Opaque multi-layer body made of polycarbonate and having weathering stability
The invention relates to opaque colored multilayer articles having a substrate layer based on polycarbonate or polymethylmethacrylate. The compositions of the substrate layer contain a titanium dioxide having particular properties as white pigment. Compared to the Kronos® 2230 white pigment which is conventionally used as white pigment for corresponding compositions and has more particularly been specially matched to polycarbonate, it is possible to achieve considerably higher weathering stability of the colored shaped bodies provided that a UV absorber-containing coating has been applied to the substrate layer. Color stability and gloss are maintained even after weathering, and brilliant colors can thus be assured.
1. A multilayer article comprising
a) a substrate layer having light transmittance in the range from 380 to 780 nm of less than 0.5%, determined at a sheet thickness of 4 mm to DIN ISO 13468-2:2006 (D65, 10°),
consisting of a thermoplastic composition based on polymethylmethacrylate or aromatic polycarbonate, comprising
i) titanium dioxide white pigment,
wherein the titanium dioxide present in the composition of the substrate layer has a rutile content of at least 60% by weight and
wherein the titanium dioxide has a coating containing silicon dioxide and aluminum oxide and titanium dioxide, and wherein the ratio of the sum total of the aluminum content and silicon content in atom %, determined by means of x-ray photon electron spectroscopy, in the coating to the titanium content in atom %, determined by means of x-ray photon electron spectroscopy, in the coating is greater than 5:1,
ii) at least two colorants that are either one organic colorant and one inorganic colorant or two organic colorants, wherein the inorganic colorant is not a titanium dioxide and not a carbon black,
b) optionally a primer layer and
c) a topcoat layer,
wherein the primer layer and/or the topcoat layer includes at least one UV absorber, characterized in that
the titanium dioxide present in the composition of the substrate layer has a median particle size D 50 , determined by means of scanning electron microscopy, of ≥0.3 μm.
2. The multilayer article as claimed in claim 1 , wherein the topcoat layer comprises at least one UV absorber from the group of the benzophenones, resorcinols, 2-(2-hydroxyphenyl)benzotriazoles, hydroxyphenyl-s-triazines, 2-cyanoacrylates and/or oxalanilides.
3. The multilayer article as claimed in claim 1 , wherein the total concentration of colorants in the thermoplastic composition of the substrate layer, excluding titanium dioxide, is 0.012% to 1.2% by weight.
4. The multilayer article as claimed in claim 1 , wherein the titanium dioxide has a median particle size D50, determined by means of scanning electron microscopy, of 0.6 μm to 1.2 μm.
5. The multilayer article as claimed in claim 1 , wherein the ratio of the sum total of the aluminum content and silicon content in atom % in the titanium dioxide coating to the titanium content in atom % in the titanium dioxide coating is at least 15:1.
6. The multilayer article as claimed in claim 1 , wherein the titanium dioxide has a median particle size D50, determined by means of scanning electron microscopy, of 0.65 μm to 1.15 μm and the ratio of the sum total of the aluminum content and silicon content in atom % in the titanium dioxide coating to the titanium content in atom % in the titanium dioxide coating is at least 19:1.
7. The multilayer article as claimed in claim 1 , wherein the thermoplastic composition of the substrate layer contains 0.1% to 0.6% by weight of at least one UV absorber.
8. The multilayer article as claimed in claim 1 , wherein the thermoplastic composition of the substrate layer contains 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol as UV absorber.
9. The multilayer article as claimed in claim 1 , wherein the amount of titanium dioxide in the thermoplastic composition of the substrate layer is 0.1% to 1.5% by weight.
10. The multilayer article as claimed in claim 1 , wherein the at least one organic colorant is selected from the group consisting of:
where
Rc and R d are independently a linear or branched alkyl radical or halogen,
n independently of the respective R is a natural number from 0 to 3, where the radical is hydrogen when n=0,
and
at least one red and/or violet colorant selected from the group consisting of the colorants of formulae (7), (8), (9), (10), (11), (12a), (12b) and/or (13)
where R is selected from the group consisting of H and p-methylphenylamine radical,
where
Ra and Rb are independently a linear or branched alkyl radical or halogen,
n independently of the respective R is a natural number from 0 to 3, where the radical is hydrogen when n=0,
optionally one or more further colorants selected from the group consisting of the yellow and orange colorants of the formulae (14), (15), (16), (17) and/or (18)
the colorant Amaplast Yellow GHS with CAS number 13676-91-01, and those from the Heliogen Blue series and the Heliogen Green series.
11. The multilayer article as claimed in claim 1 , wherein the topcoat layer is polysiloxane-based and comprises a combination of an organomodified silane with a silica sol, and wherein the topcoat layer comprises silicon dioxide particles.
12. The multilayer article as claimed in claim 1 , wherein the thickness of the substrate layer is 1.0 to 6.0 mm.
13. The multilayer article as claimed in claim 1 , wherein the multilayer article is a pipe element, part of a window frame, part of a housing of an electrical switchgear box, part of an antenna, a lamp cover, a watering can, a housing part of a tool or toolbox, part of a toy or play equipment, an antenna or antenna element, or a housing or part of a housing of a mobile communications base station.
14. The multilayer article as claimed in claim 1 , wherein the multilayer article is an element of an outer vehicle skin.
15. A method comprising utilizing white pigment titanium dioxide having a rutile content of at least 60% by weight and a median particle size D50, determined by means of scanning electron microscopy, of ≥0.3 μm, and having a coating comprising silicon dioxide, aluminum oxide and titanium dioxide, wherein the ratio of the sum total of the aluminum content and silicon content in atom % in the coating to the titanium content in atom % in the coating, determined by means of x-ray photon electron spectroscopy, is greater than 5:1, in a substrate layer in combination with a coating comprising
a topcoat layer and optionally a primer layer, wherein the topcoat layer and/or the primer layer includes at least one UV absorber,
and achieving weathering stability, expressed by a change in the color values a*, b*, L* after artificial weathering for 2500 h with xenon illumination at 0.75 W at 340 nm to ASTM G 155-13 of ΔL*<1.5, Δa*<1.5 and Δb*<1.5, of colored multilayer articles comprising a) the substrate layer having light transmittance in the range from 380 to 780 nm of less than 0.5%, determined at a sheet thickness of 4 mm to DIN ISO 13468-2:2006 (D65, 10°), consisting of a thermoplastic composition based on polymethylmethacrylate or aromatic polycarbonate and comprising
at least two colorants that are either one organic colorant and one inorganic colorant or two organic colorants, wherein the inorganic colorant is not a titanium dioxide and not a carbon black,
b) the coating comprising the topcoat layer and optionally the primer layer.