EP0752619B1 - Empfangs- und Matrizenfilms für Farbstoffimbibitionsverfahren - Google Patents

Empfangs- und Matrizenfilms für Farbstoffimbibitionsverfahren Download PDF

Info

Publication number
EP0752619B1
EP0752619B1 EP19960420194 EP96420194A EP0752619B1 EP 0752619 B1 EP0752619 B1 EP 0752619B1 EP 19960420194 EP19960420194 EP 19960420194 EP 96420194 A EP96420194 A EP 96420194A EP 0752619 B1 EP0752619 B1 EP 0752619B1
Authority
EP
European Patent Office
Prior art keywords
polymer
printing blank
dye
layer
blank according
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
EP19960420194
Other languages
English (en)
French (fr)
Other versions
EP0752619A2 (de
EP0752619A3 (de
Inventor
Wayne Arthur C/O Eastman Kodak Co. Bowman
Charles Peter c/o Eastman Kodak Co. Hagmaier
Frank Dean c/o Eastman Kodak Co. Manioci
Mitchell Joseph c/o Eastman Kodak Co Bogdanowicz
Roger Wayne c/o Eastman Kodak Co Nelson
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 claimed from US08/614,454 external-priority patent/US5620833A/en
Priority claimed from US08/614,413 external-priority patent/US5622808A/en
Priority claimed from US08/614,423 external-priority patent/US5709971A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0752619A2 publication Critical patent/EP0752619A2/de
Publication of EP0752619A3 publication Critical patent/EP0752619A3/de
Application granted granted Critical
Publication of EP0752619B1 publication Critical patent/EP0752619B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/25—Dye-imbibition processes; Materials therefor; Preparing or processing such materials

Definitions

  • This invention relates to a photographic imbibition dye transfer process and imbibition printing materials. It relates particularly to improved dye imbibition printing blanks with improved antistatic properties and reduced haze, and use of such materials in forming an imbibition print.
  • a tanned colloid relief image is formed by imagewise exposure of a suitable light sensitive layer on a support, differentially hardening the colloid layer in accordance with the imagewise exposure, and removing the colloid from the support in inverse proportion to the amount of imagewise light exposure.
  • the differential colloid hardening and removal is conventionally performed with a pyrogallol hardening developer as described, e.g., in U.S. Patent 2,837,430.
  • three separate relief images corresponding to the blue, green, and red color records of the image being reproduced may be formed in separate blue, green, and red light sensitive matrix films by three separate exposures though a color negative film.
  • Imbibition printing blanks typically comprise a dye receiving layer on a support. Where the resulting image is intended to be viewed by light projection, such as in a motion picture film, a transparent film support is generally used.
  • antistatic layers are known for use in photographic elements. Such layers, however, have not previously been used with dye imbibibition printing blanks. As the visual dye image is transfered to an imbibition printing element blank rather than being formed directly in a silver halide emulsion imaging layer of the element, and as the back side of an imbibition printing element support bearing a dye receiving layer will be in contact with such dye receiving layer when the element is rolled up, such printing elements have different requirements as to antistatic protection needs.
  • U.S. Patents 3,625,694; 3,958,995; and 3,898,088 disclose cationic (basic) mordants which may be used in dye imbibition printing blanks. Such mordants are suitable for use with anionic (acid) printing dyes.
  • a dye receiving layer comprising a cationic mordant and a hydrophilic colloid such as gelatin as a binder
  • U.S. Patents 2,882,156 and 3,709,690 disclose blanks containing mordants and polymer latices as plasticizers.
  • U.S. Patent 5,135,835 relates to heat developable photographic elements which contain a mordant, oil droplets and a polymer latex having a glass transition temperature (Tg) of 40°C or less for improving brittleness.
  • US 4 266 044 describes a receptor layer of a dye imbibition printing blank which may contain a cationic mordant, antistatic, softening orgents and polymer latices. Problems to be Solved
  • this invention provides an improved dye imbibition printing blank comprising a support bearing on one side thereof a dye-receiving layer comprising a cationic mordant, and further comprising an antistatic layer substantially free of cationic polymers.
  • the antistatic layer is provided on the opposite side of the support relative to the dye-receiving layer. Such antistatic layer provides improved antistatic properties which enable high manufacturing and processing speeds without adversely affecting printed image qualities.
  • the dye-receiving layer comprises a cationic mordant, a hydrophilic colloid and a plasticizer polymer
  • the plasticizer polymer is a latex polymer having a glass transition temperature below about 30°C comprising from about 2 to 20 wt% of units having a quaternary ammonium group.
  • the latex polymer comprises a vinyl co-polymer addition product of from about 50 to 98 weight percent of acrylic or methacrylic ester units, 0 to 48 weight percent of vinyl benzene units and 2 to 20 weight percent of the quaternary ammonium group containing unit. Use of such latex provides a dye imbibition printing blank substantially free of haze and brittleness.
  • Figure 1 depicts the absorption spectrum of a preferred UV absorbing dye.
  • Figure 2 depicts the spectral characteristics of a HOYA U-340 filter.
  • Figure 3 is a graph depicting the Matrix Exposure Profile for matrix films having various UV dye optical densities.
  • Figure 4 depicts the sensitometric curves for matrix films having varying levels of UV absorber dye exposed to UV light resulting from Example 4.
  • Figure 5 is a graph depicting the Best Fit Contrasts of the curves of Figure 4 vs. UV dye concentration.
  • Figure 6 depicts the absorption spectra of the UV absorbing dyes used in Example 5.
  • Figure 7 depicts the sensitometric curves for the matrix films exposed to UV light resulting from Example 5.
  • Dye imbibition printing blanks within the scope of one embodiment of this invention comprise a support bearing on one side thereof a dye receiving layer containing a cationic mordant, and further comprise an antistatic layer.
  • the dye image receiving layer in addition to the cationic mordant, also comprises a hydrophilic colloid, and a plasticizer polymer.
  • any antistatic conductive materials excluding cationic polymers, such as those previously suggested for use with photographic elements may be used in the printing element antistatic layer in accordance with the invention.
  • Such materials include, e.g., anionic polymers, electronic conducting non-ionic polymers, and electrically-conductive metal-containing particles such as metal halides or metal oxides in polymer binders.
  • antistatic compositions comprising a cationic polymer are also applicable for use with conventional photographic elements, such as the highly crosslinked vinylbenzyl quaternary ammonium polymer disclosed in U.S. Patent 4,070,189, such antistatic materials are excluded from the scope of the instant invention.
  • Dyes intended for printing on the cationic mordant containing printing blanks of the invention are anionic and will transfer from the front dye-receiving side of the film to the antistat backing when such sides come into contact (such as in a rolled film) if the backing contains a catonic polymeric material such as quaternary ammonium polymer, resulting in dye stain.
  • a catonic polymeric material such as quaternary ammonium polymer
  • U.S. Patent 3,033,679 discloses an antistatic layer comprised of an alkali metal salt of a copolymer of styrene and styrylundecanoic acid. Films having a metal halide, such a sodium chloride or potassium chloride, as the conducting material in a hardened polyvinyl alcohol binder are described in U.S. Patent 3,437,484. In U.S.
  • the antistatic layer is comprised of colloidal silica and an organic antistatic agent such as an alkali metal salt of an alkylaryl polyether sulfonate, an alkali metal salt of an arylsulfonic acid, or an alkali metal salt of a polymeric carboxylic acid.
  • An antistatic layer comprised of an anionic film forming polyelectrolyte, colloidal silica, and a polyalkylene oxide is disclosed in U.S. Patent 3,630,740 while U.S. Patent 3,681,070 describes a copolymer of styrene and styrene sulfonic acid as an antistatic agent.
  • Patent 4,542,095 describes antistatic compositions comprising a binder, a nonionic surface-active polymer having polymerized alkylene oxide monomers, and an alkali metal salt.
  • an antistatic layer comprising a styrene sulfonate-maleic acid copolymer, a latex binder, and an alkyl-substituted trifunctional aziridine crosslinking agent are disclosed.
  • Antistat layers comprising a polythiophene with conjugated polymer backbone in the presence of a polymeric polyanion compound are described in EP 554,588; EP 553,502; EP 564,911; DE 4,138,628.
  • any of the wide diversity of electrically-conductive metal-containing particles proposed for use heretofore in imaging elements can be used in the electrically-conductive antistatic layer of this invention.
  • useful electrically-conductive metal-containing particles include donor-doped metal oxides, metal oxides containing oxygen deficiencies, and conductive nitrates, carbides or borides.
  • particularly useful particles include conductive TiO 2 , SnO 2 , Al 2 O 3 , ZrO 2 , In 2 O 3 , ZnO, TiB 2 , ZrB 2 , NbB 3 , CrB 2 , MoB, Wb, LaB 6 , ZrN, TiN, TiC, WC, HfN, and ZrC.
  • Metal oxides, and particularly vanadium pentoxide as described, for example, in Guestaux, U.S. Patent 4,203,769, are preferred for use in the dye imbibition printing elements of the invention.
  • Antistatic layers containing vanadium pentoxide provide excellent protection against static and are highly advantageous in that they have excellent transparency and their performance is not significantly affected by changes in humidity.
  • the use of metal oxide materials is further advantageous, as their antistatic properties allow the use of a protective overcoat layer such as a layer of cellulosic material to provide abrasion protection and/or enhance frictional characteristics while still providing acceptable antistatic performance.
  • Conductive fine particles of crystalline metal oxides dispersed with a polymeric binder have been used to prepare optically transparent, humidity insensitive, antistatic layers for various imaging applications.
  • Many different metal oxides such as AnO, TiO 2 , ZrO 2 , Al 2 O 3 , SiO 2 , MgO, BaO, MoO 3 , and V 2 O 5 , are disclosed as useful as antistatic agents in photographic elements or as conductive agents in electrostatographic elements in such patents as U.S. Patents 4,275,103; 4,394,441; 4,416,963; 4,418,141; 4,431,764; 4,495,276; 4,571,361; 4,999,276; and 5,122,445.
  • Preferred metal oxides are antimony doped tin oxide, aluminum doped zinc oxide, and niobium doped titanium oxide, as these oxides have been found to provide acceptable performance characteristics in demanding environments.
  • Particular preferred metal oxides are antimony-doped tin oxide and vanadium pentoxide having good resistance to static discharge and no dye stain resulting from transfer of dye from front side to the back of the film.
  • a surface resistivity of less than 10 9 ohms per square is desired for the printing blanks to prevent static discharges during unwinding of the film and the buildup of static dirt during handling of the film.
  • Preferred binders which may be included in the antistatic layer of the printing blanks of the invention include vinylidene chloride-containing latexes and polyesterionomer dispersions, which can improve the integrety of the layer and the adhesion of the layer to the support.
  • Polyesterionomer refers to polyesters that contain at least one ionic moiety. Such ionic moieties function to make the polymer water dispersable.
  • These polymers are prepared by reacting one or more dicarboxylic acids or their functional equivalents such as anhydrides, diesters, or diacid halides with one or more diols in melt-phase polycondensation reactions well known in the art as shown in U.S. Patents 3,018,272, 3,929,489, 4,307,174 and 4,419,437. Examples of this class of polymers include, for example, Eastman AQ polyesterionomers manufactured by Eastman Chemical Company.
  • a protective overcoat may be applied thereon.
  • the protective layer can chemically isolate the antistatic layer and also serve to provide scratch and abrasion resistance.
  • the protective overcoat layers may be, e.g., cellulose esters, cellulose nitrate, polyesters, acrylic and methacrylic copolymers and homopolymers, polycarbonates, polyvinyl formal polymethyl methacrylate, polysilicic acid, polyvinyl alcohol, and polyurethanes. Such layers may be aqueous coated or organic solvent coated as appropriate.
  • the chemical resistance of the antistatic layer or an overcoat can be improved by incorporating a polymer cross-linking agent into the antistatic layer or those overcoats that have functionally crosslinkable groups.
  • Cross-linking agents such as aziridines, carbodiimide, epoxys, and the like are suitable for this purpose.
  • a suitable lubricant may also be included in the antistatic layer or protective overcoat in order to provide desired friction performance to assure good transport characteristics during manufacturing and handling of the elements of the invention.
  • Many lubricating agents can be used including higher alcohol esters of fatty acids, higher fatty acid calcium salts, metal stearates, silicone compounds, paraffins and the like.
  • Aqueous dispersed lubricants are preferred as they may be directly incorporated into an aqueous antistatic or overcoat layer, thus avoiding the need for a separately applied lubricant layer.
  • the aqueous dispersed lubricants of carnauba wax and stearates are preferred for their effectiveness in controlling friction at low lubricant levels and their excellent compatibility with aqueous overcoat polymer solutions.
  • Matting agents may also be included in the antistatic layer or overcoat thereon in order to improve transport properties of the elements of the invention on manufacturing, printing, processing, and projecting equipment. Such matting agents can also help prevent sticking between the front and back sides of the elements in a tightly wound roll. Matting agents may be silica, calcium carbonate, other mineral oxides, glass speres, ground polymers and high melting point waxes, and polymeric matte beads.
  • the antistatic layer may also contain a coating aid to improve coatability, including anionic or nonionic coating aids such as para-isononylphenoxyglycidol ethers, octylphenoxy polyethoxy ethanol, sodium salt of alkylaryl polyether sulfonate, and dioctyl esters of sodium sulfossuccinic acid, which coating aids are typically used at from 0.01 to 0.30 weight percent based on the total coating solution weight.
  • anionic or nonionic coating aids such as para-isononylphenoxyglycidol ethers, octylphenoxy polyethoxy ethanol, sodium salt of alkylaryl polyether sulfonate, and dioctyl esters of sodium sulfossuccinic acid, which coating aids are typically used at from 0.01 to 0.30 weight percent based on the total coating solution weight.
  • Cationic mordants for use in the dye receiving layer of the printing blanks in accordance with the invention are preferably quaternary ammonium and phosphonium mordants of the type described in U.S. Pats. 3,898,088 and 3,958,995.
  • the cross-linked mordants of U.S. Pat. 3,958,995 are particularly preferred.
  • Such mordants are generally of the formula: wherein A' represents units of an addition polymerizable monomer containing at least two ethylenically unsaturated groups; B' represents units of a copolymerizable ⁇ , ⁇ -ethylenically unsaturated monomer; Q is N or P; R', R", and R"' are independently carbocyclic or alkyl groups; M - is an anion; a is from about 0.25 to 5 mole percent, preferably from about 1 to 10 mole percent; b is from about 0 to 90 mole percent, preferably from about 0 to 60 mole percent; and c is from about 10 to 99 mole percent, preferably from about 40 to 99 mole percent, for effective dye mordanting.
  • any reference to a substituent by the identification of a group containing a substitutable hydrogen e.g. alkyl, amine, aryl, alkoxy, heterocyclic, etc.
  • a substitutable hydrogen e.g. alkyl, amine, aryl, alkoxy, heterocyclic, etc.
  • photographic substituents include alkyl, aryl, anilino, carbonamido, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, and further to these exemplified are halogen, cycloalkenyl, alkinyl, heterocyclyl, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclyloxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclylthio, spiro compound residues and bridged hydrocarbon compound residues.
  • the hydrophilic colloid may be any of those generally employed in the photographic field, including, for example, gelatin, colloidal albumin, polysaccharides, cellulose derivatives, water-soluble polymer or copolymer including, but not limited to polyvinyl compounds, including polyvinyl alcohol and derivatives thereof, partially hydrolyzed poly(vinylacetate-co-vinylalcohol), hydroxyethyl cellulose, poly(acrylic acid), poly(l-vinylpyrrolidone), poly(sodium styrene sulfonate), poly(2-acrylamido-2-methane sulfonic acid), polyacrylamides. Copolymers of these polymers with hydrophobic monomers may also be used.
  • Gelatin is a preferred hydrophilic colloid. This may be gelatin per se or a modified gelatin such as acetylated gelatin, phthalated gelatin, oxidized gelatin, etc. Gelatin may be base-processed, such as lime-processed gelatin, or may be acid-processed, such as acid processed ossein gelatin.
  • the dye-receiving layer of the printing blanks are hardened with a cross-linking agent.
  • a cross-linking agent Various types of hardeners are useful in conjunction with elements of the invention.
  • fast acting hardeners as disclosed in U.S. Patents 4,418,142; 4,618,573; 4,673,632; 4,863,841; 4,877,724; 5,009,990; 5,236,822.
  • the dye receiving layer of the imbibition printing blanks of the invention include a plasticizer polymer latex.
  • Such latex polymer are preferably water insoluble vinyl copolymers derived from any copolymerizable monomers, such as ⁇ , ⁇ -ethylenically unsaturated monomer (including two, three, or more repeating units) such as ethylene, propylene, 1-butene, isobutene, 2-methylpentene, 2-methylbutene, 1,1,4,4-tetramethylbutadiene, styrene, ⁇ -methylstyrene; monoethylenically unsaturated esters of aliphatic acids such as vinyl acetate, isopropenyl acetate, allyl acetate, etc.; esters of ethyleneically unsaturated mono- or dicarboxylic acids such as methyl methacrylate, ethyl acrylate, diethyl methylenemalonate, etc.; monoethylenically
  • the plasticizer polymers of the invention have a glass transition temperature of about 30°C or lower, more preferably about 20°C or lower.
  • the latex polymers comprise from about 2 tc 20 wt%, more preferably 2 to 10 wt%, of units having a quaternary ammonium group. Such units are preferably acrylic or methacrylic esters or amides to which the quaternary ammonium group is appended.
  • a preferred class of ethylenically unsaturated monomers which may be used to form the remaining 80 to 98 wt% portion of the preferred vinyl polymers of this invention includes acrylic or methacrylic esters and vinyl benzenes.
  • the units of the plasticizer latex polymer having a quaternary ammonium group are as defined in Formula I below, and in particularly preferred embodiments of the invention the plasticizer latex is of the Formula I.
  • A represents units derived from an acrylic or methacrylic ester monomer
  • B represents units derived from a vinyl benzene monomer
  • R 1 is H or methyl
  • L is -C(O)O-, -C(O)NH-, or an aromatic linking group such as phenyl
  • M is a C 1 to C 12 alkenyl linking group, which may be straight, branched, or cyclic
  • R 2 , R 3 , and R 4 are C 1 to C 6 alkyl groups
  • X - is an anionic counterion such as CH 3 SO 4 - , Cl - , Br - , or I -
  • w is 50 to 98 weight percent
  • y is 0 to 48 weight percent
  • z is 2 to 20 weight percent.
  • plasticizer polymers in accordance with one embodiment of the invention include the following:
  • plasticizer polymers may be synthesized as set forth in the representative synthesis example described below or by using other well known vinyl polymer synthesis procedures.
  • plasticizer polymer in accordance with the preferred embodiment of the invention must contain a quaternary ammonium group to give acceptable haze and coating solution stability.
  • Plasticizer latices which contain anionic groups cannot be coated because the mordant layer coating composition coagulates upon the addition of latices containing an anionic group.
  • Matrix films for use with printing blanks in imbibition printing dye transfer processes typically comprise a support bearing a light sensitive layer containing a hydrophilic colloid (typically gelatin), visible light absorbing particles (typically carbon), a silver halide light sensitive emulsion, plus various photographic addenda to provide satisfactory stability, as well as coating aids necessary for suitable manufacture.
  • Sensitizing dyes may be used in the matrix films to provide blue, green, and red light sensitivity for recording the blue, green, and red color record imagewise exposures.
  • Separate matrix films designed to optimize sensitivity for particular color record exposures may be used, or alternatively identical pan-sensitive matrix films may be used for each of the blue, green and red exposures.
  • the imbibition printing blanks described above may contain further features and layers as are known in the art.
  • Preferred supports for such blanks comprise transparent polymeric films, such as cellulose nitrate and cellulose esters (such as cellulose triacetate and diacetate), polycarbonate, and polyesters of dibasic aromatic carboxylic acids with divalent alcohols such as poly(ethylene terephthalate).
  • Photographic silver halide emulsion layers may also be included in the printing blanks of the invention.
  • a layer may be included between the support and the dye receiving layer as is known in the art in order to enable recording a sound track for the film in accordance with conventional motion picture sound track recording, exposing, and processing procedures.
  • a sound track may be printed on the blank receiver as part of the imbibition printing process.
  • the printing blank of the invention can be used in conjunction with an applied magnetic layer, such as those described in Research Disclosure, November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley House, 12 North Street, Emsworth, Hampshire P010 7DQ, ENGLAND.
  • a latex copolymer having the composition 75 wt % ethylacrylate, 20 wt % styrene, and 5 wt % 2-(N,N,N-trimethylammonium) ethylmethacrylate methosulfate is prepared as follows: to a 500 ml addition flask was added 100 ml of distilled degased water, 1 ml of Igepal CO 730, 1 ml Ethoquad 0/12, 75 g of ethyl acrylate, 20 g of styrene, 6.3 g of 80 % aqueous solution of 2-(N,N,N-trimethylammonium)ethyl methacrylate, and 0.5 g of 2,2'-azobis(2-methylpropionamidine)dihydrochloride.
  • Coated dye imbibition printing blank supports were prepared as follows:
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing a copolymer of styrene sulfonic acid sodium salt and 2-hydroxyethyl methacrylate 70/30 wt (182 mg/m 2 ), a polymer latex of methyl acrylate, vinylidene chloride, and itaconic acid (15/83/02 wt%)(60 mg/m 2 ) and Cymel 300 (melamine-formaldehyde resin crosslinking agent from American Cyanamide Co.)(18 mg/m 2 ) and on the front side with a gel subbing layer containing poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid) (14/80/6 wt%).
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing Nalco 1115 (colloidal silica from Nalco Chemical)(404 mg/m 2 ), a polymer latex of methylacrylate, vinylidene chloride, and itaconic acid 15/83/02 wt (135 mg/m 2 ) and on the front side with a gel subbing layer.
  • Nalco 1115 colloidal silica from Nalco Chemical
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing antimony-doped tin oxide (370 mg/m 2 ) and Witcobond 232 (polyurethane from Witco Corp.) (125 mg/m 2 ) and on the front side with a gel subbing layer.
  • antimony-doped tin oxide 370 mg/m 2
  • Witcobond 232 polyurethane from Witco Corp.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing antimony-doped tin oxide (226 mg/m 2 ) and a polymer latex of methyl acrylate, vinylidene chloride, and itaconic acid 15/83/02 wt (75 mg/m 2 ) followed by a layer containing Witcobond 232 (899 mg/m 2 ) and on the front side with a gel subbing layer.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing Witcobond 232 (899 mg/m 2 ) and on the front side a gel subbing layer followed by a layer containing antimony-doped tin dioxide (296 mg/m 2 ) and gelatin (52 mg/m 2 ).
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing Witcobond 232 and a polyaniline imine (1:1 ratio)(108 mg/m 2 ) followed by a layer containing Elvacite 2041 (polymethylmethacrylate from DuPont) (1076 mg/m 2 ) and on the front side a gel subbing layer.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing a polymer of N-vinylbenzyl-N,N,N-trimethylammonium chloride and ethyleneglycol dimethacrylate 93/7 wt (129 mg/m 2 ) and a polymer of acrylonitrile, vinylidene chloride and N,N-dimethylaminoethyl methacrylate methosulfate 25.1/73.4/1.5 wt (194 mg/m 2 ) and on the front side a gel subbing layer.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing a polymer of N-vinylbenzyl-N,N,N-trimethylammonium chloride and ethyleneglycol dimethacrylate 93/7 wt (129 mg/m 2 ) and a polymer of acrylonitrile, vinylidene chloride and N,N-dimethylaminoethyl methacrylate methosulfate 25.1/73.4/1.5 wt (194 mg/m 2 ) followed by a layer containing cellulose diacetate (2690 mg/m 2 ).
  • the front side was coated with a gel subbing layer.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing vanadium pentoxide (3.2 mg/m 2 ) and Eastman AQ55D (polyesterionomer from Eastman Chemical Co.) (32 mg/m 2 ).
  • the front side of the support was coated with a gel subbing layer.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing vanadium pent:oxide (296 mg/m 2 ) and Eastman AQ29D (polyesterionomer from Eastman Chemical Co.) (3.2 mg/m 2 ) followed by a layer containing Witcobond 232 (899 mg/m 2 ) and the front side was coated with a layer containing a gel sub well known in the art.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing Elvanol 71-30 (polyvinylalcohol from DuPont) (54 mg/m 2 ), Volan (methacrylato chromic chloride from DuPont) (1.9 mg/m 2 ) and potassium nitrate (5.4 mg/m 2 ).
  • Elvanol 71-30 polyvinylalcohol from DuPont
  • Volan methacrylato chromic chloride from DuPont
  • potassium nitrate 5.4 mg/m 2
  • a 5 mil polyethylene terephthalate film support was coated on the backside with a layer containing vanadium pentoxide (3.2 mg/m 2 ) and a polymer latex of acrylonitrile, vinylidene chloride and acrylic acid 15/9/76 wt (2.4 mg/m 2 ) followed by a layer containing Elvacite 2041 (1064 mg/m 2 ).
  • the front side of the support was coated with a gel subbing layer.
  • a 4.7 mil polyethylene terephthalate film support was coated on the backside with a layer containing Witcobond 232 (899 mg/m 2 ) and on the front side with a gel subbing layer.
  • Dye imbibition printing blank Samples 1-12 and a Control Sample were made using corresponding Supports 1-12 and the Control Support as follows. Each support was coated on the front side with a layer containing silver bromoiodide emulsion (1940 mg/m 2 Ag), EDTA sodium salt (83.2 mg/m 2 ), methylbensothiazolium chloride (10.1 mg/m 2 ), gelatin (3500 mg/m 2 ) and bisvinylsulfonylmethyl ether (75.6 mg/m 2 ) followed by a layer containing polymer of copoly (N-vinylbenzyl-N,N,N-trimethylammonium chloride-co-ethyleneglycol dimethacrylate) 93/7 mole (861 mg/m 2 ), Olin 10G surfactant (97.3 mg/m 2 ), potassium nitrate (39.7 mg/m 2 ), gelatin (2800 mg/m 2 ), and a polymer methacrylate methosulfate 75/25/5 wt (280 mg/
  • Desired resistivity values for surface electrical resistivity are less than about 10 9 and for water electrode resistivity are less than about 10 9 , and especially less than about 10 8 ohm/square. While all antistatic materials will improve resistivity levels to some extent, the metal oxide containing antistatic layers of Samples 3, 5, 9, 10, and 12 demonstrate especially preferable results. It is also noted the antistat in Sample 1 is not photographic development process surviving, and therefore not preferred.
  • An unwinding electrification test is used to determine if there is a "discharge” or "glow” in the unwinding nip of a roll of light sensitive film during production or handling. During this test a roll of film is unwound at a high speed. If there is a large separation charge, due to the fact that two dissimilar materials are being separated, the electric field in the unwind nip will be large. It can be large enough such that the air can no longer sustain the intense field and air breakdown will occur resulting in a static discharge. Such discharge can potentially be harmful to a light sensitive emulsion which may be used for recording a sound track in an imbibition printing blank. Table II shows the results of such an unwinding electrification test which was performed on Samples 7, 8, 11 and 12. Sample Glow observed 11 yes 7 yes 8 yes 12 no
  • Retransfer of dye from the printed front side of a dye imbibition print to the backside during storage in the roll can be a problem especially at high humidity and temperature.
  • An antistatic backing layer can play an important part in this retransfer.
  • the front sides of imbibition prints dyed with magenta dye M-1 were placed in contact with the backsides of each of Samples 1-12 and the Control Sample between two glass plates, and the assemblage was then placed in a chamber at 80 percent relative humidity and 38°C for four days. The backs of the undyed imbibition prints were then observed for the presence of transfered dye. The results are shown in Table III.
  • Samples 3, 5, 9, 10, and 12 meet the desired attributes of desired resistivity, no glow discharge and no dye retransfer. These examples all contain metal oxide antistats.
  • Dye imbibition printing blanks were prepared as follows: Component Coverage Top layer: Mordant: copoly(N-vinylbenzyl-N,N,N-trimethylammoniumchloride co-ethyleneglycol dimethacrylate) 861 mg/m 2 93/7 mole ratio Olin 10G surfactant 97.3 mg/m 2 KNO 3 antistatic agent 39.7 mg/m 2 gelatin 2799 mg/m 2 plasticizer polymer PP-1 280 mg/m 2 Bottom layer: EDTA sodium salt 83.2 mg/m 2 Methylbenzothiazolium chloride 10.1 mg/m 2 Gelatin 3498 mg/m 2 Bisvinysulfonylmethyl ether 75.6 mg/m 2
  • plasticizer polymers other than those in accordance with the preferred embodiments of the invention in the presence of the mordant in the coating composition can cause hazy coatings to occur upon drying. This difficulty is overcome by using the plasticizer latex of the preferred embodiments of the invention.
  • plasticizer latex in accordance with the preferred embodiments of the invention at reducing brittleness was also demonstrated.
  • a dye imbibition printing blank was made as described in Example 2, with PP-5 in place of PP-1 at the indicated coverages.
  • the brittleness test performed provides for quantitatively measuring the brittleness of film by subjecting it to bending. By means of a wedge, the diameter of a film loop was constantly changed through gradually decreasing openings until a failure of the film resulted. The opening of the wedge at which the film failed is the measure of its brittleness. The film was conditioned at 15 percent relative humidity and 21°C before running the test. The smaller wedge opening before the onset of failure the more flexible the film.
  • Table V shows the effectiveness of the plasticizer latex of the invention to give acceptable coatings with reduced brittleness.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (12)

  1. Druckrohling für Farbstoffimbibitionsverfahren mit einem Träger, auf dessen einer Seite eine Farbstoffempfangsschicht angeordnet ist, die ein kationisches Beizmittel umfasst, wobei der Druckrohling eine Antistatikschicht umfasst, die im wesentlichen frei von kationischen Polymeren ist.
  2. Druckrohling nach Anspruch 1, dadurch gekennzeichnet, dass die Antistatikschicht auf der gegenüberliegenden Seite des Trägers relativ zu der Farbstoffempfangsschicht angeordnet ist.
  3. Druckrohling nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Antistatikschicht ein anionisches Polymer, ein elektronisch leitendes, nicht ionisches Polymer, Metallhalogenid oder Metalloxid umfasst.
  4. Druckrohling nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Antistatikschicht ein Metalloxid und ein Polymerbindemittel umfasst.
  5. Druckrohling nach Anspruch 4, dadurch gekennzeichnet, dass die Antistatikschicht des Druckrohlings mit einer schützenden Polymerschicht überzogen ist.
  6. Druckrohling nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das kationische Beizmittel ein quaternäres Ammonium- oder Phosphoniumbeizmittel ist.
  7. Druckrohling nach Anspruch 6, dadurch gekennzeichnet, dass dem kationischen Beizmittel folgende Formel zugrunde liegt:
    Figure 00360001
    wobei A' die Einheiten eines additionspolymerisierbaren Monomers darstellt, das mindestens zwei ethylenungesättigte Gruppen umfasst; B' stellt die Einheiten eines copolymerisierbaren α-, β-ethylenungesättigten Monomers dar; Q ist N oder P; R', R" und R''' sind unabhängig carbozyklische oder Alkylgruppen; M- ist ein Anion; a ist ein Wert zwischen 0,25 und 10 Molprozent; b ist ein Wert zwischen 0 und 60 Molprozent und c ist ein Wert zwischen 40 und 99 Molprozent.
  8. Druckrohling nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Farbstoffempfangsschicht ein hydrophiles Colloid und ein Weichmacherpolymer umfasst, dass das Weichmacherpolymer ein Latexpolymer mit einer Glasübergangstemperatur von unter 30°C ist und 2 bis 20 Gewichtsprozent von Einheiten umfasst, die eine quaternäre Ammoniumgruppe aufweisen.
  9. Druckrohling nach Anspruch 8, dadurch gekennzeichnet, dass das Weichmacherpolymer ein Vinyl-Copolymer ist und dass die eine quaternäre Ammoniumgruppe umfassenden Einheiten Acryl- oder Methacrylester oder Amide sind, denen die quaternäre Ammoniumgruppe angehängt ist.
  10. Druckrohling nach Anspruch 9, dadurch gekennzeichnet, dass dem Weichmacherpolymer folgende Formel zugrunde liegt:
    Figure 00360002
    wobei A die von einem Acryl- oder Methacrylestermonomer abgeleiteten Einheiten darstellt, B stellt die von einem Vinylbenzolmonomer abgeleiteten Einheiten dar; R1 ist H oder Methyl; L ist -C(0)0-, -C(0)NH- oder eine aromatische Verbindungsgruppe; M ist eine C1 bis C12 Alkenyl-Verbindungsgruppe; R2, R3 und R4 sind C, bis C6 Alkylgruppen; X- ist ein anionisches Gegenion; w ist 50 bis 98 Gewichtsprozent; y ist 0 bis 48 Gewichtsprozent und z ist 2 bis 20 Gewichtsprozent.
  11. Druckrohling nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der Träger transparent ist.
  12. Druckrohling nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass der Druckrohling zudem eine Silberhalogenidemulsionsschicht zur Aufnahme einer Tonspur umfasst.
EP19960420194 1995-06-20 1996-06-04 Empfangs- und Matrizenfilms für Farbstoffimbibitionsverfahren Expired - Lifetime EP0752619B1 (de)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US35695P 1995-06-20 1995-06-20
US35595P 1995-06-20 1995-06-20
US36795P 1995-06-20 1995-06-20
US356 1995-06-20
US355 1995-06-20
US367 1995-06-20
US08/614,454 US5620833A (en) 1995-06-20 1996-03-12 Curve shape control in a photographic imbibition dye transfer process
US08/614,413 US5622808A (en) 1995-06-20 1996-03-12 Receiver for dye imbibition printing
US614423 1996-03-12
US614413 1996-03-12
US08/614,423 US5709971A (en) 1995-06-20 1996-03-12 Dye imbibition printing blanks with antistatic layer
US614454 1996-03-12

Publications (3)

Publication Number Publication Date
EP0752619A2 EP0752619A2 (de) 1997-01-08
EP0752619A3 EP0752619A3 (de) 1997-06-04
EP0752619B1 true EP0752619B1 (de) 2001-09-05

Family

ID=27555363

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960420194 Expired - Lifetime EP0752619B1 (de) 1995-06-20 1996-06-04 Empfangs- und Matrizenfilms für Farbstoffimbibitionsverfahren

Country Status (4)

Country Link
EP (1) EP0752619B1 (de)
JP (1) JPH095967A (de)
CN (1) CN1172968A (de)
DE (1) DE69614943D1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114703684A (zh) * 2022-04-12 2022-07-05 绍兴市柯桥区信和数码纺织技术有限公司 一种超薄面料的印花工艺

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6190846B1 (en) 1998-10-15 2001-02-20 Eastman Kodak Company Abrasion resistant antistatic with electrically conducting polymer for imaging element
JP5962400B2 (ja) * 2012-09-28 2016-08-03 大日本印刷株式会社 保護層転写シート

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625694A (en) * 1968-06-06 1971-12-07 Kodak Ltd Polymers polymeric mordants and elements containing same
GB1381263A (en) * 1971-01-11 1975-01-22 Agfa Gevaert Polymeric mordanting agents for anionic compounds
US5135835A (en) * 1986-04-18 1992-08-04 Fuji Photo Film Co., Ltd. Heat development using dye fixing materials with oil droplets and/or polymeric latexes
JP2699010B2 (ja) * 1990-05-16 1998-01-19 富士写真フイルム株式会社 拡散転写型カラー感光材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114703684A (zh) * 2022-04-12 2022-07-05 绍兴市柯桥区信和数码纺织技术有限公司 一种超薄面料的印花工艺
CN114703684B (zh) * 2022-04-12 2024-05-17 绍兴市柯桥区信和数码纺织技术有限公司 一种超薄面料的印花工艺

Also Published As

Publication number Publication date
JPH095967A (ja) 1997-01-10
DE69614943D1 (de) 2001-10-11
EP0752619A2 (de) 1997-01-08
EP0752619A3 (de) 1997-06-04
CN1172968A (zh) 1998-02-11

Similar Documents

Publication Publication Date Title
EP0772080B1 (de) Photographisches Element verwendbar als Kinofilm
US5700623A (en) Thermally stable photographic bar code label containing an antistatic layer
US5718995A (en) Composite support for an imaging element, and imaging element comprising such composite support
EP0437602A1 (de) Fotografisches hilfsmaterial mit einer antistatischen schicht und einer sperrschicht.
US5726001A (en) Composite support for imaging elements comprising an electrically-conductive layer and polyurethane adhesion promoting layer on an energetic surface-treated polymeric film
EP0878734B1 (de) Kinofilm
EP0800110B1 (de) Bilderzeugungselement mit einer elektrisch leitenden Schicht, die durch die Verarbeitung nicht beeinträchtigt wird
US3850640A (en) Coating quality and reducing static simultaneously
US5709971A (en) Dye imbibition printing blanks with antistatic layer
EP0752619B1 (de) Empfangs- und Matrizenfilms für Farbstoffimbibitionsverfahren
US5869227A (en) Antistatic layer with smectite clay and an interpolymer containing vinylidene halide
EP1065563A1 (de) Trägerfilm mit einer leitenden Schicht und einer magnetischen Schicht
US4914018A (en) Antistatic photographic base and light-sensitive element
US6025111A (en) Stable matte formulation for imaging elements
US5962207A (en) Motion picture film
US5622808A (en) Receiver for dye imbibition printing
US6740480B1 (en) Fingerprint protection for clear photographic shield
EP0829758B1 (de) Verfahren zur Herstellung eines photographischen Papieres mit einer Rückseitenschicht, die kolloidale, anorganische Oxidteilchen, ein Antistatikum und ein filmbildendes Acrylatbindemittel enthält
EP0589329B1 (de) Antistatische Filmträger und photographische Elemente, die diese antistatischen Filmträger enthalten
US5604083A (en) Antistatic film bases and photographic elements comprising said antistatic film bases
US5723274A (en) Film former and non-film former coating composition for imaging elements
US6326131B1 (en) Highly lubricated imaging element with high coefficient of friction
EP0862085A1 (de) Kinematographischer Film, der eine Russ enthaltende Rückschicht und eine elektrisch leitende Haftvermittlungsschicht aufweist, die durch die Verarbeitung nicht beeinträchtigt wird
US20020127410A1 (en) Annealable imaging support
US5952165A (en) Topcoat for motion picture film

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB IT

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB IT

17P Request for examination filed

Effective date: 19971031

17Q First examination report despatched

Effective date: 19981005

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

REF Corresponds to:

Ref document number: 69614943

Country of ref document: DE

Date of ref document: 20011011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011206

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020604

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020604

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050604