OA10540A - Amorphous plate pigmented from a crystallizable thermoplastic - Google Patents

Abstract

The invention relates to an amorphous, dyed plate with a thickness in the 1 to 20 mm range, in which the main component is a crystallisable thermoplastic and at least one organic and/or inorganic dye, a process for its production and its use. The plate of the invention may also contain a u/v stabiliser.

Description

The invention relates to an amorphous plate pigmented in a crystallizable thermoplastic, the thickness of which is in the range of 1 to 20 mm. The plate contains at least one organic and / or inorganic pigment as a colorant. It is characterized by homogeneous optical characteristics and very good mechanical characteristics. The invention further relates to a method of preparing this plate and its use. Pigmented amorphous plates having a thickness of between 1 and 20 mm are well known. These two-dimensional products consist of amorphous, non-crystallizable thermoplastics. Typical examples of such thermoplastics that can be formed into plates are, for example, polyvinyl chloride (PVC), polycarbonate (PC) and poly (methyl methacrylate) (ΡΜΜΆ). These semi-finished products are prepared on so-called extrusion trains (see Polymer Werkstoffe, Vol II, Technology 1, Georg Thieme Verlag, Stuttgart, 1984). Lafusion of the pulverulent or granulated raw material is carried out in an extruder. The amorphous thermoplastics can be easily converted afterextrusion, as the viscosity increases continuously with decreasing temperature, using calenders or other finishing tools. Amorphous thermoplastics then have a satisfactory sturdiness after processing, i.e., high viscosity / to "stand up alone" in the sizing tool. But they are flexible enough to be profiled by the tool. The melt viscosity and stiffness of the amorphous thermoplastics are so high in the sizing tool that the semi-finished product does not sag until it is cooled in the sizing tool. In the case of materials that decompose easily, such as In the extrusion stage 2 C 1 O 5 40, special process aids are required in the extrusion stage, such as, for example, anti-decomposition stabilizers and lubricants against the inner strength and, as a result, to prevent uncontrollable heating. External lubricants are needed to prevent snagging on walls and cylinders.

In the implementation of PMMA, for example, to eliminate moisture, a degassing extruder is used.

In the preparation of thermoplastic thermoplastic plates, additives are needed, some of which are expensive, which partly migrate and can cause production problems following evaporation as well as superficial deposits on the semi-finished product. The PVC plates can only be recycled with difficulty or with the aid of special neutralization or electrolysis processes. Similarly, PC and PMMA plates can only be recycled with difficulty and only at the cost of extreme loss or degradation of the mechanical characteristics. In addition to these disadvantages, the PMMA plates also have extremely low toughness toughness and burst upon breaking or mechanical stressing. In addition, the PMMA plates are easily flammable, so that they can not be used, for example, for indoor wall cladding and for the construction of exhibition halls.

In addition, PMMA and PC plates can not be cold formed. In cold forming, PMMA plates break into dangerous chips. In cold profiling, PCform plates crack filiform cracks and white rupture of plates.

EP-A-0 471 528 discloses a method for profiling an object from a poly (ethylene terephthalate) (PET) plate. Intrinsic lappiness of the PET used is in the range of 0.5 to 1.2. Both sides of the PET plate are heat-treated in a nozzle tool in a range of temperatures between the glass transition temperature and the melting temperature. The PET molded plate is extracted from the mold when the degree of crystallization of the shaped PET plate is between 25% and 50%. The PET plates disclosed in DE-A-0 471 528 are from 1 to 10 mm thick. Because the stamped section prepared from this plate is partially crystalline, so it is not transparent and the surface characteristics of the profile are determined by the stamping process, the temperatures and shapes given in this process. the optical properties (e.g., brightness, turbidity, and light transmission) of the PET plates employed are not essential. In general, the optical properties of these plates are poor and need to be improved. The plates contain neither dye nor organic or inorganic pigment.

US-A-3,496,143 discloses deep-vacuum deep drawing of a 3 mm thick PET plate, whose crystallinity must be between 5% and 25%. The crystallinity of the profiléembouti is greater than 25%. These nonplus PET plates do not meet any requirements regarding optical properties. Since the crystallinity of the plates used is already between 5% and 25%, these plates are cloudy and opaque. The plates contain no dye and no organic or inorganic pigment.

Since the aforementioned plates do not contain a photoprotector, they are suitable for outdoor applications only under certain conditions.

Moreover, until now, amorphous sheets made of thermoplastics that can be crystallized as the main component, with a thickness of 1 mm or more, or only plates having poor optical and mechanical properties, have not been able to be obtained.

The object of the present invention is to prepare a pigmented amorphous plate, having a thickness of 1 to 20 mm, which has good both mechanical and optical properties.

Good optical properties include, for example, low light transmission as well as high surface gloss.

Good mechanical properties include, among other things, high resilience and high resistance to fracture.

In addition, the plate according to the invention must be recyclable, more particularly without loss of mechanical characteristics, and hardly inflammable, so that it can be used for example for the coating of interior walls and in the construction of exhibition halls.

This problem is solved by means of a pigmented gold plate having a thickness in the range of 1 to 20 mm having as a main component a crystallizable thermoplastic and at least one organic and / or inorganic pigment as a colorant.

In addition, the present invention relates to a method for the preparation of this plate with the features of claim 23. Preferred embodiments of this method are explained in subclaims 24 to 29.

The dye concentration is preferably in the range of 0.5 to 30% by weight, based on the weight of the crystallizable thermoplastic. 5 ¢ 10540

With regard to the dyestuffs, DIN 55944 is distinguished from dyestuffs of pigments. The pigments, under the respective operating conditions, are practically insoluble in the polymers, whereas the dyestuffs are soluble (DIN 55949). The coloring effect of the pigments is caused by the particles themselves. The concept of depigment is generally related to a particle size of 0.01 μm to 1.0 μm. According to DIN 53206, a distinction is made in the definition of pigment particles between primary particles, aggregates and agglomerates.

The primary particles as formed generally in the preparation possess, due to their extraordinarily small particle size, a pronounced tendency to association. Thus, primary particles are formed from the two-dimensional association of aggregates, which have a smaller surface area than that corresponding to the sum of the surface area of their primary particles. By superimposing primary particles on each other and / or or aggregates on the corners and edges, agglomerates are formed, the total surfaces of which differ only slightly from the sum of the individual surfaces. When talking about the size of the pigment particles without more detailed information, refer to aggregates, which are found mainly after pigmentation.

In the powdery pigments, the aggregates 30 are permanently associated with agglomerates which must be distributed during the pigmentation, wet with the synthetic material and distribute homogeneously. These operations are called "scatter", which occur simultaneously. On the other hand, in pigmentation with dyes, it is a dissolution process because the result is in dissolved molecular form of the dye. 6 010540

In contrast to inorganic pigments, organic pigments are not completely insoluble, especially in the case of pigments having a simple structure with low molecular weight.

The dyes are extensively described by their chemical structure. However, the pigments having at each time an identical chemical composition can be prepared and present under different crystalline modifications. A typical example is the white pigment, titanium dioxide, which may be rutile and atanase.

In pigments, the characteristics of use by coating can be improved, that is to say, by post-treatment of the surface of the pigment particles with organic or inorganic agents. This improvement lies in particular in an ease of dispersion and in increased stability to light, weather and chemicals. Typical coating agents are, for example, fatty acids, fatty acid amides, siloxanes and aluminum oxides.

Suitable inorganic pigments are, for example, white pigments, titanium dioxide, zinc sulphide and tin sulphide, which can be coated with organic and / or inorganic substances.

The titanium dioxide particles may precipitate atanase or rutile, preferably in the majority of rutile, which, with respect to the atanase, has a better hiding power. In the preferred embodiment, the titanium dioxide particles are at least 95% rutile. They can be prepared according to a conventional process, for example by the chloride or sulfate method. The average particle size is relatively small and is preferably in the range of 0.10 to 0.30 μm. 7 0 J 0540

By titanium dioxide of the type described, it does not form vacuoles in the polymer matrix during the preparation of the plate.

The titanium dioxide particles may be coated with inorganic oxides, such as are usually used as a coating of the white pigment TiO 2 in papers or paints to improve the light fastness. It is known that TiO2 is photoactive. During the action of UV rays, free radicals are formed on the surface of the particles. These free radicals can migrate to the constituents of the paints, leading to degradation reactions and clouding. Particularly suitable oxides include aluminum, silicon, zinc or magnesium oxides or mixtures of two or more of these compounds. The TiO 2 particles provided with a coating of several of these compounds are described, for example, in EP-A-0 044 515 and EP-A-0 078 633. In addition, the coating may contain organic compounds withpolar groups and non-polar. The organic compounds must be sufficiently heat stable when extrusion is prepared from the molten polymeric material. Polar groups are, for example, -OH, -OR, -COOX, (X = R, H or Na, R = alkyl with 1 to 34 carbon atoms). Preferred organic compounds are alkanols and fatty acids with 8 to 30 carbon atoms in the alkyl group, especially fatty acids and n-alkanolsprimary with 12 to 24 carbon atoms, as well as polydiorganosiloxanes and / or polyorganohydrogensiloxanes, such as for example polydimethylsiloxane and polymethylhydrogensiloxane. The coating of the titanium particles is usually composed of 1 to 12, more preferably 2 to 6 inorganic oxides and 0.5 to 3, more particularly 0.7 to 1.5 g of organic compound relative to 100 g. of titanium dioxide particles. The coating is applied to the particles in aqueous suspension. The inorganic oxides are precipitated from water-soluble compounds, for example alkali compounds, especially sodium aluminate, aluminum hydroxide, aluminum sulphate, aluminum nitrate, sodium silicate (soluble glass) or lasilice, in aqueous suspension.

Inorganic oxides, such as Al.sub.2 O.sub.3 and SiO.sub.2, also include hydroxides or their different dehydrationdegrees, such as, for example, oxides of hydrate without their exact composition and structure being known. From the TiO 2 pigment, after baking and grinding, the aqueous hydrated oxides, for example aluminum and / or desilicon, are precipitated, then the pigments are washed and dried. Thus, this precipitation can be carried out directly in a slurry, as obtained in the preparation process after cooking and grinding. The oxides and / or hydrated oxides of the respective metals are precipitated from the water-soluble metal salts in a known pH range, for example, for aluminum, the aqueous aluminum sulphate (pH <4) is used and the precipitate is oxidized. hydrated by addition of aqueous ammonia or sodium hydroxide solution in a pH range between 5 and 9, preferably between 7 and 8.5. If starting from a solution of water glass or alkali aluminate, the pH of the TiO2 suspension should be in a strongly alkaline range (pH greater than 8). Then precipitated by addition of mineral acid, such as sulfuric acid, in a pH range of 5 to 8. After precipitation of the metal oxides, the suspension is stirred for a further 15 minutes to about 2 hours, while the precipitated layers undergo aging. The coated product is separated from the aqueous dispersion and after washing is dried at elevated temperature, especially 70 to 110 ° C. 9 010540

Typical inorganic black pigments are modifications of carbon black, which may also be coated, carbon pigments which differ from carbon black pigments by a higher ash content and oxidized black pigments, such as black iron oxide and blends of carbon black. copper, dechrome, iron oxide (mixed phase pigments).

Suitable inorganic color pigments are oxidized color pigments, hydroxyl-containing pigments, sulfur pigments and chromates.

Examples of oxides-type colored pigments are iron red oxide, titanium dioxide-nickel oxide-antimony monoxide mixed phase pigments, titanium dioxide-chromium oxide, antimony oxide-pigments. mixed phase, mixtures of iron, zinc and titanium oxides, iron oxide chromium oxide, spinels of the cobalt-aluminum-titanium-nickel-zinc oxide system and phase pigments based on other metal oxides.

Typical pigments containing hydroxyl groups are, for example, iron-equivalent hydroxide oxides, such as FeOOH.

Examples of sulfur pigments are cadmium sulphide-lessenes, cadmium-zinc sulphide, sodium-aluminum silicate with sulfur as polysulfide in the crystal lattice.

Examples of chromates are chromate depletes, which may be in the form of monoclinic, rhombic and tetragonal crystalline forms.

All colored pigments can be presented as white pigments and uncoated black pigments that are coated with organic and / or inorganic substances.

In general, organic colored pigments are distributed into azo pigments and so-called non-azo pigments.

The characteristics of the azo pigments is the azo group (-N = N-). The azo pigments may be monoazo pigments, disazo pigments, disazo condensation pigments, colored acidazo salts and mixtures of azo pigments.

The amorphous, pigmented plate contains at least one inorganic / organic pigment. In special embodiments, the amorphous plate may also contain inorganic / organic pigment mixtures as well as soluble dyes. Soluble dye concentration is then preferably in the range of 0.001 to 20% by weight, preferably 0.01 to 20% by weight, particularly preferably in the range of 0.5 to 10% by weight, based on weight of the thermosetecrystallizable.

Among the soluble dyes, the soluble colors in the oil and in the aromatics are preferred. These are azo dyes and anthraquinone dyes.

Examples of suitable soluble dyes are: Solventgelb 93 - a pyrazolone derivative, Solventgelb 16 - a soluble azo dye in oils, Fluorogrüngold - a fluorescent polycyclic dye, Solventrot 1 - an azo dye, azo descolers such as red Thermoplast BS, red deSoudan BB, Solventrot 138 - an anthraquinone derivative, fluorescent benzopyran dyes, such as Fluorolrot GK and Fluorolorange GK, Solventblau 35 - anthraquinone colorant, Solventblau - a phthalocyanine dye and a large number of others.

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

The amorphous, pigmented plate contains, as a main component, a crystallizable thermoplastic. Crystallizable crystalline or crystallized thermoplastics, respectively, are, for example, poly (ethylene terephthalate), poly (terephthalate debutylene), cycloolefin polymers and cycloolefin copolymers. , preferring the poly (ethylene terephthalate).

Crystallizable thermoplastic is understood to mean, according to the invention, crystallizable homopolymers, crystallizable copolymers, crystallizable compounds, crystallizable recyclables and other crystallizable thermoplastic variants.

By amorphous plate is meant in the sense of the present invention such plates which, although crystallizable ushermoplastique used has a crystallinity of between 5% and 65%, preferably between 25% and 65%, are not crystalline. Noncrystalline, i.e. substantially amorphous, means that the degree of crystallinity is generally less than 5%, preferably less than 2%, and is more preferably 0%. The amorphous plate according to the invention is essentially undirected.

The standard viscosity (VS) (ADA) of the thermoplastics according to the invention measured in dichloroacetic acid (ADA) according to DIN 53728 is between 800 and 6000, preferably between 950 and 5000 and particularly preferably between 1000 and 4000.

The intrinsic viscosity VI (ADA) is calculated from the standard viscosity as follows: VI (ADA) = 6.67 · 10-4 VS (ADA) + 0.118

In a particularly preferred embodiment, the pigmented amorphous plate according to the invention contains poly (ethylene terephthalate) as the main component. 12 010540

Processes for the preparation of crystallizable thermoplastics are known to those skilled in the art.

In general, the poly (ethylene terephthalates) are prepared by melt polycondensation or by polycondensation in two stages, the first step being carried out up to an average molar mass corresponding to an intrinsic viscosity VI averaging from about 0.5 to 0 , 7 - in fusion, and the continuation of condensation being implemented in solid state. Polycondensation is generally carried out in the presence of known catalyst or polycondensation catalyst systems. In the solid state condensation, the PET flakes are heated under reduced pressure or under a protective atmosphere to a temperature in the range of 180 ° to 320 ° C., until the desired molar mass is reached.

The preparation of polyethylene terephthalate is described in detail by a large number of patents, for example JP-A-606139 717, DE-C-2 429 087, DE-A-27 07 491, A-23 19 089, DE-A-16 94 461, JP-63-41 528, JP-062-39 621, DE-A-41 17 825, DE-A-42 26 737, JP-60-141 715. DE-A-27 21 501 and US-A-5,296,586.

Poly (ethylene terephthalates) with particularly high molecular weight can be prepared by polycondensation of the dicarboxylic acid-diol precondensates (oligomers) at a high temperature in a liquid coolant in the presence of conventional polycondensation catalysts and optionally modifying agents. co-condensable, when the liquid coolant is inert and free of aromatic components and having a boiling point in the range of 200 to 320 ° C, the weight ratio of precondensate (oligomer) carboxylic acid-diol used liquid coolant is in 1 80 to 80:20 range and the polycondensation is carried out in the boiling reaction mixture in the presence of a dispersion stabilizer.

The surface gloss of the plate according to the invention, measured according to DIN 67530 (angle of incidence 20 °) is preferably greater than 90, preferably greater than 100 and the light transmission, measured according to ASTM-D 1003, is preferably less than 5%, particularly preferably less than 3%.

Furthermore, the plate according to the inventionprovides a homogeneous optics, deaf.

When measuring resilience to Charpy. dupoly (ethylene terephthalate) (measured according to ISO 179 / 1D), preferably, there is no disruptions on the plate. On the other hand, the resiliency with Izod (measured according to ISO 180 / 1A) of the plate is preferably in the range 2.0 to 8.0 kJ / m 2, particularly preferably in the range of 4.0 to 6.0 kJ / m2.

Polyethylene terephthalate polymer with a crystallinity melting point Tm of 220 ° C to 280 ° C, as measured by DSC (Differential Scanning Calorimetry) with a heating rate of 10 ° C / min, preferably 23 0 ° C at 27 ° C, with a crystallization temperature interval Tc of between 75 ° C and 280 ° C, preferably between 75 ° C and 260 ° C, a glass transition temperature Tgcomprise between 65 ° C and 90 ° C and a volumetric mass according to DIN 53479 from 1.30 to 1.45 g / cm3 and a crystallinity of from 5% to 65%, preferably from 25% to 65%, are preferred polymers as starting materials for plate preparation.

The bulk density, measured according to DIN 53466 is preferably between 0.75 kg / dm3 and 1.0 kg / dm3 and particularly preferably between 0.80 kg / dm3 and 0.90 kg / dm3. 14 010540

The polydispersity Mw / Mn of poly (terephthalateethylene) measured by gas chromatography is preferably between 1.5 and 6.0, preferably between 2.5 and 6.0, and particularly preferably between 3.0 and 5, 0.

In a particularly preferred embodiment, the plate according to the invention is provided with a UV stabilizer as a photoprotector.

The photoprotective concentration is preferably in the range of 0.01 to 5% by weight, based on the weight of the crystallizable thermoplastics.

Light, in particular the ultraviolet component of the sun rays, that is to say, in the wavelength range of 280 to 400 nm, induces in the thermoplastics degradation processes, which only cause changes in appearance. changes in color, respectively as a result of yellowing, but also negatively influence the physical and mechanical characteristics. The inhibition of these photoxoxidation degradation processes is of considerable technical and economic importance, since otherwise the possibilities of application of many thermoplastics would be substantially limited.

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

In the presence of oxygen, chain cleavages are mainly observed, but not de-crosslinking. Carbon monoxide, carbon dioxide and carboxylic acids represent photooxidation products whose quantity is preponderant. In addition to the direct photolysis of the ester groups, oxidation reactions which also cause the formation of carbon dioxide via the radical-peroxide have to be taken into consideration. The photooxidation of the poly (ethylene terephthalates) can lead to the hydroperoxides and their degradation products also by dissociation of the ester groups at the α position, as well as the chain dissociations associated with this process (H. Day, DM Wiles J. Appl., Polym Sci 16, 1972, p 203).

UV stabilizers, or UV absorbers, as photoprotectants, are chemical compounds, which may be involved in the physical and chemical processes of light-induced degradation. Carbon black and other pigments can induce partial photoprotection. However, substances are not suitable for plates as they cause a color change. For amorphous plates only organic and organometallic compounds are suitable, which do not cause color change or only to a very small extent in the thermoplastic to be stabilized.

Suitable photoprotective agents or UV stabilizers are, for example, 2-hydroxybenzophenones, 2-hydrobenzotriazoles, denickel organic compounds, salicylic acid esters, decinnamate derivatives, resorcinol monobenzoates, oxanilides, hydroxybenzoates, triazines and the like. and sterically hindered amine amines, with 2-hydroxybenzotriazoles and triazines being preferred.

In a particularly preferred embodiment, the pigmented amorphous plate according to the invention contains as its main component a crystallizable poly (ethylene terephthalate) and from 0.01% by weight to 5.0% by weight of 2- (4,6-Diphenyl-1,3,5-triazin-2'-yl) -5- (hexyl) oxyphenol (structure in Figure la) or 16 C10540 from 0.01% by weight to 0.5% by weight. weight of 2,21-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol (structure in Figure 1b) .In one embodiment In addition, it is also possible to use mixtures of these two UV stabilizers or mixtures of at least one of these two UV stabilizers with other UV stabilizers, the total concentration of photoprotective agents being preferably between 0.01% by weight and 5.0% by weight. by weight relative to the weight of crystallizable poly (ethylene terephthalate).

Weathering tests have shown that after 5 to 7 years outdoors, UV stabilized plates should not show yellowing, embrittlement, superficial loss of gloss, surface cracking and degradation of mechanical properties. .

In addition, it has been found a good ability to cold profiling, completely unexpected, without rupture, without filiform crack and / or without white break, desorte that can be profiled and fold the platesconformes the invention without heat treatment.

In addition, the measurements have shown that the plate conforms to the invention ignites only with difficulty and that it is not very combustible, so that it comes, for example, to interior wall coatings and for the construction of exposure halls.

In addition, one can recycle without problem the plate conforms to the invention without polluting the environment and without loss of mechanical properties, which makes itparticulièrementappropriate for the uses of courtedurée as billboards or other articles advertisitaires.

In the UV stabilized embodiment, the plate has improved weather resistance and higher UV stability. This means that the plates are not damaged, only to an extremely low extent, by exposure to the weather and sunlight or other UV radiation, so that the plates are suitable for outdoor and outdoor applications. / or critical interior applications. In particular, the plates must not yellow, nor present a fragilization or cracking on the surface, nor a degradation of mechanical properties.

The amorphous, pigmented plate according to the invention can be prepared, for example, by an extrusion process in an extrusion train.

Such an extrusion train is. shown schematically in Figure 2. It essentially comprises a laminating extruder (1), a flat die (2) as a profiling tool, a calenderer-finisher (3) as a calibration tool, a cooling bed (4) and / or roller conveyor ( 5) for cooling, pulling cylinders (6), cut-off saw (7), diagonal cutting device (9), and possibly stacking device (8).

The process is characterized in that the crystallizable thermoplastic is optionally dried, after the bottom in the extruder, together with the coloring agent and optionally with the UV stabilizer, the melt is formed in a spinneret and then calibrated in a smoothing machine. it is smoothed before being cut to size.

The process for the preparation of the plate according to the invention is described in more detail in the example of poly (ethylene terephthalate) hereinafter. 18 010540

Drying of the poly (ethylene terephthalate) before extrusion is preferably carried out for 4 to 6 hours at a temperature of 160 to 180 ° C.

The poly (ethylene terephthalate) is melted in the extruder. Preferably, the temperature of the molten PET is in the range of 250 to 320 ° C, the temperature of the melt being able to be set essentially as well by means of the temperature of the extruder as by the residence time of the melt. extruder.

The dye (inorganic / organic pigments and possibly also soluble descolorants) and optionally the photoprotective agent can be determined in the producer of the raw materials or during the preparation of the plate in the extruder.

However, it is particularly preferred to add the dye additive (s) by means of masterbatch technology or solid pigment preparations. In doing so, the organic and / or inorganic pigment is completely dispersed as well as the solid and colorless dye. or the photoprotective agent in a solid support. As a carrier, certain resins, the polymer to be dyed itself or other polymers that are sufficiently compatible with the crystallizable thermoplastics, come into line.

It is important that the grain size and bulk density of the solid pigment preparation or masterbatch be similar to the grain size and the bulk density of the crystallizable thermoplastic, so that a homogeneous distribution can be obtained and thereby , perform lapigmentation.

The melt leaves the extruder through a die. This die is preferably a flat die. 19 010540

The PET melted in the extruder and profiled in a flat thread, calibrated by the rolls of the calender-finisher, that is to say, cooled intensely and smoothed.The rolls of the calender can be arranged for example I-shaped, F, L or S (Fig. 3).

Then, cooling of the PET material can be carried out on a roller conveyor, cutting the sides to dimensions, cutting lengthwise and finally stacking. The thickness of the PET plate essentially depends on the drawing device installed at the end of the cooling zone, the cooler cylinders (straighteners) coupled to this device according to the speed and the speed of transport of the extruder both on the one hand and on the other. difference of cylinders on the other hand.

As an extruder, it is possible to use twin or double screw extruders.

The flat die preferably consists of the body of the decomposable tool, the lips and the device for regulating the flow over the width. To do this, the device for the regulation of the flow over the width can be warped by means of clamping screw and pressure. The adjustment of the thickness is done by adjusting the lips. It is important to ensure that the temperature of the PET and lips is uniform, otherwise the PET melt flows outwardly with different thickness through the different flow paths. The calibration tool, ie the calender / finishing machine, gives shape and dimensions to PETfondu. This is done by freezing below the glass transition temperature by cooling and smoothing. We should no longer be profiled in this state, because superficial defects would form in this cooled state. For this reason, the rolls of the calandresemble are preferably used. The roll temperature of the calender 010540 should be lower than the crystallization temperature in order to avoid adhesion of the molten PET. The PET melts the flat die with a temperature of 240 to 300 ° C. The temperature of the first cooling cylinder of the calender, each time after evacuation and depending on the thickness of the plate, is between 50 and 80 ° C. The second cylinder, a little colder, cools the second or other surface.

If the temperature of the first cylinder cooler in the calandria is outside the indicated range of 50 ° C to 80 ° C, it is difficult to obtain an amorphous plate with a thickness of 1 mm or more having the required quality.

As the calibration tool freezes as fast as possible of the PET surfaces and cools the profile to such an extent that it becomes deformable, the cooling system reduces the temperature of the PET plate to substantially room temperature. Cooling can be performed on a roller train. The speed of pulling should be set exactly in relation to the speed of the rollers in order to avoid defects and variations in thickness.

As auxiliary equipment, the extrusion assembly may comprise a cut-off saw for preparing the plates in lengthwise cut, the side cut, the stacking installation and a control station. Lateral cutting or edges are advantageous because the thickness in the edge portion can sometimes be irregular. The control station measures the thickness and optics of the plate.

Thanks to the surprising large number of excellent properties, the amorphous, pigmented plate according to the invention is suitable for a large number of different applications, for example for the coating of interior walls, for the construction of exhibition halls and for articles for exhibition, for 21 010540 panels, for the installation of shops and deraillings, as promotional items, as menu card holders and as basketball billboards.

In the UV-stabilized embodiment, the plate according to the invention is also suitable for outdoor applications, such as for example roofing coatings, exterior cladding, building applications and balcony cladding. The invention is explained below with the help of exemplary embodiments without being limited to these examples.

The measurement of the different properties is carried out according to the following standards or methods. Measurement methods

brightness

The brightness of the surface is determined according to DIN 67530. The optical reflective characteristic of the surface of a plate is measured. On the basis of ASTM-D 523-78 and ISO 2813, the angle of incidence is set at 20 °. The light beam touches the controlled surface with the established angle of incidence and is reflected or scattered. The light rays are matched by the photoelectronic receiver and indicated as proportional electric magnitudes. The measured value is dimensionless and must be specified in conjunction with the angle of incidence.

Degree of white

The degree of whiteness is determined using the electric remission photometer "ELREPHO" from Zeiss Company, Oberkochem (Germany), illuminant normalized C, 2 ° reference observer. The degree of white is defined as 010540

DB = RY + 3RZ - 3RX DB = RY, RZ, RX = corresponding reflection factors in the use of the colorimetric filter Y, Z and X. As a white standard, a molded part of barium sulphate (DIN 5033, part 9) is used . Superficial defects:

The superficial defects are evaluatedvisually. Resilience an Charpy s

This quantity is determined according to ISO179 / 1D. Resilience ak Izod:

The notched resilience, respectively Izod notch resistance, is measured according to ISO 180 / 1A.

Density:

The density is determined according to DIN 53479. VS (ADA), VI (ADA):

Standard SV (ADA) viscosity is measured according to DIN 53728 in dichloroacetic acid (ADA).

The intrinsic viscosity is calculated from the standard viscosity as follows VI (ADA) = 6.67 × 10 -4VS (ADA) + 0.118

Thermal characteristics:

The thermal properties are measured as the melting point of crystallites Tm, the crystallization temperature range Tc, the postcrystallization temperature (cold crystallization) TCN and the glass transition temperature Tg are determined by differential scanning calorimetry ( "Differential Scanning Calorimetry - DSC") with a reheating speed of 10 ° C / min.

Molar mass, polydispersity:

The molar masses Mw and Mn and the resulting Mw / Mn lapolydispersity are measured by gel permeation chromatography.

Exposure to weather (both sides), UV stability

The UV stability is checked according to the ISO 4892 test specification as follows:

Test apparatusTest conditions

Duration of irradiation

Irradiation

Temperature

Relative air humidity

Xenon lamp

Irradiation cycles

Atlas Ci 64 Weather Ometer ISO 4892, weather-resistant artificial weather1000 hours (per side)

0.5 W / m2, 340 nm 63 ° C 50% inner and outer borosilicate filter 102 minutes UV rays, then 18 minutes UV rays, water mist samples, then again 10 minutes UV light, etc.

In the following examples and comparative examples, each of these is monolayer, dull pigmented boards having different thicknesses, which have been prepared in the described extrusion assembly.

The weather conditions according to the ISO 4892 test specifications were exposed to both sides of all UV-stabilized plates at a rate of 1000 hours per face in the Atlas Ci 65 Weather Ometer of the Atlas company and then, controls mechanical properties, discoloration, surface defects, turbidity and gloss. Example 1

A white pigmented, amorphous plate having a thickness of 3 mm is prepared which contains as its main component a polymer of polyethylene terephthalate and 6% by weight of titanium dioxide. The titanium dioxide is of rutile type and is coated with an inorganic coating of Al2O3 and an organic coating of polydimethylsiloxane. Titanium dioxide has an average particle size of 0.2 μm.

The poly (ethylene terephthalate), of which the pigmented plate is prepared, has a standard viscosity VS (ADA) of 1010, which corresponds to an intrinsic VI viscosity (ADA) of 0.79 dl / g. The moisture content is <0.2% and the density (DIN 53479) is 1.41 g / cm3. The crystallinity is 59%, the melting point of the crystallites being 258 ° C. as measured by DSC. The crystallization temperature range Tc is between 83 ° C and 258 ° C, the temperature deposition-crystallization (also temperature cold crystallization) TCN is 144 ° C. The Mw / Mn polydispersity of the polyethylene terephthalate polymer is 2.14. The glass transition temperature is 83 ° C.

Titanium dioxide is added as a masterbatch. The masterbatch is composed of 30% by weight of the titanium dioxide described as the active component and 70% by weight of the poly (ethylene terephthalate) polymer described as the carrier material.

Before extrusion, 80% by weight of the poly (ethylene terephthalate) polymer and 20% by weight of the titanium dioxide masterbatch are dried for 5 hours at 170 ° C in a drier and then extruded. 010540 in a single-screw extruder at an extrusion temperature of 286 ° C in a flat die on a finisher, whose cylinders are arranged in S-shape, and smooth to obtain a plate of thickness 3 mm. The temperature of the first cylinder of the calender is 73 ° C and that of each of the other cylinders 67 ° C. The draft speed and the calender rolls are 6.5 m / min.

After cooling, the edges of the 3 mm thick white plate are sawn and cut with a saw, and then stacked. .The white pigmented plate has the following characteristics:

Thickness: 3 mm

Surface brightness, face 1: 128 (viewing angle 20 °), side 2: 127

Transmission of light

Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel) Resilience an Charpy Resilience with notch aIzod Cold deformabilityCrystallinity: 0%: 110: white, homogeneous: none: no rupture: 4.8 kJ / m2 good0%

Example 2

In a similar manner to Example 1, a pigmented plate was prepared using poly (ethylene terephthalate) having the following properties: VS (ADA) VI (ADA) - DensityCrystallinity 1100 0.85 dl / g 1.38 g / cm3 44% 26 010540

Melting point of Tm crystallites

Temperature range decristallization Tc

Postcrystallization temperature

(cold crystallization) TCN

Polydispersity Mw / Mn

Transition temperature Tg

245 ° C

from 82 ° C to 245 ° C

152 ° C

2.0282 ° C

The titanium dioxide masterbatch was composed of 30% by weight of the titanium dioxide described in Example 1 and 70% by weight of the polyethylene terephthalate of this Example.

The extrusion temperature is 280 ° C. The temperature of the first cylinder of the calender is 66 ° C and those of the other 60 ° C. The draw speed and calender rolls is 2.9 m / min. The dull white pigmented PET plate has the following characteristics:

Thickness: 6 mm

Surface brightness, face 1: 121 (viewing angle 20 °), side 2: 118

Light transmissionBlack of whitePigmentation Superficial defects (speckles, bubbles, orange peel) Resilience Charpy Resilience with akIzod cut Cold deformabilityCrystallinity: 0%: 123: white, homogeneous: none: no break: 5.1 kJ / m2: good: 0% 15 27 010540

Example 3

In a similar manner to Example 2, a pigmented plate is prepared. The extrusion temperature is 275 ° C. The temperature of the first cylinder of the calender is 57 ° C. and that of the other rolls 50 ° C. The draw speed and cylinders of the lake are 1.7 m / min.

The prepared PET board has the following characteristics profile:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel) Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity 10 mm 116 114 0% 132 white, homogeneousnot breaking5,3 kJ / m2 good0%

Example 4

In a similar manner to Example 3, a pigmented plate was prepared using poly (ethylene terephthalate) having the following characteristics: VS (ADA) VI (ADA)

Density

crystallinity

Melting point descristallites Tm

Temperature range decrystallization Tc 1200 0.91 dl / g1.37 g / cm336%

242 ° C from 82 ° C to

242 ° C 28 010540

Post-temperature: 157 ° C crystallization

(cold crystallization) TCN

Polydispersity Mw / Mn: 2.2

Transition temperature: 82 ° C glassy Tg

The titanium dioxide masterbatch was composed of 30% by weight of the titanium dioxide described in Example 1 and 70% by weight of the polyethylene terephthalate of this Example.

The extrusion temperature is 274 ° C. The temperature of the first cylinder of the calender is 50 ° C and that of the other cylinders 45 ° C. The drawing speed and the calender rolls are 1.2 m / min. The dull white pigmented PET board has the following properties:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel) Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity 15 mm 112 111 0% 138 white, homogeneousnot breaking5,4 kJ / m2 good0,4%

Example 5 In a similar manner to Example 2, a pigmented plate is prepared. 50% by weight of the polyethylene terephthalate polymer of Example 2 is mixed with 30% by weight of the recycled product of this polyethylene terephthalate polymer and 20% by weight of the masterbatch of the dioxide. of titanium.

The prepared pigmented PET plate has the following characteristics:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange skin) Resilience Charpy Resistance with Izod notch Cold deformabilityCrystallinity 6 mm 119 118 0% 125 white, homogeneousnot breaking5,0 kJ / m2 good0%

Example 6

In a similar manner to Example 1, a pigmented plate is prepared. This plate is not pigmented in white but in green. The green pigmented 3 mm thick plate contains as the main component the poly (ethylene terephthalate) polymer of Example 1 and 7% by weight of green pigment 17.

The green pigment 17 is a chromium (C 1 -C 10) oxide from BASF (®Sicopalgrün 9996).

Chromium oxide, like titanium dioxide, is added as a masterbatch. The masterbatch is composed of 35% by weight of chromium oxide (Spicopalgrün 9996) and 65% by weight of the polyethylene terephthalate polymer of Example 1.

Before the extrusion, 80% by weight of the polyethylene terephthalate polymer of Example 1 is mixed with 20% by weight of the chromium oxide masterbatch and dried for 5 hours at 170 ° C. . 30 010540

Then, as described in Example 1, a 3 mm thick, green pigmented plate was prepared which had the following properties:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel) Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity 3 mm 130 129 0.5% 125 green, homogeneousnot breaking4.6 kJ / m2 good0% 10 15

Example 7

In a similar manner to Example 2, a pigmented plate is prepared. The plate contains 3% by weight of titanium dioxide and 3.5% by weight of chromium oxide.

The titanium dioxide masterbatch is composed of 30% by weight of the titanium dioxide described in Example 1 and 70% by weight of the poly (terephthalate ethylene) polymer of Example 2.

The masterbatch of the chromium oxide is composed of 35% by weight of the chromium oxide described in Example 6 (®Siopalgrün 9996) and 65% by weight of the poly (ethylene terephthalate) of Example 2 .

Before extrusion, 80% by weight of the poly (ethylene terephthalate) polymer of Example 2 was mixed with 10% by weight of the titanium dioxide masterbatch and 10% by weight of the chromium oxide masterbatch. it is dried for 5 hours at 170 ° C. 20 31 010540

Then a plate of a thickness of 6 mm is prepared as described in Example 2, which has the following profilde characteristics:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel) Resilience Charpy Resilience with Izod notch 6 mm 125 125 0% 125 green light, homogeneous no breakthrough5,3 kJ / m2 Cold deformability: good

Crystallinity: 0% 5

Comparative Example 1

In a similar manner to Example 1, a pigmented plate is prepared. The poly (ethylene terephthalate) used has a standard viscosity VS (ADA) of 760, which corresponds to an intrinsic viscosity VI (ADA) of 0.62 dl / g. The other characteristics, within the scope of measurement accuracy, are identical to those of the poly (ethylene terephthalate) of Example 1. The titanium dioxide masterbatch, the process parameters and the temperature are selected as the Example1. Due to the low viscosity, a plate could not be prepared. The stability of the melt is insufficient so that the melted material collapses on the rolls of the shell prior to cooling. 32 010540

Comparative Example 2

In a similar manner to Example 2, a pigmented plate is prepared using the poly (terephthalate ethylene) of Example 2 and the titanium dioxide masterbatch of Example 2. The temperature of the first cylinder of the calender is 83 ° C and that of each other 77 ° C.

The brightness is significantly reduced. The plate shows defects and superficial structures. Optics are unacceptable for the use of a pigmented material. The prepared plate has the following profilde characteristics:

Thickness

Surface brightness, face 1: 6 mm: 85 (untreated and transparent spots) (angle of incidence 20 °), face 2: 85 (untreated and transparent spots)

Transmission of light Degree of white Pigmentation: 125: non-homogeneous appearance, because the present surface ofprocessed structures, bubbles and cracks Surface defects (speckles, bubbles, orange peel): inhomogeneous appearance, because the present surface ofprocessed structures, bubbles and cracks Resilience Charpy Resilience with akIzod notch: no break: 5.1 kJ / m2 Cold deformabilityCrystallinity good approx. 9% 33 010540

Example 8

In a similar manner to Example 1, an amorphous plate having a thickness of 3 mm, stabilized against UV, pigmented in white, which contains as main component the poly (ethylene terephthalate) according to Example 1 and 6% in weight of titanium dioxide, as well as 1.0% by weight of UV stabilizer, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol (®Tinuvin 1577 of the Ciba Geigy Company).

Tinuvin 1577 has a melting point of 149 ° C and is heat resistant up to about 330 ° C.

1% by weight of the UVTinuvin stabilizer is incorporated into the poly (ethylene terephthalate) directly to the producer of the raw materials.

Before extrusion, 80% by weight of the poly (ethylene terephthalate) containing 1.0% by weight of Tinuvin 1577 and 20% by weight of the titanium dioxide masterbatch was dried for 5 hours at 170 ° C. in a slider. .

The prepared plate, pigmented in white, has the same characteristics as the plate of Example 1.

After each 1000 hours of weather exposure per face in an Atlas Ci 65 Weather Ometer, the PET plate has the following characteristics:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (cracks, embrittlement) Resiliency an Charpy Resistance with Izod notch 3 mm 125 123 0% 108% white, homogenous no break4.6 kJ / m2 Cold deformability good 34 010540

Crystallinity: Ο%

Example 9

In a similar manner to Example 8, a UV stabilized, pigmented plate was prepared with 1% Tinuvin 1577 using poly (terephthalate ethylene) according to Example 2.

The titanium dioxide masterbatch is composed of 30% by weight of the titanium dioxide described in Example 1 and 70% by weight of the polyethylene terephthalate of this Example.

The extrusion temperature is 280 ° C. The temperature of the first cylinder of the calender is 66 ° C. and those of the other cylinders 60 ° C. The draw speed and the calender rolls are 2.9 m / min.

The method used here corresponds to Example 2. The prepared plate, pigmented in dull white has the same characteristics as the plate of Example 2.

After 1000 hours of weathering by 20 faces in an Atlas Ci 65 Weather Ometer, the PET plate has the following characteristics:

Thickness: 6 mm Surface gloss, face 1: 118 (angle of view 20 °), face 2: 117 Light transmittance: 0% Degree of white: 121% Pigmentation: white, homogeneous Superficial defects: none (cracks, fragilisation) Resilience an Charpy: no rupture Resilience with notch ak: 5.0 kJ / m2 Izod Cold deformability: good Crystallinity: 0% 35 010540

Example 10

In a similar manner to Example 9, a UV stabilized pigment plate was prepared with 1.0% Tiinuvin 1577. The extrusion temperature was 275 ° C. The temperature of the first cylinder of the calender is 57 ° C and that of the other 50 ° C. The drawing speed and rolls of the calender is 1.7 m / min.

The process used here corresponds to the method of Example 3. The prepared PET plate has the same characteristics as the plate of Example 3.

After 1000 hours of weathering per face in an Atlas Ci 65 Weather Ometer, the PET plate has the following characteristics: - Thickness: 10 mm -. Surface gloss 1: 115 - (20 ° angle of view) 2: 112 face - Light transmittance: 0% - White degree: 128% - Pigmentation: white, homogeneous - Superficial defects: none (cracks, embrittlement ) - Resilience an year Charpy: no break - Resilience with notch a ^ -52 kJ / m2 Izod - Cold deformability: good Crystallinity: 0% 15

Example 11

In a similar manner to Example 10, a UV stabilized, pigmented plate was prepared with 1% Tiinuvin 1577 using poly (ethylene terephthalate) according to Example 4.

The titanium dioxide masterbatch is composed of 30% by weight of the titanium dioxide described in Example 1 and 70% by weight of the poly (ethylene terephthalate) of this Example. 36 010540

The extrusion temperature is 27 ° C. The temperature of the first cylinder of the calender is 50 ° C and those of the other cylinders 45 ° C. Draft speed and calender rolls are 1.2 m / min.

The process used here corresponds to the method of Example 4. The prepared, white-pigmented plate has the same characteristic profile as the plate of Example 4.

After each 1000 hours of weather exposure per face in an Atlas Ci 65 Weather Ometer, the PET plate has the following characteristics:

Thickness: 15 mm Surface brightness, face 1: 110 (angle of view 20 °), side 2: 109 Light transmission: 0% Degree of white: 134% Pigmentation: white, homogeneous Superficial defects: none (cracks, fragilisation) Resilience an Charpy: no rupture Resilience with notch ak: 5.2 kJ / m2 Izod Cold deformability: good Crystallinity: 0.4%

Example 12

In a similar manner to Example 9, a UV stabilized pigmented plate was prepared with 1.0% by weight of Tinuvin 1577. 50% by weight of the poly (ethylene terephthalate) of Example 2 was mixed with 30% by weight. recycled product weight of this poly (ethylene terephthalate) and 20% by weight of the titanium dioxide masterbatch.

The process used here corresponds to the method of Example 5. The prepared, pigmented PET plate has the same characteristic profile as the plate of Example 5.

After each 1000 hours of weather exposure per face in an Atlas Ci 65 Weather Ometer, the PET plate has the following characteristics:

Thickness: 6 mm Surface gloss, face 1: 116 (angle of repose 20 °), face 2: 116 Light transmittance: 0% Degree of white: 122% Pigmentation: white, homogeneous Superficial defects: none (cracks, fragilisation) Resilience an Charpy: no rupture Resilience with notch ak: 4.7 kJ / m2 Izod Cold deformability: good Crystallinity: 0%

Example 13

In a similar manner to Example 9, a white pigmented plate is prepared. As UV stabilizer, 0.8% by weight of 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) is used. phenol (®Tinuvin 360 from Ciba-Geigy Company), relative to the weight of the polymer.

Tinuvin 3660 has a melting point of 195 ° C and is resistant to heat up to about 350 ° C.

As in Example 8, 0.8% by weight of the UV stabilizer Tinuvin 360 is incorporated into the poly (ethylene terephthalate) directly from the producer of raw materials.

The prepared, UV stabilized plate has the following characteristics: 010540

Thickness

Surface brightness, face 1 (angle of view 20 °), sideTransmission of lightColour of white

Pigmentation Superficial defects (speckles, bubbles, orange peel) Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity: 6 mm: 123 2: 122: 0%: 128%: white, homogeneous: none: no break: 5.2 kJ / m2: good: 0%

After each 1,000 hours of weather exposure per face in the Atlas Ci 65 Weather Ometer, the PET plate has the following characteristics: - Thickness: 6 mm - Surface gloss, face 1: 118 - (angle of icidence 20 °), face 2: 117 - Light transmission: 0% - Degree of white: 123% - Pigmentation: white, homogeneous - Superficial defects: none (cracks, embrittlement) - Resilience an Charpy: no rupture - Resilience with notch ak: 5.0 kJ / m2 Izod - Cold deformability: good - Crystallinity: 0% Comparative Example 3 In a similar manner to Example 8, 10 UV stabilized white pigmented plate is prepared. The polyethylene terephthalate used has a standard viscosity VS (ADA) of 760, which corresponds to an intrinsic viscosity VI (ADA) of 0.62 dl / g. The other characteristics are, in the context of measurement accuracy, identical to the characteristics of the poly (ethylene terephthalate) of Example 1. The titanium dioxide masterbatch, the process parameters and the temperature are chosen as in Example 1 . Due to the low viscosity, a plate could not be prepared. · The stability of the melt is insufficient, so that the melt melts before cooling on the calender rolls.

Comparative Example 4

The plate obtained according to Example 1, which corresponds to the plate of Example 8, is exposed to the elements, but does not contain any UV stabilizer.

After each 1000 hours of weather exposure per face in the Ci 65 Weather Ometer Atlas, the PET plate presents the following: Characteristics - Thickness: 3 mm Surface brightness, face 1: 88 - (angle of view 20 °), face 2: 86 - Light transmission: 0% - Degree of white: 81% - Pigmentation: yellowish-white Superficial defects (cracks, weakening) the surface is dulled and shows a strong yellowing - Resilience to Charpy: complete rupture at 44 , 2 kJ / m2 - Resilience with akIzod notch: 1.6 kJ / m2 - Cold deformability: cracking - Crystallinity 0% 40 010540

Visually observed, the plaque shows a strong yellowing.

Example 14

An amorphous, white-pigmented, 3 mm thick plate is prepared which comprises poly (ethylene terephthalate) as its main component and 6% by weight of titanium dioxide.

The titanium dioxide is of the rutile type coated with an inorganic coating of Al2C3 and an organic coating of polydimethylsiloxane. Titanium dioxide has a mean particle size of 0.2 μm.

The polyethylene terephthalate, from which the pigmented plate is prepared, has a standard viscosity VS (ADA) of 3490, which corresponds to an intrinsic viscosity (ADA) of 2.45 dl / g. The moisture content is <0.2% and the density (DIN 53479) is 1.35 g / cm3. The crystallinity is 19%, the melting point of the crystallites being 243 ° C. according to DSC measurements. The decristallization temperature range Tc is between 82 ° C and 243 ° C. The Mw / Mn poly (ethylene terephthalate) dispersivity was 4.3, Mw being 225,070 g / mol and Mn 52,400 g / mol. The glass transition temperature was 83 ° C.

Titanium dioxide is added as a masterbatch. The masterbatch is composed of 30% by weight of the titanium dioxide described as the main component and 70% by weight of the polyethylene terephthalate described as the support material.

Before the extrusion, 80% by weight of the poly (ethylene terephthalate) and 20% by weight of the titanium dioxide masterbatch are dried for 5 hours at 170 ° C. in a drier and then extruded in a single-screw extruder at a temperature of 100.degree. extrusion of 286 ° C in a flat die on a calender, whose cylinders are arranged in S, and smooth to obtain plates with a thickness of 3 mm. The temperature of the first shell of the calender is 73 ° C. and that of each of the other cylinders 67 ° C. The drawing speed and calender rolls are 6.5 m / min.

After cooling, the edges of the 3 mm thick white plate are sawn and cut with a saw, and then stacked.

The prepared plate, pigmented in white, has the following characteristics:

Thickness

Surface brightness of face 1 (angle of view 20 °) faceTransmission of light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity: 3 mm: 131. 2: 129: 0%: 112%: white, homogeneous: none: no break: 4.8 kJ / m2 good0%

Example 15

In a similar manner to Example 14, a pigmented plate was prepared using poly (ethylene terephthalate) which had the following characteristics: VS (ADA) VI (ADA)

Density

crystallinity

Melting point of Tm crystallites

Crystallization temperature range Tc 2717 1.9 dl / g1.38 g / cm344%

245 ° C

from 82 ° C to 245 ° C 42 010540

Mw: 175,640 g / mol

Mn: 49580 g / mol

Polydispersity Mw / Mn: 2.02

Glass transition temperature: 82 ° C

The titanium dioxide masterbatch was composed of 30% by weight of the titanium dioxide described in Example 15 and 70% by weight of the poly (ethylene terephthalate) of this Example.

The extrusion temperature is 280 ° C. The temperature of the first cylinder of the calender is 66 ° C and those of the other cylinders 60 ° C. Draw velocity and the calender rolls is 10 2.9 m / min.

The prepared PET plate, pigmented in whiteheads has the following characteristics:

Thickness

Surface brightness, face (20 ° angle of view), fac Light transmittance Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an Charpy Resilience with notch aIzod: 6 mm1: 124 e 2: 121: 0%: 125%: white, homogeneous: none: no break: 5, 1 kJ / m2 Cold deformabilityCrystallinity good0% 15 Example 16

A pigmented plate is prepared analogously to Example 15. The extrusion temperature is 5 ° C. The temperature of the first lacalander cylinder is 57 ° C and that of the other cylinders is 43 ° C10540 ° C. The draw speed and rolls are 1.7 m / min.

The prepared PET plate has the following properties:

Thickness

Surface brightness, face 1 (angle of view 20 °), sideTransmission of lightColour of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an CharpyRepidity with notch akIzod Cold deformabilityCrystallinity: 10 mm118 2: 115: 0%: 134%: white, homogenous: no break: 5.3 kJ / m2 good0%

Example 17

A pigmented plate is prepared analogously to Example 16, using poly (ethylene terephthalate) which has the following properties: VS (ADA) VI (ADA)

Density

crystallinity

Melting point of Tm crystallites

Temperature range decristallisation Tc 3173 2.23 dl / g 1.34 g / cm3 12%

240 ° C

from 82 ° C to 240 ° C

mw

mn

Polydispersity Mw / Mn

Glass transition temperature 204 660 g / mol 55 952 g / mol 3.66

82 ° C 44 010540

The titanium dioxide masterbatch is composed of 30% by weight of the titanium dioxide described in Example 14 and 70% by weight of the polyethylene terephthalate of this Example. The extrusion temperature is 27 ° C. The temperature of the first cylinder of the calender is 50 ° C and those of the other cylinders 45 ° C. The draft speed and the calender rolls are 1.2 m / min. The prepared PET board, pigmented white, has the following feature profile:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity 15 mm 115 112 0% 141% white, homogeneousnot breaking5.4 kJ / m2 good0%

Example 18 A pigmented plate was prepared in a manner analogous to Example 15. 50% by weight of the poly (ethylene terephthalate) of Example 15 was mixed with 30% by weight of the recycled product of this poly (ethylene terephthalate). ) and 20% of the titanium dioxide masterbatch.

The prepared PET board, pigmented white, has the following property profile: 20 45 010540

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an Charpy Resilience with akIzod notch: 6 mm: 121: 120: 0%: 127%: white, homogeneous: none: no rupture: 5.0 kJ / m2 Cold deformabilityCrystallinity: good

Example 19

A pigmented plate is prepared in a manner analogous to Example 14. The plate is not pigmented in white, but in green. The green pigmented plate, 3 mm thick, contains as the main component the poly (ethylene terephthalate) of Example 14 and 7% by weight of Pigmentgrün 17.

Pigmentgrün 17 is a chromium oxide (Cr2O3) from BASF (®Sicopalgrün 9996).

Chromium oxide, like titanium dioxide, is added as a masterbatch. The masterbatch is composed of 35% by weight of chromium oxide (Spicopalgrün 9996) and 65% of the poly (terephthalate ethylene) of Example 14.

Before extrusion, 80% of the poly (ethylene terephthalate) of Example 14 is mixed with 20% by weight of the chromium oxide masterbatch and dried for 5 hours at 170 ° C.

Next, a green pigmented plate 3 mm thick was prepared as described in Example 14 which had the following properties:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity 3 mm 128 126 0.2% 127% green, homogeneousnot breaking4.6 kJ / m2 good0%

Example 20

A pigmented plate is prepared as in Example 15. The plate contains 3% by weight of titanium dioxide and 3.5% by weight of chromium oxide.

The titanium dioxide masterbatch was composed of 30% by weight of the titanium dioxide described in Example 14 and 70% by weight of the polyethylene terephthalate of Example 15. The masterbatch of titanium dioxide was The chromium oxide is composed of 325% by weight of the chromium oxide (®Sicopalgrün 9996) described in Example 19 and 65% by weight of the poly (ethylene terephthalate) of Example 15

Before extrusion, 80% of the poly (ethylene terephthalate) of Example 15 was mixed with 10% by weight of the titanium dioxide masterbatch and 10% by weight of the oxide masterbatch. chromium and is dried for 5 hours at 170 ° C.

A 6 mm thick plate is then prepared as described in Example 15, which has the following characteristics: 010540

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of light: 6 mm

Pigmentation: 126: 124: 0.2%: dull green, homogeneous Superficial defects (speckles, bubbles, orange peel, etc.): none Resilience an Charpy Resilience with notch akIzod: no rupture: 5.3 kJ / m2 Cold deformabilityCrystallinity: good

Example 21

Analogous to Example 14, an amorphous, pigmented plate having a thickness of 3 mm was prepared, which contained as main component poly-5 (ethylene terephthalate) and titanium dioxide of Example 14 and 1.0% by weight of UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol (®Tinuvin 1577 from Ciba-Geigy) . Tinuvin 1577 has a melting point of 149 ° C and is heat resistant to about 330 ° C.

Polyethylene terephthalate 1.0% by weight of the UV stabilizer is incorporated directly into the raw material producer.

The drying, extrusion and process parameters are selected as in Example 14.

The prepared, pigmented plate has the following properties:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation 3 mm 129 130 0% 114% white, homogeneous 48 Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an Charpy Resilience with notch akIzod no breakthrough4.8 kJ / m2 Cold deformability: goodCrystallinity: 0 %

After 1,000 hours of weathering each face in the Atlas Ci Weather Ometer, the PEAT plate has the following characteristics:

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience Charpy Resilience with akIzod notch 3 mm 126 125 0% 110% white, homogenous no break4.6 kJ / m2 Cold deformability: good

Crystallinity: 0% 5 Example 22

In a similar manner to Example 21, an amorphous, pigmented plate having a thickness of 3 mm is prepared. The UV stabilizer, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol (®Tinuvin 1577) is gradually added in the form of a masterbatch. The masterbatch is composed of 5% by weight of Tinuvin1577 as the active component and 95% by weight of the poly (ethylene terephthalate) of Example 14.

Before the extrusion, 60% poly (ethylene terephthalate) and 20% by weight of the titanium dioxide masterbatch of Example 14 are mixed with 20% by weight of the masterbatch of chromium oxide and dried for 5 hours at 170 ° C.

The prepared white pigmented plate has the following characteristics:

Thickness

Surface brightness, face 1 (angle of view 20 °), sideTransmission of lightColour of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) Resilience an Charpy Resilience with Izod notch Cold deformabilityCrystallinity: 3 mm: 129 2: 128: 0%: 112%: white, homogeneous: none: no rupture: 4.6 kJ / m2: good: 0%

After 1,000 hours of weathering on each face in the Atlas Ci Weather Ometer, the dePET plate has the following properties 10

Thickness

Surface brightness, face 1 (20 ° angle of view), face 2Transmission of the light Degree of white

Pigmentation Superficial defects (speckles, bubbles, orange peel, etc.) 3 mm 126 124 0% 109% b1anc, homogenous Resilience an Charpy Resilience with notch akIzod Cold deformabilityCrystallinity no fracture 4.3 kJ / m2 good 0%

Claims (30)

50 010540 CLAIMS 1. An amorphous, pigmented plate having a thickness in the range of 1 to 20 mm, characterized in that it contains as a main component a crystallizable thermoplastic and at least one colorant among organic and inorganic pigment, pigment concentration being in the meantime from 0.5 to 30% by weight, based on the weight of the crystallizable thermoplastic. 2. Plate according to claim 1, characterized in that the plate additionally contains a soluble dye. 3. Plate according to claim 2, characterized in that the concentration of soluble dye is in the range of 0.001 to 20% by weight relative to the weight of the crystallizable thermoplastic. 4. Plate according to claim 2 or 3, characterized in that the soluble dye is an azo dye or an oil-soluble anthraquinone dye and aromatic compounds. Plate according to one of the preceding claims, characterized in that the gloss of the surface measured in accordance with DIN 67530 (angle of incidence 20 °) is greater than 90. 6. Plate according to at least one of the preceding claims, characterized in that the transmission of light measured according to ASTM-D 1003 is less than 5%. 7. Plate according to one of the preceding claims, characterized in that the crystallizable thermoplastic used has a standard viscosity VS (ADA), 010540 measured in dichloroacetic acid according to DIN53728, in the range of 800 to 6000. 8. Plate according to claim 7, characterized in that the crystallizable thermoplastic used has a standard viscosity VS (ADA), measured in dichloroacetic acid according to DIN 53728, located in the range of 950 to 5000. 9. Plate according to one of the preceding claims, characterized in that the plate has a decristallinity degree of less than 5%. 10. Plate according to one of the preceding claims, characterized in that the crystallizable thermoplastic is taken from poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), a cyclo-olefinic polymer and a cycloolefin copolymer. Plate according to claim 10, characterized in that poly (ethylene terephthalate) is used as the crystallizable thermoplastic. 12. Plate according to claim 11, characterized in that the poly (ethylene terephthalate) contains recycled poly (ethylene terephthalate). 13. Plate according to claim 11 or 12, characterized in that in the measurements of the resilient Charpy, measured according to ISO 179 / 1D, there is no breakage. 14. Plate according to one of claims 11 to 13, characterized in that Izod notch resilience, measured according to ISO 180 / 1A, is in the range of 2.0 to 8.0 kJ / m2. 52 010540 15. Plate according to one of claims 11 to 14, characterized in that the poly (ethylene terephthalate) has a melting point of the crystallites, measured by DSC with a heating rate of 10 ° C / min, in the range from 220 ° C to 280 ° C. 16. Plate according to one of claims 11 to 15, characterized in that the poly (ethylene terephthalate) has a crystallization temperature, measured by DSC with a heating rate of 10 ° C / min, in the interval of 75 ° C at 280 ° C. 17. Plate according to one of claims 11 to 16, characterized in that the poly (ethylene terephthalate) used has a crystallinity in the range of 5 to 65%. 18. Plate according to one of the preceding claims, characterized in that the plate additionally contains a UV stabilizer. 19. Plate according to claim 18, characterized in that the concentration of UV stabilizer is in the range of 0.01 to 5% by weight based on the weight of the crystallizable thermoplastic. 20. Plate according to claim 18 or 19, characterized in that a UVpris stabilizer is used among 2-hydrobenzotriazoles and triazines. 21. Plate according to claim 20, characterized in that at least one UV stabilizer taken from 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol is used. and 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl-butyl) -phenol. 22. Process for the preparation of a pigmented amorphous plate according to one of the preceding claimscomprenant the following steps: melting the thermomoplastique crystallizable together with the dye in an extruder, profiling the material melt in a die and then in a calandr-finisher, calibrating, smoothing and cooling with at least two cylinders before cutting the desired size plates, the first calender of the finisher having a temperature in the range of 50 ° C to 80 ° C. 23. The method of claim 22, characterized in that the crystallizable thermoplastic is dried prior to melting. 24. The method of claim 22 or 23, characterized in that the UV stabilizer is melted together with the dye and the thermoplastic in the extruder. 25. Method according to one of claims 22 to 24, characterized in that it implements the addition of colorant and / or UV stabilizer using the masterbatch technology. 26. Process according to one of claims 22 to 25, characterized in that PET is used as a crystallizable thermoplastic. 27. The method of claim 26, characterized in that prior to melting the PET is dried for 4 to 6 hours at a temperature of 160 to 180 ° C. 28. Process according to claim 26 or 27, characterized in that the temperature of the molten PET is in the range of 250 to 320 ° C. 53 010540 29. Use of a pigmented amorphous plate according to one of claims 1 to 21 for coating the walls and in the construction of exposure halls. 30. Use of the plate provided with a UV stabilizer according to one of claims 18 to 21 in external applications. 10