WO2002062577A1 - Feuille transparente, anti-microbienne, a orientation biaxiale, partiellement cristalline, issue d'un thermoplaste cristallisable - Google Patents

Feuille transparente, anti-microbienne, a orientation biaxiale, partiellement cristalline, issue d'un thermoplaste cristallisable Download PDF

Info

Publication number
WO2002062577A1
WO2002062577A1 PCT/EP2002/000853 EP0200853W WO02062577A1 WO 2002062577 A1 WO2002062577 A1 WO 2002062577A1 EP 0200853 W EP0200853 W EP 0200853W WO 02062577 A1 WO02062577 A1 WO 02062577A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
film according
layer
weight
crystallizable
Prior art date
Application number
PCT/EP2002/000853
Other languages
German (de)
English (en)
Inventor
Ursula Murschall
Ulrich Kern
Klaus Oberländer
Harald Hessberger
Original Assignee
Mitsubishi Polyester Film Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10105108A external-priority patent/DE10105108A1/de
Priority claimed from DE2001105107 external-priority patent/DE10105107A1/de
Application filed by Mitsubishi Polyester Film Gmbh filed Critical Mitsubishi Polyester Film Gmbh
Publication of WO2002062577A1 publication Critical patent/WO2002062577A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B29C55/065—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed in several stretching steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0011—Biocides
    • 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

Definitions

  • Transparent, antimicrobial, biaxially oriented, partially crystalline film made of a crystallizable thermoplastic
  • the invention relates to a high-gloss, single- or multilayer, transparent, biaxially oriented and heat-set, partially crystalline film which contains at least one crystallizable thermoplastic as the main component. It also relates to a method for producing these films and their use.
  • films of the type mentioned, in particular films based on polyethylene terephthalate, are known and have been described in large numbers. They are not protected against the growth of mold or other microorganisms.
  • the multilayer, biaxially oriented and heat-set polyester film according to GB-A 1 465973 comprises a layer of transparent polyethylene terephthalate (PET) and a layer of likewise transparent copolyester.
  • PET polyethylene terephthalate
  • a rough structure can be impressed on the surface of the copolyester layer with the aid of rollers, so that the film can be written on.
  • EP-A 035835 describes a biaxially stretched and heat-set, multilayer polyester film which comprises a layer made of a highly crystalline polyester and, in connection therewith, a sealable layer made of an essentially amorphous, linear polyester.
  • the latter layer contains finely divided particles, the mean diameter of the particles being greater than the layer thickness. These particles form surface protrusions that prevent unwanted blocking and sticking to rollers or guides. This makes it easier to wind up and process the film.
  • the choice of particles with a larger diameter than the sealing layer and the concentrations given in the examples worsens the sealing behavior of the film.
  • the seal seam strength of the sealed film at 140 ° C. is in a range from 63 to 120 N / m (0.97 N / 15 mm to 1.8 N / 15 mm film width).
  • EP-A 432 886 describes a coextruded film with a polyester base layer, a cover layer made of a sealable polyester and a polyacrylate coating on the back.
  • the sealable top layer can consist of a copolyester with units of isophthalic acid and terephthalic acid.
  • the film on the back has improved processing properties.
  • the seal seam strength is measured at 140 ° C.
  • a seal seam strength of 761.5 N / m (11.4 N / 15 mm) is specified for an 11 ⁇ m thick sealing layer.
  • a disadvantage of the rear acrylic coating is that this side no longer seals against the sealable top layer. The film can therefore only be used to a very limited extent.
  • a coextruded, multilayer, sealable polyester film is also in the
  • the base layer of the film can contain pigment particles, in particular those made of aluminum oxide, titanium dioxide, alkali metal carbonate, calcium sulfate or barium sulfate. This leads to a white film.
  • the sealable layer additionally contains pigmentation particles, preferably silica gel particles. The particles can also be applied to the already extruded film, for example by coating with an aqueous silica gel dispersion. As a result, the film should maintain the good sealing properties and be easy to process.
  • the back contains very few particles that get into this layer mainly through the regranulate.
  • the seal seam strength is measured at 140 ° C and is more than 200 N / m (3 N / 15 mm). For a 3 ⁇ m thick
  • the sealing layer is given a sealing seam strength of 275 N / m (4.125 N / 15 mm).
  • the coextruded, multilayer polyester film known from WO 98/06575 comprises a sealable cover layer and a non-sealable base layer.
  • the base layer can be constructed from one or more layers, wherein the inner layer is in contact with the sealable layer.
  • the other (outer) layer then forms the second, non-sealable cover layer.
  • the sealable top layer can also consist of copolyesters with units of isophthalic acid and terephthalic acid. However, the top layer contains no antiblock particles.
  • the film also contains at least one UV absorber in the
  • Base layer is contained in a proportion of 0.1 to 10.0 wt .-%.
  • Zinc oxide or titanium dioxide particles with an average diameter of less than 200 nm, but preferably triazines (for example ® Tinuvin 1577 from Ciba) are used as UV absorbers.
  • the base layer is equipped with common antiblocking agents.
  • the film is characterized by a good sealability, but does not have the desired processing behavior and also has deficits in the optical properties.
  • Layers of copolyester can also be produced by applying an appropriate aqueous dispersion.
  • EP-A 144 978 describes a polyester film which has a continuous coating made of the copolyester on at least one side. The dispersion is applied to the film before stretching or before the last stretching step.
  • the polyester coating consists of a condensation product of various monomers that are capable of forming polyesters, such as isophthalic acid, aliphatic dicarboxylic acids,
  • DE-A 23 46 787 discloses, inter alia, flame-retardant films made from linear polyesters modified with carboxyphosphinic acids.
  • the raw material is very sensitive to hydrolysis and must be pre-dried very well. When drying the raw material with dryers that correspond to the prior art, it sticks together, so that a film can only be produced under the most difficult conditions.
  • the films produced under extreme, uneconomical conditions also become brittle when exposed to temperature. The mechanical properties create decrease so much that the film becomes unusable. This embrittlement occurs after 48 hours of thermal stress.
  • the object was therefore to provide a transparent, biaxially oriented, partially crystalline film which has good mechanical and optical properties and is antimicrobially treated.
  • the film should also be high-gloss.
  • the subject of the present application is accordingly a single-layer or multilayer, transparent, biaxially oriented and heat-set, partially crystalline film with a crystallizable thermoplastic as the main component, which is characterized in that the film or at least one layer therein contains an antimicrobial component of 2,4 , 4 ' -Trichlor-2 ' -hydroxy-diphenyl ether (triclosan).
  • Antimicrobial means that the growth of gram-positive and gram-negative bacteria as well as mold and yeast is greatly reduced, i.e. that the antimicrobial film is at least not overgrown by the test culture and that the growth around the film is inhibited (Hemmhof).
  • Gram-negative bacteria are, for example, escherichia coli, klebsiella pneumoniae, proteus vulgaris or salmonella.
  • Gram-positive bacteria are, for example, staphylococcus aureus, streptococcus faecalis, micrococcus luteus or corynebacterium minutissimum. Pure, defined microorganisms such as pseudomonas aeruginosa, staphylococcus aureus and escherichia are used as test organisms coli, aspergillus niger, penicillium funicolosum, chaetomium globosum, trichoderme viride or candida albicans are used. If there is no active substance against the organism, the test organism will overgrow the film sample and thus the entire surface of the petri dish.
  • the proportion of triclosan is generally between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight, in each case based on the total weight of the single-layer film or the relevant layer the multilayer film.
  • the film according to the invention has good optical properties, in particular a high surface gloss of more than 100, preferably more than 110, a light transmission of more than 64%, preferably more than 66% and a haze of less than 30%, preferably less than 25%.
  • MD longitudinal direction
  • TD transverse direction
  • the film can be easily and longitudinally oriented in its manufacture both in the longitudinal and in the transverse direction.
  • the main component of the film is a crystallizable thermoplastic.
  • Suitable crystallizable or partially crystalline thermoplastics are, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), bibenzolmodinstrument.es polyethylene terephthalate (PETBB), bibenzol- modified polybutylene terephthalate (PBTBB) and bibenzene-modified polyethylene naphthalate (PENBB), with polyethylene terephthalate (PET) and bibenzene-modified polyethylene terephthalate (PETBB) being preferred.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • PBTBB bibenzol- modified polybutylene terephthalate
  • PENBB bibenzene-modified polyethylene naphthalate
  • PET polyethylene terephthalate
  • PET polyethylene tere
  • crystallizable thermoplastics should be understood to mean crystallizable homopolymers, crystallizable copolymers, crystallizable compounds, crystallizable recyclate or other variations of crystallizable thermoplastics.
  • DMT dimethyl terephthalate
  • EG ethylene glycol
  • PG propylene glycol
  • TA terephthalic acid
  • NDA naphthalene-2,6 -dicarboxylic acid
  • IPA isophthalic acid
  • c-CHDM, £ -CHDM or c / tC DM 4-cyclohexane-dimethanol
  • DCE standard viscosity SV
  • Preferred starting materials for the production of the film according to the invention are crystallizable thermoplastics with a crystallite melting temperature Tm of 180 to
  • 365 ° C and more preferably from 180 to 310 ° C, with a crystallization temperature range Tc between 75 ° C and 280 ° C, a glass transition temperature Tg from 65 to 130 ° C (determined by differential scanning calorimetry (DSC) at a heating rate of 20 ° C / min), with a density of 1, 10 to 1, 45 (determined according to DIN 53479) and a crystallinity between 5 and 65%, preferably 20% and 65%.
  • DSC differential scanning calorimetry
  • the bulk density (measured according to DIN 53466) is between 0.75 kg / dm 3 and 1.0 kg / dm 3 , preferably between 0.80 kg / dm 3 and 0.90 kg / dm 3 .
  • the polydispersity ( ratio of Mw to Mn) of the thermoplastic, measured by gel permeation chromatography (GPC), is preferably between 1.5 and 4.0, particularly preferably between 2.0 and 3.5.
  • Main component means that the proportion of at least one partially crystalline
  • Thermoplastics is preferably between 50 and 99% by weight, particularly preferably between 75 and 95% by weight, in each case based on the total weight of the film or the total weight of the layer in the film.
  • the remaining fractions can make up other antimicrobial compounds and other additives which are customary for biaxially oriented, transparent films.
  • the film according to the invention can contain other antimicrobial compounds.
  • antimicrobial compounds are, for example, 10,10 '-oxy-bisphenoxarsine, N- trihalogenomethylthio phthalimide, Diphenylantimon-2-ethylhexanoate, copper-8-hydroxy-quinoline, tributyltin oxide and its derivatives and halogenated derivatives
  • Diphenyl ether compounds as described in WO 99/31036.
  • Derivatives of 2,4,4 'trichloro-2-hydroxy-diphenyl ether (Triclosan) are particularly preferred because they have an improved migration behavior, thermally stable and are little volatile.
  • the crystallizable thermoplastic of the core layer has a standard viscosity similar to that in the adjacent cover layer (s).
  • the cover layers consist of a polyethylene naphthalate or a polyethylene terephthalate / polyethylene naphthalate or a compound.
  • the triclosan is preferably contained in the core layer.
  • the cover layers and / or any intermediate layers which may be present can also be equipped with it.
  • the proportions of the additives here relate to the weight of the thermoplastics in the layer in question.
  • the film can also be functionalized.
  • the additional functionality is preferably that the film is UV stabilized, flame retardant, sealable, coated on one or both sides, corona and / or flame treated. This makes the film sealable, printable, writable, antistatic, metallizable or sterilizable, for example.
  • the transparent film according to the invention is UV-stable.
  • Light especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm induces degradation processes in thermoplastics.
  • the result of this is that not only does the visual appearance change as a result of color change or yellowing, but also the mechanical-physical properties of the films made of the thermoplastics are extremely negatively influenced.
  • the prevention of these photooxidative degradation processes is of considerable technical and economic importance, since otherwise the application possibilities of numerous thermoplastics are drastically restricted.
  • Polyethylene terephthalates for example, begin to absorb UV light below 360 nm; your
  • UV stabilizers i.e. UV absorbers as light stabilizers are chemical compounds that intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for transparent films because they lead to discoloration or color change.
  • Suitable UV stabilizers as light stabilizers are UV stabilizers which absorb at least 70%, preferably at least 80%, particularly preferably at least 90%, of the UV light in the wavelength range from 180 to 380 nm, preferably 280 to 350 nm.
  • UV stabilizers are also thermally stable in the temperature range from 260 to 300 ° C, i.e. they do not decompose into fission products and do not outgas.
  • Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxy-benzophenones, 2-hydroxy-benzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, benzoxazinones, sterically hindered amines and triazines, the 2 -Hydroxy-benzotriazoles, the benzoxazinones and the triazines are preferred.
  • UV stabilizers in combination with an antimicrobial finish leads to useful films with excellent properties.
  • the person skilled in the art would probably have first tried to achieve a certain UV stability via an oxidation stabilizer, but would have found after weathering that the film quickly turns yellow.
  • UV stabilizers are known from the literature which absorb UV radiation and thus offer protection. The specialist would then have one of these known and commercial UV stabilizers used, but found that the UV stabilizer has a poor thermal stability and decomposes or outgasses at temperatures between 200 and 240 ° C. In order not to damage the film, he would have had to incorporate large amounts (approx. 10 to 15% by weight) of UV stabilizer so that it really absorbs the UV light effectively. At these high concentrations, however, the film yellows shortly after production. The mechanical properties are also adversely affected.
  • Stabilizer an excellent UV protection is achieved. It was particularly surprising that the yellowness index of the film does not change compared to a non-stabilized film within the scope of the measurement accuracy. There are also no outgassing, nozzle deposits or frame evaporation, which gives the film an excellent appearance, an excellent profile and an excellent
  • the UV-stabilized film can be stretched excellently, so that it can be produced reliably and reliably on so-called "high speed film lines" up to speeds of 420 m / min. This means that the film can also be produced economically. Furthermore, it is very surprising that the regenerate can also be used again without adversely affecting the yellowness index of the film.
  • the film according to the invention contains 0.1 to 5.0% by weight of 2- (4,6-diphenyl- [1,3,5] triazin-2-yl) -5- as UV stabilizer.
  • the film according to the invention is flame-retardant. Flame retardant means that the film meets the conditions according to DIN 4102 part 2 and especially the conditions according to DIN 4102 part 1 in a so-called fire protection test and can be classified in building material class B 2 and especially B1 of the flame retardant materials.
  • the optionally flame-retardant film should pass the UL test 94 "Horizontal Burning Test for Flammability of Plastic Material" so that it can be classified in class 94 VTM-0.
  • the film accordingly contains a flame retardant which is metered in directly during film production using the so-called masterbatch technology, the proportion of the flame retardant being in the range from 0.5 to 30.0% by weight, preferably from 1.0 to 20.0 % By weight, based on the weight of the layer of the crystallizable thermoplastic, is.
  • the proportion of the flame retardant in the masterbatch is generally 5.0 to 60.0% by weight, preferably 10.0 to 50.0% by weight, in each case based on the total weight of the masterbatch.
  • Suitable flame retardants are, for example
  • halogen compounds Bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide and aluminum trihydrates.
  • the halogen compounds have the disadvantage that halogen-containing by-products can arise. In the event of fire, hydrogen halides in particular arise.
  • Another disadvantage is the low lightfastness of a film equipped with it.
  • Suitable flame retardants are, for example, organic phosphorus compounds such as carboxyphosphinic acids, their anhydrides and alkanephosphonic diesters, preferably methanephosphonic diesters, especially methanephosphonic acid bis- (5-ethyl-2-methyl-2-oxo-2 ⁇ 5 - [1, 3.2] dioxaphosphinane 5-ylmethyl ester), available under the designation ® Amgard P1045 from Albright & Wilson, USA. It is essential that the organic phosphorus compound is soluble in the thermoplastic, since otherwise the required optical properties will not be met.
  • organic phosphorus compounds such as carboxyphosphinic acids, their anhydrides and alkanephosphonic diesters, preferably methanephosphonic diesters, especially methanephosphonic acid bis- (5-ethyl-2-methyl-2-oxo-2 ⁇ 5 - [1, 3.2] dioxaphosphinane 5-ylmethyl ester), available under the designation ® Amgard P1045 from Albright
  • phenolic stabilizers As a hydrolysis stabilizer, phenolic stabilizers, alkali or alkaline earth stearates and / or alkali or alkaline earth carbonates in amounts of 0.01 to 1.0% by weight. Phenolic stabilizers are preferred in an amount of 0.05 to 0.6% by weight, in particular 0.15 to 0.3% by weight and with a molar mass of more than 500 g / mol. Pentaerythritol tetrakis [3- (3,5-di-fe / t-butyl-4-hydroxyphenyl) propionate] or 1,3,5-trimethyl-2,4,6-tris are particularly advantageous
  • the flame-retardant film according to the invention contains, as the main constituent, a crystallizable PET, 1.0 to 20.0% by weight of an organic phosphorus compound which is soluble in the thermoplastic as a flame retardant and 0.1% by weight to 1.0% by weight. % of a hydrolysis stabilizer.
  • Methanephosphonic acid bis- (5-ethyl-2-methyl-2-oxo-2 ⁇ 5 - [1, 3,2] dioxaphosphinan-5-ylmethyl ester) is preferred as the flame retardant.
  • fire protection tests according to DIN 4102 and the UL test have shown that in the case of a three-layer film, it is quite sufficient to equip the 0.5 to 2 ⁇ m thick top layers with flame retardants in order to achieve improved flame retardancy. If required and with high fire protection requirements, the core layer can also be equipped with flame retardants. H. include so-called basic equipment.
  • the film according to the invention can be provided on one or both sides with a customary functional coating.
  • the following can be used to produce the coating: acrylates according to WO 94/13476, ethyl vinyl alcohols, PVDC, water glass (Na 2 Si0 4 ), hydrophilic polyesters such as PET / I PA polyesters containing 5-sodium sulfoisophthalic acid (EP-A 144 878 , US-A 4 252 885 or EP-A 296620), vinyl acetates (WO 94/13481), polyvinyl acetates, polyurethanes, alkali or
  • the coating can contain conventional additives (for example antiblocking agents, pH stabilizers) in proportions of about 0.05 to 5.0% by weight, preferably 0.1 to 3.0% by weight, in each case based on the weight of the coating liquid , contain.
  • the substances or compositions mentioned are applied as a dilute - preferably aqueous - solution, emulsion or dispersion to one or both film surfaces.
  • the solvent is then evaporated.
  • the coating is preferably applied in-line, i.e. during the film production process, expediently before transverse stretching. Application by the "reverse gravure-roll coating" method, with which extremely homogeneous layer thicknesses are obtained, is particularly preferred. If the in-line coatings are applied after the longitudinal stretching, the temperature treatment before the transverse stretching is usually sufficient to volatilize the solvent and to dry the coating.
  • the dried coatings then have layer thicknesses of 5 to 100 nm, preferably 20 to 70 nm, in particular 30 to 50 nm.
  • the film has at least three layers and then, in a particular embodiment, comprises the base layer B, a sealable cover layer A and an optionally sealable cover layer C. If the cover layer C is also sealable, then the two cover layers are preferably identical.
  • the sealable outer layer A applied to the base layer B by coextrusion is based on polyester copolymers and consists essentially of copolyesters which are composed predominantly of isophthalic acid, bibenzene carboxylic acid and terephthalic acid units and of ethylene glycol units. The remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as can also occur in the base layer.
  • the preferred copolyesters which provide the desired sealing properties are those which are composed of ethylene terephthalate and ethylene isophthalate units and of ethylene glycol units.
  • the proportion of ethylene terephthalate is 40 to 95 mol% and the corresponding proportion of ethylene isophthalate is 60 to 5 mol%.
  • the same polymers that are also used in the base layer can be used for the optionally sealable cover layer C and for any intermediate layers.
  • the desired sealing and processing properties of the film according to the invention are obtained from the combination of the properties of the copolyester used for the sealable cover layer and the topographies of the sealable cover layer A and the optionally sealable cover layer C.
  • the seal initiation temperature of 110 ° C. and the seal seam strength of at least 1.3 N / 15 mm is achieved if the copolymers described in more detail above are used for the sealable cover layer A.
  • the best sealing properties of the film are obtained if no further additives, in particular no inorganic or organic fillers, are added to the copolymer. In this case, the lowest seal starting temperature and the highest seal seam strengths are obtained for a given copolyester.
  • the handling of the film is poor in this case, since the surface of the sealable cover layer A tends to block.
  • the film can hardly be wrapped and is not suitable for further processing on high-speed packaging machines.
  • the film is colored transparent.
  • a dye that is soluble in the thermoplastic is generally used.
  • the solubility of the dye is determined in accordance with DIN 55 949. Its proportion is expediently from 0.01 to 20.0% by weight, preferably 0.05 to 10.0% by weight, in each case based on the weight of the crystallizable thermoplastic.
  • the transparent coloring of the film is due to a wavelength-dependent absorption of the light by the dye that is molecularly dissolved in the thermoplastic.
  • Anthraquinone are particularly suitable for coloring PET, because its high glass transition temperature Tg limits the migration of the dye (see J. Koerner, Soluble dyes in the plastics industry, in VDI-Gesellschaft Kunststofftechnik, coloring plastics, VDI-Verlag, Düsseldorf [1975]).
  • Suitable soluble dyes are also C.I. Solvent Yellow 93 (a)
  • the soluble dye is preferably metered in using the masterbatch technology during film production, but can also be incorporated during the production of the raw material.
  • the proportion of soluble dyes is generally 0.01 to 40.0% by weight, preferably 0.05 to 25.0% by weight, in each case based on the weight of the crystallizable thermoplastic.
  • the film can also be corona or flame treated.
  • the treatment intensity is chosen so that the surface tension of the film is generally above 45 mN / m.
  • the base layer and / or top layer (s) can also contain other customary additives, such as stabilizers and
  • Antiblocking agents They are expediently added to the polymer or the polymer mixture before the melting.
  • Mixtures of two or more different antiblocking agents or mixtures of antiblocking agents of the same composition but different particle size can also be selected as additives.
  • the particles can be added to the individual layers in the usual concentrations, for example as a glycolic dispersion, during the polycondensation or via masterbatches during the extrusion. Pigment concentrations of 0.0001 to 10.0% by weight, based on the weight of the outer layers, have proven to be particularly suitable.
  • the film is produced by processes known per se, for example by an extrusion process on an extrusion line. It has proven to be particularly advantageous to use the triclosan and also the other additives in the form of masterbatches. With a suitable predrying or pre-crystallization of the masterbatches, the film according to the invention can be used without
  • An economical film production also includes that the used
  • Raw materials or raw material components can be dried with commercially available industrial dryers, such as vacuum, fluidized bed, fluidized bed or fixed bed dryers (shaft dryers). It is essential that the antimicrobial agents do not outgas or form wall coverings in the dryers, that the raw materials do not stick together and are not thermally broken down.
  • industrial dryers such as vacuum, fluidized bed, fluidized bed or fixed bed dryers (shaft dryers). It is essential that the antimicrobial agents do not outgas or form wall coverings in the dryers, that the raw materials do not stick together and are not thermally broken down.
  • the raw material goes through a temperature range of approx. 30 to 130 ° C at a vacuum of 50 mbar. Afterwards, drying in a hopper at temperatures of 100 to 130 ° C and a residence time of 3 to 6 hours is required.
  • the triclosan can either be metered in during the raw material production or only in the extruder used during the film production. It is preferably added as a master batch. For this purpose, it is predispersed in a solid carrier material.
  • the carrier materials for the masterbatch are the thermoplastic itself (for example polyethylene terephthalate) or other polymers which are sufficiently compatible with the thermoplastic.
  • the proportion of antimicrobial active ingredient in the masterbatch is generally 0.4 to 30% by weight, preferably 0.8 to 15% by weight, in each case based on the weight of the thermoplastic. It is important that the grain size and bulk density of the respective masterbatch are similar the grain size and the bulk density of the thermoplastic, so that a homogeneous distribution and thus a high transparency of the film is achieved.
  • the polyester films can be made from a polyester raw material, optionally further raw materials as well as the triclosan and / or other conventional additives (the latter in a customary amount of 0.1 to a maximum of 10 wt - Films are produced with the same or different surfaces.
  • the polyester film according to the invention is preferably produced by an extrusion process in which the melted polyester material is extruded through a slot die and quenched as a largely amorphous pre-film on a cooling roll. This film is then heated again and in the longitudinal direction and then in the transverse direction or in the transverse direction and then in the longitudinal direction or in the longitudinal direction
  • the stretching temperatures are generally 10 to 60 ° C. above the glass transition temperature Tg of the film material, the stretching ratio of the longitudinal stretching is usually 2 to 6, in particular 3 to 4.5, that of the transverse stretching is 2 to 5, in particular 3 to 4, 5, and that of the second carried out if necessary
  • the first longitudinal stretching can also be carried out simultaneously with the transverse stretching (simultaneous stretching).
  • the stretching is followed by the heat setting of the film at oven temperatures of 200 to 280 ° C, in particular at 220 to 270 ° C.
  • the film is then cooled and wound up.
  • the film according to the invention is outstandingly suitable for a large number of different applications, for example for goods in the medical field, in the packaging sector, as a laminating medium, for short-lived
  • UV-stabilized and / or flame-retardant films are particularly suitable for indoor or outdoor applications, in the electrical industry or in the construction sector, for greenhouses, roofing, external cladding or covers. The film is easily recyclable without loss of mechanical properties and without environmental pollution.
  • the film according to the invention and a non-antimicrobial reference film were examined in a shell test. It was the one to be checked
  • Foil is placed on the nutrient agar in a petri dish and then very thinly covered with agar, in which escherichia coli NCTC 8196 was used as test culture. If there was no active substance against the organism, the test organism grew on the film sample and thus the entire surface of the petri dish. The antimicrobial film was not overgrown by the test culture and the growth around the film was inhibited.
  • the surface gloss was measured at a measuring angle of 20 ° according to DIN 67530.
  • the yellowness index (YID) is the deviation from the colorlessness in the "yellow” direction and was measured in accordance with DIN 6167.
  • Light transmission (transparency)
  • Haze is the percentage of the transmitted light that deviates by more than 2.5 ° on average from the incident light beam.
  • the image sharpness was determined at an angle of less than 2.5 °.
  • the modulus of elasticity, the tensile strength and the elongation at break were measured in longitudinal and
  • the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
  • UV stability was tested according to the test specification ISO 4892 as follows:
  • the fire behavior was determined according to DIN 4102 part 2, building material class B2 and according to DIN 4102 part 1, building material class B1 and according to UL test 94.
  • the seal start temperature is the temperature at which a seal seam strength of at least 0.5 N / 15 mm is achieved.
  • Seal seam strength To determine the seal seam strength, two 15 mm wide strips of film were placed on top of each other and sealed at 130 ° C, a sealing time of 0.5 s and a sealing pressure of 2 bar (device: Brugger type NDS, one-sided heated sealing jaw). The seal seam strength was determined by the T-Peel method. All films were weathered on both sides with the Atlas Ci 65 Weather Ometer from Atlas according to the test specification ISO 4892 on both sides and then tested for mechanical properties, discoloration, surface defects, haze and gloss.
  • the examples and comparative examples below are single- or multi-layer, transparent films of different thicknesses, which were produced on an extrusion line.
  • Triclosan and 50% by weight polyester regenerate (inherent in film production; in addition to PET also contained small amounts of triclosan)
  • the polyethylene terephthalate RT49 (clear raw material) from which the transparent film was produced had a standard viscosity SV (DCE) of 810, which corresponds to an intrinsic viscosity IV (DCE) of 0.658 dl / g.
  • DCE standard viscosity SV
  • the longitudinal stretching ratio set during film production was 3.2 and the transverse stretching ratio was 3.7.
  • the film was then heat set at 235 ° C for about 2 seconds.
  • a transparent, three-layer A-B-A film with a total thickness of 12 ⁇ m was produced by coextrusion and subsequent stepwise orientation in the longitudinal and transverse directions.
  • Base layer B (12 ⁇ m) made from a mixture of
  • PET 50% by weight PET (type 4020, KoSa, Germany) and
  • regrind inherent in film production; in addition to PET also contained small amounts of pigment and triclosan from the
  • Example 1 10% by weight of triclosan masterbatch (as in Example 1) and 7% by weight of a masterbatch which, in addition to PET, contained 10,000 ppm of SiO 2 pigment ( ® Sylobloc from Grace).
  • the PET from which the transparent film was produced had a standard viscosity SV (DCE) of 770, which corresponds to an intrinsic viscosity IV (DCE) of 0.632 dl / g
  • the longitudinal stretching ratio set during film production was 4.2%
  • Example 2 As described in Example 2, a 12 ⁇ m thick A-B-A film was produced, this time the base layer also being antimicrobially treated with triclosan and both sides of the film additionally being coated.
  • the base layer B was made from a mixture of
  • regrind inherent in film production; in addition to PET also contained small amounts of pigment and triclosan.
  • the cover layers A were each produced from a mixture of
  • the film was coated on both sides with an aqueous dispersion using the “reverse gravure-roll coating” method.
  • the dispersion contained water
  • hydrophilic polyester containing 5-Na-sulfoisophthalic acid
  • PET / I PA polyester SP41, Ticona, USA
  • 0.15 wt .-% colloidal silica Nalco Chemical, Germany
  • 0.15 wt .-% ammonium carbonate Merck, Germany
  • the wet application weight was 2 g / m 2 per coated side. After the transverse stretching, the calculated thickness of the coating was 40 nm.
  • Example 2 was repeated with the only difference that this time the film was not antimicrobially treated with triclosan.
  • Triclosan was added in the form of a master batch of 90% PET and 10% triclosan.
  • the Si0 2 pigment was also added in the form of a master batch of PET and 10,000 ppm pigment.
  • the polyethylene terephthalate (clear raw material) from which the transparent film was produced had a standard viscosity SV (DCE) of 810, which corresponds to an intrinsic viscosity IV (DCE) of 0.658 dl / g.
  • the longitudinal stretching ratio set during film production was 3.2 and the transverse stretching ratio was 3.7.
  • the film was then heat set at 235 ° C for about 2 seconds.
  • the film was coated on both sides with an aqueous dispersion by means of a "reverse gravure-roll coating” process.
  • the dispersion contained water
  • the wet application weight was 2 g / m 2 per coated side. After the transverse stretching, the calculated thickness of the coating was 40 nm.
  • UV stabilizer As described in Example 4, a 50 ⁇ m thick monofilm was produced, but this time the film was 0.6% 2- (4,6-diphenyl- [1,3,5] triazin-2-yl) -5-hexyloxyphenol ( ® Tinuvin 1577 from Ciba-Geigy) as UV stabilizer, based on the total weight of the film.
  • the UV stabilizer was in the form of a 20%
  • the stabilizer has a melting point of 149 ° C and is thermally stable up to approx. 330 ° C.
  • EXAMPLE 6 A 19 ⁇ m thick, three-layer, antimicrobially equipped, transparent film with a layer sequence ABA was produced by coextrusion.
  • the base layer B had a thickness of 16 ⁇ m and contained PET as the main component, in addition 4% methanephosphonic acid bis- (5-ethyl-2-methyl-2-oxo-2 ⁇ 5 - [1, 3.2] dioxaphosphinane-5- ylmethyl ester) (Amgard ® P1045 from Albright & Wilson) as a flame retardant and 0.2% pentaerythritol tetrakis [3- (3,5-di-TETF-butyl-4-hydroxy-phenyl) -propionatals hydrolysis stabilizer. Flame retardants and stabilizers were added in the form of a masterbatch made from 79% PET, 20% flame retardants and 1% hydrolysis stabilizer. Layer B also contained 30% of the self-regenerated material inherent in film production.
  • the two 1.5 ⁇ m thick outer layers A also contained 0.7% triclosan and 0.1% Si0 2 pigment ( ® Sylobloc) as antiblocking agents.
  • the triclosan was added in the form of a master batch of 90% PET and 10% triclosan.
  • the PET was identical to that in Example 4 (same SV and IV).
  • Example 6 an antimicrobial ABA film with a thickness of 19 ⁇ m was produced. In contrast to this, however, the film was coated on one side with an aqueous dispersion which was identical to that in Example 4 by "reverse gravure-roll coating" The wet application weight was likewise 2 g / m 2 and the calculated thickness of the coating after the transverse stretching was 40 nm.
  • the base layer B had a thickness of 10 ⁇ m and contained PET, 0.2% triclosan and 30% self-regenerate as the main constituent.
  • the triclosan was again metered in as a masterbatch (composition as in Example 4).
  • a copolyester of 78 mol% ethylene terephthalate and 22 mol% ethylene isophthalate was used as the thermoplastic (produced by transesterification in the presence of a manganese catalyst, Mn concentration: 100 ppm). It also contained 3.0% of a masterbatch composed of 97.75% copolyester and 1.0% of a synthetic Si0 2 pigment ( ® Sylobloc 44H from Grace) and 1.25% pyrogenic Si0 2 ( ® Aerosil TT 600 from Degussa AG) as an antiblocking agent.
  • the 1 ⁇ m thick top layer C contained, besides PET, 0.7% triclosan and 3.0% of a Si0 2 pigment masterbatch of the same composition as that used for layer A.
  • the PET from which the transparent film was produced was identical to that in Example 4.
  • Example 8 As described in Example 8, a 12 ⁇ m thick, antimicrobial, transparent, coextruded, sealable ABC film was produced.
  • the non-sealable top layer C was coated on one side with an aqueous dispersion after the longitudinal stretching by "reverse gravure-roll coating".
  • the dispersion had the same composition as in Example 4.
  • the wet application weight was 2 g / m 2 .
  • the calculated thickness of the coating was 40 nm.
  • Example 10 As described in Example 9, a 12 ⁇ m thick, antimicrobial, transparent, coextruded, sealable A-B-C film was produced, which was additionally coated on the top layer C with the adhesion promoter SP41.
  • the base layer B contained 1.5% solvent blue 35 ( ® Sudan blue 2 from BASF AG, Germany).
  • the colorant is in
  • Example 11 As described in Example 10, a 12 ⁇ m thick, antimicrobial, transparent, coextruded, colored, sealable A-B-C film was produced. In contrast to Example 10, the film remained uncoated.
  • the film was corona treated on top layer C.
  • the intensity was chosen so that the surface tension after the treatment was more than 45 mN / m.
  • Example 5 Analogously to Example 5, a 50 ⁇ m thick monofilm was produced which was antimicrobially treated with 0.2% triclosan, which was metered in in the form of a 10% masterbatch.
  • the film to improve the UV stability contained 0.6% UV stabilizer (2- (4,6-diphenyl- [1,3,5] triazin-2-yl) -5-hexyloxyphenol, ® Tinuvin 1577).
  • the UV stabilizer was added in the form of a 20% master batch.
  • the film also contained 0.2% of the hydrolysis stabilizer described in Example 6 and 4% of the flame retardant also described in this example.
  • the hydrolysis stabilizer and flame retardant were metered in in the form of a masterbatch (composition as in Example 6).
  • the film also contained 5% solvent blue 35.
  • the colorant was metered in in the form of a masterbatch which, in addition to PET, contained 20% by weight of the blue colorant.
  • the film was coated on both sides with the aqueous dispersion already described in Example 4 by "reverse gravure-roll coating".
  • the wet application weight was 2 g / m 2 per coated side.
  • the calculated thickness of the coating was 40 nm.
  • a 50 ⁇ m thick, coextruded film with the layer sequence A-B-C was produced.
  • the formulation of the 47 ⁇ m thick base layer B corresponded to the formulation of the monofilm from Example 12, so it contained, in addition to PET triclosan, UV stabilizer,
  • the formulation of the 1.5 ⁇ m thick outer layers A and C corresponds to the formulation from Example 8.
  • the top layer C was coated with the SP41 adhesion promoter.
  • Example 4 As described in Example 4, a 50 ⁇ m thick transparent monofilm was produced. In contrast to Example 4, the film did not contain triclosan, so it was not antimicrobial. The film was coated on both sides as in Example 4.
  • the properties of the films according to Examples 4 to 13 (B4 to B13) and Comparative Example 2 (VB 2) are summarized in the table below.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille monocouche ou multicouche, transparente, à orientation biaxiale, thermofixée et partiellement cristalline comprenant en tant que composante principale un thermoplaste cristallisable qui présente une fraction à action anti-microbienne de 2,4,4'-trichlor-2'-hydroxy-diphényl éther (triclosane), et ayant éventuellement au moins une autre fonctionnalité. Les autres fonctionnalités possibles de la feuille sont les suivantes: elle peut être stabilisée aux rayonnements U.V., avoir une action ignifugeante, être recouverte sur une ou deux faces, présenter des aptitudes au scellement et/ou être traitée par effet couronne ou à la flamme. De manière générale, la feuille est réalisée par extrusion ou coextrusion, le triclosane et les composés utilisés pour les fonctionnalités supplémentaires étant ajoutés sous la forme d'un mélange-maître préséché ou précristallisé. La feuille peut être utilisée dans le domaine médical, en intérieur ou en extérieur, ainsi que pour l'emballage et l'élimination des déchets.
PCT/EP2002/000853 2001-02-05 2002-01-28 Feuille transparente, anti-microbienne, a orientation biaxiale, partiellement cristalline, issue d'un thermoplaste cristallisable WO2002062577A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10105107.7 2001-02-05
DE10105108A DE10105108A1 (de) 2001-02-05 2001-02-05 Funktionalisierte, transparente, antimikrobielle, biaxial orientierte, teilkristalline Folie aus einem kristallisierbaren Thermoplasten
DE10105108.5 2001-02-05
DE2001105107 DE10105107A1 (de) 2001-02-05 2001-02-05 Transparente, antimikrobielle, biaxial orientierte, teilkristalline Folie aus einem kristallisierbaren Thermoplasten

Publications (1)

Publication Number Publication Date
WO2002062577A1 true WO2002062577A1 (fr) 2002-08-15

Family

ID=26008413

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/000853 WO2002062577A1 (fr) 2001-02-05 2002-01-28 Feuille transparente, anti-microbienne, a orientation biaxiale, partiellement cristalline, issue d'un thermoplaste cristallisable

Country Status (1)

Country Link
WO (1) WO2002062577A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006070183A1 (fr) * 2004-12-30 2006-07-06 Syngenta Limited Compositions de revetement aqueuses
EP1806380A1 (fr) * 2004-08-11 2007-07-11 Mitsubishi Polyester Film Corporation Films de polyester à orientation bi-axiale
WO2007107840A2 (fr) * 2006-03-17 2007-09-27 Marc Racquet Produits antimicrobiens en forme de feuille et procédé de préparation
DE102007054132A1 (de) 2007-11-14 2009-05-20 Mitsubishi Polyester Film Gmbh Antimikrobiell ausgerüstete, biaxial orientierte Polyesterfolie
DE102007054133A1 (de) 2007-11-14 2009-05-20 Mitsubishi Polyester Film Gmbh Antimikrobiell ausgerüstete, gecoatete, biaxial orientierte Polyesterfolie
US7705078B2 (en) 2004-06-25 2010-04-27 Dupont Teijin Films U.S. Limited Partnership Antimicrobial polymeric film
ES2370331A1 (es) * 2009-06-03 2011-12-14 Abn Pipe Systems, S.L.U. Tubería para redes de distribución de agua.
WO2012036618A1 (fr) * 2010-09-17 2012-03-22 Nanexa Ab Produit polymère avec couche antimicrobienne interne et couche de protection externe
CN105097075A (zh) * 2015-08-26 2015-11-25 苏州华达彩印包装有限公司 应用于极细电缆的屏蔽护套膜及其生产工艺
CN105128488A (zh) * 2015-08-31 2015-12-09 广西点图包装有限公司 一种抗菌、杀菌包装材料
CN105236014A (zh) * 2015-08-31 2016-01-13 广西点图包装有限公司 一种抗菌、保鲜包装材料
GB2544852A (en) * 2015-10-01 2017-05-31 Clifton Packaging Group Ltd System and method for applying a coating to a film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5549924A (en) * 1987-07-17 1996-08-27 Robin Renee Thill Shlenker Method of forming a membrane, especially a latex or polymer membrane, including a deactivating barrier and indicating layer
US5906823A (en) * 1994-05-09 1999-05-25 Mixon; Grover C. Antimicrobial gloves and a method of manufacture thereof
US5965276A (en) * 1987-07-17 1999-10-12 Bio Barrier, Inc. Method of forming a membrane especially a latex or polymer membrane including multiple discrete layers
WO1999060297A1 (fr) * 1998-05-18 1999-11-25 Valpar Industrial Limited Tube plastique antimicrobien

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5549924A (en) * 1987-07-17 1996-08-27 Robin Renee Thill Shlenker Method of forming a membrane, especially a latex or polymer membrane, including a deactivating barrier and indicating layer
US5965276A (en) * 1987-07-17 1999-10-12 Bio Barrier, Inc. Method of forming a membrane especially a latex or polymer membrane including multiple discrete layers
US5906823A (en) * 1994-05-09 1999-05-25 Mixon; Grover C. Antimicrobial gloves and a method of manufacture thereof
WO1999060297A1 (fr) * 1998-05-18 1999-11-25 Valpar Industrial Limited Tube plastique antimicrobien

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7705078B2 (en) 2004-06-25 2010-04-27 Dupont Teijin Films U.S. Limited Partnership Antimicrobial polymeric film
EP1806380A1 (fr) * 2004-08-11 2007-07-11 Mitsubishi Polyester Film Corporation Films de polyester à orientation bi-axiale
EP1806380A4 (fr) * 2004-08-11 2010-06-16 Mitsubishi Polyester Film Corp Films de polyester à orientation bi-axiale
WO2006070183A1 (fr) * 2004-12-30 2006-07-06 Syngenta Limited Compositions de revetement aqueuses
US10342229B2 (en) 2004-12-30 2019-07-09 Syngenta Participations Ag Aqueous coating compositions
WO2007107840A2 (fr) * 2006-03-17 2007-09-27 Marc Racquet Produits antimicrobiens en forme de feuille et procédé de préparation
WO2007107840A3 (fr) * 2006-03-17 2008-03-13 Marc Racquet Produits antimicrobiens en forme de feuille et procédé de préparation
US8900696B2 (en) 2007-11-14 2014-12-02 Mitsubishi Polyester Film Gmbh Antimicrobially modified, coated, biaxially oriented polyester film
DE102007054132A1 (de) 2007-11-14 2009-05-20 Mitsubishi Polyester Film Gmbh Antimikrobiell ausgerüstete, biaxial orientierte Polyesterfolie
DE102007054133A1 (de) 2007-11-14 2009-05-20 Mitsubishi Polyester Film Gmbh Antimikrobiell ausgerüstete, gecoatete, biaxial orientierte Polyesterfolie
EP2060392A1 (fr) 2007-11-14 2009-05-20 Mitsubishi Polyester Film GmbH Feuille de polyester antimicrobienne et orienté de manière biaxiale
US7960010B2 (en) 2007-11-14 2011-06-14 Mitsubishi Polyester Film Gmbh Antimicrobially modified, biaxially oriented polyester film
ES2370331A1 (es) * 2009-06-03 2011-12-14 Abn Pipe Systems, S.L.U. Tubería para redes de distribución de agua.
EP2616108A4 (fr) * 2010-09-17 2015-05-27 Nanexa Ab Produit polymère avec couche antimicrobienne interne et couche de protection externe
US9629946B2 (en) 2010-09-17 2017-04-25 Nanexa Ab Polymeric protective layer
WO2012036618A1 (fr) * 2010-09-17 2012-03-22 Nanexa Ab Produit polymère avec couche antimicrobienne interne et couche de protection externe
CN105097075A (zh) * 2015-08-26 2015-11-25 苏州华达彩印包装有限公司 应用于极细电缆的屏蔽护套膜及其生产工艺
CN105128488A (zh) * 2015-08-31 2015-12-09 广西点图包装有限公司 一种抗菌、杀菌包装材料
CN105236014A (zh) * 2015-08-31 2016-01-13 广西点图包装有限公司 一种抗菌、保鲜包装材料
GB2544852A (en) * 2015-10-01 2017-05-31 Clifton Packaging Group Ltd System and method for applying a coating to a film
GB2544852B (en) * 2015-10-01 2022-06-08 Clifton Packaging Group Ltd System and method for applying a coating to a film

Similar Documents

Publication Publication Date Title
DE10126149A1 (de) Gedeckt eingefärbte, hydrolysebeständige, biaxial orientierte Folie aus einem kristallisierbaren Thermoplasten und Verfahren zu ihrer Herstellung
EP1614536A2 (fr) Feuille polyester multicouche, matte, ir-reflechissante et thermoformable
EP1261481A1 (fr) Feuille polyester matte, stable aux u.v., ignifugeante, coextrudee, son procede de realisation et son utilisation
EP1256597A2 (fr) Feuille blanche à orientation biaxiale, à base d'un thermoplastique crystallisable ayant une découpabilité
EP1268632A1 (fr) Feuille de polyester coextrudee, scellable, stabilisee aux uv, mate sur une face, a orientation biaxiale et traitee pour retarder la combustion, son procede de fabrication et son utilisation
WO2001053407A2 (fr) Feuille blanche, difficilement inflammable, stable aux uv, thermoformable, constituee d'une matiere thermoplastique cristallisable, son procede de production et son utilisation
EP1297948A2 (fr) Feuille amorphe transparente et résistante à l'hydrolyse, constituée de thermoplastes cristallisables, et son procédé de production
EP1193050B1 (fr) Feuille transparente et biaxialement orientée, constituée de thermoplastes cristallisables et résistante à l'hydrolyse, et son procédé de production
WO2002062577A1 (fr) Feuille transparente, anti-microbienne, a orientation biaxiale, partiellement cristalline, issue d'un thermoplaste cristallisable
EP1272551B1 (fr) Feuille blanche, difficilement inflammable, stable aux uv, constituee d'une matiere thermoplastique cristallisable, son procede de production et son utilisation
DE10007726A1 (de) Transparente, siegelfähige, UV-stabilisierte und flammhemmend ausgerüstete Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2002055301A1 (fr) Feuille polyester multicouche a garniture anti-microbienne et surface matte
DE10105108A1 (de) Funktionalisierte, transparente, antimikrobielle, biaxial orientierte, teilkristalline Folie aus einem kristallisierbaren Thermoplasten
WO2002068511A1 (fr) Feuille amorphe fonctionnalisee constituee d'un thermoplaste modifie par dibenzene, son procede de realisation et son utilisation
WO2002062578A1 (fr) Feuille semi-cristalline antimicrobienne, a orientation biaxiale et a teinture mate, en thermoplastique cristallisable
DE10105110A1 (de) Gedeckt eingefärbte, antimikrobielle, biaxial orientierte, teilkristalline Folie aus einem kristallisierbaren Thermoplast mit zusätzlicher Funktionalität, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10100705A1 (de) Funktionalisierte,weiße,antimikrobielle,biaxial orientierte, teilkristalline Folie aus einem kristallisierbaren Thermoplasten
WO2001060140A2 (fr) Pellicule polyester blanche, scellable, rendue stable aux u.v. et traitee ignifuge, a orientation biaxiale, procede permettant de la produire et utilisation
WO2002070253A1 (fr) Film amorphe a coloration opaque, fonctionnalise, constitue d'une matiere thermoplastique modifiee par dibenzene, son procede de production et son utilisation
DE10002153A1 (de) Amorphe, weiße, schwerentflammbare, UV-stabile, thermoformbare Folie, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2002055592A1 (fr) Feuille blanche, anti-microbienne, partiellement cristalline a orientation biaxiale comprenant un thermoplaste cristallisable
WO2002057349A1 (fr) Feuille transparente amorphe anti-microbienne composee d'un thermoplaste cristallisable, son procede de realisation et son utilisation
DE10043784A1 (de) Transparente, teilkristalline, funktionalisierte Folie aus einem bibenzolmodifizierten Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10101903A1 (de) Amorphe, antimikrobiell ausgerüstete, transparente Folie aus einem kristallisierbaren Thermoplast mit zusätzlicher Funktionalität, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1274578B1 (fr) Feuille polyester matte, stable aux u.v., peu inflammable, thermoformable, coextrudee, son procede de realisation et son utilisation

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP