Method for preparing a printing form from a photopolymerizable element
View Patent ↗The invention provides a method for preparing a printing form from a photopolymerizable element. The photopolymerizable element includes a layer of a photopolymerizable composition containing an elastomeric block copolymer of polystyrene and polybutadiene having less than 15% by weight of 1,2-coupled bond segments in the polybutadiene block, an ethylenically unsaturated compound, and a photoinitiator. The method includes imagewise exposing the photopolymerizable element to actinic radiation in the presence of atmospheric oxygen; heating the element to a temperature sufficient to cause a portion of the layer to liquefy; and contacting an exterior surface of the photopolymerizable element with a development medium to allow at least a portion of the liquefied layer to be removed by the development medium.
1. A method for preparing a printing form from a photopolymerizable element comprising:
a) providing a photopolymerizable element comprising a layer of a photopolymerizable composition comprising at least one elastomeric block copolymer having one or more non-elastomeric blocks and one or more elastomeric blocks of polybutadiene having 1,2-coupled units, an ethylenically unsaturated compound and a photoinitiator, wherein the photopolymerizable composition layer is capable of being partially liquefied, and wherein the photopolymerizable element further comprises an actinic radiation opaque layer disposed thereon forming an in-situ mask on the element;
b) imagewise exposing the photopolymerizable element through the in-situ mask to actinic radiation in the presence of atmospheric oxygen;
c) heating the element of b) to a temperature sufficient to cause a portion of the layer to liquefy; and
d) contacting an exterior surface of the photopolymerizable element with a development medium to allow at least a portion of the liquefied layer to be removed by the development medium;
wherein the 1,2-coupled butadiene units comprise less than 15% by weight of the one or more polybutadiene blocks, and the elastomeric block copolymer is at least 30% by weight, based on the total weight of the photopolymerizable composition,
wherein the photopolymerizable composition further comprises a plasticizer, wherein the plasticizer is selected only from liquid polythene plasticizers having a vinyl content of not less than 60% by weight of the polydiene, and
wherein the printing form resulting from the method has a textured printing surface.
2. The method of claim 1 wherein the 1,2-coupled butadiene units is 5 to 10% by weight of the one or more polybutadiene blocks.
3. The method of claim 1 wherein the elastomeric block copolymer has a molecular weight between 80,000 and 200,000.
4. The method of claim 1 wherein the elastomeric block copolymer has a styrene content of 15 to 35% by weight, based on the block copolymer.
5. The method of claim 1 wherein the elastomeric block copolymer comprises a mixture of a tri-block copolymer of polystyrene-polybutadiene-polystyrene, and a di-block copolymer of polystyrene-polybutadiene, wherein the di-block copolymer is less than 20% by weight based on the weight of the elastomeric binder.
6. The method of claim 1 wherein the elastomeric block copolymer is 30 to 80% by weight, based on the total weight of the composition.
7. The method of claim 1 wherein the photopolymerizable composition further comprises an additional block copolymer that is selected from the group consisting of a block copolymer of styrene and butadiene, and a block copolymer of styrene and isoprene.
8. The method of claim 7 wherein the additional block copolymer is from 5 to 30 weight % of the composition.
9. The method of claim 1 wherein the plasticizer is from 1 to 30% by weight of the photopolymerizable composition.
10. The method of claim 1 wherein the elastomeric block copolymer is a styrene-butadiene-styrene tri-block copolymer having less than 1% by weight of styrene-butadiene di-block based on the weight of the elastomeric block copolymer; 22 to 26% by weight of styrene based on the weight of the elastomeric block copolymer; less than 10% by weight of 1,2-coupled butadiene units based on the one or more polybutadiene blocks; and a molecular weight of about 100,000 to 150,000 g/mol.
11. The method of claim 1 wherein after step d) the photopolymerizable element has a relief surface, the method further comprising post-exposing the photopolymerizable element by overall exposing the relief surface to the actinic radiation.
12. The method of claim 1 wherein after step d) the photopolymerizable element has a relief surface, the method further comprising exposing the relief surface of the photopolymerizable element to radiation of between 200 and 300 nm.
13. The method of claim 1 , wherein the elastomeric block copolymer is from 40% to 75% by weight of the photopolymerizable composition.
14. The method of claim 13 , wherein the plasticizer is selected only from liquid polydiene plasticizers having a vinyl content of not less than 60% by weight of the polydiene and a molecular weight less than 5000, and the total amount of plasticizer in the photopolymerizable composition is 1 to 25% by weight, based on the total weight of the photopolymerizable composition.
15. The method of claim 1 , wherein the photopolymerizable composition contains one or more of said liquid polydiene plasticizers having a vinyl content of not less than 60% by weight of the polydiene, at least one of which is liquid 1,2-polybutadiene oil having a vinyl content of not less than 85% by weight.
16. The method of claim 1 . wherein the plasticizer is selected only from liquid polydiene plasticizers having a vinyl content of not less than 60% by weight of the polydiene and a molecular weight less than 5,000.