Radiation-curing binders and a process for their preparation

• US 8,980,970 B2
• Filed: 09/01/2005
• Issued: 03/17/2015
• Est. Priority Date: 09/09/2004
• Status: Active Grant

• Current Assignee: Allnex Netherlands B.V. (Allnex (Luxembourg) & Cy SCA)
• Original Assignee: Allnex IP SARL
• Inventors: Weikard, Jan, Greszta-Franz, Dorota, Fischer, Wolfgang, Schmitz, Jrg, Mundstock, Holger, Detrembleur, Christophe
• Primary Examiner(s): SERGENT, RABON A
• Application Number:
  US11/217,725
• Publication Number:
  US 20060052527A1
• Time in Patent Office: 3,484 Days
• Field of Search: 528/49, 528/75, 528/73, 528/45, 528/55, 528/76, 252/182.18, 252/182.2, 427/508, 522/90, 522/96, 522/97, 522/174, 564/44, 564/45, 564/46, 525/455, 525/457, 525/460
• US Class Current: 522/97
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/7837 containing allophanate groups
• CPC Class Codes: C08G 18/798 containing urethdione groups
• CPC Class Codes: C08G 18/8009 with compounds of C08G18/3203
• CPC Class Codes: C08G 18/8166 with unsaturated monofunctional alcohols or amines
• CPC Class Codes: C09D 175/14 Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds

Abstract

The invention relates to a process for preparing binders which contain 1) allophanate groups, 2) groups that react with ethylenically unsaturated compounds with polymerization on exposure to actinic radiation (radiation-curing groups) and 3) optionally NCO-reactive groups, by reacting at temperatures ≦130° C.

• A) one or more NCO-functional compounds containing uretdione groups with
• B) one or more compounds that contain isocyanate-reactive groups and groups that react with ethylenically unsaturated compounds with polymerization on exposure to actinic radiation (radiation-curing groups), and then
• C) with one or more saturated, hydroxyl-containing compounds other than B), at least one of these compounds having an OH functionality of ≧2, in the presence of
• D) a catalyst containing one or more zinc compounds,
  the reaction with compounds C) taking place at least proportionally with the formation of allophanate groups.

The present invention also relates to the binders obtained by the process of the invention.

Claims

1. A process for preparing a binder containing allophanate groups comprising the steps ofreacting

A) one or more NCO-functional compounds containing uretdione groups with

B) one or more compounds that contain isocyanate-reactive groups, uretdione-reactive groups, and contain groups that react with ethylenically unsaturated compounds with polymerization on exposure to actinic radiation , and

performing a uretdione ring-opening reaction between the product of step 1 with

C) one or more saturated, hydroxyl-containing compounds other than B), at least one of these compounds having an OH functionality of ≧

2, in the presence of

D) a catalyst containing one or more zinc compounds, wherein the process is performed at temperatures of from 20 to 100°

C. and wherein the sum of NCO groups and uretdione groups of A exceeds the sum of NCO-reactive groups and uretdione-reactive groups present in B.

2. The process of claim 1 wherein said compounds containing uretdione groups are prepared from hexamethylene diisocyanate.

3. The process of claim 1 wherein component B) comprises a member selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene oxide mono(meth)acrylate, polypropylene oxide mono(meth)acrylate and the reaction product of acrylic acid with glycidyl methacrylate.

4. The process of claim 2 wherein component B) comprises a member selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene oxide mono(meth)acrylate, polypropylene oxide mono(meth)acrylate and the reaction product of acrylic acid with glycidyl methacrylate.

5. The process of claim 1 wherein component C) comprises a member selected from the group consisting of monomeric dials, monomeric trials, polyethers and polyacetones derived therefrom having a number average molecular weight of below 1000 g/mol.

6. The process of claim 1 wherein component D) consists essentially of zinc compounds.

7. The process of claim 1 wherein component D) comprises zinc acetylacetonate and/or zinc ethylhexanoate.

8. The process of claim 2 wherein component D) comprises zinc acetylacetonate and/or zinc ethylhexanoate.

9. The process of claim 3 wherein component D) comprises zinc acetylacetonate and/or zinc ethylhexanoate.

10. The process of claim 4 wherein component D) comprises zinc acetylacetonate and/or zinc ethylhexanoate.

11. An allophanate group-containing binder prepared by a process comprisingreacting

A) one or more NCO-functional compounds containing uretdione groups with

B) one or more compounds that contain isocyanate-reactive groups, uretdione-reactive groups, and contain groups that react with ethylenically unsaturated compounds with polymerization on exposure to actinic radiation, and

performing a uretdione ring-opening reaction between the product of step 1 with

C) one or more saturated, hydroxyl-containing compounds other than B), at least one of these compounds having an OH functionality of ≧

2, the presence of

D) a catalyst containing one or more zinc compounds, wherein the process is performed at temperatures of from 20 to 100°

C. and wherein the sum of NCO groups and uretdione groups of A exceeds the sum of NCO-reactive groups and uretdione-reactive groups present in B.

12. The binder of claim 11 wherein said compounds containing uretdione groups are prepared from hexamethylene diisocyanate.

13. The binder of claim 11 wherein component B) comprises a member selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene oxide mono(meth)acrylate, polypropylene oxide mono(meth)acrylate and the reaction product of acrylic acid with glycidyl methacrylate.

14. The binder of claim 12 wherein component B) comprises a member selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene oxide mono(meth)acrylate, polypropylene oxide mono(meth)acrylate and the reaction product of acrylic acid with glycidyl methacrylate.

15. The binder of claim 11 wherein component C) comprises a member selected from the group consisting of monomeric diols, monomeric triols, polyethers and polyacetones derived therefrom having a number average molecular weight of below 1000 g/mol.

16. The binder of claim 12 wherein component C) comprises a member selected from the group consisting of monomeric diols, monomeric triols, polyethers and polyacetones derived therefrom having a number average molecular weight of below 1000 g/mol.

17. The binder of claim 14 wherein component C) comprises a member selected from the group consisting of monomeric diols, monomeric triols, polyethers and polyacetones derived therefrom having a number average molecular weight of below 1000 g/mol.

18. A coating composition comprising

a) one or more of the binders of claim 11,

b) optionally one or more polyisocyanates which contain free or blocked isocyanate groups and optionally contain groups which react with ethylenically unsaturated compounds with polymerization on exposure to actinic radiation,

c) optionally compounds other than a) which contain groups which react with ethylenically unsaturated compounds with polymerization on exposure to actinic radiation and optionally contain NCO-reactive groups,

d) optionally one or more isocyanate-reactive compounds which are free from groups which react with ethylenically unsaturated compounds with polymerization on exposure to actinic radiation, and

e) one or more initiators.

19. A substrate coated with a coating obtained from the radiation-curing binder containing allophanate groups of claim 11.