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US2691579A - Ultraviolet absorbing layers - Google Patents

Ultraviolet absorbing layers Download PDF

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Publication number
US2691579A
US2691579A US317896A US31789652A US2691579A US 2691579 A US2691579 A US 2691579A US 317896 A US317896 A US 317896A US 31789652 A US31789652 A US 31789652A US 2691579 A US2691579 A US 2691579A
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US
United States
Prior art keywords
photographic
styrene
gelatin
ultraviolet absorbing
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
US317896A
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English (en)
Inventor
Scheuring S Fierke
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
Original Assignee
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 BE523921D priority Critical patent/BE523921A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US317896A priority patent/US2691579A/en
Priority to DEE7987A priority patent/DE968112C/de
Priority to FR1099431D priority patent/FR1099431A/fr
Priority to GB30272/53A priority patent/GB749869A/en
Application granted granted Critical
Publication of US2691579A publication Critical patent/US2691579A/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
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • 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
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching

Definitions

  • This invention relates to new photographic elements protected against the harmful effects of ultraviolet radiation.
  • Color photographs on multilayer photographic material are susceptible to fading and discoloration by the action of ultraviolet radiation to which the photographs are subjected during viewing. It is also known that the residual couplers contained in the emulsion layers after formation of the picture images in certain processes, are attacked by ultraviolet radiation and form a stain which is undesirable in the finished photograph.
  • the action of ultraviolet radiation on finished color photographs is particularly noticeable in positive prints on paper or other opaque supports, since this type of print is frequently'viewed in daylight where there is a high content of ultraviolet radiation; This dye fading and yellowing appears to be caused primarily by those wavelengths of light which lie close to the visual region of the spectrum, i. e. 360-400 millimicrons.
  • the accompanying drawing illustrates schematically a cross-sectional View of a sensitive photographic element having an ultraviolet filter layer containing a synthetic resin which acts as a mordant for the ultraviolet absorbing compounds used according to my invention.
  • the ultraviolet absorbing compound is incorporated in the photographic element by bathing the photographic element, which contains a gelatin layer having incorporated therein one of the synthetic resins mentioned above, in an aqueous solution of the ultraviolet absorbing compound.
  • the ultraviolet absorbing compound which in this case is a particular type of cyan ne dye, can be incorporated directly in the gelatin layer before or during coating.
  • gelatin instead of using gelatin as the binder, other water-permeable, hydrophylic colloids can be used, such as synthetic resins (e. g. polyvinyl acetals, hydrolyzed polyvinyl acetate, etc.), hydrolyzed cellulose esters, etc.
  • the ultraviolet filter need not be an outer layer, but this layer can be placed over one of the layers subject to the harmful effects of ultraviolet radiation.
  • the ultraviolet filter layer can be placed between the blue and green sensitive layers.
  • the ultraviolet filter layer can be placed between the green and red sensitive layers. The amount of ultraviolet absorbing compound can be varied, depending upon the effect desired and the use to which the material is to be put.
  • R2 and R3 each represents an alkyl group, such as methyl, ethyl, n-propyl, etc.
  • R4 represents an alkyl group containing at least 9 carbon atoms, such as nnonyl, n-decyl, n-lauryl, n-cetyl, etc.
  • X represents an acid radical, such as chloride, bromide, iodide, perchlorate, p-toluenesulfonate, benzenesulfonate, etc.
  • Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, such as benzothiazole, 4-chlorobenzdthiazole, 5-chlorobenzothiazole, 5-methylbe'nzothiazole, 5-p
  • the dyes represented by Formula I above can advantageously be prepared according to the methods described in U. S. Patent 2,108,485 or British Patent 423,792, or other methods known in the art. Also the dyes of Formula I can be prepared according to the method described in Jones et a1. U. S. application Serial No. 291,802, filed June 4, 1952. The cyanine dyes of Formula '11 above can be prepared according to the method described in British Patent 529,440, for example.
  • Typical dyes which can be employed in my invention comprise those represented by the following formulas:
  • the coating was then-dried andsoaked in a 1% aqueous solution of 3,3diethyloxacyanine chloride for 10 minutes at'68" F.
  • the pI-I The coating was then washed running "water for 5 minutes, dried, mounted anda spectrophotomet'ric measurement made which showed that the coatin'g absorbed substantially 'all radiation between 360 and 400 'millimicrons, but transmitted substantially "all radiation of wavelengths greater than '400-mil1imicrons.
  • EXAMPLE 2 A coating was made in substantially the same manner as that described in Example 1 above, except that styrene-maleamic acid resin obtained according to U. S. Patent 2,313,565 was employed instead of the Amberlite. The coating absorbed substantially all radiation between 360 and 4.00 millimicrons but transmitted substantially all radiation of wavelength greater than 400 millimicrons.
  • EXAMPLE 3 A series of cyanine dyes were adsorbed onto a coating containing only gelatin, and the same cyanine dyes were adsorbed onto a second coating containing styrene-maleamic acid resin plus gelatin. The following procedure was used:
  • 0.1 g. of the cyanine dye was dissolved in 50 cc. of ethyl alcohol and then 50 cc. of water was added to the solution. The dyes remained in solution, and the two coatings were immersed in the solution for 5 minutes, then washed for 20 minutes in running water and dried. Density and wavelength of absorption were obtained to evaluate the retention characteristics of the dyes. The following results were noted.
  • the coatings employed in Examples 1 and 2 respectively were two strips which had been developed in a complete color process.
  • the support employed in the photographic elements of my invention can be either transparent, such as cellulose acetate, cellulose nitrate, etc., or opaque, such as paper, metal, etc.
  • the accompanying drawing illustrates schematically a cross-sectional view of a photographic element containing a layer having incorporated therein 3,3-diethylthiacyanine p-toluenesulfonate and a styrene-maleamic acid resin.
  • a support In of anysuitable material such as cellulose acetate or paper, for example, having thereon a light-sensitive photographic silver halide emulsion layer II is coated with a filter layer [2 of gelatin having incorporated therein 3,3'-diethylthiacyanine p-toluenesulfonate and a styrenemaleamic acid resin.
  • the filter layer 12 serves to protect the photographic element from the harmful efiects of ultraviolet radiation both during exposure and after completion of photographic processes. It will be understood that the drawing is merely representative of other structures which can be employed in my invention, and that the element can have other layers, not shown, such as additional light-sensitive layers, subbing layers, antihalation layers, etc.
  • the styrene-maleamic resins used in my invention have been previously described in the prior art.
  • Such resins can be designated as having a polymeric hydrocarbon chain having substituted thereon at recurring intervals phenyl groups and carboxyl groups, together with carbonamide and/or carboxylic imide groups.
  • Similar useful resins having such structure can be obtained from styrene-acrylic acid, styrenemethacrylic acid, or styrene-itaconic acid interpolymers (instead of from styrene-maleic anhydride polymers as is described above).
  • EXAMPLE B PoZystyrene-maleamic acid ammonium salt The following reagents were put to reflux in an all glass reflux outfit equipped with a mechanical stirrer. Conditions were maintained anhydrous by calcium chloride tubes on all openings to the atmosphere.
  • the sitrrer was turned on and dry ammonia was bubbled into the reaction mixture continuously for 3 /2 hours. During this time the temperature within the reaction mixture rose from a starting temperature of 23 C. to 45 C, and
  • the residual toluene was then extracted with absolute "alcohol by stirring the product with 2-3 liter portions of absolute ethyl alcohol and filtering onto a Buchner funnel. The product was then dried-as'above.
  • a photographic element comprising a sup- .port, a' photographic gelatino-silver halide emulsion layer, and a gelatin layer containing (1') an interpolymer of styrene and an unsaturated, aliphatic carboxylic compound, said interpolymer having a polymeric hydrocarbon chain having substituted at recurring intervals phenyl groups and carboxylic :groups, together with groups selected from the group consisting of carbonamide and 'carboxylic imidegroups, and (2) an ultraviolet absorbing compound selected from those represented by the following two general formulas:
  • R, R1, R2, and R3 each "represents an alkyl group
  • R4 represents an alkyl group containing at least nine carbon atomsQX represents an acid radical
  • Z and Z1-each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected "from those of the benzoxazole series, those of the thiazoline series, those of the thiazole series, and those of the benzothiazole series.
  • a photographic element comprising a supiport, :a photographic .ge'latino-silver halide emulsion layer, and a gelatin layersuperposedonsaid iphotograp'hic gelatino-silver halide emulsion, said gelatin layer containing (1) an interpolymer of styrene and a maleamic acid, and (2) an ultraviolet absorbing compound selected from those represented by the following general formula:
  • a finished photographic element comprising a-support having thereon a plurality of developed and fixed photographic emulsion layers containing coupled-dye images, at least one of said dye images being subject to fading by the action of ultraviolet radiation, said emulsion layer containing a coupled-dye image subject to fading lying between said support and a gelatin layer containing (1) an interploymer of styrene and a maleamicacid and (2) an ultraviolet absorbing compound selected from those represented by the wherein R, R1, R2, and R3 each represents an alkyl group, R4 represents an alkyl group containing at least nine carbon atoms, X represents anacid radicaLand Z and Z1 each represents the non-metallic atoms necessary to complete a 'heterocyclic nucleus selected from the group consisting of those of the benaoxazole series, those of the thiazoline series, those of the thiazole seriesand those of the benzothiazole series.
  • a photographic element according to claim l wherein the support is a paper support.
  • a photographic element comprising a support, a photographic gelatino-silver halide emulsion'layer, and a gelatin layer containing (1) an interpolymer of styrene and a maleamic acid and 2) an ultraviolet absorbing compound having the followingformula:
  • a photographic element comprising a sup- HiCr- "port, a photographic gelatino-silver halide emulsion layer, and a gelatin layer containing (1) an interpolymer of styrene and a maleamic acid and (2) an ultraviolet absorbing compound having the following formula:
  • said photographic gelatino-silver halide emulsion layer lying between said support and said gelatin layer.
  • a photographic element comprising a support, a photographic gelatino-silver halide emulsion layer, and a gelatin layer containing (1) an 5 interpolymer'of styrene and a maleamic acid and .10 (2) an ultraviolet absorbing compound having the following formula:
  • a photographic element comprising a support, a photographic gelatino-silver halide emulsion layer, and a gelatin layer containing (1) an interpolymer of styrene and a maleamic acid and (2) an ultraviolet absorbing compound having the following formula:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US317896A 1952-10-31 1952-10-31 Ultraviolet absorbing layers Expired - Lifetime US2691579A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE523921D BE523921A (hu) 1952-10-31
US317896A US2691579A (en) 1952-10-31 1952-10-31 Ultraviolet absorbing layers
DEE7987A DE968112C (de) 1952-10-31 1953-10-21 Gegen Einwirkung der ultravioletten Strahlung geschuetztes photographisches, insbesondere farbenphotographisches Material
FR1099431D FR1099431A (fr) 1952-10-31 1953-10-30 Nouveaux produits photographiques
GB30272/53A GB749869A (en) 1952-10-31 1953-11-02 Photographic elements containing ultraviolet radiation absorbing compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US317896A US2691579A (en) 1952-10-31 1952-10-31 Ultraviolet absorbing layers

Publications (1)

Publication Number Publication Date
US2691579A true US2691579A (en) 1954-10-12

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US317896A Expired - Lifetime US2691579A (en) 1952-10-31 1952-10-31 Ultraviolet absorbing layers

Country Status (5)

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US (1) US2691579A (hu)
BE (1) BE523921A (hu)
DE (1) DE968112C (hu)
FR (1) FR1099431A (hu)
GB (1) GB749869A (hu)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2875053A (en) * 1955-05-26 1959-02-24 Eastman Kodak Co Photographic elements containing polymeric esters as ultraviolet absorbing compounds

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1161508B (de) * 1957-08-09 1964-01-16 Pneumatic Scale Corp Verfahren zur Herstellung eines Auslaugbeutels
JP2533333B2 (ja) * 1987-09-01 1996-09-11 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2160907A (en) * 1936-03-31 1939-06-06 Eastman Kodak Co Filter for ultra-violet light

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB594320A (en) * 1945-03-14 1947-11-07 Timken Axle Co Detroit Steering spindle mounting for motor vehicles
DE654900C (de) * 1933-11-04 1938-01-04 I G Farbenindustrie Akt Ges Ultraviolett absorbierendes Lichtfilter
GB524320A (en) * 1939-01-23 1940-08-05 Kodak Ltd Photographic elements having short-wave light absorbing filters
BE466374A (hu) * 1939-02-17
US2313565A (en) * 1939-10-31 1943-03-09 Eastman Kodak Co Resin and its preparation
US2405106A (en) * 1944-10-27 1946-07-30 Eastman Kodak Co Photographic filter and antihalation layers
BE500324A (hu) * 1949-12-31

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2160907A (en) * 1936-03-31 1939-06-06 Eastman Kodak Co Filter for ultra-violet light

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2875053A (en) * 1955-05-26 1959-02-24 Eastman Kodak Co Photographic elements containing polymeric esters as ultraviolet absorbing compounds

Also Published As

Publication number Publication date
DE968112C (de) 1958-01-16
FR1099431A (fr) 1955-09-05
GB749869A (en) 1956-06-06
BE523921A (hu)

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