DE10002155A1 - Structurized amorphous, clear, colored thermoplastic film, used for interior and exterior purposes, e.g. cladding, advertising, display and packaging, contains ultraviolet absorber, optical brightener and dye - Google Patents

Abstract

The invention relates to an amorphous, structured, transparently colored, UV light-absorbing film made of a crystallizable thermoplastic, the thickness of which is in the range from 30 to 1000 μm, a process for its production and its use. The film contains at least one thermoplastic-soluble dye and one thermoplastic-soluble UV absorber and is characterized by good optical properties, high light transmission in the wavelength range of> = 400 nm, preferably 420 to 800 nm, by economical thermoformability and by absorption of short-wave UV light in the wavelength range of less than 380 nm.

Description

The invention relates to an amorphous, structured, transparently colored, UV light absorbent film made of a crystallizable thermoplastic, whose thickness is in the range is from 30 to 1000 microns, a process for their preparation and their use. The Film contains at least one dye that is soluble in the thermoplastic and one in Thermoplastic soluble UV absorber and is characterized by good optical properties, high light transmission in the wavelength range of ≧ 400 nm, preferably 420 to 800 nm, through an economical thermoformability and through the absorption of the short-wave UV light in the wavelength range of less than 380 nm.

Transparent and transparently colored polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC) and polyethylene terephthalate (PET) sheets with thicknesses greater than 1 mm are well known. These plates are inefficient at slow machines can be manufactured. The plates are inflexible, cannot be rolled up, are only available by the meter and coated with a protective film. The transportation of this huge slabs is uneconomical. In addition, these plates show a low Light transmission, d. H. they are cloudy, and an unsatisfactory optical Surface quality. The plates are not equipped with antiblocking agents and lubricants, so that they stick to rollers during the production process and thus defects on the Show surface. The panels are only as cut and under uneconomical Conditions thermoformable.

Transparent films are well known. The slides are usually oriented and thus have a crystallinity between 30 and 50%. These foils are  around crystalline or semi-crystalline structures. Furthermore, these films do not absorb that short-wave, aggressive UV light. From a wavelength of 280 nm, these foils leave the UV light through.

The films contain no soluble dye and are usually smooth on both sides.

The object of the present invention is to overcome the described disadvantages of the prior art Avoid technology.

The invention therefore relates to an amorphous, at least one-sided structured, transparent colored, UV light absorbing film with a thickness in the range 30 to 1000 µm, which contains a crystallizable thermoplastic as the main component, the is characterized in that they additionally have at least one in the thermoplastic soluble UV absorber, at least one optical brightener and at least one contains soluble dye, a process for their preparation and their use.

The film according to the invention has both good optical properties and 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 of ≦ 380 nm and combines high UV stability with a combination structured appearance that can be used for advertising purposes.

The good optical properties included, for example, high light transmission, low haze, high surface gloss of the unstructured surface and a homogeneous look.

A structured surface means that the film is an effective, aesthetic  Appearance. Furthermore, there are minor surface defects that occur in the Manufacturing processes can occur, hidden. In particular, the one-sided structure Film compared to a smooth film much less sensitive to Fingerprints and scratches.

A high UV stability means that the film and the molded body made from it are extremely little damaged by sunlight or other UV radiation, so that they are suitable for outdoor applications and critical indoor applications. The slide is supposed to does not yellow and does not crack or become brittle when used outdoors for several years Show surface.

A barrier against UV light means that the film's aggressive short-wave Radiations that are responsible, for example, for fat oxidation in food, completely absorbed in the wavelength range ≦ 380 nm.

Light, especially the ultraviolet portion of solar radiation, i.e. H. the Wavelength range from 280 to 400 nm, initiates degradation processes with thermoplastics, as a result not only the visual appearance due to color change or yellowing changes, but also the mechanical-physical properties be adversely affected.

The inhibition of these photooxidative degradation processes is of considerable technical and economic importance, otherwise the application possibilities of numerous Thermoplastics are drastically restricted.

Polyethylene terephthalates, for example, start below 360 nm UV light to absorb, their absorption increases considerably below 320 nm and is  very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.

In the presence of oxygen there are mainly chain cleavages, but none Networking observed. Carbon monoxide, carbon dioxide and carboxylic acids are the quantitatively predominant photo-oxidation products. In addition to direct photolysis of the ester groups, oxidation reactions still need to be considered cause peroxide radicals also the formation of carbon dioxide.

The photooxidation of polyethylene terephthalates can also take place via hydrogen elimination in the α-position of the ester groups to hydroperoxides and their decomposition products and lead to associated chain cleavages (H. Day, D. M. Wiles: J. Appl. Polym. Sci 16, 1972, page 203).

UV stabilizers or UV absorbers as light stabilizers are chemical compounds, that intervene in the physical and chemical processes of light-induced degradation can. Soot and other pigments can partially protect against light. This However, substances are unsuitable for transparent films because they are used for discoloration or Lead color change. For transparent films only organic and organometallic are Suitable compounds that the thermoplastic to be stabilized no or only one impart extremely little color or color change, d. H. which are soluble in the thermoplastic are.

Suitable UV stabilizers as light stabilizers for the purposes of the present invention UV stabilizers which are at least 70%, preferably 80%, particularly preferably 90%, of UV light in the wavelength range from 180 nm to 380 nm, preferably 280 to Absorb 350 nm. These are particularly suitable if they are in the temperature range  are thermally stable from 260 to 300 ° C, d. H. do not decompose and not to Outgassing. Suitable UV stabilizers as light stabilizers are, for example 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, nickel-organic 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 are preferred.

The UV stabilizer or stabilizers are preferably contained in the cover layer (s). At If required, the core layer can also be equipped with a UV stabilizer.

The film according to the invention contains a crystallizable as the main component Thermoplastics. Suitable crystallizable or partially crystalline thermoplastics are for example polyethylene terephthalate (PET), polybutylene terephthalate, Polyethylene naphthalate or mixtures thereof, with polyethylene terephthalate being preferred is.

According to the invention, crystallizable thermoplastics are understood to be 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. The The film can also be coated with various copolyesters or adhesion promoters. she contains the antiblocking and the usual for foils for economical production Lubricant.

The film according to the invention contains at least one UV stabilizer Light stabilizers, 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 3.0% by weight %, based on the weight of the layer of crystallizable thermoplastic.

Furthermore, the film according to the invention contains at least one in the thermoplastic soluble optical brightener, the concentration of the brightener preferably in Range from 0.001 to 0.2% by weight, in particular from 0.002 to 0.1% by weight, based on the weight of the thermoplastic.

The optical brighteners used are able to block UV rays Absorb wavelength range from approx. 360 to 380 nm and as a longer-wave, emit visible blue-violet light again. Suitable optical brighteners are bis- benzoxazoles, phenylcoumarins and bis-sterylbiphenyls, preferably phenylcoumarin, particularly preferred triazine-phenylcoumarin (Tinopal®, Ciba-Geigy, Basel).

Furthermore, the film according to the invention contains a thermoplastic soluble dye, the concentration of the soluble dye preferably in the range of 0.1% by weight and 20.0% by weight, in particular in the range from 0.5 to 10.0% by weight, based on the Weight of the crystallizable thermoplastic.

Soluble dye is understood to mean substances that are molecularly dissolved in the polymer are (DIN 55949).

The color change of the film is based on the wavelength-dependent absorption and / or scattering of light. Dyes can only absorb light, but not scatter, because a certain particle size is the physical requirement for a Scattering is.  

Coloring with dye is a solution process. As a result In this solution process, the dye is molecular, for example, in the Crystallizable thermoplastics solved. Such coloring is considered transparent, translucent, translucent or opal.

Of the various classes of soluble dyes, the fat and aromatic soluble dyes are particularly preferred. These are, for example, azo and anthraquinone dyes. They are suitable for. B. for coloring PET, because the migration of the dye is limited due to the high glass transition temperatures of PET.
(Literature J. Koerner: Soluble dyes in the plastics industry in "VDI-Gesellschaft Kunststofftechnik:": Coloring plastics, VDI-Verlag, Düsseldorf 1975).

Suitable soluble dyes are, for example: C.I. Solvent Yellow 93 (a Pyrazolone derivative), C.I. Solvent yellow 16 (a fat-soluble azo dye), fluorolegreen gold (a fluorescent polycyclic dye), C.I. Solvent red 1 (an azo dye), azo dyes such as Thermoplastrot BS, Sudanrot BB, C.I. Solventrot 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.

Mixtures of two or more of these soluble dyes are also suitable.

In a very particularly preferred embodiment, 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) oxy-phenol of the formula

or 0.01% to 5.0% by weight of 2,2-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) - phenol of the formula

In a preferred embodiment, mixtures of these two UV Stabilizers or mixtures of at least one of these two UV stabilizers can be used with other UV stabilizers, the total concentration Light stabilizers preferably between 0.01 wt .-% and 5.0 wt .-%, based on the Weight of crystallizable polyethylene terephthalate.

It is completely surprising that the use of the above UV stabilizers in Connection with an optical brightener and the soluble dye in foils to the  leads to the desired result.

However, if other commercially available UV stabilizers are used 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 lack of thermal stability and at Temperatures decomposed or outgassed between 200 ° C and 240 ° C,
• - Large amounts (approx. 10 to 15% by weight) of UV stabilizer are incorporated so that the UV light is absorbed and the film is not damaged.

At these high concentrations, the film has a yellow color even after production Appearance, with yellowness differences (YID) around the 25th affects the mechanical properties negatively.

It was therefore more than surprising that excellent UV protection was achieved even with low concentrations of the UV stabilizer and optical brightener used in accordance with the invention and with the use of the soluble dye. It was very surprising that this excellent UV protection

• - The yellowness index of the film compared to a non-stabilized film in the frame the measuring accuracy does not change;
• - No outgassing, no nozzle deposits, which made the film a has excellent optics and an excellent profile and an excellent Flatness has
• - the UV-stabilized film is characterized by excellent running safety, making them process safe and stable on high speed film lines up to Speeds of 120 m / min can be produced reliably.

This means that the film is also economically viable.

It was also very surprising that the film had the aggressive, short-wave light in the Wavelength range up to 380 nm, preferably absorbed up to 360 nm, d. H. Not lets through.

Furthermore, it is very surprising that the regrind can also be used again without to negatively influence the color value of the film.

At least one surface layer can be coated with ethylene-vinyl alcohol copolymer, ethyl Vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride coated or vapor-coated, ethylene-vinyl alcohol copolymer is preferred. In a preferred one The embodiment is the. Thickness of the barrier layer in the range from 10 nm to 8000 nm, especially 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 h.bar). 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 extrusion, preferably in an amount of 1.0 to 10.0% 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 5.0%, preferably less than 3.5%, in particular even is less than 2.0% by weight or goes to zero.

The barrier layer based on ethylene-vinyl alcohol copolymers can be used for reduction the crystallinity contain monomeric, oligomeric or polymeric substances. The each added amount depends on the tolerance, d. H. incorporation and Miscibility with the main component and the influence on the Oxygen permeability.

Examples of 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. As polyvinyl alcohol or polyamides, mixtures of ethylene-vinyl alcohol copolymers and 10 to 50% by weight of 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 can further Adhesion to the adjacent layers promoting additives in the form of monomeric contain oligomeric or polymeric substances.

For the purposes of the present invention, amorphous films are such films understood that, although the crystallizable thermoplastic has a crystallinity of 20% to 65%, preferably from 30% to 50%, are not crystalline. Not crystalline, i.e. H. in the essentially amorphous, means that the degree of crystallinity is generally below 5%, is preferably below 2%. Such a film is essentially unoriented Condition before.  

The surface gloss of the unstructured side, measured in accordance with DIN 67530 (measuring angle 20 °), is greater than 120, preferably greater than 140, the light transmission L ^* , measured in accordance with ASTM D 1003, is more than 82%, preferably more than 84% and that 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 in combination with the one-sided structure.

The standard viscosity SV (DCE) of the thermoplastic, measured in dichloroacetic acid after DIN 53728 is 600 to 1000, preferably 700 to 900.

The film according to the invention, the at least one UV stabilizer, an optical Brightener and contains a dye can be both single-layer and multi-layer his.

In the multilayer embodiment, the film is composed of at least one core layer and at least one top layer, in particular a three-layer A-B A or A-B-C structure is preferred. In the multilayered case, one of the two Top layers, which can be corona-treated, with ethylene-vinyl alcohol copolymer, Vaporized ethyl vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride. The other The top layer is then structured. The cover layers are with the usual for foils Antiblocking agents and / or lubricants formulated.

For this embodiment it is essential that the thermoplastic of the core layer is a Standard viscosity similar to that of the thermoplastic of the top layer (s) attached to the Core layer adjoins (adjoin).

In a special embodiment, the cover layers can also consist of one  Polyethylene naphthalate homopolymers or from a polyethylene terephthalate Polyethylene naphthalate copolymers or compound exist.

In this embodiment, the thermoplastics of the cover layers also have one Standard viscosity similar to the thermoplastic of the core layer.

In the multi-layer embodiment is the UV stabilizer, the optical brightener and the dye preferably contained in the cover layer or layers. However, after Also needs the core layer with UV stabilizers, optical brighteners and dye be equipped.

In contrast to the single-layer embodiment, the concentration of the or the stabilizers and the optical brightener on the weight of the thermoplastics in the equipped shift.

Surprisingly, weathering tests according to the test specification ISO 4892 have the Atlas CI65 Weather Ometer showed that it was in the case of a three layer film it is quite sufficient to cover the 0.5 µm to 10 µm thick top layers with UV Equip stabilizers to achieve improved UV stability.

As a result, they are manufactured using the known coextrusion technology multilayer films according to the invention compared to the completely UV Stabilized monofilms economically interesting, since significantly less UV stabilizer too comparable UV stability is required.

The film can also be coated on at least one side with a scratch-resistant coating Copolyester or be provided with an adhesion promoter.  

Weathering tests have shown that the films according to the invention themselves Weathering tests after an estimated 5 to 7 years of outdoor use in general no yellowing or color change towards yellow, no embrittlement, none Loss of gloss on the surface and no cracking on the surface.

When the film was manufactured, it was found that it was produced reliably leaves. Furthermore, no outgassing of the UV stabilizer in the Production process found, which is essential to the invention, since most UV Stabilizers at extrusion temperatures above 260 ° C annoying, unpleasant Show outgassing and are therefore unsuitable.

Furthermore, the film is without environmental pollution and without noticeable loss of mechanical properties can be easily recycled, making them suitable for use as a short-lived item.

Since the film also contains short-wave UV light in the wavelength range from 260 nm to 380 nm, Absorbed especially up to 360 nm, the film offers a barrier against the aggressive short-wave light, the z. B. causes the dreaded fat oxidation in food. Consequently, the film according to the invention is extremely suitable as a packaging film for sensitive goods on packaging machines in the vertical and horizontal area (vFFs and hFFs machines).

The effective structure of at least one surface is achieved by using a chrome-plated and textured take-off roller on which the melt film passes through Cooling below the glass temperature receives the desired structure. Suitable structures are, for example, three-dimensional, symmetrical structures, asymmetrical three-dimensional knobs, waves, tips and depressions, leather patterns and others,  patterns known to those skilled in the art.

If the film is smoothed, i. H. is manufactured using calender technology of I, F and L calenders, the take-off roll is the structuring roll. Using S-calenders structure the counter-rotating roll adjacent to the take-off roll.

If both surfaces are to be structured, both the take-off roller and the downstream roller structured.

The take-off roller is a metallic roller, the exact cylindrical surface of which is about the entire width is provided with a completely uniform structure. On the Roll is the negative image of the structure desired in the film.

The diameter of the roller can vary within wide limits depending on the thickness of the film. The diameter is preferably between 0.5 m and 4 m, in particular between 1 m and 3 m.

The structuring not only has aesthetic advantages. Minor surface defects that can occur during the manufacturing process are covered. The surface of a grained or textured film is less sensitive to fingerprints or Scratch.

Furthermore, the film according to the invention is suitable as a composite film, the Composite of the film - optionally with ethylene-vinyl alcohol copolymer, ethyl Vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride coating - and a second Foil exists. This second film can e.g. B. also a UV-stable thermoplastic film, a Standard thermoplastic film or a polyolefin film.  

The second film can have one or more layers and can be like the first film amorphous, d. H. be disoriented and can have at least one sealing layer. The second Film can be with or without adhesive with the first barrier film according to the invention be connected.

The thickness of this second film is preferably in the range from 30 to 500 μm.

The composite film is generally obtained by lamination or lamination of the two foils with or without an intermediate adhesive layer, by this between rollers heated to 30 ° C to 80 ° C.

The two films can, for example, with or without an adhesive layer through one Laminating processes are interconnected. But it is also, for example possible, the second, transparent colored layer on the first, coated layer by in-line coating (melt extrusion onto an existing layer).

If 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 have proven to be particularly useful 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 made of synthetic rubbers.  

Suitable solvents for the adhesive are e.g. B. hydrocarbons such as ligroin and Toluene, esters such as ethyl acetate, or ketones such as acetone and methyl ethyl ketone.

The production of the film according to the invention can, for example, according to known Extrusion processes take place in an extrusion line.

The light stabilizer, the optical brightener and the soluble dye can already be used in the Thermoplastic raw material manufacturers metered in or in the film production in the extruder be dosed.

It is preferred to add the light stabilizer, the optical brightener and Dye via masterbatch technology. Here, the additives are first in fully dispersed on a solid carrier material. The carrier materials come Thermoplastic itself, e.g. B. the polyethylene terephthalate or other polymers with the thermoplastic are sufficiently compatible, in question. After adding to the Thermoplastics for film production melt the components of the masterbatch during the extrusion and are thus dissolved in the thermoplastic.

The 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 wt .-%, preferably 0.1 to 2.0 wt .-% and
soluble dye 1.0 to 20.0% by weight, preferably 1.5 to 15.0% by weight,
the sum of the components always being 100% by weight.

It is important with the masterbatch technology that the grain size and the bulk weight of the masterbatch is similar to the grain size and bulk density of the thermoplastic,  so that a homogeneous distribution and thus a homogeneous UV stabilization take place can.

The films according to the invention can be extruded from one Thermoplastic raw material with possibly further raw materials, the UV stabilizer, the optical brightener, the dye and / or other conventional additives in the usual amount from 0.1 to a maximum of 10.0% by weight both as monofilms and as multilayer optionally coextruded films with the same or different designs Surfaces are produced, one surface being pigmented, for example, and the other surface contains no pigment. One or both surfaces can also be used the film by known methods with a conventional functional coating be provided.

The polymers or raw material mixtures are an extruder or multi-layer Films fed to several extruders. Any foreign objects or Contaminants can be filtered out of the polymer melt before extrusion. The Melt (s) are then in a mono nozzle or in a multi-layer case in one Multi-layer nozzle formed into flat melt films and in the multi-layer case layered on top of each other. Then the monofilm or multilayer film is included With the help of a structured take-off roller and, if necessary, additional rollers can also be structured, peeled off and solidified as an amorphous film. Subsequently the cooled, amorphous, structured film is 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 up to 70 nm, in particular 30 to 50 nm. The coating is preferred in-line upset, d. H. during the film manufacturing process, expediently after the  Solidification. The application of the "reverse gravure-roll coating" is particularly preferred. Process in which the coatings are extremely homogeneous in the mentioned Have layer thicknesses applied. The coatings are preferred as a solution, Suspension or dispersion applied, in particular as an aqueous solution, Suspensions or dispersions. The coatings mentioned give the Foil surface an additional function, for example, is the foil sealable, printable, metallizable, sterilizable, antistatic or improve e.g. B. the Aroma barrier or allow liability for materials that are otherwise not on the Film surface would adhere (e.g. photographic emulsion).

Examples of substances / compositions that provide additional functionality:
Acrylates such as z. B. are described in WO 94/13 476, ethyl vinyl alcohols, PVDC, water glass (Na ₂ SiO ₄ ), hydrophilic polyesters (5-sodium sulfoisophthalic acid-containing PET / IPA polyesters as described, for example, in EP-A-0 144 878, US-A-4,252,885 or EP-A-0 296 620, vinyl acetates as described, for example, in WO 94/13 481, polyvinyl acetate, polyurethanes, alkali metal or alkaline earth metal salts of C ₁₀ -C ₁₈ fatty acid, Butadiene copolymers with acrylonitrile or methyl methacrylate, methacrylic acid, acrylic acid or their esters.

The substances / compositions mentioned are in the form of a dilute solution, emulsion or Dispersion, preferably as an aqueous solution, emulsion or dispersion onto or both film surfaces applied and then the solvent evaporated. If the coatings are applied in-line, one is usually sufficient Heat treatment after solidification to volatilize the solvent and dry the coating. The dried coatings then have that desired layer thicknesses mentioned.  

Furthermore, the films can be coated, preferably in an off-line process, with metals such as aluminum or ceramic materials such as SiO _x or Al _x O _y . This improves their gas barrier properties in particular.

Due to the surprising combination of excellent properties, the Film according to the invention excellent for a variety of different applications, for example for interior cladding, for exhibition stand construction and exhibition items, as displays, for signs, for protective glazing of machines and vehicles, in Lighting sector, in shop and shelf construction, as promotional items, laminating medium, for Thermal applications of all kinds, as packaging film for sensitive and effective advertising Products.

Due to the good UV stability, 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.

In the following exemplary embodiments, the individual are measured Properties according to the following standards or processes.

Measurement methods Surface gloss

The surface gloss is measured at a measuring angle of 20 ° according to DIN 67530.

Light transmission

Under the light transmission is the ratio of the total transmitted light to the to understand the amount of incident light.

The light transmission is done with the measuring device "®Hazegard plus" according to ASTM D 1003 measured.

Cloudiness

Haze is the percentage of the transmitted light, that of the incident light The light beam deviates by more than 2.5 ° on average. The image sharpness is at an angle determined less than 2.5 °.

The haze is measured using the "Hazegard plus" measuring device in accordance with ASTM D 1003.

Surface defects

The surface defects are determined visually.

SV (DCE), IV (DCE)

The standard viscosity SV (DCE) is based on DIN 53726 in dichloroacetic acid measured.

The intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV)

IV (DCE) = 6.67. 10 ^-4 SV (DCE) + 0.118

Weathering, UV stability

The UV stability is tested according to the test specification ISO 4892 as follows
Test device: Atlas Ci 65 Weather Ometer
Test conditions: ISO 4892, ie artificial weathering
Irradiation time: 1000 hours on the non-vaporized side
Irradiation: 0.5 W / m ² , 340 nm
Temperature: 63 ° C
Relative humidity: 50%
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

The yellowness index (YID) is the deviation from the colorlessness in the "yellow" direction and will measured according to DIN 6167. Yellowness indexes (YID) of <5 are not visually visible.

Examples

The following examples and comparative examples are each transparently colored, one-sided structured foils of different thickness, which on the extrusion line described are produced.

All foils were tested for 1000 hours with the Atlas Ci according to the test specification ISO 4892 65 Weather Ometer from Atlas weathered and then regarding discoloration, the surface defects, the turbidity and the gloss checked.

example 1

It becomes a 150 µm thick, red transparent colored, one-sided structured film  produced, the main component being polyethylene terephthalate, 0.2% by weight ®Sylobloc, 1.0% by weight the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol (®Tinuvin 1577 from Ciba-Geigy), 0.002% by weight triazine-phenylcoumarin (®Tinopal der Ciba-Geigy) and 1.5% by weight of the soluble dye C.I. Solvent red 138, a Anthraquinone derivative from BASF AG (®Thermoplastrot G) contains.

Tinuvin 1577 has a melting point of 149 ° C and is thermally stable up to approx. 330 ° C.

For the purpose of homogeneous distribution, 0.2% by weight of Sylobloc, 0.002% by weight of Tinopal, 1.5% by weight C.I. Solventrot 138 and 1.0 wt .-% of the UV stabilizer in the Polyethylene terephthalate incorporated.

The polyethylene terephthalate from which the transparent colored film is made has a standard viscosity SV (DCE) of 810, which indicates an intrinsic viscosity IV (DCE) of 0.658 dl / g.

The amorphous, one-sided structured, transparent colored, UV-stabilized PET film has the following property profile:
Thickness: 150 µm
Surface gloss 1st side (unstructured side, measuring angle 20 °): 155
Light transmission (420-800 nm): 89%
Turbidity: 4.0%
Surface defects per m ² : none
Yellowness index (YID): 3.1
Coloring: homogeneous, red transparent
Absorption of UV light: all wavelengths <380 nm
Crystallinity: 0%
Structure: knobbed structure, homogeneous over length and width

Example 2

Analogously to Example 1, a transparently colored film is produced, the UV Stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxyphenol (Tinuvin 1577), the optical brighteners Tinopal and the dye C.I. Solvent red 138 in the form of a Masterbatches is metered. The masterbatch (100% by weight) consists of 5% by weight % Tinuvin 1577 as UV active ingredient, 0.02% by weight of the optical brightener Tinopal, 15.0% by weight of C.I. Solventrot 138 and the polyethylene terephthalate from example 1 together.

Before the extrusion, 90% by weight of the polyethylene terephthalate from Example 1 is mixed with 10% by weight. of the masterbatch dried at 170 C for 5 hours. The extrusion and Foil production takes place analogously to example 1.

The manufactured, transparently colored, one-sided structured, UV-stable PET film has the following property profile:
Thickness: 150 µm
Surface gloss 1st side (unstructured side, measuring angle 20 °): 160
Light transmission (420-800 nm): 91%
Turbidity: 3.8%
Surface defects (specks, orange peel, blisters, etc.): none
Yellowness index (YID): 3.4
Coloring: homogeneous, red transparent
Absorption of UV light: all wavelengths <380 nm
Crystallinity: 0%
Structure: knobbed structure, homogeneous over length and width

Example 3

Analogously to example 2, a transparently colored, 350 μm thick film is produced. The amorphous PET film produced has the following property profile:
Thickness: 350 µm
Surface gloss 1st side (unstructured side, measuring angle 20 °): 149
Light transmission (420-800 nm): 85.1%
Turbidity: 5.1%
Surface defects per m ² (specks, orange peel, blisters, etc.): none
Yellowness index (YID): 4.5
Coloring: homogeneous, red transparent
Absorption of UV light: all wavelengths <390 nm
Crystallinity: 0%
Structure: knobbed structure, homogeneous over length and width

Example 4

According to the coextrusion technology, a 150 µm thick, multi-layer PET film is used the order of layers A-B-A, where B is the core layer and A the cover layers represent. The core layer B is 146 microns thick and the two outer layers, which  covering the core layer are 2 µm thick.

The polyethylene terephthalate used for the core layer B is identical to that of Example 2, but does not contain a Sylobloc. The polyethylene terephthalate of the outer layers A is identical to the polyethylene terephthalate from Example 2, i.e. H. the top layer raw material is equipped with 0.2% by weight of Sylobloc.

Analogously to Example 2, the 5.0% by weight Tinuvin 1577, 0.02% by weight Tinopal and 15.0% by weight % C.I. Solventrot 138 masterbatch included, but only the 2 µm thick cover layers 20% by weight of the masterbatch using masterbatch technology be added.

The transparently colored, multilayer PET film that is UV-stabilized in the outer layers has the following property profile:
Layer structure: ABA
Total thickness: 150 µm
Surface gloss 1st side (unstructured side, measuring angle 20 °): 164
Light transmission: 92.2%
Turbidity: 2.2%
Surface defects (specks, orange peel, blisters, etc.): none
Yellowness index (YID): 2.9
Coloring: homogeneous, red transparent
Absorption of UV light: all wavelengths <380 nm
Crystallinity: 0%
Structure: knobbed structure, homogeneous over length and width

Example 5

Example 4 is repeated. A cover layer A is coated with ethyl vinyl alcohol, the thickness of the coating being 1000 nm.

The manufactured, amorphous, structured, transparently colored, UV-stabilized, multilayer barrier film has the following property profile:
Total thickness: 150 µm
Surface gloss 1st side (coated, unstructured side, measuring angle 20 °): 135
Light transmission: 85%
Turbidity: 5.1%
Surface defects (specks, orange peel, blisters, etc.): none
Coloring: homogeneous, red transparent
Absorption of UV light: all wavelengths <380 nm
Crystallinity: 0%
Structure: knobbed structure, homogeneous over length and width
Oxygen barrier: <5 cm ³ / (m ^2. 24 h.bar) at 23 ° C

The examples according to the invention show that the optical properties of the films meet the high requirements, while UV stability is essential is increased. The films from Examples 1 to 5 absorb the UV light in the Wavelength range up to 380 or 360 nm completely and show after 1000 hours Weathering with the Atlas CI 65 Weather Ometer no embrittlement, no noticeable  Loss of gloss and no change in the transparent coloring towards yellow.

The film from Examples 1 to 5 show an aesthetic, advertising-effective appearance. The textured surface is insensitive to fingerprints and little sensitive to scratches.

Comparative Example 1

Analogously to Example 1, a 150 µm thick PET monofilm is produced. In contrast to Example 1 contains no UV stabilizer and no optical brightener. she will made with a standard polished chrome roller with no structure.

The unstabilized, unstructured film produced has the following property profile:
Thickness: 150 µm
Surface gloss 1st side: 160
(Measuring angle 20 °) 2nd side: 155
Light transmission: 89%
Turbidity: 4.6%
Surface defects (specks, orange peel, blisters, etc.): none
Yellow number (YID): 2.7
Coloring: homogeneous, colored red
Structure: none

The film allows the short-wave radiation to pass through from 280 nm.

After weathering a page with Atlas CI 65 Weather Ometer for 1000 hours, the Film cracks and embrittlement on this surface. A precise one  Property profile - especially the mechanical properties - can therefore not can be measured more. The film also shows a visually visible yellowing (YID) <8.

The film is not very effective in advertising. Every fingerprint is visible. At least Clean or in case of mechanical contact with yourself or other objects the film looks scratched and used.

Claims (12)

1. Amorphous, at least one-sided structured, transparent colored, UV light absorbing film with a thickness in the range of 30 to 1000 microns, which contains a crystallizable thermoplastic as the main component, characterized in that it additionally has at least one thermoplastic soluble UV absorber, at least contains an optical brightener and at least one soluble dye. 2. Film according to claim 1, characterized in that the crystallized Thermoplastic a polyethylene terephthalate, polybutylene terephthalate, Polyethylene naphthalate or mixtures thereof, preferably polyethylene terephthalate, is. 3. Film according to claim 1 or 2, characterized in that the concentration of UV absorbers in the range from 0.01% by weight to 5.0% by weight, preferably 0.1% by weight % to 3 wt .-%, the concentration of the optical brightener preferably in Range from 0.001 wt% to 0.2 wt%, and the concentration of the soluble Dye in the range of 0.1 wt .-% to 20.0 wt .-%, based on the weight of the crystallizable thermoplastic. 4. Film according to one or more of claims 1 to 3, characterized in that that the UV absorbers as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organic nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, Resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, steric hindered amines and triazines, preferably 2-hydroxybenzotriazoles and triazines  and in particular 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol or 2,2'-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3, -tetramethylbutyl) phenol available. 5. Film according to one or more of claims 1 to 4, characterized in that the optical brighteners as bis-benzoxazoles, phenylcoumarins and bis- sterylbiphenyls, preferably phenylcoumarin, particularly preferably triazine phenylcoumarin are present. 6. Film according to one or more of claims 1 to 5, characterized in that as dyes fat and aromatic soluble azo, benzopyran and Anthraquinone dyes, especially C.I. Solvent Yellow 93, C.I. Solvent yellow 16, Fluorol Green Gold, C.I. Solvent Red 1, Thermoplastic Red BS, Sudan Red BB, C.I. Solvent red 138, fluorol red GK and fluorol orange GK, C.I. Solvent blue 35, C.I. Solvent blue 15: 1 are included. 7. Film according to one or more of claims 1 to 6, characterized in that that the regenerate is used. 8. Method for producing an amorphous, at least one-sided structured, transparent colored, UV light absorbing film from one crystallizable thermoplastics with a thickness in the range from 30 µm to 1000 µm, characterized in that a crystallizable thermoplastic with each at least one UV absorber soluble in the thermoplastic, at least one optical brightener and at least one soluble dye after one Extrusion process formed into a film using a structured take-off roller becomes.   9. The method according to claim 8, characterized in that the UV absorber, the optical brighteners and the soluble dye at the thermoplastic raw material manufacturer or be metered into the extruder during film production, the addition is preferred over masterbatch technology. 10. The method according to claim 8 or 9, characterized in that the master batch in addition to the thermoplastic, 2.0 to 50.0% by weight, preferably 5.0 to 30.0% by weight UV absorber, 0.05 to 5.0 wt .-%, preferably 0.1 to 2.0 wt .-% optical Brightener and 1.0 to 20.0% by weight, preferably 1.5 to 15.0% by weight, more soluble Contains dye, the sum of the components always being 100% by weight. 11. Use of the film according to one or more of claims 1 to 7 for Indoor and outdoor use. 12. Use according to claim 11 in the interior for interior paneling, for Exhibition stand construction and exhibition articles, as displays, for signs, for protective glazing from Machines and vehicles, in the lighting sector, in shop and shelf construction, as Promotional item, lamination medium, for thermal applications of all kinds, as Packaging film for sensitive and effective products and in Outdoor area for greenhouses, in the advertising sector, canopies, Exterior cladding, covers in the construction sector and illuminated advertising profiles.