HYDROXYL FUNCTIONALIZED POLYBUTADIENE POLYURETHANE HOTMELT PREPOLYMER

Abstract

A hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer that comprises the chemical reaction product of at least one polybutadiene diol, at least one chain extender having a hydroxyl functionality of two and a molecular weight of less than or equal to 300 g/mol and optionally at least one polybutadiene polyol that has a number-average mean functionality between greater than 2.0 and less than or equal to 3.0 with at least one aliphatic or alicyclic diisocyanate, is thermally vulcanizable, and at room temperature is sufficiently solid or high-viscosity that it can be rolled into a roll as a film applied to a carrier without flowing out or being squeezed out on the side.

Claims

1. A hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer, comprising the chemical reaction product of at least one polybutadiene diol, at least one chain extender having a hydroxyl functionality of two and a molecular weight of less than or equal to 300 g/mol and optionally at least one polybutadiene polyol with a number-average mean functionality between greater than 2.0 and less than or equal to 3,0 with at least one aliphatic or alicyclic diisocyanate.

2. The hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according to claim 1, wherein the at least one polybutadiene diol has a number-average mean molecular weight between greater than 1,000 g/mol and less than 5,000 g/mol.

3. The hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer of claim 1, includes the at least one polybutadiene polyol which has a number-average mean functionality between greater than 2.0 and less than or equal to 3.0 and has a number-average mean molecular weight between greater than 1,000 g/mol and less than 5,000 g/mol.

4. The hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according to claim 1, wherein the numerical proportion of the hydroxyl groups introduced for forming the hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer that originate from the at least one chain extender is between greater than or equal to 20.0% and less than or equal to 80.0%.

5. The hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according to claim 1, wherein the at least one polybutadiene polyol is present, and the numerical proportion of the hydroxyl groups introduced for forming the hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer that originate from the at least one polybutadiene polyol with a number-average mean functionality between greater than 2.0 and less than or equal to 3.0 is a maximum of 50.0%.

6. The hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according to claim 1, wherein the at least one aliphatic or alicyclic diisocyanate is or comprises isophorone diisocyanate and/or dicyclohexylmethane-4,4-diisocyanate.

7. The hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according to claim 1, wherein the ratio of the total number of isocyanate groups to the total number of hydroxyl groups of the substances participating in the chemical reaction to form the hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer is between greater than 0.65 and less than 1.0.

8. A method of producing the hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according to claim 1, wherein the chemical reaction for forming the hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer is carried out with addition of a catalyst.

9. A method of producing a hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according claim 1, wherein the chemical reaction for forming the hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer is carried out in the presence of an epoxy resin.

10. A thermally vulcanizable pressure-sensitive adhesive, comprising as a base elastomer a hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer according to claim 1.

11. An adhesive tape comprising at least one thermally vulcanizable pressure-sensitive adhesive according to claim 10.

12. A method of producing an adhesive tape according to claim 11, wherein the compounding and coating of the thermally vulcanizable pressure-sensitive adhesive is carried out in a solvent-free manner and continuously.

13. The method of claim 12, wherein, during the solvent-free, continuous compounding process, vulcanization materials, vulcanization accelerators and vulcanization auxiliaries and additives are added.

14. The method of claim 12, wherein the compounding is carried out in a continuously operating mixing assembly.

15. The method of claim 14, wherein the mixing assembly is a planetary roller extruder.

16. A method according to claim 13, wherein the compounding is carried out at least partially in a planetary roller extruder by adding the vulcanization materials, vulcanization accelerators and vulcanization auxiliaries and additives and optionally further fillers, auxiliaries and/or additives during the continuous compounding process.

17. The method of claim 16, wherein the temperature of the compound does not exceed 90 C.

18. The method of claim 8, wherein the catalyst is a bismuth and carbon-containing catalyst.

19. The method of claim 18, wherein the catalyst is a bismuth carboxylate or a bismuth carboxylate derivative.

20. A thermally-vulcanizable pressure-sensitive adhesive comprising hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer produced according the method of claim 8.

21. A thermally-vulcanizable pressure-sensitive adhesive comprising hydroxyl-functionalized polybutadiene polyurethane hotmelt prepolymer produced according the method of claim 9.

Description

EXAMPLES

Example 1

[0123] The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 1) has the following composition:

[0124] Composition of Prepolymer 1:

TABLE-US-00003 Percent ratio No. of introduced OH of number Percent by or NCO of OH groups weight groups relative to one Raw material [wt %] to percent by weight another Krasol LBH 2000 77.11 70.17 mmol OH 50 2-ethyl-1,3-hexane 5.13 70.17 mmol OH 50 diol Coscat 83 0.15 Desmodur W 17.61 133.32 mmol NCO Total 100.00

[0125] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95. The theoretical gel point is calculated at 1.0.

[0126] Prepolymer 1 is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table.

[0127] Test Results for Prepolymer 1:

TABLE-US-00004 G (at 1 rad/sec and 23 C.) 200,000 Pa G (at 1 rad/sec and 23 C.) 150,000 Pa G (at 10 rad/sec and 23 C.) 400,000 Pa G (at 10 rad/sec and 23 C.) 230,000 Pa Tack at 23 C. 0.3N Complex viscosity * at 10 rad/sec and 23 C. 46,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 600 Pa .Math. s

[0128] Use:

[0129] Prepolymer 1 was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch.

[0130] Composition of the thermally vulcanizable pressure-sensitive adhesive composed of prepolymer 1:

TABLE-US-00005 Raw material Percent by weight Prepolymer 1 87.0 Ground sulfur 80/90 8.7 MBTS 2.5 ZBEC 0.9 TBzTD 0.9

[0131] The following tensile shear strengths were achieved.

[0132] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 1:

TABLE-US-00006 Tensile shear Oil strength Test piece application Curing [MPa] Fracture pattern Steel/steel no 30 min/180 C. 6.3 cohesive Steel/steel yes 30 min/180 C. 5.9 cohesive Electrolytically galvanized yes 30 min/180 C. 6.1 partially steel/electrolytically galvanized steel cohesive/partially adhesive Hot-galvanized steel/hot-galvanized yes 30 min/180 C. 5.4 partially steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 5.5 cohesive

Example 2

[0133] The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 2) has the following composition:

[0134] Composition of Prepolymer 2:

TABLE-US-00007 Percent ratio No. of introduced of number Percent by OH or NCO groups of OH groups weight relative to percent to one Raw material [wt %] by weight another Krasol LBH 79.33 72.19 mmol OH 50 2000 2-ethyl-1,3- 5.28 72.19 mmol OH 50 hexane diol Coscat 83 0.15 Vestanat IPDI 15.24 137.16 mmol NCO Total 100.00

[0135] Laboratory batches were produced (1 l). The percent by weight of Vestanat IPDI is calculated such that the NCO/OH ratio of the prepolymer is 0.95. The theoretical gel point is calculated at 1.0.

[0136] Prepolymer 2 is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0137] Test Results for Prepolymer 2:

TABLE-US-00008 G (at 1 rad/sec and 23 C.) 170,000 Pa G (at 1 rad/sec and 23 C.) 130,000 Pa G (at 10 rad/sec and 23 C.) 320,000 Pa G (at 10 rad/sec and 23 C.) 200,000 Pa Tack at 23 C. 0.5N Complex viscosity * at 10 rad/sec and 23 C. 38,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 500 Pa .Math. s

[0138] Use:

[0139] Prepolymer 2 was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed according to the following formulation in a laboratory batch:

[0140] Composition of the thermally vulcanizable pressure-sensitive adhesive composed of prepolymer 2:

TABLE-US-00009 Percent by Raw material weight Prepolymer 2 87.0 Ground sulfur 80/90 8.7 MBTS 2.5 ZBEC 0.9 TBzTD 0.9

[0141] The following tensile shear strengths were achieved.

[0142] Test results for the thermally vulcanizable pressure-sensitive adhesive composed of prepolymer 2:

TABLE-US-00010 Oil Tensile shear Test piece application Curing strength [MPa] Fracture pattern Steel/steel no 30 min/180 C. 6.5 cohesive Steel/steel yes 30 min/180 C. 6.3 cohesive Electrolytically galvanized yes 30 min/180 C. 6.2 partially steel/electrolytically galvanized cohesive/partially steel adhesive Hot-galvanized steel/hot- yes 30 min/180 C. 5.1 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 5.6 cohesive

Example 3

[0143] The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 3) has the following composition:

[0144] Composition of Prepolymer 3:

TABLE-US-00011 No. of introduced Percent ratio OH or NCO of number of Percent by groups relative OH groups Raw material weight [wt %] to percent by weight to one another Krasol LBH 76.69 69.78 mmol OH 40 2000 2-ethyl-1,3- 7.65 104.68 mmol OH 60 hexane diol Coscat 83 0.15 Vestanat IPDI 15.51 139.57 mmol NCO Total 100.00

[0145] Laboratory batches were produced (1 l). The percent by weight of Vestanat IPDI is calculated such that the NCO/OH ratio of the prepolymer is 0.80. The theoretical gel point is calculated at 1.0. Prepolymer 3 is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0146] Test Results for Prepolymer 3:

TABLE-US-00012 G (at 1 rad/sec and 23 C.) 80,000 Pa G (at 1 rad/sec and 23 C.) 70,000 Pa G (at 10 rad/sec and 23 C.) 130,000 Pa G (at 10 rad/sec and 23 C.) 120,000 Pa Tack at 23 C. 0.6N Complex viscosity * at 10 rad/sec and 23 C. 18,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 400 Pa .Math. s

[0147] Use:

[0148] Prepolymer 3 was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch:

[0149] Composition of the thermally vulcanizable pressure-sensitive adhesive composed of prepolymer 3:

TABLE-US-00013 Percent by Raw material weight Prepolymer 3 87.0 Ground sulfur 80/90 8.7 MBTS 2.5 ZBEC 0.9 TBzTD 0.9

[0150] The following tensile shear strengths were achieved.

[0151] Test results for the thermally vulcanizable pressure-sensitive adhesive composed of prepolymer 3:

TABLE-US-00014 Oil Tensile shear Test piece application Curing strength [MPa] Fracture pattern Steel/steel no 30 min/180 C. 6.9 cohesive Steel/steel yes 30 min/180 C. 6.2 cohesive Electrolytically galvanized yes 30 min/180 C. 6.2 partially steel/electrolytically cohesive/partially galvanized steel adhesive Hot-galvanized steel/hot- yes 30 min/180 C. 6.5 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 6.1 cohesive

Example 4

[0152] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of an epoxy resin. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 4) has the following composition, including the epoxy resin:

[0153] Composition of Prepolymer 4 Including Epoxy Resin:

TABLE-US-00015 No. of introduced OH or Percent ratio of Percent by NCO groups relative number of OH weight to percent by groups to one Raw material [wt %] weight another Krasol LBH 61.67 56.12 mmol OH 50 2000 2-ethyl-1,3- 4.10 56.12 mmol OH 50 hexane diol Coscat 83 0.15 Desmodur W 14.08 106.62 mmol NCO Epikote 828 20.00 Total 100.00

[0154] Production was carried out in a 200 l mixing vessel. The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95. The theoretical gel point is calculated at 1.0.

[0155] Prepolymer 4 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0156] Test Results for Prepolymer 4 (Including Epoxy Resin):

TABLE-US-00016 G (at 1 rad/sec and 23 C.) 9,000 Pa G (at 1 rad/sec and 23 C.) 20,000 Pa G (at 10 rad/sec and 23 C.) 70,000 Pa G (at 10 rad/sec and 23 C.) 90,000 Pa Tack at 23 C. 0.7N Complex viscosity * at 10 rad/sec and 23 C. 11,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 200 Pa .Math. s

[0157] Use 1:

[0158] Prepolymer 4 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed according to the following formulation in a twin screw extruder (TSE). The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0159] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 4:

TABLE-US-00017 Percent by Raw material weight Prepolymer 4 (excluding epoxy resin) 51.9 Epikote 828 (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Luvomaxx N220 8.8 talc Pharma M 15.5

[0160] The following tensile shear strengths were achieved.

[0161] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 4:

TABLE-US-00018 Oil Tensile shear Fracture Test piece application Curing strength [MPa] pattern Steel/steel no 30 min/180 C. 10.3 cohesive Steel/steel yes 30 min/180 C. 9.8 cohesive Steel/steel yes 10 min/230 C. 9.4 cohesive Electrolytically galvanized yes 30 min/180 C. 9.1 cohesive steel/electrolytically galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 8.4 cohesive galvanized steel KTL steel/KTL steel no 30 min/140 C. 8.7 cohesive

[0162] Use 2:

[0163] Prepolymer 4 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed according to the following formulation in a twin screw extruder (TSE). The melting temperature was kept at approx. 100 C.

[0164] The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0165] Composition of the Thermally Vulcanizable Adhesive Tape Layer:

TABLE-US-00019 Percent by Raw material weight Prepolymer 4 (excluding epoxy resin) 44.8 Epikote 828 (from PBD-PU 3 production) 11.3 Ground sulfur 80/90 3.5 ZBEC 3.0 TBzTD 3.0 Luvomaxx N220 0.9 Omyacarb 5-GU 26.1 Rapidquell Quicklime CL 90-Q 3.5 talc Pharma M 3.9

[0166] Because of the extremely high content of ultra-accelerators, it was possible to set the curing temperature of the adhesive at 120 C., a level below the known range for conventional vulcanization adhesives of 130-250 C.

[0167] With the high content of ultra-accelerators and the correspondingly low curing temperature, initial signs of crosslinking were observed in the TSE (specks, gel formation).

[0168] Use 3:

[0169] In order to further reduce the compounding temperature, prepolymer 4 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer, and for this purpose, it was further mixed according to the above formulation for use 2 in a planetary roller extruder (PRE).

[0170] The objective was to lower the process temperature in order to reduce the risk of premature crosslinking, particularly with increased proportions of ultra-accelerators.

[0171] In the PRE, powdered solid substances such as talc, chalk, lime (calcium oxide), sulfur and an ultra-accelerator premix were incorporated into the PU base according to the formulation. The liquid carbon black dispersion was introduced into a downstream TWE, in which degassing was also carried out.

[0172] The prepolymer was fed via a drum extruder with forced feeding into the extruder (model Entex PRE, four-shot, diameter 70 mm, equipped with standard spindles: 7, 7, 7, 6 per shot) (temp. approx. 70 C.). The throughput was approx. 25 kg/h, rotation speed was 70 l/min. It was found that the reduced number of spindles for the last shot is advantageous for a low process temperature.

[0173] In order to reduce the complexity of dosing, premixes were prepared for talc and lime and for the ultra-accelerators ZBEC and TBzTD. Only chalk and sulfur were dosed separately. The structure is shown in FIG. 1.

[0174] The four roller cylinders were heat-treated at descending temperatures of 70/50/35/35 C., and the central spindle was heated to 20 C. The melt temperature immediately downstream of the PRE was measured at 72 C.

[0175] The compound was transferred to the TSE via a melt pump heated to 75 C. and a subsequent melt tube. The individual zones were preselected to 60 C. at a revolution speed of 110 l/min. The depressor in the degassing area ran at 250 l/min. The outlet temperature was approximately 77 C. FIG. 2 is a schematic view of this part of the system.

[0176] As it was possible to keep the temperatures in the PRE and the downstream TSE below 80 C., no fleck/gel formation occurred.

[0177] Uses 2 and 3 of prepolymer 4 show that the planetary roller extruder is the preferred device for compounding a thermally curable adhesive having a curing temperature below 130 C., as the curing reaction is not triggered at the low temperatures of this assembly in production of adhesives and adhesive tape, even with an extremely high content of curing agents and a correspondingly low curing temperature.

Example 5

[0178] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of a plasticizer. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 5) has the following composition including the plasticizer

[0179] Composition of Prepolymer 5 Including Plasticizer

TABLE-US-00020 No. of introduced OH or Percent ratio of Percent by NCO groups relative number of OH weight to percent by groups to one Raw material [wt %] weight another Krasol LBH 61.67 56.12 mmol OH 50 2000 2-ethyl-1,3- 4.10 56.12 mmol OH 50 hexane diol Coscat 83 0.15 Desmodur W 14.08 106.62 mmol NCO Palatinol N 20.00 Total 100.00

[0180] Production was carried out in a 200 l mixing vessel. The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95. The theoretical gel point is calculated at 1.0. Prepolymer 5 (including plasticizer) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0181] Test Results for Prepolymer 5 (Including Plasticizer):

TABLE-US-00021 G (at 1 rad/sec and 23 C.) 1,000 Pa G (at 1 rad/sec and 23 C.) 4.300 Pa G (at 10 rad/sec and 23 C.) 15,000 Pa G (at 10 rad/sec and 23 C.) 30,000 Pa Tack at 23 C. 0.5N Complex viscosity * at 10 rad/sec and 23 C. 3.300 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 100 Pa .Math. s

[0182] Use:

[0183] Prepolymer 5 (including plasticizer) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed according to the following formulation in a twin screw extruder. The plasticizer mixed in during prepolymer production is listed separately in the following table.

[0184] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 5:

TABLE-US-00022 Percent by Raw material weight Prepolymer 5 (excluding plasticizer) 51.9 Palatinol N (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Luvomaxx N220 8.8 talc Pharma M 15.5

[0185] The following tensile shear strengths were achieved.

[0186] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 5:

TABLE-US-00023 Oil Tensile shear Fracture Test piece application Curing strength [MPa] pattern Steel/steel no 30 min/180 C. 11.7 cohesive Steel/steel yes 30 min/180 C. 9.2 partially cohesive/partially adhesive Steel/steel yes 10 min/230 C. 7.3 partially cohesive/partially adhesive Electrolytically galvanized yes 30 min/180 C. 6.2 partially steel/electrolytically cohesive/partially galvanized steel adhesive Hot-galvanized steel/hot- yes 30 min/180 C. 5.8 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 9.9 cohesive

Example 6

[0187] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of a plasticizer. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 6) has the following composition including the plasticizer:

[0188] Composition of Prepolymer 6 Including Plasticizer:

TABLE-US-00024 No. of introduced Percent ratio of Percent by OH or NCO number of OH weight groups relative to groups to one Raw material [wt %] percent by weight another Krasol LBH 2000 61.67 56.12 mmol OH 50 2-ethyl-1,3-hexane 4.10 56.12 mmol OH 50 diol Coscat 83 0.15 Desmodur W 14.08 106.62 mmol NCO Benzoflex 9-88 SG 20.00 Plasticizer Total 100.00

[0189] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95. The theoretical gel point is calculated at 1.0.

[0190] Prepolymer 6 (including plasticizer) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0191] Test Results for Prepolymer 6 (Including Plasticizer):

TABLE-US-00025 G (at 1 rad/sec and 23 C.) 2,000 Pa G (at 1 rad/sec and 23 C.) 5,700 Pa G (at 10 rad/sec and 23 C.) 20,000 Pa G (at 10 rad/sec and 23 C.) 40,000 Pa Tack at 23 C. 0.6N Complex viscosity * at 10 rad/sec and 23 C. 4.400 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 150 Pa .Math. s

[0192] Use:

[0193] Prepolymer 6 (including plasticizer) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The plasticizer mixed in during prepolymer production is listed separately in the following table.

[0194] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 6:

TABLE-US-00026 Raw material Percent by weight Prepolymer 6 (excluding plasticizer) 51.9 Benzoflex 9-88 SG Plasticizer (from 13.0 prepolymer production) Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0195] The following tensile shear strengths were achieved.

[0196] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 6:

TABLE-US-00027 Oil Tensile shear Test piece application Curing strength [MPa] Fracture pattern Steel/steel no 30 min/180 C. 9.8 cohesive Steel/steel yes 30 min/180 C. 8.0 partially cohesive/partially adhesive Steel/steel yes 10 min/230 C. 8.1 partially cohesive/partially adhesive Electrolytically yes 30 min/180 C. 6.4 partially galvanized cohesive/partially steel/electrolytically adhesive galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 6.1 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 8.4 cohesive

Example 7

[0197] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of a plasticizer. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 7) has the following composition including the plasticizer:

[0198] Composition of Prepolymer 7 Including Plasticizer:

TABLE-US-00028 No. of introduced OH or NCO Percent ratio of number Percent by groups relative to percent by of OH groups to one Raw material weight [wt %] weight another Krasol LBH 61.67 56.12 mmol OH 50 2000 2-ethyl-1,3- 4.10 56.12 mmol OH 50 hexane diol Coscat 83 0.15 Desmodur W 14.08 .sup.106.62 mmol NCO Hexamoll 20.00 DINCH Total 100.00

[0199] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0200] The theoretical gel point is calculated at 1.0.

[0201] Prepolymer 7 (including plasticizer) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0202] Test Results for Prepolymer 7 (Including Plasticizer):

TABLE-US-00029 G (at 1 rad/sec and 23 C.) 1,500 Pa G (at 1 rad/sec and 23 C.) 5,200 Pa G (at 10 rad/sec and 23 C.) 18,000 Pa G (at 10 rad/sec and 23 C.) 35,000 Pa Tack at 23 C. 0.7N Complex viscosity * at 10 rad/sec and 23 C. 3,900 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 120 Pa .Math. s

[0203] Use:

[0204] Prepolymer 7 (including plasticizer) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The plasticizer mixed in during prepolymer production is listed separately in the following table.

[0205] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 7:

TABLE-US-00030 Raw material Percent by weight Prepolymer 7 (excluding plasticizer) 51.9 Hexamoll DINCH 13.0 (from prepolymer production) Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0206] The following tensile shear strengths were achieved.

[0207] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 7:

TABLE-US-00031 Oil Tensile shear Test piece application Curing strength [MPa] Fracture pattern Steel/steel no 30 min/180 C. 10.4 cohesive Steel/steel yes 30 min/180 C. 7.1 partially cohesive/partially adhesive Steel/steel yes 10 min/230 C. 6.4 partially cohesive/partially adhesive Electrolytically yes 30 min/180 C. 5.2 partially galvanized cohesive/partially steel/electrolytically adhesive galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 5.0 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 9.6 cohesive

Example 8

[0208] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of a plasticizer. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 8) has the following composition including the plasticizer:

[0209] Composition of Prepolymer 8 Including Plasticizer:

TABLE-US-00032 Percent by No. of introduced OH or NCO Percent ratio of number weight groups relative to percent by of OH groups to one Raw material [wt %] weight another Krasol LBH 2000 61.67 56.12 mmol OH 50 2-ethyl-1,3-hexane 4.10 56.12 mmol OH 50 diol Coscat 83 0.15 Desmodur W 14.08 .sup.106.62 mmol NCO Citric acid triethyl 20.00 ester Total 100.00

[0210] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0211] The theoretical gel point is calculated at 1.0.

[0212] Prepolymer 8 (including plasticizer) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0213] Test Results for Prepolymer 8 (Including Plasticizer):

TABLE-US-00033 G (at 1 rad/sec and 23 C.) 3,000 Pa G (at 1 rad/sec and 23 C.) 7.500 Pa G (at 10 rad/sec and 23 C.) 25,000 Pa G (at 10 rad/sec and 23 C.) 45,000 Pa Tack at 23 C. 0.8N Complex viscosity * at 10 rad/sec and 23 C. 5.100 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 150 Pa .Math. s

[0214] Use:

[0215] Prepolymer 8 (including plasticizer) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The plasticizer mixed in during prepolymer production is listed separately in the following table.

[0216] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 8:

TABLE-US-00034 Raw material Percent by weight Prepolymer 8 (excluding plasticizer) 51.9 Citric acid triethyl ester 13.0 (from prepolymer production) Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0217] The following tensile shear strengths were achieved.

[0218] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 8:

TABLE-US-00035 Oil Tensile shear Test piece application Curing strength [MPa] Fracture pattern Steel/steel no 30 min/180 C. 9.0 cohesive Steel/steel yes 30 min/180 C. 5.1 partially cohesive/partially adhesive Steel/steel yes 10 min/230 C. 5.2 partially cohesive/partially adhesive Electrolytically yes 30 min/180 C. 4.6 partially galvanized cohesive/partially steel/electrolytically adhesive galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 4.1 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 8.3 cohesive

Example 9

[0219] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of a plasticizer. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 9) has the following composition including the plasticizer

[0220] Composition of Prepolymer 9 Including Plasticizer

TABLE-US-00036 Percent by No. of introduced OH or NCO Percent ratio of number weight groups relative to percent by of OH groups to one Raw material [wt %] weight another Krasol LBH 61.67 56.12 mmol OH 50 2000 2-ethyl-1,3- 4.10 56.12 mmol OH 50 hexane diol Coscat 83 0.15 Desmodur W 14.08 .sup.106.62 mmol NCO Gravex 925 20.00 Total 100.00

[0221] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0222] The theoretical gel point is calculated at 1.0.

[0223] Prepolymer 9 (including plasticizer) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0224] Test Results for Prepolymer 9 (Including Plasticizer):

TABLE-US-00037 G (at 1 rad/sec and 23 C.) 5,000 Pa G (at 1 rad/sec and 23 C.) 11,000 Pa G (at 10 rad/sec and 23 C.) 35,000 Pa G (at 10 rad/sec and 23 C.) 60,000 Pa Tack at 23 C. 0.9N Complex viscosity * at 10 rad/sec and 23 C. 6.900 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 180 Pa .Math. s

[0225] Use:

[0226] Prepolymer 9 (including plasticizer) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The plasticizer mixed in during prepolymer production is listed separately in the following table.

[0227] Composition of the thermally vulcanizable pressure-sensitive adhesive composed of prepolymer 9:

TABLE-US-00038 Raw material Percent by weight Prepolymer 9 (excluding plasticizer) 51.9 Gravex 925 (from prepolymer 13.0 production) Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0228] The following tensile shear strengths were achieved.

[0229] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 9:

TABLE-US-00039 Oil Tensile shear Test piece application Curing strength [MPa] Fracture pattern Steel/steel no 30 min/180 C. 8.2 cohesive Steel/steel yes 30 min/180 C. 7.9 cohesive Steel/steel yes 10 min/230 C. 7.1 cohesive Electrolytically yes 30 min/180 C. 6.0 partially galvanized cohesive/partially steel/electrolytically adhesive galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 5.4 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 8.0 cohesive

Example 10

[0230] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of a plasticizer and bitumen. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 10) has the following composition, including the plasticizer and the bitumen:

[0231] Composition of Prepolymer 10 Including Plasticizer and Bitumen:

TABLE-US-00040 Percent by No. of introduced OH or NCO Percent ratio of number weight groups relative to percent by of OH groups to one Raw material [wt %] weight another Krasol LBH 2000 57.80 52.6 mmol OH 50 2-ethyl-1,3-hexane 3.85 52.6 mmol OH 50 diol Coscat 83 0.15 Desmodur W 13.20 .sup.99.94 mmol NCO Gravex 925 15.00 Azalt 50/70 DE 10.00 Total 100.00

[0232] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0233] The theoretical gel point is calculated at 1.0.

[0234] Prepolymer 10 (including plasticizer and bitumen) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0235] Test Results for Prepolymer 10 (Including Plasticizer and Bitumen):

TABLE-US-00041 G (at 1 rad/sec and 23 C.) 13,000 Pa G (at 1 rad/sec and 23 C.) 30,000 Pa G (at 10 rad/sec and 23 C.) 100,000 Pa G (at 10 rad/sec and 23 C.) 140,000 Pa Tack at 23 C. 1.3N Complex viscosity * at 10 rad/sec and 23 C. 17,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 380 Pa .Math. s

[0236] Use:

[0237] Prepolymer 10 (including plasticizer) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The plasticizer and the bitumen mixed in during prepolymer production are listed separately in the following table.

[0238] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 10:

TABLE-US-00042 Raw material Percent by weight Prepolymer 10 (excluding plasticizer and bitumen) 49.81 Gravex 925 (from prepolymer production) 9.95 Azalt 50/70 DE (from prepolymer production) 6.64 Ground sulfur 80/90 6.60 MBTS 2.00 ZBEC 0.90 TBzTD 0.90 Printex 60 8.40 talc Pharma M 14.80

[0239] The following tensile shear strengths were achieved.

[0240] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 10:

TABLE-US-00043 Oil Tensile shear Fracture Test piece application Curing strength [MPa] pattern Steel/steel no 30 min/180 C. 9.2 cohesive Steel/steel yes 30 min/180 C. 8.5 cohesive Steel/steel yes 10 min/230 C. 9.0 cohesive Electrolytically yes 30 min/180 C. 9.7 cohesive galvanized steel/electrolytically galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 7.3 partially galvanized steel cohesive/partially adhesive KTL steel/KTL steel no 30 min/140 C. 10.0 cohesive

Example 11

[0241] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of an epoxy resin. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 11) has the following composition, including the epoxy resin:

[0242] Composition of Prepolymer 11 Including Epoxy Resin:

TABLE-US-00044 No. of introduced Percent OH or NCO ratio of Percent by groups relative number of OH weight to percent by groups to one Raw material [wt %] weight another Krasol LBH-P 61.67 56.12 mmol OH 50 2000 2-ethyl-1,3-hexane 4.10 56.12 mmol OH 50 diol Coscat 83 0.15 Desmodur W 14.08 106.62 mmol NCO Epikote 828 20.00 Total 100.00

[0243] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0244] The theoretical gel point is calculated at 1.0.

[0245] Prepolymer 11 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0246] Test Results for Prepolymer 11 (Including Epoxy Resin):

TABLE-US-00045 G (at 1 rad/sec and 23 C.) 12,000 Pa G (at 1 rad/sec and 23 C.) 25,000 Pa G (at 10 rad/sec and 23 C.) 90,000 Pa G (at 10 rad/sec and 23 C.) 120,000 Pa Tack at 23 C. 0.8N Complex viscosity * at 10 rad/sec and 23 C. 15,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 300 Pa .Math. s

[0247] Use:

[0248] Prepolymer 11 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0249] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 11:

TABLE-US-00046 Percent by Raw material weight Prepolymer 11 (excluding epoxy resin) 51.9 Epikote 828 (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0250] The following tensile shear strengths were achieved.

[0251] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 11:

TABLE-US-00047 Oil Tensile shear Fracture Test piece application Curing strength [MPa] pattern Steel/steel no 30 min/180 C. 9.8 cohesive Steel/steel yes 30 min/180 C. 9.9 cohesive Steel/steel yes 10 min/230 C. 9.7 cohesive Electrolytically yes 30 min/180 C. 9.9 cohesive galvanized steel/electrolytically galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 9.7 cohesive galvanized steel KTL steel/KTL steel no 30 min/140 C. 10.2 cohesive

Example 12

[0252] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of an epoxy resin. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 12) has the following composition, including the epoxy resin:

[0253] Composition of Prepolymer 12 Including Epoxy Resin:

TABLE-US-00048 No. of introduced Percent OH or NCO ratio of Percent by groups relative number of OH weight to percent by groups to one Raw material [wt %] weight another Krasol LBH-P 61.67 56.12 mmol OH 50 2000 2-ethyl-1,3- 4.10 56.12 mmol OH 50 hexane diol Coscat 83 0.15 Desmodur W 14.08 106.62 mmol NCO 3,4- 20.00 Epoxycyclohexyl methyl-3,4- epoxycyclohexan- carboxylat Total 100.00

[0254] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0255] The theoretical gel point is calculated at 1.0.

[0256] Prepolymer 12 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0257] Test Results for Prepolymer 12 (Including Epoxy Resin):

TABLE-US-00049 G (at 1 rad/sec and 23 C.) 7,000 Pa G (at 1 rad/sec and 23 C.) 16,000 Pa G (at 10 rad/sec and 23 C.) 50,000 Pa G (at 10 rad/sec and 23 C.) 70,000 Pa Tack at 23 C. 0.7N Complex viscosity * at 10 rad/sec and 23 C. 6.600 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 180 Pa .Math. s

[0258] Use:

[0259] Prepolymer 12 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0260] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 12:

TABLE-US-00050 Percent by Raw material weight Prepolymer 12 (excluding epoxy resin) 51.9 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane 13.0 carboxylate (from prepolymer production) Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0261] The following tensile shear strengths were achieved.

[0262] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 12:

TABLE-US-00051 Oil Tensile shear Fracture Test piece application Curing strength [MPa] pattern Steel/steel no 30 min/180 C. 9.4 cohesive Steel/steel yes 30 min/180 C. 9.2 cohesive Steel/steel yes 10 min/230 C. 8.9 cohesive Electrolytically galvanized yes 30 min/180 C. 8.9 cohesive steel/electrolytically galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 9.2 cohesive galvanized steel KTL steel/KTL steel no 30 min/140 C. 9.4 cohesive

Example 13

[0263] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of an epoxy resin. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 13) has the following composition, including the epoxy resin:

[0264] Composition of Prepolymer 13 Including Epoxy Resin:

TABLE-US-00052 No. of introduced Percent OH or NCO ratio of Percent by groups relative number of OH weight to percent by groups to one Raw material [wt %] weight another Krasol LBH 3000 66.13 42.33 mmol OH 50 2-ethyl-1,3-hexane 3.09 42.33 mmol OH 50 diol Coscat 83 0.15 Desmodur W 10.62 80.42 mmol NCO Epikote 828 20.00 Total 100.00

[0265] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0266] The theoretical gel point is calculated at 1.0.

[0267] Prepolymer 13 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0268] Test Results for Prepolymer 13 (Including Epoxy Resin):

TABLE-US-00053 G (at 1 rad/sec and 23 C.) 6,000 Pa G (at 1 rad/sec and 23 C.) 15,000 Pa G (at 10 rad/sec and 23 C.) 50,000 Pa G (at 10 rad/sec and 23 C.) 80,000 Pa Tack at 23 C. 1.0N Complex viscosity * at 10 rad/sec and 23 C. 9.400 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 270 Pa .Math. s

[0269] Use:

[0270] Prepolymer 13 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0271] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 13:

TABLE-US-00054 Percent by Raw material weight Prepolymer 13 (excluding epoxy resin) 51.9 Epikote 828 (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0272] The following tensile shear strengths were achieved.

[0273] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 13:

TABLE-US-00055 Oil Tensile shear Fracture Test piece application Curing strength [MPa] pattern Steel/steel no 30 min/180 C. 10.8 cohesive Steel/steel yes 30 min/180 C. 9.9 cohesive Steel/steel yes 10 min/230 C. 10.5 cohesive Electrolytically galvanized yes 30 min/180 C. 10.2 cohesive steel/electrolytically galvanized steel Hot-galvanized steel/hot- yes 30 min/180 C. 9.9 cohesive galvanized steel KTL steel/KTL steel no 30 min/140 C. 9.0 cohesive

Example 14

[0274] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of an epoxy resin. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 14) has the following composition, including the epoxy resin:

[0275] Composition of Prepolymer 14 Including Epoxy Resin:

TABLE-US-00056 No. of introduced Percent Percent OH or NCO ratio of Percent by groups relative number of OH weight to percent by groups to one Raw material [wt %] weight another Krasol LBH 2000 61.36 55.84 mmol OH 50 2-butyl-2-ethyl-1,3- 4.48 55.84 mmol OH 50 propanediol Coscat 83 0.15 Desmodur W 14.01 106.09 mmol NCO Epikote 828 20.00 Total 100.00

[0276] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0277] The theoretical gel point is calculated at 1.0.

[0278] Prepolymer 14 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0279] Test Results for Prepolymer 14 (Including Epoxy Resin):

TABLE-US-00057 G (at 1 rad/sec and 23 C.) 10,000 Pa G (at 1 rad/sec and 23 C.) 22,000 Pa G (at 10 rad/sec and 23 C.) 80,000 Pa G (at 10 rad/sec and 23 C.) 100,000 Pa Tack at 23 C. 0.6N Complex viscosity * at 10 rad/sec and 23 C. 13,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 280 Pa .Math. s

[0280] Use:

[0281] Prepolymer 14 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0282] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 14:

TABLE-US-00058 Percent by Raw material weight Prepolymer 14 (excluding epoxy resin) 51.9 Epikote 828 (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0283] The following tensile shear strengths were achieved.

[0284] Test results for the thermally vulcanizable pressure-sensitive adhesive composed of prepolymer 14:

TABLE-US-00059 Tensile shear Oil strength Fracture Test piece application Curing [MPa] pattern Steel/steel no 30 min/180 C. 9.1 cohesive Steel/steel yes 30 min/180 C. 8.5 cohesive Steel/steel yes 10 min/230 C. 7.9 cohesive Electrolytically yes 30 min/180 C. 8.3 cohesive galvanized steel/ electrolytically galvanized steel Hot-galvanized yes 30 min/180 C. 8.1 cohesive steel/hot- galvanized steel KTL steel/ no 30 min/140 C. 8.0 cohesive KTL steel

Example 15

[0285] The chemical reaction for forming the polybutadiene polyurethane hotmelt prepolymer according to the invention was carried out in the presence of an epoxy resin. The polybutadiene polyurethane hotmelt prepolymer according to the invention (prepolymer 15) has the following composition, including the epoxy resin:

[0286] Composition of Prepolymer 15 Including Epoxy Resin:

TABLE-US-00060 No. of introduced Percent ratio of OH or NCO number of OH Percent by groups relative to groups to one Raw material weight [wt %] percent by weight another Krasol LBH 28.89 26.29 mmol OH 20 2000 poly bd R-45 31.30 26.29 mmol OH 20 HTLO 2-ethyl-1,3- 5.77 78.88 mmol OH 60 hexane diol Coscat 83 0.15 Desmodur W 13.89 105.17 mmol NCO Epikote 828 20.00 Total 100.00

[0287] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.80.

[0288] The theoretical gel point is calculated at 0.83.

[0289] Prepolymer 15 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0290] Test Results for Prepolymer 15 (Including Epoxy Resin):

TABLE-US-00061 G (at 1 rad/sec and 23 C.) 1,500 Pa G (at 1 rad/sec and 23 C.) 5,000 Pa G (at 10 rad/sec and 23 C.) 15,000 Pa G (at 10 rad/sec and 23 C.) 60,000 Pa Tack at 23 C. 1.6 N Complex viscosity * at 10 rad/sec and 23 C. 6.200 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 160 Pa .Math. s

[0291] Use:

[0292] Prepolymer 15 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0293] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 15:

TABLE-US-00062 Percent by Raw material weight Prepolymer 15 (excluding epoxy resin) 51.9 Epikote 828 (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0294] The following tensile shear strengths were achieved.

[0295] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer 15:

TABLE-US-00063 Tensile shear Oil strength Fracture Test piece application Curing [MPa] pattern Steel/steel no 30 min/180 C. 11.0 cohesive Steel/steel yes 30 min/180 C. 10.2 cohesive Steel/steel yes 10 min/230 C. 10.4 cohesive Electrolytically yes 30 min/180 C. 10.8 cohesive galvanized steel/ electrolytically galvanized steel Hot-galvanized yes 30 min/180 C. 10.1 cohesive steel/hot- galvanized steel KTL steel/ no 30 min/140 C. 9.3 cohesive KTL steel

Comparative Example 1

[0296] The chemical reaction for forming the polybutadiene polyether-polyurethane hotmelt prepolymer was carried out in the presence of an epoxy resin. The polybutadiene polyether polyurethane hotmelt prepolymer (prepolymer V1) has the following composition, including the epoxy resin:

[0297] Composition of prepolymer V1 including epoxy resin:

TABLE-US-00064 No. of introduced Percent Percent by OH or NCO ratio of number weight groups relative to of OH groups Raw material [wt %] percent by weight to one another Krasol LBH 2000 31.82 28.95 mmol OH 25 Voranol P 2000L 29.27 28.95 mmol OH 25 2-ethyl-1,3-hexane 4.23 57.90 mmol OH 50 diol Coscat 83 0.15 Desmodur W 14.53 110.01 mmol NCO Epikote 828 20.00 Total 100.00

[0298] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0299] The theoretical gel point is calculated at 1.0.

[0300] Prepolymer V1 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0301] Test Results for Prepolymer V1 (Including Epoxy Resin):

TABLE-US-00065 G (at 1 rad/sec and 23 C.) 7,000 Pa G (at 1 rad/sec and 23 C.) 18,000 Pa G (at 10 rad/sec and 23 C.) 60,000 Pa G (at 10 rad/sec and 23 C.) 80,000 Pa Tack at 23 C. 0.9 N Complex viscosity * at 10 rad/sec and 23 C. 10,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 190 Pa .Math. s

[0302] Use:

[0303] Prepolymer V1 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0304] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer V1:

TABLE-US-00066 Percent by Raw material weight Prepolymer V1 (excluding epoxy resin) 51.9 Epikote 828 (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0305] The following tensile shear strengths were achieved.

[0306] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer V1:

TABLE-US-00067 Tensile shear Oil strength Fracture Test piece application Curing [MPa] pattern Steel/steel no 30 min/180 C. 2.7 adhesive Steel/steel yes 30 min/180 C. 1.7 adhesive Steel/steel yes 10 min/230 C. 1.1 adhesive Electrolytically yes 30 min/180 C. 1.2 adhesive galvanized steel/ electrolytically galvanized steel Hot-galvanized yes 30 min/180 C. 0.7 adhesive steel/hot- galvanized steel KTL steel/ no 30 min/140 C. 4.3 cohesive KTL steel

[0307] Lower tensile shear strength values were achieved than in examples 1-16, and the fracture patterns were predominantly adhesive.

Comparative Example 2

[0308] The chemical reaction for forming the polybutadiene polyester-polyurethane hotmelt prepolymer was carried out in the presence of an epoxy resin. The polybutadiene polyester polyurethane hotmelt prepolymer (prepolymer V2) has the following composition, including the epoxy resin:

[0309] Composition of Prepolymer V2 Including Epoxy Resin:

TABLE-US-00068 No. of introduced Percent Percent by OH or NCO ratio of number weight groups relative to of OH groups Raw material [wt %] percent by weight to one another Krasol LBH 31.24 28.42 mmol OH 25 2000 Desmophen 30.20 28.42 mmol OH 25 1652 2-ethyl-1,3- 4.15 56.84 mmol OH 50 hexane diol Coscat 83 0.15 Desmodur W 14.26 107.99 mmol NCO Epikote 828 20.00 Total 100.00

[0310] Laboratory batches were produced (1 l). The percent by weight of Desmodur W is calculated such that the NCO/OH ratio of the prepolymer is 0.95.

[0311] The theoretical gel point is calculated at 1.0.

[0312] Prepolymer V2 (including epoxy resin) is solid, meltable, and has a rubbery and tacky consistency at room temperature. The test results are shown in the following table:

[0313] Test Results for Prepolymer V2 (Including Epoxy Resin):

TABLE-US-00069 G (at 1 rad/sec and 23 C.) 12,000 Pa G (at 1 rad/sec and 23 C.) 25,000 Pa G (at 10 rad/sec and 23 C.) 90,000 Pa G (at 10 rad/sec and 23 C.) 100,000 Pa Tack at 23 C. 0.5 N Complex viscosity * at 10 rad/sec and 23 C. 13,000 Pa .Math. s Complex viscosity * at 10 rad/sec and 90 C. 290 Pa .Math. s

[0314] Use:

[0315] Prepolymer V2 (including epoxy resin) was used for producing a thermally vulcanizable pressure-sensitive adhesive or a thermally vulcanizable pressure-sensitive adhesive layer and for this purpose further mixed in the following formulation in a laboratory batch. The epoxy resin mixed in during prepolymer production is listed separately in the following table.

[0316] Composition of the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer V2:

TABLE-US-00070 Percent by Raw material weight Prepolymer V2 (excluding epoxy resin) 51.9 Epikote 828 (from prepolymer production) 13.0 Ground sulfur 80/90 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Printex 60 8.8 talc Pharma M 15.5

[0317] The following tensile shear strengths were achieved.

[0318] Test Results for the Thermally Vulcanizable Pressure-Sensitive Adhesive Composed of Prepolymer V2:

TABLE-US-00071 Tensile shear Oil strength Fracture Test piece application Curing [MPa] pattern Steel/steel no 30 min/180 C. 3.3 adhesive Steel/steel yes 30 min/180 C. 1.9 adhesive Steel/steel yes 10 min/230 C. 1.2 adhesive Electrolytically yes 30 min/180 C. 1.3 adhesive galvanized steel/ electrolytically galvanized steel Hot-galvanized yes 30 min/180 C. 1.0 adhesive steel/hot- galvanized steel KTL steel/ no 30 min/140 C. 3.3 partially KTL steel cohesive/ partially adhesive

[0319] Lower tensile shear strength values were achieved than in examples 1-16, and the fracture patterns were predominantly adhesive.

Comparative Example 3

[0320] The polybutadiene polyurethane hotmelt prepolymer (prepolymer V3) has the following composition:

[0321] Composition of Prepolymer V3:

TABLE-US-00072 No. of introduced Percent Percent by OH or NCO ratio of number weight groups relative to of OH groups Raw material [wt %] percent by weight to one another Krasol LBH 2000 77.83 70.83 mmol OH 50 2-ethyl-1,3-hexane 5.18 70.83 mmol OH 50 diol Coscat 83 0.15 4,4-methylene-bis- 16.84 134.57 mmol NCO (phenyl isocyanate) Total 100.00

[0322] Laboratory batches were produced (1 l). The percent by weight of 4,4-methylene-bis-(phenyl isocyanate) is calculated such that the NCO/OH ratio of the prepolymer is 0.95. The theoretical gel point is calculated at 1.0.

[0323] Prepolymer V3 is solid and meltable at room temperature, but not tacky.

LEGEND FOR THE FIGURES

[0324] FIG. 1: Planetary roller extruder [0325] 1: Input prepolymer [0326] 2: Inlet sulfur [0327] 3: Inlet chalk [0328] 4: Inlet premix talc & lime [0329] 5: Inlet premix ultra-accelerator (ZBEC/TBzTD) [0330] 6: Outlet compound

[0331] FIG. 2: Twin screw extruder [0332] 7: Supply carbon black dispersion [0333] 8: Degassing (<0.1 bar) [0334] 9: Blister