Use of silane-modified polyolefins as adhesion promoters for the production flat laminates

Abstract

The invention relates to the use of polyolefins modified with one or more silanes as adhesion promoters for the production of flat glass/glass, glass/plastic, or plastic/plastic laminates, to corresponding laminates, and to displays containing the laminates according to the invention.

Claims

1. A laminate comprising: a flat glass body; a body applied to at least one side of the flat glass body; and an intermediate adhesion promoter layer between the flat glass body and the applied body; wherein the body applied to the flat glass body is glass, plastic or a mixture thereof, and the intermediate adhesion promoter layer comprises at least one silane modified polyolefin, the polyolefin being a polyethylene-co-propylene-co-1-butene) comprising: 2 to 25% by weight ethene; 50 to 80% by weight propene; and 7 to 98% by weight of butene wherein said polyolefin has a propylene fraction of from 50 to 80 ma % and a solubility in tetrahydrofuran at room temperature of at least 70 ma %.

2. The laminate as claimed in claim 1, wherein a thickness of the flat glass body and applied body is each at most 8 mm.

3. The laminate as claimed in claim 1, wherein a thickness of the intermediate adhesion promoter layer is at most 6.5 mm.

4. The laminate as claimed in claim 1, wherein the laminate further comprises one or more layers, which are present on one or both sides of the laminate.

5. The laminate as claimed in claim 1, wherein the laminate is flexible.

6. The laminate as claimed in claim 1, wherein the polyolefin is partially crystalline.

7. The laminate as claimed in claim 1, wherein said butene is 1-butene.

8. The laminate as claimed in claim 1, wherein the silane modified polyolefin is modified with a silane which is at least one silane selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris(2-methoxy-ethoxy-)silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyldimethylethoxysilane and vinylmethyldibutoxysilane.

9. A method for the production of the laminate as claimed in claim 1, comprising: applying said at least one silane modified polyolefin to at least one side of the flat glass body to form the intermediate adhesion promoter layer; and then applying the at least one body to the at least one intermediate adhesion promoter layer.

10. The method as claimed in claim 9, wherein said at least one silane modified polyolefin is applied in the form of a solution or melt.

11. The method as claimed in claim 9, wherein the application of said at least one silane modified polyolefin is performed by a technique selected from the group consisting of spray application, knife application, spincoating, roller application and pressure techniques.

12. The method as claimed in claim 9, wherein the at least one silane modified polyolefin is a polymer film.

13. The method as claimed in claim 9, further comprising applying one or more layers to one or both sides of the laminate.

14. A display comprising a laminate as claimed in claim 1.

15. The display as claimed in claim 14, wherein the display is a UFB display, a TFT display, a TFD display, a CSTN display, a STN display, a UBC display, an LCD display, an OLED display, a plasma display and/or a touchscreen.

16. A flexible electrical module comprising at least one laminate as claimed in claim 1.

17. A solar cell comprising the flexible electrical module as claimed in claim 16.

18. A laminate comprising: at least one flat plastic body of a first plastic; a body applied to at least one side of the flat plastic body; and an intermediate adhesion promoter layer between the flat plastic body and said body; wherein said body is of the same plastic or a plastic different from the first plastic of said flat plastic body, and the intermediate adhesion promoter layer comprises at least one silane modified polyolefin, the polyolefin being a poly(ethylene-co-propylene-co-1-butene) comprising: 2 to 25% by weight ethene; 50 to 80% by weight propene; and 7 to 98% by weight of butene wherein said polyolefin has a propylene fraction of from 50 to 80 ma % and a solubility in tetrahydrofuran at room temperature of at least 70 ma %.

19. The laminate as claimed in claim 18, wherein said butene is 1-butene.

20. A method for the production of the laminate as claimed in claim 18, comprising: applying said at least one silane modified polyolefin to at least one side of the flat plastic body of a first plastic to form the intermediate adhesion promoter layer; and then applying said body to the intermediate adhesion promoter layer.

Description

EXAMPLES

1 Polyolefins Used According to the Invention

(1) TABLE-US-00001 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 C.sub.2-fraction 4 6.5 7 8 5 11 14 1 6 8.5 [ma %] C.sub.3-fraction 68 61 63.5 58 66 60 70 0 0 1 [ma %] C.sub.4-fraction 28 32.5 29.5 34 29 29 16 99 94 90.5 [ma %] .sub.190 C. 5000 2000 10700 3300 14500 5600 6900 4000 4500 11300 [mPa .Math. s] T.sub.soft. 98 92 102 91 98 157 158 112 88 99 [ C.] PEN 19 23 18 22 15 35 26 6 9 10 [0.1 mm] T.sub.g 29 36 30 34 32 38 37 39 41 42 [ C.] H.sub.M 17.8 10.7 8.5 11.8 14.2 15.6 18.4 26.7 12.8 10.4 [J/g] Si 0.35 0.45 0.30 0.55 0.35 0.50 0.45 0.65 1.0 0.60 content [ma %] XSol* 100 100 99 100 98 95 96 100 100 98 [ma %] THFSol** 100 100 99 100 99 41 22 35 53 46 [ma %] *Fractions soluble in xylene at room temperature **Fractions soluble in tetrahydrofuran at room temperature

2 Adhesive Effect on Plexiglas (Polymethyl Methacrylate, Evonik Rhm GmbH, Molding Composition 7N)

(2) 100 g portions of the modified polyolefins are melted for one hour in a drying cabinet at 180 C. under a protective gas atmosphere (e.g. nitrogen, argon, etc.). The can containing the hot melt is then stirred on a hotplate with an IKA stirrer with kneader. 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % of dibutyltin dilaurate) are added at 170 C. and homogenized for 15 minutes. The polymer melt is then applied at a specific bonding temperature (with the aid of a thermosensor) to a polymethyl methacrylate test body (thickness: 2 mm, moulding composition 7N, Evonik Rhm GmbH). This is joined within 20 seconds to a further polymethyl methacrylate test body (thickness: 2 mm, moulding composition 7N, Evonik Rhm GmbH) in a simple overlapping manner on an area of 4 cm.sup.2, and pressed together for 5 minutes under a weight of 2 kg. Projecting adhesive polymer is removed. The bonding test specimen is then stored for 14 days at 20 C./65% relative atmospheric humidity in a climatically controlled cabinet and its mechanical properties are then tested by means of tensile tests.

(3) The following results are achieved at a bonding temperature of 170 C. (Table 2):

(4) TABLE-US-00002 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 12 VESTOPLAST 750.sup.1 0.30 (not according to the invention) 13 According to Example 1 1.10 (according to the invention) 14 According to Example 4 0.55 (according to the invention) 15 According to Example 5 0.80 (according to the invention) .sup.1Evonik Degussa GmbH

(5) The following results are achieved at a bonding temperature of 240 C. (Table 3):

(6) TABLE-US-00003 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 16 VESTOPLAST 750.sup.1 no test (not according to the invention) 17 According to Example 1 1.60 (according to the invention) 18 According to Example 4 0.70 (according to the invention) 19 According to Example 5 1.10 (according to the invention) .sup.1Evonik Degussa GmbH

3 Adhesive Effect on Polypropylene

(7) The modified polyolefins are melted for one hour at 190 C. in a drying cabinet under a protective gas atmosphere (e.g. nitrogen, argon, etc.) and then applied at a temperature of 170 C. (with the aid of a thermosensor) to a polypropylene test body (thickness: 2 mm, isotactic polypropylene, PP-DWST/manufacturer: Simona AG). This is joined within 20 seconds to a further polypropylene test body (thickness: 2 mm, isotactic polypropylene, PP-DWST/manufacturer: Simona AG) on an area of 4 cm.sup.2 in a simple overlapping manner and the two parts are pressed together for 5 minutes under a weight of 2 kg. Projecting adhesive polymer is removed. The bonded test specimen is then stored for 14 days at 20 C./65% relative atmospheric humidity in a climatically controlled cabinet and its mechanical properties are then tested by means of tensile tests (Table 4).

(8) TABLE-US-00004 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 20 VESTOPLAST 708.sup.1 1.05 (not according to the invention) 21 According to Example 1 1.75 (according to the invention) 22 According to Example 2 1.55 (according to the invention) 23 According to Example 3 1.55 (according to the invention) 24 According to Example 4 2.25 (according to the invention) 25 According to Example 5 1.70 (according to the invention) 26 According to Example 6 1.2 (according to the invention) 27 According to Example 7 1.35 (according to the invention) 28 According to Example 8 1.10 (according to the invention) 29 According to Example 9 1.55 (according to the invention) 30 According to Example 10 1.45 (according to the invention) .sup.1Evonik Degussa GmbH

4 Adhesive Effect on Polyethylene

(9) 100 g portions of the modified polyolefins are melted for one hour in a drying cabinet at 180 C. under a protective gas atmosphere (e.g. nitrogen, argon, etc.). The can containing the hot melt is then stirred on a hotplate with an IKA stirrer with kneader. 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % of dibutyltin dilaurate) are added at 170 C. and homogenized for 15 minutes. The polymer melt is then applied at 170 C. (with the aid of a thermosensor) to a polyethylene test body (thickness: 2 mm; PE-HWST, manufacturer: Simona AG). This is joined within 20 seconds to a further polyethylene test body (thickness: 2 mm; PE-HWST, manufacturer: Simona AG) on an area of 4 cm.sup.2 in a simple overlapping manner and the two parts are pressed together for 5 minutes under a weight of 2 kg. Projecting adhesive polymer is removed. The bonded test specimen is then stored for 14 days at 20 C./65% relative atmospheric humidity in a climatically controlled cabinet and its mechanical properties are then tested by means of tensile tests (Table 5).

(10) TABLE-US-00005 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 31 VESTOPLAST 750.sup.1 0.70 (not according to the invention) 32 According to Example 1 1.48 (according to the invention) 33 According to Example 4 0.83 (according to the invention) 34 According to Example 5 1.2 (according to the invention) .sup.1Evonik Degussa GmbH

5 Adhesive Effect on Poly(Ethylene Terephthalate) (PET)

(11) 100 g portions of the modified polyolefins are melted for one hour in a drying cabinet at 180 C. under a protective gas atmosphere (e.g. nitrogen, argon, etc.). The can containing the hot melt is then stirred on a hotplate with an IKA stirrer with kneader. 5 g of DBTL masterbatch consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % of dibutyltin dilaurate) are added at 170 C. and homogenized for 15 minutes. The polymer melt is then applied at 170 C. (with the aid of a thermosensor) to a polyethylene terephthalate test body (thickness: 2 mm; Axpet clear 099, manufacturer: Bayer Material Science). This is joined within 20 seconds to a further polyethylene terephthalate test body (thickness: 2 mm; Axpet clear 099, manufacturer: Bayer Material Science) on an area of 4 cm.sup.2 in a simple overlapping manner and the two parts are pressed together for 5 minutes under a weight of 2 kg. Projecting adhesive polymer is removed. The bonded test specimen is then stored for 14 days at 20 C./65% relative atmospheric humidity in a climatically controlled cabinet and its mechanical properties are then tested by means of tensile tests (Table 6).

(12) TABLE-US-00006 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 35 VESTOPLAST 750.sup.1 0.40 (not according to the invention) 36 According to Example 1 1.55 (according to the invention) 37 According to Example 4 1.23 (according to the invention) 38 According to Example 5 1.54 (according to the invention) .sup.1Evonik Degussa GmbH

6 Adhesive Effect on Polyamide-6 (PA-6)

(13) 100 g portions of the modified polyolefins are melted for one hour in a drying cabinet at 180 C. under a protective gas atmosphere (e.g. nitrogen, argon, etc.). The can containing the hot melt is then stirred on a hotplate with an IKA stirrer with kneader. 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % of dibutyltin dilaurate) are added at 170 C. and homogenized for 15 minutes. The polymer melt is then applied at 170 C. (with the aid of a thermosensor) to a polyamide-6 test body (thickness: 2 mm; Sustamid 6, manufacturer: Cadillac Plastic). This is joined within 20 seconds to a further polyamide-6 test body (thickness: 2 mm; Sustamid 6, manufacturer: Cadillac Plastic) on an area of 4 cm.sup.2 in a simple overlapping manner and the two parts are pressed together for 5 minutes under a weight of 2 kg. Projecting adhesive polymer is removed. The bonded test specimen is then stored for 14 days at 20 C./65% relative atmospheric humidity in a climatically controlled cabinet and its mechanical properties are then tested by means of tensile tests (Table 7).

(14) TABLE-US-00007 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 39 VESTOPLAST 750.sup.1 0.62 (not according to the invention) 40 According to Example 1 1.95 (according to the invention) 41 According to Example 4 1.30 (according to the invention) 42 According to Example 5 2.05 (according to the invention) .sup.1Evonik Degussa GmbH

7 Adhesive Effect on Polycarbonate

(15) 100 g portions of the modified polyolefins are melted for one hour in a drying cabinet at 180 C. under a protective gas atmosphere (e.g. nitrogen, argon, etc.). The can containing the hot melt is then stirred on a hotplate with an IKA stirrer with kneader. 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % of dibutyltin dilaurate) are added at 170 C. and homogenized for 15 minutes. The polymer melt is then applied at 170 C. (with the aid of a thermosensor) to a polycarbonate test body (thickness: 2 mm; Makrolon Mono, manufacturer: Bayer Material Science). This is then joined within 20 seconds to a further polycarbonate test body (thickness: 2 mm; Makrolon Mono, manufacturer: Bayer Material Science) on an area of 4 cm.sup.2 in a simple overlapping manner and the two parts are pressed together for 5 minutes under a weight of 2 kg. Projecting adhesive polymer is removed. The bonded test specimen is then stored for 14 days at 20 C./65% relative atmospheric humidity in a climatically controlled cabinet and its mechanical properties are then tested by means of tensile tests (Table 8).

(16) TABLE-US-00008 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 43 VESTOPLAST 750.sup.1 0.21 (not according to the invention) 44 According to Example 1 1.20 (according to the invention) 45 According to Example 4 0.70 (according to the invention) 46 According to Example 5 1.15 (according to the invention) .sup.1Evonik Degussa GmbH

8 Adhesive Effect on Glass

(17) 100 g portions of the modified polyolefins are melted for one hour in a drying cabinet at 180 C. under a protective gas atmosphere (e.g. nitrogen, argon, etc.). The can containing the hot melt is then stirred on a hotplate with an IKA stirrer with kneader. 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % of dibutyltin dilaurate) are added at 170 C. and homogenized for 15 minutes. The polymer melt is then applied at 170 C. (with the aid of a thermosensor) to a degreased glass test body (thickness: 2 mm). This is joined within 20 seconds to a further degreased glass test body (thickness: 2 mm) on an area of 4 cm.sup.2 in a simple overlapping manner and the two parts are pressed together for 5 minutes under a weight of 2 kg. Projecting adhesive polymer is removed. The bonded test specimen is then stored for 14 days at 20 C./65% relative atmospheric humidity in a climatically controlled cabinet and its mechanical properties are then tested by means of tensile tests (Table 8).

(18) TABLE-US-00009 Adhesive shear strength Example No. Polyolefin used [N/mm.sup.2] 43 VESTOPLAST 708.sup.1 <0.1 (not according to the invention) 44 According to Example 1 2.5 (according to the invention) 45 According to Example 4 3.7 (according to the invention) 46 According to Example 5 3.2 (according to the invention) .sup.1Evonik Degussa GmbH

9 Water Vapor Permeability of Polyolefin Laminates

Example 47

Not According to the Invention

(19) Using a ZSK 25 double screw extruder (Werner & Pfleiderer) with a downstream connected extrusion tool for producing blown films, a blown film is produced in a thickness of 0.052 mm at 200 C. from a high pressure polyethylene (LDPE) produced by SABIC (Sabic LDPE 2101). The determination of the water vapor permeability is then carried out according to DIN 53122 T2. A water vapor permeability of 4.6 g/m.sup.2.Math.d is measured.

Example 48

Not According to the Invention

(20) Using a ZSK 25 double screw extruder (Werner & Pfleiderer) with a downstream connected extrusion tool for producing flat films, a flat film is produced in a thickness of 0.048 mm at 200 C. from a linear low density polyethylene (LLDPE) produced by SABIC (Sabic LLDPE 3188). The determination of the water vapor permeability is then carried out according to DIN 53122T2. A water vapor permeability of 2.8 g/m.sup.2.Math.d is measured.

Example 49

Not According to the Invention

(21) Using a ZSK 25 double screw extruder (Werner & Pfleiderer) with a downstream connected extrusion tool for producing flat films, a flat film is produced in a thickness of 0.058 mm at 200 C. from an isotactic polypropylene produced by SABIC (Sabic PP 520 P). The determination of the water vapor permeability is then carried out according to DIN 53122T2. A water vapor permeability of 1.4 g/m.sup.2.Math.d is measured.

Example 50

According to the Invention

(22) The polyethylene film produced in Example 47 is coated with a melt (consisting of 100 g of polymer of Example 1 according to the invention and 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % dibutyltin dilaurate)) using a 20 m knife at a temperature of 135 C., the application weight being ca. 11 g/m.sup.2. The coated film is stored for 7 days in a climatically controlled cabinet (20 C./65% relative atmospheric humidity). The determination of the water vapor permeability is then carried out according to DIN 53122T2. A water vapor permeability of <0.001 g/m.sup.2.Math.d is measured.

Example 51

According to the Invention

(23) The polyethylene film produced in Example 48 is coated with a melt (consisting of 100 g of polymer of Example 4 according to the invention and 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % dibutyltin dilaurate)) using a 20 m knife at a temperature of 135 C., the application weight being ca. 11 g/m.sup.2. The coated film is stored for 7 days in a climatically controlled cabinet (20 C./65% relative atmospheric humidity). The determination of the water vapor permeability is then carried out according to DIN 53122T2. A water vapor permeability of <0.001 g/m.sup.2.Math.d is measured.

Example 52

According to the Invention

(24) The polypropylene film produced in Example 48 is coated with a melt (consisting of 100 g of polymer of Example 5 according to the invention and 5 g of DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % dibutyltin dilaurate)) using a 20 m knife at a temperature of 135 C., the application weight being ca. 11 g/m.sup.2. The coated film is stored for 7 days in a climatically controlled cabinet (20 C./65% relative atmospheric humidity). The determination of the water vapor permeability is then carried out according to DIN 53122T2. A water vapor permeability of <0.001 g/m.sup.2.Math.d is measured.

10. Production of Glass/Plastic Laminates

Example 53

According to the Invention

(25) A thin glass disk (thickness: 50 m; borosilicate glass AF 45; manufacturer: Schott AG) is coated at a temperature of 135 C. with a melt (consisting of 100 g of the polymer of Example 5 according to the invention and 5 g DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % dibutyltin dilaurate)) using a 20 m knife, the application weight being ca. 11 g/m.sup.2. The polypropylene film produced in Example 48 is then laminated onto this coating with the aid of a heated roller (80 C., pressing force: 500 hPa). The coated glass disk is then stored for 7 days in a climatically controlled cabinet (20 C./65% relative atmospheric humidity). A transparent flexurally elastic composite is obtained that does not delaminate or become non-transparent even after 50 bending tests (bending radius: 90 mm).

Example 54

According to the Invention

(26) A thin glass disk (thickness: 50 m; borosilicate glass D263T; manufacturer: Schott AG) is coated at a temperature of 135 C. with a melt (consisting of 100 g of the polymer of Example 5 according to the invention and 5 g DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % dibutyltin dilaurate)) using a 20 m knife, the application weight being ca. 11 g/m.sup.2. A further thin glass disk (thickness: 50 m; borosilicate glass D263T; manufacturer: Schott AG) is then laminated onto this coating immediately after the application of the modified polyolefin according to the invention. The glass laminate is stored for 7 days in a climatically controlled cabinet (20 C./65% relative atmospheric humidity). A transparent, flexurally elastic composite is obtained that does not delaminate or become non-transparent even after 50 bending tests (bending radius: 120 mm).

Example 55

According to the Invention

(27) A thin PMMA disk (thickness: 250 m; borosilicate glass D263T; manufacturer: Schott AG) is coated at a temperature of 240 C. with a melt (consisting of 100 g of the polymer of Example 5 according to the invention and 5 g DBTL masterbatch (consisting of 98 ma % VESTOPLAST 708 (Evonik Degussa GmbH) and 2 ma % dibutyltin dilaurate)) using a 20 m knife, the application weight being ca. 11 g/m.sup.2. The polypropylene film produced in Example 48 is laminated onto this coating using a heated roller (80 C., pressing force: 500 hPa). The coated glass disk is stored for 7 days in a climatically controlled cabinet (20 C./65% relative atmospheric humidity). A transparent, flexurally elastic composite is obtained, that does not delaminate or become non-transparent even after 50 bending tests (bending radius: 120 mm).