Process for the preparation of radiation curable compositions

Patent metadata

Field	Value
Publication number	US-9708515-B2
Application number	US-201214119269-A
Country	US
Kind code	B2
Filing date	Jul 6, 2012
Priority date	Jul 19, 2011
Publication date	Jul 18, 2017
Grant date	Jul 18, 2017

Abstract

The present invention relates to a process for the preparation of a radiation curable composition comprising at least one (meth)acrylic copolymer A and at least one radiation curable compound B, said process comprising a first copolymerization step, and a subsequent ring opening step.

First claim

The invention claimed is:

1. Process for the preparation of a radiation curable composition comprising at least one (meth)acrylic copolymer A and at least one radiation curable compound B, said process comprising:
(a) in a first copolymerization step, the preparation of a (meth)acrylic copolymer in the presence of at least one non-copolymerizable cyclic compound (b1) containing at least one

 group in the cycle where X═O or NH, by copolymerization of a monomer mixture M comprising:
(i) from 40 to 95 wt % of at least one (meth)acrylic monomer (a1),
(ii) from 5 to 60 wt % of at least one other copolymerizable monomer (a2) different from (meth)acrylic monomer (a1),
with the proviso that said monomers (a1) and (a2) contain no functional group that can react with the cyclic compound (b1) during copolymerization,
(iii) optionally from 0 to 20 wt % of at least one copolymerizable monomer (a3) containing at least one functional group that can react with the cyclic compound (b1),
(iv) optionally from 0 to 5 wt % of at least one copolymerizable monomer (a4) containing at least one cyclic anhydride,

(b) in a subsequent ring opening step, the preparation of the radiation curable compound B by the ring opening of the cyclic compound (b1) with at least one radiation curable compound (a5) that contains at least one hydroxyl, carboxylic acid, amine, or thiol functional group,
wherein the percentages by weight are herein relative to the total weight of the monomer mixture M and the composition after radiation curing is a viscoelastic material which remains permanently tacky.

2. Process according to claim 1 wherein the cyclic compound (b1) is a lactone or a mixture of lactones.

3. Process according to claim 1 wherein the (meth)acrylic monomer (a1) is selected from alkyl(meth)acrylates whose homopolymers have a Tg of at most −30° C.

4. Process according to claim 1 wherein the (meth)acrylic monomer (a1) is selected from butylacrylate, iso-octylacrylate, 2-ethyl hexylacrylate and mixtures thereof.

5. Process according to claim 1 wherein the copolymerizable monomer (a2) is selected from monomers whose homopolymers have a Tg of more than −30° C.

6. Process according to claim 1 wherein the copolymerizable monomer (a2) is selected from methyl(meth)acrylate, ethyl(meth)acrylate, tertbutyl(meth)acrylate, vinyl acetate, styrene and mixtures thereof.

7. Process according to claim 1 wherein the copolymerizable monomer (a3) is selected from hydroxyalkyl(meth)acrylates, the ethoxylated and/or propoxylated derivatives thereof, the adducts thereof with lactones, polyalkoxy monohydroxy mono(meth)acrylates, (meth)acrylic acid, β-carboxyethyl(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and mixtures of any of them.

8. Process according to claim 1 wherein the copolymerizable monomer (a4) is selected from maleic anhydride, itaconic anhydride, 4-methacryloyloxyethyl trimellitate anhydride and mixtures thereof.

9. Process according to claim 1 wherein in the copolymerization step:
(i) from 5 to 60 wt % of cyclic compound (b1), and
(ii) from 40 to 95 wt % of the monomer mixture M

are used, the wt % are herein relative to the total weight of cyclic compound (b1) and monomer mixture M.

10. Process according to claim 1 wherein the radiation curable compound (a5) is selected from hydroxyalkyl(meth)acrylates, the ethoxylated and/or propoxylated derivatives thereof, the adducts thereof with lactones, polyalkoxy monohydroxy (meth)acrylates, (meth)acrylic acid, β-carboxyethyl(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and mixtures of any of them.

11. Process according to claim 1 wherein the equivalent ratio of cyclic compound (b 1) to functional groups of radiation curable compound (a5) is from 1:1 to 6:1.

12. Process according to claim 1 wherein
the monomer mixture M of step (a) comprises:
(i) from 40 to 94.5 wt % of (meth)acrylic monomer (a1),
(ii) from 5 to 59.5 wt % of copolymerizable monomer (a2),
(iii) from 0.5 to 20 wt % of copolymerizable monomer (a3),
(iv) optionally from 0 to 5 wt % of copolymerizable monomer (a4),

in order to prepare a (meth)acrylic copolymer comprising functional groups originating from copolymerizable monomer (a3) that can react with the cyclic compound (b1),
and where the process further comprises a grafting step (c) wherein at least part of said functional groups are reacted with a part of the cyclic compound (b1).

13. Process according to claim 12 wherein the equivalent ratio of cyclic compound (b1) to the sum of the functional groups of copolymerizable monomer (a3) and radiation curable compound (a5) is from 1:1 to 6:1.

14. Process according to claim 12 wherein the grafting step (c) is conducted after the copolymerization step (a).

15. Process according to claim 1 wherein the monomer mixture M of step (a) comprises:
(i) from 40 to 94.5 wt % of monomer (a1),
(ii) from 5 to 59.5 wt % of copolymerizable monomer (a2),
(iii) optionally from 0 to 20 wt % of copolymerizable monomer (a3),
(iv) from 0.5 to 5 wt % of copolymerizable monomer (a4),
in order to prepare a (meth)acrylic copolymer comprising cyclic anhydride groups originating from copolymerizable monomer (a4),
and where the process comprises an adduct formation step (d) wherein at least part of the cyclic anhydride groups is reacted with at least one radiation curable compound (a6).

16. Process according to claim 15 wherein the radiation curable compound (a6) is selected from hydroxyalkyl(meth)acrylates, the ethoxylated and/or propoxylated derivatives thereof, the adducts thereof with lactones, polyalkoxy monohydroxy (meth)acrylates.

17. Process according to claim 15 wherein the equivalent ratio of functional groups of radiation curable compound (a6) to cyclic anhydride groups of monomer (a4) is from 0.5:1 to 2:1.

18. Process according to claim 1 wherein the process further comprises a capping step (e) wherein a functional end group W that is formed by the ring opening of the cyclic compound (b1) at the ring opening step (b), or both at the ring opening step (b) and grafting step (c), is capped with at least one capping compound containing at least one functional group Y capable of reacting with the functional end group W.

19. Process according to claim 18 wherein the functional end group W is a hydroxyl or a primary amine and wherein the capping compound is a mono-, a di- or a polyisocyanate.

20. Process according to claim 1 wherein the process comprises an adduct formation step (d) and a capping step (e).

21. The process according to claim 1 , further comprising including a tackifier in said composition.

Assignees

• Clark Graham
• Van Holen Jurgen
• Henkel Ag & Co Kgaa

Inventors

• Clark Graham
• Van Holen Jurgen

Classifications

• C08F220/28

  containing no aromatic rings in the alcohol moiety · CPC title

• C09J151/003 Primary

  grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09J151/04, C09J151/06 take precedence) · CPC title

• C09J133/14

  of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen · CPC title

• C08F265/06 Primary

  Polymerisation of acrylate or methacrylate esters on to polymers thereof · CPC title

• C09J151/00

  Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds (based on ABS polymers C09J155/02); Adhesives based on derivatives of such polymers · CPC title