Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems
First Claim
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1. A heat-curable epoxy resin composition free of cure-effective amounts of an amine, carboxylic anhydride, or carboxylic acid in the acid form, comprising:
- (a) at least one polyepoxide;
(b) from about 0.1 to about 50 parts of a metal carboxylate salt curing agent per hundred parts by weight of total epoxy resin, said metal carboxylate salt being selected from a Group IA or Group IIA metal and being derived from a carboxylic acid containing from 1 to 4 carboxyl groups, wherein said metal carboxylate salt is substantially soluble in said epoxy resin composition at a cure temperature of above about 100°
C.; and
(c) from about 1 to about 100 parts of a cure modifier per hundred parts by weight of total epoxy resin, said cure modifier containing polar functionality, being soluble in said epoxy resin composition at said cure temperature and having sufficient solvating strength as to increase the solubility of said metal carboxylate salt in said epoxy resin to curing effective levels at said cure temperature.
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Abstract
Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems provide exceptional latency, particularly at elevated temperature, as well as facile curing, high Tg and adhesive strength, and other attractive properties. The metal carboxylates comprise alkali metals and alkaline earth metals, aromatic and aliphatic metal carboxylates. The preferred curing systems comprise synergistic combinations of the metal carboxylates with cure modifiers.
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Citations
51 Claims
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1. A heat-curable epoxy resin composition free of cure-effective amounts of an amine, carboxylic anhydride, or carboxylic acid in the acid form, comprising:
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(a) at least one polyepoxide; (b) from about 0.1 to about 50 parts of a metal carboxylate salt curing agent per hundred parts by weight of total epoxy resin, said metal carboxylate salt being selected from a Group IA or Group IIA metal and being derived from a carboxylic acid containing from 1 to 4 carboxyl groups, wherein said metal carboxylate salt is substantially soluble in said epoxy resin composition at a cure temperature of above about 100°
C.; and(c) from about 1 to about 100 parts of a cure modifier per hundred parts by weight of total epoxy resin, said cure modifier containing polar functionality, being soluble in said epoxy resin composition at said cure temperature and having sufficient solvating strength as to increase the solubility of said metal carboxylate salt in said epoxy resin to curing effective levels at said cure temperature. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50)
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33. A composition as in claim 32 wherein said amide-alcohol is selected from one wherein in said structural formula R2 is the group --CR3 R4 --CR5 R6 --, and R3, R4, R5 and R6 may be the same or different, and may represent hydrogen, alkyl, or hydroxyalkyl groups.
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34. A composition as in claim 32 wherein said amide-alcohol is selected from one wherein in said structural formula R2 is selected from --CH2 CH2 --, --C(CH3)2 CH2 --, --C(CH2 CH3)(CH2 OH)CH2 --, --C(CH2 OH)2 CH2 --, --CH(CH2 CH3)CH2 --, --CH2 CH(CH3)--, --CH2 CH(CH2 CH3)--, --CH2 CH2 CH2 --, --CH2 CH2 CH2 CH2 --.
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35. A composition as in claim 32 wherein said amide-alcohol is selected from one wherein said structural formula
R1 =1,2-substituted-benzene, R2 =--CH2 CH2 --, m=1, and n=2; -
R1 =1,2-substituted-benzene, R2 =--C(CH3)2 CH2 --, m=1, and n=2; R1 =1,3-Substituted-benzene, R2 =--CH2 CH2 --, m=1, and n=2; R1 =1,3-substituted-benzene, R2 =--C(CH3)2 CH2 --, m=1, and n=2; R1 =1,4-substituted-benzene, R2 =--CH2 CH2 --, m=1, and n=2; R1 =1,4-substituted-benzene, R2 =--C(CH3)2 CH2 --, m=1, and n=2; R1 =phenyl, R2 =--CH2 CH2 --, m=1, and n=1; R1 =phenyl, R2 =--C(CH3)2 CH2 --, m=1, and n=1; R1 =--CH2 CH2 CH2 CH2 --, R2 =--CH2 CH2 --, m=0, and n=2; R1 =1,3-substituted-benzene, R2 =--CH2 CH2 --, m=0, and n=1;
orR1 =phenyl, R2 =--CH2 CH2 --, m=0, and n=1.
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37. A composition as in claim 31 wherein said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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38. A composition as in claim 33 wherein said amide-alcohol is present in an amount of from about 1 to about 50 parts per hundred parts by weight of total epoxy resin, said metal carboxylate salt is selected from sodium benzoate, sodium acetate or calcium benzoate present in an amount of from about 1 to about 10 parts per hundred parts by weight of total epoxy resin, and said epoxy resin is selected from bisphenol A based epoxy resins or their brominated derivatives, epoxy novolacs, triglycidyl p-aminophenol, or tetraglycidyl methylenedianiline.
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39. A composition as in claim 35 wherein said amide-alcohol is present in an amount of from about 1 to about 20 parts per hundred parts by weight of total epoxy resin, said metal carboxylate salt is selected from sodium benzoate, sodium acetate or calcium benzoate present in an amount of from about 2 to about 8 parts per hundred parts by weight of total epoxy resin, and said epoxy resin is selected from bisphenol A based epoxy resins or their brominated derivatives.
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40. A composition as in claim 17 wherein said cure modifier contains phenolic functionality, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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41. A composition as in claim 29 wherein said cure modifier is present in an amount of from about 1 to about 50 parts per hundred parts by weight of total epoxy resin, said metal carboxylate salt is selected from sodium benzoate, sodium acetate, or calcium benzoate and is present in an amount of from about 1 to about 10 parts per hundred parts by weight of total epoxy resin, and said epoxy resin is selected from bisphenol A based epoxy resins or their brominated derivatives, epoxy novolacs, triglycidyl p-aminophenol, or tetraglycidyl methylenedianiline.
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42. A composition as in claim 17 wherein said cure modifier contains imide functionality, said metal carboxylate salt is selected from a Grou pIA alkali metal salt or clacium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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43. A composition as in claim 27 wherein said cure modifier is present in an amount of from about 1 to about 50 parts per hundred parts by weight of total epoxy resin, said metal carboxylate salt comprises sodium benzoate, sodium acetate, or calcium benzoate present in an amount of from about 1 to about 10 parts per hundred parts by weight of total epoxy resin, and said epoxy resin is selected from bisphenol A based epoxy resins or their brominated derivatives, epoxy novolacs, triglycidyl p-aminophenol, or tetraglycidyl methylenedianiline.
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44. A composition as in claim 17 wherein said alcohol is monofunctional or difunctional and is selected from a benzyl, primary, or secondary alcohol, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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45. A composition as in claim 17 wherein said cure modifier is selected from an amide or a sulfonamide, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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46. A composition as in claim 16 wherein said cure modifier is selected from a quaternary ammonium or a phosphonium compound, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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47. A composition as in claim 16 wherein said cure modifier contains ether functionality, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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48. A composition as in claim 16 wherein said cure modifier contains cyanate ester functionality, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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49. A composition as in claim 16 wherein said cure modifier is selected from a sulfone or a sulfoxide, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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50. A composition as in claim 16 wherein said cure modifier contains lactone functionality, said metal carboxylate salt is selected from a Group IA alkali metal salt or calcium salt and is derived from a carboxylic acid containing 1 carboxyl group, and said epoxy resin comprises a glycidyl resin.
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15. A composition as in claim said cure modifier is present in an amount of from about 1 to about 20 parts per hundred parts by weight of total epoxy resin.
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36. A composition as in claim 53 wherein said cyanate ester is selected from the poly-cyanate esters of bisphenol A, tetramethylbisphenol F, thiodiphenol, hexafluorobisphenol A, bisphenol E, dicyclopentadienephenol condensates or their partially trimerized blends.
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51. A process for curing a heat-curable epoxy resin composition that is free of cure-effective amounts of an amine, carboxylic anhydride, or carboxylic acid in the acid form, comprising mixing together
(a) at least one polyepoxide; -
(b) from about 0.1 to about 50 parts of a metal carboxylate salt curing agent per hundred parts by weight of total epoxy resin, said metal carboxylate salt being selected from a Group IA or Group IIA metal and being derived from a carboxylic acid containing from 1 to 4 carboxyl groups, wherein said metal carboxylate salt is substantially soluble in said epoxy resin composition at the cure temperature of said composition; and (c) from about 1 to about 100 parts of a cure modifier per hundred parts by weight of total epoxy resin, said cure modifier containing polar functionality, being soluble in said epoxy resin composition at said cure temperature and having sufficient solvating strength as to increase the solubility of said metal carboxylate salt in said epoxy resin to curing effective levels at said cure temperature; and
heating said composition to a curing temperature of at least about 100°
C.
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Specification