Cationic UV-crosslinkable acrylic polymers for pressure sensitive adhesives
View Patent ↗An ultraviolet (UV) crosslinkable acrylic pressure sensitive adhesive comprises an acrylic copolymer and a cationic photoinitiator. The acrylic copolymer comprises pendant reactive functional groups. The pressure sensitive adhesive formed from the acrylic copolymer with the pendant reactive functional groups result in high green strength and/or high temperature holding strength of the adhesive.
1. An ultra-violet curable pressure sensitive adhesive comprising an acrylic polymer and a cationic photoinitiator, wherein said acrylic polymer is prepared from the group consisting of:
(i) an acrylic monomer consisting of an acrylic or methacrylic acid derivative of the formula CH 2 ═CH(R 1 )(COOR 2 ), wherein R 1 is H or CH 3 and R 2 is C 1-20 alkyl chain;
(ii) a monomer,
wherein said monomer comprises a pendant reactive functional group selected from cycloaliphatic epoxide, oxetane or mixtures thereof, and contains from about 0.001 to about 0.015 equivalent per 100 g of said acrylic polymer;
wherein the acrylic polymer (a) is essentially free of multi-(meth)acrylate, (b) has a Tg value less than 0° C., and (c) has a weight average molecular weight from about 50,000 to about 1,000,000 g/mol; and
wherein the ultra-violet curable pressure sensitive adhesive has a viscosity range of 1,000-500,000 mPa·s at 80-180° C.
2. The ultra-violet curable pressure sensitive adhesive of claim 1 wherein the (ii) monomer contain from about 0.002 to about 0.010 equivalent per 100 g of the acrylic polymer.
3. The ultra-violet curable pressure sensitive adhesive of claim 1 wherein the (ii) monomer is a cycloaliphatic epoxide having the formula:
wherein
R 1 is O, S, C═O, or linear, branched, or cyclic alkylene, or oxyalkylene, arylene,
R 2 is linear, branched, and cyclic alkyl or alkoxy, aryl, H, halogen, C═O, or part of R 1 as fused cycloaliphatic ring through a covalent bond connection,
R 3 is (CH 2 ) n , n=0-3,
X is acrylate or methacrylate, or comprises a —W—Y group, where
W is O, S, amide, carbonate, urethane, urea, siloxane or a combination thereof, and
Y is —R 4 —C(R 5 )═CH 2 , where R 4 is a linear or branched C 2-10 alkylene, C 2-10 oxyalkylene, C═O, or arylene or derivative thereof, and R 5 is H or CH 3 .
4. The ultra-violet curable pressure sensitive adhesive of claim 1 wherein the cycloaliphatic epoxide has the formula:
where R 1 ═H or CH 3 ,
or mixtures thereof.
5. The ultra-violet curable pressure sensitive adhesive of claim 4 wherein the cycloaliphatic epoxide is:
or mixtures thereof.
6. An ultra-violet curable pressure sensitive adhesive comprising an acrylic polymer and a cationic photoinitiator, wherein said acrylic polymer is prepared from:
(i) an acrylic monomer consisting of an acrylic or methacrylic acid derivative of the formula CH 2 ═CH(R 1 )(COOR 2 ), wherein R 1 is H or CH 3 and R 2 is C 1-20 alkyl chain;
(ii) a monomer,
wherein said monomer comprises a pendant reactive functional group that is present from about 0.001 to about 0.015 equivalent per 100 g of said acrylic polymer;
wherein the acrylic polymer (a) is essentially free of multi-(meth)acrylate, (b) has a Tg value less than 0° C., and (c) has a weight average molecular weight from about 50,000 to about 1,000,000 g/mol; and
wherein the pendant reactive functional group is a benzophenone having the formula:
where
Z is S, O, CH 2 , or NH,
R 1-8 are independently H, Cl, Br, I, F, C 1-24 alkoxy, C 1-24 alkyl, or aryl; and wherein at least one of R 1-8 must comprise a —W—X—Y group, where
W is a C 1-12 alkylene or C 1-12 oxyalkylene,
X is carbonate, urethane, urea, tetramethyldisiloxane or a combination thereof, and
Y is —R 9 —C(R 10 )═CH 2 , where R 9 is a linear or branched C 2-10 alkylene or C 2-10 oxyalkylene, or arylene or derivative thereof, and R 10 is H or CH 3 .
7. The ultra-violet curable pressure sensitive adhesive of claim 6 wherein the benzophenone has the formula:
or mixtures thereof.
8. The ultra-violet curable pressure sensitive adhesive of claim 1 , wherein the cationic photoinitiator has the structure of
where R is C 3 H 7 , C 12 H 25 , W is S, SO, SO 2 or CO.
9. The adhesive of claim 8 wherein the cationic photoinitiator is:
where R 1 and R 2 are independently H, CH 3 , C 2 H 5 , C 3 H 7 , C 12 H 25 , OCH 3 , OC 2 H 5 , OC 3 H 7 , or OC 12 H 25 .
10. The ultra-violet curable pressure sensitive adhesive of claim 1 further comprising a polyethylene copolymer additive.
11. The ultra-violet curable pressure sensitive adhesive of claim 10 , wherein the adhesive has a solvent content of less than about 2% by weight of the total adhesive.
12. An article of manufacture comprising the adhesive of claim 11 .
13. An ultra-violet curable pressure sensitive adhesive comprising an acrylic polymer and a cationic photoinitiator, wherein said acrylic polymer comprises:
(i) an acrylic monomer consisting of an acrylic or methacrylic acid derivative of the formula CH 2 ═CH(R 1 )(COOR 2 ), wherein R 1 is H or CH 3 and R 2 is C 1-20 alkyl chain;
(ii) a monomer, wherein the monomer comprises a plurality of pendant reactive functional groups selected from
(1) mono-substituted oxirane, and
(2) cycloaliphatic epoxide, oxetane, benzophenone or mixtures thereof, and
wherein said monomer contains from about 0.001 to about 0.015 equivalent per 100 g of said acrylic polymer;
wherein said acrylic polymer (a) is essentially free of multi-(meth)acrylate (b) has a Tg value less than 0° C., and (c) has a weight average molecular weight from about 50,000 to about 1,000,000 g/mol; and
wherein the pendant reactive functional group comprises a benzophenone having the formula:
where
Z is S, O, CH 2 , or NH,
R 1-8 are independently H, Cl, Br, I, F, C 1-24 alkoxy, C 1-24 alkyl, or aryl; and wherein at least one of R 1-8 must comprise a —W—X—Y group, where
W is a C 1-12 alkylene or C 1-12 oxyalkylene,
X is carbonate, urethane, urea, tetramethyldisiloxane or a combination thereof, and
Y is —R 9 —C(R 10 )═CH 2 , where R 9 is a linear or branched C 2-10 alkylene or C 2-10 oxyalkylene, or arylene or derivative thereof, and R 10 is H or CH 3 .
14. The ultra-violet curable pressure sensitive adhesive of claim 13 wherein the benzophenone has the formula:
or mixtures thereof.
15. The ultra-violet curable pressure sensitive adhesive of claim 13 , wherein the pendant reactive functional group comprises a mono-substituted oxirane having the formula:
where R 1 ═H or CH 3
or mixtures thereof.
16. The ultra-violet curable pressure sensitive adhesive of claim 13 , wherein the cationic photoinitiator has the structure of
where R is C 3 H 7 , C 12 H 25 , W is S, SO, SO 2 or CO.
17. The adhesive of claim 16 wherein the cationic photoinitiator is:
where R 1 and R 2 are independently H, CH 3 , C 2 H 5 , C 3 H 7 , C 12 H 25 , OCH 3 , OC 2 H 5 , OC 3 H 7 , or OC 12 H 25 .
18. The ultra-violet curable pressure sensitive adhesive of claim 13 further comprising a polyethylene copolymer additive.
19. The ultra-violet curable pressure sensitive adhesive of claim 18 , wherein the adhesive has a solvent content of less than about 2% by weight of the total adhesive.
20. An article of manufacture comprising the adhesive of claim 13 .
21. The adhesive of claim 6 , wherein the cationic photoinitiator has the structure of
where R is C 3 H 7 , C 12 H 25 , W is S, SO, SO 2 or CO.
22. The adhesive of claim 21 wherein the cationic photoinitiator is:
where R 1 and R 2 are independently H, CH 3 , C 2 H 5 , C 3 H 7 , C 12 H 25 , OCH 3 , OC 2 H 5 , OC 3 H 7 , or OC 12 H 25 .
23. The ultra-violet curable pressure sensitive adhesive of claim 6 further comprising a polyethylene copolymer additive.