US20110293921A1 - Polymer composition having heat-absorbing properties and improved colour properties - Google Patents

Polymer composition having heat-absorbing properties and improved colour properties Download PDF

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US20110293921A1
US20110293921A1 US13/104,197 US201113104197A US2011293921A1 US 20110293921 A1 US20110293921 A1 US 20110293921A1 US 201113104197 A US201113104197 A US 201113104197A US 2011293921 A1 US2011293921 A1 US 2011293921A1
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boride
inorganic
nano
composition according
composition
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Alexander Meyer
Gunther Stollwerck
Sven Gestermann
Klaus Horn
Birgit Meyer Zu Berstenhorst
Jörg Reichenauer
Andrea Scagnelli
Gianmaria Malvestiti
Massimo Tironi
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Covestro Deutschland AG
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Bayer MaterialScience AG
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Assigned to BAYER MATERIALSCIENCE AG reassignment BAYER MATERIALSCIENCE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BERSTENHORST, BIRGIT MEYER ZU, HORN, KLAUS, GESTERMANN, SVEN, STOLLWERCK, GUNTHER, MEYER, ALEXANDER, REICHENAUER, JOERG, MALVESTITI, GIANMARIA, SCAGNELLI, ANDREA, TIRONI, MASSIMO
Publication of US20110293921A1 publication Critical patent/US20110293921A1/en
Priority to US14/527,222 priority Critical patent/US9605129B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • Glazing made from compositions containing transparent thermoplastic polymers such as, for example, polycarbonate offer many advantages over conventional glazing made of glass for use in the automotive sector and for buildings. Such advantages include, for example, increased break resistance and/or an increased weight saving, which in the case of automotive glazing permit greater safety for the occupants in the event of road traffic accidents and a lower fuel consumption. Finally, transparent materials containing transparent thermoplastic polymers permit substantially greater freedom in terms of design because they are easier to mould.
  • thermoplastic polymers It is a disadvantage, however, that the high heat transmissibility (i.e. transmissibility for IR radiation) of transparent thermoplastic polymers leads to undesirable heating of the inside of motor vehicles and buildings under the action of the sun.
  • the raised temperatures on the inside reduce the comfort for the occupants or residents and can involve increased demands in terms of air conditioning, which in turn increase the energy consumption and thus eliminate the positive effects again.
  • glazing provided with appropriate heat protection is required. This is true for the automotive sector in particular.
  • NIR near-infrared
  • Penetrating solar radiation is absorbed inside a car, for example, and emitted as long-wave heat radiation having a wavelength of from 5 ⁇ m to 15 ⁇ m.
  • conventional glazing materials in particular thermoplastic polymers that are transparent in the visible range—are not transparent in that range, the heat radiation is unable to radiate to the outside. A greenhouse effect is obtained and the interior heats up. In order to keep this effect to a minimum, the transmission of the glazing in the NIR should therefore be minimised as far as possible.
  • Conventional transparent thermoplastic polymers such as, for example, polycarbonate are, however, transparent both in the visible range and in the NIR.
  • Additives for example, which exhibit as low a transparency as possible in the NIR without adversely affecting the transparency in the visible range of the spectrum are therefore required.
  • polymers based on polymethyl methacrylate (PMMA) and polycarbonate are particularly suitable for use as a glazing material. Because of its high strength, polycarbonate in particular has a very good property profile for such uses.
  • corresponding infrared absorbers are therefore used as additives.
  • IR absorber systems which have a broad absorption spectrum in the NIR range (near-infrared, 750 nm-2500 nm) while at the same time having low absorption in the visible range (low inherent colour) are of particular interest for that purpose.
  • the corresponding polymer compositions should additionally have high heat stability as well as excellent light stability.
  • IR absorbers based on organic or inorganic materials which can be used in transparent thermoplastics are known. A selection of such materials is described, for example, in J. Fabian, H. Nakazumi, H. Matsuoka, Chem. Rev. 92, 1197 (1992), in U.S. Pat. No. 5,712,332 or JP-A 06240146.
  • IR-absorbing additives based on organic materials frequently have the disadvantage, however, that they exhibit poor stability towards thermal stress or radiation. Accordingly, many of these additives do not have sufficient heat stability to be incorporated into transparent thermoplastics because temperatures of up to 350° C. are required for their processing. Moreover, during use, glazing is often exposed for prolonged periods to temperatures of more than 50° C., caused by solar radiation, which can lead to decomposition or degradation of the organic absorbents.
  • organic IR absorbers frequently do not have a sufficiently broad absorption band in the NIR range, so that their use as IR absorbers in glazing materials is inefficient, a pronounced inherent colour of such systems often also occurring, which is generally undesirable.
  • IR-absorbing additives based on inorganic materials are frequently markedly more stable as compared with organic additives.
  • the use of such systems is often also more economical because in most cases they have a markedly more favourable price/performance ratio.
  • materials based on finely divided borides, such as, for example, lanthanum hexaboride have proved to be efficient IR absorbers because they have a broad absorption band in the IR range coupled with high heat stability.
  • IR-absorbing additives from the group of the borates are suitable for transparent thermoplastics such as polymethyl methacrylate and polycarbonate on account of the advantages described above. However, it has been shown that these additives lead to unexpected colour impressions in transparent thermoplastic compositions, irrespective of their inherent colour.
  • Transparent objects are here understood as being bodies that exhibit a transmission of at least 6% and a haze of less than 3%, preferably less than 2.5%, more preferably less than 2.0%. In the case of transparent bodies, in contrast to non-transparent objects, it is normally not the remitted colour but the transmitted colour that is in the foreground.
  • the object thus acts as a colour filter.
  • colouring agents which dissolve in the polymer matrix or have such a small particle size that they cause no haze, no haze within the scope of the present invention meaning a haze of less than 3% at a given layer thickness, measured in accordance with ASTM D1003.
  • the boride-based IR absorber particles that are used do not in fact lead to haze of the corresponding glazing element (haze ⁇ 3%).
  • these particles whose size is preferably within the nanometre range, can cause scattering effects in the matrix in which they are embedded, regardless of the nature and other properties of the particles. While this scattering has only an unnoticeable effect on the transmission and accordingly the transparency of the article, the colour impression of the article is in some cases changed considerably by the scattered light, in particular in dependence on the viewing angle.
  • the IR-absorbing additives from the group of the borides lead to undesirable colour reflexes in the finished part, that is to say, for example, in a transparent panel, under certain light conditions and viewing angles.
  • corresponding panels exhibit a bluish to violet tinge according to the concentration of the inorganic IR absorber used.
  • this colour impression is not the result of the colour of the chosen added pigments and absorbers but is attributable to scattering effects of the nanoparticles, which are to be observed in particular at viewing angles of from 1 to 60°. Such scattering can adversely affect the overall colour impression of the corresponding article, for example a vehicle or a building.
  • the scattering effect is, as described, frequently perceived as a bluish-violet colour.
  • a neutral colour impression is frequently desirable, that is to say the natural colour impression is not disturbed by scattering effects. This means that the colour produced by the scattering effect must on the one hand be relatively close to the achromatic point and on the other hand close to the inherent colour of the component.
  • this colour effect is not caused by the normal absorbed or transmitted colour. This phenomenon is only caused by scattered light. Colourants or colouring pigments do not normally contribute to this colour effect. Only certain additives, such as, for example, the nano-scale boride-based IR absorbers, cause this effect. Furthermore, it must be pointed out that the scattering effect is pronounced only under certain light conditions and defined viewing angles. This is the case, for example, when the article—preferably a panel—is viewed under good light conditions, that is to say under solar radiation and at observation angles of from 1 to 60°.
  • the bluish scattering is caused by the IR additive, which consists of fine particles.
  • These particles which on average have a size, which can be determined, for example, by means of TEM (transmission electron microscopy), of preferably less than 200 nm, particularly preferably less than 100 nm, cause a scattering effect and can accordingly also lead to undesirable colour reflections.
  • TEM transmission electron microscopy
  • attempts could be made to reduce the diameter of the particles or to limit the amount of particles in the matrix.
  • this is complex because the particles must be very finely ground and the risk of reagglomeration exists or, if the particle concentration is too low, the desired effect can no longer be achieved.
  • thermoplastic moulding compositions which contain both IR absorbers and colouring pigments, inter alia carbon blacks, in order to influence both the heat-absorbing properties and the colouration.
  • measures for reducing the scattered radiation caused by boride-based IR-absorbing particles are as rarely described in the literature as that undesirable effect.
  • compositions based on polycarbonate containing boride-based inorganic IR absorbers have been described in various publications.
  • US 2004/0028920 describes masterbatches containing boride-based inorganic IR absorbers for the production of moulded parts. US 2004/0028920 neither mentions scattering effects nor describes compositions which would reduce this effect.
  • the use of carbon black is described in the general part of this application only as an agent for adjusting the colour, that is to say as a colouring agent.
  • EP 1 559 743 describes polymer compositions containing inorganic IR absorbers in combination with organic UV absorbers. However, this application does not describe the scattering effect described in the present invention. EP 1 559 743 gives no indication of how the scattering effect can be reduced.
  • WO 2007/008476 A1 Moulding compositions containing boride-based IR absorbers and specific carbon blacks are known from WO 2007/008476 A1, a synergistic effect in respect of the IR-absorbing properties being said to be achieved by the combination of these components.
  • this application does not mention the effect described herein and gives no indication of how the problem described in the present application could be solved.
  • WO 2007/008476 relates to materials which are suitable in particular for spectacles.
  • the concentrations of colouring agents, inorganic IR absorbers and nano-scale inorganic pigments used therein are, however, completely different to those used in the present invention to solve the described problem in glazing, such as automotive or architectural glazing.
  • EP 1865027 A1 describes polymer compositions of specific polycarbonates, which additionally contain lanthanum hexaboride as IR absorber. EP 1865027 does not describe the problem described in the present invention, nor can the person skilled in the art see how the problem could be solved.
  • FIG. 1 illustrates a measuring system for measuring scattering effects.
  • the invention relates to a polymer composition which absorbs infrared radiation (IR), containing a transparent thermoplastic plastic, an inorganic infrared absorber, also referred to as IR absorber hereinbelow, and at least one inorganic nano-scale pigment, and to the preparation and use of the polymer compositions according to the invention, and to products produced therefrom.
  • IR absorber also referred to as IR absorber hereinbelow
  • the present invention relates to the reduction of undesirable scattering effects caused by boride-based inorganic IR absorbers, and to the use of the polymer composition according to the invention containing such IR absorbers in the production of glazing for use in buildings, motor vehicles and railway vehicles or aircraft.
  • a still further embodiment of the present invention is a method which comprises adding carbon black to a polymer composition which comprises nano-scale particles wherein the scattering caused by the nano-scale particles is reduced.
  • the object of the present invention was to provide transparent polymer compositions having no or low haze, good IR absorption and minimised colour effects by scattering, which compositions do not exhibit the disadvantages of the compositions known from the prior art.
  • compositions in the form of a masterbatch for further processing, as well as moulded parts produced using such compositions.
  • test specimens are illuminated at an angle of incidence of 60° relative to the vertical using a white point light source with a small opening angle of less than 2° and the scattering is measured at an emergent angle of from 30° to ⁇ 80° relative to the vertical (see FIG. 1 ).
  • CIELAB colour coordinates L*, a*, b* are calculated in accordance with ASTM E 308 using illuminant D65 and a 10° observer. This colour system is described, for example, in Manfred Richter: Press in die Farbmetrik. 1984 ISBN 3-11-008209-8.
  • the b* value at an emergent angle of ⁇ 10° is used. This b* value is referred to hereinbelow as b*(60°), the value of 60° relating to the angle of incidence.
  • the measurements were carried out using a “Gon360-105” goniophotometer (Gon360 with multichannel spectrometer CAS 140) from Instrument Systems.
  • the measuring system is shown in FIG. 1 , where the reference numerals have the following meanings
  • the hemispherical reflection of the test specimen is measured in accordance with ASTM E 1331, and the CIELAB colour coordinates L*, a*, b* are calculated in accordance with ASTM E 308 using illuminant D65 and a 10° observer.
  • the corresponding b* value is denoted b*(hemispherical) hereinbelow.
  • a measure of the extent of the scattering effect is accordingly the measurement of the b* value in reflection (b*(60°)) at which the scattered light is measured.
  • the b*(60°) value of the reflected light at an emergent angle of ⁇ 10° of the moulded bodies according to the invention is preferably in the range from ⁇ 2.5 to 0.0, more preferably from ⁇ 2.3 to 0.0.
  • ⁇ b* ⁇ 1.0 The limit of ⁇ b* ⁇ 1.0 is given by the colour difference of delta E (calculated in accordance with DIN 6174) detectable by the human eye, which is less than 1.0. Because this scattering is substantially a bluish scattering, the calculation is here simplified to the difference ⁇ b*, which relates to the blue component of the light.
  • the increase in the scattered radiation is not linear.
  • the relative increase in the scattered radiation is smaller than in the middle concentration range of from 0.00100 wt. % to 0.00500 wt. %. Accordingly, a pronounced increase in the scattered radiation is to be observed in the range from 0.00100 wt. % to 0.00500 wt. %, while the increase, surprisingly, diminishes at concentrations above 0.01000 wt. %.
  • compositions according to claim 1 based on thermoplastic materials containing defined concentrations of boride-based IR absorbers as well as specific concentrations of specific inorganic, preferably nano-scale, pigments.
  • colouring agents are preferably used in the polymer compositions according to the invention, more preferably colouring agents based on anthraquinone, perinone or phthaloperinone, because glazing with a particular colouration is desirable especially in the automotive sector. It has been shown that the above-described scattering effect also occurs in such coloured polymer compositions when boride-based inorganic IR absorbers are added. Surprisingly, the scattering effect could be limited in such coloured compositions too by the use of specific concentrations of inorganic pigments.
  • the polymer compositions according to the invention contain:
  • a transparent thermoplastic plastic preferably polycarbonate, copolycarbonate, polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin, poly- or copoly-methyl methacrylates such as polymethyl methacrylate, thermoplastic polyurethanes, more preferably polycarbonate, copolycarbonate, aromatic polyesters or polymethyl methacrylate, or mixtures of the mentioned components, and particularly preferably polycarbonate and copolycarbonate,
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PBT polybutylene terephthalate
  • cyclic polyolefin poly- or copoly-methyl methacrylates
  • the borides are preferably used in an amount of from 0.00150 wt. % to 0.01500 wt. %, preferably from 0.00200 wt. % to 0.01100 wt. % and particularly preferably from 0.00270 wt. % to 0.00800 wt. %, calculated as solids content of boride in the total polymer composition.
  • the borides are used in an amount of preferably from 0.00350 wt. % to 0.00850 wt. % and particularly preferably from 0.00400 wt. % to 0.00800 wt. %, calculated as solids content of boride in the total polymer mixture.
  • solids content of boride means the boride in the form of the pure substance and not a suspension or other preparation containing the pure substance.
  • At least one inorganic, nano-scale pigment preferably carbon black, in particular nano-scale carbon black.
  • the nano-scale carbon black is used in the composition according to the invention preferably in concentrations of from 0.00080 wt. % to 0.00350 wt. %, particularly preferably from 0.00090 wt. % to 0.00300 wt. % and most particularly preferably in concentrations of from 0.00100 wt. % to 0.00280 wt. %.
  • the nano-scale carbon black is preferably used in an amount of from 0.00140 wt. % to 0.00260 wt. %, particularly preferably in an amount of from 0.00150 wt. % to 0.00250 wt. %.
  • additives such as stabilizers, antioxidants, demoulding agents, flameproofing agents, heat stabilizers, UV stabilizers, or optical brightening agents.
  • the invention further provides a process for the preparation of the compositions according to the invention and the use thereof and products produced therefrom.
  • Transparent thermoplastic plastics within the scope of the invention are, for example, polymers of ethylenically unsaturated monomers and/or polycondensation products of bifunctional reactive compounds.
  • transparent thermoplastic polymers are, for example, polycarbonates or copolycarbonates based on diphenols, poly- or copoly-acrylates and poly- or copoly-methacrylate, such as, for example, poly- or copoly-methyl methacrylates (such as PMMA), 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 polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) or polyethylene terephthalate-cyclohexanedimethanol copolymer (PETG), transparent thermoplastic polyurethanes and polystyre
  • Mixtures of a plurality of transparent thermoplastic polymers, in so far as they can be mixed with one another to give a transparent mixture, are also possible, preference being given to a mixture of polycarbonate with PMMA (more preferably with PMMA ⁇ 2 wt. %) or polyester.
  • Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,3-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
  • Polycarbonates within the scope of the present invention are both homopolycarbonates and copolycarbonates; the polycarbonates can, in known manner, be linear or branched.
  • the preparation of the polycarbonates is carried out in known manner from diphenols, carbonic acid derivatives, optionally chain terminators and branching agents.
  • Diphenols suitable for the preparation of the polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)-alkanes, bis(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)sulfides, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl)ketones, bis-(hydroxyphenyl)-sulfones, bis-(hydroxyphenyl)sulfoxides, alpha,alpha′-bis-(hydroxyphenyl)-diisopropylbenzenes, pththalimides derived from isatin or phenolphthalein derivatives, and compounds thereof alkylated and halogenated on the ring.
  • Preferred 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-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(
  • 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.
  • Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
  • Suitable chain terminators which can be used in the preparation of the polycarbonates are both monophenols and monocarboxylic acids.
  • Suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol, p-n-octylphenol, p-isooctylphenol, p-n-nonylphenol and p-isononylphenol, halophenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, 2,4,6-triiodophenol, p-iodophenol, and mixtures thereof.
  • Preferred chain terminators are phenol, cumylphenol and/or p-tert-butylphenol.
  • Suitable monocarboxylic acids are also benzoic acid, alkylbenzoic acids and halobenzoic acids.
  • Preferred chain terminators are also the phenols which are mono- or poly-substituted by C1- to C30-alkyl radicals, linear or branched, preferably unsubstituted or substituted by tert-butyl.
  • the amount of chain terminator to be used is preferably from 0.1 to 5 mol %, based on moles of diphenols used in a particular case.
  • the addition of the chain terminators can take place before, during or after the phosgenation.
  • Suitable branching agents are the compounds known in polycarbonate chemistry having a functionality of three or more than three, in particular those having three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-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)-phenol, 2,6-bis-(2-hydroxy-5′-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, hexa-(4(4-hydroxyphenyl isopropyl)-phenyl
  • the amount of branching agents optionally to be used is preferably from 0.05 mol % to 2.00 mol %, based in turn on moles of diphenols used in a particular case.
  • the branching agents can either be placed in the aqueous alkaline phase with the diphenols and the chain terminators or they can be dissolved in an organic solvent and added before the phosgenation. In the case of the transesterification process, the branching agents are used together with the diphenols.
  • the aromatic polycarbonates of the present invention have weight-average molecular weights Mw (determined by gel permeation chromatography and calibration with polycarbonate calibration) of from 5000 to 200,000, preferably from 10,000 to 80,000 and particularly preferably from 15,000 to 40,000 (this corresponds approximately to from 12,000 to 330,000, preferably from 20,000 to 135,000 and particularly preferably from 28,000 to 69,000, determined by calibration by means of polycarbonate standard).
  • Mw weight-average molecular weights Mw (determined by gel permeation chromatography and calibration with polycarbonate calibration) of from 5000 to 200,000, preferably from 10,000 to 80,000 and particularly preferably from 15,000 to 40,000 (this corresponds approximately to from 12,000 to 330,000, preferably from 20,000 to 135,000 and particularly preferably from 28,000 to 69,000, determined by calibration by means of polycarbonate standard).
  • the polymer compositions according to the invention can optionally contain, in addition to the stabilizers according to the invention, also further conventional polymer additives, such as, for example, the antioxidants, demoulding agents, flameproofing agents, colouring agents, heat stabilizers, UV stabilizers or optical brightening agents described in EP-A 0 839 623, WO-A 96/15102, EP-A 0 500 496 or “Plastics Additives Handbook”, Hans Zweifel, 5th Edition 2000, Hanser Verlag Kunststoff, in the amounts conventional for the thermoplastics in question.
  • further conventional polymer additives that are optionally present, particular preference is given to colouring agents.
  • the further polymer additives are preferably used in amounts of from 0 wt. % to 5 wt. %, more preferably from 0.1 wt. % to 1 wt %, in each case based on the amount of the total polymer compositions. Mixtures of a plurality of additives are also possible.
  • the nano-scale boride-based inorganic IR absorber particles provided by the present application are preferably a metal boride, the metal being selected from the group comprising 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.
  • the hexaboride form is particularly preferred.
  • LaB 6 lanthanum hexaboride
  • PrB 6 praseodymium boride
  • NdB 6 cerium boride
  • CeB 6 cerium boride
  • TbB 6 terbium boride
  • DyB 6 dysprosium boride
  • HoB 6 holmium boride
  • YB 6 yttrium boride
  • SmB 6 samarium boride
  • EuB 6 europium boride
  • ErB 6 erbium boride
  • TmB 6 thulium boride
  • TmB 6 ytterbium boride
  • lutetium boride LuB 6
  • the surface of these particles is preferably unoxidised; however, oxidised or partially oxidised particles can be used.
  • lanthanum hexaboride (LaB 6 ) is most particularly preferred.
  • the boride is obtained in the form of a powder.
  • the form of the finely divided particles for example, the particles can have a spherical, platelet-like, irregular or needle-like form.
  • the absorbing power for IR radiation is greater, the more crystalline the boride particles.
  • particles having low crystallinity e.g. characterised by a broad diffraction peak in the X-ray diffraction experiment
  • the colour of the particles in the powder can be, for example, greyish-black, brownish-black, greenish-black or the like.
  • the average size of the particles is preferably smaller than 200 nm, particularly preferably smaller than or equal to 150 nm and most particularly preferably smaller than 100 nm, the particle diameters preferably being greater than 5 nm, more preferably greater than 10 nm and particularly preferably greater than 15 nm.
  • the particles are transparent in the visible range of the spectrum, transparent meaning that the absorption of the IR absorbers in the visible range is low compared with the absorption in the IR range and the IR absorber does not lead to markedly increased haze of the composition or the end product in question.
  • the transparent moulded body has a transmission of at least 6% and a haze of less than 3%, preferably less than 2.5%, more preferably less than 2.0%.
  • the Tds value is preferably less than 70%, particularly preferably less than 60% and most particularly preferably less than 50%.
  • the Tds value is less than 20%, particularly preferably less than 15% (T ds ; direct solar transmittance; values are measured on optical colour sample sheets having a thickness of 4 mm. Calculation of the total transmission T ds is carried out in accordance with ISO 13837, computational convention “A”).
  • the size of the particles can be determined by means of transmission electron microscopy (TEM). Such measurements on IR absorber nanoparticles are described, for example, in Adachi et al., J. Am. Ceram. Soc. 2008, 91, 2897-2902.
  • TEM transmission electron microscopy
  • the surface of the particles can be treated.
  • the surface can be treated with a silane or provided with a titanium-based or zirconium-based layer or similar layers.
  • the resistance to moisture can be increased by means of this treatment.
  • This type of coating increases the long-term stability in respect of the IR absorption and is described, for example, in US 2005 0161642.
  • boride-based particles In addition to the boride-based particles, further particles based on SiO 2 , TiO 2 , ZrO 2 , Al 2 O 3 or MgO can—but do not necessarily have to be—present. These particles are preferably present in a size of less than 200 nm.
  • the finely divided IR absorber particles are introduced into the polymer matrix in the form of a dispersion.
  • This dispersion prevents reagglomeration and facilitates incorporation into a thermoplastic matrix such as, for example, polycarbonate.
  • Polymer-like dispersing agents are preferably used.
  • Suitable polymer-based dispersing agents are especially dispersing agents which have high light transmission, such as, for example, polyacrylates, polyurethanes, polyethers, polyesters or polyurethanes and polymers derived therefrom.
  • Preferred as dispersing agents are polyacrylates, polyethers and polyester-based polymers. Dispersing agents having high temperature stability are preferably used.
  • the blend ratio of polymeric dispersing agent to boride particles is usually from 0.2 wt. % to 50.0 wt. %, preferably from 0.5 wt. % to 50.0 wt. % and most particularly preferably from 1.0 wt. % to 40.0 wt. %, based on the amount by weight of inorganic IR absorber.
  • the IR absorber can be mixed with the dispersing agents described hereinbelow and further organic solvents, such as, for example, toluene, benzene or similar aromatic hydrocarbons, and ground in suitable mills, such as, for example, ball mills, with the addition of zirconium oxide (e.g. having a diameter of 0.3 mm) in order to prepare the desired particle size distribution.
  • suitable mills such as, for example, ball mills
  • zirconium oxide e.g. having a diameter of 0.3 mm
  • the nanoparticles are obtained in the form of a dispersion. After grinding, further dispersing agents can optionally be added.
  • the solvent is removed at elevated temperatures and reduced pressure.
  • Lanthanum hexaboride in the form of the dispersion which is suitable within the scope of the invention, is obtainable commercially from, for example, Sumitomo Metal Mining Co., Ltd., for example under the trade name KHDS 06.
  • Dispersing agents suitable for the present invention are obtainable commercially.
  • Polyacrylate-based dispersing agents are particularly suitable, Polyacrylates are obtainable, for example, from Ciba Specialty Chemicals under the trade names EFKA®, for example EFKA® 4500 and EFKA® 4530.
  • Polyester-based dispersing agents are likewise suitable.
  • Polyester-containing dispersing agents are obtainable from Avecia under the trade names Solsperse®, for example Solsperse® 22000, 24000SC, 26000, 27000, Polyurethane-based systems are also suitable. These are obtainable from Ciba Specialty Chemicals under the trade names EFKA® 4046, EFKA® 4047.
  • Texaphor® P60 and P63 are corresponding trade names of Cognis.
  • Polyether-containing dispersing agents can likewise be used. These are known, for example, under the trade names Disparlon® DA234 and DA325 of Kusumoto Chemicals.
  • the dispersing agents can be used on their own or in combinations. With regard to the thermal stability, dispersing agents from the group of the polyacrylates and polyesters are particularly preferred.
  • the IR-absorbing inorganic boride is preferably used in the polymer composition according to the invention in dispersion in an organic matrix and preferably in the concentrations described below.
  • the borides are used in an amount of from 0.00150 wt. % to 0.01500 wt. %, preferably from 0.00200 wt. % to 0.01100 wt. % and particularly preferably from 0.00270 wt. % to 0.00800 wt. %, calculated as solids content of boride in the total polymer composition.
  • the borides are used in an amount of preferably from 0.00350 wt. % to 0.00850 wt.
  • solids content of boride means the boride in the form of the pure substance and not a suspension or other preparation containing the pure substance.
  • the lanthanum hexaboride is in the form of a ready-to-use dispersion of a mixture of polymethyl methacrylate and polyester in a solids content of from 5 wt. % to 25 wt. %.
  • Organic solvents such as toluene and further inorganic particles such as zirconium dioxide can additionally be present.
  • compositions that contain from two up to and including five and particularly preferably two or three different IR absorbers.
  • the polymer-composition according to the invention does not contain any inorganic IR absorbers of the tungstate type, such as, for example, caesium tungstate, Cs 0.33 WO 3 .
  • the further IR absorber is preferably selected from the group of the tin oxides, particularly preferably antimony-doped tin oxide or indium tin oxide.
  • Compounds such as indium oxide doped with from 2 to 30 atom %, preferably from 4 to 12 atom %, tin (ITO) or with from 10 to 70 atom % fluorine can further be added.
  • tin oxide as a further IR absorber, which tin oxide is doped with from 2 to 60 atom % antimony (ATO) or with from 10 to 70 atom % fluorine.
  • ATO antimony
  • Zinc oxide doped with from 1 to 30 atom %, preferably from 2 to 10 atom %, aluminium or with from 2 to 30 atom % indium or with from 2 to 30 atom % gallium is further preferred.
  • the additional IR absorber(s) has (have) an absorption spectrum different from that of the boride used based on the absorption maxima, so that a maximum absorption range is covered by the maxima.
  • Suitable additional organic infrared absorbers are described by substance classes in, for example, M. Matsuoka, Infrared Absorbing Dyes, Plenum Press, New York, 1990. Particularly suitable are infrared absorbers from the classes of the phthalocyanines, the naphthalocyanines, the metal complexes, the azo dyes, the anthraquinones, the quadratic acid derivatives, the immonium dyes, the perylenes, the quaterylenes and the polymethines. Of those, phthalocyanines and naphthalocyanines are most particularly suitable.
  • phthalocyanines and naphthalocyanines having sterically demanding side groups are to be preferred, such as, for example, phenyl, phenoxy, alkylphenyl, alkylphenoxy, tert-butyl, (—S-phenyl), —NH-aryl, —NH-alkyl and similar groups.
  • the polymer composition contains at least one inorganic pigment, preferably carbon black.
  • the carbon black is preferably present in finely dispersed form in the organic polymer matrix and is preferably nano-scale.
  • Suitable carbon blacks have an average particle size of preferably less than 100 nanometres (nm), more preferably less than 75 nm, yet more preferably less than 50 nm and particularly preferably less than 40 nm, the average particle size preferably being greater than 0.5 nm, more preferably greater than 1 nm and particularly preferably greater than 5 nm.
  • Carbon blacks suitable within the scope of the invention differ from so-called conductive blacks in that they have only low or no electrical conductivity. Compared with the carbon blacks used here, conductive blacks have specific morphologies and superlattices in order to achieve high conductivity. By contrast, the nano-scale carbon blacks used here can very readily be dispersed in thermoplastics so that virtually no cohesive regions of carbon black occur, from which a corresponding conductivity might result. Suitable carbon blacks within the scope of the invention which are obtainable commercially are obtainable under a large number of trade names and in a large number of forms, such as pellets or powder.
  • suitable carbon blacks are obtainable under the trade names BLACK PEARLS®, in the form of wet-processed pellets under the names ELFTEX®, REGAL® and CSX®, and in a flocculent form under the names MONARCH®, ELFTEX®, REGAL® and MOGUL®—all obtainable from Cabot Corporation.
  • the carbon black types have particle sizes of from 10 to 30 nm and have a surface area of preferably from 35 to 138 m 2 per g (m 2 /g).
  • the carbon black can be treated or untreated—for example, the carbon black can be treated with specific gases, with silica or organic substances, such as, for example, butyllithium. Such treatment allows the surface to be modified or functionalised. This can promote compatibility with the correspondingly used matrix. Particular preference is given to carbon blacks marketed under the trade name BLACK PEARLS® (CAS No. 1333-86-4).
  • the nano-scale carbon black is used in the composition according to the invention preferably in concentrations of from 0.00080 wt. % to 0.00350 wt. %, particularly preferably from 0.00090 wt. % to 0.00300 wt. % and most particularly preferably in concentrations of from 0.00100 wt. % to 0.00280 wt. %.
  • the nano-scale carbon black is preferably used in an amount of from 0.00140 wt. % to 0.00260 wt. %, particularly preferably in an amount of from 0.00150 wt. % to 0.00250 wt. %.
  • the ratio of IR absorber to carbon black is from 20:1 to 0.4:1, preferably from 15:1 to 1:1. In a specific embodiment of the present invention, the ratio of IR absorber to carbon black is from 5:1 to 1.5:1.
  • concentrations indicated herein for carbon blacks and IR absorbers are preferably used for finished parts having thicknesses of from 2 mm to 8 mm, preferably from 3.5 to 7.0 mm and particularly preferably from 4 mm to 6 mm. In the case of a smaller or larger thickness, the concentrations must be increased or reduced accordingly in order to avoid, for example, too great a haze or too low an effect.
  • thicknesses of from 8 to 20 mm can be required.
  • concentrations of the IR absorbers and of the inorganic nano-scale pigment must be adapted accordingly in this case, that is to say the concentration falls as the layer thickness increases.
  • the polymer composition contains heat stabilizers.
  • Particularly suitable are phosphites and phosphonites as well as phosphines. Examples are biphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(bis(
  • TPP triphenylphosphine
  • Irgafos® 168 tris(2,4-di-tert-butyl-phenyl)phosphite
  • tris-(nonylphenyl)phosphite or mixtures thereof TPP
  • Irgafos® 168 tris(2,4-di-tert-butyl-phenyl)phosphite
  • tris-(nonylphenyl)phosphite or mixtures thereof tris-(nonylphenyl)phosphite or mixtures thereof.
  • Phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones can also be used.
  • Irganox® 1010 penentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate; CAS: 6683-19-8) and Irganox® 1076 (2,6-di-tert-butyl-4-(octadecanoxycarbonylethyl)phenol
  • the phosphine compounds according to the invention are used together with a phosphite or a phenolic antioxidant or a mixture of the two last-mentioned compounds.
  • the polymer composition according to the invention further contains an ultraviolet absorber.
  • Ultraviolet absorbers suitable for use in the polymer composition according to the invention are compounds that have as low a transmission as possible below 400 nm and as high a transmission as possible above 400 nm. Such compounds and their preparation are known in the literature and are described, for example, in EP-A 0 839 623, WO-A 96/15102 and EP-A 0 500 496.
  • Particularly suitable ultraviolet absorbers for 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 Spezialitätenchemie, Basel), 2-(2′-hydroxy-5′-(tert-octyl)-phenyl)-benzotriazole (Tinuvin® 329, Ciba Spezialitätenchemie, Basel), 2-(2′-hydroxy-3′-(2-butyl)-5′-(tert-butyl)-phenyl)-benzotriazole (Tinuvin® 350, Ciba Spezilois Rundenchemie, Basel), bis-(3-(2H-benztriazolyl)-2-hydroxy-5-tert-octyl)methane (Tinuvin® 360, Ciba Spezilois Rundeau, Basel), (2-(4,6-diphenyl-1,3,5-tri
  • the amount of ultraviolet absorber contained in the composition contains ultraviolet absorber in an amount of from 0.05 wt. % to 20.00 wt. %, in particular from 0.07 wt. % to 10.00 wt. % and most particularly preferably from 0.10 wt. % to 1.00 wt. %.
  • the compositions according to the invention preferably contain further colouring agents for adjusting the colour.
  • the colourants serve to adjust the colour in transmission—they affect the reflected colour to only a minor extent. They are preferably colouring agents based on anthraquinone, on perinone or on phthaloperinone.
  • R1 can be a linear or branched alkyl radical or halogen, preferably a halogen.
  • n is a natural number from 0 to 4.
  • substituents R1 independently of one another, can be the radicals described above and n for each designated aromatic ring represents a natural number from 0 to 3.
  • the colourants of formulae (1) and (2) are preferably used in amounts of from 0.00010 wt. % to 0.05000 wt. %, particularly preferably from 0.00100 wt. % to 0.01000 wt. %, in each case based on the total moulding composition.
  • colourants or pigments there can be used, for example, organic or inorganic pigments or organic colourants or the like.
  • inorganic pigments for example, sulfur-containing pigments such as cadmium red and cadmium yellow, pigments based on iron cyanide such as Prussian blue, oxide pigments such as titanium dioxide, zinc oxide, red iron oxide, black iron oxide, chromium oxide, titanium yellow, zinc iron brown, titanium cobalt green, cobalt blue, copper chromium black and copper iron black or chromium-based pigments such as chromium yellow.
  • Preferred organic pigments or colourants are, for example, colourants derived from phthalocyanine, such as copper phthalocyanine blue and copper phthalocyanine green, condensed polycyclic colourants and pigments, such as azo-based (e.g. nickel azo yellow), sulfur indigo colourants, perynon-based, perylene-based, quinacridone-derived, dioxazine-based, isoindolinone-based and quinophthalone-derived derivatives, anthraquinone-based, heterocyclic systems, etc.
  • cyanine derivatives, quinoline derivatives, anthraquinone derivatives, phthalocyanine derivatives are preferred.
  • MACROLEX Blue RR® MACROLEX Violet 3R®
  • MACROLEX 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 Heliogen Green
  • colourants can be used in amounts of from 0.00001 wt. % to 1.00000 wt. %, preferably from 0.00010 wt. % to 0.10000 wt. % and particularly preferably from 0.00050 wt. % to 0.05000 wt. %.
  • demoulding agents for the composition according to the invention are, for example, pentaerythritol tetrastearate (PETS) or glycerol monostearate (GMS).
  • PETS pentaerythritol tetrastearate
  • GMS glycerol monostearate
  • thermoplastic plastic an inorganic IR absorber from the group of the borides, optionally one or more colouring agents and optionally further conventional polymer additives
  • preparation of the polymer compositions according to the invention containing a thermoplastic plastic, an inorganic IR absorber from the group of the borides, optionally one or more colouring agents and optionally further conventional polymer additives is carried out by conventional incorporation processes by combining, mixing and homogenising the individual constituents, the homogenisation in particular preferably being carried out in the melt under the action of shear forces. Combining and mixing prior to melt homogenisation are optionally carried out using powder premixtures.
  • premixtures which have been prepared from solutions of the mixture components in suitable solvents, homogenisation in solution optionally being carried out and the solvent subsequently being removed.
  • the IR absorbers, colouring agents, ultraviolet absorbers and other additives of the composition according to the invention can be introduced by known processes or in the form of a masterbatch.
  • masterbatches is particularly preferred for the introduction of the IR absorber, there being used in particular masterbatches based on polycarbonate into which the IR absorbers have been introduced in the form of a ready-to-use IR absorber formulation containing dispersing agents, preferably polyacrylate-, polyether- or polyester-based dispersing agents, preferably dispersing agents having high temperature stability, such as a polyacrylate (homo- or co-polymer), such as, for example, polymethyl methacrylate, and/or polyesters or mixtures thereof, further containing auxiliary substances such as, for example, zirconium dioxide and optionally residual solvents such as, for example, toluene, benzene or similar aromatic hydrocarbons.
  • auxiliary substances such as, for example, zirconium dioxide and optionally residual solvents such as, for example, toluene, benzene or similar aromatic hydrocarbons.
  • the composition can be combined, mixed, homogenised and then extruded in conventional devices such as screw-type extruders (for example twin-screw extruder, ZSK), kneaders, Brabender or Banbury mills. After the extrusion, the extrudate can be cooled and comminuted. It is also possible for individual components to be premixed and the remaining starting materials subsequently to be added separately and/or likewise as a mixture.
  • screw-type extruders for example twin-screw extruder, ZSK
  • kneaders for example twin-screw extruders
  • Brabender Brabender
  • Banbury mills kneaders
  • the extrudate can be cooled and comminuted. It is also possible for individual components to be premixed and the remaining starting materials subsequently to be added separately and/or likewise as a mixture.
  • the IR absorber according to the invention before it is incorporated into the thermoplastic polymer matrix, is optionally mixed with the nano-scale pigment according to the invention and optionally further additives to form a masterbatch, mixing preferably taking place in the melt under the action of shear forces (for example in a kneader or twin-screw extruder).
  • This process offers the advantage that the IR absorber can better be distributed in the polymer matrix.
  • the thermoplastic plastic that also constitutes the main component of the ultimate total polymer composition is preferably chosen as the polymer matrix.
  • the masterbatch so prepared contains
  • the inorganic IR absorber is present in an acrylate matrix.
  • the transparent thermoplastic plastic is a polycarbonate.
  • the polymer compositions according to the invention can be processed to products or moulded bodies by, for example, first extruding the polymer compositions as described to form a granulate and processing the granulate by suitable processes into various products or moulded bodies in known manner.
  • compositions according to the invention can be converted, for example, by means of hot pressing, spinning, blow moulding, deep drawing, extrusion or injection moulding into products or moulded bodies, moulded objects such as parts for toys, fibres, foils, tapes, sheets such as solid sheets, multiwall sheets, twin-wall sheets or corrugated sheets, containers, pipes or other profiles.
  • moulded objects such as parts for toys, fibres, foils, tapes, sheets such as solid sheets, multiwall sheets, twin-wall sheets or corrugated sheets, containers, pipes or other profiles.
  • multilayer systems is also of interest.
  • Application can take place at the same time as or immediately after moulding of the base body, for example by coextrusion or multicomponent injection moulding.
  • application can also be to the finished moulded base body, for example by lamination with a film or by coating with a solution.
  • Sheets of a base layer and optional top layer/layers are preferably produced by (co)extrusion, however.
  • the polymer composition which has optionally been pretreated, for example by means of drying, is fed to the extruder and melted in the plastification system of the extruder.
  • the plastics melt is then pressed through a flat die or multiwall sheet die and thereby shaped, is brought to the desired final form in the roll gap of a smoothing calendar, and its shape is fixed by alternate cooling on smoothing rollers and with ambient air.
  • the temperatures necessary for extrusion of the polymer composition are set, it usually being possible to follow the manufacturer's instructions. If the polymer compositions contain, for example, polycarbonates having a high melt viscosity, they are normally processed at melt temperatures of from 260° C. to 350° C., and the cylinder temperatures of the plastification cylinder and the die temperatures are set accordingly.
  • thermoplastic melts of different compositions above one another and accordingly produce multilayer sheets or 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 die process see Johannaber/Ast: “Kunststoff-medianconom”, Hanser Verlag, 2000 and Deutschen Kunststofftechnik: “Coextrudiert Of Folien und Platten: relativesperspektiven, fashion, Anlagen und compassion, reconnects rejoin”, VDI-Verlag, 1990).
  • Preferred products or moulded bodies according to the invention are sheets, foils, glazing, for example car windows, windows of railway vehicles and aircraft, car sunroofs, roof coverings or glazing for buildings, which contain the compositions according to the invention.
  • further material components for example, can be present in the products according to the invention as further components of the products according to the invention.
  • glazing can have sealing materials at the edges of the panels.
  • Roof coverings can have, for example, metal components such as screws, metal pins or the like, which can be used to secure or guide (in the case of folding or sliding roofs) the roofing elements.
  • Further materials can also be joined to the compositions according to the invention, for example by 2-component injection moulding.
  • the corresponding structural element having IR-absorbing properties can be provided with an edge which is used, for example, for adhesive bonding.
  • the articles produced from the composition of the present invention are coated.
  • This coating serves to protect the thermoplastic material against general weathering influences (e.g. damage by sunlight) as well as against mechanical damage to the surface (e.g. scratching) and accordingly increases the resistance of the correspondingly equipped articles.
  • polycarbonate can be protected against UV radiation by means of various coatings.
  • coatings conventionally contain UV absorbers.
  • Such layers likewise increase the scratch resistance of the corresponding article.
  • the articles of the present invention can carry single-layer or multilayer systems. They can be coated on one side or on both sides.
  • the article contains a scratch-resistant lacquer containing UV absorber.
  • the multilayer product contains at least one layer containing the composition according to the invention, at least one anti-UV layer and optionally a scratch-resistant coating.
  • the article carries at least one scratch-resistant or anti-reflection coating on at least one side.
  • the preparation of the coating can be carried out by various methods.
  • coating can be carried out by various methods of vapour deposition, for example by electron beam processes, resistance heating and by plasma deposition or various sputtering methods such as high-frequency sputtering, magnetron sputtering, ion beam sputtering, etc., ion plating by means of DC, RF, HCD methods, reactive ion plating, etc. or chemical gas-phase deposition.
  • An anti-reflection coating can also be applied from solution.
  • a corresponding coating solution can be prepared via a dispersion of a metal oxide having a high refractive index, such as ZrO 2 , TiO 2 , Sb 2 O 5 or WO 3 , in a silicon-based lacquer, which coating solution is suitable for the coating of plastics articles and can be cured thermally or with UV assistance.
  • a metal oxide having a high refractive index such as ZrO 2 , TiO 2 , Sb 2 O 5 or WO 3
  • a scratch-resistant coating on plastics articles For example, lacquers based on epoxy, acrylic, polysiloxane, colloidal silica gel or inorganic/organic materials (hybrid systems) can be used. Such systems can be applied, for example, by dipping processes, spin coating, spraying processes or flow coating. Curing can be carried out thermally or by means of UV radiation. Single- or multi-layer systems can be used.
  • the scratch-resistant coating can be applied directly or after preparation of the substrate surface with a primer.
  • a scratch-resistant coating can be applied by plasma-assisted polymerisation processes, for example via an SiO 2 plasma. Anti-fog or anti-reflection coatings can likewise be produced by plasma processes.
  • a scratch-resistant coating to the resulting moulded body by means of specific injection-moulding processes, such as, for example, the back-injection of surface-treated foils.
  • Various additives such as, for example, UV absorbers derived, for example, from triazoles or triazines, can be present in the scratch-resistant coating.
  • IR absorbers of organic or inorganic nature can also be present.
  • Such additives can be contained in the scratch-resistant lacquer itself or in the primer layer.
  • the thickness of the scratch-resistant layer is from 1 to 20 ⁇ m, preferably from 2 to 15 ⁇ m. Below 1 ⁇ m, the resistance of the scratch-resistant layer is unsatisfactory. Above 20 ⁇ m, cracks occur more frequently in the lacquer.
  • the base material according to the invention which is described in the present invention, is preferably provided with an above-described scratch-resistant and/or anti-reflection layer after the injection-moulded article has been produced, because the preferred field of use is in the window or automotive glazing sector.
  • a primer containing UV absorber is preferably used in order to improve the adhesion of the scratch-resistant lacquer.
  • the primer can contain further stabilizers such as, for example, HALS systems (stabilizers based on sterically hindered amines), adhesion promoters, flow improvers.
  • HALS systems stabilizers based on sterically hindered amines
  • adhesion promoters adhesion promoters
  • flow improvers esion promoters
  • the resin in question can be selected from a large number of materials and is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition. Vol. A18, pp. 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 in most cases dissolved in suitable solvents—frequently in alcohols. Depending on the chosen resin, curing can take place at room temperature or at elevated temperatures. Temperatures of from 50° C. to 130° C. are preferably used—frequently after a large proportion of the solvent has briefly been removed at room temperature.
  • suitable solvents frequently in alcohols.
  • Temperatures of from 50° C. to 130° C. are preferably used—frequently after a large proportion of the solvent has briefly been removed at room temperature.
  • Commercially obtainable systems are, for example, SHP470, SHP470FT2050 and SHP401 from Momentive Performance Materials. Such coatings are described, for example, in U.S. Pat. No. 6,350,512 B1, U.S. Pat. No. 5,869,185, EP 1308084, WO 2006/108520.
  • Scratch-resistant lacquers are preferably composed of siloxanes and preferably contain UV absorbers. They are preferably applied by dipping or flow processes. Curing takes place at temperatures of from 50° C. to 130° C.
  • Commercially obtainable systems are, for example, AS4000, SHC5020 and AS4700 from Momentive Performance Materials. Such systems are described, for example, in U.S. Pat. No. 5,041,313, DE 3121385, U.S. Pat. No. 5,391,795, WO 2008/109072. The synthesis of these materials is in most cases carried out by condensation of alkoxy- and/or alkylalkoxy-silanes with acid or base catalysis. Nanoparticles can optionally be incorporated.
  • Preferred solvents are alcohols such as butanol, isopropanol, methanol, ethanol and mixtures thereof.
  • one-component hybrid systems can be used. These are described, for example, in EP0570165 or WO 2008/071363 or DE 2804283. Commercially obtainable hybrid systems are obtainable, for example, under the names PHC587 or UVHC 3000 from Momentive Performance Materials.
  • melt volume rate is determined in accordance with ISO 1133 (at 300° C.; 1.2 kg).
  • the test specimen is illuminated at an angle of incidence of 60° relative to the vertical using a white point light source, and the scattering is measured at an emergent angle of from 30° to ⁇ 80° relative to the vertical, and the CIELAB colour coordinates L*, a*, b* are calculated in accordance with ASTM E 308 using illuminant D65 and a 10° observer (see FIG. 1 ).
  • This colour system is described, for example, in Manfred Richter: Consum in die Farbmetrik. 1984 ISBN 3-11-008209-8.
  • the b* value with a 10° observer is used (referred to hereinbelow as b*(60°)).
  • the hemispherical reflection of the test specimen is measured in accordance with ASTM E 1331 and the CIELAB colour coordinates L*, a*, b* are calculated in accordance with ASTM E 308 using illuminant D65 and a 10° observer.
  • the corresponding b*(hemispherical) value is given in the table.
  • ⁇ b* absolute value of the difference between b*(60°) and b*(hemispherical).
  • the transmission and reflection measurements were carried out using a Perkin Elmer Lambda 900 spectral photometer with a photometer sphere (i.e. determination of total transmission by measuring both the diffuse and direct transmission and the diffuse and direct reflection). All the values were determined from 320 nm to 2300 nm.
  • the total transmission T DS was calculated in accordance with ISO 13837, computational convention “A”.
  • the transmission measurements were carried out using a Perkin Elmer Lambda 900 spectral photometer with a photometer sphere (i.e. determination of the total transmission by measuring both the diffuse and direct transmission and the diffuse and direct reflection) in accordance with ASTM D1003.
  • additive-free polycarbonate Makrolon 3108 from Bayer MaterialScience (linear bisphenol A polycarbonate) having a melt volume index (MVR) of 6 cm 3 /10 min at 300° C. and under a 1.2 kg load according to ISO 1033 is used.
  • polycarbonate Makrolon AL2647 from Bayer MaterialScience (linear polycarbonate based on bisphenol A) having an MVR of 12.5 cm 3 /10 min at 300° C. and under a 1.2 kg load according to ISO 1033 is used.
  • This polycarbonate contains UV absorber, demoulding agent and heat stabilizer.
  • Lanthanum hexaboride LaB 6 (KHDS 06 from Sumitomo Metal Mining, Japan) is used as the IR absorber.
  • the product is in the form of a dispersion.
  • the weights indicated in the examples relate to lanthanum hexaboride as pure substance, the solids content of lanthanum hexaboride in the commercial KHDS06 dispersion used being 21.5 wt. %.
  • Black Pearls® 800 from Cabot Corp. are used as the nano-scale carbon black (particle size about 17 nm).
  • Anthraquinone-based Macrolex Blue RR from Lanxess Germany GmbH is used as a further colouring agent.
  • a further colouring agent used is Heliogen Blue K 6911D from BASF SE, 67065 Ludwigshafen, Germany.
  • the granulate is dried for 3 hours in vacuo at 120° C. and then processed on an Arburg 370 injection-moulding machine having a 25-injection unit at a melt temperature of 300° C. and a tool temperature of 90° C. to form colour sample sheets measuring 60 mm ⁇ 40 mm ⁇ 4 mm.
  • Makrolon® 3108 is compounded as described above with 0.00086 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.004 wt. % KHDS 06 dispersion). The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.00108 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.005 wt. % KHDS 06 dispersion). The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.00215 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.01 wt. % KHDS 06 dispersion). The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.00430 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.02 wt. % KHDS 06 dispersion). The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.01075 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.05 wt. % KHDS 06 dispersion). The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.02150 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.1 wt. % KHDS 06 dispersion). The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.00430 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.02 wt. % KHDS 06 dispersion) and 0.0003 wt. % nano-scale carbon black. The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.00430 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.02 wt. % KHDS 06 dispersion) and 0.004 wt. % nano-scale carbon black. The results of the reflection measurement are given in Table 1.
  • Makrolon® 3108 is compounded as described above with 0.00430 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.02 wt. % KHDS 06 dispersion) and 0.0025 wt. % nano-scale carbon black. The results of the reflection measurement are given in Table 1.
  • Makrolon® AL2647 is compounded as described above with 0.00667 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.031 wt. % KHDS 06 dispersion) and 0.0005 wt. % nano-scale carbon black and, as colouring agent, 0.0055 wt. % Macrolex Red EG, 0.0039 wt. % Macrolex Blue RR and 0.0013 wt. % Heliogen Blue K6911D.
  • Table 2 The results of the reflection measurement are given in Table 2.
  • Makrolon® AL2647 is compounded as described above with 0.00667 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.031 wt. % KHDS 06 dispersion) and 0.00167 wt. % nano-scale carbon black and, as colouring agents, 0.0055 wt. % Macrolex Red EG, 0.0039 wt. % Macrolex Blue RR and 0.0013 wt. % Heliogen Blue K6911D.
  • Table 2 The results of the reflection measurement are given in Table 2.
  • Makrolon® AL2647 is compounded as described above with 0.00452 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.021 wt. % KHDS 06 dispersion) and 0.0005 wt. % nano-scale carbon black and, as colouring agents, 0.0048 wt. % Macrolex Red EG, 0.0037 wt. % Macrolex Blue RR and 0.0011 wt. % Heliogen Blue K6911D.
  • Table 2 The results of the reflection measurement are given in Table 2.
  • Makrolon® AL2647 is compounded as described above with 0.00452 wt. % lanthanum hexaboride, LaB 6 (which corresponds to 0.021 wt. % KHDS 06 dispersion) and 0.00225 wt. % nano-scale carbon black and, as colouring agents, 0.0048 wt. % Macrolex Red EG, 0.0037 wt. % Macrolex Blue RR and 0.0011 wt. % Heliogen Blue K6911D.
  • Table 2 The results of the reflection measurement are given in Table 2.
  • Example 8 shows that small amounts of carbon black are not suitable for markedly shifting the b*(60°) value towards 0 or into a range of from 0 to ⁇ 2.5. Furthermore, the ⁇ b* value is markedly above 1 and is accordingly clearly visible to the observer.
  • Example 10 shows that only relatively large amounts of carbon black exhibit the desired effect. Furthermore, the difference between the bluish tinge caused by the scattering effect and the reflected inherent colour is no longer discernible ( ⁇ b* is less than 1). Too high concentrations of carbon black, as shown in Example 9, drastically reduce the transmission and are not suitable for transparent moulded bodies. Surprisingly, it is also shown that the progression of the b* value (b*(60°)) responsible for the degree of scattering is different from that of the reflected inherent colour (b*(hemispherical)).
  • the scattering effect of the IR absorber particles is also noticeable in the colour formulations.
  • concentrations according to the invention of nano-scale pigment as is shown in Examples 12 and 14, it is possible to reduce the scattering effect (which can be recognised by the significant increase in b*(60°) in reflection, i.e. b* moves towards 0).
  • ⁇ b* for Examples 11 to 14 is in the range from 0 to 1 (i.e. the blue component of the inherent colour cannot be distinguished from the component of the scattering effect), the colour of the comparison examples with a b*(60°) outside the desired range is not acceptable for a neutral grey.
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ITRM20100225A1 (it) 2011-11-10
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CN105001574B (zh) 2018-01-05
ES2547129T3 (es) 2015-10-01
CN105001574A (zh) 2015-10-28
EP2569354B1 (de) 2015-07-22
KR20130063513A (ko) 2013-06-14
WO2011141369A1 (de) 2011-11-17
CN102985471A (zh) 2013-03-20
JP2013526626A (ja) 2013-06-24
TWI572653B (zh) 2017-03-01
US20150050484A1 (en) 2015-02-19
CN102985471B (zh) 2015-08-12
EP2569354A1 (de) 2013-03-20

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