US3645740A - Photographic silver halide light-sensitive element with gelatin subbing layer - Google Patents

Photographic silver halide light-sensitive element with gelatin subbing layer Download PDF

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Publication number
US3645740A
US3645740A US3201A US3645740DA US3645740A US 3645740 A US3645740 A US 3645740A US 3201 A US3201 A US 3201A US 3645740D A US3645740D A US 3645740DA US 3645740 A US3645740 A US 3645740A
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US
United States
Prior art keywords
photographic element
copolymer
group
subbing layer
layer
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
US3201A
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English (en)
Inventor
Fumihiko Nishio
Nobuo Tsuji
Teppei Ikeda
Hideo Kawaguchi
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.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
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 Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3645740A publication Critical patent/US3645740A/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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/915—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means using mechanical or physical means therefor, e.g. corona
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93—Macromolecular substances therefor
    • 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
    • Y10S430/151—Matting or other surface reflectivity altering material

Definitions

  • PHOTOGRAPH SILVER HALIDE LHGHT-SENSHTIVE ELEMENT WITH GELATKN SUBBlNG LAYER
  • Inventors Fumihiko Nishio; Nobuo Tsuji; Teppei lkeda; Hideo Kawaguchi, all of Kanagawa,
  • a hydrophobic film used as a support is coated with a hydrophilic silver halide emulsion layer on one side and with a back layer on the opposite side.
  • adhesion of the surface of the support with the silver halide emulsion layer or back layer is strengthened by use of a subbing layer or substratum therebetween.
  • this subbing layer is generally hydrophilic, sticking often occurs between the subbing layers coated on both surfaces of the support, between the subbing layer and a silver halide emulsion layer coated on another surface, or between the subbing layer and a back layer coated on another surface, during the steps of making a photographic element, as for example, winding up in the form of a roll or sticking in the form of a sheet. Furthermore, sticking often occurs between the subbing layer and a spindle when the subbing layer is brought into contact with the heated spindle during the making step.
  • GMA glycidyl methacrylate
  • GA a homopolymer of glycidyl acrylate
  • a copolymer of a vinyl monomer with GMA or GA into a subbing layer of a photographic element.
  • the subbing layer of this invention containing a homopolymer of GMA or GA or copolymer of vinyl monomer with GMA or GA minimizes the effects of sticking. Although not desiring to be bound by theory, it is believed that sticking is minimized due to the fact that the fine particles of polymer mat the surface of the film and the gelatin hardening action of the glycidyl group of the polymer decreases the hygroscopic characteristics of the subbing layer.
  • the subbing composition containing a homopolymer of GMA or GA or a copolymer of vinyl monomer with GMA or GA is so stable, unlike dispersions containing known matting agents, that no aggregation or settling of grains occurs even on standing for a long period of time. Furthermore, the foregoing components of the subbing layer for the photographic element according to this invention have no adverse influence on the adhesion of the silver halide emulsion layer or back layer to a support. Not only is this an essential role of a subbing layer, but also this results in a further strengthening of the adhesion through the gelatin hardening action of the glycidyl group present in the foregoing polymer.
  • the copolymer may be a terpolymer containing two or more vinyl monomers.
  • the vinyl monomer to be copolymerized with GMA or GA is a monomer which will substantially copolymerize with GMA or GA, which will not react with the glycidyl group during emulsion polymerization and which will effect emulsion polymerization even though extremely soluble in water.
  • Suitable vinyl monomers are, for example, alkyl acrylates, said alkyl group having from one to four carbon atoms; alkyl methacrylates, said alkyl group having from one to four carbon atoms; other substituted alkyl acrylates; acrylamide derivatives; methacrylamide derivatives; vinyl halides such as vinyl chloride; vinylidene halides, such as vinylidene chloride; vinylpyrrolidone; other N-vinylamides; vinylpyridines; styrene; styrene derivatives such as a-methyl styrene; butadiene; isoprene; acrylonitrile; methacrylonitrile, and the like.
  • the proportion of GMA or GA in the copolymer of GMA or GA with the vinyl monomer is preferably 3 mol percent or more. When it is less than 3 mol percent, sticking is not prevented.
  • the aqueous polymer dispersion of this invention is prepared by emulsion-polymerizing the monomer in an anionic surface agent, such as lauryl alcohol sulfate, sodium alkylbenzenesulfonate and sodium, 1,3-p-nonylphenoxy- 5,8,1 l-trioxatridecanel -sulfonate.
  • an anionic surface agent such as lauryl alcohol sulfate, sodium alkylbenzenesulfonate and sodium, 1,3-p-nonylphenoxy- 5,8,1 l-trioxatridecanel -sulfonate.
  • the emulsion polymerization can be carried out in any conventional manner.
  • an aqueous polymer dispersion can be obtained by adding to deaerated distilled water the monomer in a proportion of from 10 to 60 percent by weight, a suitable amount of the anionic surface active agent as a dispersing agent and a watersoluble polymerization initiator such as potassium persulfate and, if necessary, polymerization additives, stirring the mixture vigorously and then heating the mixture at from 50 to C. for several hours.
  • a suitable amount of the anionic surface active agent as a dispersing agent and a watersoluble polymerization initiator such as potassium persulfate and, if necessary, polymerization additives
  • the grain size of the polymer in the aqueous polymer dispersion of the invention can be controlled by the conditions of the emulsion polymerization as in the conventional manner, for example, by controlling the amount of the surface active agent as the dispersing agent, the stirring condition, the reaction time and the reaction temperature.
  • the grain size is preferably within a range of from 0.05 to 1 micron.
  • the amount of the aqueous polymer dispersion of the invention applied to the subbing layer preferably ranges from 4 mg./m. to 200 mgJm. based on the weight of the polymer. When the amount is less than the above, the sticking preventing effect is small. When the amount is more than the above, the adhesion of a subbing layer to an emulsion layer or back layer tends to deteriorate. When the subbing layer or layers have been dried, an ordinary gelatino silver halide emulsion is coated thereon and dried.
  • the other subbed surface is overcoated with a gelatin composition which contains no silver halide, but which can contain, if desired, antistatic agents, filter dyes, antihalation agents, and the like.
  • the photographic elements produced as above described are characterized by firm adherence of the layers to one another and to the hydrophobic film support without sticking, and shows excellent dimensional stability under testing, use and storage conditions.
  • a silver halide photographic emulsion layer, an antihalation layer, a backing layer and the like, which are coated on the subbed film support, are not specifically limited to those described, so long as the subbing layer mentioned above is employed.
  • the silver halide photographic emulsion can contain a silver chloride emulsion, a silver bromide emulsion, a silver chlorobromide emulsion, a silver bromoiodide emulsion, a silver chlorobromoiodide emulsion, and the like.
  • the photographic elements can have multiple silver halide emulsion layers.
  • an aqueous dispersion of a homopolymer of GMA or a homopolymer of GA or a copolymer of GMA or GA with a vinyl monomer can be added to a coating solution for subbing as used in the prior art, as it is.
  • the thus added solution is coated onto a hydrophobic film support to obtain a subbing layer having a sufficient sticking preventing effect.
  • Suitable hydrophobic film supports are supports of cellulose derivatives such as cellulose triacetate, cellulose diacetate, cellulose acetate butyrate and cellulose acetate propionate, polyethylene terephthalate, polycarbonate, polyvinyl chloride, or polystyrene.
  • the subbing composition contains an aqueous gelatin solution, a solvent, such as acetone, methylene chloride, ethylene chloride, trichloroacetate or phenol, to swell the hydrophobic film support, and a water-soluble organic solvent, such as acetone or methanol.
  • a solvent such as acetone, methylene chloride, ethylene chloride, trichloroacetate or phenol
  • the solvent used to swell the hydrophobic film support and water-soluble organic solvent can be the same.
  • PREPARATION EXAMPLE 1 800 parts of deaerated distilled water, 120 parts of GMA, purified by distillation, and 180 parts of butyl methacrylate were added to a closed-type, glass-lined reactor equipped with a temperature regulator, a stirrer, a reflux condenser, a heater and a gas inlet and purged with nitrogen gas. 5.0 parts of sodiurn laurylbenzenesulfonate, as a dispersing agent, was then added thereto and the reaction mixture was stirred vigorously at 500-800 r.p.m. for emulsification.
  • PREPARATION EXAMPLE 2 Using the same apparatus as used in Preparation Example 1, 1,754 parts of distilled water, 80 parts of GMA, 106 parts of butyl methacrylate, 9.3 parts of as a dispersing agent, and 0.5 part of potassium persulfate as a polymerization initiator were processed in a manner similar to that mentioned in Preparation Example 1 to obtain an aqueous polymer dispersion having a GMA to butyl methacrylate copolymerization ratio of 4 to 6 by mol. The grain size of the solid polymer in the thus resulting aqueous dispersion was 0.1-0.2 micron. Y
  • PREPARATION EXAMPLE 3 were faced toward each other, and a 2 kg. weight was placed on the samples. The samples were allowed to stand for a day and night in a thermostat at a temperature of 30 C. and at a relative humidity of percent. Thereafter, the ratio of the area suffering sticking to the whole area was measured.
  • the homopolymer of butyl methacrylate has not sticking preventing effect but the homopolymer or copolymer of GMA prevents sticking remarkably.
  • a photographic element comprising a hydrophobic film support having on at least one surface thereof a subbing layer containing gelatin and at least one member selected from the group consisting of particles of (l) of glycidyl methacrylate homopolymer, (2) a glycidyl acrylate homopolymer, (3) a copolymer of glycidyl methacrylate and a copolymerizable vinyl compound, and (4) a copolymer of glycidyl acrylate and a copolymerizable vinyl compound, and having a light-sensitive silver halide emulsion layer coated over at least one of said subbing layer.
  • copolymerizablevinyl compound is a member selected from the group consisting of acrylic acid; methacrylic acid;
  • alkyl acrylate said alkyl group having from one to four carbon atoms; alkyl methacrylate, said alkyl group having from one to four carbon atoms; acrylamide; methacrylamide; vinyl chloride vinylidene chloride; N-vinylamide; styrene; alphamethyl styrene; acrylonitrile; and methacrylonitrile.
  • copolymer is a member selected from the group consisting of a glycidyl methacrylate-butyl methacrylate copolymer and a glycidyl acrylate-styrene copolymer.
  • hydrophobic film support is a cellulose derivative selected from the group consisting of cellulose triacetate, cellulose diacetate cellulose acetate butylate, and cellulose acetate propionate.
  • hydrophobic film support is a synthetic resin film selected from the group consisting of polyethylene terephthalate, polycarbonate, polyvinylchloride and polystyrene.
  • subbing layer is applied as an aqueous dispersion.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
US3201A 1969-01-16 1970-01-15 Photographic silver halide light-sensitive element with gelatin subbing layer Expired - Lifetime US3645740A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP304169 1969-01-16

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US3645740A true US3645740A (en) 1972-02-29

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Country Status (6)

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US (1) US3645740A (fr)
BE (1) BE744381A (fr)
CA (1) CA939183A (fr)
DE (1) DE2001727C2 (fr)
FR (1) FR2028425A1 (fr)
GB (1) GB1271921A (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120724A (en) * 1972-10-02 1978-10-17 Fuji Photo Film Co., Ltd. Subbing material for styrene bases used in photographic elements
US4128426A (en) * 1976-03-01 1978-12-05 Konishiroku Photo Industry Co., Ltd. Process for subbing photographic hydrophobic films
US4229523A (en) * 1974-08-31 1980-10-21 Konishiroku Photo Industry Co., Ltd. Method of undercoating treatment of polyester films for photographic light-sensitive materials
EP0209118A2 (fr) 1985-07-17 1987-01-21 Konica Corporation Matériau photographique à l'halogénure d'argent
EP0228084A2 (fr) 1985-12-25 1987-07-08 Fuji Photo Film Co., Ltd. Procédé de préparation d'une image
US4863801A (en) * 1987-11-20 1989-09-05 Minnesota Mining And Manufacturing Company Surface treatment of pet film
US6162597A (en) * 1999-12-17 2000-12-19 Eastman Kodak Company Imaging elements adhesion promoting subbing layer for photothermographic imaging layers
US6165699A (en) * 1999-12-17 2000-12-26 Eastman Kodak Company Annealed adhesion promoting layer for photographic imaging elements
EP2385425A1 (fr) 2010-05-07 2011-11-09 Fujifilm Corporation Matériau photographique à l'halogénure d' argent sensible à la lumière pour cinéma
WO2012035314A1 (fr) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Papier photographique
WO2021213762A1 (fr) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Papier photographique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1497101A (en) 1975-08-04 1978-01-05 Ici Ltd Coated film assemblies
GB1583343A (en) * 1976-08-16 1981-01-28 Bexford Ltd Coated film assemblies
FR2442248A1 (fr) * 1978-11-22 1980-06-20 Inst Francais Du Petrole Compositions de copolymeres d'acrylamides et d'acrylates de glycidyle, leur preparation et leurs applications, notamment dans la recuperation assistee du petrole
EP0280330B1 (fr) * 1987-02-27 1993-07-21 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB894590A (en) * 1958-07-09 1962-04-26 Agfa Ag Photographic silver halide films comprising an anchoring layer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE631317A (fr) * 1962-04-24 1900-01-01

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB894590A (en) * 1958-07-09 1962-04-26 Agfa Ag Photographic silver halide films comprising an anchoring layer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Vol. 57, 1962, 12747a (Belg. Patent 609,582 was not available but has been ordered). *
Derwent Abstracts, Abstract of Belgium Patent 609,582, 1962. *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120724A (en) * 1972-10-02 1978-10-17 Fuji Photo Film Co., Ltd. Subbing material for styrene bases used in photographic elements
US4229523A (en) * 1974-08-31 1980-10-21 Konishiroku Photo Industry Co., Ltd. Method of undercoating treatment of polyester films for photographic light-sensitive materials
US4128426A (en) * 1976-03-01 1978-12-05 Konishiroku Photo Industry Co., Ltd. Process for subbing photographic hydrophobic films
EP0209118A2 (fr) 1985-07-17 1987-01-21 Konica Corporation Matériau photographique à l'halogénure d'argent
EP0228084A2 (fr) 1985-12-25 1987-07-08 Fuji Photo Film Co., Ltd. Procédé de préparation d'une image
US4863801A (en) * 1987-11-20 1989-09-05 Minnesota Mining And Manufacturing Company Surface treatment of pet film
US6162597A (en) * 1999-12-17 2000-12-19 Eastman Kodak Company Imaging elements adhesion promoting subbing layer for photothermographic imaging layers
US6165699A (en) * 1999-12-17 2000-12-26 Eastman Kodak Company Annealed adhesion promoting layer for photographic imaging elements
EP2385425A1 (fr) 2010-05-07 2011-11-09 Fujifilm Corporation Matériau photographique à l'halogénure d' argent sensible à la lumière pour cinéma
WO2012035314A1 (fr) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Papier photographique
WO2021213762A1 (fr) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Papier photographique

Also Published As

Publication number Publication date
CA939183A (en) 1974-01-01
DE2001727C2 (de) 1983-07-28
GB1271921A (en) 1972-04-26
BE744381A (fr) 1970-06-15
FR2028425A1 (fr) 1970-10-09
DE2001727A1 (de) 1970-07-23

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