WO2001053390A1 - Feuille thermoformable amorphe, teintee de maniere transparente, absorbant la lumiere u.v., un procede de realisation et son utilisation - Google Patents

Feuille thermoformable amorphe, teintee de maniere transparente, absorbant la lumiere u.v., un procede de realisation et son utilisation Download PDF

Info

Publication number
WO2001053390A1
WO2001053390A1 PCT/EP2001/000176 EP0100176W WO0153390A1 WO 2001053390 A1 WO2001053390 A1 WO 2001053390A1 EP 0100176 W EP0100176 W EP 0100176W WO 0153390 A1 WO0153390 A1 WO 0153390A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
film
thermoplastic
light
film according
Prior art date
Application number
PCT/EP2001/000176
Other languages
German (de)
English (en)
Inventor
Ursula Murschall
Ulrich Kern
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
Application filed by Mitsubishi Polyester Film Gmbh filed Critical Mitsubishi Polyester Film Gmbh
Publication of WO2001053390A1 publication Critical patent/WO2001053390A1/fr

Links

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
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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

  • thermoformable film Amorphous, transparently colored, UV light absorbing, thermoformable film, a process for its production and its use
  • the invention relates to an amorphous, transparently colored, UV light absorbing thermoformable film made of a crystallizable thermoplastic, the thickness of which is in the range from 30 to 1000 ⁇ m, a process for its production and its use.
  • the film contains at least one thermoplastic-soluble dye and a soluble UV absorber and is characterized by good optical properties, high light transmission in the wavelength range from> 400 nm, preferably 420 to 800 nm, by economical thermoformability and by the absorption of short-wave UV -Lights in the wavelength range of less than 380 nm.
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • Transparent films are also known.
  • the films are usually oriented and therefore have a crystallinity of between 30 and 50%.
  • These foils are crystalline or semi-crystalline structures. These films also absorb not the short-wave, aggressive UV light. From a wavelength of 280 nm, these foils let UV light through.
  • the films contain no soluble dye.
  • the object of the present invention is to avoid the disadvantages of the prior art described.
  • the invention therefore relates to an amorphous, transparently colored, UV light-absorbing, thermoformable film with a thickness in the range from 30 ⁇ m to 1000 ⁇ m, which contains a crystallizable thermoplastic as the main component and which is characterized in that it additionally contains at least one in the thermoplastic contains soluble UV stabilizer and at least one soluble dye, also a process for their preparation and their use.
  • the film according to the invention has both good optical properties and a high light transmission in the wavelength range from> 400, preferably 420 to 800 nm, has a barrier against the short-wave, aggressive UV light in the wavelength range from ⁇ 380 nm and combines a high combination UV stability with a colored appearance that can be used effectively for advertising.
  • the good optical properties included, for example, high light transmission, low haze, high surface gloss and a homogeneous, transparent color.
  • Thermoformability means that the film can be thermoformed or thermoformed on commercially available thermoforming machines without complex pre-drying to form complex and large-area shaped articles.
  • a high UV stability means that the film and the moldings made from it are extremely little damaged by sunlight or other UV radiation, making them suitable for outdoor and critical indoor applications.
  • the film or the molded body should not yellow during several years of external use and should not show any cracks or embrittlement of the surface.
  • a barrier against UV light means that the film completely absorbs the aggressive short-wave radiation, which is responsible, for example, for fat oxidation in foods, in the wavelength range ⁇ 380 nm.
  • the film according to the invention contains a crystallizable thermoplastic as the main component.
  • Suitable crystallizable or partially crystalline thermoplastics are, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, with polyethylene terephthalate being preferred.
  • crystallizable polyester is understood to mean crystallizable homopolymers, crystallizable copolymers, crystallizable compounds (mixtures), crystallizable recyclate and other variations of crystallizable thermoplastics.
  • 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. For the purpose of economical production, the film contains the antiblocking and lubricants that are customary for films.
  • UV stabilizer contains at least one UV stabilizer as a light stabilizer, the concentration of the UV stabilizer preferably in the range from 0.01% by weight to 5.0% by weight, in particular in the range from 0.1% by weight to 3 % By weight, based on the weight of the layer of the crystallizable thermoplastic, is.
  • Light in particular the ultraviolet portion of solar radiation, ie the wavelength range from 280 to 400 nm, initiates degradation processes in thermoplastics, as a result of which not only the visual appearance changes as a result of color change or yellowing, but also negatively influences the mechanical-physical properties become.
  • Polyethylene terephthalates for example, begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
  • UV stabilizers or UV absorbers as light stabilizers are chemical compounds that are involved in the physical and chemical processes of light-induced degradation can intervene. 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. For transparent, matt films, only organic and organometallic compounds are suitable which give the thermoplastic to be stabilized no or only an extremely slight color or color change, ie which are soluble in the thermoplastic.
  • UV stabilizers suitable as light stabilizers for the purposes of the present invention are UV stabilizers which absorb at least 70%, preferably 80%, particularly preferably 90%, of the UV light in the wavelength range from 180 nm to 380 nm, preferably 280 to 350 nm. These are particularly suitable if they are thermally stable in the temperature range from 260 to 300 ° C. H. do not decompose and do not lead to outgassing.
  • Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, the 2-hydroxybenzotriazoles being preferred.
  • the amorphous film according to the invention contains a dye which is soluble in the thermoplastic, the concentration of the soluble dye preferably being in the range from 0.1% by weight to 20.0% by weight, in particular in the range from 0.5 to 10% 0 wt .-%, based on the weight of the crystallizable thermoplastic, is.
  • Soluble dye is understood to mean substances that are molecularly dissolved in the polymer (DIN 55949).
  • the color change of the amorphous film is based on the wavelength-dependent absorption and / or scattering of the light. Dyes can only absorb light but do not scatter since 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 are particularly suitable e.g. for coloring
  • Suitable soluble dyes are: C.I. Solventgelb 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 138 (an anthraquinone derivative), fluorescent benzopyran dyes such as fluorol red GK and fluorol orange GK, C.I. solvent blue 35 (an anthraquinone dye), C.I. Solvent blue 15: 1 (a phthalocyanine dye) and many others.
  • C.I. Solventgelb 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 Thermoplast
  • the crystallizable thermoplastic has a diethylene glycol content of> 1.0% by weight, preferably> 1.2% by weight, in particular> 1.3% by weight and / or a polyethylene glycol content of> 1.0% by weight , preferably> 1, 2% by weight, in particular> 1.3% by weight and / or an isophthalic acid content of 3% by weight to 10% by weight.
  • the film according to the invention contains 0.01% by weight to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- ( hexyl) oxyphenol of the formula
  • mixtures of these two UV stabilizers or mixtures of at least one of these two UV stabilizers with other UV stabilizers can also be used, the total concentration being Light stabilizers are preferably between 0.01% and 5.0% by weight, based on the weight of crystallizable polyethylene terephthalate.
  • UV stabilizers that absorb the UV light and thus generally offer protection, it is found that the film quickly turns yellow after weathering and thus the color is shifted, - the UV stabilizer has a poor thermal stability and yourself at
  • UV stabilizer must be incorporated so that the UV light is absorbed and the film is not damaged.
  • the film already has a yellow appearance after production, with yellowness index differences (YID) around 25. Furthermore, the mechanical properties are negatively affected.
  • YID yellowness index differences
  • the film absorbs the aggressive, short-wave light in the wavelength range up to 380 nm, preferably up to 360 nm. H. does not let through.
  • the regrind can also be used again without negatively influencing the color value of the film.
  • At least one surface layer can be coated or vapor-coated with ethylene-vinyl alcohol copolymer, ethyl-vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride, ethylene-vinyl alcohol copolymer being preferred.
  • the thickness of the barrier layer is in the range from 10 nm to 8000 nm, in particular from 30 to 4000 nm.
  • the barrier layer serves as a gas, in particular oxygen or aroma barrier and has an oxygen permeability of ⁇ 10 cm 3 / (m 2 -24 hbar). It is based on an ethylene-vinyl alcohol copolymer with an ethylene content of 15-60 mol% and a degree of saponification of at least 90 mol%, preferably greater than 96 mol%, in particular about 99 mol%.
  • These copolymers include e.g. B. ethylene-propylene-vinyl alcohol copolymers and reaction products of ethylene-vinyl alcohol copolymers with lower aldehydes or ketones, as described in DE-OS 29 31 035 or US Pat. No. 4,212,956.
  • the ethylene-vinyl alcohol copolymers can contain water during the extrusion, preferably in an amount of 1 to 10% by weight. To achieve a high Orientation effect and thus a good gas barrier, however, it is preferable if the water content is less than 5%, preferably less than 3.5%, in particular even less than 2% by weight, or approaches zero.
  • the barrier layer based on ethylene-vinyl alcohol copolymers can contain monomeric, oligomeric or polymeric substances to reduce the crystallinity.
  • the amount added depends on the tolerance, i.e. H. the incorporability and miscibility with the main component and the influence on oxygen permeability.
  • Such products are substances containing hydroxyl and carbonyl groups, such as trimethylolpropane, neopentyl glycol and polyethylene glycols, and in particular substances which in turn already have barrier properties, e.g.
  • barrier properties e.g.
  • polyvinyl alcohol or polyamides mixtures of ethylene-vinyl alcohol copolymers and 10 to 50 wt .-% polyvinyl alcohol with a degree of hydrolysis of> 80, in particular greater than / equal to 88 mol%, and a viscosity of 0.4 10 "2 to 4 10 "2 , especially 0.4. 10 "2 to 1 ⁇ 10 " 2 Pa ⁇ s are particularly advantageous.
  • the barrier layer based on ethylene-vinyl alcohol copolymers may contain further additives in the form of monomeric, oligomeric or polymeric substances which promote adhesion to the adjacent layers.
  • amorphous film means films which, although the crystallizable thermoplastic has a crystallinity of 20% to 65%, preferably 30% to 50%, are not crystalline.
  • Such a film is essentially in the unoriented state.
  • the thermoforming process usually includes the steps of predrying, heating, molding, cooling, demolding, tempering. During the thermoforming process, it was found that the films according to the invention can surprisingly be thermoformed without prior predrying.
  • thermoformable polycarbonate or polymethyl methacrylate films which require pre-drying times of 10 - 15 hours, depending on the thickness, at temperatures from 100 ° C to 120 ° C, drastically reduces the costs of the forming process. It was also very surprising that the detail reproduction of the molded body is excellent.
  • the film can also be fed to the thermoforming process, for example as a roll.
  • the surface gloss measured according to DIN 67530 is greater than 120, preferably greater than 140, the light transmission L * , measured according to ASTM D 1003, is more than 82%, preferably more than 84% and the haze of the film, measured according to ASTM D 1003, is less than 10%, preferably less than 8%, which is surprisingly good for the UV stability achieved.
  • the standard viscosity SV (DCE) of the thermoplastic measured in dichloroacetic acid according to DIN 53728 is 600 to 1000, preferably 700 to 900.
  • the films according to the invention can be thermoformed economically on commercially available deep-drawing systems and provide excellent detail reproduction due to a higher diethylene glycol content and / or polyethylene glycol content and / or IPA content compared to the standard thermoplastic.
  • the transparent colored thermoplastic film which contains at least one UV stabilizer and a dye, can be either single-layer or multi-layer.
  • the film is composed of at least one core layer and at least one cover layer, in particular a three-layer one ABA or ABC structure is preferred.
  • one of the two outer layers which can be corona-treated, can be vapor-coated with ethylene-vinyl alcohol copolymer, ethyl-vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride.
  • the cover layers are formulated with the antiblocking agents and / or lubricants customary for thermoplastic films.
  • thermoplastic of the core layer has a standard viscosity similar to that of the thermoplastic of the cover layer (s) which adjoins the core layer.
  • the cover layers can also consist of a polyethylene naphthalate homopolymer or of a polyethylene terephthalate-polyethylene naphthalate copolymer or compound.
  • thermoplastics of the cover layers also have a standard viscosity similar to that of the thermoplastic of the core layer.
  • the UV stabilizer and the dye are preferably contained in the top layer or layers.
  • the core layer can also be equipped with UV stabilizers and dye as required.
  • the concentration of the stabilizer (s) and the concentration of the dye (s) refer to the weight of the thermoplastic in the layer equipped with UV stabilizer (s) and dye.
  • the multilayer films according to the invention produced using the known coextrusion technology become economically interesting in comparison with the completely UV-stabilized monofilms, since significantly less UV stabilizer is required for comparable UV stability.
  • the film can also be provided on at least one side with a scratch-resistant coating, with a copolyester or with an adhesion promoter.
  • Weathering tests after an estimated 5 to 7 years of outdoor use generally show no yellowing or color change in the direction of yellow, no embrittlement, no loss of gloss on the surface and no cracking on the surface.
  • the UV-stabilized film can be produced reliably. Furthermore, no outgassing of the UV stabilizer was found in the production process, which is essential to the invention, since most UV stabilizers at annealing temperatures above 260 ° C. give off unpleasant outgassing and are therefore unsuitable.
  • the film according to the invention can be easily recycled without environmental pollution and without a noticeable loss of the mechanical properties, which makes it suitable, for example, for use as a short-lived article.
  • the film Since the film also absorbs the short-wave UV light in the wave range from 260 nm to 360 nm, in particular up to 380 nm, the film offers a barrier against the aggressive short-wave light which, for. B. causes the dreaded fat oxidation in food. Consequently, the film according to the invention is outstandingly suitable as packaging film for sensitive goods on packaging machines in the vertical and horizontal range (vFFs and hFFs machines).
  • the film is suitable as a composite film, the composite consisting of the film according to the invention, optionally with ethylene-vinyl alcohol copolymer, ethyl-vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride coating and a second film.
  • This second film can e.g. can also be a UV-stable thermoplastic film, a standard thermoplastic film or a polyolefin film.
  • the second film can be single-layer or multi-layer and, like the first UV-stable film, can be amorphous, i. H. be disoriented and can have at least one sealing layer.
  • the second film can be connected to the first UV-stable barrier film according to the invention with or without adhesive.
  • the thickness of this second film is preferably in the range from 30 to 500 ⁇ m.
  • the composite film is generally obtained by laminating or laminating the two films to one another, with or without an intermediate layer of adhesive, by passing them between rollers heated to 30 ° C. to 90 ° C.
  • the two films can be connected to one another, for example, with or without an adhesive layer, by a lamination process.
  • adhesives are used, they are applied to a film surface by known methods, in particular by application from solutions or dispersions in water or organic solvents.
  • the solutions usually have an adhesive concentration of 5 to 40% by weight to give an amount of adhesive of 1 to 10 g / m 2 on the film.
  • Adhesives made from thermoplastic resins, such as cellulose esters and ethers, alkyl and acrylic esters, polyamides, polyurethanes or polyesters, or from thermosetting resins, such as epoxy resins, urea / formaldehyde, phenyl / formaldehyde or melamine / - Formaldehyde resins, or consist of synthetic rubbers.
  • thermoplastic resins such as cellulose esters and ethers, alkyl and acrylic esters, polyamides, polyurethanes or polyesters
  • thermosetting resins such as epoxy resins, urea / formaldehyde, phenyl / formaldehyde or melamine / - Formaldehyde resins, or consist of synthetic rubbers.
  • Suitable solvents for the adhesive are e.g. Hydrocarbons such as ligroin and toluene, esters such as ethyl acetate or ketones such as acetone and methyl ethyl ketone.
  • the film according to the invention can be produced, for example, by known extrusion processes in an extrusion line.
  • the light stabilizer and the soluble dye can be metered in at the thermoplastic raw material manufacturer or can be metered into the extruder during film production.
  • the additives are first fully dispersed in a solid carrier material.
  • the thermoplastic itself comes as carrier materials, e.g. B. the polyethylene terephthalate or other polymers that are sufficiently compatible with the thermoplastic, in question. After metering into the thermoplastic for film production, the components of the masterbatch melt during the extrusion and are thus dissolved in the thermoplastic.
  • concentrations of the individual additives in addition to the thermoplastic in the masterbatch are: UV absorber 2.0 to 50.0% by weight, preferably 5.0 to 30.0% by weight, optical brightener 0.05 to 5.0% by weight .-%, preferably 0.1 to 2.0 wt .-% and soluble dye 1, 0 to 20.0 wt .-%, preferably 1, 5 to 15.0 wt .-%, the sum of the components always Is 100% by weight.
  • the grain size and bulk density of the masterbatch is similar to the grain size and bulk density of the thermoplastic, so that homogeneous distribution and thus homogeneous UV stabilization can take place.
  • the films according to the invention can, according to the extrusion process, consist of a thermoplastic raw material with optionally further raw materials, the UV stabilizer, the dye and / or other conventional additives in a customary amount of 0.1 to a maximum of 10.0% by weight both as monofilms and also as multilayer, optionally coextruded films with the same or differently shaped surfaces are produced, one surface being pigmented, for example, and the other surface containing no pigment.
  • one or both surfaces of the film can be provided with a conventional functional coating by known methods.
  • the polymers or raw material mixtures are fed to an extruder or, in the case of multilayer films, to a plurality of extruders. Any foreign bodies or impurities that may be present can be filtered out of the polymer melt before extrusion.
  • the melt (s) are then formed into flat melt films in a mono nozzle or, in the multilayer case, in a multilayer nozzle, and in the multilayer case are layered one on top of the other. Subsequently, the monofilm or the multilayer film is quenched with the help of a cooling roll and considered largely amo ⁇ he, i.e. unoriented film solidified. The cooled, amorphous film is then hemmed and wound up.
  • the film can also 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 solidification. It is particularly preferred to apply the “reverse gravure roll coating” method, in which the coatings can be applied extremely homogeneously in the layer thicknesses mentioned.
  • the coatings are preferably applied as a solution, suspension or dispersion, in particular as an aqueous solution, suspensions or dispersions.
  • the coatings mentioned give the film surface an additional function, for example making the film sealable, printable, metallizable, sterilizable, antistatic or, for example, improve the aroma barrier or enable adhesion to materials that would otherwise not adhere to the film surface (e.g. photographic emulsion).
  • substances / compositions that provide additional functionality are examples of substances / compositions that provide additional functionality:
  • the substances / compositions mentioned are applied as a dilute solution, emulsion or dispersion, preferably as an aqueous solution, emulsion or dispersion, to one or both surfaces of the film and then the solvent is evaporated. If the coatings are applied in-line, a heat treatment after solidification is usually sufficient to volatilize the solvent and to dry the coating. The dried coatings then have the desired layer thicknesses mentioned.
  • the film according to the invention is outstandingly suitable for a large number of different applications, for example for interior cladding, for trade fair construction and trade fair articles, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in the store and shelf construction, as a promotional item, laminating medium, for thermal applications of all kinds, as packaging film for sensitive and effective advertising products.
  • the film is also suitable for outdoor applications, e.g. B. for greenhouses, in the advertising sector, roofing, external cladding, covers, applications in the construction sector and illuminated advertising profiles.
  • the DEG / PEG / I PA content is determined by gas chromatography after saponification in methanolic KOH and neutralization with aqueous HCl.
  • the surface gloss is measured at a measuring angle of 20 ° according to DIN 67530.
  • the light transmission is the ratio of the total transmitted light to the amount of incident light.
  • the light transmission is measured with the measuring device "® Hazegard plus” according to ASTM D 1003.
  • Haze Haze is the percentage of transmitted light that deviates from the incident light beam by an average of more than 2.5 °. The image sharpness is determined at an angle of less than 2.5 °. The haze is measured using the "Hazegard plus" measuring device in accordance with ASTM D 1003.
  • the surface defects are determined visually.
  • the standard viscosity SV (DCE) is measured based on DIN 53726 in dichloroacetic acid.
  • the intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)
  • UV stability is tested according to the test specification ISO 4892 as follows
  • the yellowness index (YID) is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 6167. Yellowness indexes (YID) of ⁇ 5 are not visually visible.
  • the following examples and comparative examples are each transparent films of different thicknesses, which are produced on the extrusion line described.
  • Example 1 There is prepared a 150 .mu.m thick, red transparent colored film comprising, as main constituent, polyethylene terephthalate, 0.2 wt .-% Sylobloc ®, 1, 0 wt .-% of the UV stabilizer 2- (4,6-diphenyl 1, 3,5-triazin-2-yl) -5- (hexyl) oxyphenol (Tinuvin ® 1577 from Ciba-Geigy) and 1, 5 wt .-% of the soluble dye Solvent Red Cl 138, an anthraquinone derivative of the Fa. BASF AG ( ® Thermoplastrot G) contains.
  • Tinuvin 1577 has a melting point of 149 ° C and is thermally stable up to approx. 330 ° C.
  • the polyethylene terephthalate from which the transparently colored film is made has a standard viscosity SV (DCE) of 810, which corresponds to an intrinsic viscosity IV (DCE) of 0.658 dl / g.
  • DCE standard viscosity SV
  • DCE intrinsic viscosity IV
  • Example 2 Analogously to Example 1, a transparently colored film is produced, the UV stabilizer being 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxyphenol (Tinuvin 1577) and Dye Cl Solventrot 138 is metered in in the form of a masterbatch.
  • the masterbatch (100% by weight) consists of 5% by weight of Tinuvin 1577 as an active ingredient, 15.0% by weight of the dye C.I. Solventrot 138 and the polyethylene terephthalate from Example 1 together.
  • Example 1 Before the extrusion, 90% by weight of the polyethylene terephthalate from Example 1 with 10% by weight of the masterbatch are dried at 170 ° C. for 5 hours. The extrusion and film production is carried out analogously to Example 1.
  • the transparent, colored, UV-stable PET film produced has the following property profile:
  • a transparently colored 350 ⁇ m thick film is produced.
  • the amorphous PET film produced has the following property profile:
  • a 150 ⁇ m thick multilayer PET film with the layer sequence ABA is produced, where B represents the core layer and A the cover layers.
  • the core layer B is 146 ⁇ m thick and the two outer layers that cover the core layer are each 2 ⁇ m thick.
  • the polyethylene terephthalate used for core layer B is identical to that from example 2, but does not contain any sylobloc.
  • the polyethylene terephthalate of the outer layers A is identical to the polyethylene terephthalate from Example 2, ie the outer layer raw material is equipped with 0.2% by weight of Sylobloc.
  • Example 2 Analogously to Example 2, the 5.0% by weight of Tinuvin 1577 and 15.0% by weight of C.I. Solventrot 138 masterbatch used, but only 20 wt .-% of the masterbatch are added to the 2 ⁇ m thick cover layers using the masterbatch technology.
  • the transparently colored, multilayer PET film that is UV-stabilized in the outer layers has the following property profile:
  • Example 4 is repeated.
  • a cover layer A is coated with ethyl vinyl alcohol, the thickness of the coating being 1000 nm.
  • the amorphous, transparently colored, UV-stabilized, thermoformable multilayer barrier film has the following property profile:
  • the examples according to the invention show that the optical properties of the films meet the high requirements, while at the same time the UV stability is significantly increased.
  • the films from Examples 1 to 5 completely absorb the UV light in the wavelength range up to 380 or 390 nm and after 1000 hours of weathering with the Atlas Cl 65 Weather Ometer show no embrittlement, no noticeable loss of gloss and no change in the transparent coloration in the direction of yellow ,
  • the films from Examples 1 to 5 can be thermoformed into molded articles on commercial deep-drawing machines, for example from Illig / Heilbronn, without predrying.
  • the detailed rendering of the deep-drawn moldings is excellent with a homogeneous surface.
  • the films can be processed economically on continuously working thermoforming machines. Comparative Example 1
  • Example 2 Analogously to Example 1, a 150 ⁇ m thick PET monofilm is produced. In contrast to Example 1, the film does not contain a UV stabilizer.
  • the unstabilized film produced has the following property profile:
  • the film allows the short-wave radiation to pass through from 280 nm.
  • the film After weathering one side with Atlas Cl 65 Weather Ometer for 1000 hours, the film shows cracks and embrittlement on this surface. A precise property profile - especially the mechanical properties - can therefore no longer be measured.
  • the film also shows a visually visible yellowing (YID)> 8.

Abstract

La présente invention concerne une feuille thermoformable amorphe, teintée de manière transparente, absorbant la lumière U.V., constituée d"un thermoplaste cristallisable dont l"épaisseur est comprise entre 30 et 1000 νm. Cette invention concerne également un procédé permettant sa réalisation, ainsi que son utilisation. La feuille comprend au moins un agent d"absorption du rayonnement U.V., soluble dans le thermoplaste, et un colorant soluble, et se caractérise par de bonnes propriétés optiques, une transmission élevée de la lumière pour des longueurs d"onde ≥ 400 nm et par l"absorption de la lumière U.V. à courte longueur d"onde pour des longueurs d"onde inférieures à 380 nm.
PCT/EP2001/000176 2000-01-20 2001-01-10 Feuille thermoformable amorphe, teintee de maniere transparente, absorbant la lumiere u.v., un procede de realisation et son utilisation WO2001053390A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10002152.2 2000-01-20
DE2000102152 DE10002152A1 (de) 2000-01-20 2000-01-20 Amorphe, transparent eingefärbte, UV-Licht absorbierende, thermoformbare Folie, ein Verfahren zu ihrer Herstellung und ihre Verwendung

Publications (1)

Publication Number Publication Date
WO2001053390A1 true WO2001053390A1 (fr) 2001-07-26

Family

ID=7628028

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/000176 WO2001053390A1 (fr) 2000-01-20 2001-01-10 Feuille thermoformable amorphe, teintee de maniere transparente, absorbant la lumiere u.v., un procede de realisation et son utilisation

Country Status (2)

Country Link
DE (1) DE10002152A1 (fr)
WO (1) WO2001053390A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6811841B1 (en) 2003-04-15 2004-11-02 3M Innovative Properties Company Light-stable structures

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL2619003T3 (pl) 2010-09-21 2015-03-31 Sekisui Chemical Co Ltd „Szyba szklana jako Head-Up-Display”
KR20140039190A (ko) 2011-04-15 2014-04-01 쌩-고벵 글래스 프랑스 발광 입자를 함유하는 필름의 제조 방법
EP2751617B1 (fr) 2011-08-29 2020-05-06 Sekisui Chemical Co., Ltd. Dispositif de production d'une image d'affichage sur une vitre composite
WO2014067697A1 (fr) 2012-10-31 2014-05-08 Saint-Gobain Glass France Pare-brise muni d'un affichage tête haute

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5206309A (en) * 1991-03-06 1993-04-27 Allied Signal Inc. Heat stable film composition comprising polyepsiloncaprolactam
WO1996038498A1 (fr) * 1995-05-29 1996-12-05 Hoechst Aktiengesellschaft Plaque coloree transparente amorphe en thermoplaste cristallisable, son procede de fabrication et son utilisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5206309A (en) * 1991-03-06 1993-04-27 Allied Signal Inc. Heat stable film composition comprising polyepsiloncaprolactam
WO1996038498A1 (fr) * 1995-05-29 1996-12-05 Hoechst Aktiengesellschaft Plaque coloree transparente amorphe en thermoplaste cristallisable, son procede de fabrication et son utilisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6811841B1 (en) 2003-04-15 2004-11-02 3M Innovative Properties Company Light-stable structures

Also Published As

Publication number Publication date
DE10002152A1 (de) 2001-07-26

Similar Documents

Publication Publication Date Title
EP1274576B1 (fr) Feuille de polyester coextrudee, thermoformable, stable aux rayons ultraviolets et mate, son procede de production et son utilisation
EP1265949B1 (fr) Film thermoformable, étiré biaxialement, transparent, stable aux uv, en matiere thermoplastique cristallisable, son procede de fabrication et son utilisation
EP1052269B2 (fr) Feuille blanche, en résine thermoplastique crystallisable, stabilisée vis-à-vis de l' UV
EP1274788B1 (fr) Feuille blanche, difficilement inflammable, stable aux uv, thermoformable, constituee d'une matiere thermoplastique cristallisable, son procede de production et son utilisation
DE10002171A1 (de) Transparente, schwerentflammbare, UV-stabile Folie aus einem kristallisierbaren Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1125968B1 (fr) Feuille blanche opaque, stabilisée aux UV, qui présente une transparence faible, à base d'un thermoplastique crystallisable
WO2001053390A1 (fr) Feuille thermoformable amorphe, teintee de maniere transparente, absorbant la lumiere u.v., un procede de realisation et son utilisation
WO2001053403A2 (fr) Feuille amorphe, structuree, transparente, teintee, absorbant la lumiere uv, son procede de production et son utilisation
DE10002164A1 (de) Weiße, UV-stabilisierte, thermoformbare Folie aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10002175A1 (de) Transparente, biaxial orientierte, UV-stabilisierte Barrierefolie, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2001053392A1 (fr) Film thermoformable, absorbant les rayons ultraviolets, transparent et amorphe, son procede de production et son utilisation
DE10002170A1 (de) Amorphe, einseitig matte, siegelfähige, UV stabilisierte, flammhemmend ausgerüstete, thermoformbare, koextrudierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2002068511A1 (fr) Feuille amorphe fonctionnalisee constituee d'un thermoplaste modifie par dibenzene, son procede de realisation et son utilisation
DE10002153A1 (de) Amorphe, weiße, schwerentflammbare, UV-stabile, thermoformbare Folie, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2002055301A1 (fr) Feuille polyester multicouche a garniture anti-microbienne et surface matte
DE10003210A1 (de) Amorphe, strukturierte, gedeckt eingefärbte flammhemmend ausgerüstete, UV-Licht absorbierende Folie, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2001053402A1 (fr) Feuille amorphe, structuree, transparente, absorbant la lumiere uv, son procede de production et son utilisation
DE10002167A1 (de) Hochtransparente, hochglänzende, UV-Licht absorbierende, siegelbare, schwerentflammbare, thermoformbare Folie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10022946A1 (de) Weisse, zumindest einseitig matte, biaxial orientierte, UV-stabilisierte und schwer entflammbare Polyesterfolie mit Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung
EP1276794B1 (fr) Feuille thermoformable, coloree, stable aux u.v., difficilement inflammable, realisee a partir d'un thermoplastique cristallisable, son procede de realisation et son utilisation
DE10002166A1 (de) Transparente, biaxial orientierte UV-stabilisierte, siegelbare Folie, 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
WO2002057349A1 (fr) Feuille transparente amorphe anti-microbienne composee d'un thermoplaste cristallisable, son procede de realisation et son utilisation
DE10003211A1 (de) Amorphe, strukturierte, gedeckt eingefärbte, UV-Licht absorbierende Folie, ein Verfahren zu ihrer Herstellung und ihre Verwendung
DE10043784A1 (de) Transparente, teilkristalline, funktionalisierte Folie aus einem bibenzolmodifizierten Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung

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
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP