US3169863A - Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions - Google Patents

Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions Download PDF

Info

Publication number
US3169863A
US3169863A US286924A US28692463A US3169863A US 3169863 A US3169863 A US 3169863A US 286924 A US286924 A US 286924A US 28692463 A US28692463 A US 28692463A US 3169863 A US3169863 A US 3169863A
Authority
US
United States
Prior art keywords
phosphoric acid
silver halide
compound
photographic
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US286924A
Inventor
Grabhofer Herbert
Muller Herbert
Posse Rolf-Fred
Ulrich Hans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa AG filed Critical Agfa AG
Application granted granted Critical
Publication of US3169863A publication Critical patent/US3169863A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3056—Macromolecular additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/15—Lithographic emulsion

Definitions

  • n has the meaning given above, and the degree of condensation X of the product of esterification may be 1 or more, for instance 1-100, preferably 1-10.
  • the substituent R may represent H or 3,lh9,853 i atented Feb. 16, l65
  • any silver halide emulsions of the developing-out type which provide a high gamma when developed with developers containing formaldehyde may be used.
  • the silver salts of such emulsions generally consist of silver chloride in a quantity of at least 50 mole percent. However, it is preferred to use emulsions in which the silver salts consist at least of 65 mole percent of silver chloride and accordingly 35 mole percent or less of silver bromide.
  • the emulsions may further contain small amounts of silver iodide, such as 1 to 2 mole percent.
  • the quantity of the above phosphoric acid esters to be added to the emulsion depends on the ratio of chloride to bromide in the emulsion, 10 to mg. per mol of silver halide may advantageously be used.
  • the emulsions can in addition be chemically sensitized with salts of noble metals, such as gold salts, with sulfur compounds or with reducing agents.
  • the emulsions can be optically sensitized with cyanine and merocyanine dyes.
  • the developers which may be employed in our invention contain as essential components a phenol type de veloper, such as hydroquinone, an alkali,such as an alkali metal carbonate, sodium or potassium carbonate, formaldehyde bisulfite and a small amount of a restrainer, such as alkali metal bromide.
  • a restrainer such as alkali metal bromide.
  • the developer can also contain sodium hydroxide, boric acid, a sequesterin g agent.
  • alkali metal carbonate and formaldehyde bisulfite the developer can contain, 'as a source of formaldehyde, paraformaldehyde, an alkali metal sulfite and a buffering agent, such as alkali metal bisulfite.
  • Such developers are well known in the art and are for instance disclosed in US. Patents 2,184,053, 2,313,523, 2,902,367 and in British Patent 643,411.
  • Such developers may contain for instance per one liter 15-25 grams or" hydroquinone, 30-70 grams of formaldehyde bisulfite, 30-90 grams of sodium carbonate monohydrate, 5-20 grams of boric acid and 1-5 grams of alkali metal bromide or 15-25 grams of hydroquinone, 5-10 grams of paraformaldehyde, 1-5 grams of potassium metabisulfite (cryst), 20-40 grams of anhydrous sodium sulphite, 5-15 grams of boric acid and l-5 grams of alkali metal bromide.
  • the phosphoric acid esters of the present invention may be added to the above lithographic developers perferably in quantities of 30-300 mg. per liter.
  • the addition of the phosphoric acid esters of the present invention to the emulsion and/or to the developer causes the gamma value to rise considerably during development, for instance from about 6-8 to above 15.
  • the margin of time during development within which sharpness of raster dots may be obtained is increased from about one minute to 3 to 4 minutes.
  • a formaldehyde containing developer having such an addition is less dependent upon temperature. Whereas a developer without this addition reacts to temperature increases of 1 to 2 C. with a marked reduction in the margin of time for development, good results may be obtained with developer temperatures of 15 to 40 C. if these phosphoric acid esters have been added. Owing to the increased time available for processing, the above graphic use.
  • the phosphoric acid esters according to the invention are prepared by the usual methods used for esterification, and the degree of condensation of the esters may be infiuenced in the desired direction by varying the reaction time, the reaction temperature and the molar proportions of the reaction components.
  • the condensation may for instance be carried through in a liquid alkaline medium, such as in pyridine or triethylamine or other tertiary amines, at temperatures of about 0 to 80 C., preferably to 50 C.
  • the crystals may be isolated by suction filtration after some of the phosphorus oxychloride has been removed by evaporation in vacuo, and the crystals may then be washed with methylene chloride on the suction filter.
  • condensation time is increased the degree of condensation X increases likewise.
  • amount of octaethyleneglycol used for the reaction is increased up to 2 moles there are obtained condensation products in which both end groups are mainly formed by -'-(o cH cH oH- radicals.
  • COMPOUND H 19.4 g. of tetraethylene glycol, 31.2 g. of pyridine and 30 g. of ester chloride (Ia) are reacted as described above and worked up. 27 g. of a viscous light brown oil are obtained. The color may be removed from the 10% aqueous solution by means of active charcoal and bleaching earth.
  • the ioily liquid presumably consists mainly "of a compound of the following theoretical formula:
  • COMPOUND W 41.4 g. of nonaethyleneglycol, 31.2 g. of pyridine and 30 g. of ester chloride (Ia) produce 20 g. of a brown syrupy polycondensate which is diluted with water to a 10% solution and purified with active charcoal and bleaching earth.
  • ester chloride (Ia) produces 20 g. of a brown syrupy polycondensate which is diluted with water to a 10% solution and purified with active charcoal and bleaching earth.
  • the following theoretical formula may be used to represent the highly viscous polycondensate:
  • Example 1 A gelatine-silver halide emulsion the silver halide of which containing 15 mole percent of AgBr and mole percent of AgCl is Washed and then ripened to'maximurn sensitivity and 4-hydroxy-6-rnethyl-l,3,3a,7-tetrazaindole or other stabilizers and a wetting agent are then added, and the emulsion is poured on to a suitable film base (A).
  • A suitable film base
  • Example 2 An emulsion accordinging to Example 1 is divided into two portions. One portion (A) has no additive while the other portion (B) has added to it 80 mg. of Compound II per mole of silver halide. Each portion is then poured on to a film base. The two samples are then illuminated and developed as in Example 1.
  • Example 3 An emulsion according to Example 1 is divided into a portion (A) without additive and a portion (B) with 80 mg. of Compound IH per mole of silver halide as additive, and the portions are poured on to a base and then treated as described under 1.
  • Exampl e 4 Film strips (Agfa-lith-ortho) illuminated behind a stepped wedge are developed in the developer mentioned in Example 1 for varying time ranging from 1 to 4 minutes, at C.
  • the same film samples are developed in the same developer after the addition of 100 rug/liter of Compound I.
  • condensation pro-duct is the condensation product of one mol of a pentaerythritol ester of phosphorochloridic acid and about 1 to 2 mols of a polyethylene glycol.
  • condensation product has the formula wherein R represents a member of the group consisting of hydrogen and radicals having the formula ⁇ -o11,-oH,-o
  • n represents an integer of at least 3 and X represents an integer of at least 1.
  • a light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least SO-mcl percent, which contains a condensation product as defined in claim 1.
  • a light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least 50-mol percent, which contains a condensation product as defined in claim 2.
  • a light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least 50-mol percent, which contains a condensation product as defined in claim 3.
  • Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 1.
  • Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 2.
  • Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Description

United States Patent Cfifice 3,16,863 PENTAERYTHRETUL PHQSPHGRKC AC1!) ESTER SENSITIZERS FOR PEZQTGGRAEH6 EMULSEONS Herbert Grabhiiler, Cologne-Flittard, Herbert Miiller, Leverknsen, Rolf-Fred Posse, Cologne-Flittard, and Hans Ulrich, Leverlrusen, Germany, assignors to Agfa Aktiengesellschaft, Leverlnisen, Germany, a corporation of Germany No Drawing. Filed June 11, 1963, Ser. No. 286,924 Claims priority, application Germany, luly 21, 1962, A 40,784 9 Claims. (Cl. 96-66) The invention relates to chemical sensitizers for photographic emulsions, to photographic emulsions and developer compositions containing these and to the production of photographic images in the presence of said sensitizers.
In the graphic arts field, particularly for raster photography, more and more films are being used which are onthe market as so-called lithographic or line films and which can be developed to very high gamma values and therefore sharp raster points in developers which contain formaldehyde.
Although the processing of such films in developers containing formaldehyde gives excellent results, it must be carried out with great care. The interval during development in which a sharp raster point is obtained, i.e. the steepest gamma, is only short. It amounts to approximately between /2 and 1 /2 minutes.
It is known to add phosphorylated alkylene oxide derivatives to photographic silver halide emulsions to improve the mechanical properties thereof. However, these compounds are unsuitable for obtaining a high contrast.
It has now been found that the gamma values of photographic emulsions and the period during development in which an extremely high gamma value is obtained can be increased, so that development can be carried out much more effectively and conveniently, if the development is carried out in the presence of spirocyclic phosphoric acid esters which are obtainable by reaction of spirocyclic pentaerythritol-di-(phosphoric acid monohalides), particularly -(monochlorides) of the formula vIn this formula, n has the meaning given above, and the degree of condensation X of the product of esterification may be 1 or more, for instance 1-100, preferably 1-10. L1 the above hypothetical formula, the substituent R may represent H or 3,lh9,853 i atented Feb. 16, l65
7 compounds of the following formula where n and X have the meaning given above:
do not produce extremely high gamma values.
Any silver halide emulsions of the developing-out type which provide a high gamma when developed with developers containing formaldehyde may be used. The silver salts of such emulsions generally consist of silver chloride in a quantity of at least 50 mole percent. However, it is preferred to use emulsions in which the silver salts consist at least of 65 mole percent of silver chloride and accordingly 35 mole percent or less of silver bromide. The emulsions may further contain small amounts of silver iodide, such as 1 to 2 mole percent.
.The quantity of the above phosphoric acid esters to be added to the emulsion depends on the ratio of chloride to bromide in the emulsion, 10 to mg. per mol of silver halide may advantageously be used. The emulsions can in addition be chemically sensitized with salts of noble metals, such as gold salts, with sulfur compounds or with reducing agents. Moreover the emulsions can be optically sensitized with cyanine and merocyanine dyes.
The developers which may be employed in our invention contain as essential components a phenol type de veloper, such as hydroquinone, an alkali,such as an alkali metal carbonate, sodium or potassium carbonate, formaldehyde bisulfite and a small amount of a restrainer, such as alkali metal bromide. If desired the developer can also contain sodium hydroxide, boric acid, a sequesterin g agent. Instead of alkali metal carbonate and formaldehyde bisulfite the developer can contain, 'as a source of formaldehyde, paraformaldehyde, an alkali metal sulfite and a buffering agent, such as alkali metal bisulfite. Such developers are well known in the art and are for instance disclosed in US. Patents 2,184,053, 2,313,523, 2,902,367 and in British Patent 643,411. Such developers may contain for instance per one liter 15-25 grams or" hydroquinone, 30-70 grams of formaldehyde bisulfite, 30-90 grams of sodium carbonate monohydrate, 5-20 grams of boric acid and 1-5 grams of alkali metal bromide or 15-25 grams of hydroquinone, 5-10 grams of paraformaldehyde, 1-5 grams of potassium metabisulfite (cryst), 20-40 grams of anhydrous sodium sulphite, 5-15 grams of boric acid and l-5 grams of alkali metal bromide.
The phosphoric acid esters of the present invention may be added to the above lithographic developers perferably in quantities of 30-300 mg. per liter.
The addition of the phosphoric acid esters of the present invention to the emulsion and/or to the developer causes the gamma value to rise considerably during development, for instance from about 6-8 to above 15. At the same time, the margin of time during development within which sharpness of raster dots may be obtained is increased from about one minute to 3 to 4 minutes. Furthermore, a formaldehyde containing developer having such an addition is less dependent upon temperature. Whereas a developer without this addition reacts to temperature increases of 1 to 2 C. with a marked reduction in the margin of time for development, good results may be obtained with developer temperatures of 15 to 40 C. if these phosphoric acid esters have been added. Owing to the increased time available for processing, the above graphic use.
. O -CH Hi described advantages render the Work much more reliable and more free from disturbance.
The phosphoric acid esters according to the invention are prepared by the usual methods used for esterification, and the degree of condensation of the esters may be infiuenced in the desired direction by varying the reaction time, the reaction temperature and the molar proportions of the reaction components. The condensation may for instance be carried through in a liquid alkaline medium, such as in pyridine or triethylamine or other tertiary amines, at temperatures of about 0 to 80 C., preferably to 50 C.
Individual condensative products will be described below in the following preparation examples.
' COMPOUND I CHg-O 0 /P-Cl O-Cfig CHz-O is deposited in the form of colorless crystals, melting point 243-245 C.
The crystals may be isolated by suction filtration after some of the phosphorus oxychloride has been removed by evaporation in vacuo, and the crystals may then be washed with methylene chloride on the suction filter.
(b) 30 g. of the ester chloride (Ia) described above are added in portions with stirring to a mixture of 37.2 g. octaethyleneglycol and 31.2 g. of pyridine, the temperature gradually rising to 35 C. After 4 hours the mixture is poured on to ice, adjusted to pH 3 with 2 N H 80 treated with saturated sodium chloride solution, and extracted with methylene chloride. After drying with potash, the methylene chloride is evaporated oif completely. 25 g. of a light brown highly viscous oil is obtained, which is diluted with water to a 10% solution for photo- The following theoretical formula is derived from the proportions of the starting materials and the molecular weight of 900 determined by osmosis:
If the reaction time is increased the degree of condensation X increases likewise. Alternatively, if the amount of octaethyleneglycol used for the reaction is increased up to 2 moles there are obtained condensation products in which both end groups are mainly formed by -'-(o cH cH oH- radicals.
COMPOUND H 19.4 g. of tetraethylene glycol, 31.2 g. of pyridine and 30 g. of ester chloride (Ia) are reacted as described above and worked up. 27 g. of a viscous light brown oil are obtained. The color may be removed from the 10% aqueous solution by means of active charcoal and bleaching earth. The ioily liquid presumably consists mainly "of a compound of the following theoretical formula:
The variation of the reaction time and proportion of component has the same eifect as disclosed in connection 'with the prescription for the preparation of Compound I.
d COMPOUND III The compound is prepared by a similar method to that used for compound (lb) by reacting 28.2 g. of hexaethyleneglycol and 31.2 g. of pyridine with 30 g. of ester chloride (Ia). Yield 17 g.
I A possible theoretical formula of the end product would be: 7
COMPOUND W 41.4 g. of nonaethyleneglycol, 31.2 g. of pyridine and 30 g. of ester chloride (Ia) produce 20 g. of a brown syrupy polycondensate which is diluted with water to a 10% solution and purified with active charcoal and bleaching earth. The following theoretical formula may be used to represent the highly viscous polycondensate:
COMPOUND V O O-GH; CHz-O O nli X 7 i o a a... .ofl a. g L o-on, onto .|x 7
The preparation of the spirocyclic carbon compounds .used for comparison in the examples will now be described.
COMPOUND VI CH3 OOH2 OHz-O CH3 (3 o \(]JOOOCH5 C-GH: CHg-O Preparation: From pentaerythritol, pyruvic acid and ethanol (Ber. 61 (1928), page 1856).
COMPOUND VII (VII) CO3 O-CEg CHz-O CH3 5 7 oo o-on -oni)son L \OO2 ont-o ix 16.6 g. of Compound VI and 18.5 g. of ioctaethylene glycol are heated for 2 hours at 150 C. in the presence 'of 0.2 g. of sodium methylate, the ethyl alcohol which is liberated distilling off. There reaction product isdiluted with Water to a 10% solution and neutralized with 1 N hydrochloric acid. Osmotic determination of the molecular weight indicated that the value of X was 2.
Example 1 A gelatine-silver halide emulsion the silver halide of which containing 15 mole percent of AgBr and mole percent of AgCl is Washed and then ripened to'maximurn sensitivity and 4-hydroxy-6-rnethyl-l,3,3a,7-tetrazaindole or other stabilizers and a wetting agent are then added, and the emulsion is poured on to a suitable film base (A). In parallel experiments, the following substances,
used as casting additives, are added to the emulsion per mole of silver halide:
(B) +80 mg; octaethylene glycol (C) +80 mg. Compound VII (D) +80 mg. Compound I All the samples are illuminated in a sensitometer behind a grey step wedge and developedfor 5 minutes at 18 C. in a developer of the following composition:
Example 2 An emulsion acording to Example 1 is divided into two portions. One portion (A) has no additive while the other portion (B) has added to it 80 mg. of Compound II per mole of silver halide. Each portion is then poured on to a film base. The two samples are then illuminated and developed as in Example 1.
Result:
Gamma Fog Emulsion A 7 0. ()5 Emulsion B 0. 05
Example 3 An emulsion according to Example 1 is divided into a portion (A) without additive and a portion (B) with 80 mg. of Compound IH per mole of silver halide as additive, and the portions are poured on to a base and then treated as described under 1.
Result:
Gamma Fog Emulsion A 6 0. 04 Emulsion B 15 0, 04
Exampl e 4 Film strips (Agfa-lith-ortho) illuminated behind a stepped wedge are developed in the developer mentioned in Example 1 for varying time ranging from 1 to 4 minutes, at C. The same film samples are developed in the same developer after the addition of 100 rug/liter of Compound I.
Result:
Gamma without additive 7. 5 15 12 6. 5 5. 5 5 +100 mg. I/l 10 15 15 15 15 15 What we claim is:
1. In a process for the production of photographic images by developing silver hmide emulsion layers in which the silver halide has a silver chloride content of at least 50 mole percent with photographic developer solutions containing formaldehyde, the improvement which comprises carrying out said development in the presence of a condensation product Of a pentaerythritol ester of phosphorochloridic acid and a polyethylene glycol with a degree of polymerization of at least 3.
2. A process as defined in claim 1 in which the condensation pro-duct is the condensation product of one mol of a pentaerythritol ester of phosphorochloridic acid and about 1 to 2 mols of a polyethylene glycol.
3. A process as defined in claim 1 in which the condensation product has the formula wherein R represents a member of the group consisting of hydrogen and radicals having the formula \-o11,-oH,-o
in which n represents an integer of at least 3 and X represents an integer of at least 1.
4. A light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least SO-mcl percent, which contains a condensation product as defined in claim 1.
5. A light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least 50-mol percent, which contains a condensation product as defined in claim 2.
6. A light-sensitive photographic material comprising a silver halide emulsion layer in which the silver halide has a silver chloride content of at least 50-mol percent, which contains a condensation product as defined in claim 3.
7. Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 1.
8. Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 2.
9. Photographic developing composition comprising hydroquinone and formaldehyde, which contains in addition a condensation product as defined in claim 3.
References Cited in the file of this patent UNITED STATES PATENTS 2,531,832 Stanton Nov. 28, 1950 2,956,881 Van Lare Oct. 18, 1960 2,961,317 Webster et al. Nov. 22, 1960 2,974,158 Lanham Mar. 7, 1961 3,005,007 Fierce et 'al. Oct. 17, 1961 3,090,799 Wahl et al. May 21, 1963

Claims (1)

1. IN A PROCESS FOR THE PRODUCTION OF PHOTOGRAPHIC IMAGES BY DEVELOPING SILVER HALIDE EMULSION LAYERS IN WHICH THE SILVER HALIDE HAS A SILVER CHLORIDE CONTENT OF AT LEAST 50 MOLE PERCENT WITH PHOTOGRAPHIC DEVELOPER SOLUTIONS CONTAINING FORMALDEHYDE, THE IMPROVEMENT WHICH COMPRISES CARRYING OUT SAID DEVELOPMENT IN THE PRESENCE OF A CONDENSATION PRODUCT OF A PENTAERYTHRITOL ESTER OF PHOSPHOROCHLORIDIC ACID AND A POLETHYLENE GLYCOL WITH A DEGREE OF POLYMERIZATION OF AT LEAST 3.
US286924A 1962-07-21 1963-06-11 Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions Expired - Lifetime US3169863A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEA40784A DE1246403B (en) 1962-07-21 1962-07-21 Process for making photographic images
DEA43236A DE1178297B (en) 1962-07-21 1963-05-31 Process for increasing the general sensitivity of photographic silver halide emulsions and photographic materials for carrying out the process

Publications (1)

Publication Number Publication Date
US3169863A true US3169863A (en) 1965-02-16

Family

ID=25963785

Family Applications (2)

Application Number Title Priority Date Filing Date
US286924A Expired - Lifetime US3169863A (en) 1962-07-21 1963-06-11 Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions
US368714A Expired - Lifetime US3385708A (en) 1962-07-21 1964-05-19 Sensitization of photographic silver halide emulsions

Family Applications After (1)

Application Number Title Priority Date Filing Date
US368714A Expired - Lifetime US3385708A (en) 1962-07-21 1964-05-19 Sensitization of photographic silver halide emulsions

Country Status (6)

Country Link
US (2) US3169863A (en)
BE (2) BE648588A (en)
CH (2) CH433977A (en)
DE (2) DE1246403B (en)
FR (2) FR1364351A (en)
GB (2) GB1045183A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385708A (en) * 1962-07-21 1968-05-28 Agfa Ag Sensitization of photographic silver halide emulsions
US3443951A (en) * 1964-07-02 1969-05-13 Agfa Gevaert Nv Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols
US3532501A (en) * 1967-02-10 1970-10-06 Gaf Corp Water-soluble acid esters of polyoxyalkylenated pentaerythritol in silver halide emulsions
CN100400542C (en) * 2006-03-30 2008-07-09 上海大学 Synthetic method for phosphate ester

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3264151D1 (en) * 1981-01-20 1985-07-25 Ciba Geigy Ag Photographic recording material and process for its preparation
US4436811A (en) * 1981-07-10 1984-03-13 Ciba-Geigy Ag Photographic material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2531832A (en) * 1947-06-12 1950-11-28 Du Pont Silver halide developers containing polyethylene glycols
US2956881A (en) * 1957-03-12 1960-10-18 Eastman Kodak Co Hemioxonol dyes containing a carbocyclic nucleus and photographic emulsions containing them
US2961317A (en) * 1958-06-19 1960-11-22 Eastman Kodak Co Holopolar dyes derived from 3-indazolinone
US2974158A (en) * 1953-04-02 1961-03-07 Union Carbide Corp Preparation of bi-heterocyclic phosphorus containing compounds
US3005007A (en) * 1959-01-19 1961-10-17 Pure Oil Co Preparation of organophosphorus compounds from glycerol and phosphorus oxyhalides
US3090799A (en) * 1959-11-17 1963-05-21 Agfa Ag Pentaerythritol esters of phosphoric acids and compositions containing the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1122834B (en) * 1960-07-01 1962-01-25 Perutz Photowerke G M B H Process for the partial desensitization and steepening of the gradation of halogen silver emulsions
BE635167A (en) * 1962-07-21

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2531832A (en) * 1947-06-12 1950-11-28 Du Pont Silver halide developers containing polyethylene glycols
US2974158A (en) * 1953-04-02 1961-03-07 Union Carbide Corp Preparation of bi-heterocyclic phosphorus containing compounds
US2956881A (en) * 1957-03-12 1960-10-18 Eastman Kodak Co Hemioxonol dyes containing a carbocyclic nucleus and photographic emulsions containing them
US2961317A (en) * 1958-06-19 1960-11-22 Eastman Kodak Co Holopolar dyes derived from 3-indazolinone
US3005007A (en) * 1959-01-19 1961-10-17 Pure Oil Co Preparation of organophosphorus compounds from glycerol and phosphorus oxyhalides
US3090799A (en) * 1959-11-17 1963-05-21 Agfa Ag Pentaerythritol esters of phosphoric acids and compositions containing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385708A (en) * 1962-07-21 1968-05-28 Agfa Ag Sensitization of photographic silver halide emulsions
US3443951A (en) * 1964-07-02 1969-05-13 Agfa Gevaert Nv Photographic light-sensitive materials containing phosphoric acid ester of aliphatic polyols
US3532501A (en) * 1967-02-10 1970-10-06 Gaf Corp Water-soluble acid esters of polyoxyalkylenated pentaerythritol in silver halide emulsions
CN100400542C (en) * 2006-03-30 2008-07-09 上海大学 Synthetic method for phosphate ester

Also Published As

Publication number Publication date
FR1396860A (en) 1965-04-23
GB1045183A (en) 1966-10-12
DE1178297B (en) 1964-09-17
BE648588A (en) 1964-11-30
BE635167A (en)
CH450156A (en) 1968-01-15
US3385708A (en) 1968-05-28
DE1246403B (en) 1967-08-03
GB1045184A (en) 1966-10-12
CH433977A (en) 1967-04-15
FR1364351A (en) 1964-06-19

Similar Documents

Publication Publication Date Title
DE961416C (en) Stabilized, highly sensitive halogen silver emulsion
US2732303A (en) Antifoggevg and hardening agents for
US3169863A (en) Pentaerythritol phosphoric acid ester sensitizers for photographic emulsions
US2981624A (en) Antifoggants and stabilizers for photographic silver halide emulsion
US2566658A (en) Silver halide emulsions containing antifogging agents
US2566659A (en) Silver halide emulsions containing antifogging agents
US3615616A (en) Photographic light-sensitive silver halide material
US3671247A (en) Development of silver halide photographic materials
US2743180A (en) Pentazaindene stabilizers for photo-graphic emulsions sensitized with alkylene oxide polymers
US4067740A (en) Trithiocarbonates as sensitizers for silver halide emulsions
US3847948A (en) Process for the preparation of novel dihydroxy-1,4-dioxanes
US3778268A (en) Light-sensitive silver halide photographic material
DE2244916A1 (en) DEVELOPMENT OF HIGH CONTRAST SILVER HALOGENIDE EMULSIONS FOR GRAPHIC PURPOSES
US3342903A (en) Pentaerythritol phosphoric acid esters
US3679423A (en) Silver halide emulsion containing acetylene dicarboxylic acid anions antifoggant
US4695535A (en) Silver halide photosensitive material
GB1575539A (en) Processing of silver halide photographic material
EP0618491B1 (en) Method for generation of negative images having ultrahigh contrast
US3827886A (en) Light-sensitive silver halide photographic materials
US3396022A (en) Quinone stabilizers and antifoggants for silver halide emulsions
US3084044A (en) Nitrogenous heterocyclic carboxyal-kylmercapto polyoxyalkylene ester photographic sensitizer
US3526507A (en) Autopositive reproduction material
US3210192A (en) Photographic material incorporating a phosphoric acid ester of a polyoxyalkylene compound
US3819608A (en) Process for hardening gelatin using particular dihydroxy dioxanes
US3346386A (en) Polycondensation products of phosphoric acid amides with aliphatic polyethers as developer adjuvants