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Title:
COATING COMPOSITIONS CONTAINING SUBSTITUTED AND UNSUBSTITUTED EXOMETHYLENE LACTONE OR LACTAM MONOMERS
Document Type and Number:
WIPO Patent Application WO/2001/064793
Kind Code:
A2
Abstract:
This invention is directed to a coating composition used for original equipment manufacturing or refinishing uses in the automotive industry, which coating composition utilizes an acrylic polymer which contains substituted or unsubstituted exomethylene lactones or lactams as a comonomer.

Inventors:
BRANDENBURG CHARLES
KING RANDAL
OIEN LARRY G
UHLIANUK PETER WILLIAM
Application Number:
PCT/US2001/005902
Publication Date:
September 07, 2001
Filing Date:
February 22, 2001
Export Citation:
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Assignee:
DU PONT (US)
International Classes:
C08F218/08; C08J7/04; C08F220/10; C08F224/00; C08F226/00; C08F226/06; C08F291/00; C09D4/00; C09D4/02; C09D133/06; C09D133/14; C09D137/00; C09D161/28; C09D167/04; C09D167/07; C09D175/04; C09D177/02; C09D183/04; (IPC1-7): C09D/
Domestic Patent References:
WO2000035960A22000-06-22
Foreign References:
DE19501182A11996-07-18
Attorney, Agent or Firm:
Benjamin, Steven C. (DE, US)
Download PDF:
Claims:
CLAIMS What is claimed is :
1. A coating composition comprising : (a) a polymer comprising at least one exomethylene lactone or lactam monomer of the structure : where X= O or NR7, n=0, 1 or 2 and R1, R2, R3, R4, R5, R6, R7 are independently selected from the group (I) consisting of H,CH (O),CN and halogen, and from the group (II) consisting ofC (O) OR9,C (O) NR10R1 1, CR12 (O),C (O) OC (O) RI3,C (O) NR14COR15,OC (O) RI6,OR17,NR18RI9 alkyl, substituted alkyl, aryl and substituted aryl ; wherein when RI, R2, R3, R4, R5, R6, R7 are selected from group (II), they may optionally form a cyclic structure with one another ; R9, R10, R11, R12, R13, R14, R15, R16, R17, R18 and R19 are H, alkyl, aryl, substituted alkyl or substituted aryl ; Rl7 is alkyl, aryl, substituted alkyl or substituted aryl ; and wherein the alkyl and substituted alkyl are ClCl2 ; and (b) at least one other copolymeirizable monomer.
2. A coating composition according to Claim 1 wherein the at least one exomethylene lactone or lactam monomer of step (a) is an amethyleney butyrolactone monomer of the structure wherein RI, R2, R5 and R6 are each independently selected from the group (I) consisting of H,CH (O),CN and halogen, and from the group (II) consisting of C (O) OR9,C (O) NR'OR'',CR'2 (0),C (0) OC (O) RI3,C (O) NR14COR15, OC (O) R 16,OR 17,NR I 8R 19 alkyl, substituted alkyl, aryl and substituted aryl ; wherein when Rl and R2 are selected from group (II), Rl and R2 may optionally form a cyclic structure ; R9, RIO, RI 1, R12, R13, R14, R15, R16, R18 and R19 are H, alkyl, aryl, substituted alkyl or substituted aryl ; R 17 is alkyl, aryl, substituted alkyl or substituted aryl ; and wherein the alkyl and substituted alkyl are ClCl2.
3. The coating composition of Claim 2 wherein the at least one exomethylene lactone or lactam monomer is unsubstututed amethyleney butyrolactone.
4. A coating composition according to Claim 1 wherein said at least one other copolymerizable monomer of step (b) is a methacrylate monomer.
5. A coating composition according to Claim 4 wherein said methacrylate monomer is selected from the group consisting of : methyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl hexyl methacrylate and mixtures thereof, and a hydroxy alkylmethacrylate or acrylate each having 14 carbon atoms in the alkyl group wherein the polymer has a number average molecular weight of about 1, 000 to about 100, 000 determined by gel permeation chromotography.
6. A coating composition according to Claim 5 wherein the polymer has a number average molecular weight of about 2, 000 to about 30, 000.
7. A coating composition according to Claim 5 wherein the polymer has a number average molecular weight of about 3, 000 to about 10, 000.
8. An acrylic polymer comprising : (a) substituted or unsubstituted exomethylene lactone or lactam ; (b) a first methacrylate monomer ; (c) a second methacrylate monomer ; and (d) a hydroxy alkyl methacrylate or acrylate monomer having 14 carbon atoms in the alkyl group.
9. An acrylic polymer of Claim 8 optionally comprising polymerized monomers of styrene.
10. The acrylic polymer of Claim 8 or 9 wherein the exomethylene lactone or lactam of step (b) has the structure : wherein R', R, R and R6 are each independently selected from the group (1) consisting of H,CH (O),CN and halogen, and from the group (II) consisting of C (O) OR9,C (O) NR'OR",CR'2 (0),C (0) OC (O) RI3,C (O) NR14COR15, OC (O) R 16,OR 17,NR I 8R 19 alkyl, substituted alkyl, aryl and substituted aryl ; wherein when R1 and R2 are selected from group (II), Rl and R2 may optionally form a cyclic structure ; R9, RIO, RI t, R12, Rl3, Rl4, Rl5, R16, Rl8 and Rls are H, alkyl, aryl, substituted alkyl or substituted aryl ; R17 is alkyl, aryl, substituted alkyl or substituted aryl ; and wherein the alkyl and substituted alkyl are ClCl2.
11. The acrylic polymer of Claim 8 or 9 wherein the first methacrylate monomer is selected from the group consisting of methyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate and mixtures thereof.
12. The acrylic polymer of Claim 8 or 9 wherein the second methacrylate monomer is selected from the group consisting of methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl hexyl methacrylate and mixtures thereof.
13. The acrylic polymer of Claim 8 or 9 wherein the hydroxy alkyl methacrylate or acrylate monomer is selected from the group consisting of hydroxy ethyl methacrylate, hydroxy propyl methacrylate, hydroxy butyl methacrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy butyl acrylate and mixtures thereof.
14. The acrylic polymer of Claim 9 containing about 035% by weight styrene, 835% by weight of amethyleneybutyrolactone, 3060% by weight of one or more methacrylates or acrylates and 1035% by weight of the hydroxy alkyl methacrylate, wherein the percentages of all components equals 100%.
15. The acrylic polymer of Claim 9 containing about 025% by weight styrene, 1035% by weight of amethyleneybutyrolactone, 3060% by weight of isobutyl methacrylate in combination with butyl acrylate and 1030% by weight hydroxy propyl methacrylate, wherein the percentages of all components equals 100%.
16. The acrylic polymer of Claim 9 containing about 035% by weight styrene, 1030% by weight of amethyleneybutyrolactone, 2060% by weight of isobornyl methacrylate, in combination with butyl acrylate and 1035% by weight hydroxy ethyl methacrylate, wherein the percentages of all components equals 100%.
17. A coating composition having a film forming binder solids content of about 3070% by weight and an organic liquid carrier, wherein the binder contains about : (a) 5080% by weight, based on the weight of the binder, of an acrylic polymer comprising : (i) at least one exomethylene lactone or lactam monomer of the structure : where X= O or NR7, n=0, 1 or 2 and R1, R2, R3, R4, R5, R6, R7 are independently selected from the group (I) consisting of H,CH (O),CN and halogen, and from the group (II) consisting ofC (O) OR9,C (O) NR'ORl 1, CR12 (O),C (O) OC (O) R13, C (O) NR14COR15,OC (O) R16,oRI 7NR18Rl 9 alkyl, substituted alkyl, aryl and substituted aryl ; wherein when R 1, R2, R3, R4, R5, R6, R7 are selected from group (II), they may optionally form a cyclic structure with one another ; R9, R10, R11, R12, R13, R14, R15, R16, R17, R18 and R 19 are H, alkyl, aryl, substituted alkyl or substituted aryl ; R 17 is alkyl, aryl, substituted alkyl or substituted aryl ; and wherein the alkyl and substituted alkyl are Clcl2 ; (ii) at least one methacrylate monomer selected from the group consisting of methyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl hexyl methacrylate and mixtures thereof ; and (iii) at least one hydroxy alkylmethacrylate or acrylate monomer each having 14 carbon atoms in the alkyl group wherein the polymer has a number average molecular weight of about 1, 000100, 000 determined by gel permeation chromotography ; and (b) 120% by weight, based on the weight of the binder, of a polyol component ; and (c) 1049% by weight, based on the weight of the binder, of a crosslinking agent selected from the group consisting of an organic polyisocyanate, a melamine formaldehyde resin and a silane or mixtures thereof.
18. A coating composition of Claim 17 wherein the polymer has a number average molecular weight of about 2, 00030, 000 determined by gel permeation chromatography.
19. A coating composition of Claim 17 wherein the polymer has a number average molecular weight of about 3, 00010, 000 determined by gel permeation chromatography.
20. A coating composition of Claim 17 wherein the polymer has a calculated Tg of at least 40°C.
21. A coating composition according to Claim 17 wherein the at least one exomethylene lactone or lactam monomer of step (a) (i) is an amethyleney butyrolactone monomer of the structure wherein Rl, R2, R5 and R6 are each independently selected from the group (I) consisting of H,CH (O),CN and halogen, and from the group (II) consisting of C(O)OR9, C(O)NR10R11, CR12(O),C(O)OC(O)R13,C(O)NR14COR15, OC (O) R16,OR1,NR18Rl9 alkyl, substituted alkyl, aryl and substituted aryl ; wherein when RI and R2 are selected from group (II), RI and R2 may optionally form a cyclic structure ; R9, RIO, Rl l, R12 Rl3 Rl4, Rl5, Rl6 R18 and Rl9 are H, alkyl, aryl, substituted alkyl or substituted aryl ; Ri is alkyl, aryl, substituted alkyl or substituted aryl ; and wherein the alkyl and substituted alkyl are ClCl2.
22. A coating composition according to Claim 17 wherein the polyol component of step (b) has the structure : Q [RIO (COCH2CH2cH2CH20) n] mH wherein : RI is a covalent bond or alkylene containing 1, 2, 3 or 4 carbon atoms ; n is about 1 to about 4 ; m is 2, 3 or 4 ; and Q is a saturated carbocyclic ring containing 5 or 6 carbon atoms, or SR2T wherein S and T are each independently saturated carbocyclic rings containing 5 or 6 carbon atoms, and R2 is a covalent bond or an alkylene group containing 1, 2, 3 or 4 carbon atoms ; provided that no more than one R I is bound to any carbocyclic carbon atom, and further provided that when Q is SR2T, each Ru ils bound to a carbon atom of the carbocyclic rings of S and T.
23. A coating composition according to Claim 17 wherein the crosslinking agent is an organic polyisocyanate comprising aliphatic polyisocyanate having an average of 2 to 6 isocyanate functionalities.
24. A coating composition according to Claim 23 wherein the organic polyisocyanate is selected from the group consisting of aliphatic isocyanates, cycloaliphatic isocyanates aromatic isocyanates, trifunctional isocyanates and isocyanate functional adducts of a polyol and a diisocyanate.
25. A coating composition according to Claim 24 wherein the organic polyisocyanate is selected from the group consisting of the biuret of hexamethylene diisocyanate, the isocyanurate of hexamethylene diisocyanate, the biuret of isophorone diisocyanate, and isophorone diisocyanate.
26. A coating composition of any of Claims 1720 additionally comprising polymerized monomers of styrene.
27. A coating composition of Claim 2 or 21 wherein the amethyleney butyrolactone monomer is amethyleneybutyrolactone.
28. A method for enhancing the mar resistance of a coating composition comprising an acrylic polymer, said polymer having at least one styrene monomer and at least one methacylate monomer comprising ; replacing all or a portion of said styrene monomer with an amethyleneybutyrolactone monomer of the structure wherein Rl, R2, R5 and R6 are each independently selected from the group (I) consisting of H,CH (O),CN and halogen, and from the group (II) consisting of C (O) OR9,C (O) NR10R11, CR12(O), C(O)OC(O)R13, C(O)NR14COR15, OC (O) Rl6,oRl7,NRt8Rl9 alkyl, substituted alkyl, aryl and substituted aryl ; wherein when Rl and R2 are selected from group (II), RUZ and R2 may optionally form a cyclic structure ; R9, R10, R11, R12 R13, R14, R15, R16, R18 and R19 are H, alkyl, aryl, substituted alkyl or substituted aryl ; Rl7 is alkyl, aryl, substituted alkyl or substituted aryl ; and wherein the alkyl and substituted alkyl are ClCl2, wherein said mar resistance of the coating composition is enhanced.
29. A method for enhancing the mar resistance of a coating composition comprising an acrylic polymer, said polymer having at least one styrene monomer and at least one methacrylate monomer comprising ; replacing all or a portion of said methacrylate monomer with an amethyleneybutyrolactone monomer of the structure wherein Rl, R2, R5 and R6 are each independently selected from the group (I) consisting of H,CH (O),CN and halogen, and from the group (II) consisting of C (O) OR9,C (O) NRl °Rl l,CRl2 (O),C (O) OC (O) RI3,C (O) NR14COR15, OC (O) R16, OR17, NR18R19 alkyl, substituted alkyl, aryl and substituted aryl ; wherein when RI and R2 are selected from group (II), RI and R2 may optionally form a cyclic structure ; R9, RIO, R11, R12, R13, R14, R15, R16, R18 and R19 are H, alkyl, aryl, substituted alkyl or substituted aryl ; R17 is alkyl, aryl, substituted alkyl or substituted aryl ; and wherein the alkyl and substituted alkyl are ClCl2, wherein said mar resistance of the coating composition is enhanced.
30. An article comprising a substrate selected from the group consisting of metal, plastic, wood, or rubber coated with the hardened coating composition of Claim 17.