WO2002062578A1 - Feuille semi-cristalline antimicrobienne, a orientation biaxiale et a teinture mate, en thermoplastique cristallisable - Google Patents

Feuille semi-cristalline antimicrobienne, a orientation biaxiale et a teinture mate, en thermoplastique cristallisable Download PDF

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Publication number
WO2002062578A1
WO2002062578A1 PCT/EP2002/000854 EP0200854W WO02062578A1 WO 2002062578 A1 WO2002062578 A1 WO 2002062578A1 EP 0200854 W EP0200854 W EP 0200854W WO 02062578 A1 WO02062578 A1 WO 02062578A1
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WO
WIPO (PCT)
Prior art keywords
film
weight
antimicrobial
film according
triclosan
Prior art date
Application number
PCT/EP2002/000854
Other languages
German (de)
English (en)
Inventor
Ursula Murschall
Ulrich Kern
Klaus Oberländer
Günther Crass
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 DE2001105109 external-priority patent/DE10105109A1/de
Priority claimed from DE10105110A external-priority patent/DE10105110A1/de
Application filed by Mitsubishi Polyester Film Gmbh filed Critical Mitsubishi Polyester Film Gmbh
Publication of WO2002062578A1 publication Critical patent/WO2002062578A1/fr

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Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • 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

  • the invention relates to an opaque colored, antimicrobial, biaxially oriented, partially crystalline film made of a crystallizable thermoplastic, the thickness of which is in the range from 1 to 500 ⁇ m, and to a process for producing this film and its use. 5
  • Covered colored films made of crystallizable thermoplastics with a thickness between 1 and 500 ⁇ m are well known. These films have no antimicrobial effect.
  • the raw material is very sensitive to hydrolysis and must be pre-dried very well. When drying the raw material with dryers which correspond to the prior art, the raw material sticks together, so that a film can only be produced under the most difficult conditions.
  • GB-A 1 465 973 describes a coextruded, two-layer polyester film, one layer of which contains isophthalic acid and terephthalic acid-containing copolyesters and the other layer of polyethylene terephthalate consists. There is no usable information in the script about the sealing behavior of the film. Due to the lack of pigmentation, the film cannot be produced reliably (film cannot be wound) and can only be processed to a limited extent.
  • EP-A 0 035 835 describes a coextruded, sealable polyester film in which, in order to improve the winding and processing behavior, particles are added to the sealing layer, the average particle size of which exceeds the layer thickness of the sealing layer.
  • the particulate additives form surface protrusions that prevent unwanted blocking and
  • EP-A 0 432 886 describes a coextruded multilayer polyester film which has a first surface on which a sealable layer is arranged and a second surface on which an acrylate layer is arranged.
  • the sealable cover layer can also consist of copolyesters containing isophthalic acid and terephthalic acid.
  • the film on the back has improved processing properties.
  • the script does not give any information about the sealing area of the film.
  • 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.
  • EP-A 0 515 096 describes a coextruded, multilayer sealable polyester film which has an additional layer on the sealable layer Additive contains.
  • the additive can contain, for example, inorganic particles and is preferably applied to the film in an aqueous layer during its production. 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. No information is given in this document on the sealing temperature range of the film.
  • the seal seam strength is measured at 140 ° C and is more than 200 N / m (3 N / 15 mm). A seal seam strength of 275 N / m (4.125 N / 15 mm) is given for a 3 ⁇ m thick sealing layer.
  • WO 98/06575 describes a coextruded multilayer polyester film which contains a sealable cover layer and a non-sealable base layer.
  • the base layer can be composed of one or more layers, the interior of the layer being in contact with the sealable layer.
  • the other (outer) layer then forms the second non-sealable cover layer.
  • the sealable top layer can consist of copolyesters containing isophthalic acid and terephthalic acid, which, however, contain no antiblocking particles.
  • the film also contains at least one UV absorber, which is added to the base layer in a weight ratio of 0.1 to 10%. Are preferred as UV absorbers
  • Triazines e.g.® Tinuvin 1577 from Ciba.
  • 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 (gloss and cloudiness).
  • WO 99/31036 describes derivatives of halogenated diphenyl ether compounds which have antimicrobial properties in combination with improved migration behavior.
  • the diphenyl ether derivatives described are thermally stable, show low volatility with a low tendency to migrate and are preferably suitable for the antimicrobial finishing of polymeric compounds, for example for the antimicrobial finishing of plastics, rubbers, paints and fibers. Furthermore, a process for the preparation of the diphenyl ether derivatives is described. None of the references teach or point to a thermoplastic film containing triclosan, and furthermore that triclosan can be incorporated into a crystallizable thermoplastic, with all antimicrobial properties being retained during the processing and use phase.
  • the object of the present invention is to avoid the disadvantages of the prior art described.
  • the invention therefore relates to an opaque colored, antimicrobial, biaxially oriented, partially crystalline film, the thickness of which ranges from 1 to
  • a crystallizable thermoplastic containing, as a principal constituent, a crystallizable thermoplastic, wherein the film is characterized in that it contains as antimicrobial component 2,4,4 'trichloro-2'-hydroxy-diphenyl ether ( "triclosan”) alone or a mixture of Triclosan with other antimicrobial substances and at least one coloring pigment.
  • triclosan 2,4,4 'trichloro-2'-hydroxy-diphenyl ether
  • the invention further relates to a method for producing this film and its use.
  • the film according to the invention has above all an antimicrobial effect.
  • Antimicrobial activity 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.
  • Test organisms are pure, defined microorganisms such as pseudomonas aeruginosa, staphylococcus aureus, escherichia coli, aspergillus niger, penicillium funicolosum, chaetomium globosum, trichoderme virid or candida albicans 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 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.
  • Good optical properties include, for example, homogeneous ones
  • Coloring a high surface gloss ( ⁇ 15), a low light transmission ( ⁇ 85%) and a low yellowness index ( ⁇ 30).
  • the good mechanical properties include a high modulus of elasticity (E MD > 3200 N / mm 2 ; E TD > 3500 N / mm 2 ) and good tensile strength values (in
  • Good stretchability includes the fact that the film can be oriented excellently and without tears in both its longitudinal and transverse directions.
  • the film according to the invention can also be recycled, i.e. the regenerate can be used again without loss of the optical and mechanical properties, e.g. without negatively affecting the yellowness index of the film.
  • the main component of the film is a crystallizable thermoplastic.
  • Suitable crystallizable or semi-crystalline thermoplastics are, for example polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), bibenzoyl-modified polyethylene terephthalate (PETBB), bibenzoyl-modified polybutylene terephthalate (PBTBB), bibenzoyl-modified polyethylene naphthalate (PENBB) or mixtures thereof, said polyethylene terephthalate , Polyethylene naphthalate and bibenzene-modified polyethylene terephthalate are preferred.
  • DMT dimethyl terephthalate
  • EG ethylene glycol
  • PG propylene glycol
  • 1,4-butanediol terephthalic acid
  • TA benzenedicarboxylic acid
  • NDC 2,6-naphthalene dicarboxylate
  • NDA 2,6-naphthalene dicarboxylic acid
  • IPA isophthalic acid
  • c-CHDM, f-CHDM or c / f-CHDM 4-cyclohexanedimethanol
  • Crystallizable homopolymers Crystallizable copolymers, crystallizable compounds, crystallizable recyclate and other variations of crystallizable thermoplastics.
  • Preferred starting materials for the production of the film are crystallizable thermoplastics which have a crystallite melting point Tm, measured by DSC (differential scanning calorimetry) with a heating rate of 20 ° C./min, from 180 ° C. to over 365 ° C., preferably from 180 ° C. to 310 ° C. C, a crystallization temperature range Tc of 75 ° C to 280 ° C, a glass transition temperature Tg of 65 ° C to 130 ° C, a density, measured according to DIN 53479, of 1, 10 to 1, 45 and a crystallinity of 5% up to 65%, preferably 20% to 65%.
  • Tm crystallite melting point measured by DSC (differential scanning calorimetry) with a heating rate of 20 ° C./min, from 180 ° C. to over 365 ° C., preferably from 180 ° C. to 310 ° C. C
  • Tc crystallization temperature range
  • Tg glass transition temperature
  • Tg
  • the main constituent means that the amount of thermoplastic is between 50.0 and 99.5% by weight, preferably between 75.0 and 99.5% by weight.
  • the remaining amount of 100% can, in addition to the inorganic pigment and triclosan, be other additives customary for biaxially oriented films.
  • the antimicrobial substance according to the invention is 2,4,4 ' trichloro-2-hydroxy-diphenyl ether (triclosan) alone or in a mixture with other antimicrobial
  • Substances such as 10,10'-oxy-bisphenoxarsin, N- (trihalogenmethylthio) phthalimide, diphenylantimony-2-ethylhexanoate, copper 8-hydroxyquinoline, tributyltin oxide and its derivatives and derivatives of halogenated diphenyl ether compounds are used.
  • the amount is generally 0.005 to 10.0% by weight, preferred as 0.01 to 5.0 wt .-%, based on the weight of the crystallizable thermoplastic, the proportion of triclosan always outweighing.
  • the film according to the invention can be either single-layer or multi-layer. It can also be coated with various copolyesters or adhesion promoters. Furthermore, it generally contains the antiblocking agents and lubricants customary for films for the purpose of economical production.
  • the triclosan can be added to both the base layer and one or both top layers.
  • the extrusion process is suitable for this, preferably including the masterbatch process, i.e. in film production. If necessary, any intermediate layers that are present can also be antimicrobial.
  • Bulk weight of the masterbatch is similar to that of the thermoplastic, so that a homogeneous distribution and thus a correspondingly homogeneous finish can take place.
  • thermoplastic itself comes as a carrier material, e.g. polyethylene terephthalate or other polymers that are sufficiently compatible with the thermoplastic, in question.
  • the masterbatch is mixed with the thermoplastic provided as the film raw material and treated together in an extruder, the components fusing together and thus being dissolved in the thermoplastic.
  • the amount of antimicrobial active ingredient is generally 0.4 to 30.0% by weight, preferably 0.8 to 15.0% by weight, based on the amount used thermoplastics.
  • care must be taken that the volatility of the triclosan is taken into account by suitable measures.
  • the film is composed of at least one core layer and at least one cover layer, a three-layer A-B-A or A-B-C structure being preferred in particular.
  • thermoplastic of the core layer has a standard viscosity similar to that of the thermoplastic of the cover layer (s) which is adjacent to the core layer.
  • the cover layers can consist of a polyethylene terephthalate, a bibenzene-modified polyethylene terephthalate polymer, a bibenzene-modified and / or unmodified polyethylene naphthalate polymer or a bibenzene-modified and / or unmodified polyethylene terephthalate-polyethylene naphthalate copolymer or compound.
  • thermoplastics of the cover layers also have similar standard viscosities as the thermoplastic of the core layer.
  • the film according to the invention contains in the base layer and / or optionally the cover layers at least one coloring pigment in a concentration in the range from 0.2 to 40.0% by weight, preferably from 0.3 to 25.0% by weight , in particular 1.0 to 25.0% by weight, based on the weight of the thermoplastic in the layer in question.
  • Inorganic white and black pigments as well as inorganic or organic colored pigments are used as color pigments.
  • the coloring pigment is preferably added using masterbatch technology, but can also be incorporated directly at the raw material manufacturer.
  • Suitable white pigments are, for example, titanium dioxide, barium sulfate, calcium carbonate, kaolin, silicon dioxide, with titanium dioxide (anatase or rutile) and barium sulfate being preferred.
  • Titanium dioxide of the type described does not create any vacuoles in the polymer matrix during film production.
  • the titanium dioxide particles which may be used can have a coating of inorganic oxides, as is usually used as a coating for TiO 2 white pigment in papers or paints to improve the light fastness.
  • TiO 2 is photoactive. When exposed to UV rays, free radicals form on the surface of the particles. These free radicals can migrate to the film-forming polymers, which leads to degradation reactions and yellowing.
  • the particularly suitable oxides include the oxides of aluminum, silicon, zinc or magnesium or mixtures of two or more of these compounds.
  • the coating can contain organic compounds with polar and non-polar groups.
  • organic compounds must be sufficiently thermostable in the production of the film by extrusion of the polymer melt.
  • Preferred organic compounds are alkanols and fatty acids with 8-30 C atoms in the alkyl group, especially fatty acids and primary n-
  • Alkanols with 12 - 24 carbon atoms as well as polydiorganosiloxanes and / or polyorganohydrogensiloxanes such as polydimethylsiloxane and polymethylhydrogensiloxane.
  • the coating of titanium dioxide particles generally consists of 1.0 to 12.0, in particular 2.0 to 6.0 g of inorganic oxides and 0.5 to 3.0, in particular 0.7 to 1.5 g of organic compounds, based on 100.0 g of titanium dioxide particles.
  • the coating is applied to the particles in aqueous suspension.
  • the inorganic oxides are made from water-soluble compounds, e.g. B. alkali, in particular Sodium nitrate, sodium silicate (water glass) or silica precipitated in the aqueous suspension.
  • inorganic oxides such as Al 2 O 3 or SiO 2
  • the hydroxides or their various dewatering stages are, for. B. understand oxide hydrate without recognizing its exact composition and structure.
  • the oxide hydrates are z. B. of aluminum and / or silicon, the pigments are then washed and dried. This precipitation can thus take place directly in a suspension, as occurs in the manufacturing process after the annealing and the subsequent wet grinding.
  • the oxides and / or oxide hydrates of the respective metals are precipitated from the water-soluble metal salts in the known pH range, for the aluminum, for example, aluminum sulfate is used in aqueous solution (pH less than 4) and by adding aqueous ammonia solution or sodium hydroxide solution in the pH range of 5 to 9, preferably from
  • the oxide hydrate precipitates.
  • the pH of the TiO 2 suspension presented should be in the strongly alkaline range (pH greater than 8).
  • the precipitation then takes place by adding mineral acid such as sulfuric acid in the pH range from 5 to 8. After the precipitation of the metal oxides, the suspension is left for another 15 minutes to about 2
  • the coated product is separated from the aqueous dispersion and, after washing, is dried at an elevated temperature, preferably at 70 to 100 ° C.
  • the film can optionally contain at least one optical brightener, which is used in amounts of from 10 ppm to 50,000 ppm, preferably from 20 ppm to 30,000 ppm, in particular from 50 ppm to 25,000 ppm, based on the weight of the crystallizable thermoplastic.
  • the optical brightener is also preferably metered in directly during film production using the so-called masterbatch technology.
  • optical brighteners used are able to absorb UV rays in the range of 360 to 380 nm and emit them again as longer-wave, visible blue-violet light.
  • Suitable optical brighteners are bis-benzoxazoles, phenylcoumarins and bis-sterylbiphenyls, preferably phenylcoumarin, in particular triazine-phenylcoumarin ( ⁇ Tinopal, Ciba-Geigy, Basel, Switzerland), ⁇ Hostalux KS (Clariant, Germany) and ⁇ Eastobrite OB-1 (Eastman ).
  • Typical inorganic black pigments are carbon black modifications, which can also be coated, carbon pigments which differ from the carbon black pigments in their higher ash content, and oxidic black pigments such as iron oxide black and copper, chromium and iron oxide mixtures. (Mixed-phase pigments).
  • Suitable inorganic colored pigments are oxidic colored pigments, hydroxyl-containing pigments, sulfidic pigments and chromates.
  • colored oxide pigments are iron oxide red, titanium oxide-nickel oxide-antimony oxide mixed-phase pigments, titanium dioxide-chromium oxide, antimony oxide mixed-phase pigments, mixtures of the oxides of iron, zinc and titanium, chromium oxide iron oxide brown, spinels of the cobalt-aluminum-titanium-nickel-zinc oxide system and mixed phase pigments based on other metal oxides.
  • Typical hydroxyl-containing pigments are, for example, oxide hydroxides of trivalent iron, such as FeOOH.
  • sulfidic pigments are cadmium sulfide selenides,
  • chromates are lead chromates, which can be monoclinic, rhombic and tetragonal in the crystal forms.
  • all colored pigments can be both uncoated and also inorganic and / or organically coated.
  • the organic colored pigments are generally divided into azo pigments and so-called non-azo pigments.
  • Azo pigments can be monoazo pigments, diazo pigments, diazo condensation pigments, salts of azo color acids and mixtures of the azo pigments.
  • the film can be coated on at least one of its surfaces, so that the coating on the finished film has a thickness of 5 to 100 nm, preferably 20 to 70 nm, in particular 30 to 50 nm.
  • the coating is preferably applied in-line, ie during the film production process, expediently after the extrusion.
  • The is particularly preferred
  • the coatings can be applied extremely homogeneously in the layer thicknesses mentioned.
  • the coatings are applied as a dilute solution, emulsion or dispersion, preferably in aqueous form, to at least one surface of the film and then the solvent is volatilized.
  • Film surface an additional function, for example the film becomes sealable, printable, metallizable, sterilizable, antistatic or improves e.g. the aroma barrier or enables adhesion to materials that would otherwise not adhere to the film surface (e.g. photographic emulsions).
  • substances / compositions that provide additional functionality are: acrylates (WO 94/13476), ethyl vinyl alcohols, polyvinylidene dichloride, water glass (Na 2 SiO 4 ), hydrophilic polyesters such as 5-Na sulfoisophthalic acid-containing PET / IPA polyesters (EP-A 0 144878 , US-A 4,252,885 or EP-A-0296620), vinyl acetate (WO 94/13481), polyvinyl acetates, polyurethanes, alkali or alkaline earth metal salts of C 10 -C 18 fatty acids, butadiene copolymers with acrylonitrile or methyl methacrylate,
  • Methacrylic acid acrylic acid or their esters.
  • the substances / compositions which impart the additional functionality can contain the customary additives such as antiblocking agents, pH stabilizers in amounts in the range from 0.05 to 5.0% by weight, preferably from 0.1 to 3.0% by weight. % contain.
  • the substances / compositions mentioned are applied as described above as a dilute solution, emulsion or dispersion to one or both film surfaces and then the solvent is evaporated. If the coatings are applied in-line 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 according to the invention can be provided with UV stability.
  • thermoplastics especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm induces degradation processes in thermoplastics, as a result of which not only does the visual appearance change due to color change or yellowing, but also has an extremely negative influence on the mechanical-physical properties of the films made of the thermoplastics.
  • Polyethylene terephthalates for example, start below 360 nm UV
  • Carbon monoxide, carbon dioxide and carboxylic acids are the predominant quantities of photooxidation products.
  • oxidation reactions must also be considered, which also result in the formation of carbon dioxide via peroxide radicals.
  • UV stabilizers also called UV absorbers, as light stabilizers are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially cause sun protection. However, these substances are unsuitable for films according to the invention, since they lead to discoloration or color change. Only organic and organometallic compounds are suitable for these foils, which give the thermoplastic to be stabilized no or only an extremely slight color or color change.
  • Suitable UV stabilizers as light stabilizers are compounds which absorb at least 70%, preferably 80%, particularly preferably 90%, of UV light in the wavelength range from 180 nm to 380 nm, preferably 280 to 360 nm. These are particularly suitable if they are in the temperature range of
  • UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organic nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and
  • Triazines with the 2-hydroxybenzotriazoles and the triazines being preferred.
  • the film according to the invention can contain at least one UV stabilizer as light stabilizer, the concentration of the UV stabilizer preferably in the range from 0.01 to 5.0% by weight, in particular in the range from 0.1 to
  • the film contains 0.01 to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxyphenol of the formula
  • UV stabilizers which absorb the UV light and thus generally offer protection
  • the UV stabilizer has poor thermal stability and decomposes or outgasses at temperatures between 200 ° C and 240 ° C, Large amounts (approx. 10 to 15% by weight) of UV stabilizer have to be incorporated so that the UV light is absorbed and the film is not damaged.
  • Nozzle deposits which leads to profile fluctuations; - Roller deposits from the UV stabilizer, which leads to impairment of the optical properties (poor cloudiness, adhesive defect, inhomogeneous surface); Deposits in the production process.
  • Film has an excellent appearance and has an excellent profile and flatness, - the UV-stabilized film is characterized by excellent running reliability, so that it can be manufactured reliably. This means that the film is also economically viable.
  • a flame retardant effect means that the film according to the invention in a so-called fire protection test fulfills the conditions according to DIN 4102 Part 2 and in particular the conditions according to DIN 4102 Part 1 and is classified in the construction class B 2 and in particular B1 of the flame retardant materials can. Furthermore, 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 according to the invention can contain at least one flame retardant which is metered in directly during film production using the so-called masterbatch technology, the concentration of the flame retardant being in the range from 0.5 to 30.0% by weight, preferably from 1.0 up to 20.0% by weight, based on the weight of the layer of the crystallizable thermoplastic.
  • concentration of the flame retardant in the masterbatch is generally in the range from 5.0 to 60.0% by weight.
  • Typical flame retardants include bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide, aluminum hydroxide, the halogen compounds being disadvantageous on account of the halogen-containing by-products formed. Furthermore, the low light resistance of a film equipped with it, in addition to the development of hydrogen halide in the event of fire, is extremely disadvantageous.
  • Suitable flame retardants which are used according to the invention are, for example, organic phosphorus compounds such as carboxyphosphinic acids, their anhydrides and alkanephosphonic acid esters, preferably methanephosphonic acid esters. It is essential that the organic phosphorus compound is soluble in the thermoplastic, since otherwise the required optical properties will not be met.
  • Phenolic stabilizers are generally used as hydrolysis stabilizers
  • Alkali / alkaline earth stearates and / or alkali / 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.
  • Pentaerythrityl tetrakis-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 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 soluble in the thermoplastic as a flame retardant and 0.1 to 1.0% by weight of a hydrolysis stabilizer in addition to the antimicrobial substance.
  • Bis- (5-ethyl-2-methyl-2-oxo-2 ⁇ 5 - [1, 3,2] dioxaphosphinan-5-ylmethyl ester) is preferred as the flame retardant.
  • thermoplastics to be used according to the invention.
  • No embrittlement after thermal stress means that the film has no embrittlement and no disadvantageous mechanical properties after 100 hours of annealing at 60 ° C. in a forced air oven.
  • films according to the invention in the thickness range 10 -
  • the surface gloss of the films according to the invention measured according to DIN 67530 (measuring angle 20 °), is ⁇ 15, preferably> 20 and the light transmission L * , measured according to ASTM D 1003, is ⁇ 85%, preferably ⁇ 80%, which for the achieved antimicrobial effect in combination with muted coloring is surprisingly good.
  • the film according to the invention has at least three layers and then in a particular embodiment comprises the base layer B, the sealable cover layer, as layers
  • cover layers A and C which may or may not be sealable.
  • cover layer C is sealable
  • cover layers A and C are identical.
  • the sealable cover 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 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%.
  • copolyesters in which the proportion of ethylene terephthalate is 50 to 90 mol% and the corresponding proportion of ethylene isophthalate is 50 to 10 mol% and in particular copolyesters in which the proportion of ethylene terephthalate is 60 to 85 mol% and the corresponding proportion Ethylene isophthalate is 40 to 15 mol%.
  • the same polymers can be used for the other, non-sealable top layer C or for any intermediate layers present, as was described above for the base layer.
  • 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 sealable or non-sealable cover layer C.
  • the seal initiation temperature of 130 ° C. and the seal seam strength of at least 0.6 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 the copolymer does not have any more
  • Additives especially no inorganic or organic fillers, are added.
  • 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.
  • a layer of the multilayer film according to the invention can also be colored transparently.
  • the film can contain at least one dye soluble in the thermoplastic, the concentration of the soluble dye preferably in the range from 0.01% by weight to 20.0% by weight, in particular in the range from 0.05 to 10.0% by weight .-%, based on the weight of the crystallizable thermoplastic.
  • Soluble dye is understood to mean substances that are molecularly dissolved in the polymer (DIN 55949).
  • the color change of the film is based on the wavelength-dependent absorption and / or scattering of the light. Dyes can only absorb light, but cannot scatter it, because a certain particle size is the physical prerequisite for scattering.
  • Coloring with dye is a solution process.
  • the dye is molecularly dissolved, for example, in the crystallizable thermoplastic.
  • Such coloring is referred to as transparent, translucent, translucent or opal.
  • the fat and aromatic soluble dyes are particularly preferred. These are, for example, azo and anthraquinone dyes. They are particularly suitable e.g. for coloring PET because the migration of the dye is restricted due to the high glass transition temperatures of PET. (Literature J. Koerner: Soluble dyes in the plastics industry in "VDI-Gesellschaft Kunststofftechnik”: Coloring plastics, VDI-Verlag, Düsseldorf 1975).
  • Suitable soluble dyes are, for example: C.I. Solvent Yellow 93 (a pyrazolone derivative), C.I. Solvent Yellow 16 (a fat-soluble azo dye), Fluorol Green Gold (a fluorescent polycyclic dye), C.I. Solvent red 1 (an azo dye), azo dyes such as Thermoplastrot BS, Sudanrot BB, C.I. Solvent Red
  • anthraquinone derivative an anthraquinone derivative
  • fluorescent benzopyran dyes such as Fluorolrot GK and Fluorolorange GK
  • C.I. Solvent blue 35 an anthraquinone dye
  • C.I. Solvent blue 15: 1 a phthalocyanine dye
  • the soluble dye is preferably metered in using masterbatch technology, but can also be incorporated directly at the raw material manufacturer.
  • the con- The concentration of the color additives is between 0.01% by weight and 40.0% by weight, preferably between 0.05% by weight and 25.0% by weight, 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 economic production includes that the raw materials or the raw material components that are required for the production of the film with commercially available
  • Industrial dryers such as vacuum dryers i.e. can be dried under reduced pressure, fluidized bed dryer, fluid bed dryer or fixed bed dryer (shaft dryer). It is essential that the antimicrobial and flame-retardant active substances and the other active substances do not outgas or form wall coverings in the dryers, that the raw materials do not stick together and are not thermally degraded.
  • the above-mentioned dryer works in general at normal pressure with temperatures between 100 and 170 ° C.
  • the raw material goes through a temperature range of approx. 30 ° C to 130 ° C at a reduced pressure of 50 mbar. After that, so-called post-drying in a hopper at temperatures of 100 to 130 ° C and a residence time of 3 to 6 hours is required.
  • the masterbatch which contains the triclosan and optionally the flame retardant and the hydrolysis stabilizer, is pre-crystallized or pre-dried.
  • This predrying involves gradual heating of the masterbatch under reduced pressure (20 to 80 mbar, preferably 30 to 60 mbar, in particular 40 to 50 mbar) and with stirring and optionally post-drying at constant, elevated temperature, likewise under reduced pressure
  • the masterbatch is preferably batchwise at room temperature from a metering container in the desired mixture together with the polymers of the base and / or outer layers and possibly other raw material components in a vacuum dryer which is used in the course of the drying or Dwell time a temperature range of 10 ° C to 160 ° C, preferably 20 ° C to 150 ° C, in particular 30 ° C to 130 ° C passes.
  • a temperature range of 10 ° C to 160 ° C preferably 20 ° C to 150 ° C, in particular 30 ° C to 130 ° C passes.
  • the raw material mixture is stirred at 10 to 70 rpm, preferably 15 to 65 rpm, in particular 20 to 60 rpm.
  • the raw material mixture pre-crystallized or pre-dried in this way is in a downstream likewise evacuated container at 90 ° to 180 ° C., preferably 100 ° C. to 170 ° C., in particular 110 ° C. to 160 ° C. for 2 to 8 hours, preferably 3 to 7 hours , especially after 4 to 6 hours.
  • the film can be produced in the dryer, for example, by means of masterbatch technology and a suitable predrying or pre-crystallization of the masterbatch.
  • the film can also be oriented in the longitudinal and transverse directions without tears. Furthermore, no outgassing was found in the production process, which is essential to the invention.
  • the film according to the invention can be produced, for example, by an extrusion process in an extrusion line.
  • the foils can e.g. by known processes from a thermoplastic raw material, 0.005 to 10.0% by weight of triclosan, at least one coloring pigment and optionally with further raw materials and / or other customary additives in a customary amount of 0.1 to a maximum of 10.0% by weight, the sum of crystallized thermoplastic and the additives is always 100%, both as
  • Monofilms as well as multilayer, optionally coextruded films with the same or differently shaped surfaces can be produced, with at least one film optionally being pigmented.
  • one or both surfaces of the film can be provided with a conventional functional coating by known methods.
  • the melted thermoplastic material is extruded through a slot die and quenched as a largely amorphous pre-film on a chill roll.
  • This slide will then heated again and stretched in the longitudinal and transverse directions or in the transverse and in the longitudinal direction or in the longitudinal, in the transverse and again in the longitudinal direction and / or transverse direction.
  • the first longitudinal stretching can optionally be carried out simultaneously with the transverse stretching (simultaneous stretching). This is followed by the heat setting of the film at oven temperatures of 200 to 280 ° C, especially at 220 to 270 ° C. The film is then cooled and wound up.
  • the standard viscosity SV (DCE) of the thermoplastic measured in dichloroacetic acid according to DIN 53728, is in the range from 600 to 1000, preferably from
  • the bulk density measured according to DIN 53466, is in the range from 0.75 to 1.0 kg / dm 3 , preferably from 0.80 to 0.90 kg / dm 3 .
  • the polydispersity of the thermoplastic Mw / Mn measured by means of GPC is in the range from 1.5 to 4.0, preferably from 2.0 to 3.5.
  • the film according to the invention is excellently suitable for a large number of different applications, for example in the interior, for example as a laminating medium, in the medical field, for protective glazing of machines and medical devices, as furniture films, as packaging film or as film in the disposal area and environmental protection. Since it has no environmental impact and can be easily recycled without loss of mechanical properties, it can be used, for example, for the production of short-lived articles and goods for the medical sector and in the packaging sector.
  • the film according to the invention is also suitable for outdoor applications, e.g. for greenhouses, roofing, external cladding, covers, furniture foils, applications in the construction sector and in the electrical industry, for applications in the refrigerator and freezer sector and for illuminated advertising profiles.
  • Hemmhof test In a shell test, the film according to the invention and a reference film which is not antimicrobially treated are examined.
  • the film to be tested is placed on the nutrient agar in a petri dish and then very thinly covered with agar in which the test organisms are located. If there is no active substance against the organism, the test organism grows over the film pattern and thus the entire surface of the
  • Petri dish A substance that inhibits growth is noticeable in that at least the film to be examined does not overgrow or, furthermore, the growth is still inhibited around the film (Hemmhof). Escherichia coli NCTC 8196 is used as the test culture.
  • the surface gloss is measured at a measuring angle of 20 ° according to DIN 67530.
  • the surface defects are visual and the surface tension is determined using the so-called ink method (DIN 53364).
  • 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 is determined at an angle of less than 2.5 °.
  • UV stability is tested according to the test specification ISO 4892 as follows
  • Xenon lamp inner and outer filter made of borosilicate
  • the yellowness index (YID) is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 6167. fire behavior
  • the fire behavior is according to DIN 4102 part 2, building material class B2 and according to DIN
  • Heat-sealed samples (sealing seam 20 mm x 100 mm) are produced with the sealing device HSG / ET from Brugger, whereby the film is sealed at different temperatures with the help of two heated sealing jaws at a sealing pressure of 2 bar and a sealing time of 0.5 s. Test strips 15 mm wide are cut from the sealed samples.
  • 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 Two are used to determine the seal seam strength using the T-Peel method
  • the examples and comparative examples below are single-layer or multilayer, covered-colored films of different thicknesses, which were produced on the extrusion line described.
  • the following stretching conditions were used: the stretch ratio was 4 for the longitudinal and transverse stretching, and the temperature was 120 ° C. and 125 ° C., respectively.
  • Heat setting was carried out at 230 ° C.
  • a 50 ⁇ m thick monofilm was produced, the main constituent being PET (type RT49, KoSa, Germany), 0.2% by weight of triclosan and 0.4% by weight of titanium dioxide (anatase type, particle diameter 0.2 ⁇ m) contained.
  • the film also contained 30.0% by weight of the self-regenerate that is inherent in the film production.
  • the titanium dioxide used (Sachtleben, Germany) was added in the form of a masterbatch which, in addition to PET, contained 70,000 ppm of titanium dioxide.
  • the triclosan was added in the form of a masterbatch which, in addition to PET
  • the film was coated on both sides with an aqueous dispersion using the “reverse gravure-roll coating” method.
  • the dispersion contained 4.2% by weight of hydrophilic polyester (5-Na-sulfoisophthalic acid-containing PET / I PA polyester, type SP41, Ticona, USA), 0.15% by weight of colloidal silicon dioxide ( ⁇ Nalco 1060 , Deutsche Nalco Chemie, Germany) as an antiblocking agent and 0.15% by weight ammonium carbonate (Merck, Germany) as a pH buffer.
  • the wet application weight is 2 g / m 2 on the coated side.
  • the calculated thickness of the coating was 40 nm.
  • Example 2 Analogously to Example 1, a 50 ⁇ m thick monofilm was produced. In contrast to example 1, the film additionally contained 0.6% by weight of the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol ( ® Tinuvin 1577 from Ciba
  • Tinuvin 1577 has a melting point of 149 ° C and is thermally stable up to approx. 330 ° C.
  • a 50 ⁇ m thick coextruded A-B-A film was produced.
  • the main component of the 46 ⁇ m thick base layer B was PET according to Example 1, 7% by weight of titanium dioxide, 0.2% by weight of hydrolysis stabilizer and 4.0% by weight of flame retardant.
  • the layer also contained 30.0% by weight of the self-regenerate that is inherent in the film production.
  • the two 2 ⁇ m thick outer layers contained 0.7% by weight of triclosan and 0.1% by weight of ⁇ Sylobloc 44H (Grace, Germany) as anti-blocking agents.
  • the triclosan was added in the form of a masterbatch which, in addition to PET, contained 10.0% by weight of triclosan.
  • the titanium dioxide was metered in in the form of a masterbatch, in addition to PET
  • titanium dioxide anatase type, particle size 0.2 ⁇ m, from Sachtleben, Germany
  • the sylobloc which is not soluble in PET, was incorporated into the PET by the raw material manufacturer.
  • the hydrolysis stabilizer and the flame retardant were metered in in the form of a master batch.
  • the masterbatch consists of 20.0% by weight of flame retardant (methanephosphonic acid bis- (5-ethyl-2-methyl-2-oxo-2 ⁇ 5 - [1, 3,2] - dioxaphosphinan-5-ylmethyl ester), 1 , 0 wt .-% hydrolysis stabilizer (pentaerythritol tetrakis-3- (3,5-di-tert-butyl-4 (hydroxylphenyl) propionate) and 79.0 wt .-% PET together.
  • flame retardant methanephosphonic acid bis- (5-ethyl-2-methyl-2-oxo-2 ⁇ 5 - [1, 3,2] - dioxaphosphinan-5-ylmethyl ester
  • hydrolysis stabilizer penentaerythritol tetrakis-3- (3,5-di-tert-but
  • Example 3 Analogously to Example 3, a 50 ⁇ m thick A-B-A film was produced. In contrast to Example 3, the film was additionally coated on one side after the longitudinal stretching in accordance with the “reverse gravure-roll coating” method described in Example 1.
  • a 12 ⁇ m thick, coextruded, sealable A-B-C film was produced.
  • the 10 ⁇ m thick base layer B contained PET as the main component according to the example
  • titanium dioxide rutile type, 0.2 ⁇ m particle diameter, from Kerr McGee
  • triclosan 30.0% by weight of the self-generated material that is inherent in the film production
  • the titanium dioxide was metered in directly from the raw material manufacturer for homogeneous distribution.
  • a copolyester composed of 78 mol% of ethylene terephthalate and 22 mol% of ethylene isophthalate was used as the thermoplastic for the 1 ⁇ m thick sealable cover layer A (produced by the transesterification process with Mn as transesterification catalyst, Mn concentration: 100 ppm).
  • the 1 ⁇ m thick, non-sealable top layer C contained, in addition to PET, 0.7% by weight of triclosan and 3.0% by weight of a masterbatch made of 97.75% by weight of PET and 1.0% by weight of Sylobloc 44H and 1.25% by weight of Aerosil TT 600 as an antiblocking agent.
  • the triclosan was added in each case in the form of a masterbatch which, in addition to PET, contained 10.0% by weight of triclosan.
  • Example 6 The triclosan was added in each case in the form of a masterbatch which, in addition to PET, contained 10.0% by weight of triclosan.
  • a 12 ⁇ m thick A-B-C film was produced analogously to Example 5.
  • this film was only coated on one side after the longitudinal stretching on the non-sealable top layer C by means of the “reverse gravure-roll coating” method as in Example 4.
  • Example 6 Analogously to Example 6, a 12 ⁇ m thick A-B-C film was produced which - as described - was coated on the top layer C with the SP41 adhesion promoter.
  • Example 6 In contrast to Example 6, the coated film contained no titanium dioxide, but 1% by weight of Cl pigment blue 28 (CoAI 2 0 4 spinel, cobalt blue, Degussa, Germany), which was incorporated directly into the PET at the raw material manufacturer.
  • Cl pigment blue 28 CoAI 2 0 4 spinel, cobalt blue, Degussa, Germany
  • Example 7 Analogously to Example 7, a 12 ⁇ m thick A-B-C film was produced. In contrast to Example 7, the film was uncoated.
  • the film was corona treated on top layer C.
  • the intensity was chosen so that the surface tension was> 45 mN / m.
  • Example 2 Analogously to Example 2, a 50 ⁇ m thick monofilm was produced which contained 0.4% by weight of titanium dioxide and which was antimicrobially treated with 0.2% by weight of triclosan, which was metered in in the form of a 10.0% by weight masterbatch has been.
  • the titanium dioxide used (anatase type, from Sachtleben, Germany) was added in the form of a masterbatch which, in addition to PET, contained 70,000 ppm of titanium dioxide.
  • the film also contained 0.6% by weight of the UV stabilizer according to the information from Example 2 and 0.2% by weight of hydrolysis stabilizer and 4.0% by weight of flame retardant according to the information from Example 3. After the longitudinal stretching, the film was coated on both sides using the “reverse gravure-roll coating” method analogous to Example 1.
  • Example 10 A 50 ⁇ m thick, coextruded film was produced. The recipe of the
  • base layer B corresponded to the formulation of the uncoated monofilm from example 9. It therefore contained, in addition to PET titanium dioxide, triclosan, a UV stabilizer, a flame retardant and a hydrolysis stabilizer.
  • Example 5 Analogously to Example 6, the film was coated on the top layer C with the SP41 adhesion promoter.
  • Comparative Example 1 A 50 ⁇ m thick monofilm was produced analogously to Example 1. In contrast to Example 1, the film did not contain triclosan, so it was not antimicrobial. The film was coated on both sides as in Example 1.
  • a 50 ⁇ m thick monofilm was produced with the following recipe:
  • PET type RT49
  • masterbatch which in addition to PET 10.0% by weight triclosan (Ciba-Geigy,
  • regrind inherent in the film production, contained not only PET but also titanium dioxide and triclosan
  • a coherently colored, three-layer A-B-A film with a total thickness of 50 ⁇ m was produced by coextrusion and subsequent stepwise orientation in the longitudinal and transverse directions with the following recipe:
  • Base layer B (44 ⁇ m thick): mixture of 43.0% by weight PET (type 4020)
  • masterbatch which, in addition to PET, contained 50.0% by weight of titanium dioxide (anatase type, from Sachtieben, Germany)
  • regrind inherent in film production, in addition to PET and titanium dioxide also contained small amounts of pigment and triclosan from the outer layers
  • Cover layers A (each 3 ⁇ m thick): mixture of
  • PET type 4020, KoSa, Germany
  • masterbatch which, in addition to PET, contained 10.0% by weight of triclosan, 7.0% by weight of masterbatch, which in addition to PET 10,000 ppm ⁇ Sylobloc 44H (Grace, Germany) contained
  • the PET from which the opaque colored film was produced had a standard viscosity SV (DCE) of 770, which corresponds to an intrinsic viscosity IV (DCE) of 0.632 dl / g.
  • DCE standard viscosity SV
  • Example 12 Analogously to Example 12, a 50 ⁇ m thick A-B-A film was produced. In contrast to Example 12, the base layer B was also equipped with triclosan.
  • Base layer B mixture of
  • masterbatch which, in addition to PET, contains 50.0% by weight of titanium dioxide (anatase type, from Sachtleben, Germany), 2.0% by weight of masterbatch which, in addition to PET, contains 10.0% by weight of % Triclosan contained 50.0% by weight of regenerate (inherent in the film production, in addition to PET also contained small amounts of pigment and triclosan)
  • Cover layers A mixture of 90.0% by weight of PET (type 4020), 3.0% by weight of masterbatch which, in addition to PET, contained 10.0% by weight of triclosan
  • the film was coated on one side in accordance with Example 1, but only using the “reverse gravure-roll coating” method.
  • Example 11 was repeated with the difference that the coated film contained no titanium dioxide, but 1.0% by weight of Cl pigment blue 28 (CoAI 2 0 4 spinel, cobalt blue, Degussa, Germany), which was incorporated directly into the PET at the raw material manufacturer ,
  • Example 12 was repeated with the difference that this film was not antimicrobially treated with triclosan.

Abstract

L'invention concerne une feuille semi-cristalline antimicrobienne, à orientation biaxiale et à teinture mate, présentant une épaisseur comprise entre 1 et 500 νm. Outre un thermoplastique cristallisable comme élément principal, cette feuille comprend un composant antimicrobien et au moins un pigment colorant. Comme composant antimicrobien, on utilise du 2,4,4'-trichloro-2'-hydroxy-diphényléther (« triclosan »), seul ou en combinaison avec d'autres substances antimicrobiennes. Selon l'utilisation prévue, la feuille peut être également fonctionnalisée, c'est-à-dire qu'elle peut être par exemple stabilisée aux UV, ignifuge, scellable, enduite sur une face ou sur les deux faces, traitée par décharge corona et/ou par flamme. L'invention concerne en outre un procédé de production de cette feuille et son utilisation.
PCT/EP2002/000854 2001-02-05 2002-01-28 Feuille semi-cristalline antimicrobienne, a orientation biaxiale et a teinture mate, en thermoplastique cristallisable WO2002062578A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10105109.3 2001-02-05
DE2001105109 DE10105109A1 (de) 2001-02-05 2001-02-05 Gedeckt eingefärbte, antimikrobielle, biaxial orientierte, teilkristalline Folie aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10105110.7 2001-02-05
DE10105110A DE10105110A1 (de) 2001-02-05 2001-02-05 Gedeckt eingefärbte, antimikrobielle, biaxial orientierte, teilkristalline Folie aus einem kristallisierbaren Thermoplast mit zusätzlicher Funktionalität, Verfahren zu ihrer Herstellung und ihre Verwendung

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WO2002062578A1 true WO2002062578A1 (fr) 2002-08-15

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EP1806380A1 (fr) * 2004-08-11 2007-07-11 Mitsubishi Polyester Film Corporation Films de polyester à orientation bi-axiale
EP1918096A2 (fr) * 2006-11-02 2008-05-07 Mitsubishi Polyester Film GmbH Feuille de polyester multicouches, blanche pouvant être découpée par laser
ITPD20110341A1 (it) * 2011-10-31 2013-05-01 Ultrabatch S R L Corpo laminare per realizzare coperture di serre e metodo di coltivazione in serra

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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
EP1918096A2 (fr) * 2006-11-02 2008-05-07 Mitsubishi Polyester Film GmbH Feuille de polyester multicouches, blanche pouvant être découpée par laser
EP1918096A3 (fr) * 2006-11-02 2009-03-11 Mitsubishi Polyester Film GmbH Feuille de polyester multicouches, blanche pouvant être découpée par laser
US7833617B2 (en) 2006-11-02 2010-11-16 Mitsubishi Polyester Film Gmbh Multilayer, white, laser-cuttable polyester film
ITPD20110341A1 (it) * 2011-10-31 2013-05-01 Ultrabatch S R L Corpo laminare per realizzare coperture di serre e metodo di coltivazione in serra
WO2013064970A1 (fr) * 2011-10-31 2013-05-10 Ultrabatch S.R.L. Corps laminaire pour fabriquer des toits de serre et procédé de culture en serre
CN103957692A (zh) * 2011-10-31 2014-07-30 超霸责任有限公司 用于制造温室屋顶的层状体和温室栽培方法
US10015933B2 (en) 2011-10-31 2018-07-10 Cytec Industries Inc. Laminar body for making greenhouse roofs and methods of greenhouse cultivation

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