitizing dye per kg. of emulsion:
In addition, the following ingredients are added per kg. of emulsion: g. of 1-(3'-sulfo-4'-phenoxy)-phenyl-3-heptadecyl-pyrazolone as magenta coupler; 250 mg. of 1,3,3a,7- tetraaza-4-hydroxy-6-methyl indene as stabilizer; ml. of a 5% aqueous solution of saponin as wetting agent; 2.5 ml.
of a aqueous solution of formaldehyde as hardener.
The emulsion was divided into 7 equal samples and the following substances were added per kg. of emulsion to the individual samples:
Sample A: Comparison sample without additive Sample B: 1.0 g. of compound I Sample C: 3.0 g. of compound I-II Sample D: 1.0 g. of compound XII Sample E: 1.0 g. of compound IV Sample F: 0.3 g. of compound XI Sample G: 1.0 g. of compound XIV The samples are applied onto a support of cellulose acetate and dried. They are then exposed behind a step wedge and processed in the usual manner. Processing is carried out as follows:
Color development 7 minutes short stop bath 5 minutes washing 5 minutes bleaching bath 5 minutes washing 5 minutes fixing bath 5 minutes washing 10 minutes The color developer has the following composition:
make up to 1 liter with water W v The color density of the magenta layers was determined with a Macbeth Quanta Log, Model TD- 102 densitometer, a green color filter being interposed in the path of the beam of measuring light.
TABLE 2 Sample Sensitivity Gamma Fog A Blank 0.61 0. 16 B 2.5 0.63 0.18
An increase by 3 here also represents double sensitivity or a sensitivity increase of one shutter stop.
EXAMPLE 3 The thiomorpholine compounds of the invention are also effective when applied in color developers, as illustrated by the following Example. Each of the following substances is added to a color developer in an amount of l g. per liter:
Sample A: Comparison sample without additive Sample B: compound I Sample C: compound 11 Sample D: compound XV (0.5 g. per liter).
The color developer has the following composition: Diethyl-p-pheny1enediamine sulfate 2.75 g., hydroxylamine sulfate 1.2 g., sodium sulfite anhydrous 2.0 g., sodium hexametaphosphate 2.0 g., potassium carbonate anhydrous 75.0 g., potassium bromide 2.0 g., make up to 1 liter with water.
A conventional commercial color photographic multilayer material having on a support'a red-sensitive silver bromide emulsion layer with a cyan coupler, a green-sensitive emulsion layer with a magenta coupler and a blue-sensitive emulsion layer containing a yellow coupler, is exposed behind a step wedge and processed in the usual manner.
Color development 7 minutes stop bath 2 minutes washing 15 minutes bleaching bath 5 minutes washing 5 minutes fixing bath 5 minutes washing 10 minutes Intermediate bath, bleaching bath and fixing bath have the compositionreferredto above.
The color densities of the individual layers of the multilayer material are measured with a Macbeth Quanta Log, Model TD 102" densitometer, the appropriate color filter" being interposed in each case into the path of the beam.
An increase by 3 again denotes a sensitivity increase of one shutter stop or double the sensitivity.
We claim:
1. In a process for the production of photographic images by exposure and development of photographic materials which have atleast one silver bromide emulsion layer, the improvement consisting of developing the exposed" material in effective contact with a 1,4-thiazane of the following formula:
S N-R in which R stands for hydrogen or alkyl containing up to carbon atoms and 5. The process of claim 1, wherein the 1,4-thiazane has the following formula:
;.li qnsit terhrqm e at n em on taining per mol of silver bromide 3 mg. to 20 g of a 1,4- thiazane of the following formula:
S N-R in which R stands for hydrogen or alkyl containing up to 5 carbon atoms;
R represents (1) hydrogen, (2) a linear or branched alkyl group containing up to 12 carbon atoms, (3) a radical of the phenyl series, (4) an aliphatic carboxylic acyl group having up to five carbon atoms, (5) a carbamoyl group, or (6) an amino group. 7. The emulsion of claim 6 containing additionally up to 10 mol percent of silver iodide based on the silver bromide.
8. The emulsion of claim 6, wherein R represents alkyl, substituted with phenyl, hydroxyl, cyano, carboxyl or alkoxy.
9. The light-sensitive emulsion according to claim 6,
in which the thiazine has the formula:
10. The light-sensitive emulsion according to claim 6,
in which the thiazane has the formula:

Claims (11)

  1. 2. A process according to claim 1, wherein the compound containing at least one diazosulphone group is present in an amount within the range of 0.01 to 5 percent by weight based on the weight of photopolymerisable ethylenically unsaturated organic compound present.
  2. 3. A process according to claim 1, wherein a light source is used emitting light in the wavelength range of 2500-5000 A., particularly 3000-5000 A.
  3. 4. A process according to claim 1, wherein a light source is used emitting light in the wavelength range of 2500-7000 A. and wherein a photooxidation sensitizer of the class consisting of acridine, phenazine, thiazine or xanthene dyes is present in the photopolymerisation composition in an amount between 0.001 and 0.1 percent by weight with respect to the ethylenically unsaturated organic compound present.
  4. 5. A process according to claim 1, wherein the photopolymerisation initiator is (phenylsulphonyl)-(p-tolyl)-diimide.
  5. 6. A process according to claim 1, wherein the photopolymerisation initiator is (p-acetamidophenyl-sulphonyl)-(p-tolyl)-diimide.
  6. 7. A process according to claim 1, wherein the photopolymerisation initiator is the sodium salt of (phenyl-sulphonyl)-(p-sulphophenyl)-diimide.
  7. 8. A process according to claim 1, wherein the photopolymerisation initiator is (p-tolylsulphonyl)-(p-acetamidophenyl)-diimide.
  8. 9. A process according to claim 1, wherein the photopolymerisation initiator is (m-carboxy-phenyl-sulphonyl)-(p-carboxyphenyl)-diimide.
  9. 10. A process of producing a polymeric photographic relief image, which comprises exposing to a pattern of actinic light radiation a photographic element comprising a support and a light-sensitive layer comprising a photopolymerisable ethylenically unsaturated organic compound and as a photopolymerisation initiator a compound containing at least one diazosulphone group, said compound corresponding to one of the formulae: X-SO2-N N-Y and X''-SO2-N N-Z-N N-SO2-X'' wherein: X represents phenyl, naphthyl, or phenyl substituted in ortho, meta or paraposition with respect to the sulphonyl group by alkyl of one to four carbon atoms, carboxyl, amino, dialkylamino wherein the alkyl groups comprise one to four carbon atoms, acylamino wherein the acyl group comprises two to seven carbon atoms, phenylazo or nitrophenylazo; X'' represents phenyl, aminophenyl or alkylphenyl wherein the alkyl group comprises one to four carbon atoms; Y represents pyridyl, anthraquinonyl, naphthyl, acridinyl, benzothiazolyl or a group of the formula
  10. 11. A process according to claim 10 wherein the pattern of actinic light radiation emits light in the wavelength of 2500-5000 A., particularly 3000-5000 A.
  11. 12. A process according to claim 10, wherein the pattern of actinic light radiation emits light in the wavelength of 2500-7000 A and wherein the light-sensitive layer also comprises a photooxidation sensitizer of the class consisting of acridine, phenazine, thiazine or xanthene dyes in an amount between 0.001 and 0.1 percent by weight with respect to the ethylenically unsaturated organic compound present.
US818381A 1968-05-06 1969-04-22 Photopolymerization of ethylenically unsaturated organic compounds Expired - Lifetime US3617280A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419443A (en) * 1980-11-11 1983-12-06 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4426445A (en) 1980-05-07 1984-01-17 Fuji Photo Film, Co., Ltd. Silver halide photographic light-sensitive material
EP0106306A2 (en) 1982-10-14 1984-04-25 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3099558A (en) * 1959-06-26 1963-07-30 Gen Aniline & Film Corp Photopolymerization of vinyl monomers by means of a radiation absorbing component in the presence of a diazonium compound
US3138460A (en) * 1960-11-14 1964-06-23 Gen Aniline & Film Corp Photopolymerization and stratum transfer process
US3166539A (en) * 1948-12-31 1965-01-19 Degussa Polymerization of acrylate mixtures of polymer/monomer using a catalyst system of a tertiary-amine and a quadrivalent sulfur compound
US3192194A (en) * 1961-12-01 1965-06-29 Du Pont Diazothioether heterocyclic compounds
US3278304A (en) * 1963-04-22 1966-10-11 Gevaert Photo Prod Nv Photopolymerization of ethylenically unsaturated organic compositions
US3467518A (en) * 1964-06-15 1969-09-16 Agfa Gevaert Nv Photochemical cross-linking of polymers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166539A (en) * 1948-12-31 1965-01-19 Degussa Polymerization of acrylate mixtures of polymer/monomer using a catalyst system of a tertiary-amine and a quadrivalent sulfur compound
US3099558A (en) * 1959-06-26 1963-07-30 Gen Aniline & Film Corp Photopolymerization of vinyl monomers by means of a radiation absorbing component in the presence of a diazonium compound
US3138460A (en) * 1960-11-14 1964-06-23 Gen Aniline & Film Corp Photopolymerization and stratum transfer process
US3192194A (en) * 1961-12-01 1965-06-29 Du Pont Diazothioether heterocyclic compounds
US3278304A (en) * 1963-04-22 1966-10-11 Gevaert Photo Prod Nv Photopolymerization of ethylenically unsaturated organic compositions
US3467518A (en) * 1964-06-15 1969-09-16 Agfa Gevaert Nv Photochemical cross-linking of polymers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4426445A (en) 1980-05-07 1984-01-17 Fuji Photo Film, Co., Ltd. Silver halide photographic light-sensitive material
US4419443A (en) * 1980-11-11 1983-12-06 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0106306A2 (en) 1982-10-14 1984-04-25 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material

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CH526794A (en) 1972-08-15
GB1256393A (en) 1971-12-08
DE1772375A1 (en) 1971-03-18
FR2007937A1 (en) 1970-01-16
BE732547A (en) 1969-11-06

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