Granted Patent B2

US 8,808,968 · App. 13/591,375 · Granted Aug 19, 2014

Abstract

Claims (45)

1. A method of producing a relief image printing element from a photocurable printing blank, the method comprising the steps of:

a) providing a photocurable printing blank, the photocurable printing blank comprising:

i) a backing or support layer;

ii) at least one photocurable layer disposed on the backing or support layer, wherein the at least one photocurable layer comprises:

1) a binder;

2) one or more monomers;

3) a photoinitiator; and

4) an additive selected from the group consisting of (i) a phosphite selected from the group consisting of tris(nonylphenyl)phosphite, diphenyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris(tridecyl)phosphite, trilauryl phosphite, disteraryl pentaerythriol diphosphite, diisodecyl phenyl phosphite, diphenyl isodecyl phosphite, diphenyl octyl phosphite, diphenyl isooctyl phosphite, diphenyl tri isodecyl monophenyl dipropyleneglycol diphosphite, alkyl bisphenol A phosphite, tetraphenyl dipropyleneglycol diphosphite, poly(dipropyleneglycol) phenyl phosphite, tris(dipropylene glycol) phosphite, and dioleyl hydrogen phosphite and combinations of one or more of the foregoing, (ii) thioether amine compounds, and (iii) combinations of one or more of the foregoing;

iii) a laser ablatable mask layer disposed on the at least one photocurable layer, the laser ablatable mask layer comprising a radiation opaque material;

b) selectively laser ablating the laser ablatable mask laser to create an in situ negative of a desired image in the laser ablatable mask layer;

c) exposing the at least one photocurable layer to actinic radiation through the in situ negative to selectively crosslink and cure portions of the at least one photocurable layer; and

d) developing the exposed at least one photocurable layer of the photocurable printing blank to reveal the relief image therein, said relief image comprising a plurality of relief printing dots,

wherein the presence of the additive in the at least one photocurable layer enhances surface cure of the at least one photocurable layer without requiring a high intensity UV light source, an inert gas chamber or a laminated membrane.

2. The method according to claim 1 , wherein the additive comprises tris(nonylphenyl)phosphite.

3. The method according to claim 1 , wherein the additive is a thioether amine compound selected from the group consisting of 2,6-di-tert-butyl-4-(4,6- bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 4-[[4,6-bis(nonylsulfanyl)-1,3,5-triazin-2-yl ] amino]-2,6-ditert-butylphenol, 4-[[4,6-bis(octadecylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-ditert -butylphenol, 4-[[4,6-octylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-bis(2-methylnonan-2-yl)phenol, 4-[[4,6-bis(hexylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-ditert-butylphenol, 4-[[4,6-bis(heptylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-ditert-butylphenol, 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]-2-tert-butyl-6-methylphenol, 4-[[4,6-bis(ethylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-ditert-butylphenol, 4-[[4,6-bis(2,4,4-trimethylpentan-2-ylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-ditert-butylphenol, 4-[[4,6-bis(2-octylsulfanylethylsulfanyl) -1,3 ,5-triazin-2-yl]amino]-2,6-ditert-butylphenol, 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-dibutylphenol, 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-dimethylphenol, 2,6-ditert-butyl-4-[[4-(3,5-ditert-butyl-4-hydroxyanilino)-6-octylsulfanyl-1,3,5-triazin-2-yl]amino]phenol, 4-[[4,6-bis(pentylsulfanyl)-1,3,5-triazin-2-yl]amino-2,6-dimethylphenol, 4-[[4,6-bis(hexylsulfanyl)-1,3,5-triazin-2-yl]amino]-2-tert -butylphenol, 2,6-ditert-butyl-4-[(4-octylsulfanyl-1,3,5-triazin-2-yl)amino]phenol, 4-[[4,6-bis(ethylsulfanyl)-1,3,5-triazin-2-yl]amino]-2,6-dimethylphenol, 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]-butylamino]-2,6-ditert-butylphenol, 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]-cyclohexylamino]-2,6-ditert-butylphenol, 2-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl]amino]-6-tert-butylphenol, 2-tert-butyl-6-methyl-4-[[4-octylsulfanyl-6-[(2,2,6,6,-tetramethylpiperidin -4-yl)amino]-1,3,5-triazin-2-yl ]amino]phenol, 4-[[4,6-bis(octylsulfanylmethyl)-1,3,5-triazin-2-yl)amino]-2,6-ditert-butylphenol, 4-[[4,6-bis(octylsulfanyl)-1,3,5-triazin-2-yl)methylamino]-2,6-ditert-butylphenol, 4-[(4-amino-6-chloro-1,3,5-triazin-2-yl)amino]-2,6-ditert -butylphenol, and 4-[(4-cyclohexyl-6-cyclohexylsulfanyl-1,3,5-triazin-2-yl)amino]-2,6-di(propan-2-yl)phenol.

4. The method according to claim 3 , wherein the additive comprises 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol.

5. The method according to claim 1 , wherein the at least one photocurable layer comprises an antioxidant selected from the group consisting of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, butylated hydroxytoluene, alkylated phenols, alkylated bis-phenols, polymerized trimethyldihydroquinone, dilauryl thiopropionate, and combinations of one or more of the foregoing.

6. The method according to claim 5 , wherein the antioxidant comprises 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyebenzene.

7. The method according to claim 1 , wherein the at least one photocurable layer further comprises one or more materials selected from the group consisting of plasticizers, antiozonants, fillers, reinforcing agents, thermal polymerization inhibitors, UV absorbers and combinations of one or more of the foregoing.

8. The method according to claim 7 , wherein the one or more materials comprise a plasticizer.

9. The method according to claim 1 , wherein the relief image printing element has a Shore A hardness of between about 45 and about 70.

10. The method according to claim 9 , wherein the relief image printing element has a Shore A hardness of between about 50 and about 65.

11. The method according to claim 1 , wherein the edge sharpness of the relief printing dots, defined as the ratio of the radius of curvature r e at the intersection of a shoulder and the top of the relief printing dot to the width of the dot's top printing surface p is less than about 5%.

12. The method according to claim 11 , wherein the ratio of r e :p is less than about 2%.

13. The method according to claim 1 , wherein the planarity of the top surface of the relief printing dots, measured as the radius of curvature across the top surface of the relief printing dots and the radius of curvature across the top surface of the relief printing dots, is greater than the thickness of the at least one photocurable layer.

14. The method according to claim 1 , wherein an average shoulder angle, measured as the angle between a shoulder of the dot across the width of the dot's top or printing surface, is less than about 30°.

15. The method according to claim 14 , wherein an average shoulder angle, measured as the angle between a shoulder of the dot across the width of the dot's top or printing surface, is less than about 20°.

16. The method according to claim 1 , wherein the exposed at least one photocurable layer is developed using solvent development.

17. The method according to claim 1 , wherein the exposed at least one photocurable layer is developed using thermal development.

18. A method of producing a relief image printing element from a photocurable printing blank, the method comprising the steps of:

a) providing a photocurable printing blank, the photocurable printing blank comprising:

i) a backing or support layer;

ii) at least one photocurable layer disposed on the backing or support layer, wherein the at least one photocurable layer comprises:

1) a binder;

2) one or more monomers;

3) a photoinitiator;

4) an additive selected from the group consisting of phosphites, phosphines, thioether amine compounds, and combinations of one or more of the foregoing; and

5) an antioxidant selected from the group consisting of 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)benzene, alkylated phenols, alkylated bis-phenols, polymerized trimethyldihydroquinone, dilauryl thiopropionate, and combinations of one or more of the foregoing;

iii) a laser ablatable mask layer disposed on the at least one photocurable layer, the laser ablatable mask layer comprising a radiation opaque material;

b) selectively laser ablating the laser ablatable mask laser to create an in situ negative of a desired image in the laser ablatable mask layer;

c) exposing the at least one photocurable layer to actinic radiation through the in situ negative to selectively crosslink and cure portions of the at least one photocurable layer; and

d) developing the exposed at least one photocurable layer of the photocurable printing blank to reveal the relief image therein, said relief image comprising a plurality of relief printing dots,

wherein an edge sharpness of the relief printing dots, defined as the ratio of the radius of curvature r e at the intersection of a shoulder and the top of the relief printing dot to the width of the dot's top printing surface p is less than about 5%;

wherein the presence of the additive in the at least one photocurable layer enhances surface cure of the at least one photocurable layer without requiring a high intensity UV light source, an inert gas chamber or a laminated membrane.

19. The method according to claim 18 , wherein the additive is a phosphine selected from the group consisting of triphenyl phosphine, tri-p-tolylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylpropylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dipropylphenylphosphine, divinylphenylphosphine, divinyl-p-methoxyphenylphosphine, divinyl-p-bromophenylphosphine, divinyl-p-tolylphosphine, diallylphenylphosphine, divinyl-p-bromophenylphosphine, and diallyl-p-tolylphosphine and combinations of one or more of the foregoing.

Assignments (10)