Cross-linked polycarbonate resin with improved chemical and flame resistance
View Patent ↗Processes for increasing the chemical resistance of a surface of a formed article are disclosed. The formed article is produced from a polymeric composition comprising a photoactive additive containing photoactive groups derived from a monofunctional benzophenone. The surface of the formed article is then exposed to ultraviolet light to cause crosslinking of the photoactive additive and produce a crosslinked surface. The crosslinking enhances the chemical resistance of the surface. Various means for controlling the depth of the crosslinking are also discussed.
1. A method for preparing an article that has a high probability of passing a UL94 V1 test, comprising:
(a) designing a polymeric composition to be exposed to a designed dosage (D) of UV radiation, wherein the polymeric composition comprises:
(i) a cross-linkable polycarbonate resin having endcaps derived from 4-monohydroxybenzophenone and a weight average molecular weight of 15,000 to 30,000, and
(ii) optionally one or more polymeric base resins, and
wherein the polymeric composition has a designed weight percentage of the endcaps derived from 4-monohydroxybenzophenone (HBP), a designed melt flow rate (MF) and a designed weight average molecular weight (MW);
(b) preparing the cross-linkable polycarbonate resin by interfacial polymerization;
(c) optionally blending the cross-linkable polycarbonate resin with the optional one or more polymeric base resins to form the polymeric composition;
(d) forming an article from the polymeric composition; and
(e) exposing the formed article to the designed UV dosage;
wherein D, HBP, MF, and MW are selected based on an flame performance equation as follows:
Sqrt( p ( FTP )+0.01)=−0.37308+(0.05345× D )+(0.22797 ×HBP )−(2.06081×10 −6 × MW )−(0.092440× MF )+(2.81460×10 −6 × MW×MF )+(0.000583× D 2 )
wherein p(FTP) is the probability of a first time pass in a UL94 V1 test at 1.2 mm thickness after UV exposure and after 7 days of aging at 70° C.; p(FTP) is 0.7 or greater; D is at least 12 J/cm 2 of UVA radiation; and MF is from 7 to 20 g/10 min measured at 300° C./1.2 kg/360 sec dwell.
2. The method of claim 1 , wherein the UV radiation is filtered to provide at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation, as measured using an EIT PowerPuck.
3. The method of claim 1 , wherein the UV radiation is unfiltered and provides at least 12 J/cm 2 of UVA radiation and and at least 0.45 J/cm 2 of UVC radiation, as measured using an EIT PowerPuck.
4. The method of claim 1 , wherein D, HBP, MF, and MW are also selected based on a percentage retention of tensile elongation equation as follows:
Sqrt( ER+ 1.04)=−29.23264+(0.62157× D )+(1.57655× HBP )+(1.27584×10 −3 × MW )−(1.63711×10 −5 ×D×MW )−(0.002382 × D 2 )
wherein ER is the percentage retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm; wherein the UV radiation is provided by a UV light source that provides at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation as measured using an EIT PowerPuck; and ER is 85% or higher.
5. The method of claim 1 , wherein D and MF are also selected based on a Delta YI equation as follows:
Ln(Delta YI)=1.01074+(0.08387× D )−(0.041908× MF )−(0.00077× D 2 )+(2.41546×10 −3 × MF 2 )
wherein Delta YI is the change in YI after exposure to at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation at 3.2 mm thickness, measured before UV exposure and at least 48 hours after UV exposure; wherein the UV radiation is provided by a UV light source that provides at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation; and wherein the delta YI is 15 or less.
6. The method of claim 5 , wherein the delta YI is 10 or less.
7. The method of claim 5 , wherein the delta YI is 8 or less.
8. The method of claim 1 , wherein D, HBP, MF, and MW are also selected based on a percentage retention of tensile elongation equation as follows:
Sqrt( ER+ 1.04)=−30.25285+(0.62157× D )+(1.57655× HBP )+(1.27584×10 −3 ×MW)−(1.63711×10 −5 ×D×MW )−(0.002382 × D 2 )
wherein ER is the percentage retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm; wherein the UV radiation is provided by a filtered UV light source that provides at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation, as measured using an EIT PowerPuck; and ER is 85% or higher.
9. The method of claim 1 , wherein D and MF are also selected based on a Delta YI equation as follows:
Ln(Delta YI)=0.44154+(0.07712× D )−(0.041908× MF )−(0.00077× D 2 )+(2.41546×10 −3 ×MF 2 )
wherein Delta YI is the change in YI after exposure to at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation at 3.2 mm thickness, measured before UV exposure and at least 48 hours after UV exposure; wherein the UV radiation is provided by a filtered UV light sourcethat provides at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation, as measured using an EIT PowerPuck; and wherein the delta YI is 15 or less.
10. The method of claim 9 , wherein the delta YI is 10 or less.
11. The method of claim 9 , wherein the delta YI is 8 or less.
12. The method of claim 1 , wherein MW is from 15,000 to 30,000.
13. The method of claim 1 , wherein HBP is from 1.2 wt % to 4 wt %.
14. The method of claim 1 , wherein the polymeric composition comprises a polymeric base resin, and the polymeric base resin is a polycarbonate resin that does not contain photoactive groups.
15. The method of claim 14 , wherein the weight ratio of the cross-linkable polycarbonate resin to the polymeric base resin is from about 50:50 to about 85:15.
16. The polymeric composition prepared by the method of claim 1 .
17. A method for preparing an article that has a low delta YI after exposure to unfiltered UV radiation, comprising:
(a) designing a polymeric composition to be exposed to a designed dosage (D) of unfiltered UV radiation, wherein the polymeric composition comprises:
(i) a cross-linkable polycarbonate resin having endcaps derived from 4-monohydroxybenzophenone and a weight average molecular weight of 15,000 to 30,000, and
(ii) optionally one or more polymeric base resins, and
wherein the polymeric composition has a designed weight percentage of the endcaps derived from 4-monohydroxybenzophenone (HBP), a designed melt flow rate (MF) and a designed weight average molecular weight (MW);
(b) preparing the cross-linkable polycarbonate resin by interfacial polymerization;
(c) optionally blending the cross-linkable polycarbonate resin with the optional one or more polymeric base resins to form the polymeric composition;
(d) forming an article from the polymeric composition; and
(e) exposing the formed article to the designed UV dosage;
wherein D and MF are selected based on a Delta YI equation as follows:
Ln(Delta YI)=1.01074+(0.08387× D )−(0.041908× MF )−(0.00077× D 2 )+(2.41546×10 −3 × MF 2 )
wherein Delta YI is the change in YI after exposure to at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation at 3.2 mm thickness, measured before UV exposure and at least 48 hours after UV exposure; wherein the unfiltered UV radiation provides at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation; and wherein the delta YI is 15 or less.
18. The method of claim 17 , wherein D, HBP, MF, and MW are also selected based on a retention of tensile elongation equation as follows:
Sqrt( ER+ 1.04)=−29.23264+(0.62157× D )+(1.57655× HBP )+(1.27584×10 −3 × MW )−(1.63711×10 −5 ×D×MW )−(0.002382 × D 2 )
wherein ER is the percentage retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm; and ER is 85 % or higher.
19. The method of claim 18 , wherein the delta YI is 10 or less.
20. The method of claim 18 , wherein the delta YI is 8 or less.
21. The method of claim 17 , wherein MF is from 7 to 20 g/10 min measured at 300° C./1.2 kg/360 sec dwell.
22. The method of claim 17 , wherein MW is from 15,000 to 30,000.
23. The method of claim 17 , wherein HBP is from 1.2 wt % to 4 wt %.
24. The method of claim 17 , wherein the polymeric composition comprises a polymeric base resin, and the polymeric base resin is a polycarbonate resin that does not contain photoactive groups.
25. The method of claim 24 , wherein the weight ratio of the cross-linkable polycarbonate resin to the polymeric base resin is from about 50:50 to about 85:15.
26. The polymeric composition prepared by the method of claim 17 .
27. A method for preparing an article that has a high percentage of retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm, comprising:
(a) designing a polymeric composition to be exposed to a designed dosage (D) of unfiltered UV radiation, wherein the polymeric composition comprises:
(i) a cross-linkable polycarbonate resin having endcaps derived from 4-monohydroxybenzophenone and a weight average molecular weight of 15,000 to 30,000, and
(ii) optionally one or more polymeric base resins, and
wherein the polymeric composition has a designed weight percentage of the endcaps derived from 4-monohydroxybenzophenone (HBP), a designed melt flow rate (MF) and a designed weight average molecular weight (MW);
(b) preparing the cross-linkable polycarbonate resin by interfacial polymerization;
(c) optionally blending the cross-linkable polycarbonate resin with the optional one or more polymeric base resins to form the polymeric composition;
(d) forming an article from the polymeric composition; and
(e) exposing the formed article to the designed UV dosage;
wherein D, HBP, MF, and MW are selected based on a percentage retention of tensile elongation equation as follows:
Sqrt( ER+ 1.04)=−29.23264+(0.62157× D )+(1.57655× HBP )+(1.27584×10 −3 ×MW )−(1.63711×10 −5 ×D×MW )−(0.002382 × D 2 )
wherein ER is the percentage retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm; wherein the unfiltered UV radiation provides at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation; and ER is 85 % or higher.
28. The method of claim 27 , wherein D and MF are also selected based on a Delta YI equation as follows:
Ln(Delta YI)=1.01074+(0.08387× D )−(0.041908× MF )−(0.00077× D 2 )+(2.41546×10 −3 ×MF 2 )
wherein Delta YI is the change in YI after exposure to at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation at 3.2 mm thickness, measured before UV exposure and at least 48 hours after UV exposure; wherein the unfiltered UV radiation provides at least 12 J/cm 2 of UVA radiation and at least 0.45 J/cm 2 of UVC radiation; and wherein the delta YI is 15 or less.
29. The method of claim 28 , wherein the delta YI is 10 or less.
30. The method of claim 28 , wherein the delta YI is 8 or less.
31. The method of claim 27 , wherein MF is from 7 to 20 g/10 min measured at 300° C./1.2 kg/360 sec dwell.
32. The method of claim 27 , wherein MW is from 15,000 to 30,000.
33. The method of claim 27 , wherein HBP is from 1.2 wt % to 4 wt %.
34. The method of claim 27 , wherein the polymeric composition comprises a polymeric base resin, and the polymeric base resin is a polycarbonate resin that does not contain photoactive groups.
35. The method of claim 33 , wherein the weight ratio of the cross-linkable polycarbonate resin to the polymeric base resin is from about 50:50 to about 85:15.
36. The polymeric composition prepared by the method of claim 27 .
37. A method for preparing an article that has a low delta YI after exposure to filtered UV radiation, comprising:
(a) designing a polymeric composition to be exposed to a designed dosage (D) of filtered UV radiation, wherein the polymeric composition comprises:
(i) a cross-linkable polycarbonate resin having endcaps derived from 4-monohydroxybenzophenone and a weight average molecular weight of 15,000 to 30,000, and
(ii) optionally one or more polymeric base resins, and
wherein the polymeric composition has a designed weight percentage of the endcaps derived from 4-monohydroxybenzophenone (HBP), a designed melt flow rate (MF) and a designed weight average molecular weight (MW);
(b) preparing the cross-linkable polycarbonate resin by interfacial polymerization;
(c) optionally blending the cross-linkable polycarbonate resin with the optional one or more polymeric base resins to form the polymeric composition;
(d) forming an article from the polymeric composition; and
(e) exposing the formed article to the designed UV dosage;
wherein D and MF are selected based on a Delta YI equation as follows:
Ln(Delta YI)=0.44154+(0.07712× D )−(0.041908× MF )−(0.00077× D 2 )+(2.41546×10 −3 ×MF 2 )
wherein Delta YI is the change in YI after exposure to at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation at 3.2 mm thickness, measured before UV exposure and at least 48 hours after UV exposure; wherein the UV radiation is provided by a filtered UV light source that provides at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation, as measured using an EIT PowerPuck; and wherein the delta YI is 15 or less.
38. The method of claim 37 , wherein D, HBP, MF, and MW are also selected based on a percentage retention of tensile elongation equation as follows:
Sqrt( ER+ 1.04)=−30.25285+(0.62157× D )+(1.57655×HBP)+(1.27584×10 −3 ×MW)−(1.63711×10 −5 ×D ×MW)−(0.002382 × D 2 )
wherein ER is the percentage retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm; and ER is 85% or higher.
39. The method of claim 37 , wherein the delta YI is 10 or less.
40. The method of claim 37 , wherein the delta YI is 8 or less.
41. The method of claim 37 , wherein MF is from 7 to 20 g/10 min measured at 300°C./1.2 kg/360 sec dwell.
42. The method of claim 37 , wherein MW is from 15,000 to 30,000.
43. The method of claim 37 , wherein HBP is from 1.2 wt % to 4 wt %.
44. The method of claim 37 , wherein the polymeric composition comprises a polymeric base resin, and the polymeric base resin is a polycarbonate resin that does not contain photoactive groups.
45. The method of claim 44 , wherein the weight ratio of the cross-linkable polycarbonate resin to the polymeric base resin is from about 50:50 to about 85:15.
46. The polymeric composition prepared by the method of claim 37 .
47. A method for preparing an article that has a high percentage of retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm, comprising:
(a) designing a polymeric composition to be exposed to a designed dosage (D) of filtered UV radiation, wherein the polymeric composition comprises:
(i) a cross-linkable polycarbonate resin having endcaps derived from 4-monohydroxybenzophenone and a weight average molecular weight of 15,000 to 30,000, and
(ii) optionally one or more polymeric base resins, and
wherein the polymeric composition has a designed weight percentage of the endcaps derived from 4-monohydroxybenzophenone (HBP), a designed melt flow rate (MF) and a designed weight average molecular weight (MW);
(b) preparing the cross-linkable polycarbonate resin by interfacial polymerization;
(c) optionally blending the cross-linkable polycarbonate resin with the optional one or more polymeric base resins to form the polymeric composition;
(d) forming an article from the polymeric composition; and
(e) exposing the formed article to the designed UV dosage;
wherein D, HBP, MF, and MW are selected based on a percentage retention of tensile elongation equation as follows:
Sqrt( ER+ 1.04)=−30.25285+(0.62157× D )+(1.57655× HBP )+(1.27584×10 −3 ×MW)−(1.63711×10 −5 ×D×MW )−(0.002382 × D 2 )
wherein ER is the percentage retention of tensile elongation after exposure to acetone at a thickness of 3.2 mm; wherein the UV radiation is provided by a filtered UV light source that provides at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation, as measured using an EIT PowerPuck; and ER is 85% or higher.
48. The method of claim 47 , wherein D and MF are also selected based on a Delta YI equation as follows:
Ln(Delta YI)=0.44154+(0.07712× D )+(0.041908× MF )−(0.00077× D 2 )+(2.41546×10 −3 ×MF 2 )
wherein Delta YI is the change in YI after exposure to at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation at 3.2 mm thickness, measured before UV exposure and at least 48 hours after UV exposure; wherein the UV radiation is provided by a filtered UV light source that provides at least 12 J/cm 2 of UVA radiation and no detectable UVC radiation, as measured using an EIT PowerPuck; and wherein the delta YI is 15 or less.
49. The method of claim 48 , wherein the delta YI is 10 or less.
50. The method of claim 48 , wherein the delta YI is 8 or less.
51. The method of claim 47 , wherein MF is from 7 to 20 g/10 min measured at 300° C./1.2 kg/360 sec dwell.
52. The method of claim 47 , wherein MW is from 15,000 to 30,000.
53. The method of claim 47 , wherein HBP is from 1.2wt % to 4 wt %.
54. The method of claim 47 , wherein the polymeric composition comprises a polymeric base resin, and the polymeric base resin is a polycarbonate resin that does not contain photoactive groups.
55. The method of claim 54 , wherein the weight ratio of the cross-linkable polycarbonate resin to the polymeric base resin is from about 50:50 to about 85:15.
56. The polymeric composition prepared by the method of claim 47 .