Fluorinated coating and phototools made therewith

1. An oligomer comprising the reaction product of an epoxy silane, a multifunctional (meth)acrylate, and a polymerizable fluorochemical; wherein the multifunctional (meth)acrylate is selected from the groups (a)-(e):

(a) di(meth)acryl containing compounds selected from 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol monoacrylate monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic diacrylate, alkoxylated cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone modified neopentylglycol hydroxypivalate diacrylate, caprolactone modified neopentylglycol hydroxypivalate diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, hydroxypivalaldehyde modified trimethylolpropane diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tricyclodecanedimethanol diacrylate, triethylene glycol diacrylate, and tripropylene glycol diacrylate;

(b) tri(meth)acryl containing compounds selected from glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated triacrylates, propoxylated triacrylates, trimethylolpropane triacrylate, and tris(2-hydroxyethyl)isocyanurate triacrylate;

(c) higher functionality (meth)acryl containing compounds selected from ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate, and caprolactone modified dipentaerythritol hexaacrylate;

(d) oligomeric (meth)acryl compounds selected from urethane acrylates, polyester acrylates and epoxy acrylates; and

(e) nanoparticles that have been surface-modified with (meth)acrylate groups.

2. The oligomer of claim 1 , wherein the polymerizable fluorochemical comprises an epoxy group.

3. The oligomer of claim 1 , wherein the polymerizable fluorochemical comprises a hydrolysable silane group.

4. The oligomer of claim 1 , wherein the polymerizable fluorochemical comprises a fluorinated (meth)acrylate.

5. The oligomer of claim 1 , wherein the polymerizable fluorochemical comprises the reaction product of a fluorinated (meth)acrylate and an epoxy (meth)acrylate.

6. The oligomer of claim 1 , wherein the polymerizable fluorochemical comprises the reaction product of a fluorinated (meth)acrylate and a silane (meth)acrylate.

7. The oligomer of claim 1 , wherein the polymerizable fluorochemical comprises the reaction product of a fluorinated (meth)acrylate, an epoxy (meth)acrylate, and a silane (meth)acrylate.

8. The oligomer of claim 1 , wherein the polymerizable fluorochemical comprises a polymerizable fluorinated urethane.

9. The oligomer of claim 8 , wherein the polymerizable fluorinated urethane comprises hydrolysable silane groups.

10. The oligomer of claim 1 , wherein the epoxy silane is gamma-glycidoxypropyl trimethoxysilane or beta-(3,4-epoxycyclohexyl)ethyl trimethoxysilane.

11. A composition comprising the reaction product of:

(a) an epoxy (meth)acrylate and/or a silane (meth)acrylate; and

(b) the oligomer of claim 1 .

12. The composition of claim 11 , further comprising a multifunctional epoxide.

13. The composition of claim 12 , wherein the multifunctional epoxide is: bis-(3,4-epoxycyclohexylmethyl) adipate; 1,4-cyclohexanedimethanol diglycidyl ether; or glycerol propoxylate triglycidyl ether.

14. The composition of claim 11 , wherein:

the epoxy silane comprises from about 5 to about 90 wt. %;

the multifunctional (meth)acrylate comprises from about 5 to about 90 wt. %; and

the polymerizable fluorochemical comprises from about 5 to about 60 wt. %;

all relative to the total weight of the oligomer.

15. The composition of claim 11 , further comprising a curable silane represented by the formula:

Si(R 6 ) d (R 7 ) 4-c

wherein:

R 6 comprises an alkyl, aryl, arylalkylenyl or alkylarylenyl group;

R 7 comprises a halide, hydroxyl, aryloxy, acyloxy or polyalkyleneoxy group;

and d is 0, 1 or 2.

16. The composition of claim 15 , further comprising a multifunctional epoxide.

17. The composition of claim 11 , further comprising tetraethyl orthosilicate.

18. The composition of claim 11 , further comprising a radical photoinitiator and a photoacid generator.

19. An article comprising a coating disposed on a substrate, the coating having a thickness of from about 0.5 to about 40 um And comprising the composition of claim 11 .

20. The article of claim 19 , wherein the substrate comprises an optically clear substrate that provides an image and the article is a phototool.

21. An assembly comprising:

the phototool of claim 20 ;

a photoresist disposed on the coating; and

a metal substrate disposed on the photoresist opposite the coating.

22. The assembly of claim 21 , wherein the photoresist comprises a photosensitive emulsion.