WO2008107133A1

WO2008107133A1 - Product with improved paint adhesion

Info

Publication number: WO2008107133A1
Application number: PCT/EP2008/001639
Authority: WO
Inventors: Timo Kuhlmann; Claus RÜDIGER; Michael Wagner
Original assignee: Bayer Materialscience Ag
Priority date: 2007-03-07
Filing date: 2008-03-01
Publication date: 2008-09-12
Also published as: DE102007011070A1

Abstract

The present invention relates to a product having a layer comprising a thermoplastic and a paint layer that is in contact with the layer comprising the thermoplastic, wherein the layer having the thermoplastic contains 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-I,3,5-triazine.

Description

Product with improved paint adhesion

The present invention relates to a product comprising a layer containing thermoplastic and a resist layer in contact with the layer containing thermoplastic, the layer containing thermoplastic 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6 -di (4-phenyl) phenyl-1,3,5-triazine.

Articles comprising a layer containing thermoplastic and a lacquer layer applied to the layer containing thermoplastic are known.

Problematic in paint systems, i. Articles made from a single layer and a lacquer layer applied to the layer is usually the adhesion of the lacquer layer to the layer, the so-called lacquer adhesion

Generally, various techniques are used in the art to modify the surface of plastic substrates such that a paint layer subsequently applied to the plastic component will adhere better.

These methods are used, for example, to remove interfering contaminants and release agents, to derive charges from the surface or to eliminate production-related defects.

In addition to the purely mechanical pretreatment methods, such as brushing or grinding, surfactant-containing, aqueous solutions or solvent-based cleaners are generally used under the influence of temperature.

In addition to an adhesion-enabling cleaning step, there are a number of methods of substrate pretreatment in which the substrate surface is changed by different processes in their chemical nature. These include the glow discharges of plasmas, the corona discharge, flaming with an oxidizing flame, fluorination or satinizing. An overview of the common pretreatment methods for plastic surfaces offer the "Basf manual painting technology" (ISBN 3-87870-324-4) and the "textbook of paint technology" (ISBN 3-87870-569-7). Depending on the process, these processes, which are commercially widespread and implemented in common coating systems, have some disadvantages.

Especially with the plasma glow discharge is to point out the very expensive and complex plant technology as well as the cost-intensive use, which by the maintenance of a

High vacuum chamber are to explain. For a brief overview, see the article "Surface Treatment of Polymers with Glow Discharges "by Christian Oeh and Herwig Brunner, published in the" Vacuum in Research and Practice "(2000), No.1, 35-40.

In contrast, corona discharges are at atmospheric pressure and thus easier to control. A disadvantage here is the uniform pretreatment of 3-dimensional components.

Flaming with oxidizing flame is a cost effective and therefore widespread process. Problematic again is the uniform pretreatment of 3-dimensional or temperature-sensitive components.

In addition, the improvement in the adhesion between a substrate and a lacquer layer has been described by special adhesive layers or adhesive layers variously in the literature.

In this context, DE 30 44 804 describes multilayer systems comprising a polycarbonate substrate, an applied, the adhesion promoting primer layer of thermoset acrylic polymers, which is equipped with 15 to 75 wt% of a UV absorber, and an applied thereto organopolysiloxane cover layer.

EP 0 107 657 discloses polycarbonate substrates which are impregnated with a UV absorber and have a coating on this impregnation which comprises an adhesion-promoting primer layer and a top layer of the curable organopolysiloxane arranged thereon.

US Pat. No. 4,389,432 describes special adhesion promoters between plastic substrates and organopolysiloxane coatings arranged thereon, it being possible for the adhesion promoter layers to contain UV absorbers.

EP 1 308 084 describes inter alia thermoplastic olefin substrates additized with UV absorbers, which are provided with a color layer, an adhesion promoter and a clearcoat.

US 2006/0234061 describes multilayer systems comprising a UV protective layer which comprises polyalkylene (meth) acrylate and compounds of the 2,4-bis (4-phenylphenyl) -6- (2-hydroxypgenyl) -1,3- triazines and a second, polycarbonate-containing layer.

WO 99/55471 discloses a plasma process for applying UV protective coatings comprising compounds of the hydroxyphenyl-s-triazine type inter alia to thermoplastic and in particular crosslinked thermoplastic materials. 2- [2-Hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine (CAS No. 204583-39-19) is UV Absorbers have been described for example in EP 1 308 084.

However, the improvement of the adhesion between a substrate and layers applied thereto by means of appropriate adhesion promoters requires additional processing steps and is thus relatively complicated.

Thus, in contrast to the prior art, there is an increased demand for multilayer systems based on substrate materials, which per se have improved adhesion to applied lacquer layers in order to avoid the pretreatment of the substrate surface with the mentioned disadvantages.

This need exists, inter alia, for those multilayer systems which are suitable for outdoor applications e.g. used in architectural glazing. In order to be able to ensure a long service life of the components, the substrates used for this purpose, which have suitable stabilizers, e.g. against the action of UV radiation, usually provided with protective layers, which are applied for example by means of a coating, coextrusion or a combination of coextrusion and subsequent coating.

It has been found that a product comprising a layer comprising thermoplastic and a lacquer layer which is in contact with the layer containing thermoplastic, the layer comprising thermoplastic being 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4, Contains 6-di (4-phenyl) phenyl-l, 3,5-triazine, having a surprisingly increased paint adhesion. In this case, the layer containing thermoplastic may be both the base layer of the multi-layer system and a coextrusion layer which may be applied thereto, which in turn is then painted. The present invention therefore also relates to the use of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-I, 3,5-triazine to improve the paint adhesion to thermoplastics and a process comprising the steps of a) preparing a product comprising a layer comprising thermoplastic and 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1, 3,5-triazine and b) coating this layer.

Thermoplastics for the purposes of the present invention include polycarbonates, copolycarbonates, polyestercarbonates, aromatic polyesters such as polybutylene terephthalate or polyethylene terephthalate, polyamides, polyesteramides, polyacrylates and polymethacrylates such as, for example, polyalkyl (meth) acrylates and in particular polymethyl methacrylate, polyurethanes, polyolefins, halogen-containing polymers, polysulfones , Polyethersulfone, Polyetherketone, polysiloxanes, polystyrenes, copolymers of styrene or of alpha-methylstyrene with dienes or acrylic derivatives, graft polymers based on acrylonitrile / butadiene / styrene or on Acrylate rubber-based graft copolymers (see, for example, the graft polymers described in EP-A 640 655) and mixtures thereof.

Particularly preferred thermoplastics in the context of the present invention are polycarbonates, more precisely homopolycarbonates, copolycarbonates and thermoplastic polyestercarbonates.

The polycarbonates and copolycarbonates according to the invention generally have average molecular weights (weight average) of from 2,000 to 200,000, preferably from 3,000 to 150,000, in particular from 5,000 to 100,000, very particularly preferably from 8,000 to 80,000, in particular from 12,000 to 70,000 (determined according to GPC with polycarbonate calibration).

In this context, they furthermore preferably have average molecular weights ^M _{w of} from 18,000 to 40,000 g / mol, more preferably from 26,000 to 36,000 g / mol and particularly preferably from 28,000 to 35,000 g / mol, determined by measuring the rel. Solution viscosity in dichloromethane at 25 ^° C. or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering or by gel permeation chromatography (GPC) with polycarbonate calibration.

For the preparation of polycarbonates for the compositions according to the invention, see, for example, "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol.

Interscience Publishers, New York, London, Sydney 1964, on D.C. PREVORSEK, B.T.

DEBONA and Y. KESTEN, Corporate Research Center, Allied Chemical Corporation,

Moristown, New Jersey 07960, "Synthesis of Poly (ester) Carbonates Copolymer" in Journal of

Polymer Science, Polymer Chemistry Edition, Vol. 19, 75-90 (1980), on D. Freitag, U. Grigo, P.R. Müller, N. Nouvertne, BAYER AG, "Polycarbonates" in Encyclopaedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pp. 648-718, and finally to Dres.

Grigo, K. Kircher and P.R. Müller "Polycarbonate" in Becker / Braun, plastic manual, volume

3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna

1992, pages 117-299. The preparation is preferably carried out by the phase boundary process or the melt transesterification process and will first be described by way of example in the phase boundary process.

Preferred starting compounds are bisphenols of the general formula HO-Z-OH, wherein Z is a divalent organic radical having from 6 to 30 carbon atoms and containing one or more aromatic groups. Examples of such compounds are bisphenols which belong to the group of dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, indane bisphenols, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) ketones and α, α'-bis (hydroxyphenyl) diisopropylbenzenes. Particularly preferred bisphenols belonging to the aforementioned linking groups are bisphenol-A, tetraalkylbisphenol-A, 4,4- (meta-phenylenediisopropyl) diphenol (bisphenol M), 4,4- (para-phenylenediisopropyl) diphenol, N-phenyl- Isatin bisphenol, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC), bisphenols of the 2-hydrocarbyl-3,3-bis (4-hydroxyaryl) phthalimidines type, in particular 2- Phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, and optionally mixtures thereof. Particular preference is given to homopolycarbonates based on bisphenol A and copolycarbonates based on the monomers bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. The bisphenol compounds to be used according to the invention are reacted with carbonic acid compounds, in particular phosgene or in the melt transesterification process diphenyl carbonate or dimethyl carbonate.

Polyestercarbonates are obtained by reacting the abovementioned bisphenols, at least one aromatic dicarboxylic acid and optionally carbonic acid equivalents. Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone dicarboxylic acids. A portion, up to 80 mole%, preferably from 20 to 50 mole%, of the carbonate groups in the polycarbonates may be replaced by aromatic dicarboxylic acid ester groups.

Inert organic solvents used in the interfacial process include, for example, dichloromethane, the various dichloroethanes and chloropropane compounds, tetrachloromethane, trichloromethane, chlorobenzene, and chlorotoluene. Preference is given to using chlorobenzene or dichloromethane or mixtures of dichloromethane and chlorobenzene.

The interfacial reaction can be accelerated by catalysts such as tertiary amines, in particular N-alkylpiperidines or onium salts. Tributylamine, triethylamine and N-ethylpiperidine are preferably used. In the case of the melt transesterification process, the catalysts mentioned in DE-A 42 38 123 are used.

The polycarbonates can be deliberately and controlled branched by the use of small amounts of branching. Some suitable branching agents are: isatin biscresol, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2; 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane; l, 3,5-tri- (4-hydroxyphenyl) benzene; l, l, l-tri- (4-hydroxyphenyl) ethane; Tri- (4-hydroxyphenyl) -phenylmethane; 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane; 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol; 2,6-bis- (2-hydroxy-5'-methyl-benzyl) -4-methyl phenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane; Hexa- (4- (4-hydroxyphenyl-isopropyl) -phenyl) -orthoterephthalic acid ester; Tetra (4-hydroxyphenyl) methane; Tetra (4- (4-hydroxyphenylisopropyl) phenoxy) methane; α, α ', α "-tris- (4-hydroxyphenyl) -l, 3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3,3-bis (3-methyl-4-hydroxyphenyl) - 2 oxo-2,3-dihydroindole; 1,4-bis- (4 ', 4 "-dihydroxytriphenyl) -methyl) -benzene and in particular: 1,1,1-tri- (4-hydroxyphenyl) -ethane and bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

The optionally used 0.05 to 2 mol%, based on diphenols, of branching agents or mixtures of the branching agents can be used together with the diphenols but can also be added at a later stage of the synthesis.

Chain terminators can be used. The chain terminators used are preferably phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof in amounts of 1-20 mol%, preferably 2-10 mol%, per mole of bisphenol. Preference is given to phenol, 4-tert-butylphenol or cumylphenol.

Chain terminators and branching agents may be added separately or together with the bisphenol to the syntheses.

The inventively preferred polycarbonate is bisphenol A homopolycarbonate.

Alternatively, the polycarbonates according to the invention can also be prepared by the melt transesterification process. The melt transesterification process is described, for example, in the Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 10 31 512 described.

In the melt transesterification process, the aromatic dihydroxy compounds already described in the phase boundary process are transesterified in the melt with carbonic acid diesters with the aid of suitable catalysts and optionally further additives

Carbonic acid diesters according to the invention are those of the formula (1) and (2)

Formula 1)

in which

R, R ¹ and R "are independently H, optionally branched Ci-C ₃₄ -alkyl / cycloalkyl, C ₇ - C ₃₄ alkaryl or C _O -C _J4 - may represent aryl,

for example

Diphenylcarbonate, butylphenyl-phenylcarbonate, di-butylphenylcarbonate, isobutylphenyl-phenylcarbonate, di-isobutylphenylcarbonate, tert-butylphenyl-phenylcarbonate, di-tert-butylphenylcarbonate, n-pentylphenyl-phenylcarbonate, di (n-pentylphenyl) carbonate, n-hexylphenyl-phenylcarbonate , Di- (n-hexylphenyl) carbonate, cyclohexylphenyl-phenylcarbonate, di-cyclohexylphenylcarbonate, phenylphenol-phenylcarbonate, di-phenylphenolcarbonate, isooctylphenyl-phenylcarbonate, di-isooctylphenylcarbonate, n-nonylphenyl-phenylcarbonate, di (n-nonylphenyl) carbonate, cumylphenyl -phenyl carbonate, di-cumylphenyl carbonate,

Naphthylphenyl-phenylcarbonate, di-naphthylphenylcarbonate, di-tert-butylphenyl-phenylcarbonate, di- (di-tert-butylphenyl) carbonate, dicumylphenyl-phenylcarbonate, di (dicumylphenyl) carbonate, 4-phenoxyphenyl-phenylcarbonate, di- (4-phenoxyphenyl ) carbonate, 3-pentadecylphenyl-phenylcarbonate, di (3-pentadecylphenyl) carbonate, tritylphenyl-phenylcarbonate, di-tritylphenylcarbonate,

prefers

Diphenyl carbonate, tert-butylphenyl phenyl carbonate, di-tert-butylphenyl carbonate,

Phenylphenol-phenylcarbonate, di-phenylphenolcarbonate, cumylphenyl-phenylcarbonate, di-cumylphenylcarbonate,

particularly preferably diphenyl carbonate.

It is also possible to use mixtures of the said carbonic diesters.

The proportion of carbonic acid ester is 100 to 130 mol%, preferably 103 to 120 mol%, particularly preferably 103 to 109 mol%, based on the dihydroxy compound.

As catalysts in the context of the invention, basic catalysts such as, for example, alkali metal and alkaline earth metal hydroxides and oxides but also ammonium or phosphonium salts, referred to below as onium salts, are used in the melt transesterification process as described in the cited literature. Onium salts, particularly preferably phosphonium salts, are preferably used here. Phosphonium salts in the context of the invention are those of the formula (3)

Formula (3)

in which

R ^{M may be the} same or different Ci-Cio-alkyls, Ce-Cio-aryls, C ₇ -Cio-aralkyls or Cs-Cβ-cycloalkyls, preferably methyl or Cβ-Cπ-aryls, more preferably methyl or phenyl, and

X ^"is an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate, a halide, preferably chloride, or may be an alcoholate of the formula OR, wherein R is Ce-Q ₄ -ATyI or C ₇ -C ₂ -aralkyl, preferably phenyl, Preferred catalysts are

Tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, tetraphenylphosphonium phenolate, more preferably tetraphenylphosphonium phenolate.

The catalysts are preferably used in amounts of from ^10.sup.-8 to 10.sup.- ³ mol, based on one mole of bisphenol, more preferably in amounts of from 10.sup.- ⁷ to 10.sup.-1 mole.

Other catalysts can be used alone or optionally in addition to the onium salt to increase the rate of polymerization. These include salts of alkali metals and alkaline earth metals, such as hydroxides, alkoxides and aryloxides of lithium, sodium and potassium, preferably sodium hydroxide, alkoxide or aryloxide salts. Most preferred are sodium hydroxide and sodium phenolate. The amounts of cocatalyst can range from 1 to 200 ppb, preferably from 5 to 150 ppb, and most preferably from 10 to 125 ppb, each calculated as sodium.

The transesterification reaction of the aromatic dihydroxy compound and the carbonic diester in the melt is preferably carried out in two stages. In the first stage, the melting of the aromatic dihydroxy compound and the carbonic diester at temperatures of 80 to 250 ⁰ C, preferably 100 to 230 ⁰ C, particularly preferably 120 to 190 ⁰ C under normal pressure in 0 to 5 hours, preferably 0.25 to 3 hours instead. After addition of the catalyst is by applying vacuum (up to 2 mm Hg) and increasing the temperature (up to 260 ⁰ C) by distilling off the monophenol, the oligocarbonate from the aromatic dihydroxy Made compound and the carbonic acid diester. In this case, the majority of vapors from the process accumulates. The oligocarbonate thus prepared has an average molecular weight Mw (determined by measuring the relative solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering) in the range from 2000 g / mol to 18,000 g / mol, preferably 4,000 g / mol to 15,000 g / mol.

In the second stage, in the polycondensation by further increasing the temperature to 250 to 320 ⁰ C, preferably 270 to 295 ° C and a pressure of <2 mm Hg produced the polycarbonate. The remainder of the vapors are removed from the process.

The catalysts can also be used in combination (two or more) with each other.

When using alkali metal alkaline earth metal catalysts, it may be advantageous to add the alkali metal / alkaline earth metal catalysts at a later time (eg, after the oligocarbonate synthesis in the second stage polycondensation).

The reaction of the aromatic dihydroxy compound and the carbonic acid diester to the polycarbonate can be carried out batchwise or preferably continuously, for example in stirred vessels, thin-film evaporators, falling film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors and high-viscosity disk reactors.

Analogous to the phase boundary process, branched poly- or copolycarbonates can be prepared by using polyfunctional compounds.

The polycarbonates and copolycarbonates according to the invention may also contain other aromatic polycarbonates and / or other plastics such as aromatic polyester carbonates, aromatic polyesters such as polybutylene terephthalate or polyethylene terephthalate, polyamides, polyimides, polyesteramides, polyacrylates and polymethacrylates such as, for example, polyalkyl (meth) acrylates and in particular polymethyl methacrylate, polyacetals, Polyurethanes, polyolefins, halogen-containing polymers, polysulfones, polyethersulfones, polyether ketones, polysiloxanes, polybenzimidazoles, urea-formaldehyde resins, melamine-formaldehyde resins, phenol-formaldehyde resins, alkyd resins, epoxy resins, polystyrenes, copolymers of styrene or of alpha-methylstyrene with dienes or Acrylic derivatives, graft polymers based on acrylonitrile / butadiene / styrene or acrylate rubber-based graft copolymers (see, for example, the graft polymers described in EP-A 640 655) or silicone rubbers in a known manner, for example are mixed, for example by Compoundiemng. The polycarbonates according to the invention and optionally further thermoplastics contained can also be added in conventional amounts for the customary additives for these thermoplastics, such as fillers, further UV stabilizers, heat stabilizers, antistatic agents and pigments; optionally, the Entfoπnungsverhalten, the flow behavior, and / or the flame retardancy can be improved by the addition of external mold release agents, flow agents, and / or flame retardants (eg, alkyl and aryl phosphites, phosphates, phosphanes, - low molecular weight carboxylic acid esters, halogen compounds, salts , Chalk, quartz powder, glass and carbon fibers, pigments and their combination). Such compounds are z. In WO 99/55772, pages 15-25, EP 1 308 084 and in the corresponding chapters of the "Plastics Additives Handbook", ed. Hans Zweifel, 5 ^Λ Edition 2000, Hanser Publishers, Munich. described.

Under paints in the context of the present invention are intended

Sol-gel systems, sol-gel systems with siloxane bridges (1),

Sol-gel lacquer systems which are bonded to the thermoplastic via a bonding agent layer (2), Sol-gel lacquer systems which additionally contain a thermoplastic (3), lacquer systems which are cured by UV radiation or electron radiation (4 )

- paint systems that are thermally cured (5),

Lacquer systems which are cured by UV radiation and contain inorganic particles (6),

- As well as polyurethane-based paint systems are understood (7).

Hereinafter, commercially available coating systems for thermoplastics, in particular for polycarbonates, are assigned to the above-mentioned generally described coating systems by the number assignment in parentheses. Such paint systems can be used in the context of the present invention.

The company Momentive Performance Materials (Hudson River Road, Waterford, NY 12118, USA) sells among others the following coating systems:

PHC 587 (1; 3; 5), PHC 587B (1; 3; 5), SHP401 / AS4000 (1; 2; 5), SHP401 / AS4002 (1; 2; 5), SHP470 / AS4700 (1; 2; 5), SHC 3000 (1; 5), SHC 5020 (1; 5), SHC 6000 (1; 5), UVHC 3000 (4; 6), UVHC 3000S (4; 6), UVHC 7000 (4; 6) , UVHC 8556 (4), UVHC 8558 (4), UVHC 8559 (4) and OM 1000 (4).

Red Spot Paint & Varnish Co., Inc. (PO Box 418, Evansville, IN 477703-0418, USA) distributes, among others, the following paint systems: UVT 146 (4), UVT 200 (4), UVT 200 Vl (4), UVT 200 V2 (4), UVT 200 V3 (4), UVT 200 V4 (4), UVT 200 V5 (4), UVT 200 V6 (4) as well as UVT 200 Ql (4).

The company Mitsubishi Rayon Co., Ltd. (3-19, Kyobashi, 2-Chome, Chuo-Ku, Tokyo 104, Japan) sells among others the following lacquer systems:

Acryking KlOl (5), Acryking K103 (5), Acryking F-328 (5), Acryking PH-220 (5), Acryking PH-328 (5) and Acryking PH 700 (5).

The company Rohm & Haas Company (2701 East 170th Street, Lansing, IL 60438, USA) sells among others the following paint systems:

LS123 (5), LPC1000 / LTC4000 (Lensgard I), LTC5000 (Lensgard ll) and LUC7000 (Lensgard IE).

The company KRD Coatings GmbH (Vierlander Strasse 7, 21502 Geesthacht, Germany) distributes, among other things, the following coating systems:

KASI ^® PCN (1, 5), KASI ^® Matte PCN (1, 5), KASI ^® White PCN (1, 5), KASI ^® PCN 1.5 (1; 5), KASI ^® PC Flex (l, 5) , KASI ^® PC Softflex (l, 5), KASI ^® GenFlex (1; 5), KASI ^® SunFlex (l, 5), KASI ^® AS (1; 5), KASI ^® AS / 8 (1; 5), KASI ^® AS Dur (1; 5), KASI ^® AS hard PC (1; 5), KASI ^® AG (1; 5), KASI ^® cascade (1; 5), KASI ^® AF UV (4), KASI ^® UVP (4) KASI ^® AFT (1; 5), KASI ^® IR (1; 5), KASI ^® AD (1; 5) and KASI ^® frost (1; 5)

The company Sherwin-Williams Automotive Finishes Coφ. (388 Robins Drive, Troy, MI 48083, USA) sells, among others, the following paint systems:

V88VC31 and Permaclear IV.

Stanley Electric Co., Ltd. (2-9-13, Nakameguro, Meguro-KU, Tokyo 153, Japan) sells among others the following lacquer systems: SH-41 and SH-50.

The company Röhm GmbH & Co. KG (Krischenalle, 64293 Darmstadt, Germany) sells among others the following paint system:

Acryplex 100PSR 100SR.

Furthermore flüssigkeitsspreitende systems such as Makrolon ^® Modifϊer DPI -1700 and Makrolon ^® Modifier DP can be from 1 to 1701 from Lanxess AG used.

In addition, other polycarbonate coating systems are disclosed, for example, by AMECA (Automotive Manufacturers Equipment Compliance Agency, Inc.) in the "List of Acceptable Plastics for Optical Lenses and Reflex Reflectors Used on Motor Vehicles".

The above-mentioned coatings can be applied to various surfaces, including layers containing thermoplastic in the sense of the present invention, by means of flooding, dipping, spraying, rolling or spin coating. The curing of the coatings can be carried out thermally or with the aid of radiation, in this case in particular with UV radiation or electron radiation.

For the purposes of the present invention, both the lacquering of the base layer of a multi-layer system and of a coextrusion layer optionally applied thereto are meant here.

In this context, the production of corresponding plates made of polycarbonate will be described below by way of example: Coextruded solid polycarbonate plates may, for. B. with the aid of the following machines and apparatuses - the main extruder with a screw of length 33 D and a diameter of 70 mm with degassing - a coextruder for applying the cover layer with a screw of length 25 D and a diameter of 35 mm-one special coextrusion slot die with a width of 450 mm - a smoothing calender - a roller conveyor - a withdrawal device - a cutting device (saw) - a storage table.

Coextruded polycarbonate web plates can, for. B. using the following machines and apparatus: the main extruder with a screw of length 33 D and a diameter of 70 mm with degassing

the coexadapter (feedblock system)

a coextruder for applying the cover layer with a screw of length 25 D and a diameter of 30 mm

the special slot die with 350 mm width

the calibrator

the roller conveyor

the trigger device

- the cutting device (saw)

the storage table.

In both plate types, the polycarbonate granules of the base material are fed to the hopper of the main extruder, the coextrusion material of the coextruder. In the respective plasticizing cylinder / screw, the melting and conveying of the respective material takes place. Both material melts are combined in the coexadapter and form a composite after leaving the die and cooling. The other facilities are used for transporting, cutting and depositing the extruded sheets.

Sheets without a coextrusion layer are prepared accordingly either by not operating the coextruder or by filling it with the same polymer composition as the main extruder. The present invention therefore also relates to a process for producing a sheet according to the invention comprising the steps of a) extruding a composition comprising thermoplastic and 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4 -phenyl) phenyl-1,3,5-triazine, b) calendering and c) varnishing

The present invention therefore also relates to a plate according to the invention, characterized in that the lacquer layer covers 95% of the surface of the layer containing thermoplastic, and a double-coextruded plate according to the invention, characterized in that the lacquer layers cover 95% of the coextrusion layers

Coextrusion layers and the other understood in the context of the present invention layers are not limited to polycarbonate as a thermoplastic, but may contain other disclosed in the present invention thermoplastics or plastics such as in particular polyacrylates and polymethacrylates such as polyalkyl methacrylates and in particular polymethyl methacrylate contain or consist of these. Coating layers according to the invention in the form of coextrusion layers may here comprise as polymer matrix a polyacrylate consisting of alkyl methacrylate, preferably having alkyl chain lengths of less than 10 carbon atoms (-CnH 2n + 1 with n <10), especially preferably with n = 1 (methyl methacrylate). This also applies to corresponding paint layers. Such layers of cured coating formulations contain as binder material a physically drying polyacrylate resin containing methyl methacrylate as main component and possibly another alkyl methacrylate with a longer, linear or branched alkyl chain (-C _n H _{2n +!} With n> l), preferably 1 <n <10, especially preferably linear with n = 3 (butyl methacrylate). The ratio of the two Methacrylateinheiten is 75 to 100% methyl methacrylate or 25 to 0% alkyl methacrylate, preferably 85 to 100% methyl methacrylate or 15% to 0% alkyl methacrylate, more preferably 90 to 100% methyl methacrylate and 10% to 0% alkyl methacrylate.

The preparation of compositions for the layer containing thermoplastic is carried out by conventional incorporation methods and can be, for example, by mixing solutions of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl -l, 3,5-triazines with a solution of thermoplastic and optionally further additives in suitable solvents. If the thermoplastic is polycarbonate, preference is given to solvents such as dichloromethane, haloalkanes, haloaromatics, chlorobenzene and xylenes. The substance mixtures are then preferably homogenized in a known manner by extrusion. The solution mixtures are preferably worked up in a known manner by evaporation of the solvent and subsequent extrusion, for example, compounded.

In addition, the composition can be mixed in conventional mixing devices such as screw extruders (for example twin-screw extruder, ZSK), kneaders, Brabender or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed. Mechanical properties:

Studies on mechanical properties of the compositions for the layer containing thermoplastics can be carried out according to the following standards:

The impact resistance can be determined according to DIN EN ISO 180, EN ISO 20180, ASTM D256, DIN EN ISO 179, DIN EN 20179, DIN 53453 or corresponding standards.

The determination of the notched IZOD impact strength can be carried out, for example, according to ISO 180/1 A, ISO 180/1 AR or ISO 180 / IB on specimens of geometry 80 * 10 * 4 mm ³ or according to ISO 180 / 4A on specimens of geometry 63 , 5 * 12,7 * 3,2 mm ³ .

The measurement of Charpy impact strength, for example, according to ISO 179 / leA, ISO 179 / leB or ISO 179 / leC or ISO 179 / lfA, ISO 179 / lfB or ISO 179 / lfC on specimens of geometry 80 * 10 * 4 mm ³ carried out.

The impact toughness of notched and uncut specimens can be determined in accordance with DIN EN ISO 8256, DIN EN 28256, DIN 53448 or corresponding standards.

Further mechanical characteristics such as tensile modulus, yield stress, yield strain, ultimate stress, elongation at break or nominal elongation at break can be obtained from a tensile test according to DIN EN ISO 527, DIN EN 20527, DIN 53455/53457, DIN EN 61, ASTM D638 or corresponding standards.

Stress and strain characteristics such. B. bending elastic modulus, bending stress at conventional deflection (3.5% bending stress), bending strength, flexural strength at flexural strength, bending stress at break or bending elongation at break provides a bending test according to DIN EN ISO 178, DIN EN 20178, DIN 53452/53457, DIN EN 63, ASTM D790 or equivalent standards.

The Vicat softening temperature (VST) can be determined according to DIN ISO 306, ASTM Dl 525, or corresponding standards.

Force and deflection characteristics are obtained from a puncture test according to DIN EN ISO 6603-2 or corresponding standards.

weathering: The weathering of samples can be carried out by various methods. These include the Xenon WOM method according to ASTM G6, ASTM G151, ASTM Gl 55, DIN EN ISO 4892-2, SAE J 1885 or VDA 75202, the LSL-WOM method according to DIN EN ISO 4892-3, the Xenotest ^® High Energy according to DIN EN ISO 4892-2 or DIN EN 50014, the spray test according to ASTM Bl 17, DIN 50021, DIN EN ISO 7253, DIN EN 9227 or ISO 11503 and the QUV test according to ISO 4892-3 or ASTM Gl 54 and ASTM G53.

Rheological properties:

The determination of the melt index (MFR, MVR) is carried out according to ISO 1133 or according to ASTM D1238 MVR.

The melt viscosity is measured in accordance with ISO 11443 or DIN 54811.

Solution viscosities can be e.g. according to the standards ISO 1628-1 / -4 or DIN 51562-3.

Optical measurements:

The determination of the degree of gloss can with a reflectometer on plates of geometry 150 * 105 * 2 mm ³ , wherein in addition to thicknesses of 2 mm and those of 3 mm, 3.2 mm and 4 mm come into consideration. For this measurement the DIN 67530, ISO 2813, ASTM D523 or corresponding standards are used.

Turbidity and transmission determinations are carried out in accordance with DIN 5036, ASTM D1003, ASTM E179 or ISO 13468.

The yellowness index YI is calculated according to ASTM E313.

Reflection measurements can be carried out according to DIN 5036 or ASTM El 79.

The ISO 105-A02 can be used to determine the gray scale.

Adhesion tests:

The following adhesion tests are carried out using one or more of the following methods: (a) adhesive tape tear off (3M 898 adhesive tape used) without and with crosshatching (analogous to ISO 2409 or ASTM D 3359),

(b) Adhesive tape tear off the crosshatch after at least 10 days storage in water at 65 ° C (analogous to ISO 2812-2 and ASTM 870-02), and

(c) Adhesive tape tear on the cross-hatch after at least 4 hours of storage in about 100 ⁰ C warm water.

In general, commercially available paint systems for thermoplastic substrates survive the test (a) without objection. Due to the direct effect of elevated temperature in combination with moisture or water, as indicated in tests (b) and (c), the elevated test conditions are expected to cause differences in paint adhesion, which in turn depends on the binder of the paint formulation used Pretreatment of the substrate and ultimately depend on the surface nature of the substrate or its Additivierung.

The above test methods can be applied to compositions for the layer containing thermoplastics and in selected cases also to the corresponding multilayer systems.

In a further embodiment, the present invention relates to a product comprising a layer containing thermoplastic and a lacquer layer which is applied to the layer containing thermoplastic, wherein the layer containing thermoplastic 0.03 wt% to 5.0 wt%, preferably 0.03 Wt% to 2.0% by weight of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine.

In a further embodiment, the present invention relates to a product comprising a layer containing thermoplastic and a lacquer layer which is applied to the layer containing thermoplastic, wherein the layer containing thermoplastic 0.03 wt% to 0.2 wt%, preferably 0.03 % By weight to 0.15% by weight of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine. In a separate embodiment of the present invention, this is the base layer of the considered multilayer system.

In a further embodiment, the present invention relates to a product comprising a layer containing thermoplastic and a lacquer layer which is applied to the layer containing thermoplastic, wherein the layer containing thermoplastic 1.0 wt% to 5.0 wt%, preferably 1.0 Wt% to 2.0% by weight of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine. In a separate embodiment of the invention, this is a coextrusion layer. The data in% by weight always refer to the total composition of the respective layer.

Production of examples:

The device for compounding consists of:

Metering device for the components

• A co-rotating twin-screw mixer (ZSK 53 from Werner & Pfleiderer) with a screw diameter of 53 mm

• A hole nozzle for forming melt strands

• A water bath for cooling and strengthening the strands

• A granulator.

With the aid of the compounding device described above, the following compositions of Examples 1 to 33 are prepared.

Makrolon® 3108 550115 is commercially available from Bayer MaterialScience AG.

Makrolon® 3108 550115 is EU / FDA quality and contains no UV absorber. The melt volume flow rate (MVR) according to ISO 1133 is 6.0 cmV (10 min) at 300 ⁰ C and 1.2 kg load.

In the preparation of the compounds, the procedure is such that 95% by weight of Makrolon® 3108 550115 granulate 5% by weight of a powder mixture of Makrolon® 3108 550115 powder containing the substances mentioned in the examples, is metered, so that in the Examples mentioned mixtures (compounds) result. Examples

Example 1:

100.00% by weight Makrolon 3108 550115

Example 2:

• 99.80% by weight Makrolon® 3108 550115

• 0.20% by weight of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine

Example 3;

• 99.80% by weight Makrolon® 3108 550115

• 0.20% by weight of Tinuvin 350® from Ciba

Example 4;

• 99.80% by weight Makrolon® 3108 550115

• 0.20% by weight of Tinuvin 329® from Ciba

Example 5:

• 99.80% by weight Makrolon® 3108 550115

• 0.20% by weight of Tinuvin 360® from Ciba

Example 6;

• 98.00% by weight Makrolon® 3108 550115

2.0% by weight of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine

Example 7:

• 98.00% by weight Makrolon® 3108 550115

2.0% by weight of Tinuvin 360® from Ciba

Example 8; 98.00% by weight Makrolon® 3108 550115

2.0% by weight of Tinuvin 1577® from Ciba

Example 9;

98.00% by weight Makrolon® 3108 550115

2.0% by weight of Uvinul® 3030 from BASF AG

The compounds of Examples 1 to 33 are then processed into plates of geometry 150 * 105 * 3.2 mm ³ . This is done with a Klöckner Ferromatik FM160 with a screw diameter of 45 mm.

The following coating materials based on the manufacturer's instructions for application by flooding, spraying or knife coating are applied to the plates of geometry 150 * 105 * 3.2 mm ³ produced under Examples 1 to 9. Before the paint application, a cleaning step of the specimens with isopropanol and the blowing off of the specimens with ionized air.

Paint Systems A - PHC 587 (Momentive Performance Materials ^* )

The coating solution is reduced in viscosity with isopropanol or with n-butanol in such a way that a dry layer thickness of at least 6-8 μm results on the test specimen.

The application of the filtered material takes place at 23 ° C ± 5 ° C and at a rel. Humidity of 40% ± 10% in a clean and dust-free atmosphere within a room of clean room class 1000 or less. After application, the coating material, which is still enriched with solvents, dries on the specimen at room temperature until it dries for about 10 to 30 minutes, depending on the atmospheric humidity and ambient temperature. Subsequently, the coating is cured in a convection oven for at least 30 minutes at an object temperature of> 125 ° C.

Paint Systems B - SHP401 / AS4000 fMomentive Performance Materials)

The primer SHP401 is reduced with a solvent mixture consisting of 2-methoxy-propanol and diacetone alcohol (85:15) or with pure 2-methoxy-propanol in its viscosity such that a dry film thickness of at least 0.5 .mu.m results on the sample.

The application of the filtered material takes place at 23 ° C ± 5 ° C and at a rel. Humidity of 40% ± 10% in a clean and dust-free atmosphere within a room of clean room class 1000 or less.

After application, the coating material, which is still enriched with solvents, dries on the specimen at room temperature until it dries for about 10 to 45 minutes, depending on the atmospheric humidity and ambient temperature.

The scratch-resistant coating AS4000 is reduced in its viscosity with isopropanol or with n-butanol such that a dry layer thickness of at least 4.5-6.5 μm results on the coated specimen. The solids content of the coating solution can be reduced to about 15%.

The application of the filtered material on the previously coated with SHP401 specimen is carried out at 23 ⁰ C ± 5 ⁰ C and at a rel. Humidity of 40% ± 10% in a clean and dust-free atmosphere within a room of clean room class 1000 or less.

After application, the coating material, which is still enriched with solvents, dries on the specimen at room temperature until it dries for about 10 to 45 minutes, depending on the atmospheric humidity and ambient temperature. Subsequently, the coating is cured in a convection oven for at least 30 minutes at an object temperature of> 125 ° C.

Paint System C - KASI ^® SunFlex (KRD Coatings GmbH)

The coating solution is reduced in viscosity with a mixture of isopropyl glycol: 2-methoxy-propanol (70:30), 2-methoxy-propanol or with n-butanol in such a way that a dry layer thickness of at least 6 - 10 μm results. The application of the filtered material takes place at 23 ° C ± 5 ⁰ C and at a rel. Humidity of 40% ± 10% in a clean and dust-free atmosphere within a room of clean room class 1000 or less.

After application, a evaporation time of the still solvent-enriched coating material on the specimen follows at room temperature for about 20 to 30 minutes depending on humidity and ambient temperature. Subsequently, the coating is cured in a convection oven for 2 hours at an object temperature of 130-135 ⁰ C.

Lackvstem D - UVHC 3000 fMomentive Performance Materials)

The coating solution is reduced in viscosity with suitable solvents such that a dry film thickness of at least 9-15 μm results on the test specimen.

The application of the filtered material is carried out at 20 ⁰ C to 25 ⁰ C and at a rel. Humidity of 40% ± 10% in a clean and dust-free atmosphere within a room of clean room class 1000 or less.

After application, a flash-off time of the still solvent-enriched coating material follows on the specimen in two steps. First, an evaporation phase takes place at room temperature for approx. 1 - 2 minutes, depending on the humidity and ambient temperature. Then the coated specimen at about 65 ⁰ C - 75 ⁰ C in a convection oven for 2 - 6 minutes to complete removal of the solvent is dried. Here, the relative humidity during the entire process is below 50%.

After evaporation of the solvents contained, the curing of the coating material is followed by UV radiation. For this purpose, a UV system SLP 399 from Hackemack is used with a UV module KTR 2061, which harbors a Hg emitter with 80 W / cm ² lamp power. The amount of radiation required for hardening is regulated by the belt speed of the transport belt KTR 3371 from Hackemack in such a way that the amount of UV-A energy is between 6 and 12 J / cm ² (eg 3 x 2 m / min belt speed approx. 8.1 J) / cm ² energy input).

Paint Shop E - UVT 200 (Red Spot Paint & Varnish Co .. Inc

The coating solution is reduced in viscosity with a mixture of isopropanol and n-butanol (3: 2) in such a way that a dry layer thickness of at least 10 to 15 μm results. The application of the filtered material takes place at 2O ⁰ C to 25 ° C and at a rel. Humidity of 40% ± 10% in a clean and dust-free atmosphere within a room of clean room class 1000 or less.

After application, a flash-off time of the still solvent-enriched coating material follows on the specimen in two steps. First, an evaporation phase at room temperature for about 5 - 6 minutes. Then the coated specimen is further dried at about 75 ° C in a convection oven for 7 minutes. Here, the relative humidity during the entire process is below 50%.

After evaporation of the solvents contained, the curing of the coating material is followed by UV radiation. For this purpose, a UV system SLP 399 of the company

Hackemack with a UV module KTR 2061, the Hg emitter with 80 W / cm ²

Lamp power holds, used. The amount of radiation required for curing is over the

Belt speed of the conveyor belt KTR 3371 Hackemack regulated so that the UV-A energy amount between 3.5 - 5.5 J / cm ² is (eg, 3 x 3 m / min belt speed about 5.1 J / cm ² energy input ).

The following adhesion tests are carried out on the painted panels.

(a) adhesive tape tear off (3M 898 adhesive tape used) without and with crosshatching (analogous to ISO 2409 or ASTM D 3359),

(b) adhesive tape on cross-cut by min. 10 days of storage at 65 ⁰ C water (similar to ISO 2812-2 and ASTM 870-02), and

Claims

claims

I. Product comprising a layer comprising thermoplastic and a lacquer layer applied to the layer comprising thermoplastic, the layer containing thermoplastic containing 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4 -phenyl) phenyl-l, 3,5-triazine.

2. Product according to claim 1, wherein the product is a plate.

A plate according to claim 2, wherein the layer containing thermoplastic is a coextrusion layer overlying a base layer.

4. Plate according to claim 3, wherein the plate consists of a base layer having coextrusion layers and lacquer layers on both sides.

5. Product according to claim 1, wherein the layer containing thermoplastic consists essentially of polycarbonate.

A plate according to claim 3, wherein the thermoplastic is polycarbonate and the base layer comprises polycarbonate.

A plate according to claim 3, wherein the thermoplastic is acrylate and the base layer comprises polycarbonate.

8. A product according to claim 1, characterized in that the layer containing Themoplast 0.01 to 15 parts by weight of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4- phenyl) phenyl-l, 3,5-triazine based on 100 parts of thermoplastic.

9. Product according to claim 1, characterized in that the lacquer layer is a sol-gel lacquer layer.

10. Product according to claim 9, characterized in that the sol-gel lacquer layer contains siloxane bridges.

I I. Product according to claims 9 to 10, characterized in that there is a Haftveimittlerschicht between the sol-gel coating system and the thermoplastic.

12. Product according to claims 9 to 10, characterized in that the sol-gel coating system additionally contains a thermoplastic.

13. Product according to claims 1 to 8, characterized in that the paint system is cured by UV radiation or electron radiation.

14. Product according to claims 1 to 8, characterized in that the paint system is thermally cured.

15. A product according to claim 13, characterized in that the paint system is cured by UV radiation and contains inorganic particles.

16. Product according to claims 1 to 8, characterized in that the paint system is polyurethane-based.

17. Plate according to claim 2, characterized in that the lacquer layer covers 95% of the surface of the layer containing thermoplastic.

18. Plate according to claim 4, characterized in that the lacquer layer cover 95% of the coextrusion layers.

19. Use of 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1,3,5-triazine to improve the paint adhesion to thermoplastics.

20. A process comprising the steps of a) preparing a product comprising a layer comprising thermoplastic and 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-1, 3, 5-triazine and b) coating this layer.

21. A process for producing the plate according to claim 2, comprising the steps of a) extruding a composition comprising thermoplastic and 2- [2-hydroxy-4- (2-ethylhexyl) oxy] phenyl-4,6-di (4-phenyl) phenyl-l, 3,5-triazine, b) calendering and c) varnishing.