US3392022A - Removable antihalation layers for photographic film - Google Patents

Removable antihalation layers for photographic film Download PDF

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Publication number
US3392022A
US3392022A US580084A US58008466A US3392022A US 3392022 A US3392022 A US 3392022A US 580084 A US580084 A US 580084A US 58008466 A US58008466 A US 58008466A US 3392022 A US3392022 A US 3392022A
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United States
Prior art keywords
antihalation
cellulose acetate
photographic film
layer
cellulose
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US580084A
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English (en)
Inventor
Gerald C Gandy
George W Pierce
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Eastman Kodak Co
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Eastman Kodak Co
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Filing date
Publication date
Priority to DE19651472857 priority Critical patent/DE1472857C/de
Priority to BE669912A priority patent/BE669912A/xx
Priority to FR32064A priority patent/FR1447096A/fr
Priority to GB40927/65A priority patent/GB1115935A/en
Priority to US580084A priority patent/US3392022A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to DE1597543A priority patent/DE1597543C3/de
Priority to GB41929/67A priority patent/GB1192797A/en
Priority to FR120943A priority patent/FR1536784A/fr
Priority to BE703939D priority patent/BE703939A/xx
Application granted granted Critical
Publication of US3392022A publication Critical patent/US3392022A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/835—Macromolecular substances therefor, e.g. mordants

Definitions

  • This invention relates to photographic film supplied with a removable antihalation layer comprising cellulose mixed esters containing radicals such as hexahydrophthalyl or tetrahydrophthalyl. More particularly, the invention relates to such film having an antihalation backing layer especially adapted for easy removability comprising cellulose acetate hexahydrophthalate or cellulose acetate tetrahydrophthalate in admixture with an alkylmethac-rylate-methacrylic acid copolymer and an antihalation material such as a dye.
  • antihalation layers on photographic films are Well recognized. Many proposals have been made for overcoming halation. Usually the adverse effects from halation are minimized with a light absorbing layer on one of the surfaces of the photographic support, such as a backing layer, whereby the rays which would otherwise be reflected into the photosensitive layer are absorbed.
  • a backing layer contains carbon or graphite dispersed in the backing material. Colloidal carbon dispersions useful in antihalation backings have been described in Staud et al. US. Patent No. 2,271,234, issued Jan. 27, 1942.
  • Another type of antihalation layer is one which contains a colored material such as a dye which absorbs much of the visible spectrum.
  • alkali soluble materials have been referred to as useful carriers for antihalation materials such as cellulose acetate phthalate as described in Simmons U.S. Patent No. 2,327,828, issued Aug. 24, 1943.
  • cellulose acetate phthalate By the use of that material, it is possible to provide an antihalation layer of colloidal carbon finely dispersed in a coating solution diluted with organic solvents to obtain the desired coating consistency.
  • a carrier of that type the antihalation layer is removable upon treatment in alkaline photographic developers.
  • Cellulose acetate phthalate although having many desirable properties for this purpose, has been prone to create problems of transfer of the antihalation material to a gelatin photographic emulsion when the emulsion and the backing contact each other at comparatively high relative humidities and temperatures. Defects are occasionally encountered in the use of cellulose acetate phthalate backing layers, particularly with certain photographic products of the color film type. These defects have been generally referred to as moisture mottle.
  • One object of our invention is to provide backing layers having greater hydrolytic stability than those in which cellulose acetate phthalate is employed. Another object of our invention is to provide antihalation layers which act to reduce the moisture mottle of certain photographic films and result in backing transfer thresholds at higher relative humidities than with cellulose acetate phthalate 3,392,022 Patented July 9, 1968 backing layers. Another object of our invention is to provide antihalation layers which are especially adapted for easy removability in alkaline photographic developers. Other objects of our invention will appear hereinafter.
  • antihalation coatings for photographic film comprising cellulose acetate hexahydrophthalate or cellulose acetate tetrahydrophthalate and antihalation material results in improved photographic products compared with those having antihalation layers of the cellulose acetate phthalate type.
  • the antihalation layers of our invention are easily applied to photographic film supports from organic solvents and flexible layers of good adherence to the film support results. These layers are easily removed by use of alkaline developers which convert cellulose acetate hexahydrophthalate or cellulose acetate tetrahydrophthalate to the form of a salt which is water-soluble. However, in the alkaline developer solu tions these salts dissolve slowly.
  • antihalation coatings of the invention containing none of said copoiymers, while very useful, still require a bufiing or wiping step after treatment with the alkaline developer solutions for complete removal of all backing remnants. This procedure complicates photographic film processing and requires expensive equipment. The presence of the fine polymeric particles in the developer does not adversely affect developer activity.
  • antihalation coatings comprising only the said copolymer and antihalation material, i.e. containing no cellulose acetate hexahydroor tetrahydrophthalate component, come oit in undesirably large flakes or sheets which tend to contaminate the alkaline processing solution and interfere with the operation.
  • inventions of our invention include the use of the antihalation layers of the invention containing a major amount of, or only the hexa'hydroor tetra-hydrophthalate material on photographic films such as multilayer color films requiring high moisture resistance.
  • the antihalation layers of the invention containing a major amount of, or only the hexa'hydroor tetra-hydrophthalate material on photographic films such as multilayer color films requiring high moisture resistance.
  • Films not requiring the utmost moisture resistance property in the antihalation layer advantageously contain both the phthalate and copolymer materials.
  • cellulose acetate having 35-42% acetyl content is dissolved in a lower fatty acid and hydrolyzed with mineral acid to acetyl content of about 26-34% followed by esterification with the appropriate polycarboxylic acid anhydride using basic catalyst.
  • These cellulose esters are applied to the film base in solution in organic solvents and may be either in acid form or in the form of their salts.
  • the cellulose acetate hexahydroand tetrahydrophthalates which have been found to be especially useful in the preparation of antihalation layers in accordance with our invention are those having a content of hexahydrophthalyl or tetrahydrophthalyl within the range of 18-38%, based on the total ester.
  • Various combinations have been found to be useful as solvents for the mixture of cellulose ester and antihalation material which is to be applied to the film base and the solvents are selected by the operator in accordance with those which are most useful in connection with the particular film support to which the layer is ap plied.
  • Antihalation layers in accordance with our invention may be applied to various types of film supports such as of cellulose nitrate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, or of synthetic resin as, for example, polycarbonate, polystyrene or polyester film base.
  • film supports such as of cellulose nitrate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, or of synthetic resin as, for example, polycarbonate, polystyrene or polyester film base.
  • the antihalation material used may be a carbon dispersion, dispersed colloidal carbon being commonly known and used in the photographic art in the preparation of antihalation layers.
  • an antihalation dye can be used instead of colloidal carbon.
  • the dye may be directly mixed with the cellulose ester, ie with cellulose acetate hexahydroor tetrahydrophthalate, or the cellulose ester layer may be applied to the support and a dye coating may be applied thereover so as to penetrate into the surface only of the cellulose ester coating. Proceeding in this manner avoids migration of the dye into the film support itself particularly in the case of a dye which may have a tendency to migrate from one layer to another.
  • the antihalation material employed in the cellulose ester layer is present in suflicient amount to absorb to a substantial degree the light which passes through the film base upon exposing the photographic film.
  • the carbon used is desirably one which can be dispersed with the antihalation binder either by a hot milling technique, by a homogenizer, by a Kady mill or by some type of paint mill, e.g., Peerless carbon black sold by the Columbian Carbon Co.
  • the lower alkylmethacrylate-methacrylic acid copolymer is simply incorporated with the cellulose acetate hexahydroor tetrahydrophthalate, with or without antihalation material, by conventional methods for obtaining homogeneous mixtures such as agitation, mixing, mechanical blending, etc., preferably in a mutual solvent for these polymeric materials.
  • the proportions of cellulose acetate hexahydroor tetrahydrophthalate to the said copolymer can vary over a wide range depending, for example, upon the degree of moisture resistance or removability required of the antihalation layer.
  • the total solids in the coating compositions can advantageously range from about 2 to or even more if desired.
  • the thickness of the antihalation layer from the above compositions can vary from 0.00005 to 0.00010 inch, although excellent results are obtainable with layers of greater thickness.
  • These compositions are applied to the support materials, and more especially to cellulose ester film supports, e.g. cellulose acetate, in the manner previously described herein.
  • the antihalation dye compounds may also be either incorporated in the coating compositions or they may be applied from suitable solutions thereof over the coated layer. If desired, conventional antistatic materials may also be included in the above described compositions.
  • Suitable alkali dispersible lower alkylmethacrylatemethacrylic acid copolymers wherein the said alkyl group 4 is straightor branch-chained, and contains from 1 to 4 carbon atoms, include methylmethacrylate-methacrylic acid, ethylmethacrylate-methacrylic acid, propylmethacrylate-methacrylic acid, isopropylmethacrylate-methacrylic acid, butylmethacrylate-methacrylic acid, etc.
  • copolymers wherein the molar ratios of the alkylmethacrylate component to the methacrylic acid component are advantageous for good alkali-dispersibility from 1:3 to 3:2 (equivalent on a weight basis to approximately from 28 to 72% of alkylmethacrylate units and conversely from 72 to 28% of methacrylic acid units).
  • Such copolymers are known substances, and methods for their preparation are well known to the art. These copolymers while generally soluble in aqueous alkaline solutions, in the presence of the cellulose acetate tetrahydroand hexahydrophthalates dissolve slowly in the alkaline photographic solutions. It is not understood how these cellulose estersand copolymers coact so as to effect removability of the antihalation as fine particles in the alkaline developer solutions.
  • a support 10 of any suitable material such as cellulose ester or synthetic resin is coated with a photosensitive emulsion layer 11 or with a suitable subbing layer (not shown) between the support 10 and the emulsion layer 11 and on the opposite side with an antihalation layer 12 consisting of cellulose acetate hexahydroor tetrahydrophthalate, preferably in admixture with a copolymer of a lower alkylmethacrylate and methacrylic acid, and dispersed thereon colloidal carbon or carrying a dye having antihalation properties.
  • an antihalation layer 12 consisting of cellulose acetate hexahydroor tetrahydrophthalate, preferably in admixture with a copolymer of a lower alkylmethacrylate and methacrylic acid, and dispersed thereon colloidal carbon or carrying a dye having antihalation properties.
  • Example 1 There was applied to a cellulose triacetate film support on one side a gelatin-silver halide photographic emulsion layer and on the opposite side an antihalation layer from a coating composition composed of the following:
  • the antihalation dye penetrates into the surface of the cellulose ester coating but there was no migration of the dye to the film base proper.
  • Example 3 This example illustrates an embodiment of the invention wherein a mixture of cellulose acetate hexahydrophthalate and a lower alkylmethacrylate-methacrylic acid copolymer was employed as the carrier for the antihalation compound.
  • Percent Methyl methacrylate-methacrylic acid copolymer (1:1 mole ratio of ester to acid components) 2.00 Cellulose acetate hexahydrophthalate (36% hexahydrophthalyl) 1.50 Acetone 11.00 Methyl Cellosolve 27.00 Ethyl alcohol 40.40 Distilled water 18.00 Syloid #311 (a trade name for a synthetic silica matting agent sold by Davison Chemical Corp.) 0.10
  • the solvent composition in above Example 3 can be varied substantially and still produce excellent antihalation layers.
  • the acetone can vary about from 8 to 12%, the methyl cellosolve about from 18 to 35%, the distilled water about from to 20%, and the ethyl alcohol can vary sufiiciently to make up a total of 100% of composition.
  • Methanol can replace the ethyl alcohol.
  • the cellulose acetate hexahydrophthalate can be replaced wholly or in part by cellulose acetate tetrahydrophthalate.
  • the mentioned silica is used as a matting agent and is optional, but when used it can vary advantageously about from 0.05 to 0.20%.
  • Other silicas can also be used, if desired, such as Ludox AM (a trade name for an aluminum modified colloidal silica sold by E. I. du Pont de Nemours and Co.).
  • the dye compounds employed in the preceding example are well known.
  • the dye compounds used in above Example 3 are described in Gaspar US. Patent No. 2,274,782, issued Mar. 3, 1942, or in Heseltine US. Patent No. 3,148,187, issued Sept. 8, 1964.
  • Other known antihalation dyes can also be used in our invention.
  • a photographic film support provided with a layer comprising a cellulose ester containing acetate radicals and radicals selected from the group consisting of hexahydrophthalyl and tetrahydrophthalyl and antihalation material.
  • Photographic film support in accordance with claim 3 wherein said antihalation material is colloidal carbon.
  • Photographic film support in accordance with claim 3 wherein said antihalation material is an antihalation dye compound.
  • Photographic film support in accordance with claim 7 wherein said antihalation material is an antihalation dye compound.
  • a photographic film comprising a film support having on one side a gelatin-silver halide emulsion layer and having on the opposite side an antihalation layer comprising a cellulose ester containing acetate radicals and radicals selected from the group consisting of hexahydrophthalyl and tetrahydrophthalyl and antihalation material.
  • said antihalation layer also contains a copolymer of a lower alkylmethacrylate and methacrylic acid, in the molar ratio of from 1:3 to 3:2 of said alkylmethacrylate to said methacrylic acid.
  • a photographic film in accordance with claim 11 wherein said antihalation material is colloidal carbon.
  • a photographic film in accordance with claim 11 wherein said antihalation material is an antihalation dye compound.
  • a photographic film in accordance with claim 15 wherein said antihalation material is an antihalation dye compound.
  • An antihalation composition comprising a cellulose ester containing acetate radicals and radicals selected from the group consisting of hexahydrophthalyl and tetrahydrophthalyl, and antihalation material.
  • compositions in accordance with claim 17 wherein said composition also contains a copolymer of a lower alkylmethacrylate and methacryiic acid, in the molar ratio of from 1:3 to 3:2 of said alkylmethacrylate to said methacrylic acid.
  • An antihalation composition of claim 19 wherein said antihalation material is an antihalation dye compound.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
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US580084A 1964-09-29 1966-09-16 Removable antihalation layers for photographic film Expired - Lifetime US3392022A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DE19651472857 DE1472857C (de) 1964-09-29 1965-09-17 Photographisches Aufzeichnungsmaterial mit Lichthofschutzschicht
FR32064A FR1447096A (fr) 1964-09-29 1965-09-21 Couche anti-halo éliminable en milieu basique et son utilisation dans les produits photographiques
BE669912A BE669912A (xx) 1964-09-29 1965-09-21
GB40927/65A GB1115935A (en) 1964-09-29 1965-09-27 Removable antihalation layers for photographic film
US580084A US3392022A (en) 1964-09-29 1966-09-16 Removable antihalation layers for photographic film
DE1597543A DE1597543C3 (de) 1964-09-29 1967-09-11 Photographisches Aufzeichnungsmaterial mit Lichthofschutzschicht
GB41929/67A GB1192797A (en) 1964-09-29 1967-09-14 Removable Antihalation Layers for Photographic Film
FR120943A FR1536784A (fr) 1964-09-29 1967-09-14 Nouvelle couche antihalo éliminable en milieu basique et ses applications en photographie
BE703939D BE703939A (xx) 1964-09-29 1967-09-15

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US40002864A 1964-09-29 1964-09-29
US580084A US3392022A (en) 1964-09-29 1966-09-16 Removable antihalation layers for photographic film

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US3392022A true US3392022A (en) 1968-07-09

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US580084A Expired - Lifetime US3392022A (en) 1964-09-29 1966-09-16 Removable antihalation layers for photographic film

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US (1) US3392022A (xx)
BE (2) BE669912A (xx)
DE (1) DE1597543C3 (xx)
GB (2) GB1115935A (xx)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6261752B1 (en) 1999-01-29 2001-07-17 Ferrania S.P.A. Alkaline soluble mixture composed of cellulose derivatives

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4917367B1 (xx) * 1970-04-07 1974-04-30
IT1157195B (it) * 1978-09-27 1987-02-11 Minnesota Mining & Mfg Perfezionamento nel procedimento di preparazione di un materiale fotografico avente uno strato antialonico imbibibile in bagno alcalino e rimovibile in bagno acquoso e prodotto ottenuto
US5656746A (en) * 1996-03-28 1997-08-12 The Proctor & Gamble Company Temporary wet strength polymers from oxidized reaction product of polyhydroxy polymer and 1,2-disubstituted carboxylic alkene
US5698688A (en) * 1996-03-28 1997-12-16 The Procter & Gamble Company Aldehyde-modified cellulosic fibers for paper products having high initial wet strength

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1884035A (en) * 1932-02-20 1932-10-25 Eastman Kodak Co Photographic film with antihalation coating
US1954337A (en) * 1932-10-01 1934-04-10 Eastman Kodak Co Superficial coating for photographic elements
US2327828A (en) * 1941-03-26 1943-08-24 Eastman Kodak Co Colloidal carbon antihalation layer
US2976168A (en) * 1959-03-06 1961-03-21 Eastman Kodak Co Method of applying antihalation layers to polyester film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1884035A (en) * 1932-02-20 1932-10-25 Eastman Kodak Co Photographic film with antihalation coating
US1954337A (en) * 1932-10-01 1934-04-10 Eastman Kodak Co Superficial coating for photographic elements
US2327828A (en) * 1941-03-26 1943-08-24 Eastman Kodak Co Colloidal carbon antihalation layer
US2976168A (en) * 1959-03-06 1961-03-21 Eastman Kodak Co Method of applying antihalation layers to polyester film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6261752B1 (en) 1999-01-29 2001-07-17 Ferrania S.P.A. Alkaline soluble mixture composed of cellulose derivatives

Also Published As

Publication number Publication date
DE1597543A1 (de) 1970-08-13
DE1472857A1 (de) 1969-01-09
DE1597543B2 (de) 1974-08-08
GB1115935A (en) 1968-06-06
BE669912A (xx) 1966-01-17
GB1192797A (en) 1970-05-20
DE1597543C3 (de) 1975-03-27
BE703939A (xx) 1968-02-01

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