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EP0684278A1 - Poymères contenant du 4,4'-bis(5-methyl-2-benzoxazolyl) stilbène comme unique azurant optique - Google Patents

Poymères contenant du 4,4'-bis(5-methyl-2-benzoxazolyl) stilbène comme unique azurant optique Download PDF

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Publication number
EP0684278A1
EP0684278A1 EP95420123A EP95420123A EP0684278A1 EP 0684278 A1 EP0684278 A1 EP 0684278A1 EP 95420123 A EP95420123 A EP 95420123A EP 95420123 A EP95420123 A EP 95420123A EP 0684278 A1 EP0684278 A1 EP 0684278A1
Authority
EP
European Patent Office
Prior art keywords
polymer
optical brightener
bis
benzoxazolyl
stilbene
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.)
Withdrawn
Application number
EP95420123A
Other languages
German (de)
English (en)
Inventor
Richard Hsu-Shien C/O Eastman Kodak Co. Wang
Todd Richard C/O Eastman Kodak Co. Skochdopole
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
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0684278A1 publication Critical patent/EP0684278A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—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
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes

Definitions

  • This invention relates to polymers comprising an optical brightener and the use of such polymers in photographic elements.
  • optical brighteners have many commercial uses. To make polymer products attractively white, optical brighteners are used to mask the inherent yellowness of the polymers and to brighten their white appearance. Such polymers find use in, for example, photographic supports and elements comprising a paper base material having thereon a polyolefin coating containing a white pigment and an optical brightener. These supports are particularly useful in photographic elements such as color prints because they exhibit good brightness and excellent dimensional stability and are highly resistant to the action of aqueous acid and alkaline photographic processing solutions.
  • the polyolefin coating provides a very smooth surface which is desirable when thin layers, such as silver halide emulsion layers, are to be coated thereover. US-A-3,411,908 described such as support which has achieved widespread commercial acceptance.
  • optical brightener The purpose of the optical brightener is to make the white areas of the support appear even brighter.
  • the optical brightener fluoresces upon irradiation with UV (ultraviolet) light, emitting visible light, usually bluish in hue, thus enhancing the brightness of the support.
  • Optical brighteners for use in photographic print materials must absorb UV light, especially in the region from the brightness of the print, and have the desired brightening power.
  • the optical brightener must be nonmigrating so that it remains in the polyolefin coating and does not exude as a surface film on the polyolefin. Such exudation not only can give rise to a nonuniform brightness of the reflection surface of the support, but also readily transfers to any other surface contacted with it. For example, brightener transferred nonuniformly to the back side of the adjacent layer of support results in visual imperfections. Brightener when migrated to the surface of the front side, can when would in roll form, adversely affect subsequent coating and finishing operations and, in consequence, the quality and performance of the final element.
  • US-A-4,794,071 discloses a photographic element containing a fluorescent bis(benzoxazolyl) stilbene optical brightener mixture.
  • the support in the disclosed element is comprised of a paper base material having thereon a polyolefin coating containing a white pigment and a mixture of optical brighteners, such mixture comprising certain fluorescent bis(benzoxazolyl)stilbenes.
  • the present invention provides a polymer comprising 4,4'-bis(5-methyl-2 benzoxazolyl) stilbene as the sole optical brightener.
  • the use of a single optical brightener from the mixture unexpectedly provides improvements in resistance to exuding and improved optical brightening.
  • the invention further provides a photographic element comprising a paper support having at least one side thereof and a polymer coating containing a white pigment and 4,4'-bis(5-methyl-2 benzoxazolyl) stilbene as the sole optical brightener.
  • the 4,4'-bis(5-methyl-2 benzoxazolyl) stilbene has the structure:
  • the amount of the brightener which is used in the polymer is an amount effective to brighten the reflective layer.
  • Such amounts of the mixture can be from 0.01 percent to 0.25, preferably 0.04 to 0.10, percent by weight based on the total weight of the polymer, including the white pigment.
  • the polymer can be any polymer, especially polyolefins and polyvinyl chloride. Representative of these materials are polyethylene, polypropylene, polystyrene, polybutylene, and copolymers thereof. Polyethylene of low, medium or high density is preferred.
  • the polyolefin can by copolymerized with one or more copolymerizable monomers including vinyl stearate, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, acrylamide, methacrylic acid, methylmethacrylate, ethyl methacrylate, metacrylamide, butadiene, isoprene, and vinyl chloride.
  • the polymers can be copolymers with polyesters, such as polyethylene terephthalate, polysulfones, polyurethanes, polyvinyls, polycarbonates, cellulose esters, such as cellulose acetate and cellulose propionate, and polyacrylates.
  • polyesters such as polyethylene terephthalate, polysulfones, polyurethanes, polyvinyls, polycarbonates, cellulose esters, such as cellulose acetate and cellulose propionate, and polyacrylates.
  • Preferred polyolefins are film forming and adhesive to paper.
  • Polyethylene having a density in the range of from 0.910 g/cm3 is particularly preferred.
  • the optical brightener can be incorporated into the polymer by conventional methods. Preferred are methods so that the brightener is uniformly dispersed within a polyolefin. Such methods include a melt extrusion process, a kneader extruder, a roll mill, a high shear mixer, or a twin-screw compounder.
  • the white pigment incorporated in the polymer layer can be, calcium carbonate, titanium dioxide, zinc oxide, zinc sulfide, zirconium dioxide, white lead, lead sulfate, lead chloride, lead aluminate, lead phthalate, antimony trioxide, white bismuth, tin oxide, white manganes, white tungsten and combination thereof.
  • the pigment is used in any form that is conveniently dispersed within the polymer.
  • the preferred pigment is titanium dioxide.
  • the titanium dioxide preferably is anatase, rutile or combinations of these forms.
  • Enhanced image resolution in a photographic element can be obtained by the addition of functional amounts of such highly white-light reflective pigments to the polyolefin layer.
  • the white pigment is used in the range from 3 to 35 percent, more preferably 5 to 25 percent by weight based on the total weight of the polyolefin coating. Titanium dioxide at levels of 5 to 20 percent is particularly useful.
  • the polymer coating can contain, if desired, a variety of additives including antioxidants such as 4,4'-butylidene-bis(6-tert-butyl-meta-cresol), dilauryl-3,3'-thiodipropionate, N-butylated-p-aminiphenol, 2,6-ditert-butyl-p-cresol, 2,6-di-tert-butyl-4-methylphenol, N,N-disalicyidene-1,2-diaminipropane, tetra(2,4-di-tert-butylphenyl)-4,4'-diphenyldiphenyldiphosphonite, octadecyl 3-(3'',5'-di-tert-butyl-4'-hydroxyphenyl propionate), combinations of the above, and the like; heat stabilizers, such as higher aliphatic acid metal salts such as magnesium stea
  • emulsion side resins can contain one or more pigments, such as the blue, violet or magenta pigments described in US-A-3,501,298, or pigments such as barium sulfate, colloidal silica, calcium carbonate and the like.
  • pigments such as the blue, violet or magenta pigments described in US-A-3,501,298, or pigments such as barium sulfate, colloidal silica, calcium carbonate and the like.
  • the paper base material employed in accordance with the invention can be any paper base material which as heretofore been considered useful for photographic support.
  • the weight and thickness of the support can be varied depending on the intended use. A preferred weight range is from 20 g/m2 to 500 g/m2. Preferred thicknesses are 20 mm to 500 mm. It is preferred to use a paper base material calendered to a smooth surface.
  • the paper base material can be made from any suitable paper stock preferably comprising hard or softwood. Either bleached or unbleached pulp can be utilized as desired.
  • the paper base material can also be prepared from partially esterified cellulose fibers or from a blend of wood cellulose and a suitable synthetic fiber such as a blend of wood cellulose and polyethylene fiber.
  • the paper base material can contain, if desired, agents to increase the strength of the paper such as wet strength resins, for example, the amino-aldehyde or polyamideepichlorohydrin resins, and dry strength agents, for example, starches, including both ordinary starch and cationic starch, or polyacrylamide resins.
  • wet strength resins for example, the amino-aldehyde or polyamideepichlorohydrin resins
  • dry strength agents for example, starches, including both ordinary starch and cationic starch, or polyacrylamide resins.
  • the amino-aldehyde, polyamide-epichlorohydrin and polyacylamide resins are used in combination as described in US-A-3,592,731.
  • water soluble gums for example, cellulose ethers such as carboxymethyl cellulose, sizing agents, for example, a ketene dimer, sodium stearate which is precipitated onto the pulp fibers with a polyvalent metal salt such as alum, aluminum chloride or aluminum sulfate; fluorescing agent; antistatic agents; filters, including clays or pigments such as titanium dioxide; dyes; and so forth.
  • cellulose ethers such as carboxymethyl cellulose
  • sizing agents for example, a ketene dimer, sodium stearate which is precipitated onto the pulp fibers with a polyvalent metal salt such as alum, aluminum chloride or aluminum sulfate
  • fluorescing agent such as alum, aluminum chloride or aluminum sulfate
  • antistatic agents such as titanium dioxide
  • filters including clays or pigments such as titanium dioxide; dyes; and so forth.
  • paper is a preferred support, the nature of the support is not a critical feature of the invention.
  • the paper support may be substituted by a synthetic paper or a plastic film.
  • the coating of the paper base material with the polyolefin preferably is by extrusion from a hot melt as is known in the art.
  • the paper base material preferably is treated with corona discharge to obtain good adhesion before the polyolefin coating is extruded thereon, as described in US-A-3,411,908.
  • the invention can be practiced within a wide range of extrusion temperatures, for example, 150°-350°C., and speeds for example, 60 m/min. to 460 m/min., depending on the particular intended application of the support. For many applications, preferred extrusion temperatures are 310°-330°C.
  • the optical brightener is stable to such temperatures.
  • the aforedescribed polyolefin coating over which the silver halide emulsion is applied, is coated onto the paper base material in a coverage of 1 to 100 g/m2, at a uniform thickness ranging from 1 to 100 mm.
  • About the same coverage of clear polyetheylene coating preferably is applied to the side of the paper base material opposite to the pigmented polyolefin coating.
  • the polyolefin coatings are particularly effective in preventing acid and alkaline photographic processing solutions from penetrating to the paper base.
  • photographic elements in accordance with this invention comprise the above-described optically brightened photographic support and at least one silver halide emulsion layer.
  • Any of the known silver halide emulsion layers such as those described in Research Disclosure , Vol. 176, December 1978, Item 7643 and Research Disclosure , Vol. 225, January 1983, Item 22534, the disclosures of which are hereby incorporated by reference in their entirety, are useful in preparing photographic elements in accordance with this invention.
  • the photographic element is prepared by coating the support with one or more layers comprising a dispersion of silver halide crystals in an aqueous solution of gelatin, and optionally, one or more stubbing layers, and so forth.
  • the coating process is generally carried out on a continuously operating machine wherein a single layer or a plurality of layers are applied to the support.
  • layers are generally coated simultaneously on the support as described in US-A-2,761,791, and US-A-3,508,947. Additional useful coating and drying procedures are described in Research Disclosure , Vol. 176, December 1978, Item 17643.
  • Blend A A mixture of 60% polyethylene, 31% TiO2, 7.5% ZnO, 1.25% calcium stearate, 0.25% antioxidant, 0.15% optical brightener and low level of red and blue colorants was blended extruded at 200°C and pelletized. This was labeled Blend A
  • CIELAB b* values as specified by the CIELAB 1976 colorimetricy measurement system, were obtained in two different measurement modes: (1) UVI (ultraviolet portion of the spectrum included in the incident light beam) and (2) UVO (ultraviolet portion of the spectrum filtered out of the incident beam).
  • a measure of the effectiveness of the optical brightener was obtained by subtracting the value of b* at UVO conditions from b* at UVI conditions. This calculates the contribution to the blueness of the support by the included optical brightener. The larger the negative number for this value, called delta b*, the larger the optical brightening effect.
  • Coated paper samples were also tested for optical brightener migration. This was accomplished by placing stacks of 4-inch (0.1016 mm) wide by 12-inch (0.3048 mm) long strips in an oven controlled to a specific temperature and relative humidity. Samples were periodically withdrawn, examined under UV light and given a visual rating based on the amount of the optical brightener present at the surface of the polyethylene coating. The number of days needed to reach a severe level of migration was recorded. A severe level of migration had perhaps 20% or more of the surface coated with the optical brightener (visible as yellowness on the surface, due to its inability to fluoresce once it crystallizes at the surfaces).
  • a mixture of PVC (100 parts per hundred) (Geon 300, 100 phr), Dioctyl phthalate (40 parts per hundred), heat stabilizer comprising a mixture of zinc, barium and cadnium carboxylates (1.5 parts per hundred), TiO2 (2 parts per hundred), and optical brightener (0.01 and 0.01 parts per hundred) were blended, dispersed, hot two-roll milled at 160-165°C and pressed into 30-mil (0.735 mm) flexible film.
  • the yellowness of these film samples were determined by using a Gardner color difference meter and described as b-values
  • Compound I is the most effective fluorescent whitening agent for PVC among all optical brighteners tested, including mixtures of optical brighteners that include compound I.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Paper (AREA)
EP95420123A 1994-05-24 1995-05-10 Poymères contenant du 4,4'-bis(5-methyl-2-benzoxazolyl) stilbène comme unique azurant optique Withdrawn EP0684278A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24827994A 1994-05-24 1994-05-24
US248279 1994-05-24

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EP0684278A1 true EP0684278A1 (fr) 1995-11-29

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EP95420123A Withdrawn EP0684278A1 (fr) 1994-05-24 1995-05-10 Poymères contenant du 4,4'-bis(5-methyl-2-benzoxazolyl) stilbène comme unique azurant optique

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5817448A (en) * 1996-01-25 1998-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0271256A (ja) * 1988-06-24 1990-03-09 Mitsubishi Paper Mills Ltd 写真用支持体
JPH02168249A (ja) * 1988-12-22 1990-06-28 Mitsubishi Paper Mills Ltd 写真材料の処理方法
US5075206A (en) * 1989-03-28 1991-12-24 Mitsubishi Paper Mills Limited Photographic support with titanium dioxide pigment polyolefin layer on a substrate
US5198330A (en) * 1991-10-11 1993-03-30 Eastman Kodak Company Photographic element with optical brighteners having reduced migration

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0271256A (ja) * 1988-06-24 1990-03-09 Mitsubishi Paper Mills Ltd 写真用支持体
JPH02168249A (ja) * 1988-12-22 1990-06-28 Mitsubishi Paper Mills Ltd 写真材料の処理方法
US5075206A (en) * 1989-03-28 1991-12-24 Mitsubishi Paper Mills Limited Photographic support with titanium dioxide pigment polyolefin layer on a substrate
US5198330A (en) * 1991-10-11 1993-03-30 Eastman Kodak Company Photographic element with optical brighteners having reduced migration

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 113, no. 26, 24 December 1990, Columbus, Ohio, US; abstract no. 241360 *
CHEMICAL ABSTRACTS, vol. 114, no. 18, 6 May 1991, Columbus, Ohio, US; abstract no. 174874 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5817448A (en) * 1996-01-25 1998-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic material and method for processing the same

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