Bird protection glazing

Abstract

The invention relates to at least partly transparent or translucent molded plastic parts for producing noise protection walls, facade components, and glazings which ensure effective bird protection. In particular, the invention relates to molded plastic parts comprising g) at least one substrate layer (matrix/base layer) containing at least one thermoplastic polymer, wherein the substrate layer comprises a base layer and a coextrusion layer adjoining said base layer, said coextrusion layer comprising at least one IR absorber; a) optionally at least one cover layer on at least one face of the substrate layer; and b) optionally a primer or an intermediate layer between the layers a) and b). The invention is characterized in that the molded plastic part has markings in the substrate layer, said markings reducing the transparency of the molded part in the wavelength range of 380 to 780 nm in the marked regions.

Claims

1. A plastics molding comprising a) at least one substrate layer comprising at least one thermoplastic polymer, where the substrate layer comprises a base layer and, adjacent thereto, a coextruded layer, and where the coextruded layer comprises at least one IR absorber, b) optionally at least one outer layer on at least one side of the substrate layer, c) optionally a primer or intermediate layer between the layers a) and b), wherein the plastics molding comprises, in the substrate layer, markings which reduce the transparency of the molding in the wavelength range from 380 to 780 nm in the marked region.

2. The plastics molding as claimed in claim 1, wherein the coextruded layer comprises at least one UV absorber.

3. The plastics molding as claimed in claim 1, wherein an arrangement of the markings is uniform/homogeneous on the area of the plastics molding.

4. The plastics molding as claimed in claim 1, wherein the markings are in the coextruded layer.

5. The plastics molding as claimed in claim 1, wherein the markings do not leave any uncovered transparent areas of average diameter greater than 250 mm.

6. The plastics molding as claimed in claim 1, wherein the average diameter of the markings, irrespective of the shape thereof, is at least 5 mm and less than 300 mm.

7. The plastics molding as claimed in claim 1, wherein the markings are linear and horizontally oriented with a line width of from 1.5 mm to 15 mm, with regular separation of from 1.5 cm to 10.0 cm, where the extent of coverage of the surface of the molding is from 4% to 25%.

8. The plastics molding as claimed in claim 1, wherein the markings are linear and vertically oriented with a line width of from 3 mm to 20 mm, with regular separation of from 4 cm to 20 cm, where the extent of coverage of the surface of the molding is from 2% to 25%.

9. The plastics molding as claimed in claim 1, wherein the markings are not linear, and the extent of coverage of the surface of the molding is from 5% to 40%.

10. The plastics molding as claimed in claim 1, wherein the transparency (light transmittance) of the markings is less than 5.0%.

11. The plastics molding as claimed in claim 1, wherein the contrast, between a marked and an unmarked location defined as quotient calculated from the difference between the light transmittance of the unmarked and the marked location as dividend and from the sum of light transmittance of the marked and the unmarked location as divisor, is at least 90%.

12. The plastics molding as claimed in claim 1, wherein the IR absorber in the coextruded layer is selected from the group consisting of lanthanum borides and carbon black.

13. The plastics molding as claimed in claim 1, wherein the thermoplastic polymer of the substrate layer is polycarbonate.

14. The plastics molding as claimed in claim 1, wherein the markings are introduced by an Nd:YAG laser with 1064 nm wavelength, or by a UV (ultraviolet) laser (Nd:YVO.sub.4 laser) with 355 nm wavelength.

15. A method for the production of bird-protected glazing comprising utilizing the plastics moldings as claimed in claim 1.

16. The plastics molding as claimed in claim 1, wherein the light transmittance of the unmarked regions is 15%-95% in the wavelength range from 380 nm to 780 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the results of experimental series 1.

(2) FIG. 2 shows the results of experimental series 2.

(3) FIG. 3 shows the results of experimental series 3.

(4) FIG. 4 shows the results of experimental series 4.

(5) FIG. 5.1 shows the results from color sample plaques composed of pellets made of mixtures 1 to 9.

(6) FIG. 5.2 shows the results from composites 3A to 9A composed of foils and color sample plaques comprising pellets made of mixture 1.

(7) FIG. 6.1 shows results from a sheet of 8.1 with markings from a UV laser.

(8) FIG. 6.2 shows results from a sheet of 8.2 with markings from a UV laser.

(9) FIG. 7.1 shows results from a sheet of 8.1 with markings from an IR laser.

(10) FIG. 7.2 shows results from a sheet of 8.2 with markings from an IR laser.

EXAMPLES

(11) Inventive examples are used below for a more detailed description of the invention; the determination methods described here are used for all corresponding variables in the present invention unless otherwise stated.

(12) Materials for the Production of the Test Samples:

(13) Component A)

(14) Linear bisphenol A polycarbonate having terminal groups based on phenol with melt volume rate (MVR) 6 cm/10 min, measured at 300 C. with 1.2 kg load in accordance with ISO 1033, hereinafter termed PC 1.

(15) Linear bisphenol A polycarbonate having terminal groups based on phenol with melt volume rate (MVR) 10 cm.sup.3/10 min, measured at 300 C. with 1.2 kg load in accordance with ISO 1033, hereinafter termed PC 3.

(16) PC 3 also comprises an additive mixture composed of mold-release agent, heat stabilizer, and UV stabilizer. Pentaerythritol tetrastearate (CAS 115-83-3) is used as mold-release agent, triphenylphosphine (CAS 603-35-0) is used as heat stabilizer, and Tinuvin 360 (CAS 103597-45-1) is used as UV stabilizer.

(17) Component B)

(18) B1) Black Pearls 800

(19) Nanoscale carbon black (particle size about 17 nm) from Cabot Corp. (CAS No. 1333-86-4)
B2) Quaterrylene dye (Lumogen IR-765 from BASF SE, Germany, Cas. No. 943969-69-5)
B3) Antimony tin oxide (FMDS 874 from Sumitomo Metal Mining, Japan, Cas. No. 953384-75-3)
B4) Cesium tungstate, Cs.sub.0.33WO.sub.3, (YMDS 874 from Sumitomo Metal Mining, Japan, Cas. No. 1258269-41-8) The product takes the form of a dispersion. The weight data in the examples relate to the cesium tungstate as pure substance; the solids content of cesium tungstate in the commercial YMDS 874 dispersion used here is 20% by weight. The tungstate here is not zinc-stabilized.
B5) Lanthanum hexaboride, LaB.sub.6 (KHDS 872G2 from Sumitomo Metal Mining, Japan, CAS No. 949005-03-2) The product takes the form of a powder dispersion. The weight data in the examples relate to the product KHDS 872G2; the solids content of lanthanum hexaboride in the commercial KHDS 872G2 dispersion used here is 10.0% by weight.

(20) The following polymer compositions (hereinafter termed mixtures) were produced:

(21) TABLE-US-00001 Mixture Content of No. PC1 PC3 Component B component B 1 100.0000 2 100.0000 3 99.9950 B1 0.0050 4 99.9995 B2 0.0005 5 99.9800 B3 0.0200 6 99.9900 B4 0.0100 7 99.9700 B4 0.0300 8 99.9950 B5 0.0050 9 99.9900 B5 0.0100 10 99.9930 B1 0.0070 11 99.9700 B5 0.0300 * data in % by weight
Production of the Polymer Compositions Via Compounding:

(22) The additives were compounded in a ZE25 twin-screw extruder from KraussMaffei Berstorff, at a barrel temperature of 300 C. and, respectively, a melt temperature of 318 C., and a rotation rate of 100 rpm, with throughput 10 kg/h, using the component quantities stated in the table above. In order to provide better mixing here, the procedure begins with manufacture of a mixture of a portion of PC 1 and of the respective component B (5% by weight mixture, based on the entire composition). This mixture is metered into the remaining quantity of PC 1 during the compounding process.

(23) Production of the Test Samples:

(24) The respective pellets of the mixtures 1 to 9 are dried in vacuo for 4 hours at 120 C. and then processed in an Arburg 370 injection-molding machine with an injection unit with melt temperature 300 C. and mold temperature 90 C., to give color sample plaques with the following dimensions: 60 mm60 mm1 mm 60 mm60 mm2 mm 50 mm75 mm4 mm
Production of Thin Foils from the Color Sample Plaques:

(25) Color sample plaques composed of pellets from the mixtures 1 and 3 to 9 measuring 60 mm60 mm1 mm were pressed in a PW20 precision hydraulic press from Paul-Otto Weber GmbH, Remshalden to give flat foils of thickness about 100 m. For this, the plaques of thickness 1 mm were plastified for 5 minutes by contact with the press plates controlled to from 320 C. to 340 C. After the plastification time, the samples were molded to give a foil of thickness about 100 m by using a closure force of from 100 to 200 kN. Before removal of the foils from the press they were cooled to about 100 C. to 130 C. in the press with constant closure force of from 100 to 200 kN.

(26) Production of Composites from Foils and Color Sample Plaques Comprising Pellets Made of Mixture 1

(27) Foils comprising pellets made of mixtures 3 to 9 were then joined to color sample plaques comprising pellets made of mixture 1 in a PW20 precision hydraulic press from Paul-Otto Weber GmbH, Remshalden to give a secure composite measuring 50 mm75 mm4 mm. For this, the combinations of plaque and foil were plastified by contact with the press plates for 5 minutes (upper plate temperature 160 C.; lower plate temperature 150 C.). After the plastification time the combinations were joined to give a durable composite by using a closure force of 50 kN for 2 minutes.

(28) TABLE-US-00002 Foil (pellets Plaque (pellets Composite made of mixture) made of mixture) 3-A 3 1 4-A 4 1 5-A 5 1 6-A 6 1 7-A 7 1 8-A 8 1 9-A 9 1
Laser Marking of Color Sample Plaques and Composites
(Laser-Inscription System from ACI Laser GmbH)

(29) A laser-inscription system from ACI Laser GmbH, composed of a COMFORT workstation with DPL Genesis Marker 163 (8W) and MagicMarkV3 inscription software, was used for the marking experiments below. The laser beam source is composed of an excitation source (laser diode) followed by a lens system and also a resonator based on an Nd:YAG (neodymium-doped yttrium aluminum garnet) laser crystal to produce the beam. The wavelength of the resultant laser beam is 1064 nm, and the beam is focused onto the color sample plaques and, respectively, composites by way of a beam-deflector unit after passage through an F-Theta 100 lens.

(30) The frequency and the advance rate of the laser were varied at constant pulse width (3 s) in order to vary the processing latitude of the laser/of the laser-marking process.

(31) The processing latitude was selected in such a way that when color sample plaques composed of pellets made from mixtures 3 to 9 are used in the process a marking is obtained over a substantial area, its darkness depending on the additives used in the matrix of the color sample plaque. When color sample plaques composed of pellets made of mixture 1 or 2 are subjected to these specific conditions there is almost no visually discernible marking.

(32) 1.sup.st Experimental Series

(33) A grid of 88 markings was applied on a color sample plaque at constant pulse width (3 s).

(34) Frequency on the ordinate: 5.0; 7.0; 9.0; 11.0; 13.0; 15.0; 17.0; 19.0 [kHz]

(35) Advance rate on the abscissa: 500; 600; 700; 800; 900; 1000; 1500; 2000 [mm/s]

(36) FIG. 1 gives an indication of the results of experimental series 1.

(37) 2.sup.nd Experimental Series

(38) A grid of 88 markings was applied on a color sample plaque at constant pulse width (3 s).

(39) Frequency on the ordinate: 3.0; 4.0; 5.0; 6.0; 7.0; 8.0; 9.0; 10.0 [kHz]

(40) Advance rate on the abscissa: 700; 750; 800; 850; 900; 950; 1000; 1050 [mm/s]

(41) FIG. 2 gives an indication of the results of experimental series 2.

(42) 3.sup.rd Experimental Series

(43) A grid of 88 markings was applied on a color sample plaque at constant pulse width (3 its).

(44) Frequency on the ordinate: 7.0; 7.5; 8.0; 8.5; 9.0; 9.5; 10.0; 10.5 [kHz]

(45) Advance rate on the abscissa: 700; 725; 750; 775; 800; 825; 850; 875 [mm/s]

(46) FIG. 3 provides an indication of the results of experimental series 3.

(47) 4.sup.th Experimental Series

(48) A grid of 44 markings was applied on a color sample plaque at constant pulse width (3 s).

(49) Frequency on the ordinate: 7.0; 7.5; 8.0; 8.5 [kHz]

(50) Advance rate on the abscissa: 700; 725; 750; 775 [mm/s]

(51) FIG. 4 gives an indication of the results of experimental series 4.

(52) From experimental series 1 to 4 it is clear that the additional substances in the color sample plaques composed of pellets made of mixtures 3 to 9 (termed examples 3 to 9 in the figures) permit better marking than in color sample plaques composed of pellets made of the mixtures 1 and 2 (termed examples 1 and 2 in the figures) without additional substances. Under the prevailing processing conditions, color sample plaques composed of pellets made of the mixtures 3, 8, and 9 have the greatest contrast.

(53) 5.sup.th Experimental Series

(54) An assembly of 3 linear markings was applied at a width of 3 mm and at a separation of 3 cm on color sample plaques and composites (50 mm75 mm4 mm), at constant pulse width (3 s).

(55) Frequency: 8.0 [kHz]

(56) Advance rate: 725 [mm/s]

(57) FIG. 5.1 gives an indication of the results from color sample plaques composed of pellets made of mixtures 1 to 9.

(58) From experimental series 5.1 it is clear that the additional substances in the color sample plaques composed of pellets made of mixtures 3 to 9 (termed examples 3 to 9 in the figures) permit better marking than in color sample plaques composed of pellets made of the mixtures 1 and 2 (termed examples 1 and 2 in the figures) without additional substances. Under the prevailing processing conditions, color sample plaques composed of pellets made of the mixtures 3, 8, and 9 have the greatest contrast.

(59) FIG. 5.2 gives an indication of the results from composites 3A to 9A composed of foils and color sample plaques comprising pellets made of mixture 1.

(60) Experimental series 5.2 shows clearly that marking of a thin foil of thickness about 100 m composed of the pellets of the mixtures 3 to 9 is possible in the composites. Composites 3A, 8A, and 9A obtained under the prevailing processing conditions have the greatest contrast.

(61) 6. Determination of Optical Properties

(62) A square marking with edge length 10 mm was applied on color sample plaques composed of pellets of the mixtures 1 to 9 (50 mm75 mm4 mm) at constant pulse with (3 s).

(63) Frequency: 8.0 [kHz]

(64) Advance rate: 725 [mm/s]

(65) The color is determined in transmission by a Lambda 900 spectrophotometer from Perkin Elmer with photometer sphere by a method based on ASTM E1348, using the weighting factors and formulae described in ASTM E308.

(66) The CIELAB color coordinates L*, a*, b* are calculated for illuminant D 65 with 10 standard observer.

(67) The transmission measurements (light transmittance; Ty) were made in a Lambda 900 spectrophotometer from Perkin Elmer with photometer sphere in accordance with ISO 13468-2 (i.e. determination of total transmittance via measurement of diffuse transmission and direct transmittance). Optical parameters are determined with a 30 mm.sup.2 stop to provide adjustment appropriate to the measurement unit and to the field of measurement.

(68) The optical properties of the marked regions were determined in comparison with unmarked regions on the color sample plaques. The results are collated in the table below.

(69) TABLE-US-00003 Color sample plaque Color sample plaque Marking on color composed of without marking sample plaque pellets made of Ty Ty mixture L* a* b* [%] L* a* b* [%] 1 86.4 0.39 0.58 68.8 73.0 0.05 1.29 45.17 2 92.3 0.36 1.15 81.4 82.8 0.01 2.8 61.8 4 79.0 0.25 1.48 54.9 69.9 0.58 7.5 40.6 5 86.2 2.71 0.66 68.4 78.5 2.25 2.60 54.1 6 77.8 0.44 1.09 52.8 78.9 0.10 3.83 54.7 7 91.3 1.36 1.24 79.1 58.2 0.12 3.48 26.1 8 77.0 0.70 1.88 51.5 40.5 1.86 8.96 11.9 9 85.6 1.56 2.73 67.2 31.4 2.34 10.09 6.8
7. Effect of the Marking on the Toughness of the Color Sample Plaque with Additional Substance

(70) An assembly of 3 linear markings was applied at a width of 3 mm and at a separation of 2 cm on color sample plaques composed of pellets of the mixtures 1 to 9 (60 mm60 mm2 mm), at constant pulse width (3 s).

(71) Frequency: 8.0 [kHz]

(72) Advance rate: 725 [mm/s]

(73) Puncture impact tests in accordance with DIN EN ISO 6603-2 were carried out on the color sample plaques thus prepared. The fracture behavior of the color sample plaques and the total energy absorbed by the plaques were determined on impact of the drop weight onto the marked side and onto the unmarked side, and are shown in the table below. As can be seen, the marking of the color sample plaques has no significant effect on the fracture behavior of, or the energy absorbed by, the color sample plaques.

(74) TABLE-US-00004 Color sample plaques Color sample plaque Puncture impact on the Puncture impact on the composed of without marking marked frontal side unmarked reverse side pellets made of Optical Total Optical Total Optical Total mixture assessment energy [J] assessment energy [J] assessment energy [J] 1 2.1 62.3 2.0 59.4 2.6 51.8 2 2.0 65.5 2.2 54.6 2.1 46.9 3 1.9 65.5 2.3 56.3 2.0 38.4 4 2.1 62.1 2.7 53.0 2.2 42.8 5 2.0 65.0 2.3 52.0 2.1 40.7 6 2.4 65.9 2.2 55.1 2.3 46.7 7 2.1 61.1 2.5 54.8 2.3 46.4 8 2.0 64.9 2.5 49.4 2.1 36.3 9 2.0 65.4 2.0 34.4 2.0 33.1

(75) The optical assessment of the samples after puncture impact was carried out in accordance with the following system.

(76) TABLE-US-00005 Assessment Assessment criterion 1 No crack outside of the impact area 2 Radial/straight crack: stable propagation; not extending to the periphery on one or both sides of the impact area 3 Tangential/curved crack; maximal circumferential extent up to 90; not extending to the periphery on one or both sides of the impact area 4 Tangential/curved crack; circumferential extent more than 90; not extending to the periphery on one or both sides of the impact area 5 Impact removes compact fragments larger than the impact area 6 Sample breaks into a plurality of fragments
8. Production of Bisphenol a Polycarbonate Sheets of Thickness 15 mm with a Modified Coextruded Layer:

(77) Polycarbonate sheets of thickness 15 mm were manufactured using PC 1 (linear bisphenol A polycarbonate from Bayer AG, Leverkusen with melt flow index (MFR) 6 cm.sup.3/10 min in accordance with ISO 1133 at 300 C. with 1.2 kg load) as base material for the extrusion process. During the production process the mixture 10 and, respectively, the mixture 11 was introduced by way of a coextruder, thus applying an external skin based on the mixture 10 and, respectively, 11 on the lower and upper side of the polycarbonate sheet composed of PC 1. 8.1 Bisphenol A polycarbonate sheet of thickness 15 mm with a coextruded layer of thickness 60 m applied on both sides based on mixture 10 comprising 70 ppm of Black Pearls 800. 8.2 Bisphenol A polycarbonate sheet of thickness 15 mm with a coextruded layer of thickness 60 m applied on both sides based on mixture 11 comprising 0.03% of KHDS 872-G2.
9. Markings using a UV laser

(78) A TruMark 6350 laser-marking system from Trumpf based on an Nd:YVO.sub.4 laser medium emitting a laser wavelength of 355 nm was used for the marking of the sheets of 8.1 and 8.2. The focus diameter used with a lens with focal length 260 mm was 57 m. Maximal power was 5 W at a pulse frequency of 33 kHz. The markings were made with a pulse width of 10 ns.

(79) FIG. 6.1 gives an impression of results from a sheet of 8.1 with markings from a UV laser,

(80) FIG. 6.2 gives an impression of results from a sheet of 8.2 with markings from a UV laser.

(81) A UV laser can achieve fully satisfactory marking of the coextruded layers of 8.1 and 8.2. Homogeneous, high-contrast markings are obtained on the bisphenol A polycarbonate sheets.

(82) 10. Markings Using a DPL Genesis Marker 163 (SW) IR Laser

(83) A laser-inscription system from ACI Laser GmbH, composed of a COMFORT workstation with DPL Genesis Marker 163 (8W) and MagicMarkV3 inscription software, was used for the marking experiments below. The laser beam source is composed of an excitation source (laser diode) followed by a lens system and also a resonator based on an Nd:YAG (neodymium-doped yttrium aluminum garnet) laser crystal to produce the beam. The wavelength of the resultant laser beam is 1064 nm, and the beam is focused onto the sheets of 8.1 and 8.2 by way of a beam-deflector unit after passage through an F-Theta 100 lens.

(84) The advance rate of the laser was 500 mm/s, and the pulse frequency was set to 8 kHz. The pulse width was 3 s. The distance between the individual lines of which the resultant marking is composed was 0.1 mm (in each case on the left-hand side of the figure) or else 0.05 mm (in each case on the right-hand side in the figure).

(85) FIG. 7.1 gives an indication of results from a sheet of 8.1 with markings from an IR laser.

(86) FIG. 7.2 gives an indication of results from a sheet of 8.2 with markings from an IR laser.

(87) Homogeneous high-contrast markings are obtained under the prevailing conditions in example 10 here both for sheets of example 8.1 and for sheets of example 8.2.