US2391181A - Protective overcoating - Google Patents

Protective overcoating Download PDF

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Publication number
US2391181A
US2391181A US533742A US53374244A US2391181A US 2391181 A US2391181 A US 2391181A US 533742 A US533742 A US 533742A US 53374244 A US53374244 A US 53374244A US 2391181 A US2391181 A US 2391181A
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US
United States
Prior art keywords
resin
emulsion
layer
photographic
methacrylic acid
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
US533742A
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English (en)
Inventor
Louis M Minsk
Walter J Weyerts
Wendell H Mcdowell
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.)
Eastman Kodak Co
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Eastman Kodak Co
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
Priority to BE432945D priority Critical patent/BE432945A/xx
Priority to FR956711D priority patent/FR956711A/fr
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US533742A priority patent/US2391181A/en
Application granted granted Critical
Publication of US2391181A publication Critical patent/US2391181A/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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K23/00—DC commutator motors or generators having mechanical commutator; Universal AC/DC commutator motors
    • H02K23/62—Motors or generators with stationary armatures and rotating excitation field
    • 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
    • Y10S430/162—Protective or antiabrasion layer

Definitions

  • PROTECTIVE OVERCOATING Filed May 2, 1944 PROTECTIVE O VERC'OA TING E MULS ION SUBB/NG' LAYER- WATERPROOF/N6 LAYER SUPPORT WA TERPROOF/NG' LAYER LOUIS M. MINSK K WALTER J .WE YE'R'IIS' T VENDELL H. M DOWELL INVENTORS BY Q MM A TTORNE YS Patented Dem 18, 194s uurrso s'rA'ra-s PATENT orrics raornc'rivr: OVEROOATING Louis M. Minsk, Walter J. Weyerts, and Wendell 1 H. McDowell, Rochester, N. Y., asslgnors to Eastman Kodak Company, Rochester, N. Y., a
  • This invention relates to photographic material, and particularly to a protective overcoating for photographic emulsions.
  • overcoating layers for photographic emulsions. These layers may be applied before exposure of the photographic emulsion in which case they must be permeable to, or removable in, the photographic developing solutions so that development of the emulsion can take place.
  • an emulsion overcoating consisting of a resin having free acidic groups, such as polyvinyl acetate phthalate or rosin-maleic anhydride resin. These materials are used as overcoatings for the emulsion to prevent action of the water or hypo on the positive emulsion during the printing operation.
  • the materials disclosed in this patent are not uniformly removable in the developing solution and have not proven satisfactory in practice.
  • an object of the present invention to provide a resin overcoating material for photographic emulsions which will permit printing of the emulsions from wet negatives.
  • a further object is to provide an emulsion overcoating material which will be readily removable in alkaline photographic developing solutions, so that development of the exposed emulsion may take place in the customary manner.
  • the overcoating material which we propose to use is made by copolymerizing methacrylic acid and an alkylmethacrylate, such as methyl-@- methacrylate, ethyl-a-methacrylate, or butyl-amethacrylate in a suitable solvent, such as ethyl alcohol, using a catalyst, such as benzoyl peroxide. Mixtures of the alkyl methacrylates may also be employed so that a ternary copolymer is produced.
  • an alkylmethacrylate such as methyl-@- methacrylate, ethyl-a-methacrylate, or butyl-amethacrylate in a suitable solvent, such as ethyl alcohol
  • a catalyst such as benzoyl peroxide
  • the copolymer produced in this way may be precipitated and isolated from the reaction mixture, or the reaction dope may be diluted to form a. suitable coating solution and coated on the emulsion without isolation of the copolymer.
  • suitable coating solution and coated on the emulsion without isolation of the copolymer.
  • Example 1 The following ingredients were placed in a 22- liter round-bottom flask, attached through a glass joint to a large reflux condenser:
  • the reaction mixture was heated on a steam bath and maintained at vigorous reflux for 22 to 30 hours. Th resin was then precipitated by pouring the dope into 20 gallons of cold water which was vigorously stirred. The suspension of resin in water was stirred for an additional 20 to 30 minutes during which time anysoft precipitate hardened.
  • the product was obtained in the form of granules and was then washed with eight 20- gallon portions of hot water, allowing 1 hour soaking with each one. The product was dried at 50 C. We have found that the resin may be centrifuged before drying and then dried at room temperature.
  • the resin dope 01)- tained after heating on the steam 'bath for 22 to 1 30 hours may be used directly for coating after dilution with suitable solvents.
  • Example 2 The reaction mixture was heated on the steam bath under reflux for 19 hours. The dope was then diluted with about an equal volume of absolute alcohol and the resin precipitated by pouring the dope into distilled water. The fibrous precipitate obtained was washed with distilled water.
  • This solution is coated so that after drying a resin concentration of about 0.6 gram per square foot of emulsion surface is obtained.
  • the reaction mixture described above contains substantially equal proportions of methacrylic acid and methyl-a-methacrylate, the latter being slightly in predominance.
  • the proportions of methacrylic acid may vary, however, from about 30% to about 60%, and the proportion of methyl-a-methacrylate from about 70% to about 40%.
  • a typical photographic material constructed according to our invention is shown in the accompanying drawing.
  • 10 is the support of baryta-coated paper having on each side waterproofing layers H of cellulose nitrate applied from the following solution:
  • the cellulose nitrate is preferably a high alcohol soluble, low viscosity material, such as one having a methyl alcohol solubility of l lo-100%, a
  • the baryta coating side of the support is then coated with a subbing layer i2 of gelatin coated from the following solution:
  • the subbing layer I2 is followed by a customary gelatino-silver halide emulsion layer 13 and the protective layer ll of the copolymer of methacrylic acid and methyl-a-methacrylate prepared as described above.
  • a customary gelatino-silver halide emulsion layer 13 and the protective layer ll of the copolymer of methacrylic acid and methyl-a-methacrylate prepared as described above it is desirable to apply a thin gelatin coating over the emulsion before applying the resin layer. It may also be desirable to include plasticizers in the resin dope.
  • the coatings prepared as described above ailord adequate protection for the emulsion against the action ofwater and hypo in the negative during the usual contact printing times.
  • the resin layer does not crack or peel from the emulsion during storage of the sensitive material and is readily removable in the alkaline developing solution upon development of the exposed material.
  • hypo protective over-coatings of our invention can also be applied to sensitive emulsion layers on'supports of cellulose esters, synthetic resins; glass or other materials.
  • Methacrylic acid methyl-a-methacrylate resin grams Ethyl alrnhnl m' 1470 Methyl Cellosolve cc 163 Fuchsine Y grams 6.2 (ii-ethyl 2 benzoxazole) (l-ethyl 2,5-
  • mixtures of resins can be used, such as a mixture of the above resin with a butyl methacrylate-methacrylic acid copolymer.
  • a sensitive photographic element comprising a support having thereon a light-sensitive emulsion layer and over said layer a layer of a copolymer of methacrylic acid and an alkyl methacrylate insoluble in water but soluble in alkaline photographic developing solutions.
  • a sensitive photographic element comprising a support having thereon a light-sensitive emulsion layer and over said layer a layer of a copolymer of methacrylic acid and methyl-@- methacrylate insoluble in water but soluble in alkaline photographic developing solutions.
  • a sensitive photographic element comprising a paper support having thereon a light-sensitive emulsion layer and over said layer a layer of a resin formed by copolymerizing substantially equal parts of methacrylic acid and methyl-amethacrylate, said resin being insoluble in water, but soluble in alkaline photographic processing solutions.
  • a sensitive photographic element comprising a support having thereon a light-sensitive emulsion layer and a superficial layer of a copolymer of methacrylic acid and an alkyl methacrylate insoluble in water but soluble in alkaline photographic developing solutions.
  • a sensitive photographic element comprising a support having thereon a light-sensitive emulsion layer and a superficial layer of a copolymer of methacrylic acid and methy -amethacrylate insoluble in water but soluble in alkaline photographic developing solutions.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
US533742A 1944-05-02 1944-05-02 Protective overcoating Expired - Lifetime US2391181A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE432945D BE432945A (en, 2012) 1944-05-02
FR956711D FR956711A (en, 2012) 1944-05-02
US533742A US2391181A (en) 1944-05-02 1944-05-02 Protective overcoating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US533742A US2391181A (en) 1944-05-02 1944-05-02 Protective overcoating

Publications (1)

Publication Number Publication Date
US2391181A true US2391181A (en) 1945-12-18

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US533742A Expired - Lifetime US2391181A (en) 1944-05-02 1944-05-02 Protective overcoating

Country Status (3)

Country Link
US (1) US2391181A (en, 2012)
BE (1) BE432945A (en, 2012)
FR (1) FR956711A (en, 2012)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2452705A (en) * 1944-03-03 1948-11-02 Ilford Ltd Package of photographic lightsensitive papers
US2563469A (en) * 1947-02-18 1951-08-07 Du Pont Light sensitive elements for color photography
US2590296A (en) * 1947-09-09 1952-03-25 Dufay Chromex Ltd Photographic multilayer stripping film
US2607711A (en) * 1949-10-27 1952-08-19 Minnesota Mining & Mfg Adhesive tapes and liners having low-adhesion coatings
US2686122A (en) * 1947-03-07 1954-08-10 Harold C Purdy Photographic light-sensitive element
US2725296A (en) * 1951-09-14 1955-11-29 Eastman Kodak Co Two-layer integral negative positive photographic material
US2830900A (en) * 1956-10-04 1958-04-15 Polaroid Corp Process of washing and protecting photographic silver images, and photographic products thereof
US2866705A (en) * 1953-07-01 1958-12-30 Polaroid Corp Process of washing and protecting photographic silver images
US2874045A (en) * 1954-02-26 1959-02-17 Polaroid Corp Process of washing and protecting photographic silver images
US2992101A (en) * 1957-02-18 1961-07-11 Eastman Kodak Co Suppression of newton's rings in printing color films
US3201249A (en) * 1961-08-25 1965-08-17 Eastman Kodak Co Composite film element and composition therefor including anti-halation material
US3201251A (en) * 1961-08-21 1965-08-17 Eastman Kodak Co Composite film element
US3253922A (en) * 1961-09-18 1966-05-31 Eastman Kodak Co Anti-static treatment for photographic products on polyethylene coated paper
US3767448A (en) * 1971-11-29 1973-10-23 Eastman Kodak Co Photographic process
US4056396A (en) * 1973-02-12 1977-11-01 Fuji Photo Film Co., Ltd. Layers used to prevent reticulation in photographic elements
DE2730994A1 (de) * 1976-07-08 1978-01-12 Fuji Photo Film Co Ltd Verfahren zur bilderzeugung
US4255515A (en) * 1977-11-19 1981-03-10 Konishiroku Photo Industry Co., Ltd. Photographic films
US4266015A (en) * 1977-09-13 1981-05-05 Minnesota Mining And Manufacturing Company Light sensitive materials with fluorinated polymer antistats
EP0097037A3 (en) * 1982-06-14 1985-01-30 Eastman Kodak Company Radiation-sensitive photographic element having a protective overcoat layer
US5370982A (en) * 1992-10-20 1994-12-06 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US20060147658A1 (en) * 2003-06-18 2006-07-06 Fuji Photo Film B.V. Ink-jet recording medium
US20060222787A1 (en) * 2003-10-03 2006-10-05 Fuji Photo Film B.V. Recording medium
US20060222788A1 (en) * 2003-10-03 2006-10-05 Fuji Photo Film B.V. Recording medium

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2452705A (en) * 1944-03-03 1948-11-02 Ilford Ltd Package of photographic lightsensitive papers
US2563469A (en) * 1947-02-18 1951-08-07 Du Pont Light sensitive elements for color photography
US2686122A (en) * 1947-03-07 1954-08-10 Harold C Purdy Photographic light-sensitive element
US2590296A (en) * 1947-09-09 1952-03-25 Dufay Chromex Ltd Photographic multilayer stripping film
US2607711A (en) * 1949-10-27 1952-08-19 Minnesota Mining & Mfg Adhesive tapes and liners having low-adhesion coatings
US2725296A (en) * 1951-09-14 1955-11-29 Eastman Kodak Co Two-layer integral negative positive photographic material
US2866705A (en) * 1953-07-01 1958-12-30 Polaroid Corp Process of washing and protecting photographic silver images
US2874045A (en) * 1954-02-26 1959-02-17 Polaroid Corp Process of washing and protecting photographic silver images
US2830900A (en) * 1956-10-04 1958-04-15 Polaroid Corp Process of washing and protecting photographic silver images, and photographic products thereof
US2992101A (en) * 1957-02-18 1961-07-11 Eastman Kodak Co Suppression of newton's rings in printing color films
US3201251A (en) * 1961-08-21 1965-08-17 Eastman Kodak Co Composite film element
US3201249A (en) * 1961-08-25 1965-08-17 Eastman Kodak Co Composite film element and composition therefor including anti-halation material
US3253922A (en) * 1961-09-18 1966-05-31 Eastman Kodak Co Anti-static treatment for photographic products on polyethylene coated paper
US3767448A (en) * 1971-11-29 1973-10-23 Eastman Kodak Co Photographic process
US4056396A (en) * 1973-02-12 1977-11-01 Fuji Photo Film Co., Ltd. Layers used to prevent reticulation in photographic elements
DE2730994A1 (de) * 1976-07-08 1978-01-12 Fuji Photo Film Co Ltd Verfahren zur bilderzeugung
US4142894A (en) * 1976-07-08 1979-03-06 Fuji Photo Film Co., Ltd. Method for forming images
US4266015A (en) * 1977-09-13 1981-05-05 Minnesota Mining And Manufacturing Company Light sensitive materials with fluorinated polymer antistats
US4255515A (en) * 1977-11-19 1981-03-10 Konishiroku Photo Industry Co., Ltd. Photographic films
EP0097037A3 (en) * 1982-06-14 1985-01-30 Eastman Kodak Company Radiation-sensitive photographic element having a protective overcoat layer
US5370982A (en) * 1992-10-20 1994-12-06 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US20060147658A1 (en) * 2003-06-18 2006-07-06 Fuji Photo Film B.V. Ink-jet recording medium
US20060159872A1 (en) * 2003-06-18 2006-07-20 Fuji Photo Film B.V. Ink-jet recording medium
US20060222787A1 (en) * 2003-10-03 2006-10-05 Fuji Photo Film B.V. Recording medium
US20060222788A1 (en) * 2003-10-03 2006-10-05 Fuji Photo Film B.V. Recording medium

Also Published As

Publication number Publication date
FR956711A (en, 2012) 1950-02-06
BE432945A (en, 2012)

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