US3165412A - Silver halide emulsions - Google Patents

Silver halide emulsions Download PDF

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Publication number
US3165412A
US3165412A US138627A US13862761A US3165412A US 3165412 A US3165412 A US 3165412A US 138627 A US138627 A US 138627A US 13862761 A US13862761 A US 13862761A US 3165412 A US3165412 A US 3165412A
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US
United States
Prior art keywords
issued
gelatin
acid
silver halide
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
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US138627A
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English (en)
Inventor
Louis M Minsk
Edward P Abel
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to BE622443D priority Critical patent/BE622443A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US138627A priority patent/US3165412A/en
Priority to DEE23252A priority patent/DE1157915B/de
Priority to FR909651A priority patent/FR1335297A/fr
Priority to GB35569/62A priority patent/GB1010917A/en
Application granted granted Critical
Publication of US3165412A publication Critical patent/US3165412A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K9/00—Arc welding or cutting
    • B23K9/20—Stud welding
    • B23K9/201—Stud welding of the extremity of a small piece on a great or large basis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification

Definitions

  • This invention relates to the use in gelatin-silver halide photographic emulsions of gelatin-compatible polyvinyl alcohol derivatives which beneficially influence the density of the developed silver image.
  • the maximum optical density of the silver image of a photographic film after exposure, wet processing and dry ing and hence the covering power appears to depend not only upon the amount of silver which results from the development process, but also upon the Way the silver is laid down in the photographic element during processing and the stresses to which it is subjected in the drying step.
  • covering power refers to the ratio of the optical density of the developed silver to the actual quantity of silver.
  • the increase of density by the use of a poly(vinyl alco hol) half ester of an aliphatic dicarboxylic acid has been found in photographic emulsions having various rations of gelatin to half ester.
  • Our invention relates to silver halide photographic emulsions in which from 10 to 30 weight percent of the carrier for the silver halide is composed of a poly(vinyl alcohol) half ester of an aliphatic dicarboxylic acid.
  • Emulsions containing such proportions of poly(vinyl alcohol) half esters of an aliphatic dicarboxylic acid give increased covering power and hence higher contrast, speed and maximum density than do corresponding coatings in which gelatin is the sole carrier for the silver halide.
  • Our invention is particularly directed to the incorporation of water-soluble poly(vinyl alcohol) half esters of aliphatic dicarboxylic acids in gelatin-silver halide photographic emulsion compositions in which the silver halide is, for example, silver chloride, silver bromoiodide, or the like.
  • the compositions of our invention are prepared by mixing aqueous gelatin compositions with the Watersoluble half esters in a proportion which gives a composition having the desired properties.
  • the polyvinyl alcohol half esters of aliphatic dicarboxylic acid composition are added to a photographic gelatin silver halide emulsion and coated on a suitable support, the composition is resistant to leaching out during photographic processing and is able to contribute its effect during and after processing.
  • Another object of our invention is to prepare suc emulsions without adverse effect on other sensitometric characteristics such as the fog, density, resolution, and acutance, and without adverse effect on physical characteristics such as flexibility and clarity of the coated layer.
  • Other objects of our invention will appear herein.
  • a photographic silver halide emulsion of a poly(vinyl alcohol) half ester of an aliphatic dicarboxylic acid the dicarboxylic acid having a carbon chain length of 2 to 7 carbon atoms reacted with a poly(vinyl alcohol) to the extend of between 7.0 and 90 mole percent.
  • a poly (vinyl alcohol) we mean poly(viny1 acetate) that has been hydrolyzed to about 50 to 100 mole percent poly(vinyl alcohol) with the preferred range of poly(vinyl alcohol) being from about to 1-00 mole percent.
  • poly(vinyl alcohol) half esters of an aliphatic dicarboxylic acid of our invention fall within the following general formula:
  • the dope was diluted'with approximately an equal volume of dimethyl forrnarnide, cooled and was poured, in a fine stream, into stirred acetone.
  • the prodnot which precipitated was washed in fresh acetone several times and dried in a desiccator under a constantly applied water pump vacuum at room temperature.
  • Pertinent data are given in Tables I and II. V
  • the dope was stored. in a refrigerator. A solid content was determined by drying a sample at 100 C. for 16 hours. Asample of the cold dope was acidified with cold aqueous 12% HBr and iso- Titration showed that very little hydrolysis had occurred.
  • the copolymer appears to be permanently stable in solution, when it is dissolved and stored as'directed in Example 1.
  • ACETATE-VINYL ACID SUCCINATE In a 500 ml. flask equipped with a reflux condenser, stirrer and thermometer were placed 220 ml. pyridine (EK Co. 214) and 44 g. of incompletely hydrolized poly (vinyl acetate) (88 mole percent vinyl alcohol-Elvanol 51-05). The suspension was heated with stirring in a steam bath to C. when 40 g. of succinic anhydride (BK Co. 868) were added. The heating and stirring were continued for 2 hours during which time the temperature rose to a high of 106 C; and dropped to '9596 C. and doping occurred. The dope was cooled to 55 C.
  • Example 1 The procedure in Example 1 was used to get the copolymer into solution.
  • EXAMPLE 4 COPOLY(VINYL ALCOHOL-VINYL ACID SUCCINATE
  • a 3 liter fiaskequipped with a reflux condenser, stirrer and thermometer were placed 1200 .ml. dimethylformamide (EK Co. 5870) and 264 g. of poly(vinyl alcohol), Elvanol 70-05, which is essentially completely hydrolyzed.
  • the suspension was stirred and heated in a steam bath Whll 240 g. succinic anhydride (EK Co. 868) followedby ml. of pyridine (EK Co. 214) were added. In about 15 minutes the slurry became a light tan dope.
  • the heating and stirring were continued for a total of 1% hours.
  • the dope was cooled to 50 C., diluted with 200 ml. of dime ylfo'rmamide and precipitated by pouring into 12 gal. of stirred acetone. soft cake was milled repeatedlyin a W-P mill with fresh acetone. at room temperature under a constantly applied mechanical pump vacuum. The yield was 45 1 g. Analysisof the product indicated a content (combined vinyl acid succinate) of 29.7 mole percent.
  • Example 1 The procedure in Example 1 is used to get the copolymer into. solution.
  • Example 1 The procedure in Example 1 was used to get the copolymer into solution.
  • Example 1 The procedure in Example 1 is used to get the copolymer into solution.
  • normal emulsion addenda e.g., spreading agents, hardeners,'etc.
  • a coarse-grained gelatin-silver bromoiodide emulsion containing the normal emulsion addenda, e.g., coating aids, hardeners, etc., and 178 g. gelatin per mole of silver halide was coated with and without 43 g. of the following succinoylated polyvinyl alcohol per mole of silver.
  • polyvinyl alcohol half ester of dicarboxylic acid in accordance with our invention are added to the gelatin composition or to a photographic emulsion in a proportion Within the range of up to 30% of the total colloid present.
  • the preferred range of the polyvinyl alcohol half ester of dicarboxylic acid is between 20 and 30% depending on the increase in density desired.
  • Levels of polyvinyl alcohol half ester of dicarboxylic acid substantially above 30% of the total colloid present in a layer causes troublesome problems such as undesirable viscosity increase and haze or opalescence in the coating when it is dried down.
  • photographic emulsions used in practicing our invention are of the developing-out type.
  • the emulsions can also be treated Withsalts of the noble metals such as ruthenium, rhodi'um,,palladium, i'rid ium and platinum.
  • the noble metals such as ruthenium, rhodi'um,,palladium, i'rid ium and platinum.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate and a sodium chloropalladite, which are used' for sensitizing in amounts "below that which produces any substantial fog inhibition, as described in Smith and Trivelli US. Patent 2,448,060, issued August 31, 1948, and as anti-foggants in higher amounts, as described in Trivelli and Smith US...
  • the emulsions can also be chemically sensitized with A gold salts as described in Waller etal. US. Patent 2,399,-
  • the emulsions can also be optically sensitized' with 'cyanine and merocyanine dyes, such as those described in Brooker US. Patents 1,846,301, issued February 23,
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray US. Patent 2,728,663 issued December 27, 1955; Carrolland Murray US. Patent, 2,728,664, issued December 27, 1955; and Leubner and Murray US. Patent 2,728,665, issued December 27, 1955; or with gold salts as described in Damschroder US. Patent 2,597,856, issued May 27, 1952,;and Yutzy and Lcermakers US. Patent 2,597,915, issued May 27, 1952; the triazo1esofHeimbach and Kelly US. Patent- 2,444,608, issued July 6, 1948; the azaindenes of Heimbach and Kelly US. Patents 2,444,605, and 2,444,606,
  • the emulsions may al'soicontain speed increasing com pounds of the quaternary ammonium type of Carroll US. Patent 2,271,623, issued February 3; 1942;, Carroll and Allen US. Patent 2,288,226, issuedJunej30, 11942; and Carroll, and Spence U.S. Patent 2,334,864; issued November 23, 1943; or the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10,
  • The'emulsions may contain a suitable'gelatin plasticizer such as glycerin; a dihydroxy alkane such asv 1,5-pentane diol as described in, Milton and Murray US. application Serial No. 588,951, filed June 4, 1956; an ester ofan ethylene bis-glycolic acid 7 such as ethylene bis(methyl glycolate) as described in Milton US. application Serial No. 662,564,,filed May 31', 1957; bis(ethoxy diethylene glycol) succinate as described in, Gray U.S.,afpplication Serial No.
  • the plasticizer may be added to the emulsion beforeor after the addition of a sensitizing dye, if used. 7 i J
  • the emulsions may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted aliphatic acid such as'mucobrornic' acid as described in White US.
  • Patent 2,080,019 issued May 11, 1937; a compoundhaving a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7- octene-2,3,5,6-tetracarboxylic dianhydridep or a .dicarboxylic or-a disulfonic acid chloride suchas:terephthaloyl chloride as described in Allen andCarroll US.
  • Patent 2,725,305 issued November 29, 1955 a bie ster of methanesulfonic acid such as 1,2-di-(methane-sulfonoxy) ethane as described in Allen and LaaksofU S.
  • Patent 2,726,162, issued December 6, 1955 1,3-dihydroxymethylbenzimidazol-Z- one as describedinJuly, Knott and PollalcUS.
  • Patent. 2,732,316 issued January 24, 1956
  • a dialdehyde or a sodium bisulfite derivative thereof such as ,B-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness US.
  • patentapplicationSerial No. 556,031,'filed December 29, 1955 a bis aziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) asde scribed in Allen and Webster US patent application Serial No.
  • the emulsions may contain a. coating aid *such as saponin; a lauryl or oleoyl monoether of polyethylene glycol as described in Knox and Davis US; Patent 2,831,766, issued April 22, 1958; a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis US. Patent 2,719,087, issued September 27, 1955; an acylated alkyl taurine such as the sodium salt of N-ole oyl-N-methyl taurine as described in Knox,
  • the addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other nonoptically sensitized emulsions they may also be used in orthochromatic, panchromatic, and infrared sensitive emulsions. They may be added to the emulsion before or after any sensitizing dyes which are used.
  • Various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide.
  • These agents can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott U.S. Patent 2,592,250, issued April 8, 1952.
  • a gelatin-silver halide photographic emulsion of good density properties containing about 10-30%, based on the weight of the gelatin, of a saturated aliphatic dicarboxylic acid half ester of polyvinyl alcohol, said acid having a carbon chain length of 4-7 carbon atoms.
  • a gelatin-silver halide photographic emulsion of good density properties containing about 10-30%, based on the weight of the gelatin, of the succinic acid half ester of polyvinyl alcohol.
  • a gelatin-silver halide photographic emulsion of good density properties containing about 10-30%, based on the Weight of the gelatin, of the glutaric acid half ester of polyvinyl alcohol.
  • a gelatin-silver halide photographic emulsion of good density properties containing about 10-30%, based on the weight of the gelatin, of the adipic acid half ester of polyvinyl alcohol.
  • a photographic element comprising a support containing thereon a layer of a gelatin-silver halide photographic emulsion containing about 1030%, based on the weight of the gelatin, of a saturated aliphatic dicarboxylic acid half ester of polyvinyl alcohol, said acid having a carbon chain length of 4-7 carbon atoms.
  • a photographic element comprising a support having thereon a photosensitive layer of a gelatin-silver halide photographic emulsion containing about 10-30%, based on the weight of the gelatin, of the succinic acid half ester of polyvinyl alcohol.
  • a photographic element comprising a support having thereon a photosensiitve layer of a gelatin-silver halide photographic emulsion containing about l030%, based on the weight of the gelatin, of the glutaric acid half ester of polyvinyl alcohol.
  • a photographic element comprising a support having thereon a photoensitive layer of a gelatin-silver halide photographic emulsion containing about 1030%, based on the weight of the gelatin, of the adipic acid half ester of polyvinyl alcohol.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US138627A 1961-09-18 1961-09-18 Silver halide emulsions Expired - Lifetime US3165412A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE622443D BE622443A (en)) 1961-09-18
US138627A US3165412A (en) 1961-09-18 1961-09-18 Silver halide emulsions
DEE23252A DE1157915B (de) 1961-09-18 1962-07-24 Photographische Gelatine-Silbersalzemulsion, insbesondere hiermit beschichtetes photographisches Material
FR909651A FR1335297A (fr) 1961-09-18 1962-09-17 Nouvelle émulsion photographique à grand pouvoir couvrant
GB35569/62A GB1010917A (en) 1961-09-18 1962-09-18 Improvements in photographic silver halide emulsions

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US138627A US3165412A (en) 1961-09-18 1961-09-18 Silver halide emulsions

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US3165412A true US3165412A (en) 1965-01-12

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847620A (en) * 1971-11-15 1974-11-12 Mitsubishi Paper Mills Ltd Method for producing silver halide photographic photosensitive emulsion
US3877947A (en) * 1971-01-19 1975-04-15 Nobuo Tsuji Photographic element
US3877946A (en) * 1971-01-19 1975-04-15 Fuji Photo Film Co Ltd Photographic element

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002328087A1 (en) * 2001-08-30 2003-03-10 Hitachi Chemical Co., Ltd. Thermosetting polyvinyl alcohol binder resin composition, slurry of electrode mix, electrode, non-aqueous electrolysis solution-containing secondary battery and use of thermosetting polyvinyl alcohol binder resin as electrode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2828289A (en) * 1955-03-09 1958-03-25 Eastman Kodak Co Polyvinyl acetal acid dicarboxylates and their preparation
US2882161A (en) * 1955-06-29 1959-04-14 Eastman Kodak Co Photographic emulsions containing synthetic polymer vehicles
US3000741A (en) * 1958-05-30 1961-09-19 Gevaert Photo Prod Nv Preparation of silver halide emulsions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2828289A (en) * 1955-03-09 1958-03-25 Eastman Kodak Co Polyvinyl acetal acid dicarboxylates and their preparation
US2882161A (en) * 1955-06-29 1959-04-14 Eastman Kodak Co Photographic emulsions containing synthetic polymer vehicles
US3000741A (en) * 1958-05-30 1961-09-19 Gevaert Photo Prod Nv Preparation of silver halide emulsions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3877947A (en) * 1971-01-19 1975-04-15 Nobuo Tsuji Photographic element
US3877946A (en) * 1971-01-19 1975-04-15 Fuji Photo Film Co Ltd Photographic element
US3847620A (en) * 1971-11-15 1974-11-12 Mitsubishi Paper Mills Ltd Method for producing silver halide photographic photosensitive emulsion

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Publication number Publication date
BE622443A (en))
FR1335297A (fr) 1963-08-16
GB1010917A (en) 1965-11-24
DE1157915B (de) 1963-11-21

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