US3158484A - Light-sensitive colloid silver halide photographic elements - Google Patents

Light-sensitive colloid silver halide photographic elements Download PDF

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Publication number
US3158484A
US3158484A US149809A US14980961A US3158484A US 3158484 A US3158484 A US 3158484A US 149809 A US149809 A US 149809A US 14980961 A US14980961 A US 14980961A US 3158484 A US3158484 A US 3158484A
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United States
Prior art keywords
silver halide
preparation
compound
compounds
added
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
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US149809A
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English (en)
Inventor
Willems Jozef Frans
Thiers Robrecht Julius
Munck Joseph Louis De
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Gevaert Photo Producten NV
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Gevaert Photo Producten NV
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Priority claimed from GB1569559A external-priority patent/GB920637A/en
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • phite di-n-propyl phosphite, di-isopropyl phosphite, di-nbutyl phosphite and mixtures thereof, such as methyl ethyl phosphite.
  • the trialkyl phosphites can also be employed With particularly good results being obtained from triethyl phosphite.
  • the epoxy compounds suitable for use in the instant invention include 1,2 di(2',3'-epoxypropoxy)ethane, 1,4 bis- (2,3'-epoxypropoxy)butane and similar epoxides including those more fully described in British patent specification No. 793,915.
  • the polyepoxy compounds provide particularly good results.
  • the illustrative aliphatic aldehydes include formaldehyde, acetaldehyde, isobutyraldehyde, and isopropionaldehyde.
  • the ratio of the two reagents used in the condensation may vary Within wide limits and depends upon the desired properties which are intended to be ascribed to the condensation product. The ratios, however, must be judiciously selected so that water soluble condensation products are obtained. Suitable ratios are, for example, 1 mol of polyoxyalkylene compound and 1 mol of phosphonic acid ester or phosphoric acid ester; 1 mol of polyoxyalkylene compound and 0.5 mol of polyepoxide compound; 1 mol of polyoxyalkylene compound and 1 mol of aldehyde and 1 mol polyglycol per mol of acid or acid anhydride.
  • ratios may vary over a relatively wide range so long as the condensate remains water soluble.
  • operable ratios of polyoxyaikylene compounds to the second reagent vary from about 1:5 to :1. The selection of the proper ratio is within the ability of one skilled in the art in view of the instant teaching.
  • the condensation products according to the instant invention can be prepared by mixing the reagents while heating at temperatures from slightly above ambient to above about 240 C. while stirring.
  • the selection of the proper temperature depends upon the reagent chosen and upon the desired rate of reaction. As a rough rule of thumb, the rate for a given reaction is doubled for each rise in temperature.
  • a suitable catalyst may be employed. It may be desirable at times to terminate the reaction by heating under reduced pressure.
  • PREPARATION 2 A solution of 25 g. of polyglycol (average molecular weight: 1000), 2.25 g. of paraformaldehyde and 3 drops of concentrated sulphuric acid in cm. of toluene is boiled for 2 days. Before filtering, another 50 cm. of toluene are added. The toluene is then distilled oil under reduced pressure. The residue is dissolved in chloroform and filtered. After evaporation of the chloroform the remaining powder is Washed with ether whereby 13 g. of a white powder are obtained.
  • PREPARATION 3 50 g. of polyglycol (average molecular weight: 1000), and 4.9 g. of maleic anhyd-ride are heated together under nitrogen atmosphere for 3 hours at 200 to 230 C. The reaction product obtained is washed with a mixture consisting of 4 parts of ether and one part of benzene. 30 g. of a light-brown solid substance soluble in water and alcohols are obtained.
  • PREPARATION 4 30 g. of polyglycol (average molecular weight: 300) and 4.9 g. of maleic anhydride are heated together under nitrogen atmosphere for 1 hour at 200 C. The reaction product obtained is washed with a mixture consisting of 3 parts of ether and 4 parts of benzene. After drying under vacuum, 17 g. of a viscous yellow oil are obtained.
  • PREPARATION 5 50 g. of polyglycol (average molecular weight: 1000) and 10 g. of sebacic acid are heated together under nitrogen atmosphere for 7 hours at 210 0., whereby water vapor evolves. On cooling, 52 g. of a resinous product which is quite soluble in water are obtained.
  • PREPARATION 6 50 g. of polyglycol (average molecular weight: 1000) are dissolved in anhydrous acetone to which 4.2 g. of hexamethylene diisocyauate are added. The reaction mixture is boiled for 7 hours whereafter the solvent is removed under reduced pressure. 52 g. of a white solid powder which is soluble in Water are obtained.
  • PREPARATION 7 30 g. of polyglycol (average molecular weight: 600), 6.7 g. of diglycolic acid and 3 g. of paratoluene sulphouic acid are heated under inlet of nitrogen for 1 hour at normal pressure and next for 5 hours at 2 mm. Hg. at 200 C. After cooling, a viscous oil which is quite soluble in water is obtained.
  • PREPARATION 8 20 g. of polyglycol (average molecular weight: 1000), 2.68 g. of diglycolic acid and 2 mg. of paratoluene sulphonic acid are heated for 1 /2 hours at normal pressure and for 5 hours at 2 mm. Hg at 200 C. After cooling, a viscous oil which is quite soluble in water is obtained.
  • PREPARATION 9 A solution of 30 g. of polyglycol (average molecular weight: 300) and 14.8 g. of phthalic anhydride are heated at 210 C. for 6 hours under nitrogen atmosphere. After cooling, a very viscous oil is obtained.
  • PREPARATION 10 A solution of 20 g. of polyglycol (average molecular Weight: 1000) and 3 g. of phthalic anhydride are heated at 210 C. for 6 hours under nitrogen atmosphere. After cooling, a resin is obtained.
  • PREPARATION 11 PREPARATION 12 50 g. (0.05 mol) of polyglycol (average molecular weight: 1000) dissolved in 125 cm. of tetrahydrofurane are dried over sodium sulphate and at 60-65 C. this solution is dropwise added within a period of 5 hours to a suspension of 10.9 g. (0.05 mol) of pyromellitic dianhydride in 75 cm. of tetrahydrofurane. The solution obtained is filtered over Norit and under vacuum evaporated on the water bath. The residue obtained is an oil which is washed with ether. Yield: 30 g. of end product.
  • PREPARATION 14 A mixture of 100 g. of polyethylene glycol (average molecular weight: 1000) and 13.8 g. of diethyl phosphite is gradually heated on the oil-bath under nitrogen atmosphere in the presence of a trace of magnesium at 200 C. for 3 hours whereby ca. cm. of ethanol are distilled over. Then the reaction mixture is heated under reduced pressure for 4 hours at 200 C. The reaction product is obtained in the form of a quite water-soluble wax.
  • PREPARATION 15 A mixture of 100 g. of polyethylene glycol (average molecular weight: 1000) and 18.2 g. triethyl phosphate is gradually heated on the oil-bath under nitrogen atmosphere and in the presence of a trace of magnesium for3 hours at 200 C., whereby ca. 12 cm. of ethanol are distilled over. Then the reaction mixture is heated under reduced pressure for 4 hours at 200 C. The reaction product is obtained in the form of a quite water-soluble wax.
  • the compounds according to the invention may be added to the emulsions or brought into intimate contact with silver halide emulsion layers by dissolving them in water or in an aqueous mixture of organic solvents which do'not have a deleterious elfect on silver halide emulsions and .by adding the solution obtained to an emulsion or applying it to an emulsion layer as a coating composition.
  • the compounds can be introduced into the emulsion at various stages during its preparation; for example, they may be incorporated a a separate addition, or mixed with one or more of the other ingredients used at the initial precipitation of the silver halide grains, during the physical or chemical ripening process, or at some other point prior to coating the emulsion. Preferably, they are added after the chemical ripening and just before coating the emulsion.
  • the optimum amount of the compound to be added to the emulsion depends on the particular compound chosen, the nature of the colloid binding agent for the silver halide grains and the amount and kind of silver halide in the emulsion. In general, however, the compounds according tothe invention are added in a quantity of mg. to 7 gm.'per mol silver halide. If necessary, however, still other quantities of these compounds can be added which fall outside these limits.
  • the process of the present invention can be combined I with a method for increasing the sensitivity of the photo:
  • a sulphur-containing compound such as allyl isothiocyanate, allyl thiourea and sodium thiosulphate
  • small amounts of reduction sensitizers such as the tin compounds described in Belgian specifications Nos. 493,- 464 and 568,687, the imino-aminomethane sulphinic acid compounds described in British specification No. 789,823 or small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodrum.
  • the new process is advantageously superimposed on the sensitizing action of compounds originally present in gelatin.
  • stabilizing agents such as, for example, mercury compounds and the compounds claimed and re ferred to in the statement of prior art of Belgian specifications Nos. 571,916 and 571,917 may be added to the emulsion. It is also usual to sensitize and/or to stabilize silver halide emulsions by incorporating therein cadmium salts or by carrying out their processing in the presence of cadmium salts. Still other ingredients such as antifogging agents, color couplers, developing substances,
  • the new compounds are elfective in increasing the X-ray sensitivity and the general light sensitivity of orthochromatic, panchromatic, and all special emulsions, as well as of the ordinary non-spectrally sensitized ones.
  • they can be added without or with optical sensitizing dyes and in the latter case before or after them.
  • They are also useful with a variety of emulsions, since the production of pronounced speed is increased in either negative or positive types of emul- SlOl'lS.
  • a stabilizing agent Water up to such as S-hydroxy-7-methyl-s-triazo1o-(4,5a)-pyrimidine SENSITOMETRIC RESULTS and of other usual ingredients, the emulsion is coated onto a suitable support (sample 1).
  • e Further samples were prepared by adding to the same sample Compound added 252 Gamma Fog emulsion prior to coating and, per mol silver halide presy ent, the amounts of developing accelerators listed below.
  • Example 10' Exam le 8 The following results were obtained in exactly the same To one sample of an emulsionaccording to Example 5 manner as described i Example 9 is added before coating 0.2 g. of Carbowax (sample 1) and to another sample 0.2 g. of compound according to Rem preparation 8 (sample 2). Both samples are stored for Sample Compound added tive Gamma Fog some days at considerable relative humidity and high temperature, and next developed for 4 minutes in developer from Example 1 None 100 0,4 0.08 2 0.333 g. compound of preparation 102 0.48 0.09 a 3.4. compound of preparation 16. 106 o. 54 0. 09 4 3.4 g. compound of preparation 17. 105 0. 50 0. 09
  • Example 11 2 compmmd 8 116 The following sensi-tometric results are obtained in the same manner as described in Example 9, but the samples are developed for 7 minutes at 20 C. in a solution of the Example 9 following composition:
  • Example 12 were prepared by adding prior to coating to the same Example 12 emulsion and per mol silver halide present the amounts of developing accelerators listed below. They are then A Washed coarsely grallled gelatine Silver ifldObrOmide treated as sample 1. After drying and exposure they are emulsionwherein the silver halide consists of 98.2 mol developed for 7 minutes at 20 C. in a Solution 0011- percent silver bromide and 1.8 mol percent silver iodide is sistrng of: ripened at 42 C.
  • a stabilizing agent Water 300 such as 5 -hydroXy-7-methyl-s-triazolo-(2.3a) -pyrimidine M y -p- P1181101 phate g and of other usual ingredients, the emulsion is coated Hydroquinone 3 onto a suitable support (sample 1).
  • R is an alkylene group of from 2 to 3 carbon atoms
  • Emulsions based on other waterpermeable colloids may equally well be treated according to the present invention.
  • colloids are for instance to be mentioned: agar-agar, zein, collodion, water-soluble cellulose derivatives such as hydrolyzed cellulose acetate; cellulose esters of hydroxycarboxylic acids, for example lactic or glycolic acid; alkali metal salts of cellulose esters of dicarboxylic acids such as phthalic acid; polyvinyl alcohol, and partially hydrolyzed polyvinyl acetate and interpolymers of vinyl acetate with unsaturated compounds such as styrene and maleic acid, water-soluble polyvinyl acetals and other hydrophilic synthetic or natural resins or polymeric compounds.
  • the new developing accelerators may be used for sensitizing the known types of silver chloride, silver bromide, silver iodide emulsions and emulsions containing mixtures of these halides.
  • the methods as described in the above examples are not limited, as far as the quantity and the nature of the developing accelerator to be added or the moment of the addition are concerned. Indeed, for obtaining an optimum efiect, all particular techniques in the preparation of light-sensitive emulsions should be taken into account.
  • An advantage of this invention is the compatability of the new developing accelerators with color couplers and optical sensitizing dyes, which fact is of great importance for using the new developing accelerators for increasing the general light-sensitivity of color photographic material containing one or more light sensitive layers.
  • a further advantage of the process lies in the simplicity of its general application as for instance in the manufacture of light-sensitive materials for amateur and professional photography and cinematography, for motion pictures, for graphic processes and for scientific and industrial applications.
  • a light-sensitive photographic material comprising a support and at least one gelatino silver halide emulsion layer containing an alkylene oxide polymer in an amount between 0.2 g. and 7.00 g. per mol silver halide, said alkylene oxide polymer being a condensation product of (1) a FHO group, wherein R2 is a member of the group consisting of hydrogen and an alkyl radical containing [tom 1 to 4 carbon atoms.
  • a light-sensitive photographic material comprising a support and at least one gelatino silver halide emulsion 7 layer containing an alkylene oxide polymer in an amount sisting of an aliphatic aldehyde, and an aliphatic diisocya- 13 14 nate, said alkylene oxide polymer having the general H formula: I
  • n is a. positive RO(CH CH O) Q,(CH CH O)x R H wherein x represents a positive integer from 2 to 35, y represents a positive integer from 2 to 20, Q represents a member selected from the tribalonsisting of 5 integer from 2 to 20.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US149809A 1959-05-07 1961-10-24 Light-sensitive colloid silver halide photographic elements Expired - Lifetime US3158484A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1569559A GB920637A (en) 1959-05-07 1959-05-07 Improvements in or relating to light-sensitive colloid silver halide photographic elements
NL257213 1960-10-24

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3253919A (en) * 1962-06-12 1966-05-31 Eastman Kodak Co Sensitizers for photographic silver halide emulsions
US3416922A (en) * 1963-07-04 1968-12-17 Azoplate Corp Resinous printing plate compositions containing light-sensitive nitrones
US3507661A (en) * 1966-08-03 1970-04-21 Minnesota Mining & Mfg Gelatin containing dispersions having gelatin reactive polymers therein and coatings prepared therefrom
US3516844A (en) * 1966-07-28 1970-06-23 Eastman Kodak Co Coating of gelatin silver halide photographic emulsions
US3656956A (en) * 1968-01-30 1972-04-18 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
US4239851A (en) * 1978-02-02 1980-12-16 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
US7250202B1 (en) 1998-06-18 2007-07-31 Ilford Imaging Ch Gmbh Recording sheets for ink jet printing

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3986990A (en) * 1973-01-10 1976-10-19 Stauffer Chemical Company Flame retardant polyurethane foam containing polyalkylene glycol alkyl poly-phosphites
US4436811A (en) 1981-07-10 1984-03-13 Ciba-Geigy Ag Photographic material
DE3660522D1 (en) * 1985-03-26 1988-09-15 Agfa Gevaert Nv A method of effecting high contrast development of a image-wise exposed photographic silver halide emulsion layer material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970578A (en) * 1930-11-29 1934-08-21 Ig Farbenindustrie Ag Assistants for the textile and related industries
US2630424A (en) * 1949-12-13 1953-03-03 Du Pont Polymers of formal esters
US2716062A (en) * 1953-07-01 1955-08-23 Eastman Kodak Co 4-hydroxy-6-alkyl-1, 3, 3a, 7-tetrazaindene stabilizers for emulsions sensitized with alkylene oxide polymers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2423549A (en) * 1945-01-10 1947-07-08 Du Pont Silver halide photographic emulsions sensitized by polyalkylene glycols
US2728666A (en) * 1952-11-08 1955-12-27 Eastman Kodak Co Stabilization of emulsions sensitized with alkylene oxide polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970578A (en) * 1930-11-29 1934-08-21 Ig Farbenindustrie Ag Assistants for the textile and related industries
US2630424A (en) * 1949-12-13 1953-03-03 Du Pont Polymers of formal esters
US2716062A (en) * 1953-07-01 1955-08-23 Eastman Kodak Co 4-hydroxy-6-alkyl-1, 3, 3a, 7-tetrazaindene stabilizers for emulsions sensitized with alkylene oxide polymers

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3253919A (en) * 1962-06-12 1966-05-31 Eastman Kodak Co Sensitizers for photographic silver halide emulsions
US3416922A (en) * 1963-07-04 1968-12-17 Azoplate Corp Resinous printing plate compositions containing light-sensitive nitrones
US3516844A (en) * 1966-07-28 1970-06-23 Eastman Kodak Co Coating of gelatin silver halide photographic emulsions
US3507661A (en) * 1966-08-03 1970-04-21 Minnesota Mining & Mfg Gelatin containing dispersions having gelatin reactive polymers therein and coatings prepared therefrom
US3656956A (en) * 1968-01-30 1972-04-18 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
US4239851A (en) * 1978-02-02 1980-12-16 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US7250202B1 (en) 1998-06-18 2007-07-31 Ilford Imaging Ch Gmbh Recording sheets for ink jet printing
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization

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BE609497A (en))
GB945340A (en) 1963-12-23
NL106658C (en))
DE1167649B (de) 1964-04-09
NL257213A (en))
GB947790A (en) 1964-01-29
BE590553A (en))
DE1145014B (de) 1963-03-07

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