Polymer composition having heat-absorbing properties and high stability

ES 2 547 019 T3

DESCRIPTION

Polymeric composition with heat-absorbing properties and high stability

The invention relates to a heat-absorbing polymer composition containing a transparent thermoplastic plastic, cesium tungstate as an inorganic infrared absorber with a phosphine-based stabilizer; as well as the preparation and use of polymeric compositions according to the invention and the articles manufactured from them. In particular, the present invention relates to the use of the polymer composition according to the invention containing this stabilized inorganic IR absorber for the manufacture of sheets for glazing for use in buildings, motor vehicles and railways and airplanes.

Glazing of compositions containing transparent thermoplastic polymers such as, for example, polycarbonate, offer many advantages for the vehicle sector and for buildings compared to conventional glazing made of glass. These include, for example, increased breakage safety or weight savings, which in the case of automobile glazing enables occupant safety in the event of accidents and reduced fuel use. Finally, transparent materials containing transparent thermoplastic polymers, due to their simpler formability, allow essentially greater design freedom.

The disadvantage is, however, that the high heat permeability (ie permeability to IR radiation) of transparent thermoplastic polymers in the event of exposure to the sun causes unwanted heating inside vehicles and buildings. Increased temperatures in the interior space reduce the comfort of the occupants or inhabitants and can lead to increased demands on air conditioning, which in turn increase energy consumption and additionally compensate for the positive effects. In order, in spite of everything, to comply with the requirement of a lower energy consumption associated with a high comfort for the occupants, glazing is necessary that is provided with a corresponding protection against heat. This is especially true for the automotive industry.

As has long been known, most of the solar energy corresponds, in addition to the visible region of light between 400 nm and 750 nm, to the near infrared (NIR) region between 750 nm and 2500 nm. Incident solar radiation is absorbed, for example, inside the car and emitted as long-wave thermal radiation with a wavelength of 5 mm to 15 mm. Since common glazing materials, especially thermoplastic polymers transparent in the visible region, are not transparent in this region, thermal radiation cannot radiate outside. A greenhouse effect is obtained and the interior space is heated. To keep this effect as low as possible, the transmission of the glazing in the NIR region should therefore be minimized. The usual transparent thermoplastic polymers such as, for example, polycarbonates are, however, both in the visible region and in the NIR region, transparent.

Therefore, for example, additives are necessary which have the lowest possible transparency in the NIR region without adversely influencing the transparency in the visible region of the spectrum.

Among the transparent thermoplastic plastics polymers based on poly (methyl methacrylate) (PMMA) and polycarbonate are particularly good for use as suitable glazing materials. Due to its high toughness, polycarbonate especially has a very good property profile for application purposes of this type.

To impart heat-absorbing properties to these plastics, corresponding infrared absorbers are therefore used as additives. Especially interesting for this purpose are IR absorber systems which have a broad absorption spectrum in the NIR region (near infrared, 750 nm - 2500 nm) and simultaneously a low absorption in the visible region (reduced eigen color). The corresponding polymer compositions should also exhibit high thermostability as well as outstanding photostability.

A plurality of IR absorbers based on organic or inorganic materials are known that can be used in transparent thermoplastics. A selection of such materials is described, for example, by J. Fabian, H. Nakazumi, H. Matsuoka, Chem. Rev. 92, 1197 (1992), in US-A 5,712,332 or in JP-A 06240146.

However, IR absorbent additives based on organic materials often have the disadvantage that they have poor stability against thermal load or radiation. Thus, many of these additives are not thermoset enough to be incorporated into transparent thermoplastics, since temperatures of up to 330 ° C are required for their processing. In addition, glazing in use is often exposed for a long period of time to temperatures above 50 ° C, due to solar radiation, which can cause decomposition or degradation of organic absorbents.

Furthermore, organic IR absorbents often do not have a sufficiently wide absorption band in the IR region, so that their use as IR absorbents in glazing materials is ineffective, additionally often a strong eigen color of these systems, which generally it is not desirable.

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IR absorbent additives based on organic materials are often significantly more stable compared to organic additives. The use of these systems is also frequently cheaper, since in most cases they present a clearly more favorable price / performance ratio. Thus, finely divided boride-based materials, such as, for example, lanthanum hexaboride, have been shown to be beneficial as they have a wide absorption band associated with high thermostability. Borides based on La, Ce, Pr, Nd, Tb, Dy, Ho, Y, Sm, Eu, ER, Tm, Yb, Lu, Sr, Ti, Zr, Hf, V, Ta, Cr, Mo, W and Ca of this type are described, for example, in DE 103 92 543 T5 or EP 1 559 743 A1.

A disadvantage of these additives is, however, their significant inherent color. Boride-containing additives give the clear plastic a characteristic green coloration upon incorporation, which is often undesirable as it severely limits the scope for achieving a neutral coloration.

To compensate for the self color, larger amounts of other colorants are often used, which, however, impairs the optical properties of the composition and causes a markedly lower transmission in the visible region. This is especially undesirable in vehicle glazing or is not allowed in special cases where the driver's vision must not be impaired.

Furthermore, IR absorbent additives from the group of tungsten compounds are known which have a lower self absorption in the visible spectral region compared to the inorganic IR absorbents known from the state of the art based on boride.

The preparation and use of these substances in thermoplastic materials are described, for example, by H. Takeda,

K. Adachi, J. Am. Ceram. Soc. 90, 4059-4061, (2007), and in documents WO 2005/037932 A1, JP 2006219662 A, JP 2008024902 A, JP 2008150548 A, WO 2009/059901 A2 and JP 2008214596 A. As a disadvantage it is highlighted, no However, the lack of long-term stability against thermal load. While the thermal instability of tungsten oxides is known per se and for example has been described by Romanyuk et al .; J. Phys. Chem. C 2008, 112, 11090 - 11092, it is also shown in the incorporation of these compounds in a polymeric matrix that in case of thermal storage at high temperature of the corresponding polymeric compositions, such as, for example, in case of a polycarbonate composition , the absorption in the IR region is significantly reduced.

For a use of the compositions in the glazing sector, especially for automobile glazing, it is absolutely necessary, however, that the corresponding IR absorbent polymer compositions have long-term stability against elevated temperatures. By elevated temperatures is meant, for example, temperatures that a polycarbonate article can absorb in the event of intense solar radiation (for example, 50 ° C - 110 ° C). Furthermore, it must be ensured that the compositions can be processed under normal processing conditions without reducing the IR absorbent properties therewith.

Furthermore, it is known in thermoplastic materials to improve the processing properties to use thermostabilizers such as, for example, phosphites, hindered phenols, aromatic, aliphatic or aliphatic aromatic phosphines, lactones, thioethers and hindered amines (HALS, hindered amine light stabilizers).

From WO-A 01/18101 molding compositions are known which contain a thermoplastic plastic and a phthalo- or naphthalocyanine dye, which may contain antioxidants such as phosphites, hindered phenols, aromatic, aliphatic or phosphines to improve processing stability. aliphatic-aromatics, lactones, thioethers and hindered amines. In contrast to this document, the present invention relates to compositions containing inorganic tungsten-based IR absorbers.

From EP 1266931 A1 organic IR absorbers are known in polycarbonate compositions in combination with phosphines. However, no indication on the combination of inorganic IR absorbents, especially tungsten-based inorganic IR absorbents, with phosphines for stabilizing the absorbent in a thermoplastic matrix is ​​disclosed in EP 1266931 A1.

In EP 1559743 A1 polycarbonate compositions containing inorganic boride-based IR absorbers in combination with thermostabilizers such as phosphonites and phosphines are described, in which these additives serve to stabilize the polycarbonate matrix. Tungsten-based compositions are not described. It is not known whether the stabilizers mentioned above have an influence on inorganic IR absorbents.

US 2006/0251996 A1 discloses multilayer plates containing a core layer containing a thermoplastic polymer and an IR absorbent additive, the IR absorbent additive being a metal oxide. Furthermore, the core layer additionally contains heat stabilizers. However, no polymer composition with a phosphine stabilized IR absorbent according to the present invention, nor phosphine stabilized master mixes, is disclosed in US 2006/0251996 A1. In particular, document US 2006/0251996 A1 also does not describe the use of a nano-scale IR absorber embedded in a dispersant.

In all the thermoplastic compositions published to date with IR absorbents, the thermostabilizer acts, however, exclusively stabilizing the corresponding polymeric matrix, especially

ES 2 547 019 T3 in processing. Thus, the coloration of the polycarbonate after exposure to light can be limited by the use of these systems, as described in EP 1266931 A1.

Therefore, there is a goal to find IR absorbent systems with reduced self color, as well as simultaneously high thermostability and stability against exposure to light and to provide corresponding compositions with thermoplastic materials. These additives must simultaneously have a broad absorption characteristic in the NIR region, while presenting an economically acceptable or even interesting price / performance ratio. Another object of the present invention was to provide stabilizers that clearly improve the long-term stability of known IR absorbents, as well as to provide compositions with IR absorbents and stabilizers in a high concentration in a thermoplastic polymer as masterbatches for further processing.

Surprisingly, it has been shown that certain stabilizers improve the thermostability of IR absorbent tungstates, especially cesium tungstate, so that the object of the present invention is achieved by compositions with cesium tungstate as IR absorbent additive, which have a lower self-absorption in the visible spectral region compared to inorganic IR absorbers known from the state of the art based on boride and produce thermoplastic materials with a lower self-color, in which the inorganic IR absorbers are stabilized to achieve higher long-term stability against thermal load with a stabilizer from the group of phosphines.

The cesium tungstate according to the invention is a substance of type b2) MxWyOz (M = Cs; x / y = 0.001-1.000; z / y = 2.2-3.0). It is particularly preferably Cs0.33 WO3.

In a particular embodiment of the present invention, the individual use of Cs0.33WO3 as an inorganic IR absorbent is very particularly preferred. Compounds with Cs / W ratios of 0.20 and 0.25 are also known.

Furthermore, in this regard, it is noted that only a certain group of stabilizers is effective, while other stabilizers constructed in a similar way are either ineffective or even harmful and further accelerate the worsening of IR absorption. Within the framework of the present invention it was possible to demonstrate that stabilizers based on phosphorus in the form of their phosphine are beneficial and stabilize IR absorbing cesium tungstates, while the individual use of stabilizers containing phosphorus of the phosphites, phosphonates or phosphonites type it has been shown to be ineffective to ineffective. When using phosphates, phosphoric acids, derivatives of phosphoric acid or corresponding stabilizers that contain these compounds or can form them, an even faster deterioration of the tungstates according to the invention occurs.

Phosphines, in the context of the present invention, are derived from compounds of the general type PnHn + 2, especially PH3, preferably all hydrogen atoms being replaced by aliphatic and / or aromatic hydrocarbon residues, the aromatic hydrocarbon residues being able to have other substituents such as, for example, alkyl groups. The phosphines can have one phosphorous atom or else several phosphorous atoms bridged by corresponding aliphatic and / or aromatic hydrocarbons.

Phosphites in the context of the present invention should be understood to mean phosphonic acids (often also referred to as phosphor acid esters) with the general structure P (OR) 3, R being represented by aliphatic and / or aromatic hydrocarbon residues, the aromatic hydrocarbon residues may have other substituents such as, for example, alkyl groups.

Phosphonates should be understood as compounds derived from the structure R-PO (OH) 2, in which R represents aliphatic and / or aromatic hydrocarbon radicals, the aromatic hydrocarbon radicals may have other substituents such as, for example, alkyl groups. The OH groups of the basic structure can be partially or totally esterified with OR functionalities, R in turn representing aliphatic and / or aromatic hydrocarbon residues, the aromatic hydrocarbon residues being able to have other substituents such as, for example, alkyl groups, or be partially or totally deprotoned, the total negative charge being compensated by a corresponding counterion.

Phosphonites in the context of the present invention should be understood as esters, especially diesters of phosphorous acids of the RP (OR) 2 type, R being represented by aliphatic and / or aromatic hydrocarbon residues, the aromatic hydrocarbon residues may have other substituents such as, for example, alkyl groups. Phosphonites can have one phosphorous atom or else several phosphorous atoms bridged by corresponding aliphatic and / or aromatic hydrocarbons.

In the context of the present invention, phosphate salts, partial or total esters and condensates of phosphoric acid (H3PO4) should be understood.

The object of the present invention is therefore achieved by a polymer composition containing

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a) a transparent thermoplastic plastic, preferably polycarbonate, polystyrene, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol (PETG) copolymer, poly (butylene terephthalate) (PBT), cyclic polyolefin or poly ( methyl methacrylate), other preferred polycarbonates, aromatic polyesters or polymethacrylate, and particularly preferably polycarbonate or mixtures of the mentioned components,

b) at least one inorganic cesium tungstate IR absorbent,

c) at least one compound a phosine compound, preferably triphenylphosphine (TPP), trialkylphenylphosphine, trinaphthylphosphine or bisdiphenylphosphinoethane, triphenylphosphine (TPP) being particularly preferred.

As shown in the state of the art, the stabilizing effect of phosphines on inorganic IR absorbers is not known and, therefore, it has been very surprising that the IR performance of these systems can be improved in the long term by means of certain stabilizers based on phosphine.

The problem underlying the present invention of stabilizing tungstates as inorganic IR stabilizers in polymeric compositions is further solved by using phosphine compounds to stabilize, especially long-term stabilize, tungstates.

An object of the invention is also a process for the preparation of compositions according to the invention, as well as their use and the articles made with them.

The particle diameter of the cesium tungstates according to the invention is preferably less than 200 nm, particularly preferably less than 100 nm. The particles are transparent in the visible region of the spectrum, meaning that the absorption of these IR absorbers in the visible region of light, compared to the absorption in the IR region, is low and that the IR absorbers do not produce any clear opacity. increased or a distinct reduction in transmission (in the visible region of light) of the corresponding composition or final product.

Type b2) tungstates have an amorphous, cubic, tetragonal or hexagonal tungsten bronze structure, in which M represents Cs.

For the preparation of materials of this type, for example, tungsten trioxide, tungsten dioxide, a hydrate of a tungsten oxide, tungsten hexachloride, ammonium tungstate or tungsten acid and optionally other salts containing the element are mixed. M, such as, for example, cesium carbonate, in certain stoichiometric ratios, so that the molar ratio of the individual components is expressed by the formula MxWyOz. This mixture is then treated at temperatures between 100 ° C and 850 ° C in a reducing atmosphere, for example an argon-hydrogen atmosphere, and then the powder obtained is heated to temperatures between 550 ° C and 1200 ° C in an atmosphere of inert gas.

For the preparation of the inorganic IR absorbent nanoparticles according to the invention, the IR absorbent can be mixed with the dispersants described below and other organic solvents such as, for example, toluene, benzene or similar aromatic hydrocarbons and ground in a suitable mill. such as, for example, ball mills, with the addition of zirconium oxide (for example with a diameter of 0.3 mm) to produce the desired particle size distribution. The nanoparticles are obtained in the form of a dispersion. After grinding, other dispersants can be added, if necessary. The solvent is removed at elevated temperatures and under reduced pressure. Nanoparticles having a mean size of less than 200 nm, particularly preferably less than 100 nm, are preferred.

The size of the particles can be determined using the transmission electron spectroscope (TEM). Measurements of this type on IR absorbent nanoparticles are described, for example, by Adachi et al., J. Am. Ceram. Soc. 2008, 91,2897-2902.

The preparation of the tungstates according to the invention is accurately described, for example, in EP 1 801 815 A1 and is commercially available, for example, from Sumitomo Metal Mining Co., Ltd. (Japan) under the name YMDS 874.

For their use in transparent thermoplastics, the particles obtained in this way are dispersed in an organic matrix, for example in an acrylate, and if necessary, as described above, they are ground in a mill using suitable adjuvants such as, for example , zirconium dioxide, and optionally organic solvents such as, for example, toluene, benzene or similar hydrocarbons.

Suitable polymer-based dispersants are above all dispersants exhibiting high light transmission, such as, for example, polyacrylates, polyurethanes, polyethers, polyesters or polyetherurethanes, as well as polymers derived therefrom.

Polymers based on polyacrylates, polyethers and polyesters are preferred dispersants, with polyacrylates such as, for example, polyacrylates being particularly preferred as high temperature stable dispersants.

ES 2 547 019 T3 poly (methyl methacrylate) and polyesters. Mixtures of these polymers or also acrylate-based copolymers can also be used. In JP 2008214596 and by Adachi et al. J. Am Ceram. Soc. 2007, 90 4059-4061, for example, dispersion aids of this type and processes for the preparation of tungstate dispersions are described.

Suitable dispersants for the present invention are commercially available. In particular, dispersants based on polyacrylate are suitable. Suitable dispersants of this type can be obtained, for example, under the trade designation EF-KA®, for example EFKA® 4500 and EFKA® 4530 from Ciba Specialty Chemicals. Polyester-containing dispersants are also suitable. They can be obtained, for example, under the trade names Solsperse®, for example Solsperse® 22000, 24000SC, 26000, 27000 from Avecia. Polyether-containing dispersants are also known, for example under the trade names Dispar-lon® DA234 and DA325 from the company Kusumoto Chemicals. Polyurethane-based systems are also suitable. Polyurethane-based systems are available under the trade names EFKA® 4046, EFKA® 4047 from Ciba Specialty Chemicals. Texaphor® P60 and P63 are corresponding Cognis trade names.

The amount of IR absorbents in the dispersant is 0.2% by weight to 50.0% by weight, preferably 1.0% by weight - 40.0% by weight, more preferably 5% by weight - 35% by weight, and most preferably 10% by weight - 30% by weight, relative to the dispersion used according to the invention of the inorganic IR absorbent. In addition to the pure IR absorbent substance and the dispersant, other adjuvants such as, for example, zirconium dioxide, as well as residual solvents such as, for example , toluene, benzene, or similar aromatic hydrocarbons.

There is no limitation regarding the amount of the absorbent inorganic IR tungstate according to the invention in the polymer compositions according to the invention. Usually the tungstates are used in an amount of 0.0001% by weight - 10.0000% by weight, preferably 0.001% by weight - 1000% by weight and particularly preferably 0.002% by weight - 0.100% by weight calculated as a proportion of tungstate solids in the total polymer composition.

In a particular embodiment of the invention, the amount of cesium tungstate used according to the invention is 0.009% by weight - 0.020% by weight, preferably 0.012% by weight to 0.018% by weight, in turn indicated as a proportion of tungstate solids in the total polymer composition. The tungstate solid content in the present context means tungstate as a pure substance and not a dispersion, suspension or other preparation containing the pure substance, the following data also referring to the tungstate content always refer to this solid content, provided that not explicitly stated otherwise.

These concentrations are preferably used for finished parts with thicknesses of 2mm - 8mm, preferably 3.5mm - 7.0mm and particularly preferably 4mm - 6mm.

In a further embodiment, in addition to the cesium tungstate according to the invention, additionally other IR absorbents can optionally be used as IR absorbents, their ratio in relation to quantity and / or yield in such a mixture, however, being lower in each case. to that of the wolframato described above. In mixtures, compositions containing from two to even five and particularly two or three different IR absorbers are preferred in this regard.

The additional IR absorbent is preferably selected from the group containing borides and tin oxides, particularly preferably LaB6 or antimony doped tin oxide or indium tin oxide.

In an alternative embodiment of the present invention, the polymer composition according to the invention does not contain any inorganic IR absorbents of the metal boride type such as, for example, lanthanum hexaboride, LaB6.

In another preferred embodiment, the additional IR absorber (s) have / have an absorption spectrum different from that of the cesium tungstate used with respect to the absorption maxima, so that an absorption region is covered. maximum with maximums.

Suitable additional organic infrared absorbers are described according to substance class, for example, by M. Matsuoka, Infrared Absorbing Dyes, Plenum Press, New York, 1990. Particularly suitable are infrared absorbers of the classes of phthalocyanines, naphthalocyanines, metal complexes, azo dyes, anthraquinones, quadratic acid derivatives, immonium dyes, perylenes, quaterylenes, as well as polymethines. Phthalocyanines and naphthalocyanines are very particularly suitable thereof.

Due to the improved solubility in thermoplastics, phthalocyanines and naphthalocyanines with sterically demanding side groups such as, for example, phenyl, phenoxy, alkylphenyl, alkylphenoxy, tert-butyl, (-Sphenyl), -NH-aryl, -NH-alkyl and similar group.

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Other inorganic IR absorbers are, for example, boride- or nitride-based substances such as, for example, lanthanum hexaboride.

Furthermore, compounds such as indium oxide can be used, which is doped with 2 to 30 atom%, preferably 4 to 12 atom% of tin (ITO) or 10 to 70 atom% of fluorine.

The combination with tin oxide as an additional IR absorber, which is doped with 2 to 60 atom% of antimony (ATO) or 10 to 70 atom% of fluorine, is particularly preferred.

Also particularly suitable is tin oxide which is doped with 1 to 30 atom%, preferably with 2 to 10 atom% of aluminum or with 2 to 30 atom% of indium or with 2 to 30 atom% gallium.

Mixtures of the aforementioned IR absorbers are particularly suitable, since the skilled person can achieve an optimization of the absorption in the near infrared region by means of a suitable choice.

Phosphine compounds in the context of the invention are all organic hydrogen phosphide (phosphine) derivatives and salts thereof. With regard to the choice of phosphines there is no limitation, the phosphine compounds being preferably selected from the group comprising aliphatic phosphines, aromatic phosphines and aliphatic-aromatic phosphines.

The phosphine compounds can be primary, secondary, and tertiary phosphines. Tertiary phosphines are preferably used, aromatic phosphines being particularly preferred and tertiary aromatic phosphines being very particularly preferred.

In a preferred embodiment of the invention, triphenylphosphine (TPP), trialkylphenylphosphine, bisdephenylphosphinoethane or a trinaphthylphosphine are used, of which triphenylphosphine (TPP) or mixtures of these phosphines are very particularly preferred.

Basically mixtures of different phosphines can be used.

In a special embodiment of the present invention, the phosphine compounds according to the invention are used together with a phosphite or a phenolic antioxidant or a mixture of both of the last-mentioned compounds.

In another particular embodiment, the IR absorbent according to the invention is mixed before its incorporation into the thermoplastic polymeric matrix with the phosphine stabilizer according to the invention or a mixture containing a phosphine compound according to the invention together with a phosphite or an antioxidant phenolic or a mixture of both compounds mentioned last.

The preparation and properties of phosphine compounds are known to the person skilled in the art and are described, for example, in EP-A 0 718 354 and in Ullmanns Enzyklopadie der Technischen Chemie, 4^to ed., volume 18, pages 378-398 and Kirk-Othmer, 3rd ed., volume 17, pages 527-534.

With regard to the amount of the phosphine compounds present in the polymer composition, there is no limitation. The phosphines are preferably used in an amount of from 0.0001% by weight to 10.0000% by weight, particularly preferably from 0.01% by weight to 0.20% by weight, relative to the mass of the total polymer composition. In a particular embodiment of the present invention, phosphines are used in an amount of 0.05% by weight to 0.15% by weight relative to the mass of the total polymer composition. When using a quantity of the phosphine compound, it must be taken into account that under certain processing conditions the substance oxidizes as a function of the temperature and the residence time. The oxidized portion is no longer available for the stabilization of the cesium tungstate. Therefore, the number of processing steps and the corresponding process conditions must be taken into account.

Preferably, the amount of unoxidized phosphine compounds in the final product is> 0.01% by weight, more preferably> 0.02% by weight.

By using the aforementioned phosphine stabilizers, the cesium tungstate IR absorbents of the present invention, especially Cs0.33WO3, can be stabilized in the long term in the polymer matrix and a reduction in IR absorption prevented. In this connection, triphenylphosphine (TPP) is particularly preferably used as stabilizer.

To stabilize the thermoplastic matrix, additional phosphorus-based stabilizers can be used, provided that these do not adversely influence the effect of the stabilizers described above.

Although phosphines obviously stabilize IR absorbent tungstates, it has surprisingly been found that phosphates, phosphoric acids, phosphoric acid derivatives or corresponding stabilizers which contain these compounds or can form them, cause more rapid damage to the tungstates according to the invention and, hence a reduction in IR absorption.

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Suitable additional stabilizers are phosphites or phenolic antioxidants or mixtures thereof, which can be used without having a negative effect on the stability of the IR absorbent together with the phosphines described above. Suitable commercially available products are, for example, Irgafos® 168 ((2,4-di-tert-butyl-phenyl) tris-phosphite) and Irganox® 1076 (2,6-di-tert-butyl-4- (octadecanoxycarbonylethyl ) phenol), in each case individually or in combination.

The amount of optionally used phosphites is preferably 0.20% by weight - 0.01% by weight, particularly preferably 0.10% by weight - 0.02% by weight. The amount of phenolic antioxidants used optionally is preferably 0.100% by weight - 0.001% by weight, especially preferably 0.050% by weight - 0.005% by weight.

In a preferred embodiment, the polymer composition according to the invention also contains an ultraviolet absorber. Ultraviolet absorbers suitable for use in the polymer composition according to the invention are compounds which have the lowest possible transmission of less than 400 nm and the highest possible transmission of greater than 400 nm. Compounds of this type and their preparation are known from the literature and are described, for example, in documents EP-A 0 839 623, WO-A 96/15102 and EP-A 0 500 496. Ultraviolet absorbents particularly suitable for their use in the composition according to the invention are benzotriazoles, triazines, benzophenones and / or arylated cyanoacrylates.

Particularly suitable ultraviolet absorbers are hydroxy-benzotriazoles, such as 2- (3 ', 5'-bis- (1,1-dimethylbenzyl) -2'-hydroxy-phenyl) -benzotriazole (Tinuvin® 234, Ciba Spezialitatenchemie, Basel), 2 - (2'-hydroxy-5 '- (terthoctyl) -phenyl) -benzotriazole (Tinuvin® 329, Ciba Spezialitatenchemie, Basel), 2- (2'-hydroxy-3' - (2-butyl) -5 '- ( tert-butyl) phenyl) -benzotriazole (Tinuvin® 350, Ciba Spezialitatenchemie, Basel), bis- (3- (2H-benzotriazolyl) -2-hydroxy-5-tertiary) methane, (Tinuvin® 360, Ciba Spezialitatenchemie, Basel), (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) -phenol (Tinuvin® 1577, Ciba Spezialitatenchemie, Basel), as well as benzophenones 2,4-dihydroxy-benzophenone (Chimasorb® 22, Ciba Spezialitatenchemie, Basel) and 2-hydroxy-4- (octyloxy) -benzophenone (Chimassorb® 81, Ciba, Basel), 2-cyano-3,3-diphenyl ester 2-propenoic acid -, 2,2-bis [[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl) oxy] -methyl] -1,3-propanediilic acid (9CI) (Uvinul® 3030, bAsF AG Ludwigshafen), 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine (CGX UVA 006, Ciba Spezialitatenchemie, Basel) or tetra-bismalonate ethyl-2,2 '- (1,4-phenylene-dimethylidene) (Hostavin® B-Cap, Clariant AG).

Mixtures of these ultraviolet absorbers can also be used.

With regard to the amount of the ultraviolet absorber present in the composition, there is no limitation, as long as the desired absorption of UV radiation is guaranteed, as well as a sufficient transparency of the shaped body manufactured from the composition. According to a preferred embodiment of the invention, the composition contains ultraviolet absorbent in an amount from 0.05% by weight to 20.00% by weight, especially from 0.07% by weight to 10.00% by weight and particularly preferably 0.10% by weight to 1.00% by weight.

Transparent thermoplastic plastics in the context of the invention are, for example, polymerizates of ethylenically unsaturated monomers and / or polycondensed bifunctional reactive compounds. Examples of transparent thermoplastic polymers are, for example, polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or copolymethacrylates such as, for example, poly- or copoly (methyl methacrylates), as well as copolymers with styrene such as , for example, transparent polystyrene acrylonitrile (PSAN) or polymers based on ethylene and / or propylene, as well as aromatic polyesters such as PET, PEN or PETG and transparent thermoplastic polyurethanes. They can also be introduced by mixing polymers based on cyclic olefins (for example TOPAS TM, a commercial product from Ticona), poly- or copolycondensates of terephthalic acid such as, for example, poly- or copoly (ethylene terephthalate) (PET or CoPET) or PETG.

Mixtures of various transparent thermoplastic polymers are also possible. Poly (methyl methacrylates), aromatic polyesters, polycarbonates or copolycarbonates are preferred, with polycarbonate being particularly preferred.

Particularly preferred polycarbonates according to the invention are homopolycarbonate based on bisphenol A, homopolycarbonate based on 1,3-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and copolycarbonates based on both monomers bisphenol A and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Polycarbonates, in the context of the present invention, are both homopolycarbonates and copolycarbonates; the polycarbonates can be, in a known way, linear or branched.

The preparation of the polycarbonates is carried out in a known way from diphenols, derivatives of carbonic acid, optionally chain interrupters and branching agents.

Details on the preparation of polycarbonates have been documented in many patent documents for approximately 40 years.For example, here we can refer to Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Volume 9, Inter-science Publishers, New York , London, Sydney 1964, to D. Freitag, U. Grigo, PR Müller, H. Nouvertne ', BAYER AG, Polycarbonates in Encyclopedia of Polymer

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Science and Engineering, Volume 11, second edition, 1988, pages 648-718 and finally to Drs. U. Grigo, K. Kirchner and PR Müller Polycarbonate in Becker / Braun, KunststoffHandbuch, volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pages 117-299.

Diphenols, for example hydroquinone, resorcin, dihydroxydiphenyl, bis- (hydroxyphenyl) -alkane, bis (hydroxyphenyl) -cycloalkane, bis- (hydroxyphenyl) sulfide, bis- (hydroxyphenyl) ether, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) -sulfone, bis- (hydroxyphenyl) -sulfoxide, alpha, alpha'-bis- (hydroxyphenyl) diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, as well as their alkylated compounds, alkylated in the nucleus and halogenated in the nucleus.

Suitable diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane,

1.1- bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (3,5-di-methyl-4-hydroxyphenyl) -pdiisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane.

Particularly preferred diphenols are 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane,

2.2- bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 1,1-bis- (4-hydroxyphenyl) - cyclohexane and 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

These and other suitable diphenols are described, for example, in US-A 2 999 825, US-A 3 148 172, US-A 2 991 273, US-A 3 271 367, US-A 4 982 014 and US-A 4 982 014 and -A 2 999 846, in documents DE-A 1 570 703, DE-A 2063 050, DE-A 2 211 956 and DE-A 3 832 396, in document FR-A 1 561 518, in monograph H Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, as well as JP-A 62039/1986, JP-A 62040/1986 and JP-A 105550/1986.

In the case of homopolycarbonates only one diphenol is used, in the case of copolycarbonates several diphenols are used.

Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.

Suitable chain switches that can be used in the preparation of the polycarbonates are both monophenols and also monocarboxylic acids. Suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso-nonylphenol, halogenated phenols such as p-chlorophenol, 2, 4-dichlorophenyl, p-bromophenol and 2,4,6-tribromophenol, 2,4,6-triiodophenol, p-iodophenol, as well as their mixtures.

Preferred chain switches are phenol, cumylphenol and / or p-tert-butylphenol.

Suitable monocarboxylic acids are also benzoic acid, alkylbenzoic acids and halogenobenzoic acids.

Preferred chain switches are also phenols which are monosubstituted or polysubstituted with linear or branched C1 to C30 alkyl moieties, preferably unsubstituted or substituted with tert-butyl.

The amount of chain switches to be used is preferably 0.1 to 5% by moles, with respect to the moles of the diphenols used in each case. The addition of the chain switches can be done before, during or after the phosgenation.

Suitable branching agents are trifunctional or higher functional compounds known in polycarbonate chemistry, especially those with three or more than three phenolic OH groups.

Suitable branching agents are, for example, floroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl2,4,6-tri (4-hydroxyphenyl) - heptane, 1,3,5-tri (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) phenylmethane, 2,2-bis- [4 , 4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenylisopropyl) -phene 2,6-bis- (2-hydroxy-5'-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, Hexa- (4-hydroxyphenylisopropyl) -phenyl) ester of orthotherephthalic acid, tetra- (4-hydroxyphenyl) -methane, tetra- (4- (4-hydroxyphenylisopropyl) phenoxy) -methane and 1,4-bis - ((4 ', 4-dihydroxytriphenyl) -methyl) -benzene, as well as 2,4-dihydroxybenzoic acid, trimesinic acid, cyanuric chloride and 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3 -dihydro-indole.

The amount of branching to be used if appropriate is preferably 0.05 to 2.00% by mole, in turn based on the moles of the diphenols used in each case.

The branching agents can be present either with the diphenols and chain interrupters in the aqueous alkaline phase or added dissolved in an organic solvent prior to phosgenation. In case of using transesterification procedures, the branching agents are used together with the diphenols.

ES 2 547 019 T3

The aromatic polycarbonates of the present invention have weight average molecular weights Mw (determined by gel permeation chromatography and calibration with polycarbonate calibration) of between 5000 and 200,000, preferably between 10,000 and 80,000 and particularly preferably between 15,000 and 40,000 ( this corresponds to approximately between 12,000 and 330,000, preferably between 20,000 and 135,000 and particularly preferably between 28,000 and 69,000 determined by calibration using a polystyrene standard)

The polymer compositions according to the invention may contain, in addition to the stabilizers according to the invention, optionally additional customary polymer additives such as antioxidants, mold release agents, flame retardant materials, colorants, heat stabilizers, UV stabilizers or optical brighteners described in EP-A documents. 0 839 623, WO-A 96/15102, EP-A 0 500 496 or in Plastics Additives Handbook, Hans Zweifel, 5^to 2000 edition, Hanser Verlag, Munich) in the usual amounts for the corresponding thermoplastics, with the dyes being particularly preferred of the optionally contained additional customary polymeric additives mentioned, in a special embodiment.

Preferably, the additional polymeric additives are used in amounts of 0% by weight to 5% by weight, more preferably 0.1% by weight to 1% by weight, relative to the amount of the corresponding total polymer composition. Mixtures of various additives are also suitable.

In a particular embodiment of the present invention, the polymeric composition is free of phosphates, phosphoric acids, derivatives of phosphoric acid or corresponding stabilizers that contain these compounds or that can form them.

Dyes or pigments in the context of the present invention are sulfur-containing pigments such as cadmium red and cadmium yellow, iron cyanide-based pigments such as Prussian blue, oxide pigments such as titanium dioxide, zinc oxide, iron oxide red, iron oxide black, chromium oxide, titanium yellow, zinc-iron-based brown, titanium-cobalt-based green, cobalt blue, copper-chromium-based black and copper-iron-based black or chromium-based pigments such as chromium yellow, phthalocyanine-derived colorants such as copper-phthalocyanine blue and copper-phthalocyanine green, condensed polycyclic colorants and pigments such as azo-based dyes (e.g. nickel-azo yellow), sulfur-indigo dyes, perinone-based derivatives, perylene-based, quinacridone derivatives, dioxazine-based, isoindolinone-based and quinophthalone derivatives, anthraquinone-based heterocyclic systems.

Specific examples of commercial products are, for example, MACROLEX® Blau RR, MACROLEX® Violet 3R, MACRO-LEX® Violet B (Lanxess AG, Germany), Sumiplast® Violet RR, Sumiplast® Violet B, Sumiplast® Blue OR, (Sumitomo Chemical Co., Ltd.), Diaresin® Violet D, Diaresin® Blue G, Diaresin® Blue N (Mitsubishi Chemical Corporation), Heliogen® Blue or Heliogen® Green (BASF AG, Germany).

Of these, cyanine derivatives, quinoline derivatives, anthraquinone derivatives, phthalocyanine derivatives are preferred.

Particularly suitable mold release agents for the compositions according to the invention are, for example, pentaerythritol stearate (PETS) or glycerol monostearate (gMs).

The processes for preparing the polymeric compositions according to the invention are known to those skilled in the art.

The preparation of the polymeric compositions according to the invention containing a thermoplastic plastic, cesium tungstate as inorganic IR absorber, a phosphine compound and optionally other customary polymeric additives is carried out with customary incorporation procedures by bringing together, mixing and homogenizing the individual components , in particular homogenization preferably taking place in the melt under the action of shear forces. If necessary, the gathering and mixing are carried out before homogenization of the melt using powdered premixes.

It is also possible to use premixes which have been prepared from solutions of the components of the mixture in suitable solvents, where appropriate being homogenized in solution and then removing the solvent.

In particular, in this connection, IR absorbers, phosphine compounds, ultraviolet absorbers and other additives can be incorporated into the composition according to the invention by known methods or as a masterbatch.

The use of masterbatches is especially for the incorporation of preferred IR absorbents, especially polycarbonate-based masterbatches being used, in which the IR absorbent has been incorporated in the form of a ready-to-use IR absorbent formation containing dispersants, preferably dispersants based on polyacrylate, polyether or polyester, of which preferably dispersants stable at high temperatures, such as a polyacrylate (homopolymer or copolymer), such as, for example, poly (methyl methacrylate) and / or polyesters or their mixtures, which also contain adjuvants such as, for example, zirconium dioxide and given

ES 2 547 019 T3 is the residual solvent such as, for example, toluene, benzene or other similar aromatic hydrocarbons. By using these masterbatches in combination with the corresponding IR absorbent formulation agglomeration of the IR absorbent in the polymer composition is usefully prevented.

In this context, the composition can be pooled, mixed, homogenized and then extruded in common devices such as screw extruders (eg twin screw extruders, EDTs), kneaders, Brabender or Banbury mills. After extrusion, the extrudate can be cooled and ground. It is also possible to premix the individual components and then add the remaining starting materials individually and / or also in admixture.

In a particular embodiment, the cesium tungstate IR absorbent according to the invention is mixed with the phosphine stabilizer according to the invention or with a mixture containing a phosphine compound according to the invention together with a phosphite or a phenolic antioxidant with a mixture of the two last mentioned compounds giving a master mix, mixing preferably taking place in the melt before the action of shear forces (for example in a kneader or a twin screw extruder). This process offers the advantage that the IR absorbent is also already protected during the formation of composites and damage to it is avoided. For the preparation of the masterbatch, the preferred polymeric matrix is ​​the thermoplastic plastic, which also represents the main component of the final total polymeric composition.

The prepared master mix contains

to. 85.00% by weight - 98.89% by weight, preferably 93.00% by weight - 98.89% by weight of a transparent thermoplastic plastic;

b. 0.1% by weight - 2.0% by weight of Cs0.33WO3; Y

c. 1.0% by weight - 4.8% by weight of dispersant

d. 0.01% by weight - 0.20% by weight of a phosphine-based stabilizer, preferably triphenylphosphine (TPP),

and. optionally 0-8.0% by weight of another adjuvant and / or additive, such as, for example, zirconium dioxide, the sum of the components ae being 100% by weight.

In a preferred embodiment the inorganic IR absorbent is present in an acrylate matrix. In another preferred embodiment, the transparent thermoplastic plastic is a polycarbonate. Another preferred embodiment provides triphenylphosphine (TPP) as a stabilizer.

The polymer compositions according to the invention can be processed to give articles or molded bodies, for example extruding the polymer compositions first as described, giving a granulate and this granulate is processed by suitable processes to give different articles or molded bodies in a specific way. known.

The compositions according to the invention can be transformed in this context, for example, by hot pressing, spinning, blow molding, deep drawing forming, extrusion or injection molding into molded articles or bodies, molded objects such as toy parts, fibers, films, bands, plates such as massive plates, cellular plates, bialveolar plates or corrugated plates, containers, tubes or other profiles. Also of interest is the use of multilayer systems. The application can be carried out during or immediately after the shaping of the basic body, for example by coextrusion or injection molding of several components. The application can, however, also be carried out on the ready molded basic body, for example by lamination with a film or by coating with a solution.

The base layer plates and optional cover layer / optional cover layers are, however, preferably produced by (co) extrusion.

For extrusion, the pretreated polymer composition is fed, if necessary, by drying in the extruder, for example, and melted in the plasticizing system of the extruder. The plastic melt is then pressed through a wide slot die or a honeycomb plate die and in this respect is shaped, shaped into the desired final shape in the gap between rolls of a satin calender and fixed. the shape by reciprocal cooling on satin rollers and the surrounding air. The temperatures necessary for the extrusion of the polymer composition are adjusted, and the manufacturer's instructions can usually be followed. If the polymer compositions contain, for example, polycarbonates with a high melt viscosity, these are normally processed at melt temperatures of 260 ° C to 320 ° C, with the cylinder temperatures of the plasticizer cylinder being adjusted, as well as the temperatures of nozzle correspondingly.

ES 2 547 019 T3

By using one or more side extruders and a multi-channel die or optionally melt adapters before a wide slot die, thermoplastic melts of different compositions can be arranged one on top of the other and thus produce plates. or multilayer foils (for coextrusion see, for example, EP-A 0 110 221, EP-A 0 110 238 and EP-A 0 716 919, for details of the adapter and nozzle procedure see Johannaber / Ast: ”Kunststoff- Maschinenführer, Hanser Verlag, 2000 and Gesellschaft Kunststofhechnik:“ Coextrudierte Folien und Platten: Zukunftsperspektiven, Anforderungen, Anlagen und Herstellung, Qualitatssicherung, VDI-Verlag, 1990).

Preferred articles or shaped bodies according to the invention are plates, films, glazing, for example car windows, car sunroofs, panoramic roofs, roofs or building glazing containing the compositions according to the invention. In this connection, bialveolar plates or multialveolar plates can also be used. As additional components of the articles according to the invention, in addition to the compositions according to the invention, for example parts of other materials may be present in the articles according to the invention. For example, glazing may have sealing materials on the edges of the glazing. The roofs can have, for example, metallic materials such as screws, metal pins or the like, which can serve to fix or guide (in the case of folding or sliding roofs) the roof elements. Furthermore, other materials can be joined with the compositions according to the invention, for example in 2-component injection molding. Thus, the corresponding component with IR absorbent properties can be provided with an edge which serves, for example, for its adhesion.

Articles containing the polymer composition of the present invention have opacity values ​​of less than 5%, preferably less than 4%.

Furthermore, the articles present a TDS value preferably <80% (TDS: direct solar transmittance; the values ​​are measured on color sample plates with a thickness of 4 mm. The calculation of the total transmission TDS is carried out according to the ISO 13837 standard, computational convention A).

In a particular embodiment, the articles of the composition of the present invention are coated. This coating serves as protection of the thermoplastic material against general meteorological influences (for example damage caused by sunlight), as well as against mechanical damage to the surface (for example scratching) and therefore increases the stability of the article. corresponding finish.

It is known that polycarbonate can be protected against UV radiation by means of different coatings. These coatings usually contain UV absorber. These layers also increase the scratch resistance of the corresponding article. The articles of the present invention may carry single-layer or multi-layer systems. They can be coated on one side or on both sides. In a preferred embodiment the article contains a scratch resistant varnish containing UV absorber.

In glazing materials, the article carries at least one scratch resistant or anti-reflection coating on at least one side.

The production of the coating, for example an antireflection coating, can be carried out by different processes. For example, a coating can be carried out by various evaporative metallization processes, for example by electron beam processes, resistance heating, as well as by plasma deposition or various spraying processes such as high frequency spraying, magnetron spraying, sputtering ion beam, etc, ion plating by DC, RF, HCD procedures, reactive ion plating, etc, or gas phase chemical deposition. Furthermore, the anti-reflection coating can also be applied from a solution. Thus, by dispersing a metal oxide with a high refractive index such as ZrO2, TiO2 Sb2Os or WO3 in a silicone-based varnish a corresponding coating solution can be produced, which is suitable for coating plastic articles and can harden thermally or UV-protective.

Various methods are known for producing a scratch resistant coating on plastic articles. For example, varnishes based on epoxy, acrylic, polysiloxane, colloidal silica gel, or inorganic / organic (hybrid systems) can be used. These systems can be applied, for example, by dipping processes, spin coating, spray processes or fluid coating. Curing can be carried out thermally or by means of UV radiation. Single or multi-layer systems can also be used. The scratch resistant coating can be applied, for example, directly or after surface preparation of the substrate with a primer (primer). Furthermore, a scratch resistant coating can be applied by plasma protected polymerization procedures, for example by a SiO2 plasma. Anti-condensation and anti-reflection coatings can also be produced by plasma processes. Furthermore, it is possible to apply by certain injection molding processes, such as, for example, back injection of surface treated films, a scratch resistant coating to the resulting molded body. Various additives may be present in the scratch-resistant layer, such as, for example, UV absorbers, derived for example from triazoles or triazines. In addition, IR absorbents of organic or inorganic nature may be present. These additives can be present in the scratch resistant varnish itself or in the primer coat. The thickness of the scratch resistant layer is 1 pm, - 20 pm,

ES 2 547 019 T3 preferably 2 pm, -15 pm. Below 1 pm the strength of the scratch resistant layer is insufficient. Above 20 mm, cracks frequently appear in the varnish. The base material according to the invention, which has been described in the present invention, is preferably provided after the injection-molded article has been finished with a scratch-resistant and / or anti-reflection layer described, since the sector of preferred use is in the window and automobile glazing sector.

For polycarbonates a primer containing UV absorbers is preferably used to improve the adhesion of the scratch resistant varnish. The primer may contain additional stabilizers such as HALS systems (hindered amine stabilizers), adhesives, flow aids. The corresponding resin can be selected from a plurality of materials and is described, for example, in Ullmann's Encylopedia of Industrial Chemistry, 5^to edition, Vol. A18, pages 368-426, VCH, Weinheim 1991. Polyacrylates, polyurethanes, phenol-based, melamine-based, epoxy and alkyd systems or mixtures of these systems can be used. The resin is most often dissolved in suitable solvents, often alcohols. Depending on the selected resin, curing can be carried out at room temperature or at increased temperatures. Preferably temperatures between 50 ° C and 130 ° C are used, often thereafter a large part of the solvent is briefly removed at room temperature. Commercially available systems are, for example, SHP470, SHP470FT2050 and SHP401 from Momentive Performance Materials. Coatings of this type are described, for example, in US 6350512 B1, US 5869185, EP 1308084, WO 2006/108520.

Scratch-resistant varnishes (hard coatings) preferably consist of siloxanes and preferably contain UV absorbers. They are preferably applied by immersion or flow procedures. Curing takes place at temperatures of 50 ° C - 130 ° C. Commercially available systems are, for example, AS4000, SHC5020 and AS4700 from Momentive Performance Materials. Systems of this type are described, for example, in documents US 5041313, DE 3121385, US 5391795, WO 2008/109072. The synthesis of these materials is generally carried out by condensation of alkoxy- and / or alkylalkoxysilanes with acidic or basic catalysis. Nanoparticles can optionally be incorporated. Preferred solvents are alcohols such as butanol, isopropanol, methanol, ethanol, and mixtures thereof.

Instead of primer / scratch resistant coatings combinations, one-component hybrid systems can be used. These are described in EP0570165 or WO 2008/071363 or DE 2804283. Commercially available hybrid systems can be obtained, for example, under the designations PHC587 or UVHC 3000 in Momentive Performance Materials.

Examples

In the following, the invention will be described by means of the embodiments in more detail, using the determination procedures described herein for all the corresponding quantities in the present invention, provided that the contrary has not been described.

The determination of the volumetric melt index (MVR) is carried out according to ISO 1133 (at 300 ° C; 1.2 kg).

Determination of the TDS value (direct solar transmittance):

Transmission and reflection measurements were carried out on a Perkin Elmer Lambda 900 spectral photometer with photometric sphere (i.e. determination of total transmission both by measurement of diffuse and direct transmission as well as diffuse and direct reflection). All values ​​were determined from 320 nm to 2300 nm.

The calculation of the total transmission TDS was carried out according to ISO 13837, computational convention A).

The thermal storage of the samples is carried out in an oven with air circulation. Thermal storage was carried out at 110 ° C. From the measured values, the percentage change of the corresponding values ​​was calculated. The results are represented in table 1.

Makrolon 2608 (linear bisphenol A polycarbonate) polycarbonate from Bayer Material Science with a volumetric melt index (MVR) of 12 cm was used to produce the sample bodies.³/ 10 min at 300 ° C and 1.2 kg load according to ISO 1133.

The incorporation of the additives to form a composite material was carried out in a two-shaft extruder from the company KrausMaffei Berstorff tYp ZE25 at a shell temperature of 260 ° C or a mass temperature of 270 ° C and a rotation frequency of 100 rpm with the amounts of additives indicated in table 1.

The granules are dried at 120 ° C for 3 hours under vacuum and then processed in an injection molding machine of the Arburg 370 type with a unit of 25 injections at a mass temperature of 300 ° C and a temperature of the 90 ° C tool giving color sample plates with the measurements of 60mm x 40mm x 4mm.

ES 2 547 019 T3

As IR absorbent, a cesium tungstate dispersion (Cs0.33WO3), (YMDS 874 from Sumitomo Metal Mining, Japan) is used, the solids content of cesium tungstate in the dispersion being 25% by weight. The weight data in the examples refer to cesium tungstate as a pure substance.

As stabilizers for the stabilization of the inorganic IR absorbent the following compounds were used:

T1: triphenylphosphine (TPP, Sigma-Aldrich, 82018 Taufkirchen, Germany)

T2: tris (2,4-di-tert-butyl-phenyl) phosphite (Irgafos® 168 from Ciba Specialty Chemicals, Basel, Switzerland).

T3: 1,2-bis- (diphenyphosphino) -ethane (Sigma-Aldrich, 82018 Taufkirchen, Germany)

T4: tri-o-tolylphosphine (Sigma-Aldrich, 82018 Taufkirchen, Germany)

Example 1 (comparative example)

A composite of Makrolon® 2608 with 0.015% by weight of cesium tungstate, Cs0.33WO3, (corresponding to 0.060% by weight of a dispersion of YMDS 874) was produced as described above. The results of the thermal storage are indicated in Table 1.

Example 2 (comparative example)

A composite of Makrolon® 2608 was produced with 0.015% by weight of cesium tungstate, Cs0.33WO3, (corresponding to 0.060% by weight of a dispersion of YMDS 874) and 0.1% by weight of Irgafos 168 such as described above. The results of the thermal storage are indicated in Table 1.

Example 3 (according to the invention)

To Makrolon® 2608 was added 0.015% by weight of cesium tungstate, Cs0.33WO3, (corresponding to 0.060% by weight of a dispersion of YMDS 874) and 0.1% by weight of 1,2-bis- ( diphenylphosphino) -ethane under the conditions described above.

Example 4 (according to the invention)

A composite of Makrolon® 2608 was produced with 0.015% by weight of cesium tungstate, Cs0.33WO3, (corresponding to 0.060% by weight of a dispersion of YMDS 874) and 0.1% by weight of triphenylphosphine (TPP ) as described above. The results of the thermal storage are indicated in Table 1.

Example 5 (according to the invention)

To Makrolon® 2608 was added 0.015% by weight of cesium tungstate, Cs0.33WO3, (corresponding to 0.060% by weight of a dispersion of YMDS 874) and 0.1% by weight of tri-o-tolylphosphine in the conditions described above.

Table 1: Modification of IR properties after thermal storage

<td>Example no.</td><td>Stabilizer used</td><td>ATds (500 h)</td><td>ATds (1000 h)</td>

<td>1 (comparative)</td><td> -</td><td> 4,6</td><td> 5,1</td>

<td>2 (comparative)</td><td>T2</td><td> 4,0</td><td> 4,8</td>

<td>3 (according to the invention)</td><td>T3</td><td> 2,3</td><td> 2,6</td>

<td>4 (according to the invention)</td><td>T1</td><td> 2,0</td><td> 2,0</td>

<td>5 (according to the invention)</td><td>T4</td><td> 2,1</td><td> 2,6</td>

Table 2: Modification of IR properties after thermal storage in%

<td>Example no.</td><td>Stabilizer used</td><td>ATds (500 h) [%]</td><td>ATds (1000 h) [%]</td>

<td>1 (comparative)</td><td> -</td><td> 8,5</td><td> 9,6</td>

<td>2 (comparative)</td><td>T2</td><td> 7,6</td><td> 9,1</td>

<td>3 (according to the invention)</td><td>T3</td><td> 4,6</td><td> 5,2</td>

ES 2 547 019 T3

<td>4 (according to the invention)</td><td>T1</td><td> 3,8</td><td> 3,8</td>

<td>5 (according to the invention)</td><td>T4</td><td> 3,9</td><td> 4,8</td>

The samples produced from the compositions according to the invention show a reduced modification in ATDS compared to the compositions not according to the invention. Even after 1000 h of thermal alteration at 110 ° C, the compositions according to the invention show good IR absorption properties.

Surprisingly, the addition of additional heat stabilizers that are not based on phosphine does not produce any clear improvement in IR absorption properties (example 2). The TDS value of the compositions according to the invention increases after thermal storage significantly less with respect to the starting value before thermal storage than that of the comparative examples, which means a better IR absorption property after thermal storage.