US2698240A - Photographic films and their preparation - Google Patents

Photographic films and their preparation Download PDF

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Publication number
US2698240A
US2698240A US290332A US29033252A US2698240A US 2698240 A US2698240 A US 2698240A US 290332 A US290332 A US 290332A US 29033252 A US29033252 A US 29033252A US 2698240 A US2698240 A US 2698240A
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Prior art keywords
ester
film
color
former
stratum
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US290332A
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Alles Francis Peter
Saner William Russell
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication date
Priority to BE513652D priority Critical patent/BE513652A/xx
Priority to IT490247D priority patent/IT490247A/it
Priority to NL95537D priority patent/NL95537C/xx
Priority to NL90105D priority patent/NL90105C/xx
Priority to BE513653D priority patent/BE513653A/xx
Priority to NLAANVRAGE7200830,A priority patent/NL171162B/en
Priority to NLAANVRAGE7408133,A priority patent/NL171126B/en
Priority claimed from US15127450 external-priority patent/US2627088A/en
Priority to GB3486/51A priority patent/GB718422A/en
Priority to GB21834/51A priority patent/GB688528A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US290332A priority patent/US2698240A/en
Priority to DEP8062A priority patent/DE942313C/en
Priority to CH319261D priority patent/CH319261A/en
Priority to DEP8093A priority patent/DE925032C/en
Priority to CH318468D priority patent/CH318468A/en
Priority to FR1061332D priority patent/FR1061332A/en
Priority to FR1064786D priority patent/FR1064786A/en
Priority to GB11602/53A priority patent/GB727705A/en
Publication of US2698240A publication Critical patent/US2698240A/en
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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
    • G03C1/76—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • 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
    • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • G03C1/7954—Polyesters
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/327—Macromolecular coupling substances
    • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/08—Homopolymers or copolymers of vinylidene chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/10—Polyurethanes from polyacetals

Definitions

  • This invention relates to photographic film elements. More particularly it relates to transparent photographic film elements which have a polyvinyl acetal color formersilver halide dispersion anchored to the support by means of a substratum composed of a copolymer of vinylidene chloride, an acrylic ester and itaconic acid. Still more particularly it relates to such elements wherein the film base is composed of an oriented highly polymeric linear ester of a dicarboxylic acid and a dihydric alcohol. The invention also relates to a method of preparing such elements.
  • An object of this invention is to provide photographic film elements wherein a polyvinyl acetal color formersilver halide dispersion is firmly anchored to a film base.
  • Another object is to provide such elements which have improved dimensional stability.
  • 'A further object is to provide such elements wherein the film base is composed of an oriented highly polymeric ester of a dicarboxylic acid and a dihydric alcohol. Still other objects will be apparent from the following description of the invention.
  • polyvinyl acetal color formers which are hydrophilic to water-soluble in character, as the binding agent for silver halide grains has been disclosed in a number of patents in the past six years. It has been difficult, however, to obtain adequate anchorage between thin layers composed of such dispersions and the usual types of hydrophobic film base. This is particularly true of film base composed of highly polymeric esters of dicarboxylic acids and dihydric alcohols and especially films composed of polyethylene terephthalates. These polyvinyl acetal dispersions do not have good adherence to the conventional gelatin sublayers which have been used for many years in anchoring colloid silver halide emulsion layers to hydrophobic films.
  • the polyvinyl acetal silver halide dispersion layer has been applied, or (2) by first applying to the layer of copolymer a'thin layer of a hydroxyl polymer which contains a plurality of recurring intralinear groups as polymer-forming units, said polymers being water-soluble to hydrophilic in character.
  • the adherence of the latter intermediate substratum can also be improved by heatingthe coated film base to a temperature of at least 70 C. before applying the silver halide dispersion. This heating step, however, can be applied after thepolyvinyl acetal color-.former-silver halide dispersion has been coated onto the layer of hydroxyl polymer.
  • Synthetic hydroxyl polymers of the water-soluble and hydrophilictype include polyvinyl alcohol and its partially substituted water-soluble lower fatty acidesters, lower alkyl esters, and lower acetals.
  • Polyvinyl alcohol is a tough, white, amorphous material. water. The more highly polymerized varieties are soluble in hot water and the medium or lower polymers aresol uble in cold water. They are usuallyprepared by hydrolysis of polyvinyl esters, such as polyvinyl acetate,
  • the solutions used to coat the substratum of the synthetic hydroxyl polymer, free from color former nuclei may contain a coagulating agent, e. g., boric acid or a boric acid ester of a polyhydric alcohol, e. g., an ester prepared by reacting an alcohol. such as ethylene glycol, diethylene glycol, triethylene glycol, erythritol, sorbitol, mannitol, etc., with boric acid or a mixture of boric acid and borax, by heating the admixture to C. to C'. A copious evolution of Water occurs.
  • the resulting products are viscous syrups or resins of a colloidal nature and have a high molecular weight and complex structure.
  • boriborates They are readily soluble in Water but are substantially insoluble in hydrocarbons but probably hydrolyze to the boric acid and glycol in water. Their preparation is described in United States Patents 1,953,741, 2,223,349, 2,223,948, 2,223,949, and 2,224,011. These compounds have been referred to as boriborates:
  • a hydrophobic film which may be composed of a cellulose carboxylic acid ester, e. g., cellulose acetate, cellulose acetate proprionate, cellulose acetate butyrate, cellulose nitrate, cellulose propionate; a superpolymer, e. g., a superpolyamide (nylon), an orientable highly polymeric linear ester of a dicarboxylic acid and a dihydric alcohol, e. g., polyethylene terephthalate, polyvinyl chloride, etc., is coated with a copolymer of vinylidene chloride, an acrylic ester and itaconic acid either from an organic solvent solution or from an aqueous dispersion.
  • a cellulose carboxylic acid ester e. g., cellulose acetate, cellulose acetate proprionate, cellulose acetate butyrate, cellulose nitrate, cellulose propionate
  • a superpolymer e. g
  • the solvent should have only a mild solvent actiononthe base so that it will not appreciably dissolve the film base but have a superficial effect and merely soften or bite into the surface of the base.
  • the substrata composed of a vinyl alcohol polymer and/or the polyvinyl acetal color former-silver halide dispersion coatings are formed by coating them onto the layer of vinylidene chloride copolymer.
  • the useful ethylenically unsaturated esters which may be used in the copolymers are the alkyl esters of acrylic and methacrylic acids having from 1 to 18 carbon atoms in the alkyl group- (e. g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, methyl acrylate,
  • the .copolymers of this invention .canbe :coated ,on ,the hydrophobic film base or support b,y any suitabletechs nique, e. g., coating from ahopper, skiml coating where the surface .of the film passes under arollerandcontacts with the surface of the liquid coatingnwith applicator or transfer rolls, spray coating, etc. Doctor blades, air doctor blades, etc., can be used to remove excess liquid.
  • Example I A sample of polyethylene terephthalate filmbasehaving a thicknessof 0.003 inch, melting pointof above 200 C. and an intrinsic viscosity of 0.50 in a mixture of 2,4,6-trichlorophenol and phenol (70:100' parts by weight) was coated with an aqueous dispersion of the vinylidene chloride-methyl acrylate-itaconic acid copolymer described in Alles & SanerU. S. patent'application Ser. No. 151,274, filed March 22, 1950, now PatentNo. 2,627,088.
  • the film was coated with a polyvinyl acetal color-former-silver halide dispersion, containing approximately 1.77% by weight of. silver iodobromide, composed of approximately 0.9% silver iodide and 99.1% silver bromide, dispersed in the polymeric colorformer (4.12% by weight of the total dispersion.) described in U. S. Patent 2,513,190.
  • the silver halide dispersion was found to have good adherence to the film base.
  • the film was exposed and processed as follows:
  • Example II A second color film with a polyethylene terephthalate base of the kind described in Example I was treated as in said example except that the film was stretched biaxially after the vinylidene chloride-methyl.acrylate-itaconic acid copolymer layer had been applied and before the color former emulsion was applied. The resulting film was exposed and processed-as, described in Example I with similar results.
  • Examplelll A sample of a polyethylene terephthalate film base of the type used in Example .I was treatedwith a copolymer of vinylidene chloride-methyl acrylate-itaconic acid of the type used in Example I, then stretched biaxlally and coated with a solution of.the.following composition:
  • Example I After dryingatSO C., the ,film was heatedlat C. for 2 minutes and coated with a color-former dispersion of the type describedin Example I.
  • the above polyvinyl acetal is described in Example. I'of Martin 2,513,189.
  • Example V A sample of apolyethyleneterephthalatefilm base of the'type used in Example], was coated on'both-sides with a copolymer of vinylidene chloride of the :type used in Example I, stretchedbiaxially, and: was coated on one 'sidewith the twosubbing solutions asset forth in Example III. After drying," the film waszsubjectedto a temperatureof 100 C. for'severalminutes'and was then-coated-with the following-dispersionsand solutions, in the order listed.
  • heating temperature of at least 70 C. has been referred to above the examples include higher temperatures and indeed temperatures up to 150 C. or more can be used if they do not deleteriously affect the coated layers. This can be determined visually with respect to the particular color former.
  • temperatures up to 150 C. or more can be used if they do not deleteriously affect the coated layers. This can be determined visually with respect to the particular color former.
  • the heating step may precede the application of the polyvinyl acetal color former layer.
  • the invention is not limited to the use of the specific polyvinyl acetal color formers given in the examples as many other hydrophilic to water-soluble acetals of this general type can be substituted with similar results.
  • suitable polyvinyl acetal color formers are those described in the following U. S. Patents: Jennings 2,397,864, Woodward 2,423,572, Mc- Queen 2,464,597, Corner & Woodward 2,465,067, Martin 2,472,910, Martin 2,538,257, Martin 2,476,988, Mc- Queen 2,477,462, Martin 2,489,655, McQueen 2,513,190, and Martin 2,518,704.
  • color films for multicolor photography they will contain several superposed polyvinyl acetal color-former-silver halide emulsion layers which are so arranged and sensitized that they record different colors of the visible spectrum.
  • These color formers can be selected to yield yellow, blue-green (cyan), and magenta, etc., quinoneimine, aszomethine,
  • Filter dyes may be present in one or more of the above color former layers or in a separate stratum, e. g., a polyvinyl alcohol or equivalent hydroxyl polymer layer as described above.
  • a yellow filter dye is used in a stratum above the two light-sensitive layers most distant from the camera side of the film.
  • An advantage of the invention is that it provides a simple and effective process for improving the anchorage between a polyvinyl acetal color former layer and a hydrophobic film base. Another advantage is that the process can be carried out with conventional equipment. Still other advantages will be apparent from the above.
  • the process which comprises coating a light-insensitive, water-permeable hydroxyl polymer layer onto a stratum composed of a tri-component copolymer made from 35 to 96% of vinylidene chloride, 3.5 to 64.5% of an ethylenically unsaturated ester and 0.5 to 25% of itaconic acid monomers, all percentages being by weight, said ester being taken from the group consisting of alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group, acrylonitrile, methacrylonitrile and vinyl chloride; said stratum being on an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C.
  • a photographic element comprising a film base composed of an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C. to 300 (3., bearing in order a substratum composed of a tri-component copolymer made from 35 to 96% of vinylidene chloride, 3.5 to 64.5 of an ethylenically unsaturated ester and 0.5 to 25 of itaconic acid monomers, all percentages being by weight, said ester being taken from the group consisting of alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group, acrylonitrile, methacrylonitrile and vinyl chloride: said stratum being a layer of a water-soluble to hydrophilic hydroxyl polymer containing a plurality of intralinear --CHzCHOH-- groups as polymer units and at least one layer of lightsensitive silver halides dispersed in a poly
  • a photographic element comprising a film base composed of an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C. to 300 C., bearing in order a substratum comgposed alof av Kiri-701111301160! --.eopolyn'ler macle from ⁇ 351.10

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Description

United States Patent O PHOTOGRAPHIC FILMS AND THEIR PREPARATION Francis Peter Alles, Westficld, and William Russell Saner, Plainfield, N. J., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 27, 1952, Serial No. 290,332
11 Claims- (Cl. 95-9) This invention relates to photographic film elements. More particularly it relates to transparent photographic film elements which have a polyvinyl acetal color formersilver halide dispersion anchored to the support by means of a substratum composed of a copolymer of vinylidene chloride, an acrylic ester and itaconic acid. Still more particularly it relates to such elements wherein the film base is composed of an oriented highly polymeric linear ester of a dicarboxylic acid and a dihydric alcohol. The invention also relates to a method of preparing such elements.
An object of this invention is to provide photographic film elements wherein a polyvinyl acetal color formersilver halide dispersion is firmly anchored to a film base.
Another object is to provide such elements which have improved dimensional stability. 'A further object is to provide such elements wherein the film base is composed of an oriented highly polymeric ester of a dicarboxylic acid and a dihydric alcohol. Still other objects will be apparent from the following description of the invention.
The use of polyvinyl acetal color formers, which are hydrophilic to water-soluble in character, as the binding agent for silver halide grains has been disclosed in a number of patents in the past six years. It has been difficult, however, to obtain adequate anchorage between thin layers composed of such dispersions and the usual types of hydrophobic film base. This is particularly true of film base composed of highly polymeric esters of dicarboxylic acids and dihydric alcohols and especially films composed of polyethylene terephthalates. These polyvinyl acetal dispersions do not have good adherence to the conventional gelatin sublayers which have been used for many years in anchoring colloid silver halide emulsion layers to hydrophobic films.
It has been found that if a hydrophobic film base is coated with a thin layer of a copolymer of vinylidene chloride, an acrylic ester and itaconic acid that this layer has excellent adherence to the film base and can be made to adhere tenaciously to a layer of polyvinyl acetal color former-silver halide dispersion in two ways, (1) by heating the coated film element to a temperature of at least 70 C. after the polyvinyl acetal silver halide dispersion layer has been applied, or (2) by first applying to the layer of copolymer a'thin layer of a hydroxyl polymer which contains a plurality of recurring intralinear groups as polymer-forming units, said polymers being water-soluble to hydrophilic in character. The adherence of the latter intermediate substratum can also be improved by heatingthe coated film base to a temperature of at least 70 C. before applying the silver halide dispersion. This heating step, however, can be applied after thepolyvinyl acetal color-.former-silver halide dispersion has been coated onto the layer of hydroxyl polymer.
Synthetic hydroxyl polymers of the water-soluble and hydrophilictype include polyvinyl alcohol and its partially substituted water-soluble lower fatty acidesters, lower alkyl esters, and lower acetals. Polyvinyl alcohol is a tough, white, amorphous material. water. The more highly polymerized varieties are soluble in hot water and the medium or lower polymers aresol uble in cold water. They are usuallyprepared by hydrolysis of polyvinyl esters, such as polyvinyl acetate,
2,698,240 Patented Dec. 28, 1954 partly hydrolyzed esters which contain a large number of recurring vinyl alcohol units I (-CH2CHOH) copolymers with various mono-ethylenically unsaturated compounds having a terminal CH2=C group, such as It is soluble in vinyl chloride, acrylic acid esters, e. g., methyl acrylate; methacrylic acid esters, e. g., methyl methacrylate; and mono-olefins, e. g., ethylene. The completely hydrolyzed ethylene/vinyl acetate interpolymerswhich are described in McQueen 2,397,866 and Roland 2,386,347 form an important class of synthetic hydroxyl polymers useful as binding agents for the silver halide emulsions made in accordance with this invention.
The solutions used to coat the substratum of the synthetic hydroxyl polymer, free from color former nuclei, may contain a coagulating agent, e. g., boric acid or a boric acid ester of a polyhydric alcohol, e. g., an ester prepared by reacting an alcohol. such as ethylene glycol, diethylene glycol, triethylene glycol, erythritol, sorbitol, mannitol, etc., with boric acid or a mixture of boric acid and borax, by heating the admixture to C. to C'. A copious evolution of Water occurs. The resulting products are viscous syrups or resins of a colloidal nature and have a high molecular weight and complex structure. They are readily soluble in Water but are substantially insoluble in hydrocarbons but probably hydrolyze to the boric acid and glycol in water. Their preparation is described in United States Patents 1,953,741, 2,223,349, 2,223,948, 2,223,949, and 2,224,011. These compounds have been referred to as boriborates:
In carrying out the invention a hydrophobic film which may be composed of a cellulose carboxylic acid ester, e. g., cellulose acetate, cellulose acetate proprionate, cellulose acetate butyrate, cellulose nitrate, cellulose propionate; a superpolymer, e. g., a superpolyamide (nylon), an orientable highly polymeric linear ester of a dicarboxylic acid and a dihydric alcohol, e. g., polyethylene terephthalate, polyvinyl chloride, etc., is coated with a copolymer of vinylidene chloride, an acrylic ester and itaconic acid either from an organic solvent solution or from an aqueous dispersion. When an organic solvent solution is used the solvent should have only a mild solvent actiononthe base so that it will not appreciably dissolve the film base but have a superficial effect and merely soften or bite into the surface of the base. The substrata, composed of a vinyl alcohol polymer and/or the polyvinyl acetal color former-silver halide dispersion coatings are formed by coating them onto the layer of vinylidene chloride copolymer.
In order that the three component copolymers described above will adhere to the base tenaciously and have the requisite degree of flexibility, it is essential that the initial relative proportions of monomers in the reaction mixture be within the following ranges:
The useful ethylenically unsaturated esters which may be used in the copolymers are the alkyl esters of acrylic and methacrylic acids having from 1 to 18 carbon atoms in the alkyl group- (e. g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, methyl acrylate,
of concentration of 0.1% to 1.0%.. improved solubility and viscosity valuesare-obtainedv byconductiugdhe polymerization in the. presence. of. mercaptans. such; as; ethyl mercaptan, lauryl 'mercaptan, tertiary dod'ecyl'mercaptan, etc., whichare effective, in reducingicrosswlifnking. inthe copolymer. In general, themercaptanmshould beused inconcentrations of 0.l,%..to 5.0%.by, weight, based on the, weight of polymerizable monomerspresent. in the charge.
The .copolymers of this invention .canbe :coated ,on ,the hydrophobic film base or support b,y any suitabletechs nique, e. g., coating from ahopper, skiml coating where the surface .of the film passes under arollerandcontacts with the surface of the liquid coatingnwith applicator or transfer rolls, spray coating, etc. Doctor blades, air doctor blades, etc., can be used to remove excess liquid.
The invention will be further illustrated but isnot intended to be limited by the following examples.
Example I A sample of polyethylene terephthalate filmbasehaving a thicknessof 0.003 inch, melting pointof above 200 C. and an intrinsic viscosity of 0.50 in a mixture of 2,4,6-trichlorophenol and phenol (70:100' parts by weight) was coated with an aqueous dispersion of the vinylidene chloride-methyl acrylate-itaconic acid copolymer described in Alles & SanerU. S. patent'application Ser. No. 151,274, filed March 22, 1950, now PatentNo. 2,627,088. After drying at 50 C., and heating for two minutes at 100 C., the film was coated with a polyvinyl acetal color-former-silver halide dispersion, containing approximately 1.77% by weight of. silver iodobromide, composed of approximately 0.9% silver iodide and 99.1% silver bromide, dispersed in the polymeric colorformer (4.12% by weight of the total dispersion.) described in U. S. Patent 2,513,190. After drying, the silver halide dispersion was found to have good adherence to the film base. The film was exposed and processed as follows:
(1) Developed for minutes-a t--68 F. in a solution having the following composition:
Grams Para-aminodiethylaniline hydrochloride 2.5 Sodium sulfite 10.0 Sodium carbonate 46.8 Potassium bromide- 2.0
Water to make 1 liter (2) Given a 30second rinse in water, (3) Treated for 5 minutes at 68 F. in the. following fixing bath:
Sodium thiosulfate v grams 240.0 Sodium sulfite d0 :0 Sodium tetraborate do- 18.0 Glacial acetic acid cc' 12.0 Potassium aluminum sulfate "grams-.. 20.0
Water to make 3-liters (4) Given a 5 minute rinse in water, (5) Treated for 5 minutes at 68 F. in the following bleaching bath:
Grams Potassium ferricyanide -,u 100.0 Boric acid 10.0 Sodium tetraborate 5.0
The wet and dry anchorage, after processing, were found to be'satisfactory'.
Example II A second color film with a polyethylene terephthalate base of the kind described in Example I was treated as in said example except that the film was stretched biaxially after the vinylidene chloride-methyl.acrylate-itaconic acid copolymer layer had been applied and before the color former emulsion was applied. The resulting film was exposed and processed-as, described in Example I with similar results.
Examplelll A sample of a polyethylene terephthalate film base of the type used in Example .I was treatedwith a copolymer of vinylidene chloride-methyl acrylate-itaconic acid of the type used in Example I, then stretched biaxlally and coated with a solution of.the.following composition:
Percent Meta (benzoylacetamido)benzaldehyde sodiumo-sulfobenzaldehyde-polyvinyl mixediacetal 5 Water 79 M hano After dryingatz507 C.,.the,film was further treated with a solutionofthe following composition:
Percent Meta (benzoylacetamido)benzaldehyde sodiumo-sulfobenzaldehyde-polyvinyl mixed acetal Boric acid 1.:1 Diisopropanolamine 1.3 Acetone 40.0 Ethyl alcohol 72f) .5533
After dryingatSO C., the ,film was heatedlat C. for 2 minutes and coated with a color-former dispersion of the type describedin Example I. The adhesion, both wetrand 'dry, after exposing' the'film -and processing in the usual manner, was.good. The above polyvinyl acetal is described in Example. I'of Martin 2,513,189.
Example] V After-drying at-50 C., the film washeatedat C.
: for- 5 minutes and was further treated with a solution of the following composition:
Percent Boric acid; 1.9 Diisopropanolamine 1.3 Water 96.8
Afterdryingrat 50 C.; the .filrn was :coated ,withrapolyvinyl-acetal tcolor-former silver halide. emulsion, containing 1.77% by weight:of:silver iodobromide, composed of approximately 0.9% silver iodide and 99.1% silver bromide, dispersed in .thepolymeric color former (4.12% by weight of the total emulsion) described in Martin U. S. Patent No. 2,513,190. After. drying, theemulsion wasfound-to have. goodfadherence. to. the film, base. lt wasexposed andprocessedas described in Example 1. Wet and .dry. anchorage, after processing, werev good.
Example" V" A sample of apolyethyleneterephthalatefilm base of the'type used in Example], was coated on'both-sides with a copolymer of vinylidene chloride of the :type used in Example I, stretchedbiaxially, and: was coated on one 'sidewith the twosubbing solutions asset forth in Example III. After drying," the film waszsubjectedto a temperatureof 100 C. for'severalminutes'and was then-coated-with the following-dispersionsand solutions, in the order listed.
(1) Apolyvinyl acetal color-former-silver halide dis.- persion containing 1.7 7 byweight of silver-iodobromide; composed of approximately 0.9% silver 'i0dld-aIldi99.'1%
silver bromide, dispersed in the polymeric color former (4.12% by weight of the total dispersion) described in U. 5. Patent No. 2,513,190.
(2) A 1.15% solution of polyvinyl alcohol (99% hydroiyzed polyvinyl acetate, a 4% solution of which, in
water, had a viscosity of D5 centipoises at C.) in a mixture of water and alcohol.
(3 A polyvinyl acetal color-former-silver halide dispersion containing approximately 2.2% silver bromide dispersed in the polymeric color rormer (2.8% by weight of the total dispersion) described in U. S. Patent 2,489,655.
(4) 'lhe same solution given under (2).
(5) A polyvinyl acetal color-former-silver halide dispersion containing approximately 1.15% silver bromide dispersed in the polymeric color former (4.15% by weight of the total dispersion) described in U. S. Patent 2,476,988. This dispersion also contained dissolved ghefiain, the yellow dye Tartrazine (Colour Index No.
After drying, this composite light-sensitive element was found to adhere well to the film base. The film was exposed and processed as described in Example I. The wet and dry anchorage were found to be satisfactory.
While a heating temperature of at least 70 C. has been referred to above the examples include higher temperatures and indeed temperatures up to 150 C. or more can be used if they do not deleteriously affect the coated layers. This can be determined visually with respect to the particular color former. When a gelling hydroxyl polymer sublayer or non-gelling hydroxyl polymer sublayer is used the heating step may precede the application of the polyvinyl acetal color former layer.
'lhe invention is, of course, not limited to the foregoing examples as any of the film bases referred to above may be substituted, in some cases without stretching, with similar results.
Similarly, the invention is not limited to the use of the specific polyvinyl acetal color formers given in the examples as many other hydrophilic to water-soluble acetals of this general type can be substituted with similar results. Among such additional suitable polyvinyl acetal color formers are those described in the following U. S. Patents: Jennings 2,397,864, Woodward 2,423,572, Mc- Queen 2,464,597, Corner & Woodward 2,465,067, Martin 2,472,910, Martin 2,538,257, Martin 2,476,988, Mc- Queen 2,477,462, Martin 2,489,655, McQueen 2,513,190, and Martin 2,518,704.
It is to be understood that in the case of color films for multicolor photography they will contain several superposed polyvinyl acetal color-former-silver halide emulsion layers which are so arranged and sensitized that they record different colors of the visible spectrum. These color formers can be selected to yield yellow, blue-green (cyan), and magenta, etc., quinoneimine, aszomethine,
etc., dyes in the appropriate layers as is common in the art and described in Jennings 2,497,864 and other patents described above. Filter dyes may be present in one or more of the above color former layers or in a separate stratum, e. g., a polyvinyl alcohol or equivalent hydroxyl polymer layer as described above. In general, a yellow filter dye is used in a stratum above the two light-sensitive layers most distant from the camera side of the film.
An advantage of the invention is that it provides a simple and effective process for improving the anchorage between a polyvinyl acetal color former layer and a hydrophobic film base. Another advantage is that the process can be carried out with conventional equipment. Still other advantages will be apparent from the above.
This invention is a continuation-in-part of U. S. application Ser. No. 151,274, filed March 22, 1950.
As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.
What is claimed is:
1. The process which comprises coating a waterperrneable hydroxyl polymer layer onto a stratum composed of a tri-component coploymer made from to 96% of vinylidene chloride, 3.5 to 64.5% of an ethylenically unsaturated ester and 0.5 to 25% of itaconic acid monomers, all percentages being by weight, said ester being taken from the group consisting of alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group, acryonitrile, methacrylonitrile and vinyl chloride: said stratum being on a hydrophobic 6 film base, and heating the coated layer to a temperature from 70 C. to 150 C.
2. A process as set forth in claim 1 wherein said hydroxyl polymer is a polyvinyl acetal color-former.
3. A process as set forth in claim 2 wherein said acetal has light-sensitive silver salts uniformly dispersed therethrough.
4. 'lhe process which comprises coating a Waterpermeable hydroxyl polymer layer onto a stratum composed of a tri-component copolymer made from 35m 96% of vinylidene chloride, 3.5 to 64.5 of an ethylenically unsaturated ester and 0.5 to 25% of itaconic acid monomers, all percentages being by weight, said ester being taken from the group consisting of alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group, acrylonitrile, methacrylo nitrile and vinyl chloride; said stratum being on an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C. to 300 C., and heating the coated base to a temperature from 70 C. to 130 C.
5. A process as set forth in claim 4 wherein said bydroxyl polymer is a polyvinyl acetal color-former.
6. A process as set forth in claim 5 wherein said acetal has light-sensitive silver halides uniformly dispersed therethrough.
7. The process which comprises coating a light-insensitive, water-permeable hydroxyl polymer layer onto a stratum composed of a tri-component copolymer made from 35 to 96% of vinylidene chloride, 3.5 to 64.5% of an ethylenically unsaturated ester and 0.5 to 25% of itaconic acid monomers, all percentages being by weight, said ester being taken from the group consisting of alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group, acrylonitrile, methacrylonitrile and vinyl chloride; said stratum being on an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C. to 300 C., heating the coated base to a temperature from 70 C. to 130 C., coating an aqueous dispersion of light-sensitive silver halides in a polyvinyl acetal color-former onto said polymer layer and drying the resulting film element.
8. The process which comprises coating a light-insensitive, water-permeable hydroxyl polymer layer onto a stratum composed of a tri-component copolymer made from 35 to 96% of vinylidene chloride, 3.5 to 64.5% of an ethylenically unsaturated ester and 0.5 to 25% of itaconic acid monomers, all percentages being by weight, said ester being taken from the group consisting of alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group, acrylonitrile, methacrylonitrile and vinyl chloride; said stratum being on an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C. to 300 C., coating an aqueous dispersion of light-sensitive silver halides in a polyvinyl acetal color-former onto said polymer layer and drying the resulting film element, heating the coated base to a temperature from 70 C. to C.
9. A photographic element comprising a film base composed of an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C. to 300 (3., bearing in order a substratum composed of a tri-component copolymer made from 35 to 96% of vinylidene chloride, 3.5 to 64.5 of an ethylenically unsaturated ester and 0.5 to 25 of itaconic acid monomers, all percentages being by weight, said ester being taken from the group consisting of alkyl esters of acrylic and methacrylic acids having 1 to 18 carbon atoms in the alkyl group, acrylonitrile, methacrylonitrile and vinyl chloride: said stratum being a layer of a water-soluble to hydrophilic hydroxyl polymer containing a plurality of intralinear --CHzCHOH-- groups as polymer units and at least one layer of lightsensitive silver halides dispersed in a polyvinyl acetal color-former.
10. A photographic element comprising a film base composed of an oriented highly polymeric ester of a polymethylene glycol of 2 to 10 carbon atoms and terephthalic acid, said ester having a melting point from 200 C. to 300 C., bearing in order a substratum comgposed alof av Kiri-701111301160! --.eopolyn'ler macle from} 351.10
96% of vinylidene chloride, ;3'.5"-:to r64';$% 20f :.ethylenically unsaturated ester:and-'0.5l=to;25%:of.itaconic acid monomers, :allwpercentages :being by .weight,.=s aid :ester being takenCfrorn;;theugroupeconsistingzof alkyl esters ..of v.acrylic .:.and :.methacry1ic'--acids %having .1 to 18 carbon atoms in the alkyl group, acrylonitrile, -meth acrylonitrilexand vinyl chloride: said..stratum being a 1 layer of polyvinyl ;alcohol andqat least one layer of-light- .-sensitive silver ,halides dispersed. in :arpolyvinyl zacetal color-former having -av plurality :of -YCH2..C'HOH groups was-polymer units.
intralinear Number Name Date 398,039 DIAlelio Oct. 6, 1942 ..2;491,023 Alles etaal. .Dec. 13, 1949 :10 2 534,326 Weaver Dec. 19, 1950 :.2;'6 0 6,835 Jennings Aug. 12, 1952 2,627,088 Alles-set'al.v ...Feb.'31 195

Claims (1)

1. THE PROCESS WHICH COMPRISES COATING A WATERPERMEABLE HYDROXYL POLYMER LAYER ONTO A STRATUM COMPOSED OF A TRI-COMPONENT COPLOYMER MADE FROM 35 TO 96% OF VINYLIDENE CHLORIDE 3.5 TO 64.5% OF AN ETHYLENICALLY UNSATURATED ESTER AND 0.5 TO 25% OF ITACONIC ACID MONOMERS, ALL PERCENTAGES BEING BY WEIGHT, SAID ESTER BEING TAKEN FROM THE GROUP CONSISTING OF ALKYL ESTERS OF ACRYLIC AND METHACRYLIC ACIDS HAVING 1 TO 18 CARBON ATOMS IN THE ALKYL GROUP, ACRYONITRILE, METHACRYLONITRILE AND VINYL CHLORIDE: SAID STRATUM BEING ON A HYDROPHOBIC FILM BASE, AND HEATING THE COATED LAYER TO A TEMPERATURE FROM 70* C. TO 150* C.
US290332A 1950-03-22 1952-05-27 Photographic films and their preparation Expired - Lifetime US2698240A (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
BE513652D BE513652A (en) 1950-03-22
IT490247D IT490247A (en) 1950-03-22
NL95537D NL95537C (en) 1950-03-22
NL90105D NL90105C (en) 1950-03-22
BE513653D BE513653A (en) 1950-03-22
NLAANVRAGE7200830,A NL171162B (en) 1950-03-22 PROCESS FOR THE PREPARATION OF CYAN GROUPS CONTAINING AROMATIC POLYETHERS AND OBJECTS OBTAINED FROM THIS.
NLAANVRAGE7408133,A NL171126B (en) 1950-03-22 METHOD AND EQUIPMENT FOR BRINGING A LIQUID INTO CONTACT WITH A GAS.
GB3486/51A GB718422A (en) 1950-03-22 1951-02-13 Preparation of molecularly oriented coated films
GB21834/51A GB688528A (en) 1950-03-22 1951-09-17 Photographic light-sensitive elements
US290332A US2698240A (en) 1950-03-22 1952-05-27 Photographic films and their preparation
DEP8062A DE942313C (en) 1950-03-22 1952-07-24 Adhesive photographic films
CH319261D CH319261A (en) 1950-03-22 1952-07-25 Photographic element
DEP8093A DE925032C (en) 1950-03-22 1952-07-29 Process for the production of films coated with adhesive layers and suitable as a base for the production of photographic films
CH318468D CH318468A (en) 1950-03-22 1952-08-02 Process for the production of films provided with at least one water-permeable layer of a colloidal substance
FR1061332D FR1061332A (en) 1950-03-22 1952-08-07 Process for preparing oriented coated films
FR1064786D FR1064786A (en) 1950-03-22 1952-08-07 photographic film element
GB11602/53A GB727705A (en) 1950-03-22 1953-04-27 Improvements in or relating to the production of film elements

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US15127450 US2627088A (en) 1950-03-22 1950-03-22 Preparation of oriented coated films
GB21834/51A GB688528A (en) 1950-03-22 1951-09-17 Photographic light-sensitive elements
US290332A US2698240A (en) 1950-03-22 1952-05-27 Photographic films and their preparation

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US2836494A (en) * 1957-01-14 1958-05-27 Du Pont Photographic emulsions and elements
US2873207A (en) * 1955-02-21 1959-02-10 Dietzgen Co Eugene Diazotype reproduction material and method
US2943937A (en) * 1956-06-12 1960-07-05 Eastman Kodak Co Surface conditioning and subbing of oriented linear polyester photographic film support
US2984569A (en) * 1954-05-19 1961-05-16 Gevaert Photo Prod Nv Manufacture of photographic films
US3023101A (en) * 1955-04-14 1962-02-27 Agfa Ag Photographic film
US3025163A (en) * 1957-03-29 1962-03-13 Agfa Ag Photographic element having polycarbonate sub-layer
US3043710A (en) * 1959-02-20 1962-07-10 Du Pont Fluorescent screens
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US3215554A (en) * 1962-01-22 1965-11-02 Gevert Photo Producten N V Subbing layer for magnetic recording materials
US3249434A (en) * 1961-03-16 1966-05-03 Polaroid Corp Process for recovering processed photographic sheet material
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US2794742A (en) * 1955-08-03 1957-06-04 Eastman Kodak Co Photographic elements and their preparation
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US3215554A (en) * 1962-01-22 1965-11-02 Gevert Photo Producten N V Subbing layer for magnetic recording materials
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US7163743B2 (en) 2003-04-04 2007-01-16 E. I. Du Pont De Nemours And Company Polyester monofilaments
US20050238900A1 (en) * 2004-04-27 2005-10-27 Thorsten Kiehne White, steam-sterilizable and extrusion-coatable polyester film
US7147925B2 (en) 2004-04-27 2006-12-12 Mitsubishi Polyester Film Gmbh White, steam-sterilizable and extrusion-coatable polyester film
US20050287382A1 (en) * 2004-06-26 2005-12-29 Oliver Klein Extrusion-coatable polyester film comprising poly(m--xyleneadipamide)
US20050287381A1 (en) * 2004-06-26 2005-12-29 Herbert Peiffer Polyester film comprising poly(-xyleneadipamide)
US7141307B2 (en) 2004-06-26 2006-11-28 Mitsubishi Polyester Film Gmbh Extrusion-coatable polyester film comprising poly(m-xyleneadipamide)
US20050287380A1 (en) * 2004-06-26 2005-12-29 Oliver Klein Adhesion-promoting polyester film comprising poly(m-xyleneadipamide)
US20050287378A1 (en) * 2004-06-26 2005-12-29 Oliver Klein Metallized or ceramic-coated polyester films comprising poly(m-xyleneadipamide)
US20100112343A1 (en) * 2008-11-05 2010-05-06 Anderson Jerrel C Safety glazings with improved weatherability
US8080311B2 (en) 2008-11-05 2011-12-20 E. I. Du Pont De Nemours And Company Safety glazings with improved weatherability
WO2014085148A1 (en) 2012-11-28 2014-06-05 Eastman Kodak Company Porous organic polymeric films and preparation

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GB688528A (en) 1953-03-11
BE513652A (en) 1900-01-01
GB727705A (en) 1955-04-06
CH319261A (en) 1957-02-15
NL95537C (en) 1900-01-01
NL171162B (en) 1900-01-01
GB718422A (en) 1954-11-17
CH318468A (en) 1957-01-15
NL171126B (en) 1900-01-01
FR1061332A (en) 1954-04-12
IT490247A (en) 1900-01-01
FR1064786A (en) 1954-05-18
NL90105C (en) 1900-01-01
BE513653A (en) 1900-01-01

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