Radiant energy curable polyester resin composition

• US 6,037,385 A
• Filed: 11/07/1997
• Issued: 03/14/2000
• Est. Priority Date: 04/10/1996
• Status: Expired due to Fees

• Current Assignee: HEHR International Incorporated (LCI Industries)
• Original Assignee: HEHR International Incorporated (LCI Industries)
• Inventors: Smith, Stuart B.
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US08/965,713
• Time in Patent Office: 858 Days
• Field of Search: 522/107, 522/93, 522/137, 522/81, 522/174, 522/168, 522/179, 525/36, 525/38, 525/39
• US Class Current: 522/93
• CPC Class Codes: C08F 283/006 on to polymers provided for in C08G18/00 C08F283/004 takes precedence
• CPC Class Codes: C08F 283/01 on to unsaturated polyesters C08F283/004 takes precedence
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3821 Carboxylic acids; Esters thereof with monohydroxyl compounds
• CPC Class Codes: C08G 18/4615 containing nitrogen
• CPC Class Codes: C08G 18/50 having heteroatoms other than oxygen
• CPC Class Codes: C08G 18/5024 containing primary and/or secondary amino groups
• CPC Class Codes: C08G 18/6705 Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
• CPC Class Codes: C08G 18/673 containing two or more acrylate or alkylacrylate ester groups
• CPC Class Codes: C08G 18/678 containing nitrogen
• CPC Class Codes: C08G 18/68 Unsaturated polyesters
• CPC Class Codes: C08G 18/765 alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08G 18/797 containing carbodiimide and/or uretone-imine groups
• CPC Class Codes: C08G 2115/06 to carbodiimide or uretone-imine groups
• CPC Class Codes: C08L 67/06 Unsaturated polyesters
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 75/14 Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y10T 428/2933 Coated or with bond, impregnation or core

Abstract

An acrylic urethane prepolymer composition and an unsaturated polyester resin composition to which the prepolymer has been added. The prepolymer composition includes an acrylic urethane prepolymer prepared by the reaction of diisocyanate, such as MDI, with an hydroxyl-containing acrylate monomer, such as a pentaerythritol triacrylate. The prepolymer composition contains a styrene monomer and an inhibitor, such as benzoquinone, to retard the reaction of the prepolymer and styrene monomer prior to the addition of the prepolymer composition into the polyester resin composition and a photoinitiator to promote the polymerization of the resin by exposure to radiant energy. The employment of the urethane prepolymer composition provides for the reduction in the amount of styrene monomer used in the unsaturated resin composition and also provides for improved chemical and physical properties of the photocured, unsaturated resin composition.

Claims

1. A liquid, photo radiation curable, unsaturated, polyester resin composition of improved physical and chemical properties, which composition comprises:

a) an unsaturated polyester resin containing ethylenic unsaturation and prepared by the reaction of a dicarboxylic acid and a dihydroxy alcohol;

b) a styrene monomer in an amount of less than about 40% by weight of the composition;

c) a liquid acrylic-urethane prepolymer as a diluent additive, the prepolymer prepared by the reaction of the NCO groups of a polyisocyanate or a polyisocyanate prepolymer in a stoichiometric or slight excess amount with a hydroxy-functional polyacrylate monomer;

d) an inhibitor in an amount to retard the premature reaction of the prepolymer and the styrene monomer;

e) a photoinitiator in an amount to promote the radiation polymerization of the unsaturated resin composition on exposure to radiation.

2. The composition of claim 1 wherein the photoinitiator is present in an amount of from 0.01 to 5.0 weight percent of the composition.

3. The composition of claim 1 wherein the photoinitator promotes radiant polymerization of the composition on exposure to radiant energy in the range of about 250 to 450 nanometers.

4. The composition of claim 1 which includes a peroxide catalyst in an amount to promote the curing of the styrene monomer, the polyester resin, and the acrylic-urethane prepolymer.

5. The composition of claim 4 wherein the peroxide catalyst is in an amount of about 0.1% to 2.5% by weight of the composition.

6. The composition of claim 4 which includes a metal salt promoter in a cure promoting amount to provide an exothermic curing reaction.

7. The composition of claim 6 which includes an amino or amide accelerator in an amount to accelerate the curing reaction.

8. The composition of claim 1 wherein the prepolymer comprises from about 5% to 30% by weight of the composition.

9. The composition of claim 1 wherein the styrene monomer comprises less than about 30% by weight of the composition.

10. The composition of claim 1 wherein the inhibitor comprises a quinone compound.

11. The composition of claim 1 wherein the hydroxyl-functional polyacrylate monomer comprises a tri, tetra or penta acrylate monomer.

12. The composition of claim 1 wherein the acrylate monomer comprises a pentaerythritol polyacrylate.

13. The composition of claim 1 wherein the acrylate monomer comprises an hydroxyl-functional ethyoxylated or propoxylated polyacrylate monomer.

14. The composition of claim 1 wherein the diisocyanate comprises methylene di-para-phenylene isocyanate or a methylene di-para-phenylene isocyanate urethane prepolymer.

15. The composition of claim 1 which includes glass fiber or particulate filler material.

16. The composition of claim 1 wherein the composition is characterized by a sprayable liquid viscosity and includes up to 30% by weight of the composition of glass fibers to prepare a fiber glass polyester resin cured laminate.

17. The composition of claim 16 characterized by a cure time and roll-out time of less than about five minutes.

18. The cured polyester resin composition of claim 16.

19. The composition of claim 1 wherein the peroxide catalyst comprises a methyl ethyl ketone and includes a metal fatty acid promoter, and the acrylate monomer comprises a pentaerythritol triacrylate, and the diisocyanate comprises methylene di-p-phenylene isocyanate (MDI).

20. The composition of claim 1 which includes a wetting agent in a flow-modifying amount to reduce deformations in the subsequently cured polyester resin composition surface.

21. The composition of claim 1 which includes up to about 15% by weight of a particulate flame-retardant material.

22. The composition of claim 1 which includes about 1% to 10% by weight of a light-reflective material.

23. The composition of claim 1 which includes about 0.01 % to 5% by weight of fumed silica as a viscosity-modifying agent.

24. The cured polyester resin composition of claim 1.

25. A liquid, photo radiation curable, unsaturated, polyester resin composition which comprises:

a) an unsaturated polyester resin containing ethylenic unsaturation and prepared by the reaction of a dicarboxylic acid and a dihydroxy alcohol;

b) a styrene monomer in an amount of from 5% to about 40% by weight of the composition;

c) from about 5% to 30% by weight of the composition as a diluent additive of a liquid acrylic-urethane prepolymer prepared by the reaction of the NCO groups of methylene di-para-phenylene isocyanate or methylene di-paraphenylene isocyanate prepolymer, with a pentaerythritol polyacrylate;

d) an inhibitor in an amount to retard the premature reaction of the prepolymer and the styrene monomer;

e) a photoinitiator in an amount to promote the radiation polymerization of the unsaturated resin composition on exposure to radiation.

26. The radiation-cured polyester resin composition of claim 25 which contains glass fibers.

27. The composition of claim 25 which includes a peroxide-curing catalyst.

28. The composition of claim 25 wherein the unsaturated polyester resin is prepared by the reaction of a neopentyl glycol and ortho or iso phthalic acid-maleic anhydride.