EP0671994A4 - Film de copolyester recouvert d'une couche primaire de polymeres acryliques. - Google Patents

Film de copolyester recouvert d'une couche primaire de polymeres acryliques.

Info

Publication number
EP0671994A4
EP0671994A4 EP93900176A EP93900176A EP0671994A4 EP 0671994 A4 EP0671994 A4 EP 0671994A4 EP 93900176 A EP93900176 A EP 93900176A EP 93900176 A EP93900176 A EP 93900176A EP 0671994 A4 EP0671994 A4 EP 0671994A4
Authority
EP
European Patent Office
Prior art keywords
film
biaxially oriented
primer
film according
coating
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Withdrawn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
EP93900176A
Other languages
German (de)
English (en)
Other versions
EP0671994A1 (fr
Inventor
Cynthia Bennett
E-Won Choe
John Anthony Flint
Bodo Kuhmann
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.)
Mitsubishi Polyester Film GmbH
Original Assignee
Hoechst AG
Hoechst Celanese Corp
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 Hoechst AG, Hoechst Celanese Corp filed Critical Hoechst AG
Publication of EP0671994A1 publication Critical patent/EP0671994A1/fr
Publication of EP0671994A4 publication Critical patent/EP0671994A4/fr
Withdrawn legal-status Critical Current

Links

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
    • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • G03C1/7954—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93—Macromolecular substances therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G03G7/004—Organic components thereof being macromolecular obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
    • G03G7/0073—Organic components thereof
    • G03G7/008—Organic components thereof being macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention relates to biaxially oriented PENBB film coated on one or both sides with acrylic polymers which render the copolyester film surface receptive to additional reprographic or matte coatings applied thereto, and to film containing the reclamation product of such coated film.
  • Oriented polyester films particularly biaxially oriented film composed of polyethylene terephthalate (PET), are widely used as a base for drafting film, photographic film, and reprographic film, as well as for packaging and labeling applications.
  • PET polyethylene terephthalate
  • Polyester films especially PET films, have disadvantages which still need to be overcome, e.g., UV resistance, dimensional stability, heat stabili- ty, and hydrolysis resistance are still poor.
  • PET film is hydrophobic and is not readily receptive to coating in most applications where the film is to serve as a base or support for other coatings, and must therefore be first coated on one or both sides with a primer coating which adheres to the film and is receptive as well to other coatings applied to it.
  • U.S. Patent IMos. 2,627,088 and 2,698,240 teach a primer coating for PET film comprising a terpolymer composition of vinylidene chloride, acrylic ester and itaconic acid.
  • This primer layer is said to have excellent adhesion to the polyester surface and to water or alcohol based photographic gelatin layers subsequently coated thereon.
  • Another known PET film primer includes copolymers of a vinyl haloge- noester, such as vinyl chloroacetate which may be copolymerized with numerous different monomers such as acrylic and methacrylic acids, esters and amides, olefins and vinyl alcohols as disclosed in U.S. Patent No. 3,674,531. Such copolymers may also be crosslinked by the inclusion of melamine or urea formaldehyde resins in the composition.
  • the primed PET film is stated to exhibit enhanced adhesion to a variety of coatings applied thereto, including reprographic coatings.
  • thermoset, acrylic or methacrylic coatings taught in U.S. Patent No. 3,819,773, which can be applied to the PET film from aqueous medium.
  • a primer layer enhances the adhesion of organic solvent based reprographic and drafting layers applied thereto.
  • film primed with the acrylic coatings described therein may be reclaimed in the film forming extruder by mixing it with 50 percent by weight or more of virgin polyester and refeeding the mixture to the film- forming extruder.
  • problems of discoloration or degradation caused by certain prior art primer coatings are reduced. While this is true in comparison with the chlorine-containing primers discussed abo ⁇ ve, the acrylic primer coatings of U.S. Patent No. 3,819,773, which are crosslinked using the resinous crosslinking agents disclosed therein, still are found to give rise to an undesirable yellowing of the finished film containing such primed film as reclaim, particularly when compared to film based solely on virgin polymer.
  • a primer coated biaxially oriented self- supporting mono- or multilayer copolyester film wherein the copolyester is PENBB and wherein the primer coating contains an acrylic polymer provides excellent UV resistance, good dimensional stability, heat stability and hydroly ⁇ sis resistance, lower moisture absorption, improved stiffness (tensile strength and modulus), while providing excellent adhesion to many organic solvent based coatings subsequently applied thereto, and reciaimability when re ⁇ processed during the manufacture of the PENBB film while giving rise to hardly any degradation of the film.
  • U.S. Patent No. 3,008,934 discloses copolyesters containing as acid derived units 4,4'-bibenzoate and a host of other dicarboxylates including 2,6-naphthalic dicarboxylate. It also discloses oriented fibers and films prepa ⁇ red from these copolyesters, however, biaxially oriented PENBB films are not disclosed or envisioned. In particular, those films with improved stiffness
  • PENBB as mentioned hereinbefore is a copolyester containing as acid- derived unit at least 5 mole percent of a radical of the formula
  • PENBB is a copolyester wherein at least 80 mole percent of the acid derived units (NBB) consist of bibenzoate (20 to 80 mole percent, preferably 40 to 60 mole percent) and naphthalate (80 to 20 mole percent, preferably 60 to 40 mole percent). The remaining 20 or less mole percent may consist of other acid derived units, which e.g. affect the melting point or the crystallization kinetics.
  • NNBB acid derived units
  • naphthalate 80 to 20 mole percent, preferably 60 to 40 mole percent
  • the remaining 20 or less mole percent may consist of other acid derived units, which e.g. affect the melting point or the crystallization kinetics.
  • at least 80 mole percent of the diol-derived units consist of -O(CH 2 ) -O-units. The remaining
  • 20 or less mole percent consist of other diol-derived units, which e.g. may also affect the melting point or the crystallization kinetics. It may also be desirable to replace minor amounts of the acid- and/or diol-derived units with hydroxycarboxyiic-acid-derived units, e.g. such derived from p-hydroxyben- zoic acid.
  • the polymer melt is extruded through a die onto a chill roll where it solidifies, is then biaxially oriented, heat set, optionally post treated and wound on a roll.
  • the IV value inherent viscosity, as measured in a 1 : 1 weight-ratio mixture of pentafiuorophenol and hexafluoroisopropanol at a concentration of 0.2 g/dl and a temperature of 25 ⁇ C
  • the IV value of the PENBB polymer after extrusion be > 0.5 di/g and preferably > 0.55 dl/g.
  • Biaxial drawing is performed such that the birefringeance is ⁇ 0.2, preferably ⁇ 0.1 to ensure adequately isotropic properties.
  • Birefringeance as mentioned herein is the absolute value of the difference between the maximum and minimum refractive indices in the plane of the film, as measured on common instruments such as Abbe refractome- ter, optical bench or compensators.
  • in-line or off-line coating can be used.
  • the solidified film as ex ⁇ truded on the chill roll should be obtained in an essentially amorphous state. To achieve this, the melt film must be pinned to the chill roll by a known method such as electrostatic pinning or vacuum, air knife or the like.
  • the biaxial orientation of the film is achieved by stretching the film at elevated temperature in the machine (MD) and transverse direction (TD).
  • This stretching can be either simultaneous or sequential.
  • the first stretching step can be in either MD or TD, followed by stretching in the other direction.
  • the orientation in MD can also be achieved in several steps, either one after another prior to stretching in TD, or before and after the TD stretching.
  • Preferred temperatures for stretching lie bet ⁇ ween the glass transition temperature and about 30 * C above the cold cry ⁇ stallization temperature of the PENBB copolymer composition in use (both temperatures can easily be measured on amorphous films by DSC).
  • the total stretch ratios ( ⁇ ) in MD and TD lie between 1 : 2 and 1 : 10, preferably between 1 : 2.5 and 1 : 5'.
  • the product of the total stretch ratios should be between 1 to 30, and preferably between 5 to 20.
  • relaxation steps can be included in the orientation and heat setting processes.
  • the heat setting takes place at a temperature between the cold cry- stallization temperature and the melt temperature of the copolymer composi ⁇ tion.
  • a surface treatment such as corona, plasma or flame treatment should be employed before winding the film on a roll.
  • the film Prior to coating the PENBB film surface with the acrylic coating compo- sition, the film may be surface treated in a conventional manner by exposure to, e.g. an electric corona, plasma or flame treatment.
  • Electric corona disch ⁇ arge is a conventional surface treatment which is commonly performed on a film to enhance its surface qualities, especially its adhesive and printing properties.
  • Electric corona discharge methods and apparatus are described in U.S. Patent Nos. 3,057,792 and 4,239,973. If the surface treatment follo ⁇ wed by the coating occurs before stretch orientation, heating the film before stretch orientation will drive off the water.
  • the corona treatment followed by the acrylic polymer coating may occur during the in-line manufacturing process, either before stretch orientation, or between the machine draw and transverse draw of biaxial stretch orientation, or after stretch orientation. If the surface treatment and coating steps occur after stretch orientation, it is necessary to completely dry the film before winding. If the surface treatment and coating occur before orientation, or between draw during orientation, the later orientation steps which require the film to be heated would drive off the excess water from the acrylic polymer coating. Preferably, the corona treatment and subsequent acrylic polymer coating occur between draws during the stretch orientation step.
  • the mono- or multilayer biaxially oriented PENBB film is coated on the corona, plasma or flame treated surface preferably with an aqueous disper ⁇ sion of the acrylic coating composition described below.
  • the coating compo ⁇ sition may conveniently be applied as an aqueous dispersion or emulsion using any of the well known coating techniques.
  • the film may be coated by roller coating, spray coating, gravure coating, or slot coating.
  • the heat applied to the film during the subsequent pre-heating, stretching, and heat setting stages is generally sufficient to evaporate the water and crosslink the acrylic coating, if a crosslinkable monomer comprises a portion of the acrylic coating.
  • the coated, biaxially oriented PENBB film may then be heat treated for a period of time necessary to crystallize the film. Crystallization imparts the improved dimensional stability and excellent tensile properties to the PENBB film.
  • the so coated, crystallized and biaxially oriented PENBB film is then wound onto a roll.
  • the acrylic copolymers used as primer layers according to this inven ⁇ tion consist essentially of at least about 50 percent by weight of one or more polymerized acrylic and/or methacrylic monomers.
  • the acrylic copolymer may contain from about 1 to 15 percent by weight of a copolymerizable comonomer, which in its copolymerized state is then capa ⁇ ble of intermolecular crosslinking by the application of heat with or without the addition of a separate resinous crosslinking agent.
  • the acrylic component of the primer copolymers is preferably present at a level of from about 50 to 99 percent by weight and preferably comprises an ester of acrylic acid or methacrylic acid, especially an alkyl ester wherein the alkyl group contains up to 10 carbon atoms such as methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, t-butyl, hexyl, heptyl and n-octyl.
  • Acrylic copolymers derived from a lower alkyl (C, to C 4 ) acrylate, especially ethyl acrylate, together with a lower alkyl methacrylate provide particularly effecti ⁇ ve adhesion between the PENBB film and superimposed reprographic or matte layers.
  • Primer copolymers comprising an alkyl acrylate, e.g. ethyl acrylate or butyl acrylate, together with an alkyl methacrylate, e.g. methyl methacrylate, desirably in a total proportion in the range of about 70 to 95 weight percent, are particularly preferred.
  • the acrylate comonomer of such acrylic/methacry- lic combinations is preferably present in a proportion in the range of 15 to 65 mole percent and the methacrylate comonomer preferably in a proportion exceeding that of the acrylate comonomer generally by an amount in the range of 5 to 20 mole percent.
  • the methacrylate is preferably present in a proportion in the range of 35 to 85 mole percent.
  • crosslinking comonomers examples include N-meth ⁇ lol acrylamide, N-methylol methacrylamide and their corresponding ethers; epoxide materials such as glycidyl acrylate, glycidyl methacrylate and allyl- glycidyl ether; carboxyl containing monomers such as crotonic acid, itaconic acid or acrylic acid; anhydrides such as maleic anhydride or itaconic anhydri ⁇ de; hydroxy containing monomers such as allyl alcohol and hydroxy ethyl or propyl acrylate or methacrylate; amides such as acrylamide, methacrylamide or maleamide; and isocyanates such as vinylisocyanate or allylisocyanate.
  • Preferred comonomers from the above are N-methylolacrylamide and N-methylolmethacrylamide, mainly because copolymer chains containing one of these monomers are capable of condensing with one another with the ap ⁇ plication of heat to form the desired inter-molecular crosslinking.
  • copolymers containing the other functional monomers it is necessary to form blends of two or more copolymers containing different functional como- nomers to achieve the desired crosslinking, e.g. blending an acrylic/crotonic acid copolymer with an acrylic copolymer containing isocyanate, epoxide or N-methylol functionality capable of reacting with acidic functional groups.
  • blended acrylic copolymers include copolymers containing monomers having epoxide functionality combi- ned with copolymers containing monomers having amine, acid anhydride, carboxyl, hydroxyl, or N-methylol functionality; copolymers containing mono ⁇ mers having N-methylol or N-methylol ether functionality combined with copolymers containing monomers having isocyanate functionality combined with copolymers containing monomers having carboxyl or hydroxyl functiona- lity; and so forth.
  • the functional monomers present in the mixed copolymer systems are present in approximately equimolar amounts.
  • the acrylic copolymers also may contain up to about 49 percent by weight of one or more halogen-free non-acrylic monoethylenically unsaturated monomers interpolymerized therewith.
  • Suitable comonomers include dialkyl maleates such as dioctyl maleate, di-isooctyl maleate and dibutyl maleate; vinyl esters of versatic acid; vinyl acetate, styrene, acrylonitrile and similar materials.
  • the preferred crosslinking mixed copolymer compositions for the purposes of this invention are approximately 50/50 blends of an ethyl acryla- te/methyl methacrylate/crotonic acid copolymer with an ethyl acrylate/methyl methacrylate/glycidylacrylate copolymer, blends of an ethyl acrylate/methyl methacrylate/methacrylamide copolymer with an ethylacrylate/methyl metha- crylate/N-methylolacrylamide copolymer; and compositions based on copoly ⁇ mers of ethyl acrylate/methyl methacrylate/N-methylolacrylamide such as copolymers containing from about 50 to 99 percent by weight of acrylic and/or methacrylic monomers, 0 to 49 percent by weight of the mono-ethyle- nically unsaturated monomer and about 1 to 15 percent by weight N-methy- lolacrylamide.
  • copolymers containing from about 70 to 90 percent by weight of acrylic and/or methacrylic monomers, about 0 to 25 percent by weight of the mono-ethylenically unsaturated monomer, and from about 5 to 10 percent by weight N-methyoiacrylamide.
  • the polymeric acrylic primer composition does not require the presence of an external crosslinking agent such as a melamine or urea/formaldehyde condensate.
  • the primer coating is applied to the base mono- or multilayer PENBB film preferably as an aqueous dispersion or latex and at a solids concentration within the range of about 0.5 to 15 percent, preferably about 3 to 10 percent by weight.
  • the preferred solids level is such as to yield a final dry coating thickness within the range of about 1 nm to 300 nm, which translates into a solids level on a dry weight basis of from 1 mg/m 2 to 300 mg/m 2 .
  • the preferred thickness range of the dried PENBB copolyester primer is from 15 to 50 nm, with 25 nm being the target thickness.
  • the thickness of the base mono- or multilayer film to which the coating is applied may range from about 1 to about 250 ⁇ m.
  • the coating may be applied to one or both sides of the mono- or multilayer PENBB film, or it may be applied to one side only with optionally a different coating applied to the opposite side.
  • Additives known in the .art may be present in the coating formulation such as antistatic agents, wetting agents, surfactants, pH regulating agents, anti-oxidants, dyes, pigments, slip agents such as colloidal silica, and the like. Normally, it is desirable to in ⁇ clude a surfactant to enhance the wettability of the aqueous coating to the base PENBB film.
  • PENBB film primed with the above acrylic composition has excellent utility as a film base for the production of photosensitive reprographic films.
  • Such films are prepared by forming a coating on a surface of the primed PENBB film of a photosensitive composition comprising an organic solvent solution of a resinous binder containing or impregnated with a light-sensitive diazionium compound, and drying said coating.
  • Resinous binders suitable for this purpose include cellulose acetate butyrate, cellulose acetate, cellulose acetate propionate as well as vinyl polymers such as polyvinyl acetate.
  • Suitable solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether and mixtures thereof.
  • the primed PENBB film of this invention forms an excellent substrate for the application of matte coatings which render the film suitable for use as a drawing or drafting material.
  • matte coatings may be based on an organic composition comprising a resinous binder and a finely divided particulate material which serves as a "toothing agent.”
  • the resinous binder may include the resinous materials referred to above as well as acrylic or methacrylic resins.
  • the organic solvents may also include those listed above.
  • Particulate materials include finely divided (less than 10 ⁇ m particle size) clays or silica. Other ingredients such as thickeners or dispersing agents may also be present in such matte formulations. Similar matte formulations are disclosed for example in British Patent No. 1 ,072,122 and U.S. Patent No. 3,624,021.
  • the primed biaxially oriented PENBB films de- monstrate good adhesion to organic solvent based printing inks and markedly improved UV resistance, dimensional stability and stiffness (tensile strength) when compared with unprimed films, especially unprimed PET films.
  • These inks may comprise organic solvent dispersions or solutions of pigments and/or dyes in combination with acrylic resins or other resins and thickening agents.
  • the excellent UV resistance, dimensional stability, stiff ⁇ ness (tensile strength) and adhesive qualities of PENBB film primed with the crosslinked acrylic copolymer layers of this invention to organic solvent based coatings applied thereto renders such film of more universal utility to the manufacturer of finished reprographic, graphic and packaging products.
  • Reprographic adhesion is evaluated using a lacquer comprising (in parts by weight) 9 parts cellulose acetate butyrate of "20 second" grade dissolved in a mixture of 88 parts ethylene glycol monomethyl ether (methyl cellosolve) and 3 parts methyl ethyl ketone with Rhodamine B dye added for color (3 parts of a 1 percent Rhodamine B dye in n-butanol).
  • the lacquer is applied to the coated surface of the film by means of a wire-wound bar, Meyer rod No. 70, and cured in an oven for 5 minutes at 60 ⁇ C.
  • the coating is scored with a cross-hatched pattern by means of scalpel.
  • a strip of adhe ⁇ sive tape (Scotch tape 610) is adhered to the cross-hatched area, rubbed with a fingernail to insure intimate contact and then pulled rapidly from the film.
  • the mechanical properties are measured in a tensile testing machine made by Zwick (Ulm, Germany) on 15 mm wide strips of film.
  • the initial distance between the chucks is 100 mm and the crosshead speed is 100 mm/min for strength determination and 10 mm/min for the tensile modulus determination.
  • the UV resistance is tested by measuring the retention of tensile elongation after exposure to UV light in a "Suntest" apparatus manufactured by Heraeus (Hanau, Germany) for 14 days.
  • EXAMPLE A latex comprising 4.5 percent by weight solids of a copolymer of 60 weight percent of methyl methacrylate, 35 weight percent ethyl acrylate, and
  • N-methyloiacrylamide 5 weight percent of N-methyloiacrylamide, and a surfactant are applied as a primer coating to a PENBB film which is made of 289 parts by weight of dimethyl 2,6-naphthalene dicarboxylate, 322 parts by weight of dimethyl 4,4'-bibenzoate, 368 parts by weight of ethylene glycol.
  • Granules of this polymer, having a melting point of 281 °C are melted in a single screw ex ⁇ truder at temperatures of 280 to 320°C and extruded through a sheet die onto a cooling roll, temperature controlled at 30°C.
  • a 120 ⁇ m thick film is obtained which is clear and transparent. Its density is 1.31 g/cm 3 .
  • This pre- film is then sequentially biaxially oriented.
  • the longitudinally drawn film is corona treated by a corona discharge apparatus and thereinafter coated with the latex described above by reverse gravure coating.
  • the corona treated longitudinally drawn, coated film is dried at a temperature of about 100°C. Thereafter the film is stretched in the transverse direction.
  • the biaxially drawn film is heat set at a temperature of 230°C. These heat treatments result in the crosslinking of the primer coating.
  • the thus obtained primer coated PENBB film shows the following characteristics compared to a similarly coated PET film.
  • stiffness tensile strength, tensile modulus
  • elongation at break elongation at break
  • shrinkage elongation at break
  • UV resistance elongation at break
  • the film produced according to the above example is tested for reprographic adhesion as set forth above and provides greater than 95 percent adhesion as compared with a control uncoa- ted polyester film which exhibited 0 percent adhesion.

Abstract

L'invention concerne un film de polyester monocouche ou multicouche autoporteur, à orientation biaxiale recouvert d'une couche primaire, le copolyester utilisé étant du PENBB et la couche primaire contenant un polymère acrylique. Le PENBB est un copolyester contenant des unités représentées par la formule (I).
EP93900176A 1992-12-09 1992-12-09 Film de copolyester recouvert d'une couche primaire de polymeres acryliques. Withdrawn EP0671994A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1992/010699 WO1994013476A1 (fr) 1992-12-09 1992-12-09 Film de copolyester recouvert d'une couche primaire de polymeres acryliques

Publications (2)

Publication Number Publication Date
EP0671994A1 EP0671994A1 (fr) 1995-09-20
EP0671994A4 true EP0671994A4 (fr) 1995-11-08

Family

ID=22231617

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93900176A Withdrawn EP0671994A4 (fr) 1992-12-09 1992-12-09 Film de copolyester recouvert d'une couche primaire de polymeres acryliques.

Country Status (2)

Country Link
EP (1) EP0671994A4 (fr)
WO (1) WO1994013476A1 (fr)

Families Citing this family (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0674584A4 (fr) * 1992-12-09 1995-11-22 Hoechst Ag Film de pennbb oriente biaxialement utilise pour le vitrage, l'optique et la fabrication d'articles resistant aux intemperies.
DE19741878A1 (de) 1997-09-23 1999-03-25 Hoechst Diafoil Gmbh Mehrschichtige, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19741877A1 (de) 1997-09-23 1999-03-25 Hoechst Diafoil Gmbh Biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19813270A1 (de) 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Polyesterfolie mit hoher Sauerstoffbarriere und verbesserter Haftung zu Metallschichten, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19813271A1 (de) * 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Transparente Polyesterfolie mit hoher Sauerstoffbarriere, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19813266A1 (de) 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Polyesterfolie mit hoher Sauerstoffbarriere, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19813264A1 (de) 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Polyesterfolie mit an den Anwendungszweck angepaßter Oberflächentopographie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19813269A1 (de) 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Siegelfähige Polyesterfolie mit hoher Sauerstoffbarriere, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19813267A1 (de) 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Transparente Polyesterfolie mit hoher Sauerstoffbarriere und zusätzlicher Funktionalität, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19813268A1 (de) 1998-03-25 1999-09-30 Hoechst Diafoil Gmbh Verwendung einer transparenten Polyesterfolie als Gas/Aromabarrierefolie
DE19814710A1 (de) 1998-04-01 1999-10-07 Hoechst Diafoil Gmbh Mehrschichtige, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung als Magnetbandfolie
DE19817841A1 (de) 1998-04-22 1999-10-28 Hoechst Diafoil Gmbh Mehrschichtige, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19817842A1 (de) 1998-04-22 1999-10-28 Hoechst Diafoil Gmbh Einschichtige, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19834603A1 (de) 1998-07-31 2000-02-03 Hoechst Diafoil Gmbh Matte, koextrudierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19834602A1 (de) 1998-07-31 2000-02-03 Hoechst Diafoil Gmbh Mehrschichtige, biaxial orientierte Polypropylenfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19839007A1 (de) 1998-08-29 2000-03-02 Hoechst Diafoil Gmbh Verfahren zur Herstellung von biaxial orientierten PET-Folie und Verwendung derselben für Folienkondensatoren in der SMD-Technik
DE19839848A1 (de) 1998-09-02 2000-04-13 Hoechst Diafoil Gmbh Mehrschichtige, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung als Magnetbandfolie mit optimierten elektromagnetischen Eigenschaften
DE19842376A1 (de) 1998-09-16 2000-03-23 Hoechst Diafoil Gmbh Biaxial orientierte Polypropylenfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1116745A4 (fr) * 1998-09-25 2005-04-13 Yupo Corp Film de resine thermoplastique et feuille etiquette comprenant ledit film
DE19849661A1 (de) 1998-10-29 2000-05-04 Mitsubishi Polyester Film Gmbh Koextrudierte, biaxial orientierte Polyesterfolie für die Metallisierung, Verfahren zu ihrer Herstellung und ihre Verwendung
EP0999041A3 (fr) 1998-11-03 2001-01-31 Mitsubishi Polyester Film GmbH Feuille multicouche comprenant une feuille de polyester orientée biaxialement présentant des bonnes propriétés de barrière à l'oxygène, procédé de fabrication et utilisation
DE19932384A1 (de) 1999-07-14 2001-01-18 Mitsubishi Polyester Film Gmbh Weiße, biaxial orientierte Polyesterfolie mit Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung
DE10002178A1 (de) 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matte, UV-stabile, koextrudierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10002169A1 (de) 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matte, UV-stabile, thermoformbare, koextrudierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10002160A1 (de) 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Matte, UV-stabile, schwerentflammbare koextrudierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10007719A1 (de) 2000-02-19 2001-08-23 Mitsubishi Polyester Film Gmbh Weiß-opake Folie mit niedriger Transparenz aus einem kristallisierbaren Thermoplasten mit zusätzlicher Funktionalität
DE10035328A1 (de) 2000-07-20 2002-01-31 Mitsubishi Polyester Film Gmbh Opake Polyesterfolie enthaltend Cycloolefincopolymer (COC) mit guter Oberflächenhaftung, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10119023A1 (de) * 2001-04-18 2002-10-24 Mitsubishi Polyester Film Gmbh Mehrschichtige transparente biaxial orientierte Polywsterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10352430A1 (de) 2003-11-10 2005-06-09 Mitsubishi Polyester Film Gmbh Peelfähige Polyesterfolie mit verbesserter Sauerstoffbarriere, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10352431A1 (de) 2003-11-10 2005-06-09 Mitsubishi Polyester Film Gmbh Peelfähige Polyesterfolie mit selbsttätiger Entlüftung, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10352432A1 (de) 2003-11-10 2005-06-09 Mitsubishi Polyester Film Gmbh Weiße, heißsiegelbare, peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10352444A1 (de) 2003-11-10 2005-06-09 Mitsubishi Polyester Film Gmbh Haftvermittelte, heißsiegelbare und peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102004030979A1 (de) 2004-06-26 2006-01-19 Mitsubishi Polyester Film Gmbh Extrusionsbeschichtbare Polyesterfolie enthaltend Poly(m-xylol-adipinamid)
DE102004032595A1 (de) 2004-07-06 2006-02-16 Mitsubishi Polyester Film Gmbh Matte, thermoformbare, IR-reflektierende Polyesterfolie
DE102004032596A1 (de) 2004-07-06 2006-02-16 Mitsubishi Polyester Film Gmbh Mehrschichtige, matte, thermoformbare, IR-reflektierende Polyesterfolie
DE102004049609A1 (de) 2004-10-12 2006-04-13 Mitsubishi Polyester Film Gmbh Polyesterfolie mit hydrophiler Beschichtung, Verfahren zu ihrer Herstellung und ihre Verwendung
DE502006001168D1 (de) 2005-06-01 2008-09-04 Mitsubishi Polyester Film Gmbh Weiss-opake Folie mit niedriger Transparenz und verbesserter Durchschlagsfestigkeit
DE102006023293A1 (de) 2006-05-18 2007-11-22 Mitsubishi Polyester Film Gmbh Biaxial orientierte Polyesterfolie für die Blechlaminierung
US8158230B2 (en) 2007-11-06 2012-04-17 Mitsubishi Polyester Film, Inc. Tamper evident composite film
DE102009021713A1 (de) 2009-05-18 2010-11-25 Mitsubishi Polyester Film Gmbh Peelbare, transparente Polyesterfolie für unpolare Substrate mit Antifogbeschichtung
DE102016209214A1 (de) 2016-05-27 2017-11-30 Mitsubishi Polyester Film Gmbh Heißsiegelbare und peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102016222146A1 (de) 2016-11-11 2018-05-17 Mitsubishi Polyester Film Gmbh Biaxial orientierte, heißsiegelbare und peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102017117328A1 (de) * 2017-07-31 2019-01-31 Mitsubishi Polyester Film Gmbh Peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
GB2571256B (en) * 2018-02-14 2020-08-19 Camvac Ltd Thermally laminated film
DE102018214185A1 (de) 2018-08-22 2020-02-27 Mitsubishi Polyester Film Gmbh Polyesterfolie mit Beschichtung

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57189823A (en) * 1981-05-20 1982-11-22 Toray Ind Inc Production of polyester film
US4592953A (en) * 1983-12-12 1986-06-03 American Hoechst Corporation Polyester film primed with crosslinked vinyl acetate polymers
US4571363A (en) * 1983-12-12 1986-02-18 American Hoechst Corporation Polyester film primed with crosslinked acrylic polymers
US4556606A (en) * 1983-12-30 1985-12-03 General Electric Company UV-Stabilized coated polyester-carbonate articles and process
FR2644105B1 (fr) * 1989-03-08 1991-07-05 Rhone Poulenc Films Films polyester composites, leur procede d'obtention et leur utilisation comme support de revetements finals d'application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
No further relevant documents disclosed *

Also Published As

Publication number Publication date
EP0671994A1 (fr) 1995-09-20
WO1994013476A1 (fr) 1994-06-23

Similar Documents

Publication Publication Date Title
EP0671994A1 (fr) Film de copolyester recouvert d'une couche primaire de polymeres acryliques
EP0674591A1 (fr) Film de copolyester oriente biaxialement revetu d'une premiere couche de polymeres d'acetate de vinyle
US4571363A (en) Polyester film primed with crosslinked acrylic polymers
US5051475A (en) Polyester-based film
CA1260340A (fr) Pellicules a enduit antistatique
US6485818B2 (en) Polyester film for imaging media
EP1040156B1 (fr) Film de polyester revetu oriente
US4592953A (en) Polyester film primed with crosslinked vinyl acetate polymers
US5709926A (en) Reclaimable transparencies for plain paper copiers
JP2886024B2 (ja) コーティング剤及び該剤を塗布した易接着性ポリエステルフイルム
JP3122001B2 (ja) 積層フイルム
JP2739772B2 (ja) 酢酸ビニル重合体で下塗りされた二軸配向共重合ポリエステルフィルム
JP2685355B2 (ja) アクリルポリマーで下塗りしたコポリエステルフィルム
JP3269155B2 (ja) 空洞含有ポリエステルフィルム積層体
EP0673310A1 (fr) Film de copolyester oriente biaxialement recouvert d'une couche primaire de silane fonctionnel et stratifies produits avec ce film
JPH09141808A (ja) 積層フイルム
JP3183084B2 (ja) 積層フィルム
JPH08197687A (ja) 積層フイルム
JPH10193542A (ja) 制電性ポリエステルフィルム
JPH06184337A (ja) 帯電防止性ポリエステルフィルム
JPH09314779A (ja) 易接着性ポリエステルフィルム
JPH0985919A (ja) ジアゾ易接着用積層ポリエステルフィルム
JPH08151466A (ja) 積層フィルム
JPH051164A (ja) 帯電防止性ポリエステルフイルム
JPH09169090A (ja) 易接着性ポリエステルフィルム

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

17P Request for examination filed

Effective date: 19950602

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT LU NL

A4 Supplementary search report drawn up and despatched

Effective date: 19950921

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): DE FR GB IT LU NL

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KUHMANN, BODO

Inventor name: FLINT, JOHN, ANTHONY

Inventor name: CHOE, E-WON

Inventor name: BENNETT, CYNTHIA

17Q First examination report despatched

Effective date: 19971006

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HOECHST DIAFOIL GMBH

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

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19991012