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WO2001053093A1 - Feuille polyester amorphe, transparente, scellable, absorbant les u.v., ignifugeante, thermoformable, son procede de realisation et son utilisation - Google Patents

Feuille polyester amorphe, transparente, scellable, absorbant les u.v., ignifugeante, thermoformable, son procede de realisation et son utilisation Download PDF

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Publication number
WO2001053093A1
WO2001053093A1 PCT/EP2001/000216 EP0100216W WO0153093A1 WO 2001053093 A1 WO2001053093 A1 WO 2001053093A1 EP 0100216 W EP0100216 W EP 0100216W WO 0153093 A1 WO0153093 A1 WO 0153093A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
weight
sealable
flame
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2001/000216
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German (de)
English (en)
Inventor
Ursula Murschall
Wolfgang Dietz
Günther Crass
Herbert Peiffer
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Mitsubishi Polyester Film GmbH
Original Assignee
Mitsubishi Polyester Film GmbH
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Filing date
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Publication of WO2001053093A1 publication Critical patent/WO2001053093A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/702—Amorphous
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2590/00—Signboards, advertising panels, road signs
    • 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
    • B32B2605/00—Vehicles

Definitions

  • thermoformable polyester film Amorphous, transparent, sealable, UV-absorbing, flame-retardant, thermoformable polyester film, process for its production and its use
  • the invention relates to an amorphous, transparent UV-absorbent, flame-retardant, sealable, coextruded polyester film whose thickness is in the range from 30 to 2000 ⁇ m, consisting of at least one base layer B and cover layers A and C applied to this base layer on both sides.
  • the film additionally contains at least one UV stabilizer as a light stabilizer and one flame retardant.
  • the invention further includes a method for making the film and using it.
  • the foils and articles made from them are particularly suitable for outdoor applications such as for greenhouses, canopies.
  • the films are also very suitable for covering and thus for protecting metallic surfaces on which the films are heat-sealed.
  • films that do not contain UV-absorbing materials show yellowing and deterioration of the mechanical properties after a short time due to photo-oxidative degradation by sunlight.
  • the films and articles made from them are particularly suitable for applications where fire protection or flame retardancy is required.
  • the films can be thermoformed economically on commercially available deep-drawing systems.
  • the molded body produced has good detail rendition.
  • Sealable, biaxially oriented polyester films are known in the prior art. Sealable, biaxially oriented polyester films which are equipped with one or more UV absorbers are also known. This according to the state of the Technically known films are characterized either by a good sealing behavior, a good appearance or by an acceptable processing behavior.
  • GB-A 1 465 973 describes a co-extruded, two-layer polyester film, one layer of which contains isophthalic acid-containing and terephthalic acid-containing copolyesters and the other layer of polyethylene terephthalate. 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 0035835 describes a coextruded, sealable polyester film in which particles are added to improve the winding and processing behavior in 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 sticking to rollers or guides.
  • No further details regarding the incorporation of antiblocking agents are given about the other, non-sealable layer of the film. It remains open whether this layer contains antiblocking agents.
  • the choice of particles with a larger diameter than the sealing layer and the concentrations given in the examples deteriorate the sealing behavior of the film.
  • the script does not give any information on the sealing temperature range of the film.
  • the seal seam strength is measured at 140 ° C and is in a range from 63 to 120 N / m (0.97 N / 15 mm to 1.8 N / 15 mm film width).
  • EP 0432886 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 consist of copolyesters containing isophthalic acid and terephthalic acid.
  • the film on the back has improved processing properties. Information on the sealing area of the film are not made in scripture.
  • 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 acrylic coating on the back 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 0515096 describes a coextruded, multilayer sealable polyester film which contains an additional additive on the sealable layer.
  • the additive can e.g. contain inorganic particles and is preferably applied in an aqueous layer to the film during its manufacture. 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 cover 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%. Triazines, for example ® Tinuvin 1577 from Ciba, are preferably used as UV absorbers.
  • the base layer is equipped with common antiblocking agents.
  • the film is characterized by a good sealability, but does not have the desired processing behavior and exhibits also deficits in the optical properties (gloss and cloudiness).
  • the film is not thermoformable and is not flame retardant.
  • a flame-retardant raw material is described in DE AS 2346787.
  • the use of the raw material for films and fibers is also claimed.
  • the raw material mentioned is sensitive to hydrolysis and must be predried 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.
  • the films produced under uneconomical conditions become brittle when exposed to temperature, i.e. the mechanical properties decrease sharply due to embrittlement, making the film unusable. This embrittlement occurs after 48 hours of exposure to heat.
  • the film Since the film is intended in particular for outdoor use and / or critical indoor use, it should have a high UV stability.
  • a high UV stability means that the films are not or only extremely little damaged by sunlight or other UV radiation. In particular, the films should not yellow over several years of external use, should not show embrittlement or cracking of the surface, and should also not show any deterioration in the mechanical properties.
  • High UV stability means that the film absorbs the UV light and only lets light through in the visible range.
  • a flame-retardant effect means that the transparent film meets the conditions according to DIN 4102 Part 2 and in particular the conditions according to DIN 4102 Part 1 in a so-called fire protection test and can be classified in the building material class B 2 and in particular B1 of the flame retardant materials.
  • the film should pass the UL test 94 "Vertical Burning Test for Flammability of Plastic Material" so that it can be classified in class 94 VTM-0. This means that the film will not work 10 seconds after the Bunsen burner is removed burns more, no glow is observed after 30 seconds and no dripping is found.
  • Economic production includes the fact that the raw materials or the raw material components required to produce the flame-retardant film can be dried with industrial dryers that meet the standard of technology. It is essential that the raw materials do not stick together and are not thermally broken down.
  • These state-of-the-art industrial dryers include vacuum dryers, fluidized bed dryers, fluid bed dryers, fixed bed dryers, (shaft dryers). These dryers operate at temperatures between 100 and 170 ° C, where the flame-retardant raw materials stick together and have to be mined so that film production is not possible.
  • the raw material goes through a temperature range of approx. 30 to 130 ° C with a vacuum of approx. 50 mbar. Afterwards, a so-called drying in a hopper at temperatures of 100 to 130 ° C and a residence time of 3 to 6 hours is required. Even here, this raw material sticks extremely.
  • No embrittlement at short temperatures means that after 100 hours of tempering at 100 ° C in a convection oven, the film shows no embrittlement and no bad mechanical properties.
  • thermoformability means that the film can be thermoformed or thermoformed on commercially available thermoforming machines without economical predrying, the thermoformed molded body having good detail rendering.
  • the object is achieved according to the invention by providing an amorphous, coextruded, UV-stabilized and flame-retardant, thermoformable sealable polyester film with at least one base layer B, a sealable cover layer A and a further, non-sealable cover layer C, wherein the sealable cover layer A has a seal starting temperature of 110 ° C and a seal seam strength of at least 1.3 N / 15 mm, the distinguishing features of which It can be seen that the sealable cover layer A has a surface roughness, expressed as R a value, of ⁇ 30 nm and a measured value of the gas flow in the range from 500 to 4000 s and that the non-sealable cover layer C has a coefficient of friction of this layer against itself, expressed as a COF value of ⁇ 0.5, a surface roughness, expressed as R a value, in the range from 40 nm to 100 nm, a measured value of the gas flow of ⁇ 120 s and a number of elevations N per mm 2
  • the UV stabilizer (s) is (are) expediently metered in directly as masterbatch (s) in film production, the concentration of the UV stabilizer (s) within a layer preferably being between 0.01 and 5 wt .-%, based on the weight of the respective layer of the polyester used, lies.
  • the film according to the invention contains 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 to 20.0 wt .-%, based on the weight of the layer of crystallizable thermoplastic, is.
  • a ratio of flame retardant to thermoplastic in the range from 60 to 40% by weight to 10 to 90% by weight is generally maintained in the production of the masterbatch.
  • Typical flame retardants include bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide, aluminum trihydrates, the halogen compounds being disadvantageous because of the halogen-containing by-products formed.
  • 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 dimethyl methylphosphonate. It is essential to the invention that the organic phosphorus compound is soluble in the thermoplastic, since otherwise the required optical properties are not met.
  • Phenolic stabilizers, alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates are generally used as hydrolysis stabilizers 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-tertiary-butyl-4-hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) benzene are particularly advantageous.
  • the film has at least three layers and then comprises as layers the base layer B, the sealable cover layer A and the non-sealable cover layer C.
  • the base layer B of the film preferably consists of at least 70% by weight of a thermoplastic polyester. Polyesters made of ethylene glycol and are suitable for this
  • Terephthalic acid polyethylene terephthalate, PET
  • 1,4-bis-hydroximethyl- cyclohexane and terephthalic acid poly-1, 4-cyclohexanedimethylene terephthalate, PCDT
  • ethylene glycol, naphthalene-2,6-dicarboxylic acid and biphenyl-4,4'-dicarboxylic acid polyethylene-2,6-naphthalate bibenzoate, PENBB).
  • polyesters which consist of at least 90 mol%, preferably at least 95 mol%, of ethylene glycol and terephthalic acid units or of ethylene glycol and naphthalene-2,6-dicarboxylic acid units.
  • the remaining monomer units originate from other suitable aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as can also occur in layer A or layer C.
  • the thermoplastic is e.g. characterized in that the diethylene glycol content (DEG content) and / or polyethylene glycol content (PEG content) is greater than or equal to 1.0% by weight, in particular greater than or equal to 1.2% by weight.
  • the DEG content and / or PEG content is in the range from 1.3% by weight to 5% by weight.
  • it can also contain isophthalic acid (IPA) in a concentration of 3% by weight to 10% by weight.
  • IPA isophthalic acid
  • the films can be thermoformed economically on commercially available thermoforming machines and deliver excellent detail reproduction due to the higher diethylene glycol content and / or polyethylene glycol content and / or I PA content compared to standard thermoplastics.
  • Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic glycols of the general formula HO- (CH 2 ) n -OH, where n represents an integer from 3 to 6 (in particular propane-1,3-diol, butane-1 , 4-diol, pentane-1,5-diol and hexane-1, 6-diol) or branched aliphatic glycols with up to 6 carbon atoms.
  • cyclohexanediols in particular cyclohexane-1,4-diol
  • Suitable other aromatic diols correspond, for example, to the formula HO-C 6 H 4 -XC 6 H 4 -OH, where X represents -CH 2 -, -C (CH 3 ) 2 -, -C (CF 3 ) 2 -, -O-, -S- or -SO 2 -.
  • bisphenols of the formula HO-C 6 H 4 -C 6 H 4 -OH are also very suitable.
  • Suitable aromatic dicarboxylic acids are preferably benzene dicarboxylic acids, naphthalene dicarboxylic acids (for example naphthalene-1, 4- or 1,6-dicarboxylic acid), biphenyl-x, x'-dicarboxylic acids (especially biphenyl-4,4'-dicarboxylic acid), diphenylacetylene-x, x ' -dicarboxylic acids (especially diphenylacetylene-4,4'-dicarboxylic acid) or stilbene-x, x'-dicarboxylic acids.
  • cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid) should be mentioned.
  • aliphatic dicarboxylic acids the (C 3 -C 1g ) alkanedioic acids are particularly suitable, the alkane fraction being straight-chain or branched.
  • the production of the polyesters can e.g. according to the transesterification process.
  • the starting point is dicarboxylic acid esters and diols, which are reacted with the usual transesterification catalysts, such as zinc, calcium, lithium, magnesium and manganese salts.
  • the intermediates are then polycondensed in the presence of generally customary polycondensation catalysts, such as antimony trioxide or titanium salts. It can also be produced by the direct esterification process in the presence of polycondensation catalysts. Here one starts directly from the dicarboxylic acids and the diols.
  • the sealable outer layer A applied to the base layer B by coextrusion is based on polyester copolymers and essentially consists of copolyesters which are composed predominantly of isophthalic acid and terephthalic acid units and of ethylene glycol units. The remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as can also occur in the base layer.
  • the preferred copolyesters that provide the desired sealing properties are those constructed from ethylene terephthalate and ethylene isophthalate units and from 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 very preferred are copolyesters in which the proportion of ethylene terephthalate is 60 to 85 mol% and the corresponding The proportion of ethylene isophthalate is 40 to 15 mol%.
  • the same polymers as described above for the base layer B can be used for the other, non-sealable top layer C or for any intermediate layers that are present.
  • 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 non-sealable cover layer C.
  • the seal initiation temperature of 110 ° C and the seal seam strength of at least 1.3 N / 15 mm is achieved if the copolymers described in more detail above are used for the sealable cover layer A.
  • the best sealing properties of the film are obtained if no further additives, in particular no inorganic or organic fillers, are added to the copolymers. In this case, the lowest seal starting temperature and the highest seal seam strengths are obtained for a given copolyester.
  • the handling of the film is poor in this case, since the surface of the sealable cover layer A tends to block. The film can hardly be wrapped and is practically not suitable for further processing on high-speed packaging machines. In order to improve the handling of the film and the processability, it is necessary to modify the sealable cover layer A.
  • the roughness of the sealable top layer should be less than 30 nm. In the other case, the sealing properties are negatively influenced in the sense of the present invention.
  • the measured value of the gas flow should be in the range from 500 to 4000 s. At values below 500 s, the sealing properties within the meaning of the present
  • the topography of the non-sealable cover layer C should be characterized by the following set of parameters:
  • the coefficient of friction (COF) of this side against itself should be less than 0.5. Otherwise the winding behavior and further processing of the film are unsatisfactory.
  • the roughness of the non-sealable top layer should be greater than 40 nm and less than 100 nm. Values smaller than 40 nm have negative effects on the winding and processing behavior of the film and values larger than 100 nm impair the optical properties (gloss, haze) of the film.
  • the measured value of the gas flow should be in the range below 120 s. At values above 120, the winding and processing behavior of the film is negatively affected.
  • the number of elevations N per mm 2 of film surface is correlated with the respective height h using the following equation:
  • UV stabilizers which are suitable for incorporation into polyesters can be selected for the film according to the invention.
  • suitable UV stabilizers are known in the art and e.g. described in more detail in WO 98/065575, in EP-A-0 006 686, in EP-A-0 031 202, EP-A-0 031 203 or in EP-A-0 076 582.
  • Light especially the ultraviolet portion of solar radiation, i.e. H. 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 the mechanical-physical properties are negatively influenced.
  • 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 can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for transparent films because they lead to discoloration or color change. For transparent, matt films, only organic and organometallic compounds are suitable which give the thermoplastic to be stabilized no or only an extremely small color or color change, i.e. H. 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, ie they do not decompose and do not lead to outgassing.
  • Suitable UV stabilizers are light stabilizers 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 and the triazines being preferred.
  • 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 of light stabilizer preferably being between 0.01% by weight and 5.0% by weight. -%, based on the weight of crystallizable polyethylene terephthalate.
  • the UV stabilizer or stabilizers are preferably contained in the cover layer (s). If necessary, the core layer can also be equipped with a UV stabilizer.
  • UV stabilizers absorb the UV light and thus offer protection
  • the person skilled in the art would have used commercially available stabilizers. He would have noticed that the UV stabilizer lacks thermal stability and decomposes and outgasses at temperatures between 200 ° C and 240 ° C; he must incorporate large amounts (approx. 10 to 15% by weight) of UV stabilizer so that the UV light is absorbed and so that the film is not damaged.
  • the light stabilizer can be metered in at the thermoplastic raw material manufacturer or metered into the extruder during film production.
  • the addition of the light stabilizer via masterbatch technology is particularly preferred.
  • the light stabilizer is fully dispersed in a solid carrier material.
  • Suitable carrier materials are the polyethylene terephthalate itself or also other polymers which are sufficiently compatible with the thermoplastic.
  • 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 transparent, flame-retardant film according to the invention contains, as the main component, a crystallizable polyethylene terephthalate, 1 to 20% by weight of an organic phosphorus compound soluble in polyethylene terephthalate as a flame retardant and 0.1 to 1.0% by weight of a hydrolysis stabilizer ,
  • 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 and is soluble in PET, since otherwise the required optical
  • the flame retardant is preferably contained in the non-sealable cover layer C.
  • the base layer B or also the sealable top layer A must be equipped with flame retardants.
  • the concentration of the flame retardant (s) relates to the weight of the thermoplastics in the layer equipped with flame retardants.
  • fire protection tests according to DIN 4102 and the UL test have shown that in the case of a three-layer film, it is quite sufficient to equip the 0.5 to 10 ⁇ m thick top layers with flame retardants in order to achieve improved flame retardancy.
  • the core layer can also be equipped with flame retardants, i.e. include so-called basic equipment.
  • the flame-retardant, multi-layer films produced with the known coextrusion technology become economically very interesting for production in comparison to the monofilms that are completely finished in high concentrations, since significantly less flame retardants and significantly less UV absorbers are required.
  • the flame-retardant film can be produced in the dryer without gluing using masterbatch technology, suitable predrying or pre-crystallization of the masterbatch and by using low concentrations of hydrolysis stabilizer. Furthermore, no outgassing and deposits were found in the production process.
  • the film according to the invention does not become brittle at a temperature load of 100 ° C. over a longer period of time, which is more than surprising. This result is due to the synergistic effect of suitable pre-crystallization, pre-drying, masterbatch technology and hydrolysis stabilizer. Furthermore, the film according to the invention can be easily recycled, which makes it suitable, for example, for use as short-lived advertising signs, for trade fair construction and for other promotional items where fire protection is desired and prescribed.
  • films according to the invention in the thickness range from 30 to 2000 ⁇ m already meet the building material classes B2 and B1 according to DIN 4102 and UL test 94.
  • the flame retardant is added using masterbatch technology.
  • the flame retardant is fully dispersed in a carrier material.
  • Polyethylene terephthalate or other polymers which are compatible with the polyethylene terephthalate are suitable as the carrier material.
  • the grain size and the bulk density of the masterbatch is similar to the grain size and the bulk density of the thermoplastic, so that a homogeneous distribution and thus a homogeneous flame retardancy can take place.
  • the masterbatch which contains the flame retardant and optionally 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 a 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 has a temperature range from 10 ° C to during the drying or dwell time 160 ° C, preferably 20 ° C to 150 ° C, in particular 30 ° C to 130 ° C passes.
  • the raw material mixture is at 10 to 70 rpm, preferably 15 to 65 rpm, in particular stirred 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 post-dried for 4 to 6 hours.
  • the base layer B can additionally contain conventional additives, such as, for example, stabilizers and / or antiblocking agents.
  • the other two layers A and C additionally contain conventional additives, such as stabilizers and / or antiblocking agents. They are expediently added to the polymer or the polymer mixture before the melting. For example, phosphorus compounds such as phosphoric acid or phosphoric acid esters are used as stabilizers.
  • Typical antiblocking agents are inorganic and / or organic particles, for example calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, LiF, calcium, barium , Zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polystyrene or acrylate particles.
  • inorganic and / or organic particles for example calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, LiF, calcium, barium , Zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polystyrene or acrylate particles.
  • the particles can the individual layers in the respective advantageous concentrations, e.g. as a glycolic dispersion during polycondensation or via masterbatches during extrusion.
  • Preferred particles are SiO 2 in colloidal and in chain-like form. These particles are very well integrated into the polymer matrix and only slightly generate vacuoles. Vacuoles generally cause cloudiness and are therefore appropriate Avoid moderately.
  • the particle diameters of the particles used are not restricted. To achieve the object, however, it has proven to be expedient to use particles with an average primary particle diameter of less than 100 nm, preferably less than 60 nm and particularly preferably less than 50 nm and / or particles with an average primary particle diameter of greater than 1 ⁇ m, preferably greater than 1.5 ⁇ m and particularly preferably greater than 2 ⁇ m. However, these particles described last should not have an average particle diameter that is greater than 5 ⁇ m.
  • the particle concentration in the base layer B is between 0 and 0.15% by weight, preferably between 0 and 0.12% by weight and in particular between 0 and 0.10% by weight.
  • the particle diameter of the particles used is not restricted, but particles with an average diameter of greater than 1 mm are particularly preferred.
  • the film consists of three layers, the base layer B and cover layers A and C applied to both sides of this base layer, the cover layer A being sealable against itself and against the cover layer C.
  • the top layer C has more pigments (ie higher pigment concentration) than the top layer A.
  • the pigment concentration in this second cover layer C is between 0.1 and 1.0%, advantageously between 0.12 and 0.8% and in particular between 0.15 and 0.6%.
  • the other sealable cover layer A, which is opposite the cover layer C, is less filled with inert pigments.
  • the concentration of the inert particles in the Layer A is between 0.01 and 0.2% by weight, preferably between 0.015 and 0.15% by weight and in particular between 0.02 and 0.1% by weight.
  • an intermediate layer between the base layer and the cover layers.
  • This can in turn consist of the polymers described for the base layers. In a particularly preferred embodiment, it consists of the polyester used for the base layer. It can also contain the usual additives described.
  • the thickness of the intermediate layer is generally greater than 0.3 ⁇ m and is preferably in the range from 0.5 to 5 ⁇ m, in particular in the range from 1.0 to 20 ⁇ m and very particularly preferably in the range from 1.0 to 15 ⁇ m.
  • the thickness of the cover layers A and C is generally greater than 0.5 ⁇ m and is generally in the range from 0.5 to 10 ⁇ m, the cover layers A and
  • C can be the same or different thickness.
  • the total thickness of the polyester film according to the invention can vary within certain limits. It is 30 to 2000 ⁇ m, in particular 50 to 1800 ⁇ m, preferably 100 to 1500 ⁇ m.
  • the invention further relates to a process for producing the polyester film according to the invention by the coextrusion process known per se.
  • the polymers or the polymer mixtures for the individual layers are compressed and liquefied in their own extruders, and the additives that may have been added may already be contained in the polymer or in the polymer mixture. Any foreign bodies or impurities that may be present can be separated from the polymer melt by suitable filters before extrusion.
  • the melts are then simultaneously through a Flat die (slot die) pressed, and the pressed multi-layer film is drawn off on one or more take-off rollers, where it cools and solidifies.
  • the solidified film is then optionally corona or flame treated on the surface layer intended for the treatment.
  • one or both surface (s) of the film can be coated in-line by the known methods.
  • the in-ue coating can serve, for example, to improve the adhesion of the metal layer or a possibly applied printing ink, but also to improve the antistatic behavior or the processing behavior.
  • the film can also be coated.
  • Typical coatings are adhesion-promoting, antistatic, slip-improving or adhesive layers. It is advisable to apply these additional layers to the film by means of inline coating using aqueous dispersions after the solidification.
  • thermoforming process usually includes the steps of predrying, heating, molding, cooling, demolding and tempering.
  • thermoforming process it was surprisingly found that the film according to the invention can be deep-drawn without prior predrying.
  • This advantage compared to thermoformable polycarbonate and polymethyl methacrylate films, which require drying times of 10 to 15 hours depending on the thickness at temperatures of 100 to 120 ° C, drastically reduces the costs of the forming process.
  • thermoforming The following process parameters were surprisingly found for thermoforming.
  • the film according to the invention is notable for excellent sealability, very good stability to UV light, very good handling and very good processing behavior.
  • the sealable cover layer A seals not only against itself (fin sealing) but also against the non-sealable cover layer C (lab sealing).
  • the sealing start temperature is only shifted upwards by approx. 10 K, while the sealing seam strength is not deteriorated by more than 0.3 N / 15.
  • the film absorbs 100% of the short-wave, aggressive UV light in the wavelength range of less than 380 nm, while non-UV-treated amorphous films allow the UV light to pass through at a wavelength of greater than 280 nm.
  • the film fulfills the fire tests according to DIN 4102 part 1 and part 2 and thus the building material classes B2 and B1 and can be classified in the group of flame-retardant materials.
  • UL test 94 is also passed.
  • the film shows no embrittlement after 200 hours of tempering in a forced-air drying cabinet.
  • the film can be used on commercially available thermoforming machines, e.g. B. from Illig / Heilbronn, economically thermoformed without pre-drying to form complex bodies. men.
  • the detail reproduction of the molded bodies is excellent with a homogeneous surface.
  • the gloss and the haze of the film compared to films according to the prior art could be improved.
  • the regenerate can be fed back into the extrusion in a concentration of 20 to 60% by weight, based on the total weight of the film, without the physical properties of the film being adversely affected.
  • the film Due to its excellent sealing properties, its very good handling and its very good processing properties, the film is particularly suitable for processing on high-speed machines.
  • the film is suitable for a variety of different applications, for example for interior cladding, for trade fair construction and trade fair items, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in shop and shelf construction, as promotional items , Lamination medium and for thermoforming applications of all kinds.
  • the transparent film according to the invention is still suitable for outdoor applications, such as for greenhouses, roofing, external cladding, covering of materials such as Steel sheets, applications in the construction sector and illuminated advertising profiles, shadow mats, electrical applications.
  • Table 1 summarizes the most important film properties according to the invention at a glance.
  • the films were weathered according to the test specification ISO 4892 for 1000 hours with the Atlas Ci 65 Weather Ometer from Atlas and then tested for mechanical properties, discoloration, surface defects, haze and gloss
  • the friction was determined according to DIN 53 375.
  • the sliding friction number was measured 14 days after production.
  • the surface tension was determined using the so-called ink method (DIN 53364).
  • Haze The haze according to wood was determined in accordance with ASTM-D 1003-52, however, in order to utilize the optimal measuring range, measurements were taken on four layers of foil lying one above the other and a 1 ° slit aperture was used instead of a 4 ° perforated aperture.
  • the gloss was determined in accordance with DIN 67 530.
  • the reflector value was measured as an optical parameter for the surface of a film. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 20 °. A light beam hits the flat test surface at the set angle of incidence and is reflected or scattered by it. The light rays striking the photoelectronic receiver are displayed as a proportional electrical quantity. The measured value is dimensionless and must be specified together with the angle of incidence.
  • the size distribution of elevations on film surfaces is determined using a scanning electron microscope and an image analysis system.
  • the scanning electron microscope XL30 CP from Philips is used with an integrated image analysis program AnalySIS from Soft-Imaging System.
  • a thin metal layer e.g. made of silver.
  • a is the angle between the sample surface and the direction of propagation of the metal vapor.
  • This oblique vaporization creates a shadow behind the elevation. Since the shadows are not yet electrically conductive, the sample is then vapor-deposited or sputtered with a second metal (for example gold), the second coating hitting the sample surface perpendicularly and therefore no shadows being produced in the second coating.
  • a second metal for example gold
  • the shadows of the elevations are visible due to the material contrast of the metals.
  • the sample is oriented in the SEM so that the shadows run parallel to an image edge.
  • the following conditions are set on the SEM for image acquisition: secondary electron detector, working rod distance 10 mm, acceleration voltage 10 kV and spot 4.5.
  • the brightness and contrast are set so that all image information is shown as gray values and the intensity of the background noise is so low that it is not detected as a shadow.
  • the length of the shadows is measured with the image analysis.
  • the threshold value for shadow detection is placed at the point where the 2nd derivative of the gray value distribution of the image crosses the zero point.
  • the image is smoothed with an NxN filter (size 3, 1 iteration).
  • the setting of a frame ensures that elevations that are not fully represented in the image are not measured.
  • the magnification, the frame size and the number of evaluated images are selected so that a total of 0.36 mm 2 film surface is evaluated.
  • the surveys determined in this way are divided into classes in order to arrive at a frequency distribution. The division is made into 0.05 mm wide classes between 0 and 1 mm, whereby the smallest class (0 to 0.05 mm) is not used for further evaluations.
  • the diameters (spread perpendicular to the direction of the shadow) of the surveys are similarly classified into 0.2 mm wide classes from 0 to 10 mm, whereby the smallest class is also used for further evaluation.
  • the principle of the measuring method is based on the air flow between a film side and a smooth silicon wafer plate.
  • the air flows from the environment into an evacuated room, the interface between the film and the silicon wafer plate serving as flow resistance.
  • a round film sample is placed on a silicon wafer plate, in the middle of which a hole ensures the connection to the recipient.
  • the recipient is evacuated to a pressure less than 0.1 mbar. The time in seconds that the air needs to cause a pressure increase of 56 mbar in the recipient is determined.
  • the modulus of elasticity, tensile strength and elongation at break are measured in the longitudinal and transverse directions according to ISO 527-1-2.
  • UV stability is tested according to the test specification ISO 4892 as follows:
  • Test device Atlas Ci 65 Weather Ometer
  • Test conditions ISO 4892, i.e. H. Artificial weathering Irradiation time: 1000 hours (per side)
  • Xenon lamp inner and outer filter made of borosilicate Irradiation cycles: 102 minutes of UV light, then 18 minutes of UV light: with water spraying the samples, then again 102 minutes of UV light, etc.
  • Yellowness index is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 6167. Yellowness index (YID) values of ⁇ 5 are not visually visible.
  • Fire behavior The fire behavior is determined according to DIN 4102 part 2, building material class B2 and according to DIN 4102 part 1, building material class B1 and according to UL test 94.
  • Polyethylene terephthalate chips produced by the transesterification process with Mn as the transesterification catalyst, Mn concentration: 100 ppm) with a DEG content of 1.6% by weight were dried at 150 ° C. to a residual moisture content of below 100 ppm and fed to the extruder for the base layer B. Chips of polyethylene terephthalate and a filler were also fed to the extruder for the non-sealable top layer C.
  • chips were made from a linear polyester consisting of an amorphous copolyester with 78 mol% ethylene terephthalate and 22 mol% ethylene isophthalate (produced by the transesterification process with Mn as the transesterification catalyst, Mn concentration: 100 ppm).
  • the copolyester was dried at a temperature of 100 ° C. to a residual moisture content of below 200 ppm and fed to the extruder for the sealable outer layer A.
  • the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxyphenol ( ® Tinuvin 1577) is metered in in the form of masterbatches.
  • the masterbatches consist of 5% by weight of Tinuvin 1577 as an active ingredient and 95% by weight of polyethylene terephthalate (for the top layer C) or 95% by weight of polyethylene isophthalate (for the top layer A).
  • the 5% by weight Tinuvin 1577 masterbatches are only added to the two thick top layers with 20% by weight using the masterbatch technology.
  • the hydrolysis stabilizer and the flame retardant are metered in in the form of a masterbatch.
  • the masterbatch is composed of 20% by weight of flame retardant, 1% by weight of hydrolysis stabilizer and 79% by weight of polyethylene terephthalate.
  • the hydrolysis stabilizer is pentaerythrityl tetrakis 3- (3,5-di-tertiary-butyl-4-hydroxylphenyl) propionate.
  • the flame retardant is dimethyl methyl phosphonate (Armgard P 1045).
  • the masterbatch has a bulk density of 750 kg / m 3 and a softening point of 69 ° C.
  • Top layer A mixture of:
  • UV masterbatch based on polyethylene isophthalate 20.0% by weight UV masterbatch based on polyethylene isophthalate with 5% by weight
  • Aerosil TT600 pyrogenic SiO 2 from Degussa
  • Base layer B 90.0% by weight of polyethylene terephthalate with an SV value of 800 and one
  • Top layer C mixture of:
  • masterbatch 20.0% by weight of masterbatch, which contains flame retardant and hydrolysis stabilizer 20.0% by weight of UV masterbatch based on polyethylene terephthalate with 5
  • the film in this and in all the following examples was weathered for 1000 hours with the Atlas Ci 65 Weather Ometer from Atlas in accordance with the test specification ISO 4892 and then tested for discoloration, surface defects, haze and gloss.
  • the cover layer thickness of the sealable layer A was increased from 4 to 6.0 ⁇ m.
  • the sealing properties have improved as a result, in particular the seal seam strength has become significantly greater.
  • Example 2 In comparison to Example 1, a 500 ⁇ m thick film was now produced.
  • the cover layer thickness of the sealable layer A was 6.0 ⁇ m and that of the non-sealable layer C was 3.0 ⁇ m.
  • Example 3 the copolymer for the sealable outer layer A was changed. Instead of the amorphous copolyester with 78 mol% polyethylene terephthalate and 22 mol% ethylene terephthalate, an amorphous copolyester with 70 mol% polyethylene terephthalate and 30 mol% ethylene terephthalate was now used.
  • the raw material was processed on a twin-screw extruder with degassing without it having to be pre-dried.
  • the cover layer thickness of the sealable layer A was again 6.0 ⁇ m and that of the non-sealable layer C was 3.0 ⁇ m. Comparative Example 1
  • Example 1 is repeated. However, the sealable top layer is not pigmented.
  • the film contains no UV absorber and no flame retardant.
  • the film After 1000 hours of weathering, the film shows severe cracking, embrittlement and a visible yellowing.
  • the film does not meet the fire tests according to DIN 4102 part and part 2 and the UL test 94.
  • the films from Examples 1 to 4 meet building material classes B1 and B2 according to DIN 4102 Part 1 and Part 2.
  • the foils can therefore be classified in the building material class of flame-retardant materials.
  • the films meet UL test 94.
  • the films from Examples 1 to 4 show no embrittlement after 200 hours of tempering at 100 ° C. in a forced-air drying cabinet.
  • the foils do not break when folded, i.e. the mechanical properties are essentially retained after the tempering.
  • the films from Examples 1 to 4 show no crack formation on the surface and no signs of embrittlement.
  • the optical properties of gloss and haze are almost unchanged.
  • the yellowness index is less than 4.
  • the films from Examples 1 to 4 absorb 100% of the aggressive short-wave UV light in the wavelength range less than 380 nm.
  • the films from Examples 1 to 4 can be thermoformed into complex shaped bodies on commercially available deep-drawing machines from Wig / Heilbronn, without predrying.
  • the detail reproduction of the molded bodies is excellent with a homogeneous surface.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille polyester coextrudée amorphe, transparente, absorbant les U.V., ingnifugeante, scellable, dont l'épaisseur est comprise entre 30 et 2000 mu m et qui est constituée d'au moins une couche de base B et de couches de recouvrement A et C appliquées sur les deux côtés de cette couche de base, lesdites couches de recouvrement comprenant en supplément au moins un agent de stabilisation aux U.V. servant d'agent de protection contre la lumière, et un agent ignifugeant. La couche de recouvrement scellable A présente une température d'amorçage de scellage de 110 DEG C et une résistance de soudure par scellage d'au moins 1,3 N/15 mm, une rugosité de surface, exprimée sous forme de valeur Ra, < 30 nm, et une valeur de mesure du flux gazeux comprise entre 500 et 4000 s. La couche non scellable C présente un coefficient de frottement de cette couche par rapport à elle-même, exprimé sous forme de valeur COF, < 0,5, une rugosité de surface, exprimée sous forme de valeur Ra, comprise entre 40 nm et 100 nm, une valeur de mesure du flux gazeux < 120 s, et un nombre d'élévations N au mm<2> de surface de feuille, qui, en se servant de la hauteur h correspondante, peut être calculé au moyen des équations suivantes : AC1-BC1 . log h/ mu m < NC/mm<2> < AC2-BC2 . log h/ mu m avec 0,01 mu m < h < 10 mu m et AC1 = 0,29; BC1 = 3,30; AC2 = 1,84 ; et BC2 = 2,70.
PCT/EP2001/000216 2000-01-20 2001-01-10 Feuille polyester amorphe, transparente, scellable, absorbant les u.v., ignifugeante, thermoformable, son procede de realisation et son utilisation Ceased WO2001053093A1 (fr)

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DE10002149.2 2000-01-20
DE10002149A DE10002149A1 (de) 2000-01-20 2000-01-20 Amorphe, transparente, siegelfähige, UV-absorbierende, flammhemmend ausgerüstete, thermoformbare Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2368810A (en) * 2000-11-09 2002-05-15 Toppan Printing Co Ltd Treatment of a surface of a polymer
EP1679054B2 (fr) 2005-01-11 2017-04-12 The Procter & Gamble Company Partie centrale scelée pour un article absorbant
DE602005020412D1 (de) * 2005-01-11 2010-05-20 Procter & Gamble Dichte Verbindung der Hülle eines absorbierenden Kernes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2766200A1 (fr) * 1997-07-17 1999-01-22 Toray Plastics Europ Sa Films polyester composites metallises a proprietes barriere
EP0947982A2 (fr) * 1998-04-01 1999-10-06 Mitsubishi Polyester Film GmbH Film de polyester multicouche à orientation biaxiale, son procédé de fabrication et son utilisation comme supports d'enregistrements magnétiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2766200A1 (fr) * 1997-07-17 1999-01-22 Toray Plastics Europ Sa Films polyester composites metallises a proprietes barriere
EP0947982A2 (fr) * 1998-04-01 1999-10-06 Mitsubishi Polyester Film GmbH Film de polyester multicouche à orientation biaxiale, son procédé de fabrication et son utilisation comme supports d'enregistrements magnétiques

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