Thermally vulcanisable adhesive and adhesive strip produced therefrom

Abstract

Thermally vulcanisable, meltable adhesives and processes have a meltable polybutadiene-polyurethane, ground sulphur and optionally at least one vulcanisation accelerator, at least one filling material, at least one epoxide resin, at least one tackifier resin, bitumen, at least one softener and further auxiliary and additive materials, wherein said adhesives and processes can be thermally vulcanised within a temperature range of 130° C. to 230° C., such that same, as well as an adhesive strip produced from same, can be used for adhesion and/or sealing in the automotive industry, as well as in structural work on oiled sheet metal, and in the painting line on e-coated or otherwise painted sheet metal, for example, for crimp fold adhesion, for crimp fold sealing, for seam sealing, for lining adhesion, for hole closure and much more.

Claims

1. An adhesive tape comprising a thermally vulcanizable, meltable pressure-sensitive adhesive, wherein the thermally vulcanizable, meltable pressure-sensitive adhesive comprises a meltable polybutadiene-polyurethane and ground sulphur, wherein the meltable polybutadiene-polyurethane comprises the chemical reaction product of at least one polybutadiene-diol, at least one chain extender having a hydroxyl functionality of two and a molar mass of less than or equal to 300 g/mol, and optionally at least one polybutadiene-polyol having a number-averaged average functionality of between greater than 2.0 and less than or equal to 3.0, with at least one aliphatic or alicyclic diisocyanate.

2. The adhesive tape according to claim 1, wherein the thermally vulcanizable, meltable pressure-sensitive adhesive further comprises one or more substances independently selected from a list consisting of at least one vulcanization accelerator, at least one filler, epoxy resins, tackifier resins, bitumens, and plasticizers.

3. The adhesive tape according to claim 1, wherein the thermally vulcanizable, meltable pressure-sensitive adhesive further comprises further auxiliaries and additives.

4. The adhesive tape according to claim 1, wherein a numerical fraction of hydroxyl groups introduced for forming the meltable polybutadiene-polyurethane and originating from at least one chain extender is between greater than or equal to 20.0% and less than or equal to 80.0%.

5. The adhesive tape according to claim 1, wherein a numerical fraction of hydroxyl groups introduced for forming the meltable polybutadiene-polyurethane and originating from an optional at least one polybutadiene-polyol having a number-averaged average functionality of between greater than 2.0 and less than or equal to 3.0 is not more than 50.0%.

6. The adhesive tape according to claim 1, wherein at least one aliphatic or alicyclic diisocyanate is or comprises at least one selected from isophorone diisocyanate and dicyclohexylmethane 4,4′-diisocyanate.

7. The adhesive tape according to claim 1, wherein a ratio of a total number of isocyanate groups to a total number of hydroxyl groups in compounds participating in a chemical reaction to provide the meltable polybutadiene-polyurethane is between greater than or equal to 0.3 and less than or equal to 1.3.

8. The adhesive tape according to claim 2, wherein the at least one filler comprises ground chalk and ground calcium oxide, the weight fraction thereof in the thermally vulcanizable, meltable pressure-sensitive adhesive together being between 10.0 and 70.0 weight percent.

9. The adhesive tape according to claim 2, wherein the at least one filler comprises ground talc, the weight fraction thereof in the thermally vulcanizable, meltable pressure-sensitive adhesive being between 10.0 wt % and 50.0 wt %.

10. The adhesive tape according to claim 1, further comprises at least one tackifier resin having a weight fraction thereof in the thermally vulcanizable, meltable pressure-sensitive adhesive being f between 1.0 wt % inclusive and 30.0 wt % inclusive, said at least one tackifier resin being a terpene resin.

11. The adhesive tape according to claim 2, wherein the at least one vulcanization accelerator is at least one selected from one or more mercapto accelerators, one or more thiuram accelerators, one or more dithiocarbamate accelerators, and a combination of two or all of these accelerators, the concentration of the at least one vulcanization accelerator in the thermally vulcanizable, meltable pressure-sensitive adhesive being between at least 0.1 wt % and not more than 15.0 wt %.

12. A process for producing the thermally vulcanizable, meltable pressure-sensitive adhesive according to claim 1, wherein a chemical reaction to give the meltable polybutadiene-polyurethane takes place with addition of a catalyst comprising bismuth and carbon.

13. A process for producing the thermally vulcanizable, meltable pressure-sensitive adhesive according to claim 1, wherein a chemical reaction to give the meltable polybutadiene-polyurethane takes place in the presence of an epoxy resin.

14. A process for producing the adhesive tape according to claim 1, wherein production takes place in a solvent-free, continuous compounding and coating operation.

15. The process according to claim 14, wherein the production takes place in a solvent-free, continuous compounding and coating operation by metered addition of the sulphur and of the optional vulcanization accelerators, fillers and also of the further auxiliaries and additives during the continuous compounding operation into the continuously operating compounding extruder.

16. The process according to claim 15, wherein the compounding extruder is a planetary roller extruder.

17. The process according to claim 16, wherein a temperature of the compounded formulation does not exceed 90° C.

Description

EXAMPLES

Inventive Example 1

(1) The composition of the polybutadiene-polyurethane (PBD-PU 1) is as follows:

(2) Composition PBD-PU 1:

(3) TABLE-US-00003 Number of Percentage OH or NCO groups ratio of Weight introduced, based number of OH fraction on percentage groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 77.11  70.17 mmol OH 50 2-Ethyl-1,3-hexanediol 5.13  70.17 mmol OH 50 Coscat 83 ® 0.15 Desmodur W ® 17.61 133.32 mmol NCO Total 100.00

(4) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(5) PBD-PU 1 at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below.

(6) Test Results PBD-PU 1:

(7) 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 Complex viscosity η* at 10 rad/sec and 23° C. 46 000 Pas Complex viscosity η* at 10 rad/sec and 90° C. 600 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(8) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 1 was blended further in a laboratory batch in accordance with the formula below, and shaped to form a film.

(9) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 1:

(10) TABLE-US-00005 Raw material Weight percent PBD-PU 1 90.0 Ground sulphur 80/90° 10.0

(11) The results achieved were as follows:

(12) Tack at 23° C.: 0.2 N

(13) Tensile Shear Strength:

(14) TABLE-US-00006 Tensile shear Oil strength Fracture Test specimen application Curing [MPa] mode Steel/steel no 30 min/200° C. 5.9 cohesive Steel/steel yes 30 min/200° C. 5.6 cohesive Electrogalvanized yes 30 min/200° C. 4.8 partially steel/electro- cohesive/ galvanized steel partially adhesive Hot dip yes 30 min/200° C. 5.1 partially galvanized steel/ cohesive/ hot dip partially galvanized steel adhesive

Inventive Example 2

(15) The composition of the polybutadiene-polyurethane (PBD-PU 2) is as follows:

(16) Composition PBD-PU 2:

(17) TABLE-US-00007 Number of Percentage OH or NCO groups ratio of Weight introduced, based number of fraction on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 75.02  68.27 mmol OH 50 2-Ethyl-1,3-hexanediol 4.99  68.27 mmol OH 50 Coscat 83 ® 0.15 Desmodur W ® 19.84 150.19 mmol NCO Total 100.00

(18) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 1.10. The theoretical gel point is computed to be 1.0.

(19) PBD-PU 1 at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below.

(20) Test Results PBD-PU 2:

(21) TABLE-US-00008 G′ (at 1 rad/sec and 23° C.) 150 000 Pa G″ (at 1 rad/sec and 23° C.) 120 000 Pa G′ (at 10 rad/sec and 23° C.) 340 000 Pa G″ (at 10 rad/sec and 23° C.) 230 000 Pa Complex viscosity η* at 10 rad/sec and 23° C. 41 000 Pas Complex viscosity η* at 10 rad/sec and 90° C. 540 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(22) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 2 was blended further in a laboratory batch in accordance with the formula below, and shaped to form a film.

(23) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 2:

(24) TABLE-US-00009 Raw material Weight percent PBD-PU 2 90.0 Ground sulphur 80/90° 10.0

(25) The results achieved were as follows:

(26) Tack at 23° C.: 0.3 N

(27) Tensile Shear Strength:

(28) TABLE-US-00010 Tensile shear Oil strength Fracture Test specimen application Curing [MPa] mode Steel/steel no 30 min/200° C. 6.5 cohesive Steel/steel yes 30 min/200° C. 6.9 cohesive Electrogalvanized yes 30 min/200° C. 5.9 partially steel/electro- cohesive/ galvanized steel partially adhesive Hot dip yes 30 min/200° C. 5.7 partially galvanized steel/ cohesive/ hot dip partially galvanized steel adhesive

Inventive Example 3

(29) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of an epoxy resin. The composition of the polybutadiene-polyurethane (PBD-PU 3), including the epoxy resin, is as follows

(30) Composition PBD-PU 3:

(31) TABLE-US-00011 Number of Percentage OH or NCO groups ratio of Weight introduced, based number of fraction on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 61.67  56.12 mmol OH 50 2-Ethyl-1,3-hexanediol 4.10  56.12 mmol OH 50 Coscat 83 ® 0.15 Desmodur W ® 14.08 106.62 mmol NCO Epikote 828 ® 20.00 Total 100.00

(32) Production took place in a 200 litre mixing vessel. The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(33) PBD-PU 3 (including epoxy resin) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(34) Test Results PBD-PU 3 (Including Epoxy Resin):

(35) TABLE-US-00012 G′ (at 1 rad/sec and 23° C.) 9000 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 Complex viscosity η* at 10 rad/sec and 23° C. 11 000 Pas Complex viscosity η* at 10 rad/sec and 90° C. 200 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(36) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the twin-screw extruder. The epoxy resin, mixed in as early as during polybutadiene-polyurethane production, is listed separately in the table below.

(37) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(38) TABLE-US-00013 Raw material Weight percent PBD-PU 3 (excluding epoxy resin) 51.9 Epikote 828 ® (from PBD-PU 3 production) 13.0 Ground sulphur 80/90° 6.9 MBTS 2.1 ZBEC 0.9 TBzTD 0.9 Luvomaxx N220 ® 8.8 Talc Pharma M ® 15.5

(39) The results achieved were as follows:

(40) Tack (before thermal vulcanization) at 23° C.: 0.6 N

(41) Peel Adhesion (Before Thermal Vulcanization):

(42) TABLE-US-00014 Peel adhesion, Peel adhesion, Test Oil immediate after 30 minutes specimen application (N/cm) (N/cm) Steel yes 0.03 0.12
Tensile Shear Strength (after Thermal Vulcanization):

(43) TABLE-US-00015 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode 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 Electrogalvanized steel/ yes 30 min/180° C. 9.1 cohesive electrogalvanized steel Hot dip galvanized steel/ yes 30 min/180° C. 8.4 cohesive hot dip galvanized steel CEC steel/CEC steel no 30 min/140° C. 8.7 cohesive

Inventive Example 4

(44) Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(45) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was used. For this purpose, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the twin-screw extruder. In the table below, the epoxy resin already mixed in during polybutadiene-polyurethane production is again listed separately.

(46) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(47) TABLE-US-00016 Weight Raw material percent PBD-PU 3 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 3 production) 11.3 Ground sulphur 80/90° 3.5 MBTS 2.0 ZBEC 1.0 TBzTD 1.0 Luvomaxx N220 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 5.9

(48) The results achieved were as follows:

(49) Tack (before thermal vulcanization) at 23° C.: 0.5 N

(50) Peel Adhesion (Before Thermal Vulcanization):

(51) TABLE-US-00017 Peel adhesion, Peel adhesion, Test Oil immediate after 30 minutes specimen application (N/cm) (N/cm) Steel yes 0.04 0.15
Tensile Shear Strength (after Thermal Vulcanization):

(52) TABLE-US-00018 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode Steel/steel no 30 min/180° C. 17.6 cohesive Steel/steel yes 30 min/180° C. 16.1 cohesive Electrogalvanized steel/ yes 30 min/180° C. 16.9 cohesive electrogalvanized steel Hot dip galvanized steel/ yes 30 min/180° C. 15.9 cohesive hot dip galvanized steel CEC steel/CEC steel no 30 min/130° C. 7.2 cohesive CEC steel/CEC steel no 30 min/160° C. 15.5 cohesive

Inventive Example 5

(53) Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(54) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was used. For this purpose, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the twin-screw extruder (TSE).

(55) In the table below, the epoxy resin already mixed in during polybutadiene-polyurethane production is again listed separately.

(56) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(57) TABLE-US-00019 Weight Raw material percent PBD-PU 3 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 3 production) 11.3 Ground sulphur 80/90° 7.0 MBTS 2.0 ZBEC 1.0 TBzTD 1.0 Luvomaxx N220 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 2.4

(58) The results achieved were as follows:

(59) Tack (before thermal vulcanization) at 23° C.: 0.5 N

(60) Peel Adhesion (Before Thermal Vulcanization):

(61) TABLE-US-00020 Peel adhesion, Peel adhesion, Test Oil immediate after 30 minutes specimen application (N/cm) (N/cm) Steel yes 0.03 0.13
Tensile Shear Strength (after Thermal Vulcanization):

(62) TABLE-US-00021 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode Steel/steel no 30 min/180° C. 27.9 cohesive Steel/steel yes 30 min/180° C. 26.3 cohesive Electrogalvanized steel/ yes 30 min/180° C. 24.1 cohesive electrogalvanized steel Hot dip galvanized steel/ yes 30 min/180° C. 26.1 cohesive hot dip galvanized steel CEC steel/CEC steel no 30 min/130° C. 10.5 cohesive CEC steel/CEC steel no 30 min/160° C. 24.8 cohesive

Inventive Example 6

(63) Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(64) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was used. For this purpose, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the twin-screw extruder. The prepolymer here was fed into the extruder via a drum melt and forced feeding system (T about 70° C., throughput about 16 kg/h, extruder speed 300 1/min). The melt temperature was maintained at around 100° C., so that there was no crosslinking.

(65) In the table below, the epoxy resin already mixed in during polybutadiene-polyurethane production is again listed separately.

(66) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(67) TABLE-US-00022 Weight Raw material percent PBD-PU 3 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 3 production) 11.3 Ground sulphur 80/90° 3.5 ZBEC 1.0 TBzTD 1.0 Luvomaxx N220 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 7.9

(68) The results achieved were as follows:

(69) Tack (before thermal vulcanization) at 23° C.: 0.5 N

(70) Peel Adhesion (Before Thermal Vulcanization):

(71) TABLE-US-00023 Test Oil Peel adhesion, Peel adhesion, specimen application immediate (N/cm) after 30 minutes (N/cm) Steel yes 0.04 0.15

(72) Curing temperature (DSC): 156° C.

(73) Tensile Shear Strength (after Thermal Vulcanization):

(74) TABLE-US-00024 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode Steel/steel No 30 min/180° C. 14.2 cohesive Steel/steel Yes 30 min/180° C. 12.9 cohesive Electrogalvanized steel/ Yes 30 min/180° C. 11.8 cohesive electrogalvanized steel Hot dip galvanized steel/ Yes 30 min/180° C. 10.7 cohesive hot dip galvanized steel CEC steel/CEC steel No 30 min/130° C. 6.3 cohesive CEC steel/CEC steel No 30 min/160° C. 11.9 cohesive

Inventive Example 6a

(75) Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(76) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was used. For this purpose, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the planetary roller extruder (PRE). The prepolymer here was fed into the extruder via a drum melt and forced feeding system (T about 70° C., throughput about 16 kg/h, extruder speed 300 1/min). The melt temperature was maintained at around 100° C., so that there was no crosslinking. The objective was to lower the operating temperature in order to diminish the risk of premature crosslinking particularly at elevated proportions of ultra-accelerator.

(77) In the PRE, the powder solids such as talc, chalk, lime (calcium oxide), sulphur and an ultra-accelerator premix were incorporated, depending on formula, into the PU base. The liquid carbon black dispersion was introduced in a downstream TSE, where devolatization was also performed.

(78) The prepolymer here was fed into the extruder (Entex PRE model, four-shot, diameter 70 mm, equipped with standard spindles: 7, 7, 7, 6 per shot) (T around 70° C.) via a drum melt and forced feeding system. (The throughput was around 25 kg/h, the speed 70 1/min). It was found that the reduced spindle count in the last shot is advantageous for a low operating temperature.

(79) To reduce the complexity of metering, premixes were prepared for talc and lime and also for the ultra-accelerators ZBEC and TBzTD. Only chalk and sulphur were metered separately. FIG. 1 shows the construction.

(80) The four roller cylinders were heated descendingly at 70/50/35/35° C., and the central spindle at 20° C. The melt temperature immediately downstream of the PRE was found to be 72° C. The compounded formulation was transferred into the TSE via a melt pump and downstream melt hose, which were heated at 75° C. The individual zones were preselected at 60° C. at a speed of 110 1/min. The hold-down device in the devolatizing region ran at 250 1/min. The exit temperature was approximately 77° C. FIG. 2 shows this plant component schematically.

(81) In the table below, the epoxy resin already mixed in during polybutadiene-polyurethane production is again listed separately.

(82) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(83) TABLE-US-00025 Weight Raw material percent PBD-PU 3 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 3 production) 11.3 Ground sulphur 80/90° 3.5 ZBEC 1.0 TBzTD 1.0 Luvomaxx N220 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 7.9

(84) The example shows that with the preferred use of a planetary roller extruder, advantageously, the operating temperatures can be lower.

Inventive Example 7

(85) Production of the Inventive Adhesive and the Inventive Adhesive Tape Laver:

(86) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was used. For this purpose, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the twin-screw extruder similarly to Inventive Example 6.

(87) In the table below, the epoxy resin already mixed in during polybutadiene-polyurethane production is again listed separately.

(88) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(89) TABLE-US-00026 Weight Raw material percent PBD-PU 3 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 3 production) 11.3 Ground sulphur 80/90° 3.5 ZBEC 1.5 TBzTD 1.5 Luvomaxx N220 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 6.9

(90) The results achieved were as follows:

(91) Tack (before thermal vulcanization) at 23° C.: 0.5 N

(92) Peel Adhesion (Before Thermal Vulcanization):

(93) TABLE-US-00027 Peel adhesion, Peel adhesion, Test Oil immediate after 30 minutes specimen application (N/cm) (N/cm) Steel yes 0.04 0.18

(94) Curing temperature (DSC): 139° C.

(95) Tensile Shear Strength (after Thermal Vulcanization):

(96) TABLE-US-00028 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode Steel/steel no 30 min/180° C. 17.8 cohesive Steel/steel yes 30 min/180° C. 17.3 cohesive Electrogalvanized steel/ yes 30 min/180° C. 17.6 cohesive electrogalvanized steel Hot dip galvanized steel/ yes 30 min/180° C. 15.6 cohesive hot dip galvanized steel CEC steel/CEC steel no 30 min/130° C. 12.3 cohesive CEC steel/CEC steel no 30 min/160° C. 15.2 cohesive

Inventive Example 8

(97) Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(98) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was used. For this purpose, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the twin-screw extruder. In the table below, the epoxy resin already mixed in during polybutadiene-polyurethane production is again listed separately.

(99) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(100) TABLE-US-00029 Raw material Weight percent PBD-PU 3 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 3 production) 11.3 Ground sulphur 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

(101) The results achieved were as follows:

(102) Tack (before thermal vulcanization) at 23° C.: 0.4 N

(103) Peel Adhesion (Before Thermal Vulcanization):

(104) TABLE-US-00030 Peel adhesion, Peel Test Oil immediate adhesion, after 30 minutes specimen application (N/cm) (N/cm) Steel Yes 0.04 0.18

(105) The curing temperature of the adhesive was adjustable below the range known for customary vulcanization adhesives of 130-250° C., owing to the very high level of ultra-accelerators, and was 120° C.

(106) Tensile Shear Strength (after Thermal Vulcanization):

(107) TABLE-US-00031 Oil Tensile shear Test specimen applicaton Curing strength [MPa] Fracture mode Steel/steel no 30 min/180° C. 17.8 cohesive Steel/steel yes 30 min/180° C. 17.1 cohesive Electrogalvanized yes 30 min/180° C. 17.0 cohesive steel/electrogalvanized steel Hot dip galvanized steel/hot yes 30 min/180° C. 15.9 cohesive dip galvanized steel CEC steel/CEC steel no 30 min/130° C. 15.4 cohesive CEC steel/CEC steel no 30 min/160° C. 15.8 cohesive

(108) With the present high level of ultra-accelerators and with the correspondingly low curing temperature, initial crosslinking phenomena became evident in the TSE (specks, gelling).

Inventive Example 8a

(109) Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(110) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 3 (including epoxy resin) was used. Because of the initial crosslinking phenomena evident in the TSE, PBD-PU 3 (including epoxy resin) was blended further in accordance with the formula below in the planetary roller extruder similarly to Inventive Example 6a. In the table below, the epoxy resin already mixed in during polybutadiene-polyurethane production is again listed separately.

(111) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 3:

(112) TABLE-US-00032 Raw material Weight percent PBD-PU 3 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 3 production) 11.3 Ground sulphur 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

(113) It was possible to keep the temperatures in the PRE and downstream TSE below 80° C., and so there was no specking/gel.

(114) Inventive Examples 6-8a, each with increasing level of curing agents and hence falling curing temperatures, show that the planetary roller extruder represents the preferred apparatus for the compounding of thermally curable adhesives, since the cure reaction does not exhibit offset during the production of adhesive and adhesive tape, owing to the low temperatures with this assembly, even when the level of curing agents is very high and the curing temperature, correspondingly, is low.

Inventive Example 9

(115) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of an epoxy resin and a tackifier resin. The composition of the polybutadiene-polyurethane (PBD-PU 9), including the epoxy resin and the tackifier resin, is as follows:

(116) Composition PBD-PU 9:

(117) TABLE-US-00033 Number of OH or NCO Percentage ratio Weight groups introduced, of number of fraction based on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 54.99 50.04 mmol OH 50 2-Ethyl-1,3-hexanediol 3.66 50.04 mmol OH 50 Coscat 83 ® 0.13 Desmodur W ® 12.56 95.09 mmol NCO Epikote 828 ® 17.84 Dercolyte S115 ® 10.82 Total 100.00

(118) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(119) PBD-PU 9 (including epoxy resin and tackifier resin) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(120) Test Results PBD-PU 9 (Including Epoxy Resin and Tackifier Resin):

(121) TABLE-US-00034 G′ (at 1 rad/sec and 23° C.) 30 000 Pa G″ (at 1 rad/sec and 23° C.) 45 000 Pa G′ (at 10 rad/sec and 23° C.) 130 000 Pa  G″ (at 10 rad/sec and 23° C.) 140 000 Pa  Complex viscosity η* at 10 rad/sec and 23° C.  19 000 Pas Complex viscosity η* at 10 rad/sec and 90° C.    260 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(122) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 9 (including epoxy resin and tackifier resin) was blended further in accordance with the formula below in the laboratory batch and shaped to form a film.

(123) The epoxy and tackifier resins, mixed in as early as during polybutadiene-polyurethane production, are listed separately in the table below.

(124) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 9:

(125) TABLE-US-00035 Raw material Weight percent PBD-PU 9 (excluding epoxy and tackifier resins) 47.5 Epikote 828 ® (from PBD-PU 9 production) 11.9 Dercolyte S115 ® (from PBD-PU 9 production) 7.2 Ground sulphur 80/90° 7.2 MBTS 2.2 Printex 60 ® 1.0 Omyacarb 5-GU ® 19.4 Rapidquell ® Quicklime CL 90-Q 3.6

(126) The results achieved were as follows:

(127) Tack (before thermal vulcanization) at 23° C.: 1.2 N

(128) Peel Adhesion (Before Thermal Vulcanization):

(129) TABLE-US-00036 Peel adhesion, Peel Test Oil immediate adhesion, after 30 minutes specimen application (N/cm) (N/cm) Steel yes 0.2 1.8
Tensile Shear Strength (after Thermal Vulcanization).

(130) TABLE-US-00037 Oil Tensile shear Test specimen application Curing strength [MPa] Fracture mode Steel/steel no 30 min/180° C. 14.2 cohesive Steel/steel yes 30 min/180° C. 13.8 cohesive Electrogalvanized yes 30 min/180° C. 13.6 cohesive steel/electrogalvanized steel Hot dip galvanized steel/hot yes 30 min/180° C. 12.4 cohesive dip galvanized steel

Inventive Example 10

(131) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of an epoxy resin and a tackifier resin. The composition of the polybutadiene-polyurethane (PBD-PU 10), including the epoxy resin and the tackifier resin, is as follows:

(132) Composition PBD-PU 10:

(133) TABLE-US-00038 Number of OH or NCO Percentage ratio Weight groups introduced, of number of fraction based on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 54.99 50.04 mmol OH 50 2-Ethyl-1,3-hexanediol 3.66 50.04 mmol OH 50 Coscat 83 ® 0.13 Desmodur W ® 12.56 95.09 mmol NCO Epikote 828 ® 17.84 Wingtack ® 10 10.82 Total 100.00

(134) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(135) PBD-PU 10 (including epoxy resin and tackifier resin) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(136) Test Results PBD-PU 10 (Including Epoxy Resin and Tackifier Resin):

(137) TABLE-US-00039 G′ (at 1 rad/sec and 23° C.) 18 000 Pa G″ (at 1 rad/sec and 23° C.) 32 000 Pa G′ (at 10 rad/sec and 23° C.) 100 000 Pa  G″ (at 10 rad/sec and 23° C.) 120 000 Pa  Complex viscosity η* at 10 rad/sec and 23° C.  16 000 Pas Complex viscosity η* at 10 rad/sec and 90° C.    220 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(138) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 10 (including epoxy resin and tackifier resin) was blended further in accordance with the formula below in the laboratory batch and shaped to form a film.

(139) The epoxy and tackifier resins, mixed in as early as during polybutadiene-polyurethane production, are listed separately in the table below.

(140) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 10:

(141) TABLE-US-00040 Raw material Weight percent PBD-PU 10 (excluding epoxy and tackifier resins) 47.5 Epikote 828 ® (from PBD-PU 10 production) 11.9 Wingtack ® 10 (from PBD-PU 10 production) 7.2 Ground sulphur 80/90° 7.2 MBTS 2.2 Printex 60 ® 1.0 Omyacarb 5-GU ® 19.4 Rapidquell ® Quicklime CL 90-Q 3.6

(142) The results achieved were as follows:

(143) Tack (before thermal vulcanization) at 23° C.: 1.0 N

(144) Peel Adhesion (Before Thermal Vulcanization):

(145) TABLE-US-00041 Peel adhesion, Peel Test Oil immediate adhesion, after 30 minutes specimen application (N/cm) (N/cm) Steel Yes 0.1 0.28
Tensile Shear Strength (after Thermal Vulcanization):

(146) TABLE-US-00042 Oil Tensile shear Test specimen application Curing strength [MPa] Fracture mode Steel/steel no 30 min/180° C. 13.7 cohesive Steel/steel yes 30 min/180° C. 12.2 cohesive Electrogalvanized yes 30 min/180° C. 11.9 cohesive steel/electrogalvanized steel Hot dip galvanized steel/hot yes 30 min/180° C. 12.1 cohesive dip galvanized steel

Inventive Example 11

(147) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of an epoxy resin and bitumen. The composition of the polybutadiene-polyurethane (PBD-PU 11), including the epoxy resin and the bitumen, is as follows:

(148) Composition PBD-PU 11:

(149) TABLE-US-00043 Number of OH or NCO groups Percentage ratio Weight introduced, of number of fraction based on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 54.99 50.04 mmol OH 50 2-Ethyl-1,3-hexanediol 3.66 50.04 mmol OH 50 Coscat 83 ® 0.13 Desmodur W ® 12.56 95.09 mmol NCO Epikote 828 ® 17.84 Azalt 50/70 DE ® 10.82 Total 100.00

(150) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(151) PBD-PU 11 (including epoxy resin and bitumen) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(152) Test Results PBD-PU 11 (Including Epoxy Resin and Bitumen):

(153) TABLE-US-00044 G′ (at 1 rad/sec and 23° C.) 25 000 Pa G″ (at 1 rad/sec and 23° C.) 39 000 Pa G′ (at 10 rad/sec and 23° C.) 110 000 Pa G″ (at 10 rad/sec and 23° C.) 130 000 Pa Complex viscosity η* at 10 rad/sec and 23° C. 17 000 Pas Complex viscosity η* at 10 rad/sec and 90° C. 240 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Laver:

(154) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 11 (including epoxy resin and bitumen) was blended further in accordance with the formula below in the laboratory batch and shaped to form a film.

(155) The epoxy resin and bitumen, mixed in as early as during polybutadiene-polyurethane production, are listed separately in the table below.

(156) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 11:

(157) TABLE-US-00045 Weight Raw material percent PBD-PU 11 (excluding epoxy resin and bitumen) 47.5 Epikote 828 ® (from PBD-PU 11 production) 11.9 Azalt 50/70 DE ® (from PBD-PU 11 production) 7.2 Ground sulphur 80/90° 7.2 MBTS 2.2 Printex 60 ® 1.0 Omyacarb 5-GU ® 19.4 Rapidquell ® Quicklime CL 90-Q 3.6

(158) The results achieved were as follows:

(159) Tack (before thermal vulcanization) at 23° C.: 1.2 N

(160) Peel Adhesion (Before Thermal Vulcanization):

(161) TABLE-US-00046 Peel adhesion, Peel adhesion, Test Oil immediate after 30 minutes specimen application (N/cm) (N/cm) Steel Yes 0.1 0.22
Tensile Shear Strength (after Thermal Vulcanization):

(162) TABLE-US-00047 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode Steel/steel no 30 min/180° C. 13.2 cohesive Steel/steel yes 30 min/180° C. 14.9 cohesive Electrogalvanized yes 30 min/180° C. 13.7 cohesive steel/electrogalvanized steel Hot dip galvanized steel/ yes 30 min/180° C. 13.1 cohesive hot dip galvanized steel

Inventive Example 12

(163) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of an epoxy resin. The composition of the polybutadiene-polyurethane (PBD-PU 12), including the epoxy resin, is as follows:

(164) Composition PBD-PU 12:

(165) TABLE-US-00048 Number of OH or Percentage NCO groups ratio Weight introduced, of number of fraction based on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 61.67 56.12 mmol OH 50 2-Ethyl-1,3-hexanediol 4.10 56.12 mmol OH 50 Coscat 83 ® 0.15 Desmodur W ® 14.08 106.62 mmol NCO 3,4-Epoxycyclohexyl- 20.00 methyl 3′,4′- epoxycyclohexane- carboxylate Total 100.00

(166) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(167) PBD-PU 12 (including epoxy resin) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(168) Test Results PBD-PU 12 (Including Epoxy Resin):

(169) TABLE-US-00049 G′ (at 1 rad/sec and 23° C.) 7000 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 Complex viscosity η* at 10 rad/sec and 23° C. 6600 Pas Complex viscosity η* at 10 rad/sec and 90° C. 180 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(170) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 12 (including epoxy resin) was blended further in accordance with the formula below in the laboratory batch, and shaped to form a film.

(171) The epoxy resin, mixed in as early as during polybutadiene-polyurethane production, is listed separately in the table below.

(172) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 12:

(173) TABLE-US-00050 Weight Raw material percent PBD-PU 12 (excluding epoxy resin) 44.8 3,4-Epoxycyclohexylmethyl 3′,4′-epoxycyclohexane- 11.3 carboxylate (from PBD-PU 12 production) Ground sulphur 80/90° 3.5 ZBEC 1.5 TBzTD 1.5 Printex60 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 6.9

(174) The results achieved were as follows:

(175) Tack (before thermal vulcanization) at 23° C.: 0.4 N

(176) Peel Adhesion (Before Thermal Vulcanization):

(177) TABLE-US-00051 Peel adhesion, Peel adhesion, Test Oil immediate after 30 minutes specimen application (N/cm) (N/cm) Steel yes 0.03 0.15
Tensile Shear Strength (after Thermal Vulcanization):

(178) TABLE-US-00052 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode Steel/steel no 30 min/180° C. 15.2 Cohesive Steel/steel yes 30 min/180° C. 14.7 Cohesive Electrogalvanized yes 30 min/180° C. 13.6 Cohesive steel/electrogalvanized steel Hot dip galvanized steel/ yes 30 min/180° C. 14.9 Cohesive hot dip galvanized steel CEC steel/ CEC steel no 30 min/130° C. 13.1 Cohesive CEC steel/CEC steel no 30 min/160° C. 15.9 Cohesive

Inventive Example 13

(179) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of a plasticizer. The composition of the polybutadiene-polyurethane (PBD-PU 13), including the plasticizer, is as follows:

(180) Composition PBD-PU 13:

(181) TABLE-US-00053 Number of OH or Percentage NCO groups ratio Weight introduced, of number of fraction based on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 61.67 56.12 mmol OH 50 2-Ethyl-1,3-hexanediol 4.10 56.12 mmol OH 50 Coscat 83 ® 0.15 Desmodur W ® 14.08 106.62 mmol NCO Gravex 925 ® 20.00 Total 100.00

(182) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(183) PBD-PU 13 (including plasticizer) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(184) Test Results PBD-PU 13 (Including Plasticizer):

(185) TABLE-US-00054 G′ (at 1 rad/sec and 23° C.) 5000 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 Complex viscosity η* at 10 rad/sec and 23° C. 6900 Pas Complex viscosity η* at 10 rad/sec and 90° C. 180 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(186) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 13 (including plasticizer) was blended further in accordance with the formula below in the laboratory batch, and shaped to form a film.

(187) The plasticizer, mixed in as early as during polybutadiene-polyurethane production, is listed separately in the table below.

(188) Composition of the thermally vulcanizable adhesive tape layer based on PBD-PU 13:

(189) TABLE-US-00055 Weight Raw material percent PBD-PU 13 (excluding plasticizer) 44.8 Gravex 925 ® (from PBD-PU 13 production) 11.3 Ground sulphur 80/90° 3.5 ZBEC 1.5 TBzTD 1.5 Printex 60 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 6.9

(190) The results achieved were as follows:

(191) Tack (before thermal vulcanization) at 23° C.: 0.5 N

(192) Peel Adhesion (Before Thermal Vulcanization):

(193) TABLE-US-00056 Peel adhesion, Peel adhesion, Test Oil immediate after 30 minutes specimen application (N/cm) (N/cm) Steel Yes 0.03 0.11
Tensile Shear Strength (after Thermal Vulcanization):

(194) TABLE-US-00057 Tensile Oil shear appli- strength Fracture Test specimen cation Curing [MPa] mode Steel/steel No 30 min/180° C. 13.2 cohesive Steel/steel Yes 30 min/180° C. 13.7 cohesive Electrogalvanized Yes 30 min/180° C. 12.1 cohesive steel/electrogalvanized steel Hot dip galvanized steel/ Yes 30 min/180° C. 12.0 cohesive hot dip galvanized steel CEC steel/CEC steel No 30 min/130° C. 11.6 cohesive CEC steel/CEC steel No 30 min/160° C. 13.6 cohesive

Inventive Example 14

(195) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of an epoxy resin. The composition of the polybutadiene-polyurethane (PBD-PU 14), including the epoxy resin, is as follows:

(196) Composition PBD-PU 14:

(197) TABLE-US-00058 Number of OH or Percentage NCO groups ratio Weight introduced, of number of fraction based on percentage OH groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 63.44 57.73 mmol OH 50 2-Ethyl-1,3-hexanediol 4.22 57.73 mmol OH 50 Coscat 83 ® 0.15 Vestanat IPDI ® 12.19 109.69 mmol NCO Epikote 828 ® 20.00 Total 100.00

(198) Production took place in a laboratory batch (1 litre). The weight fraction of Vestanat IPDI® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(199) PBD-PU 14 (including epoxy resin) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(200) Test Results PBD-PU 14 (Including Epoxy Resin):

(201) TABLE-US-00059 G′ (at 1 rad/sec and 23° C.) 7000 Pa G″ (at 1 rad/sec and 23° C.) 14 000 Pa G′ (at 10 rad/sec and 23° C.) 50 000 Pa G″ (at 10 rad/sec and 23° C.) 80 000 Pa Complex viscosity η* at 10 rad/sec and 23° C. 9400 Pas Complex viscosity η* at 10 rad/sec and 90° C. 190 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Laver:

(202) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 14 (including epoxy resin) was blended further in accordance with the formula below in the laboratory batch, and shaped to form a film.

(203) The epoxy resin, mixed in as early as during polybutadiene-polyurethane production, is listed separately in the table below.

(204) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 14:

(205) TABLE-US-00060 Raw material Weight percent PBD-PU 14 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 14 production) 11.3 Ground sulphur 80/90° 3.5 ZBEC 1.5 TBzTD 1.5 Printex 60 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 6.9

(206) The results achieved were as follows:

(207) Tack (before thermal vulcanization) at 23° C.: 0.7 N

(208) Peel Adhesion (Before Thermal Vulcanization):

(209) TABLE-US-00061 Test Oil Peel adhesion, Peel adhesion, after specimen application immediate (N/cm) 30 minutes (N/cm) Steel yes 0.05 0.15
Tensile Shear Strength (after Thermal Vulcanization):

(210) TABLE-US-00062 Tensile shear Oil Strength Fracture Test specimen application Curing [MPa] mode Steel/steel No 30 min/180° C. 12.2 cohesive Steel/steel Yes 30 min/180° C. 12.5 cohesive Electrogalvanized Yes 30 min/180° C. 12.7 cohesive steel/electro- galvanized steel Hot dip galvanized Yes 30 min/180° C. 11.9 cohesive steel/hot dip galvanized steel CEC steel/CEC steel No 30 min/130° C. 10.8 cohesive CEC steel/CEC steel No 30 min/160° C. 12.4 cohesive

Inventive Example 15

(211) The chemical reaction to give the polybutadiene-polyurethane took place in the presence of an epoxy resin. The composition of the polybutadiene-polyurethane (PBD-PU 15), including the epoxy resin, is as follows:

(212) Composition PBD-PU 15:

(213) TABLE-US-00063 Number of OH Percentage or NCO groups ratio of Weight introduced, based number of OH fraction on percentage groups to Raw material [wt %] weight fraction one another Krasol LBH 2000 ® 28.89  26.29 mmol OH 20 Poly bd R-45 HTLO ® 31.30  26.29 mmol OH 20 2-Ethyl-1,3-hexanediol 5.77  78.88 mmol OH 60 Coscat 83 ® 0.15 Desmodur W ® 13.89 105.17 mmol NCO Epikote 828 ® 20.00 Total 100.00

(214) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.80. The theoretical gel point is computed to be 0.83.

(215) PBD-PU 15 (including epoxy resin) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(216) Test Results PBD-PU 15 (Including Epoxy Resin):

(217) TABLE-US-00064 G′ (at 1 rad/sec and 23° C.) 1500 Pa G″ (at 1 rad/sec and 23° C.) 5000 Pa G′ (at 10 rad/sec and 23° C.) 15 000 Pa G″ (at 10 rad/sec and 23° C.) 60 000 Pa Complex viscosity η* at 10 rad/sec and 23° C. 6200 Pas Complex viscosity η* at 10 rad/sec and 90° C. 160 Pas
Production of the Inventive Adhesive and the Inventive Adhesive Tape Layer:

(218) For producing the inventive adhesive and the inventive adhesive tape layer, PBD-PU 15 (including epoxy resin) was blended further in accordance with the formula below in the laboratory batch, and shaped to form a film.

(219) The epoxy resin, mixed in as early as during polybutadiene-polyurethane production, is listed separately in the table below.

(220) Composition of the Thermally Vulcanizable Adhesive Tape Layer Based on PBD-PU 15:

(221) TABLE-US-00065 Raw material Weight percent PBD-PU 15 (excluding epoxy resin) 44.8 Epikote 828 ® (from PBD-PU 15 production) 11.3 Ground sulphur 80/90° 3.5 ZBEC 1.5 TBzTD 1.5 Printex 60 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 6.9

(222) The results achieved were as follows:

(223) Tack (before thermal vulcanization) at 23° C.: 1.5 N

(224) Peel Adhesion (Before Thermal Vulcanization):

(225) TABLE-US-00066 Test Oil Peel adhesion, Peel adhesion, after specimen application immediate (N/cm) 30 minutes (N/cm) Steel Yes 0.08 0.19
Tensile Shear Strength (after Thermal Vulcanization):

(226) TABLE-US-00067 Tensile shear Oil strength Fracture Test specimen application Curing [MPa] mode Steel/steel No 30 min/180° C. 13.8 cohesive Steel/steel Yes 30 min/180° C. 13.1 cohesive Electrogalvanized Yes 30 min/180° C. 12.9 cohesive steel/electro- galvanized steel Hot dip galvanized Yes 30 min/180° C. 12.4 cohesive steel/hot dip galvanized steel CEC steel/CEC steel No 30 min/130° C. 12.5 cohesive CEC steel/CEC steel No 30 min/160° C. 10.6 cohesive

Comparative Example 1

(227) The chemical reaction to give the polyurethane took place in the presence of an epoxy resin. The composition of the polyurethane (PU-C1), including the epoxy resin, is as follows:

(228) Composition PU-C1:

(229) TABLE-US-00068 Number of Percentage OH or NCO groups ratio of Weight introduced, based number of OH fraction on percentage groups to Raw material [wt %] weight fraction 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-hexanediol 4.23  57.90 mmol OH 50 Coscat 83 ® 0.15 Desmodur W ® 14.53 110.01 mmol NCO Epikote 828 ® 20.00 Total 100.00

(230) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 1.0.

(231) PU-C1 (including epoxy resin) at room temperature is solid, meltable and, in terms of consistency, rubber-like and tacky. The test results are summarized in the table below:

(232) Test Results PU-C1 (Including Epoxy Resin):

(233) TABLE-US-00069 G′ (at 1 rad/sec and 23° C.) 7000 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 Complex viscosity η* at 10 rad/sec and 23° C. 10 000 Pas Complex viscosity η* at 10 rad/sec and 90° C. 190 Pas
Production of the Comparative Adhesive Tape Layer:

(234) For producing the comparative adhesive tape layer, PU-C1 (including epoxy resin) was blended further in accordance with the formula below in the laboratory batch, and shaped to form a film.

(235) The epoxy resin, mixed in as early as during polyurethane production, is listed separately in the table below.

(236) Composition of the Comparative Adhesive Tape Layer Based on PU-C1:

(237) TABLE-US-00070 Raw material Weight percent PU-C1 (excluding epoxy resin) 44.8 Epikote 828 ® (from PU-C1 production) 11.3 Ground sulphur 80/90° 3.5 ZBEC 1.5 TBzTD 1.5 Printex 60 ® 0.9 Omyacarb 5-GU ® 26.1 Rapidquell ® Quicklime CL 90-Q 3.5 Talc Pharma M ® 6.9

(238) The results achieved were as follows:

(239) Tack (before thermal vulcanization) at 23° C.: 0.6 N

(240) Peel Adhesion (Before Thermal Vulcanization):

(241) TABLE-US-00071 Test Oil Peel adhesion, Peel adhesion, after specimen application immediate (N/cm) 30 minutes (N/cm) Steel yes 0.05 0.12
Tensile Shear Strength (after Thermal Vulcanization):

(242) TABLE-US-00072 Tensile shear Oil strength Fracture Test specimen application Curing [MPa] mode Steel/steel no 30 min/180° C. 1.3 adhesive Steel/steel yes 30 min/180° C. 1.1 adhesive Electrogalvanized yes 30 min/180° C. 1.2 adhesive steel/electro- galvanized steel Hot dip galvanized yes 30 min/180° C. 1.4 adhesive steel/hot dip galvanized steel CEC steel/CEC steel no 30 min/130° C. 0.6 cohesive CEC steel/CEC steel no 30 min/160° C. 0.9 cohesive

Comparative Example 2

(243) The composition of the polyurethane (PU-C2), is as follows:

(244) Composition PU-C2:

(245) TABLE-US-00073 Number of Percentage OH or NCO groups ratio of Weight introduced, based number of OH fraction on percentage groups to Raw material [wt %] weight fraction one another Poly bd R-45 HTLO ® 78.49  65.93 mmol OH 50 2-Ethyl-1,3-hexanediol 4.82  65.93 mmol OH 50 Coscat 83 ® 0.15 Desmodur W ® 16.55 125.26 mmol NCO Total 100.00

(246) Production took place in a laboratory batch (1 litre). The weight fraction of Desmodur W® is calculated so that the NCO/OH ratio of the polyurethane is 0.95. The theoretical gel point is computed to be 0.67.

(247) PU-C2 at room temperature is solid and not meltable.

BRIEF DESCRIPTION OF THE FIGURES

(248) FIG. 1 illustrates a planetary roller extruder in an embodiment, wherein 1: Feed of polybutadiene-polyurethane 2: Inlet for sulphur 3: Inlet for chalk 4: Inlet for talc & lime premix 5: Inlet for ultra-accelerator premix (ZBEC/TBzTD) 6: Outlet for compounded formulation

(249) FIG. 2 illustrates a twin screw extruder in an embodiment, wherein 7: Carbon black dispersion feed line 8: Devolatization (<0.1 bar) 9: Blister