Interpenetrating dual cure resin compositions

• US 4,128,600 A
• Filed: 01/14/1977
• Issued: 12/05/1978
• Est. Priority Date: 01/14/1977
• Status: Expired due to Term

• Current Assignee: General Mills Chemicals, Inc. (Henkel AG & Co KGaA)
• Original Assignee: General Mills Chemicals, Inc. (Henkel AG & Co KGaA)
• Inventors: Emeott, Marvin, Jevne, Allan, Skinner, Earl
• Primary Examiner(s): Michl, Paul R.
• Application Number:
  US05/759,311
• Time in Patent Office: 690 Days
• Field of Search: 260/77.5 CR, 260/859 R, 260/885, 204/159.16, 204/159.19
• US Class Current: 525/123
• CPC Class Codes: C08G 18/6229 Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• 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 18/638 characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
• 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: C08L 57/00 Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08L 75/04 Polyurethanes
• 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. An interpenetrating radiation-sensitive resin composition comprising:

(a) from about 40% to about 90% by weight of a saturated polyol which is a hydroxy functional acrylic copolymer of;

(1) methyl methacrylate;

(2) butyl acrylate, and

(3) hydroxyethyl acrylate and,

(b) from about 10% to about 60% by weight of a reactive diluent having a radiation sensitive pi bond and having a boiling point greater than that of benzene, and mixtures thereof said reactive diluent being a fully substituted polyacrylate or polymethacrylate of a polyfunctional alcohol.

2. The composition of claim 1 wherein the reactive diluent is selected from the group consisting of diol diacrylates, triol triacrylates, and tetrol tetraacrylates and mixtures thereof.

3. The composition of claim 2 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.

4. The composition of claim 3 wherein the reactive diluent is 1,6-hexane diol diacrylate at from about 20% to about 50% by weight and from about 50% to about 80% by weight of a hydroxyfunctional copolymer of:

(a) methyl methacrylate,

(b) butyl acrylate, and

(c) hydroxyethyl acrylate in a molar ratio of a;

b;

c of from about 4;

1;

1 to about 1;

4;

3.

5. An interpenetrating urethane-linking, radiation-sensitive resin composition comprising:

(a) from about 40% to about 90% by weight of a saturated polyol which is a hydroxy functional acrylic copolymer of;

(1) methyl methacrylate;

(2) butyl acrylate, and

(3) hydroxyethyl acrylate and,

(b) from about 10% to about 60% by weight of a reactive diluent selected from the group consisting of the fully substituted polyacrylates and polymethacrylates of poly-functional alcohols, 2-ethylhexylacrylate, isodecylacrylate, diallyl maleate, styrene, divinylbenzene, vinyl acetate, and N-vinyl-2-pyrrolidone, and mixtures thereof; and

,

(c) from about 80% to about 120% on a hydroxylisocyanate equivalent basis of a polyisocyanate.

6. The composition of claim 5 wherein the sum of the polyisocyanate functionality and hydroxy functionality is greater than four.

7. The composition of claim 5 wherein the reactive diluent is 1,6-hexane diol diacrylate.

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

1 to about 1;

4.

9. The composition of claim 8 wherein the polyisocyanate is present at from about 95% to 105% on a hydroxyl-isocyanate equivalent basis.

10. The composition of claim 9 wherein the polyisocyanate is selected from the group consisting of diisocyanates and triisocyanates and mixtures thereof.

11. The composition of claim 10 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 adduct of hexamethylene diisocyanate and water,

(f) trimethyl hexamethylene diisocyanate,

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

and mixtures thereof.

12. The composition of claim 5 wherein the weight ratio of (a) plus (c) to (b) is from about 80:

20 to about 20;

80.