Laser-imageable flexographic printing precursors and methods of imaging

1. A laser-engraveable composition comprising one or more elastomeric rubbers in an amount of at least 30 weight % and up to and including 80 weight %, based on the total laser-engravable composition weight, wherein the laser-engraveable composition further comprises at least 10 parts and up to and including 100 parts of one or more controlled long chain branching ethylene-propylene-diene (CLCB EPDM) elastomeric rubbers, based on parts per hundred of the total weight of elastomeric rubbers (phr) in the laser-engraveable composition,

the laser-engraveable composition further comprising at least the following component b), with or without the following component a):

a) at least 2 phr and up to and including 30 phr of a near-infrared radiation absorber and at least 1 phr and up to and including 80 phr of an inorganic, non-infrared radiation absorber filler, wherein the weight ratio of the near-infrared radiation absorber to the inorganic, non-infrared radiation absorber filler is from 1:40 to 30:1, and

b) at least 2 phr and up to and including 30 phr of a near-infrared radiation absorber, and at least 3 phr and up to and including 20 phr of a vulcanizing composition that comprises a mixture of at least first and second peroxides,

wherein the first peroxide has a t 90 value of at least 1 minute and up to and including 6 minutes as measured at 160° C., and the second peroxide has a to value of at least 8 minutes and up to and including 20 minutes as measured at 160° C., and

wherein the weight ratio of the near-infrared radiation absorber to the vulcanizing composition is from 1:10 to 10:1, and

comprising a conductive or non-conductive carbon black, carbon fibers, or carbon nanotubes as the near-infrared radiation absorber.

2. The laser-engraveable composition of claim 1 comprising component a) wherein the weight ratio of the near-infrared radiation absorber to the inorganic, non-infrared radiation absorber filler is from 1:30 to 20:1.

3. The laser-engraveable composition of claim 1 that exhibits a t 90 value of at least 1 minute and up to and including 17 minutes at 160° C.

4. The laser-engraveable composition of claim 1 further comprising one or more non-CLCB EPDM elastomeric rubbers.

5. The laser-engraveable composition of claim 4 wherein the weight ratio of the one or more CLCB EPDM elastomeric rubbers to the one or more non-CLCB EPDM elastomeric rubbers is from 1:3 to 5:1.

6. The laser-engraveable composition of claim 4 wherein the weight ratio of the one or more CLCB EPDM elastomeric rubbers to the one or more non-CLCB EPDM elastomeric rubbers is from 1:1 to 3:1.

7. The laser-engraveable composition of claim 1 further comprising:

a) a high molecular weight non-CLCB EPDM elastomeric rubber that has a molecular weight of at least 20,000,

b) a low molecular weight non-CLCB EPDM elastomeric rubber that has a molecular weight of at least 2,000 and less than 20,000, or

c) a mixture of a high molecular weight non-CLCB EPDM elastomeric rubber and a low molecular weight non-CLCB EPDM elastomeric rubber at a weight ratio of the high molecular weight non-CLCB EPDM elastomeric rubber to the low molecular weight non-CLCB EPDM elastomeric rubber of from 1:1 to 4:1.

8. A laser-engraveable composition comprising one or more elastomeric rubbers in an amount of at least 30 weight % and up to and including 80 weight %, based on the total laser-engravable composition weight, wherein the laser-engraveable composition further comprises at least 10 parts and up to and including 100 parts of one or more controlled long chain branching ethylene-propylene-diene (CLCB EPDM) elastomeric rubbers, based on parts per hundred of the total weight of elastomeric rubbers (phr) in the laser-engraveable composition,

the laser-engraveable composition further comprising both of the following components a) and b):

a) at least 2 phr and up to and including 30 phr of near-infrared radiation absorber and at least 1 phr and up to and including 80 phr of an inorganic, non-infrared radiation absorber filler, wherein the weight ratio of the near-infrared radiation absorber to the inorganic, non-infrared radiation absorber filler is from 1:40 to 30:1, and

b) at least 2 phr and up to and including 30 phr of the near-infrared radiation absorber, and at least 3 phr and up to and including 20 phr of a vulcanizing composition that comprises a mixture of at least first and second peroxides,

wherein the first peroxide has a t 90 value of at least 1 minute and up to and including 6 minutes as measured at 160° C., and the second peroxide has a t 90 value of at least 8 minutes and up to and including 20 minutes as measured at 160° C., and

wherein the weight ratio of the near-infrared radiation absorber to the vulcanizing composition is from 1:10 to 10:1, and

comprising a conductive or non-conductive carbon black, carbon fibers, or carbon nanotubes as the near-infrared radiation absorber,

wherein component a) comprises silica particles, calcium carbonate particles, or both silica and calcium carbonate particles as the non-infrared radiation absorber filler.

9. A flexographic printing precursor that is laser-engraveable to provide a relief image, the flexographic printing precursor comprising a laser-engraveable layer prepared from a laser-engraveable composition comprising one or more elastomeric rubbers in an amount of at least 30 weight % and up to and including 80 weight %, based on the total laser-engraveable composition weight, the laser-engraveable composition comprising at least 10 parts and up to and including 100 parts of one or more controlled long chain branching ethylene-propylene-diene (CLCB EPDM) elastomeric rubbers, based on parts per hundred of the total weight of elastomeric rubbers (phr) in the laser-engraveable composition,

the laser-engraveable composition further comprising one or both of the following components a) and b):

a) at least 2 phr and up to and including 30 phr of a near-infrared radiation absorber and at least 1 phr and up to and including 80 phr of an inorganic, non-infrared radiation absorber filler, wherein the weight ratio of the near-infrared radiation absorber to the inorganic, non-infrared radiation absorber filler is from 1:40 to 30:1, and

b) at least 2 phr and up to and including 30 phr of a near-infrared radiation absorber, and at least 3 phr and up to and including 20 phr of a vulcanizing composition that comprises a mixture of at least first and second peroxides,

wherein the first peroxide has a t 90 value of at least 1 minute and up to and including 6 minutes as measured at 160° C., and the second peroxide has a t 90 value of at least 8 minutes and up to and including 20 minutes as measured at 160° C., and

wherein the weight ratio of the infrared radiation absorber to the vulcanizing composition is from 1:10 to 10:1,

the flexographic printing precursor further comprising a substrate over which the laser-engraveable layer is disposed, wherein the substrate comprises a fabric web disposed over a polymeric film.

10. The flexographic printing precursor of claim 9 wherein the laser-engraveable layer has a Δ torque (M Δ =M H −M L ) of at least 10 and up to and including 25.

11. The flexographic printing precursor of claim 9 wherein the laser-engraveable composition comprises component a) wherein the weight ratio of the near-infrared radiation absorber to the inorganic, non-infrared radiation absorber filler is from 1:30 to 20:1.

12. The flexographic printing precursor of claim 9 wherein the laser-engraveable composition further comprises one or more non-CLCB EPDM elastomeric rubbers and the one or more CLCB EPDM elastomeric rubbers are present in an amount of at least 15 phr and up to and including 70 phr.

13. The flexographic printing precursor of claim 9 wherein the weight ratio of the one or more CLCB EPDM elastomeric rubbers to the one or more non-CLCB EPDM elastomeric rubbers is from 1:3 to 5:1.

14. The flexographic printing precursor of claim 9 wherein the weight ratio of the one or more CLCB EPDM elastomeric rubbers to the one or more non-CLCB EPDM elastomeric rubbers is from 1:1 to 3:1.

15. The flexographic printing precursor of claim 9 wherein the laser-engraveable composition further comprises:

a) a high molecular weight non-CLCB EPDM elastomeric rubber that has a molecular weight of at least 20,000,

b) a low molecular weight non-CLCB EPDM elastomeric rubber that has a molecular weight of at least 2,000 and less than 20,000, or

c) a mixture of the high molecular weight non-CLCB EPDM elastomeric rubber and the low molecular weight non-CLCB EPDM elastomeric rubber at a weight ratio of the high molecular weight non-CLCB EPDM elastomeric rubber to the low molecular weight non-CLCB EPDM elastomeric rubber of from 1:1 to 4:1.

16. The flexographic printing precursor of claim 9 wherein carbon black is present as the near-infrared radiation absorber in an amount of at least 5 phr and up to and including 30 phr.

17. The flexographic printing precursor of claim 9 wherein the laser-engraveable layer has a dry thickness of at least 50 μm and up to and including 4,000 μm.

18. The flexographic printing precursor of claim 9 wherein the laser-engraveable composition further comprises carbon nanotubes, carbon fibers, or a conductive carbon black that has a dibutyl phthalate (DBP) absorption value of at least 110 ml/100 g, wherein the carbon nanotubes, carbon fibers, or conductive carbon black is present in an amount of at least 3 phr and up to and including 30 phr.

19. A system for providing a flexographic printing member, comprising:

the flexographic printing precursor of claim 9 ,

a source of imaging near-infrared radiation that is capable of emitting imaging near-infrared radiation and that is selected from the group consisting of a laser diode, a multi-emitter laser diode, a laser bar, a laser stack, a fiber laser, or a combination thereof, and

a set of optical elements coupled to the one or more sources of imaging near-infrared radiation to direct imaging near-infrared radiation from the one or more sources of imaging near-infrared radiation onto the flexographic printing member.

20. A method for preparing the flexographic printing precursor of claim 9 comprising:

providing a laser-engraveable composition comprising one or more elastomeric rubbers in an amount of at least 30 weight % and up to and including 80 weight %, based on the total laser-engraveable composition weight, the laser-engraveable composition further comprising at least 10 parts and up to and including 100 parts of one or more controlled long chain branching ethylene-propylene-diene (CLCB EPDM) elastomeric rubbers, based on parts per hundred of the total weight of elastomeric rubbers (phr) in the laser-engraveable composition,

the laser-engraveable composition further comprising one or both of the following components a) and b):

a) at least 2 phr and up to and including 30 phr of a near-infrared radiation absorber and at least 1 phr and up to and including 80 phr of an inorganic, non-infrared radiation absorber filler, wherein the weight ratio of the near-infrared radiation absorber to the inorganic, non-infrared radiation absorber filler is from 1:40 to 30:1, and

b) at least 2 phr and up to and including 30 phr of the near-infrared radiation absorber that is a carbon black, and at least 3 phr and up to and including 20 phr of a vulcanizing composition that comprises a mixture of at least first and second peroxides,

wherein the first peroxide has a t 90 value of at least 1 minute and up to and including 6 minutes as measured at 160° C., and the second peroxide has a t 90 value of at least 8 minutes and up to and including 20 minutes as measured at 160° C., and

wherein the weight ratio of the carbon black to the vulcanizing composition is from 1:5 to 5:1, and

formulating the laser-engraveable composition into a laser-engraveable layer on a substrate comprising one or more layers of a fabric on a polymeric film.

21. A method for preparing a flexographic printing precursor comprising:

providing a laser-engraveable composition comprising one or more elastomeric rubbers in an amount of at least 30 weight % and up to and including 80 weight %, based on total laser-engraveable composition weight,

the laser-engraveable composition further comprising:

at least 2 phr and up to and including 30 phr of a near-infrared radiation absorber, and at least 3 phr and up to and including 20 phr of a peroxide composition or a composition comprising a mixture of a sulfur composition and a peroxide composition,

wherein the weight ratio of the near-infrared radiation absorber to the vulcanizing composition is from 1:10 to 10:1, and the peroxide composition comprises a mixture of at least first and second peroxides, wherein the first peroxide has a t 90 value of at least 1 minute and up to and including 6 minutes as measured at 160° C., and the second peroxide has a t 90 value of at least 8 minutes and up to and including 20 minutes as measured at 160° C., and

formulating the laser-engraveable composition into a laser-engraveable layer.

22. The method of claim 21 wherein the laser-engraveable composition exhibits a t 90 value of at least 1 minute and up to and including 17 minutes at 160° C.