US3294540A - Lith-type emulsions with block co-polymers - Google Patents

Lith-type emulsions with block co-polymers Download PDF

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US3294540A
US3294540A US331141A US33114163A US3294540A US 3294540 A US3294540 A US 3294540A US 331141 A US331141 A US 331141A US 33114163 A US33114163 A US 33114163A US 3294540 A US3294540 A US 3294540A
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polymer
block
polymers
lith
block polymer
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US331141A
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Charles A Goffe
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US331141A priority Critical patent/US3294540A/en
Priority to DE19641447659 priority patent/DE1447659A1/de
Priority to FR997778A priority patent/FR1416850A/fr
Priority to GB51378/64A priority patent/GB1092814A/en
Priority to US596043A priority patent/US3433639A/en
Application granted granted Critical
Publication of US3294540A publication Critical patent/US3294540A/en
Priority to GB49903/67A priority patent/GB1199988A/en
Priority to DE19671597553 priority patent/DE1597553A1/de
Priority to FR127164A priority patent/FR93238E/fr
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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
    • G03C1/04—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
    • 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

  • This invention relates to photography and particularly to improved photographic silver halide emulsions of the lith-type.
  • Photographic films used in the graphic arts for making half-tone or line images should be capable of producing extremely high contrast and good image sharpness. These factors contribute in the case of half-tone images to high dot quality, that is, to the production of half-tone dots of high density and sharpness.
  • the photographic elements of the lith-type that is, elements that have a fine grain high contrast silver halide emulsion containing at least 60 mole percent chloride, less than 40 mole percent bromide and less than about mole percent iodide, require the use of pure hydroquinone developer solutions having very low free sulfite ion concentration in the alkaline solution in order to produce the high contrast and high dot quality required for good quality half-tone reproduction.
  • Such developer solutions are unstable, having very short tray or tank life after exposure to air, so that the solutions must be mixed fresh just before they are to be used for processing and then discarded.
  • the films and processes available do not produce the desired latitude and have the desired ease in exposing and processing the film to produce the required quality. This has resulted from the contrast of the image reproduction in the photographic elements being overly sensitive to development time, and from a nonlinearity in the relationship between the film speed and development time, causing unequal increases in film speed from equal increases in development time.
  • a photographic light sensitive element comprising a support, at least one hydrophilic colloid layer containing a very fine grain photographic silver halide emulsion having at least 60 mole percent chloride, less than 40 mole percent bromide and less than about 5 mole percent iodide, and at least one hydrophilic colloid layer containing certain water-soluble block polymers of polyoxypropylene and polyoxyethylene such that the block polymer is contiguous with the silver halide.
  • the water-soluble block polymers used in photographic elements according to my invention include those block polymers in which the polyoxypropylene chain (or moiety) has an average molecular weight between 800 and 3,000 and in which the polyoxyethylene units consti- "ice tute from about 10 to about percent by weight of the polymer.
  • the image reproductions produced in my lith-type emulsion layers are of excellent quality.
  • the conventional alkaline, pure hydroquinone, low free-sulfite developer may be used to develop my exposed elements, it is also advantageous to use a developer having from 10 to about 30 grams of an alkali sulfite per liter of the developer solution.
  • Y represents an organic radical having a valence of x, said radical being the residue of an organic compound containing atoms selected from the class consisting of carbon, hydrogen, oxygen, nitrogen and sulfur with x active hydrogen atoms, such as, the residue of polyhydroxy compounds, e.g., ethylene glycol, 1,2-propanediol, 1,5-pentanediol, 1,2,3-propanetriol, sucrose, etc., the residue of a polybasic acid, e.g., oxalic acid, malonic acid, succinic acid, maleic acid, citric acid, etc., the residue of a polyamine, e.g., ethylenediamine, 1,3- diaminopropylene, etc., the residue of a polyamide, e.g., malonamide, succinamide, etc., the residue of a polythiol, e.g., 1,2 ethylenedithiol, 1,3 -.propylenedithiol
  • b represents an integer of from 14 to 52; a and c are each integers such that the sum of a-i-c has a total of from 4 to 48 and the polyoxyethylene groups constitute between 10 and 70 percent by weight of the block polymer.
  • the block polymers of Formula II and of Formula I where R represents the hydrogen atom are described in Lundsted U.S. Patent 2,674,619, issued April 6, 1954, and Lundsted U.S. Patent 3,022,335, issued February 20, 1962.
  • the block polymers of Formula I in which R is hydrogen are readily converted to compounds where R represents an organic residue by reaction with the appropriate reagent in a suitable inert organic solvent that is preferably anhydrous.
  • alkyl halides such as alkyl chlorides, alkyl bromides, etc., are used to advantage to replace the terminal hydrogen atom of the block polymer with an alkyl group.
  • Alkylp-toluenesulfonates are also used to advantage to place an alkyl group on the end of the block polymers.
  • the appropriate acid chloride or acid anhydride such as, acetyl chloride, propionyl chloride, stearoyl chloride, benzoyl chloride, acetic anhydride, etc., are used to advantage to prepare block polymers of Formula I in which R is an alkyl carbonyl or an aryl carbonyl group. These reactions are well known to those skilled in the'art. Many of the block polymers of Formulas I and II are available commercially.
  • My photographic elements coated with a lith-type emulsion containing my block polymers of polyoxypropylene and polyoxyethylene are valuable for use in graphic art reproduction.
  • My elements are particularly valuable when developed with a dihydroxybenzene developer with a high free sulfite ion concentration in an alkaline solution.
  • My elements provide the following advantages:
  • the quality of the silver images produced in lithtype emulsion layers is conveniently measured in terms of contrast (i.e., 'y) and dot quality.
  • Photographic image contrast is the slope of the straight line portion of a graph of optical density of the image vs. log of exposure.
  • Dot quality is a measure of the quality of the reproduction of a half-tone image. Lith-type photographic elements exposed to a half-tone image, and developed, produce areas commonly referred to as shadow dots and areas known as highlight areas. Intermediate between these two extremes are areas of varying size.
  • the dot quality used herein is a measure of the areas referred to as 50% dots (i.e., /2 clear and /2 developed density) and is expressed -in a progressive scale Where 9 is excellent and "1 is extremely poor. A 50% dot quality below "6 is generally not acceptable.
  • block polymers used to advantage according to my invention are the following typical polymers used for illustrative purposes.
  • Block polymer 1 Average Percent poly- Block Polymer Y Group derived Value of 'n in oxyethylene No. Irom- Formula I by weight of Block polymer 1 1,2-propanediol 30 2 d0 30 20 3 .do 22 40 4 .do 30 50 5. d0 30 40 6- d0 47 20 7 do 39 10 8. 1,5-pentauediol 24 50 9 1,2,3,-propanetriol 36 48 10 Ethyleuediamine- 32 50 These block polymers are available commercially under the tradename Pluronic. Block polymers 1 through 7 are sold under the trade name Pluronic L61, L62, L44, P65, L64, L92 and L81, respectively.
  • the block polymers used according to my invention are water soluble and are advantageously added in a water solution to the aqueous hydrophilic colloid (either with or without the silver halide) before it is coated.
  • the block polymers are used to advantage over a wide range of concentrations.
  • the operable range of concentrations is from .001 to 1.00 gram of block polymer per mole of silver, while the preferred range is from 0.010 to 0.200 gram per mole of silver.
  • the optimum concentration of a given block polymer used in my elements depends upon the results desired, the particular silver halide emulsion, the developer solution, etc., and is readily determined by methods well known in the art.
  • the determination of the optimum concentration is preferably made by employing the block polymer in the silver halide emulsion layer or in an adjacent hydrophilic colloid layer according to the element that is desired.
  • the fine grain silver halide emulsions used to advantage have silver halide crystals preferably containing at least 60 mole percent chloride, less than 40 mole percent bromide and less than about 5 mole percent iodide.
  • the emulsions can be prepared as described by MacWilliam U.S. 2,756,148, issued July 24, 1956. These emulsions may be used without being sensitized, however, it is advanageous to spectrally sensitize them according to methods well known in the art to make them orthosensitized or panchromatically-sensitized.
  • the silver halide is dispersed in hydrophilic colloid materials used as binders, including gelatin, collodion, gum arabic, cellulose ester derivatives, such as, alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in U.S. Patent 2,949,442, issued August 16, 1960, polyvinyl alcohol, and others well known in the art.
  • hydrophilic colloid materials used as binders including gelatin, collodion, gum arabic, cellulose ester derivatives, such as, alkyl esters of carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in U.S. Patent 2,949,442, issued August 16, 1960, poly
  • polymeric gelatin substitutes examples include copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acrylamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; the copolymers of allylamine, acrylic acid and styrene; the copolymers of allylamine, methacrylic acid and acrylonitrile; alkyl acrylateacrylic acid copolymers, e.g., copolymers of butyl acrylateacrylic acid, etc.
  • any of the hydrophilic colloids described hereinbefore may be used to advantage as a binder for coating my polymers.
  • onium salts such as, quaternary ammonium salts, sulfonium salts and phosphonium salts
  • onium salts such as, quaternary ammonium salts, sulfonium salts and phosphonium salts
  • quaternary ammonium salts include nonyl pyridinium perchlorate, hexoxymethyl pyridinium perchlorate, ethylene bis-dioxymethyl pyridinium perchlorate and others described by Carroll U.S.
  • 2,288,226, issued June 30, 1942 such as bis(lauryl methyl sulfonium p-toluene sulfonate) 1,2-ethane, N,N-trimethylene dioxymethyl pyridinium perchlorate etc., the sulfonium salts of Carroll et al. U.S. 2,275,727, issued March 10, 1942, such as, n-decyl dimethyl sulfonium p-toluene sulfonate, n-nonyl dimethyl sulfonium p-toluene sulfonate, etc., and the phosphonium salts of Carroll et al. U.S. 2,271,622, issued February 3, 1942, such as, tetramethylene bis-triethyl phosphonium bromide, lauryltriethylphosphonium bromide, etc.
  • My light-sensitive emulsions can be coated to advantage on any of the conventional photographic supports, including glass, cellulose acetate, polystyrene, polyalkyleneterephthalate, etc.
  • the block polymers can be coated advantageously in the silver halide emulsion layer, or in a hydrophilic colloid layer that is either under or over the silver halide emulsion layer so that the block polymer the development time, the slope of the resultant curve will approach as K approaches a constant value.
  • Evenness of development is the slope of the plot of K against time. In the above table, evenness of development is exis contiguous to the silver halide. pressed in this way. The smaller the number, the more My invention is still further illustrated by the following even the development. This value indicates the even examples. spacing between the sensitometric curves for eqaul differ- Example 1 ences in development time.
  • FIG. 3 snows curves 1 through 4 for a lith element outside my invention containing block polymer A de- Hydroquinone 15 scnbed previously Sodium formaldehyde bi lfit 501)
  • IG. 4 shows curves 1 through 4 for my lith element s i carbonate 3 containing my block polymer No. 3.
  • FIG. 5 shows curves 1 hrough 4 for my lith elesodiu lfit 2,5 ment containing my block polymer No. 5. Potassium bromide 0.75
  • FIG. 6 shows curves 1 through 4 for my lith ele- Water to make 1.0 liter. ment containing my block polymer No. 7.
  • the polymer PEO is the oleyl ether of polyethylene oxide shown by FIG. 4 when a lith emulsion contains one having an average molecular weight of 1500.
  • Example 3 A.very fine grain high contrast gelatino silver chlorobromide emulsion in which 70 percent of the halide was the chloride was prepared and divided into three equal portions. One portion wa used as a control. Oleyl ether of polyoxyethylene (molecular weight 1540) was .added to the second portion and stock polymer No. 2
  • My lith elements coated with fine grain high contrast silver halide emulsions containing at least 60 mole percent chloride, less than 40 mole percent bromide and less than about 5 mole percent iodide contain certain water-soluble block polymers of polyoxypropylenc and polyoxyethylene.
  • the block polymer is incorporated in the light-sensitive layer or in a layer adjacent to the lightsensitive layer so that the polymer and silver halide are contiguous.
  • the block polymers used to advantage according to my invention include those in which the polyoxypropylene chain has an average molecular weight between 800 and 3000, and in which the polyoxyethylene units constitute from about 10 to about 70 percent ,by weight of the block polymer.
  • My elements give high contrast images with high dot quality and good evenness of development with lith developer solutions. My elements are particularly valuable because they produce these high quality image reproductions even when stable high free-sulfite developer solutions are used. Since lith" elements containing simple polyoxyethylene and certain block polymers of polyoxy-propylene and polyoxyethylene that are outside my invention produce low contrast and poor dot quality, it is unexepected that my elements containing my block polymers produce the high quality images that characterize them, especially with the stable high free-sulfite developer solutions.
  • a light-sensitive photographic element comprising a support coated with at least one hydrophilic colloid layer containing a silver halide emulsion in which the chloride comprises at least 6,0 mole percent of the halide, and at least one hydrophilic colloid layer containing a watersoluble block polymer of polyoxypropylene and poly oxyethylene in which the polyoxypropylene moiety has an average molecular weight between 800 and 3,000 and the polyoxyethylene units constitute from about 10 to about 70 percent by weight of said polymers, such that the said block polymer is contiguous to the said silver halide.
  • Y represents an organic radical having a valence of X
  • n is an integer
  • x is an integer greater than 1, so that the values of n and x are such that the molecular weight of the said polymer exclusive of Y, E and R is between 800 and 3,000
  • E represents a polyoxyethylene chain constituting from about 10 to about 70 percent by weight of said polymer
  • R is a member selected from the class consisting of the hydrogen atom, an alkyl group, an alkyl carbonyl group, and an aryl carbonyl group.
  • b represents an integer of from 14 to 52
  • a and each represent integers such that the sum of a+c represents an integer of from 4 to 48 and the polyoxyethylene groups constitute between and 70 percent by weight of said polymer
  • a photographic element of claim 1 in which the water-soluble block polymer and the silver halide emulsion are in the same hydrophilic colloid layer.
  • a photographic element of claim 1 in which the water-soluble block polymer is in a hydrophilic colloid layer coated over the hydrophilic colloid layer containing the silver halide emulsion.
  • a photographic element of claim 1 in which the Water-soluble block polymer is in a hydrophilic colloid layer coated under the hydrophilic colloid layer containing the silver halide emulsion.
  • a photographic element comprising a transparent support coated with alight-sensitive layer comprising:
  • a water-soluble block polymer comprising a waterinsoluble polyoxypropylene chain having water-soluble polyoxyethylene groups at each end of said polyoxypropylene chain in which the molecular weight of the polyoxypropylene chain is 1750 and the polyoxyethylene groups constitute 10 percent by weight of said copolymer.
  • a photographic element comprising a transparent support coated with a light-sensitive layer comprising:
  • a silver chlorobromoiodide emulsion containing (c) a water-soluble block polymer comprising a waterinsoluble polyoxypropylene chain having water-soluble polyoxyethylene groups at each end of said polyoxypropylene chain in which the molecular weight of the polyoxypropylene chain is 1750 and the polyoxyethylene groups constitute 20 percent by weight of said polymer.
  • a photographic element comprising a transparent support coated with a light-sensitive layer comprising:
  • a water-soluble block polymer comprising a waterinsoluble polyoxypropylene chain having water-soluble polyoxyethylene groups at each end of said polyoxypropylene chain in which the molecular weight of the polyoxypropylene chain is 1200 and the polyoxyethylene groups constitute 40 percent by weight of said polymer.
  • a photographic element comprising a transparent support coated with a light-sensitive layer comprising:
  • a water-soluble block polymer comprising a waterinsoluble polyoxypropylene chain having water-soluble polyoxyethylene groups at each end of said polyoxypropylene chain in which the molecular weight of the polyoxypropylene chain is 1750 and the polyoxyethylene groups constitute 40 percent by weight of said polymer.
  • a photographic element comprising a transparent support coated with a light-sensitive layer comprising:
  • a water-soluble block polymer comprising a waterinsoluble polyoxypropylene chain having water-soluble polyoxyethylene groups at each end of said polyoxypropylene chain in which the molecular weight of the polyoxypropylene chain is 2750 and the polyoxyethylene groups constitute 20 percent by weight of the said polymer.

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  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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US331141A 1963-12-17 1963-12-17 Lith-type emulsions with block co-polymers Expired - Lifetime US3294540A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US331141A US3294540A (en) 1963-12-17 1963-12-17 Lith-type emulsions with block co-polymers
DE19641447659 DE1447659A1 (de) 1963-12-17 1964-11-26 Photographisches Material
FR997778A FR1416850A (fr) 1963-12-17 1964-12-08 Nouveau produit photosensible pour la reproduction photomécanique
GB51378/64A GB1092814A (en) 1963-12-17 1964-12-17 Sensitive silver halide photographic materials and emulsions therefor
US596043A US3433639A (en) 1963-12-17 1966-11-07 Photographic emulsion containing a block polymer sensitized with saponin
GB49903/67A GB1199988A (en) 1963-12-17 1967-11-02 Photographic Silver Halide Emulsions and Sensitive Materials Prepared Therefrom
DE19671597553 DE1597553A1 (de) 1963-12-17 1967-11-06 Lichtempfindliches,photographisches Material
FR127164A FR93238E (fr) 1963-12-17 1967-11-07 Nouveau produit photosensible pour la reproduction.

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3433639A (en) * 1963-12-17 1969-03-18 Eastman Kodak Co Photographic emulsion containing a block polymer sensitized with saponin
US3516830A (en) * 1965-09-17 1970-06-23 Eastman Kodak Co Photographic silver halide emulsions and elements
US3518085A (en) * 1965-09-23 1970-06-30 Eastman Kodak Co Lith-type emulsions containing a polyalkyleneoxy polymer and a 3-pyrazolidone developing agent
US3632340A (en) * 1968-09-09 1972-01-04 Eastman Kodak Co Cored direct positive silver halide emulsion developed with polyhydroxybenzene
US3650759A (en) * 1968-07-09 1972-03-21 Fuji Photo Film Co Ltd Silver halide emulsion containing 1.2-glycol as sensitizer and antifoggant
US3709689A (en) * 1969-04-02 1973-01-09 Agfa Gevaert Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages
US3895948A (en) * 1971-12-28 1975-07-22 Fuji Photo Film Co Ltd Silver halide light-sensitive material containing a heterocyclic thione and a polyalkylene oxide
DE2525320A1 (de) * 1974-06-06 1975-12-18 Fuji Photo Film Co Ltd Photographisches silberhalogenid- aufzeichnungsmaterial
DE2710026A1 (de) * 1976-03-08 1977-09-15 Fuji Photo Film Co Ltd Bilderzeugungsverfahren
EP0112162A2 (de) 1982-12-13 1984-06-27 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial
EP0124795A2 (de) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidemulsionen
US5310633A (en) * 1992-05-13 1994-05-10 Fuji Photo Film Co., Ltd. Bleach-fixing composition for color photographic material and method for processing a color photographic material with the same
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
US20060165625A1 (en) * 2005-01-22 2006-07-27 Verrall Andrew P Water-soluble film article having salt layer, and method of making the same
US7250202B1 (en) 1998-06-18 2007-07-31 Ilford Imaging Ch Gmbh Recording sheets for ink jet printing

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58190943A (ja) * 1982-04-30 1983-11-08 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料の現像方法

Citations (6)

* 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
US2674619A (en) * 1953-10-19 1954-04-06 Wyandotte Chemicals Corp Polyoxyalkylene compounds
US3022335A (en) * 1955-03-30 1962-02-20 Wyandotte Chemicals Corp Surface active polyoxyalkylene compounds having a plurality of heteric polyoxypropylene-polyoxyethylene chains
US3030209A (en) * 1958-07-02 1962-04-17 Eastman Kodak Co High-contrast photographic silver chloride emulsions and method of processing
US3084044A (en) * 1960-12-09 1963-04-02 Gen Aniline & Film Corp Nitrogenous heterocyclic carboxyal-kylmercapto polyoxyalkylene ester photographic sensitizer
US3193386A (en) * 1961-11-29 1965-07-06 Du Pont Silver halide emulsions and elements containing antifoggants

Patent Citations (6)

* 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
US2674619A (en) * 1953-10-19 1954-04-06 Wyandotte Chemicals Corp Polyoxyalkylene compounds
US3022335A (en) * 1955-03-30 1962-02-20 Wyandotte Chemicals Corp Surface active polyoxyalkylene compounds having a plurality of heteric polyoxypropylene-polyoxyethylene chains
US3030209A (en) * 1958-07-02 1962-04-17 Eastman Kodak Co High-contrast photographic silver chloride emulsions and method of processing
US3084044A (en) * 1960-12-09 1963-04-02 Gen Aniline & Film Corp Nitrogenous heterocyclic carboxyal-kylmercapto polyoxyalkylene ester photographic sensitizer
US3193386A (en) * 1961-11-29 1965-07-06 Du Pont Silver halide emulsions and elements containing antifoggants

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3433639A (en) * 1963-12-17 1969-03-18 Eastman Kodak Co Photographic emulsion containing a block polymer sensitized with saponin
US3516830A (en) * 1965-09-17 1970-06-23 Eastman Kodak Co Photographic silver halide emulsions and elements
US3518085A (en) * 1965-09-23 1970-06-30 Eastman Kodak Co Lith-type emulsions containing a polyalkyleneoxy polymer and a 3-pyrazolidone developing agent
US3650759A (en) * 1968-07-09 1972-03-21 Fuji Photo Film Co Ltd Silver halide emulsion containing 1.2-glycol as sensitizer and antifoggant
US3632340A (en) * 1968-09-09 1972-01-04 Eastman Kodak Co Cored direct positive silver halide emulsion developed with polyhydroxybenzene
US3709689A (en) * 1969-04-02 1973-01-09 Agfa Gevaert Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages
US3895948A (en) * 1971-12-28 1975-07-22 Fuji Photo Film Co Ltd Silver halide light-sensitive material containing a heterocyclic thione and a polyalkylene oxide
DE2525320A1 (de) * 1974-06-06 1975-12-18 Fuji Photo Film Co Ltd Photographisches silberhalogenid- aufzeichnungsmaterial
DE2710026A1 (de) * 1976-03-08 1977-09-15 Fuji Photo Film Co Ltd Bilderzeugungsverfahren
US4144069A (en) * 1976-03-08 1979-03-13 Fuji Photo Film Co., Ltd. Method of image formation
EP0112162A2 (de) 1982-12-13 1984-06-27 Konica Corporation Lichtempfindliches photographisches Silberhalogenidmaterial
EP0124795A2 (de) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Photographische Silberhalogenidemulsionen
US5310633A (en) * 1992-05-13 1994-05-10 Fuji Photo Film Co., Ltd. Bleach-fixing composition for color photographic material and method for processing a color photographic material with the same
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
US20060165625A1 (en) * 2005-01-22 2006-07-27 Verrall Andrew P Water-soluble film article having salt layer, and method of making the same
US8728449B2 (en) * 2005-01-22 2014-05-20 Monosol Llc Water-soluble film article having salt layer, and method of making the same

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GB1092814A (en) 1967-11-29
DE1447659A1 (de) 1969-02-20

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