Interpenetrating dual cure resin compositions

• US 4,342,793 A
• Filed: 09/29/1980
• Issued: 08/03/1982
• Est. Priority Date: 01/14/1977
• Status: Expired due to Term

• Current Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Original Assignee: Henkel Corporation (Henkel AG & Co KGaA)
• Inventors: Emeott, Marvin, Jevne, Allan, Skinner, Earl
• Primary Examiner(s): Michl, Paul R.
• Application Number:
  US06/191,802
• Time in Patent Office: 673 Days
• Field of Search: 528/75, 525/123, 525/131, 204/159.16, 204/159.19, 427/44
• US Class Current: 427/493
• CPC Class Codes: C08G 18/62 Polymers of compounds having carbon-to-carbon double bonds
• CPC Class Codes: C08G 18/637 characterised by the in situ polymerisation of the compounds having carbon-to-carbon double bonds in a reaction mixture of saturated polymers and isocyanates
• CPC Class Codes: C08G 2270/00 Compositions for creating interpenetrating networks
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C09D 175/04 Polyurethanes

Abstract

Curable resin compositions are prepared containing a radiation-sensitive reactive diluent and a saturated polyol. Curing is accomplished by mixing the reactive diluent and the polyol with a polyisocyanate, followed by exposure of the resultant composition to radiation to polymerize the reactive diluent and then, by thermal curing, to form the hydroxyisocyanate (urethane) linkage. The fully cured resin composition is described as interpenetrated or one in which there is no cross-linking between the reactive diluent and urethane linked co-polymer. The interpenetrated resin compositions form tough and hard coatings on various substrates.

Claims

1. A method for forming an interpenetrated urethane linked coating composition on a substrate involving the steps of radiation and thermal curing by:

(a) preparing a mixture containing;

(1) from about 40 percent to about 90 percent by weight of a saturated polyol; and

(2) from about 10 percent to about 60 percent by weight of a reactive diluent having a radiation sensitive pi bond and a boiling point greater than benzene and mixtures thereof; and

(3) from about 80 percent to about 120 percent on a hydroxyl-isocyanate equivalent basis of a polyisocyanate;

(b) applying the mixture to a substrate subjecting the coating so formed to sufficient radiation to polymerize the reactive diluent thereby partially curing the coating; and

(c) then exposing the partially cured coating of (b) to sufficient thermal energy to form the urethane link,

thereby forming the interpenetrated cured coating on the substrate.

2. The method of claim 1 wherein the sum of isocyanate functionality is greater than four.

3. The method of claim 2 wherein the saturated polyol is a hydroxy functional copolymer of (a) methyl methacrylate, (b) butyl acrylate, and (c) hydroxyethyl acrylate.

4. The method of claim 3 wherein the polyisocyanate is a di- or trifunctional isocyanate.

5. The method of claim 4 wherein the polyisocyanate is selected from the group consisting of:

(a) toluene diisocyanate;

(b) xylene diisocyanate;

(c) isophorone diisocyanate;

(d) hexamethylene diisocyanate;

(e) the triisocyanate condensation product of hexamethylene diisocyanate and water;

(f) trimethyl hexamethylene diisocyanate; and

,

(g) aliphatic diisocyanates having from 12 to 40 carbon atoms in the aliphatic moiety, and,

mixtures thereof.

6. The method of claim 1 wherein the reactive diluent is 1,6-hexanediol diacrylate.

7. The method of claim 6 wherein the reactive diluent is a mixture of 1,6-hexanediol diacrylate and N-vinyl-2-pyrrolidone in a respective weight ratio of from about 4:

1 to about 1;

4.

8. The method of claim 7 wherein the radiation is ultraviolet.

9. The method of claim 8 wherein a free radical initiator is present.

10. The method of claim 8 wherein the thermal energy is applied at a temperature range of from about 0 degrees to about 300 degrees C.

11. The method of claim 7 wherein the radiation is electron beam.

12. The method of claim 1 wherein the reactive diluent is selected from the group consisting of:

(a) 1,6-hexane diol diacrylate;

(b) ethylene glycol diacrylate;

(c) trimethylol propane triacrylate;

(d) triethylene glycol diacrylate;

(e) neopentyl diol diacrylate; and

(f) pentaerythritol tetraacrylate,

and mixtures thereof.