US20060046041A1 - Opaque, white film with low transparency made from a crystallizable thermoplastic - Google Patents

Opaque, white film with low transparency made from a crystallizable thermoplastic Download PDF

Info

Publication number
US20060046041A1
US20060046041A1 US11/250,259 US25025905A US2006046041A1 US 20060046041 A1 US20060046041 A1 US 20060046041A1 US 25025905 A US25025905 A US 25025905A US 2006046041 A1 US2006046041 A1 US 2006046041A1
Authority
US
United States
Prior art keywords
film
thermoplastic
weight
barium sulfate
opaque
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.)
Abandoned
Application number
US11/250,259
Inventor
Ursula Murschall
Ulrich Kern
Klaus Oberlaender
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to US11/250,259 priority Critical patent/US20060046041A1/en
Publication of US20060046041A1 publication Critical patent/US20060046041A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041Optical brightening agents, organic pigments
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045Sulfates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495Thickness [relative or absolute]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers

Definitions

  • the invention relates to an opaque, white biaxially oriented film with low transparency made from a crystallizable thermoplastic and having a thickness of from 10 to 500 ⁇ m, where at least one surface of the film has optionally been provided with an additional functionality.
  • the film comprises at least barium sulfate and an optional optical brightener, and has good orientability, low transparency, and also very good optical and mechanical properties.
  • the invention further relates to a process for producing this film and to the use of the film.
  • the object of the present invention was to provide an opaque, white biaxially oriented film with a thickness of from 10 to 500 ⁇ m and optionally having at least one additional functionality and which, besides having good orientability, good mechanical properties and good optical properties and a low Yellowness Index, above all has a high level of whiteness and low transparency and can be produced simply and cost-effectively and does not cause any disposal problems.
  • the good optical properties include uniform, streak-free coloration, low luminous transmittance/transparency ( ⁇ 30%), acceptable surface gloss ( ⁇ 10), and also a low Yellowness Index (dependent on thickness, ⁇ 45 for 250 ⁇ m films and ⁇ 20 for 50 ⁇ m films).
  • the good mechanical properties include a high modulus of elasticity (E MD ⁇ 3300 N/mm 2 ; E TD ⁇ 4200 N/mm 2 ), and also good tear strengths (in MD ⁇ 120 N/mm 2 ; in TD ⁇ 170 N/mm 2 ) and finally also good longitudinal (MD) and transverse (TD) elongations at break (in MD ⁇ 120%; in TD ⁇ 50%).
  • Good orientability includes excellent capabilities of the film for orientation during its production, both longitudinally and transversely, without break-offs.
  • the novel film should moreover be recyclable, that is to say that any cut material arising during continuous film production can be fed back into the production operation, in particular without loss of optical or mechanical properties, so that the film can still be used for interior applications and in constructing exhibition stands, for example.
  • an opaque white film with a thickness of from 10 to 500 ⁇ m whose principal constituent is a crystallizable thermoplastic, and whose characterizing features are that the film comprises at least barium sulfate and optionally at least one optical brightener, that the barium sulfate and/or the optional optical brightener have been incorporated directly into the crystallizable thermoplastic or are fed as a masterbatch during film production, and that at least one surface of the film bears an optional functional coating with a thickness of from 5 to 100 nm.
  • the novel film comprises, as principal constituent, a crystallizable thermoplastic.
  • suitable crystallizable or semicrystalline thermoplastics are polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and preference is given to polyethylene terephthalate.
  • a crystallizable thermoplastic is
  • the present invention also provides a process for producing this film, comprising:
  • the novel film may have one layer, i.e. have only one base layer and the optional functional coating, or else have two or more layers, i.e. have one base layer, at least one outer layer on the base layer and the optional functional coating, the combination of base layer and outer layer expediently being produced by way of coextrusion technology.
  • the film optionally comprises at least barium sulfate as pigment, and the amount of pigment here is preferably from 0.2 to 40% by weight, based on the weight of the crystallizable thermoplastic.
  • the barium sulfate is preferably fed by way of what is known as masterbatch technology during film production.
  • the film comprises at least one optical brightener, and the amount of the optical brightener used here is from 10 to 50,000 ppm, in particular from 20 to 30,000 ppm, particularly preferably from 50 to 25,000 ppm, based on the weight of the crystallizable thermoplastic. It is preferable for the optical brightener, too, to be fed by way of what is known as masterbatch technology during film production.
  • optical brighteners according to the invention are capable of absorbing UV radiation in the region from 360 to 380 nm and of re-emitting this as longer-wavelength, visible blue-violet light.
  • Suitable optical brighteners are bisbenzoxazoles, phenylcoumarins and bisstearylbiphenyls, in particular phenylcoumarin, and particularly preferably triazine phenylcoumarin, which is obtainable as the product TINOPAL® (Ciba-Geigy, Basle, Switzerland), or else HOSTALUX® KS (Clariant, Germany), or EASTOBRITE® OB-1 (Eastman).
  • blue dyes soluble in polyester may also be added if this is useful.
  • Dyes which have proven successful are cobalt blue, ultramarine blue and anthraquinone dyes, in particular Sudan Blue 2 (BASF, Ludwigshafen, Germany).
  • the amounts of the blue dyes used are from 10 to 10,000 ppm, in particular from 20 to 5000 ppm, particularly preferably from 50 to 1000 ppm, based on the weight of the crystallizable thermoplastic.
  • a preferred embodiment of the invention uses precipitated grades of barium sulfate.
  • Precipitated barium sulfate is obtained as a fine-particle colorless powder from barium salts and sulfates or sulfuric acid, and the particle size of the powder can readily be controlled via the conditions of precipitation.
  • Precipitated barium sulfate may be prepared by the usual processes, which are described in Kunststoff-Journal 8, No. 10, 30-36 and No. 11, 36-31 (1974).
  • the amount of barium sulfate is from 0.2 to 40% by weight, preferably from 0.5 to 30% by weight, particularly preferably from 1 to 25% by weight, based on the weight of the crystallizable thermoplastic.
  • the average grain size of the barium sulfate is relatively small and is preferably from 0.1 to 5 ⁇ m, particularly preferably from 0.2 to 3 ⁇ m (Sedigraph method).
  • the density of the barium sulfate used is from 4 to 5 g/cm 3 .
  • the novel film comprises, as principal constituent, a crystallizable polyethylene terephthalate, and also from 1 to 25% by weight of precipitated barium sulfate, appropriately with a particle diameter of from 0.4 to 1 ⁇ m, particularly preferably BLANC FIXE® XR-HX or BLANC FIXE® HXH from Sachtleben Chemie, Germany.
  • the surface gloss of the novel film measured to DIN 67530 (measurement angle 20°) is greater than or equal to 10, preferably greater than or equal to 15.
  • the luminous transmittance (transparency) of the novel film is less than or equal to 30%, preferably less than or equal to 25%.
  • the coloration is uniform and streak-free over the entire running length and the entire width of the film.
  • the novel film is whiter, that is to say has less yellow tinge, and has lower light transmittance, that is to say has lower transparency than a film provided only with barium sulfate as pigment.
  • the longitudinal modulus of elasticity (ISO 527-1-2) of the novel film is greater than or equal to 3300 N/mm 2 , preferably greater than or equal to 3500 N/mm 2 . Its transverse modulus of elasticity (ISO 527-1-2) is greater than or equal to 4200 N/mm 2 , preferably greater than or equal to 4400 N/mm 2 .
  • the standard viscosity SV (DCA) of the polyethylene terephthalate preferably used for the novel film, measured in dichloroacetic acid to DIN 53728, is from 600 to 1100, preferably from 700 to 1000.
  • the opaque white polyethylene terephthalate film which comprises at least barium sulfate, an optional optical brightener and, if desired, blue dyes may have either one layer or else two or more layers.
  • the film has a structure of at least one base layer and at least one outer layer, and particular preference is given here to a three-layer A-B-A or A-B-C structure.
  • the polyethylene terephthalate of the base layer it is appropriate for the polyethylene terephthalate of the base layer to have a standard viscosity similar to that of the polyethylene terephthalate of the outer layer(s) directly adjacent to the base layer.
  • the outer layers may also be composed of a polyethylene naphthalate homopolymer or of a polyethylene terephthalate-polyethylene naphthalate copolymer, or of a compound.
  • the thermoplastics of the outer layers likewise have a standard viscosity similar to that of the polyethylene terephthalate of the base layer.
  • the barium sulfate, and also the optional optical brightener and, if present, the blue dye are preferably present in the base layer.
  • modification of the outer layers is also possible, if required.
  • the amounts given for the additives are based on the weight of the thermoplastics in the layer provided with the additive(s).
  • novel film is easy to recycle without pollution of the environment and without loss of mechanical properties, making it suitable, for example, for use as short-lived promotional placards, labels or other promotional requisites.
  • An example of a production process for producing the novel film is extrusion on an extrusion line.
  • the barium sulfate, the optional optical brightener and, if present, the blue dye may be incorporated into the thermoplastic as early as when the thermoplastic polymer is prepared, or else fed into the extruder by way of masterbatch technology during film production.
  • the barium sulfate, the optional optical brightener and, if present, the blue dye is particularly preferable for the barium sulfate, the optional optical brightener and, if present, the blue dye to be added by way of masterbatch technology.
  • the additives here are fully dispersed in a solid carrier material.
  • Carrier materials which may be used are the thermoplastic itself, e.g. the polyethylene terephthalate, or else other polymers sufficiently compatible with the thermoplastic.
  • the particle size and the bulk density of the masterbatch(es) are similar to the particle size and the bulk density of the thermoplastic, so that uniform dispersion is achieved, and with this a uniform level of whiteness and thus also uniform opacity.
  • the polyester films may be produced by known processes from a polyester with, if desired, other polymers, and also with the optional optical brightener, the barium sulfate, if desired with the blue dye, and/or with a usual amount of from 0.1 to a maximum of 10% by weight of other customary additives, either in the form of monofilms or else in the form of, if desired, coextruded films having two or more layers and with identical or differently constructed surfaces, where one surface may have provision of pigment, but no pigment is present in the other surface.
  • known processes can be used to provide one or both surfaces of the film with an optional functional coating.
  • At least one of the surfaces of the film is coated, so that on the finished film a coating of from 5 to 100 nm, preferably from 20 to 70 nm, in particular from 30 to 50 nm is present.
  • the coating is preferably applied in-line, i.e. during the film-production process, appropriately prior to the transverse stretching. Particular preference is given to application by reverse gravure-roll coating, which is capable of applying the coatings extremely uniformly with the layer thicknesses mentioned.
  • the coatings are preferably applied as solutions, suspensions or dispersions, particularly preferably as an aqueous solution, suspension or dispersion.
  • the coatings mentioned give the surface of the film an additional function, making the film sealable, printable, metallizable, sterilizable or antistatic, for example, or improving the flavor barrier, for example, or permitting adhesion to materials (e.g. photographic emulsions) which would not adhere to the surface of the film without the coating.
  • substances/compositions which give additional functionality are:
  • acrylates for example as described in WO 94/13476, ethylvinyl alcohols, PVDC, waterglass (Na 2 SiO 4 ), hydrophilic polyesters, such as PET/IPA polyesters containing the sodium salt of 5-sulfoisophthalic acid, as described in EP-A-0 144 878 or U.S. Pat. No.
  • vinyl acetates for example, or in EP-A-0 296 620, vinyl acetates, as described in WO 94/13481, for example, polyvinyl acetates, polyurethanes, silanes, the alkali metal or alkaline earth metal salts of C 10 -C 18 fatty acids, butadiene copolymers with acrylonitrile or methyl methacrylate, methacrylic acid, acrylic acid or esters thereof.
  • the substances/compositions which give the additional functionality may comprise from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, of the customary additives, e.g. antiblocking agents or pH stabilizers.
  • the substances/compositions mentioned are applied as dilute solution, emulsion or dispersion, preferably as aqueous solution, emulsion or dispersion, to one or both surfaces of the film, and the solvent is then evaporated. If the coatings are applied in-line prior to the transverse stretching, it is usual for the heat treatment during the transverse stretching and subsequent heat-setting to suffice for evaporating the solvent and drying the coating.
  • the dried coatings then have layer thicknesses of from 5 to 100 nm, preferably from 20 to 70 nm, in particular from 30 to 50 nm.
  • the polyester material melted in the extruder is extruded through a slot die and quenched on a chill roll, as a substantially amorphous prefilm.
  • This prefilm is then reheated and stretched longitudinally and transversely, or transversely and longitudinally, or longitudinally, transversely and again longitudinally and/or transversely.
  • the stretching temperatures are from T g +10 K to T g +60 K (T g is the glass transition temperature)
  • the longitudinal stretching ratio according to the invention is from 2 to 5, in particular from 2.5 to 4.5
  • the transverse stretching ratio is from 2 to 5, in particular from 3 to 4.5
  • the ratio for any second longitudinal stretching carried out is from 1.1 to 3.
  • the first longitudinal stretching may, if desired, be carried out simultaneously with the transverse stretching (simultaneous stretching). Stretching is followed by the heat-setting of the film at oven temperatures of from 200 to 260° C., in particular from 220 to 250° C. Following the heat-setting, the film is cooled and wound up.
  • the longitudinal process parameters include in particular the longitudinal stretching ratio and the longitudinal stretching temperature. It was highly surprising that the transparency could be markedly affected by varying the longitudinal stretching ratio. If, for example, a film plant produces a film whose transparency is above the values according to the invention, novel films with a lower transparency can be produced by increasing the longitudinal stretching ratio during the longitudinal stretching procedure. A relative increase of 7% in the longitudinal stretching ratio gave a relative reduction of from 15 to 20% in transparency.
  • a major advantage is that the production costs for the novel film are only insignificantly higher than those for a film made from standard polyesters.
  • the other processing properties and use properties of the novel film remain essentially unchanged or indeed show improvement.
  • the method of film production ensures that the regrind can be used again in a proportion of up to 50% by weight, preferably from 10 to 50% by weight, based in each case on the total weight of the film, without any appreciable adverse resultant effect on the physical properties of the film.
  • the surprising combination of excellent properties makes the novel film highly suitable for a variety of different applications, such as interior decoration, for constructing exhibition stands, for exhibition requisites, for displays, for placards, for labels, for protective glazing of machines or of vehicles, in the lighting sector, in the fitting out of shops or of stores, as a promotional requisite or a laminating material, in applications associated with food or drink or, depending on the functionality of one or both surfaces, as a photographic film, as a graphic film, a laminatable film, a metallizable film or a printable film.
  • the luminous transmittance/transparency is the ratio of total light transmitted to the amount of incident light.
  • Luminous transmittance is measured using “Hazegard plus” test equipment to ASTM D 1003.
  • the modulus of elasticity, tear strength and elongation at break are measured longitudinally and transversely to ISO 527-1-2.
  • the standard viscosity SV (DCA) is measured by a method based on DIN 53726 in dichloroacetic acid.
  • the Yellowness Index YID is the deviation from the colorless condition in the “yellow” direction and is measured to DIN 6167.
  • the whiteness is determined according to Berger, generally using more than 20 mutually superposed layers of film, and with the aid of the ELREPHO® electrical reflectance photometer from Zeiss, Oberkochem, Germany, with standard aluminant C and a 2° standard observer.
  • W whiteness
  • RY, RZ and RX corresponding reflection factors using the Y, Z and X color measurement filter.
  • the whiteness standard used is a barium sulfate pressing (DIN 5033, Part 9). A detailed description is found in Hansl Loos “Farbbuz” [Color measurement], Verlagp and Hydr, Itzehoe (1989), for example.
  • each of the films is a single-layer opaque white film, produced on the extrusion line described.
  • An opaque white film of 50 ⁇ m thickness was produced and comprised polyethylene terephthalate (RT32, KoSa, Germany) as principal constituent, 18% by weight of barium sulfate (BLANC FIX® XR-HX, Sachtleben Chemie), 200 ppm of optical brightener (TINOPAL®, Ciba-Geigy, Basle) and 40 ppm of blue dye (SUDAN BLUE® 2, BASF, Ludwigshafen).
  • barium sulfate BLANC FIX® XR-HX, Sachtleben Chemie
  • TINOPAL® Ciba-Geigy, Basle
  • blue dye SIDAN BLUE® 2
  • the additives barium sulfate, optical brightener and blue dye were added as masterbatches.
  • the polyethylene terephthalate used to prepare the masterbatches had a standard viscosity SV (DCA) of from 900 to 1100.
  • the masterbatch (1) was composed of clear polymer, 50% by weight of barium sulfate and 600 ppm of optical brightener.
  • the masterbatch (2) comprised 2000 ppm of blue dye, besides clear polymer.
  • the longitudinal stretching ratio set during film production was 3.1. After longitudinal stretching, both sides of the film were coated with an aqueous dispersion, using reverse gravure-roll coating.
  • the dispersion comprised, besides water, 4.2% by weight of hydrophilic polyester (PET/IPA polyester containing the sodium salt of 5-sulfoisophthalic acid, SP41®, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (NALCO® 1060, Deutsche Nalco Chemie, Germany) as antiblocking agent, and also 0.15% by weight of ammonium carbonate (Merck, Germany) as pH buffer.
  • the wet application weight was 2 g/m 2 for each side coated. After transverse stretching, the calculated thickness of the coating was 40 nm.
  • Example 1 was repeated, except that the film had no blue dye.
  • a coextruded, opaque white ABA film of thickness 75 ⁇ m was produced, where A are the outer layers and B is the base layer.
  • the mixing specification for the base layer of 71 ⁇ m thickness corresponded to the mixing specification of Example 2.
  • the outer layers of 2 ⁇ m thickness comprised 93% by weight of clear polymer, and also 7% by weight of a masterbatch which comprised, besides clear polymer, 10,000 ppm of silicon dioxide (SYLOBLOC®, Grace, Germany).
  • This film has high surface gloss.
  • the longitudinal stretching ratio was 3.3.
  • the film was coated in a manner similar to that of Example 1, but only on one side.
  • Example 3 was repeated.
  • the longitudinal stretching ratio was reduced to 2.8, while the longitudinal stretching temperatures remained unchanged.
  • the film was not coated after longitudinal stretching.
  • Comparative Example 1 was repeated, but the film was not provided with optical brightener.
  • the film comprised only 18% by weight of barium sulfate, and this was incorporated directly during preparation of the polymer.
  • the standard viscosity of the barium sulfate-containing polymer was 810. The film was not coated after longitudinal stretching.

Abstract

The invention relates to an opaque, white film with a thickness of from 10 to 500 μm whose principal constituent is a crystallizable thermoplastic. The film comprises barium sulfate and an optional optical brightener. Optionally, at least one surface of the film bears a functional coating with a thickness of from 5 to 100 nm, in order to confer on the film surface an additional function such as sealability, printability, metallizability, sterilizability, antistatic properties, aroma barrier properties or improved adhesion to materials which would not adhere to the film surface without the coating, for example photographic emulsions.

Description

  • This application is a continuation of parent co-pending U.S. application Ser. No. 09/779,156, filed Feb. 8, 2001. This application further claims priority through its parent U.S. application to German Application No. 100 07 719.6, filed Feb. 19, 2000. Both U.S. application Ser. No. 09/779,156 and German Application No. 100 07 719.6 are hereby incorporated by reference herein in their entirety.
  • The invention relates to an opaque, white biaxially oriented film with low transparency made from a crystallizable thermoplastic and having a thickness of from 10 to 500 μm, where at least one surface of the film has optionally been provided with an additional functionality. The film comprises at least barium sulfate and an optional optical brightener, and has good orientability, low transparency, and also very good optical and mechanical properties. The invention further relates to a process for producing this film and to the use of the film.
  • BACKGROUND OF THE INVENTION
  • In many food and drink packaging applications, there is demand for a high level of barrier action with respect to gases, water vapor and flavors. For this reason, use is usually made of polypropylene films which have been metallized or have been coated with polyvinylidene chloride (PVDC). In the case of PVDC-coated films—as with metallizing—the coating takes place in a second operation, which makes the packaging markedly more expensive. Ethylene-vinyl alcohol copolymers (EVOH) likewise exhibit strong barrier action. However, films modified with EVOH are particularly sensitive to moisture, and this limits their range of application. In addition, due to their poor mechanical properties they have relatively high thickness or have to be laminated with other materials at high cost. The disposal of EVOH-modified films after they have been used is also more complicated than that of other films. In addition to this, some raw materials are not approved by the authorities or are unsuitable for producing packaging for food or drink.
  • DESCRIPTION OF THE INVENTION
  • The object of the present invention was to provide an opaque, white biaxially oriented film with a thickness of from 10 to 500 μm and optionally having at least one additional functionality and which, besides having good orientability, good mechanical properties and good optical properties and a low Yellowness Index, above all has a high level of whiteness and low transparency and can be produced simply and cost-effectively and does not cause any disposal problems.
  • The good optical properties include uniform, streak-free coloration, low luminous transmittance/transparency (≦30%), acceptable surface gloss (≧10), and also a low Yellowness Index (dependent on thickness, ≦45 for 250 μm films and ≦20 for 50 μm films).
  • The good mechanical properties include a high modulus of elasticity (EMD≧3300 N/mm2; ETD≧4200 N/mm2), and also good tear strengths (in MD≧120 N/mm2; in TD≧170 N/mm2) and finally also good longitudinal (MD) and transverse (TD) elongations at break (in MD≧120%; in TD≧50%).
  • Good orientability includes excellent capabilities of the film for orientation during its production, both longitudinally and transversely, without break-offs.
  • The novel film should moreover be recyclable, that is to say that any cut material arising during continuous film production can be fed back into the production operation, in particular without loss of optical or mechanical properties, so that the film can still be used for interior applications and in constructing exhibition stands, for example.
  • This object is achieved by an opaque white film with a thickness of from 10 to 500 μm whose principal constituent is a crystallizable thermoplastic, and whose characterizing features are that the film comprises at least barium sulfate and optionally at least one optical brightener, that the barium sulfate and/or the optional optical brightener have been incorporated directly into the crystallizable thermoplastic or are fed as a masterbatch during film production, and that at least one surface of the film bears an optional functional coating with a thickness of from 5 to 100 nm.
  • The novel film comprises, as principal constituent, a crystallizable thermoplastic. Examples of suitable crystallizable or semicrystalline thermoplastics are polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and preference is given to polyethylene terephthalate.
  • For the purposes of the present invention, a crystallizable thermoplastic is
  • 1. a crystallizable homopolymer;
  • 2. a crystallizable copolymer;
  • 3. a crystallizable compound;
  • 4. a crystallizable recycled material, or
  • 5. another type of crystallizable thermoplastic.
  • The present invention also provides a process for producing this film, comprising:
  • 6. production of a film from at least one base layer and, if desired, (an) outer layer(s), by extrusion or, if desired, coextrusion;
  • 7. biaxial orientation of the film;
  • 8. heat-setting of the oriented film; and
  • 9. optional functionalization of at least one surface of the film prior to, during or after steps 2 and/or 3.
  • The novel film may have one layer, i.e. have only one base layer and the optional functional coating, or else have two or more layers, i.e. have one base layer, at least one outer layer on the base layer and the optional functional coating, the combination of base layer and outer layer expediently being produced by way of coextrusion technology.
  • According to the invention, the film optionally comprises at least barium sulfate as pigment, and the amount of pigment here is preferably from 0.2 to 40% by weight, based on the weight of the crystallizable thermoplastic. The barium sulfate is preferably fed by way of what is known as masterbatch technology during film production.
  • According to the invention, the film comprises at least one optical brightener, and the amount of the optical brightener used here is from 10 to 50,000 ppm, in particular from 20 to 30,000 ppm, particularly preferably from 50 to 25,000 ppm, based on the weight of the crystallizable thermoplastic. It is preferable for the optical brightener, too, to be fed by way of what is known as masterbatch technology during film production.
  • The optical brighteners according to the invention are capable of absorbing UV radiation in the region from 360 to 380 nm and of re-emitting this as longer-wavelength, visible blue-violet light.
  • Suitable optical brighteners are bisbenzoxazoles, phenylcoumarins and bisstearylbiphenyls, in particular phenylcoumarin, and particularly preferably triazine phenylcoumarin, which is obtainable as the product TINOPAL® (Ciba-Geigy, Basle, Switzerland), or else HOSTALUX® KS (Clariant, Germany), or EASTOBRITE® OB-1 (Eastman).
  • Besides the optional optical brightener, blue dyes soluble in polyester may also be added if this is useful. Dyes which have proven successful are cobalt blue, ultramarine blue and anthraquinone dyes, in particular Sudan Blue 2 (BASF, Ludwigshafen, Germany).
  • The amounts of the blue dyes used are from 10 to 10,000 ppm, in particular from 20 to 5000 ppm, particularly preferably from 50 to 1000 ppm, based on the weight of the crystallizable thermoplastic.
  • It was highly surprising that the use of the abovementioned combination of barium sulfate and optional optical brightener and, if present, blue dyes in the films in conjunction with the increased longitudinal stretching ratio during film production gave the desired result.
  • It is also very surprising that the cut material produced while film production is running can also be reused as regrind for the production process without any adverse effect on the Yellowness Index of the film.
  • A preferred embodiment of the invention uses precipitated grades of barium sulfate. Precipitated barium sulfate is obtained as a fine-particle colorless powder from barium salts and sulfates or sulfuric acid, and the particle size of the powder can readily be controlled via the conditions of precipitation. Precipitated barium sulfate may be prepared by the usual processes, which are described in Kunststoff-Journal 8, No. 10, 30-36 and No. 11, 36-31 (1974).
  • According to the invention, the amount of barium sulfate is from 0.2 to 40% by weight, preferably from 0.5 to 30% by weight, particularly preferably from 1 to 25% by weight, based on the weight of the crystallizable thermoplastic.
  • The average grain size of the barium sulfate is relatively small and is preferably from 0.1 to 5 μm, particularly preferably from 0.2 to 3 μm (Sedigraph method). The density of the barium sulfate used is from 4 to 5 g/cm3.
  • In one particularly preferred embodiment, the novel film comprises, as principal constituent, a crystallizable polyethylene terephthalate, and also from 1 to 25% by weight of precipitated barium sulfate, appropriately with a particle diameter of from 0.4 to 1 μm, particularly preferably BLANC FIXE® XR-HX or BLANC FIXE® HXH from Sachtleben Chemie, Germany.
  • The surface gloss of the novel film, measured to DIN 67530 (measurement angle 20°) is greater than or equal to 10, preferably greater than or equal to 15.
  • The luminous transmittance (transparency) of the novel film, measured to ASTM-D 1003, is less than or equal to 30%, preferably less than or equal to 25%. The coloration is uniform and streak-free over the entire running length and the entire width of the film.
  • As a result of the synergistic action of the additives barium sulfate, optional optical brightener, and, if present, blue dye in conjunction with an optimized longitudinal stretching ratio, the novel film is whiter, that is to say has less yellow tinge, and has lower light transmittance, that is to say has lower transparency than a film provided only with barium sulfate as pigment.
  • The longitudinal modulus of elasticity (ISO 527-1-2) of the novel film is greater than or equal to 3300 N/mm2, preferably greater than or equal to 3500 N/mm2. Its transverse modulus of elasticity (ISO 527-1-2) is greater than or equal to 4200 N/mm2, preferably greater than or equal to 4400 N/mm2.
  • The standard viscosity SV (DCA) of the polyethylene terephthalate preferably used for the novel film, measured in dichloroacetic acid to DIN 53728, is from 600 to 1100, preferably from 700 to 1000.
  • The intrinsic viscosity IV (DCA) is calculated from the standard viscosity SV (DCA) as follows:
    IV(DCA)=6.67·10−4 SV(DCA)+0.118
  • The opaque white polyethylene terephthalate film which comprises at least barium sulfate, an optional optical brightener and, if desired, blue dyes may have either one layer or else two or more layers.
  • In the embodiment having two or more layers, the film has a structure of at least one base layer and at least one outer layer, and particular preference is given here to a three-layer A-B-A or A-B-C structure.
  • For the embodiment having two or more layers, it is appropriate for the polyethylene terephthalate of the base layer to have a standard viscosity similar to that of the polyethylene terephthalate of the outer layer(s) directly adjacent to the base layer.
  • In one particular embodiment, the outer layers may also be composed of a polyethylene naphthalate homopolymer or of a polyethylene terephthalate-polyethylene naphthalate copolymer, or of a compound. In this particular embodiment, the thermoplastics of the outer layers likewise have a standard viscosity similar to that of the polyethylene terephthalate of the base layer.
  • In the embodiment having two or more layers, the barium sulfate, and also the optional optical brightener and, if present, the blue dye are preferably present in the base layer. However, modification of the outer layers is also possible, if required.
  • Unlike in the single-layer embodiment, in the film having two or more layers the amounts given for the additives are based on the weight of the thermoplastics in the layer provided with the additive(s).
  • There may also, if required, be provision of a scratch-resistant coating on one or more sides of the novel film.
  • In addition, the novel film is easy to recycle without pollution of the environment and without loss of mechanical properties, making it suitable, for example, for use as short-lived promotional placards, labels or other promotional requisites.
  • An example of a production process for producing the novel film is extrusion on an extrusion line.
  • According to the invention, the barium sulfate, the optional optical brightener and, if present, the blue dye may be incorporated into the thermoplastic as early as when the thermoplastic polymer is prepared, or else fed into the extruder by way of masterbatch technology during film production.
  • It is particularly preferable for the barium sulfate, the optional optical brightener and, if present, the blue dye to be added by way of masterbatch technology. The additives here are fully dispersed in a solid carrier material. Carrier materials which may be used are the thermoplastic itself, e.g. the polyethylene terephthalate, or else other polymers sufficiently compatible with the thermoplastic.
  • It is important that the particle size and the bulk density of the masterbatch(es) are similar to the particle size and the bulk density of the thermoplastic, so that uniform dispersion is achieved, and with this a uniform level of whiteness and thus also uniform opacity.
  • The polyester films may be produced by known processes from a polyester with, if desired, other polymers, and also with the optional optical brightener, the barium sulfate, if desired with the blue dye, and/or with a usual amount of from 0.1 to a maximum of 10% by weight of other customary additives, either in the form of monofilms or else in the form of, if desired, coextruded films having two or more layers and with identical or differently constructed surfaces, where one surface may have provision of pigment, but no pigment is present in the other surface. In addition, known processes can be used to provide one or both surfaces of the film with an optional functional coating.
  • Optionally, at least one of the surfaces of the film is coated, so that on the finished film a coating of from 5 to 100 nm, preferably from 20 to 70 nm, in particular from 30 to 50 nm is present. The coating is preferably applied in-line, i.e. during the film-production process, appropriately prior to the transverse stretching. Particular preference is given to application by reverse gravure-roll coating, which is capable of applying the coatings extremely uniformly with the layer thicknesses mentioned. The coatings are preferably applied as solutions, suspensions or dispersions, particularly preferably as an aqueous solution, suspension or dispersion. The coatings mentioned give the surface of the film an additional function, making the film sealable, printable, metallizable, sterilizable or antistatic, for example, or improving the flavor barrier, for example, or permitting adhesion to materials (e.g. photographic emulsions) which would not adhere to the surface of the film without the coating. Examples of substances/compositions which give additional functionality are:
  • acrylates, for example as described in WO 94/13476, ethylvinyl alcohols, PVDC, waterglass (Na2SiO4), hydrophilic polyesters, such as PET/IPA polyesters containing the sodium salt of 5-sulfoisophthalic acid, as described in EP-A-0 144 878 or U.S. Pat. No. 4,252,885, for example, or in EP-A-0 296 620, vinyl acetates, as described in WO 94/13481, for example, polyvinyl acetates, polyurethanes, silanes, the alkali metal or alkaline earth metal salts of C10-C18 fatty acids, butadiene copolymers with acrylonitrile or methyl methacrylate, methacrylic acid, acrylic acid or esters thereof.
  • The substances/compositions which give the additional functionality may comprise from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, of the customary additives, e.g. antiblocking agents or pH stabilizers.
  • The substances/compositions mentioned are applied as dilute solution, emulsion or dispersion, preferably as aqueous solution, emulsion or dispersion, to one or both surfaces of the film, and the solvent is then evaporated. If the coatings are applied in-line prior to the transverse stretching, it is usual for the heat treatment during the transverse stretching and subsequent heat-setting to suffice for evaporating the solvent and drying the coating. The dried coatings then have layer thicknesses of from 5 to 100 nm, preferably from 20 to 70 nm, in particular from 30 to 50 nm.
  • In the preferred extrusion process for producing the polyester film, the polyester material melted in the extruder is extruded through a slot die and quenched on a chill roll, as a substantially amorphous prefilm. This prefilm is then reheated and stretched longitudinally and transversely, or transversely and longitudinally, or longitudinally, transversely and again longitudinally and/or transversely. According to the invention, the stretching temperatures are from Tg+10 K to Tg+60 K (Tg is the glass transition temperature), the longitudinal stretching ratio according to the invention is from 2 to 5, in particular from 2.5 to 4.5, and the transverse stretching ratio is from 2 to 5, in particular from 3 to 4.5, and the ratio for any second longitudinal stretching carried out is from 1.1 to 3. The first longitudinal stretching may, if desired, be carried out simultaneously with the transverse stretching (simultaneous stretching). Stretching is followed by the heat-setting of the film at oven temperatures of from 200 to 260° C., in particular from 220 to 250° C. Following the heat-setting, the film is cooled and wound up.
  • An entirely unexpected finding was that the process parameters for the longitudinal stretching are a variable which significantly affects the optical properties (transparency) of the film. The longitudinal process parameters include in particular the longitudinal stretching ratio and the longitudinal stretching temperature. It was highly surprising that the transparency could be markedly affected by varying the longitudinal stretching ratio. If, for example, a film plant produces a film whose transparency is above the values according to the invention, novel films with a lower transparency can be produced by increasing the longitudinal stretching ratio during the longitudinal stretching procedure. A relative increase of 7% in the longitudinal stretching ratio gave a relative reduction of from 15 to 20% in transparency.
  • A major advantage is that the production costs for the novel film are only insignificantly higher than those for a film made from standard polyesters. The other processing properties and use properties of the novel film remain essentially unchanged or indeed show improvement. In addition, the method of film production ensures that the regrind can be used again in a proportion of up to 50% by weight, preferably from 10 to 50% by weight, based in each case on the total weight of the film, without any appreciable adverse resultant effect on the physical properties of the film.
  • The surprising combination of excellent properties makes the novel film highly suitable for a variety of different applications, such as interior decoration, for constructing exhibition stands, for exhibition requisites, for displays, for placards, for labels, for protective glazing of machines or of vehicles, in the lighting sector, in the fitting out of shops or of stores, as a promotional requisite or a laminating material, in applications associated with food or drink or, depending on the functionality of one or both surfaces, as a photographic film, as a graphic film, a laminatable film, a metallizable film or a printable film.
  • The examples below illustrate the invention in more detail.
  • The following standards and methods are used here when testing individual properties.
  • Test Methods
  • Surface Gloss
  • Surface gloss is measured with a measurement angle of 20° to DIN 67530.
  • Luminous Transmittance/Transparency
  • For the purposes of the present invention, the luminous transmittance/transparency is the ratio of total light transmitted to the amount of incident light.
  • Luminous transmittance is measured using “Hazegard plus” test equipment to ASTM D 1003.
  • Surface Defects and Uniform Coloration
  • Surface defects and uniform coloration are determined visually.
  • Mechanical Properties
  • The modulus of elasticity, tear strength and elongation at break are measured longitudinally and transversely to ISO 527-1-2.
  • SV (DCA) and IV (DCA)
  • The standard viscosity SV (DCA) is measured by a method based on DIN 53726 in dichloroacetic acid.
  • The intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
    IV(DCA)=6.67·10−4 SV(DCA)+0.118
    Yellowness Index
  • The Yellowness Index YID is the deviation from the colorless condition in the “yellow” direction and is measured to DIN 6167.
  • Whiteness
  • The whiteness is determined according to Berger, generally using more than 20 mutually superposed layers of film, and with the aid of the ELREPHO® electrical reflectance photometer from Zeiss, Oberkochem, Germany, with standard aluminant C and a 2° standard observer. The whiteness is defined as W=RY+3RZ−3RX. W=whiteness, and RY, RZ and RX=corresponding reflection factors using the Y, Z and X color measurement filter. The whiteness standard used is a barium sulfate pressing (DIN 5033, Part 9). A detailed description is found in Hansl Loos “Farbmessung” [Color measurement], Verlag Beruf and Schule, Itzehoe (1989), for example.
  • In the examples and comparative examples below, each of the films is a single-layer opaque white film, produced on the extrusion line described.
  • EXAMPLE 1
  • An opaque white film of 50 μm thickness was produced and comprised polyethylene terephthalate (RT32, KoSa, Germany) as principal constituent, 18% by weight of barium sulfate (BLANC FIX® XR-HX, Sachtleben Chemie), 200 ppm of optical brightener (TINOPAL®, Ciba-Geigy, Basle) and 40 ppm of blue dye (SUDAN BLUE® 2, BASF, Ludwigshafen). The additives barium sulfate, optical brightener and blue dye were added as masterbatches.
  • The polyethylene terephthalate used to prepare the masterbatches had a standard viscosity SV (DCA) of from 900 to 1100.
  • The masterbatch (1) was composed of clear polymer, 50% by weight of barium sulfate and 600 ppm of optical brightener. The masterbatch (2) comprised 2000 ppm of blue dye, besides clear polymer.
  • Prior to extrusion, 36% by weight of the masterbatch (1), 2% by weight of the masterbatch (2) and 62% by weight of clear polymer were dried at a temperature of 150° C. and then melted in the extruder. The melt was extruded through a flat-film die, cooled by a chill roll and then further processed.
  • The longitudinal stretching ratio set during film production was 3.1. After longitudinal stretching, both sides of the film were coated with an aqueous dispersion, using reverse gravure-roll coating. The dispersion comprised, besides water, 4.2% by weight of hydrophilic polyester (PET/IPA polyester containing the sodium salt of 5-sulfoisophthalic acid, SP41®, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (NALCO® 1060, Deutsche Nalco Chemie, Germany) as antiblocking agent, and also 0.15% by weight of ammonium carbonate (Merck, Germany) as pH buffer. The wet application weight was 2 g/m2 for each side coated. After transverse stretching, the calculated thickness of the coating was 40 nm.
  • EXAMPLE 2
  • Example 1 was repeated, except that the film had no blue dye.
  • EXAMPLE 3
  • The mixing specification of the film of Example 3 and its coating corresponded to those of the film of Example 2, but the longitudinal stretching ratio was increased to 3.3, while the longitudinal stretching temperatures remained unchanged.
  • EXAMPLE 4
  • A coextruded, opaque white ABA film of thickness 75 μm was produced, where A are the outer layers and B is the base layer. The mixing specification for the base layer of 71 μm thickness corresponded to the mixing specification of Example 2. The outer layers of 2 μm thickness comprised 93% by weight of clear polymer, and also 7% by weight of a masterbatch which comprised, besides clear polymer, 10,000 ppm of silicon dioxide (SYLOBLOC®, Grace, Germany). This film has high surface gloss. The longitudinal stretching ratio was 3.3. The film was coated in a manner similar to that of Example 1, but only on one side.
  • COMPARATIVE EXAMPLE 1
  • Example 3 was repeated. The longitudinal stretching ratio was reduced to 2.8, while the longitudinal stretching temperatures remained unchanged. The film was not coated after longitudinal stretching.
  • COMPARATIVE EXAMPLE 2
  • Comparative Example 1 was repeated, but the film was not provided with optical brightener. The film comprised only 18% by weight of barium sulfate, and this was incorporated directly during preparation of the polymer. The standard viscosity of the barium sulfate-containing polymer was 810. The film was not coated after longitudinal stretching.
  • The opaque white PET films produced in Examples 1 to 4 and the films produced according to Comparative Examples 1 and 2 had the property profiles shown in the table below:
    TABLE
    Properties Ex. 1 Ex. 2 Ex. 3 Ex. 4 Comp. Ex. 1 Comp. Ex. 2
    Thickness [μm] 50 50 50 75 50 50
    Surface gloss 20 20 20 165 20 20
    side 1
    (Measurement angle 20°) 20 20 20 165 20 20
    side 2
    Luminous transmittance/ 20 20 16 12 25 24
    transparency [%]
    Yellowness Index (YID) 12 14 14 18 15 24
    Whiteness by the Berger 93 91 91 90 91 84
    Method [%]
    Longitudinal modulus of 3600 3600 3650 3650 3350 3500
    elasticity [N/mm2]
    Transverse modulus of 5200 5300 5200 5300 5300 5300
    elasticity [N/mm2]
    Longitudinal tear strength 150 155 155 150 150 150
    [N/mm2]
    Transverse tear strength 240 240 235 240 250 250
    [N/mm2]
    Longitudinal elongation at 175 180 175 170 180 175
    break [%]
    Transverse elongation at 70 75 75 75 70 80
    break [%]
    Coloration brilliant brilliant brilliant brilliant brilliant white tinged yellow
    white white white white
    Adhesion with respect to 1 1 1 on one 2 2
    printing inks and side 1
    photographic emulsions 1 = excellent;
    2 = poor

Claims (16)

1. An opaque, white film with a thickness of from 10 to 500 μm, said film comprising thermoplastic and a pigment, said thermoplastic consisting entirely of polyester and said pigment comprising barium sulfate, said film further exhibiting a modulus of elasticity in the transverse direction of greater than or equal to 4200 N/mm2.
2. The film as claimed in claim 1, wherein the thermoplastic has been selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate.
3. The film as claimed in claim 1, wherein from 0.2 to 40% by weight of barium sulfate is present as pigment in the film, based on the weight of the thermoplastic.
4. The film as claimed in claim 1, said film further comprises optical brightener, said optical brightener present in an amount of from 10 to 50,000 ppm based on the weight of the thermoplastic.
5. The film as claimed in claim 4, wherein the optical brightener has been selected from the group consisting of bisbenzoxazoles, phenylcoumarins and bisstearylbiphenyls.
6. The film as claimed in claim 4, wherein, in addition to the optical brightener, a polyester-soluble blue dye selected from the group consisting of cobalt blue, ultramarine blue, anthraquinone dyes or combinations of these, is also present in the film, and wherein the amount of blue dye present in the film is from 10 to 10,000 ppm, based on the weight of the thermoplastic.
7. The film as claimed in claim 1, wherein the barium sulfate is present as precipitated barium sulfate in the film in an amount of from 0.5 to 30% by weight, based on the weight of the thermoplastic, and wherein the average grain size of the barium sulfate is from 0.1 to 5 μm (Sedigraph method).
8. The film as claimed in claim 1, wherein the surface gloss of the film, measured to DIN 67530 (measurement angle 20°) is ≧10, and wherein the luminous transmittance (transparency) of the film, measured to ASTM-D 1003 is ≦30%.
9. The film as claimed in claim 1, wherein the film has one or more layers, and the film having more than one layer comprises at least one base layer and at least one outer layer.
10. The film as claimed in claim 1, wherein at least one of the surfaces of the film bears a functional coating said coating comprising substances or compositions selected from the group consisting of acrylates, ethylvinyl alcohols, PVDC, waterglass (Na2SiO4), hydrophilic polyesters, vinyl acetates, polyvinyl acetates, polyurethanes, silanes, the alkali metal or alkaline earth metal salts of C10-C18 fatty acids, butadiene copolymers with acrylonitrile or methyl methacrylate, methacrylic acid, acrylic acid or esters thereof and mixtures of these.
11. The film as claimed in claim 10, wherein the coating comprises from 0.05 to 5% by weight of additional additives.
12. An opaque white film with a thickness of from 10 to 500 μm, comprising (i) a single thermoplastic consisting of polyester and (ii) barium sulfate, wherein the film exhibits tear strengths in the transverse direction of greater than or equal to 170 N/mn?
13. The opaque white film as claimed in claim 12, wherein said opaque white film further comprises regrind formed from said film in amounts of up to 50 weight percent, said film having a thickness of up to 50 microns and exhibiting a yellowness of up to 20.
14. The opaque white film as claimed in claim 12, wherein said opaque white film further comprises regrind formed from said film in amounts of up to 50 weight percent, said film having a thickness of from 50 to 250 microns and exhibiting a yellowness of up to 45.
15. The opaque, white film as claimed in claim 1, wherein the luminous transmittance of said film is 15 to 20% lower than the luminous transmittance of a comparable film formed from said thermoplastic having the same thickness as said film and lower longitudinal orientation than said film.
16. An opaque, white film with a thickness of from 10 to 500 μm, comprising a crystallizable thermoplastic and barium sulfate wherein said crystallizable thermoplastic consists entirely of polyester, said film exhibiting an elongation at break of greater than or equal to 120% in the machine direction.
US11/250,259 2000-02-19 2005-10-14 Opaque, white film with low transparency made from a crystallizable thermoplastic Abandoned US20060046041A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/250,259 US20060046041A1 (en) 2000-02-19 2005-10-14 Opaque, white film with low transparency made from a crystallizable thermoplastic

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10007719.6 2000-02-19
DE10007719A DE10007719A1 (en) 2000-02-19 2000-02-19 White-opaque film with low transparency made of a crystallizable thermoplastic with additional functionality
US09/779,156 US7182997B2 (en) 2000-02-19 2001-02-08 Opaque, white film with low transparency made from a crystallizable thermoplastic and having additional functionality
US11/250,259 US20060046041A1 (en) 2000-02-19 2005-10-14 Opaque, white film with low transparency made from a crystallizable thermoplastic

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US09/779,156 Continuation US7182997B2 (en) 2000-02-19 2001-02-08 Opaque, white film with low transparency made from a crystallizable thermoplastic and having additional functionality

Publications (1)

Publication Number Publication Date
US20060046041A1 true US20060046041A1 (en) 2006-03-02

Family

ID=7631624

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/779,156 Expired - Fee Related US7182997B2 (en) 2000-02-19 2001-02-08 Opaque, white film with low transparency made from a crystallizable thermoplastic and having additional functionality
US11/250,259 Abandoned US20060046041A1 (en) 2000-02-19 2005-10-14 Opaque, white film with low transparency made from a crystallizable thermoplastic

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/779,156 Expired - Fee Related US7182997B2 (en) 2000-02-19 2001-02-08 Opaque, white film with low transparency made from a crystallizable thermoplastic and having additional functionality

Country Status (5)

Country Link
US (2) US7182997B2 (en)
EP (1) EP1125970B1 (en)
JP (1) JP2001279074A (en)
KR (1) KR20010082696A (en)
DE (2) DE10007719A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060275593A1 (en) * 2005-06-01 2006-12-07 Ulrich Kern White opaque film having low transparency and improved dielectric strength

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001053407A2 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh White flame-resistant uv-stable thermoformable film made from a crystallisable thermoplastic
DE10002163A1 (en) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh White thermo formable film useful in displays, for labels, illumination, and electronics, contains a white pigment, a crystalline thermoplastic, and a UV stabilizer
US7360504B2 (en) * 2003-01-09 2008-04-22 T.F.H. Publications, Inc. Radiopaque animal chew
DE102004031794A1 (en) * 2004-07-01 2006-01-26 Mitsubishi Polyester Film Gmbh Process for the preparation of biaxially oriented films based on crystallizable thermoplastics using a condensed regenerate
EP1806380A4 (en) * 2004-08-11 2010-06-16 Mitsubishi Polyester Film Corp Biaxially oriented polyester films
JP4943648B2 (en) * 2004-12-21 2012-05-30 三菱樹脂株式会社 Optical polyester film
JP5239448B2 (en) * 2007-06-04 2013-07-17 東レ株式会社 Antistatic white polyester film
US20090269566A1 (en) * 2008-04-23 2009-10-29 Berry Plastics Corporation Pre-stretched multi-layer stretch film
US7695699B2 (en) * 2008-05-21 2010-04-13 Duan Jiwen F Metal sulfate alcohol composition and process therewith
DE102008047683A1 (en) * 2008-09-18 2010-03-25 Mitsubishi Polyester Film Gmbh Hazy polyester film with improved light transmission
DE102009006014A1 (en) * 2009-01-23 2010-08-05 Sachtleben Chemie Gmbh Polymer compositions with inorganic fillers and process for their preparation
FR2952063B1 (en) * 2009-10-30 2012-10-12 Seb Sa THERMOPLASTIC POLYMER MATERIAL BASED ON PET AND METHOD OF MANUFACTURING SUCH ARTICLE
KR20120135206A (en) 2010-01-13 2012-12-12 미츠비시 폴리에스테르 필름 인코포레이티드 Process for recycling waste film and product made therefrom
US9273193B2 (en) 2010-09-25 2016-03-01 Nike, Inc. Regrind polyurethane with glycol or polyol additive
KR101666577B1 (en) * 2011-04-21 2016-10-17 코오롱인더스트리 주식회사 White film for Solar Cell Module and Manufacturing method thereof
WO2015035282A1 (en) * 2013-09-06 2015-03-12 Polyone Corporation Radiopaque, optically translucent thermoplastic compounds
US11028299B2 (en) * 2013-11-19 2021-06-08 Mitsubishi Polyester Film, Inc Anti-powdering and anti-static polymer film for digital printing
CN103818070B (en) * 2013-12-13 2017-02-15 合肥乐凯科技产业有限公司 White polyester film and preparation method thereof
EP2887129B1 (en) 2013-12-23 2020-04-22 Essilor International Transparent optical article having a colorless appearance
WO2015097492A1 (en) * 2013-12-23 2015-07-02 Essilor International (Compagnie Generale D'optique) Transparent optical article having a reduced yellowness appearance
CN105252753B (en) * 2014-07-18 2017-10-31 天津万华股份有限公司 Prepared without antimony type biaxially oriented polyester film
WO2017094083A1 (en) * 2015-11-30 2017-06-08 日立化成株式会社 Food packaging film

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252885A (en) * 1977-03-25 1981-02-24 Bexford Limited Polyester coated films using an aqueous polyester dispersion and photographic layer
US4384040A (en) * 1980-06-14 1983-05-17 Felix Schoeller, Jr. Waterproof photographic paper
US4780402A (en) * 1975-10-23 1988-10-25 Imperial Chemical Industries, Plc Films of a light sensitive element having a support polyethylene terephthalate containing barium sulfate particles
US5660931A (en) * 1994-03-17 1997-08-26 Skc Limited Polymeric film with paper-like characteristics
US6521351B2 (en) * 2000-02-19 2003-02-18 Mitsubishi Polyester Film Gmbh Opaque, white UV-resistant film with low transparency made from a crystallizable thermoplastic
US6641924B1 (en) * 1999-07-14 2003-11-04 Mitsubishi Polyester Film Gmbh White, biaxially oriented polyester film with cycloolefin copolymer (COC), process for producing the film, and its use
US6939600B2 (en) * 2000-02-19 2005-09-06 Mitsubishi Polyester Film Gmbh Opaque, white film with low transparency made from a crystallizable thermoplastic

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2517293B2 (en) 1987-06-25 1996-07-24 メクト株式会社 Cell and tissue repair agent
WO1994013476A1 (en) 1992-12-09 1994-06-23 Hoechst Aktiengesellschaft Copolyester film primed with acrylic polymers
WO1994013481A1 (en) 1992-12-09 1994-06-23 Hoechst Aktiengesellschaft Biaxially oriented copolyester film primed with vinyl acetate polymers
CN1103794C (en) 1996-08-05 2003-03-26 东丽株式会社 Thermoplastic resin composition and sheets and cards made from the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4780402A (en) * 1975-10-23 1988-10-25 Imperial Chemical Industries, Plc Films of a light sensitive element having a support polyethylene terephthalate containing barium sulfate particles
US4252885A (en) * 1977-03-25 1981-02-24 Bexford Limited Polyester coated films using an aqueous polyester dispersion and photographic layer
US4384040A (en) * 1980-06-14 1983-05-17 Felix Schoeller, Jr. Waterproof photographic paper
US5660931A (en) * 1994-03-17 1997-08-26 Skc Limited Polymeric film with paper-like characteristics
US6641924B1 (en) * 1999-07-14 2003-11-04 Mitsubishi Polyester Film Gmbh White, biaxially oriented polyester film with cycloolefin copolymer (COC), process for producing the film, and its use
US6521351B2 (en) * 2000-02-19 2003-02-18 Mitsubishi Polyester Film Gmbh Opaque, white UV-resistant film with low transparency made from a crystallizable thermoplastic
US6939600B2 (en) * 2000-02-19 2005-09-06 Mitsubishi Polyester Film Gmbh Opaque, white film with low transparency made from a crystallizable thermoplastic

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060275593A1 (en) * 2005-06-01 2006-12-07 Ulrich Kern White opaque film having low transparency and improved dielectric strength
US7238419B2 (en) * 2005-06-01 2007-07-03 Mitsubishi Polyester Film Gmbh White opaque film having low transparency and improved dielectric strength

Also Published As

Publication number Publication date
EP1125970B1 (en) 2005-12-28
EP1125970A1 (en) 2001-08-22
KR20010082696A (en) 2001-08-30
DE10007719A1 (en) 2001-08-23
DE50108497D1 (en) 2006-02-02
JP2001279074A (en) 2001-10-10
US7182997B2 (en) 2007-02-27
US20020136880A1 (en) 2002-09-26

Similar Documents

Publication Publication Date Title
US20060046041A1 (en) Opaque, white film with low transparency made from a crystallizable thermoplastic
US6855758B2 (en) Hydrolysis-resistant, transparent, biaxially oriented film made from a crystallizable thermoplastic, and process for its production
US6939600B2 (en) Opaque, white film with low transparency made from a crystallizable thermoplastic
US7211306B2 (en) Peelable polyester film with self-venting, process for its production and its use
US6641924B1 (en) White, biaxially oriented polyester film with cycloolefin copolymer (COC), process for producing the film, and its use
US6884517B2 (en) High-whiteness, biaxially oriented polyester film, its use and process for its production
US7833617B2 (en) Multilayer, white, laser-cuttable polyester film
US20030068511A1 (en) Transparent, multilayer, biaxially oriented polyester film, and process for its production
US7829175B2 (en) Multilayer, white polyester film
US6849325B2 (en) White biaxially oriented film made from a crystallizable thermoplastic and having a high level of whiteness
US20030091843A1 (en) Hydrolysis-resistant, transparent, amorphous film made from a crystallizable thermoplastic, and process for its production
US20100119742A1 (en) Multilayer, white, biaxially oriented polyester film with metallic-luster outer layer
US20110171424A1 (en) Transparent polyester film comprising baso4 particles
US6719940B2 (en) White, biaxially oriented polyester film with cycloolefin copolymer and process for producing the film
US20200189244A1 (en) Multi-layer card and film assembly
US20140162051A1 (en) White, weathering-resistant, biaxially oriented polyester film matt on at least one side, its use and process for its production
US7670687B2 (en) Amber-colored polyester film with particular suitability for metallization and steel-lamination
DE102005058916A1 (en) White biaxially oriented polyester film especially for use as a cover for yoghurt pots has a base layer containing a white pigment and a matte cover layer containing a white pigment and also an antiblocking agent
DE102007051241A1 (en) Multilayer white-opaque biaxially-oriented polyester film, which is matt on one side for packing goods and foods, has base layer, cover layer, amorphous surface layer, and further layer arranged between base layer and cover layer
EP1245618B1 (en) White biaxially orineted film made from a crystallizable thermoplastic with good cuttability
DE102005058917A1 (en) Biaxially oriented polyester film useful for food-or-drink containers e.g. yoghurt pot comprises base layer of whitening pigment and outer layer of whitening pigment and antiblocking agent with specific median particle diameter
DE10042332A1 (en) Composite film used for e.g. food packaging, decorative materials, embossing films and labels, comprises a white pigmented biaxially oriented polyester film with a base layer comprising a thermoplastic polyester and a cycloolefin copolymer
DE10043778A1 (en) Thermoplastic film useful e.g. for wall coverings, comprises bibenzene-modified polymer, barium sulfate and optical brightener
DE10022947A1 (en) Matte white biaxially oriented polyester film, e.g. useful for food packaging, includes a cycloolefin copolymer and a white pigment.

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION