Curable compositions containing an epoxy resin, a difunctional phenol and a polyfunctional phenol

Claim 2

A compositon which comprises (A) at least one aromatic based epoxy resin having an average number of epoxide groups per molecule of more than 2; and (B) a phenolic hydroxyl-containing component consisting essentially of a mixture of (1) at least one phenolic hydroxyl-containing compound having an average of not more than 2 phenolic hydroxyl groups per molecule; and (2) at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; (C) optionally, at least one ketone solvent as the only solvent for components (A) and (B); and (D) optionally, one or more stabilizers; and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.75:1 to about 1.5:1; component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.1:1 to about 0.65:1; (C) is present in an amount of from about zero to about 75 weight percent based upon the combined weight of components (A), (B), (C) and (D); and component (D) is present in an amount of from about zero to about 1 percent by weight based upon the weight of component (A).

Claim 3

A composition of claim 1 wherein (a) component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.2:1 to about 0.6:1; (b) components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.85:1 to about 1:4:1; and (c) component (C) is present in an amount of from about 5 to about 50 percent by weight based upon the combined weight of components (A), (B), (C) and (D); and (d) component (D) is present in an amount of from about 0.05 to about 1 percent by weight based upon the weight of component (A).

Claim 4

A composition of claim 2 wherein (a) component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.3:1 to about 0.55:1; (b) components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group from about 0.9:1 to about 1.3:1; (c) component (C) is present in an amount of from about 10 to about 25 percent by weight based upon the combined weight of components (A), (B), (C) and (D); and (d) component (D) is present in an amount of from about 0.1 to about 0.8 percent by weight based upon the weight of component (A).

Claim 5

A composition of claim 1, 2 or 3 wherein (a) component A is an epoxy resin represented by the following formulas I or II or a combination of such epoxy resins ##STR4## wherein each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is as defined above; each R' is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; m has a value from about 0.1 to about 7; and m' has a value from zero to about 3; (b) component (B-1) is a phenolic hydroxyl-containing compound represented by the following formulas III or IV or a combination of such phenolic hydroxyl-containing compounds ##STR5## wherein each A, is independently a divalent hydrocarbyl or a halogen substituted divalent hydrocarbyl group having from 1 to about 12, preferably from 1 to about 6, carbon atoms, --O--, --S--, --S--S--, --SO--, --SO 2 --, or --CO--; each X is independently hydrogen, an alkyl or an alkoxy group having suitably from 1 to about 10 carbon atoms or a halogen; and n has a value of zero or 1; (c) component (B-2) is a phenolic hydroxyl-containing compound represented by the following formulas V or VI or a combination of such phenolic hydroxyl-containing compounds ##STR6## wherein each A', R', X and m are as defined above; and (d) component (D), when present, is selected from the group consisting of organic and inorganic acids, and salts of organic and inorganic acids.

Claim 6

A composition of claim 4 wherein (a) component (A-1) is a diglycidyl ether represented by formula II wherein n has a value of 1 and n' has a value from zero to about 2; (a) component A is a polyglycidyl ether represented by formula II wherein m has a value from about 1 to about 5 (b) component (B-1) is a phenolic hydroxyl-containing compound represented by formula IV wherein n has a value of 1; (c) component (B-2) is a phenolic hydroxyl-containing compound represented by formula V wherein m has a value from about 1.01 to about 7; and (d) component (D) is p-toluene sulfonic acid, benzene sulfonic acid, methyl p-toluene sulfonate, ammonium perchlorate, fluoboric acid, perchloric acid, nitric acid or any combination thereof.

Claim 7

A composition of claim 5 wherein (a) component A-2 is a polyglycidyl ether of a phenol-formaldehyde novolac epoxy resin; (b) component (B-1) is bisphenol A or tetrabromo bisphenol A; (c) component (B-2) is a phenol-formaldehyde novolac resin; (d) component (C) is acetone; and (e) component (D) is p-toluene sulfonic acid, benzene sulfonic acid, or methyl p-toluene sulfonate.

Claim 8

A curable composition which comprises (A) at least one aromatic based epoxy resin having an average number of epoxide groups per molecule of more than 2; (B) a phenolic hydroxyl-containing component consisting essentially of a mixture of (1) at least one phenolic hydroxyl-containing compound having an average of not more than 2 phenolic hydroxyl groups per molecule; and (2) at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; (c) optionally, at least one ketone solvent for component (A) as the only solvent in the composition except for minor amounts of any solvent for component (C); (D) optionally, one or more stabilizers; and (D) a catalytic quantity of at least one catalyst for effecting the reaction between components (A) and (B); and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.75:1 to about 1.5:1; component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.1:1 to about 0.65:1; component (C) is present in an amount of from about zero to about 75 weight percent based upon the combined weight of components (A), (B), (C), (D) and (E); component (D) is present in an amount of from about zero to about 1 percent by weight based upon the weight of component (A) and component (E) is present in an amount of from about 0.00005 to about 0.01 mole of catalyst per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 9

A curable composition which comprises (A) at least one aromatic based epoxy resin having an average number of epoxide groups per molecule of more than 2; (B) a phenolic hydroxyl-containing component consisting essentially of a mixture of (1) at least one phenolic hydroxyl-containing compound having an average of not more than 2 phenolic hydroxyl groups per molecule; and (2) at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; (c) optionally, at least one ketone solvent for component (A) as the only solvent in the composition except for minor amounts of any solvent for component (C); (D) optionally, one or more stabilizers; and (D) a catalytic quantity of at least one catalyst for effecting the reaction between components (A) and (B); and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.75:1 to about 1.5:1; component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.1:1 to about 0.65:1; component (C) is present in an amount of from about zero to about 75 weight percent based upon the combined weight of components (A), (B), (C), (D) and (E); component (D) is present in an amount of from about zero to about 1 percent by weight based upon the weight of component (A) and component (E) is present in an amount of from about 0.00005 to about 0.01 mole of catalyst per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 10

A curable composition of claim 7 wherein (a) component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.2:1 to about 0.6:1; (b) components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.85:1 to about 1.4:1; (c) component (C) is present in an amount of from about zero to about 50 weight percent based upon the combined weight of components (A), (B), (C), (D) and (E); (d) component (D) is present in an amount of from about 0.05 to about 1 percent by weight based upon the weight of component (A); and (e) component (E) is present in an amount of from about 0.00005 to about 0.05 mole per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 11

A curable composition of claim 8 wherein (a) component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.3:1 to about 0.55:1; (b) components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.9:1 to about 1.3:1; (c) component (C) is present in an amount of from about zero to about 25 weight percent based upon the combined weight of components (A), (B), (C), (D) and (E); (d) component (D) is present in an amount of from about 0.0.1 to about 0.8 percent by weight based upon the weight of component (A); and (e) component (E) is present in an amount of from about 0.0001 to about 0.03 mole per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 12

A curable composition of claim 7, 8 or 9 wherein (a) A-2 is an epoxy resin represented by the following formulas I or II or a combination of such epoxy resins ##STR7## wherein each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is as defined above; each R' is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; m has a value from about 0.1 to about 7; and m' has a value from zero to about 3; (b) component (B-1) is a phenolic hydroxyl-containing compound represented by the following formulas III or IV or a combination of such phenolic hydroxyl-containing compounds ##STR8## wherein each A, is independently a divalent hydrocarbyl or a halogen substituted divalent hydrocarbyl group having from 1 to about 12, preferably from 1 to about 6, carbon atoms --O--, --S--, --S--S--, --SO--, --SO 2 --, or --CO--; each X is independently hydrogen, an alkyl or an alkoxy group having suitably from 1 to about 10 carbon atoms or a halogen; and n has a value of zero or 1; (c) component (B-2) is a phenolic hydroxyl-containing compound represented by the following formulas V or VI or a combination of such phenolic hydroxyl-containing compounds ##STR9## wherein each A', R', X and m are as defined above; (d) component (E) is a phosphonium compound or an imidazole.

Claim 13

A curable composition of claim 10 wherein (a) component A is a polyglycidyl ether represented by formula I wherein m has a value from about 1 to about 5; (b) component (B-1) is a phenolic hydroxyl-containing compound represented by formula III wherein n has a value of 1; (c) component (B-2) is a phenolic hydroxyl-containing compound represented by formula V wherein m has a value from about 1.01 to about 7; (d) component (D) is selected from the group consisting of organic and inorganic acids, salts of inorganic acids; esters of organic acids; and any combination thereof; and (e) component (E) is selected from the group consisting of phosphonium compounds, ammonium compounds, imidazoles and any combination thereof.

Claim 14

A curable composition of claim 11 wherein (a) component A is a polyglycidyl ether of a phenol-formaldehyde novoalc epoxy resin; (b) component (B-1) is bisphenol A or tetrabromo bisphenol A; (c) component (B-2) is a phenol-formaldehyde novolac resin; (d) component (C) is acetone; (e) component (D) is p-toluene sulfonic acid, benzene sulfonic acid, methyl p-toluene sulfonate or any combination thereof; and (f) component (E) is a quaternary phosphonium halide, a quaternary phosphonium acetate·acetic acid complex, 2-methylimidazole, the reaction product of a quaternary phosphonium acetate·acetic acid complex and fluoboric acid in a respective molar ratio of from about 1:0.9 to about 1:1.25, or any combination thereof.

Claim 15

In a laminating varnish comprising (A) an epoxy resin component, (B) a curing agent from said epoxy resin and (C) a solvent; the improvement which comprises employing as the epoxy resin, component (A), at least one aromatic based epoxy resin having an average number of epoxide groups per molecule of more than 2; employing as said curing agent, component (B), a phenolic hydroxyl-containing composition consisting essentially of a mixture of (1) at least one phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule; and (2) at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; employing as the solvent, component (C), at least one ketone solvent as the only solvent present in the composition except for minor amounts of any solvent for component (D); and optionally, (D) a catalytic quantity of at least one catalyst for effecting the reaction between components (A) and (B); and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.75:1 to about 1.5:1; component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.1:1 to about 0.65:1; and component (C) is present in an amount of from about 5 to about 75 percent by weight based upon the total weight of the varnish composition; and component (D) is present in an amount which provides from about zero to about 0.01 moles of component (D) per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 16

In a laminating varnish comprising (A) an epoxy resin component, (B) a curing agent from said epoxy resin and (C) a solvent; the improvement which comprises employing as the epoxy resin, component (A), at least one aromatic based epoxy resin having an average number of epoxide groups per molecule of more than 2; employing as said curing agent, component (B), a phenolic hydroxyl-containing composition consisting essentially of a mixture of (1) at least one phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule; and (2) at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; employing as the solvent, component (C), at least one ketone solvent as the only solvent present in the composition except for minor amounts of any solvent for component (D); and optionally, (D) a catalytic quantity of at least one catalyst for effecting the reaction between components (A) and (B); and wherein components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.75:1 to about 1.5:1; component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.1:1 to about 0.65:1; and component (C) is present in an amount of from about 5 to about 75 percent by weight based upon the total weight of the varnish composition; and component (D) is present in an amount which provides from about zero to about 0.01 moles of component (D) per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 17

A laminating varnish of claim 13 wherein (a) component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component A of from about 0.2:1 to about 0.6:1; (b) components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.85:1 to about 1.4:1; (c) component (C) is present in an amount of from about 5 to about 50 percent by weight based upon the total weight of the varnish composition; and (d) component (D) is present in an amount of from about 0.00005 to about 0.01 mole of catalyst per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 18

A laminating varnish of claim 14 wherein (a) component (B1) is present in an amount which provides a ratio of phenolic hydroxyl groups per epoxide group contained in component (A) of from about 0.3:1 to about 0.55:1; (b) components (A) and (B) are present in quantities which provide a ratio of phenolic hydroxyl groups for each epoxy group of from about 0.9:1 to about 1.3:1; (c) component (C) is present in an amount of from about 10 to about 25 percent by weight based upon the total weight of the varnish composition; and (d) component (D) is present in an amount of from about 0.0001 to about 0.03 mole of catalyst per 100 parts by weight of the combined weight of component (A) and component (B).

Claim 19

A laminating varnish of claim 13, 14 or 15 wherein (a) component A-2 is an epoxy resin represented by the following formulas I or II or a combination of such epoxy resins ##STR10## wherein each A' is independently a divalent hydrocarbyl group having from -b 1 to about 10 carbon atoms; each R is as defined above; each R' is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; m has a value from about 0.1 to about 7; and m' has a value from zero to about 3; (b) component (B-1) is a phenolic hydroxyl-containing compound represented by the following formulas III or IV or a combination of such phenolic hydroxyl-containing compounds ##STR11## wherein each A, is independently a divalent hydrocarbyl or a halogen substituted divalent hydrocarbyl group having from 1 to about 12, preferably from 1 to about 6, carbon atoms, --O--, --S--, --S--S--, --SO--, --SO 2 --, or --CO--; each X is independently hydrogen, an alkyl or an alkoxy group having suitably from 1 to about 10 carbon atoms or a halogen; and n has value of zero or 1; (c) component (B-2) is a phenolic hydroxyl-containing compound represented by the following formulas V or VI or a combination of such phenolic hydroxyl-containing compounds ##STR12## wherein each A', R', and X and m are as defined above; and (d) component (D) is a phosphonium compound, an ammonium compound or an imidazole.

Claim 20

A laminating varnish of claim 16 wherein (a) component A is a polyglycidyl ether represented by formula I wherein m has a value from about 1 to about 5; (b) component (B-1) is a phenolic hydroxyl-containing compound represented by formula IV wherein n has a value of 1; and (c) component (B-2) is a phenolic hydroxyl-containing compound represented by formula V wherein m has a value from about 1.01 to about 7.

Claim 21

A laminating varnish of claim 17 wherein component A is a polyglycidyl ether of a phenol-formaldehyde novolac epoxy resin; (B) component (B-1) is bisphenol A or tetrabromo bisphenol A; (c) component (B-2) is a phenol-formaldehyde novolac resin; (d) component (C) is acetone; and (e) component (D) is a quaternary phosphonium halide, a quaternary phosphonium acetate·acetic acid complex, an imidazole, the reaction product of a quaternary phosphonium acetate·acetic acid complex and fluoboric acid in a respective molar ratio of from about 1:0.9 to about 1:1.25, or any combination thereof.

Claim 22

A substrate impregnated with a laminating varnish of claims 13, 14, or 15.

Claim 23

A substrate impregnated with a laminating varnish of claim 16.

Claim 24

A substrate impregnated with a laminating varnish of claim 17.

Claim 25

A substrate impregnated with a laminating varnish of claim 18.

Claim 26

A laminate resulting from curing one or more plies of a substrate of claim 19.

Claim 27

A laminate of claim 23 which has an outer layer of an electrical conducting material.

Claim 28

A laminate of claim 24 wherein the electrical conducting material is copper.

Claim 29

A laminate resulting from curing one or more plies of a substrate of claim 20.

Claim 30

A laminate of claim 26 which has an outer layer of an electrical conducting material.

Claim 31

A laminate of claim 27 wherein the electrical conducting material is copper.

Claim 32

A laminate resulting from curing one or more plies of a substrate of claim 21.

Claim 33

A laminate of claim 29 which has an outer layer of an electrical conducting material.

Claim 34

A laminate of claim 30 wherein the electrical conducting material is copper.

Claim 35

A laminate resulting from curing one or more plies of a substrate of claim 22.

Claim 36

A laminate of claim 32 which has an outer layer of an electrical conducting material.

Claim 37

A laminate of claim 33 wherein the electrical conducting material is copper.

Claim 38

The product resulting from curing the curable composition of claim 7, 8, or 9.

Claim 39

The product resulting from curing the curable composition of claim 10.

Claim 40

The product resulting from curing the curable composition of claim 11.

Claim 41

The product resulting from curing the curable composition of claim 12.

Claim 42

A curing agent composition for epoxy resins which comprises a mixture of (A) a phenolic hydroxyl-containing component consisting essentially of a mixture of (1) from about 7 to about 81 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule; and (2) from about 93 to about 19 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; (B) at least one ketone solvent for component (A) as the only solvent in the composition except for minor amounts of any solvent for component (C); and (C) optionally, a catalytic quantity of at least one catalyst for effecting the reaction between an epoxy resin and component (A); and wherein component (B) is present in quantities of from about 5 to about 75 percent by weight based upon the total weight of the curing agent composition.

Claim 43

A curing agent composition for epoxy resins which comprises a mixture of (A) a phenolic hydroxyl-containing component consisting essentially of a mixture of (1) from about 7 to about 81 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 1 but not more than 2 phenolic hydroxyl groups per molecule; and (2) from about 93 to about 19 equivalent percent of at least one phenolic hydroxyl-containing compound having an average of more than 2 phenolic hydroxyl groups per molecule; (B) at least one ketone solvent for component (A) as the only solvent in the composition except for minor amounts of any solvent for component (C); and (C) optionally, a catalytic quantity of at least one catalyst for effecting the reaction between an epoxy resin and component (A); and wherein component (B) is present in quantities of from about 5 to about 75 percent by weight based upon the total weight of the curing agent composition.

Claim 44

A curing agent composition of claim 39 wherein (a) component (A) comprises from about 30 to about 70 equivalent percent of component (1) and from about 70 to about 30 equivalent percent of component (2); and (b) component (B) is present in an amount of from about 5 to about 50 weight percent based upon the total weight of the curing agent composition.

Claim 45

A curing agent composition of claim 40 wherein (a) component (a) comprises from about 40 to about 50 equivalent percent of component (1) and from about 60 to about 50 equivalent percent of component (2); and (b) component (B) is present in an amount of from about 10 to about 25 percent by weight based upon the total weight of the curing agent composition.

Claim 46

A curing agent compositon of claim 39, 40 or 41 wherein (a) component (A-1) is a phenolic hydroxyl-containing compound represented by the following formulas III or IV or a combination of such phenolic hydroxyl-containing compounds ##STR13## wherein each A, is independently a divalent hydrocarbyl or a halogen substituted divalent hydrocarbyl group having from 1 to about 12, preferably from 1 to about 6, carbon atoms, --O--, --S--, --S--S--, --SO--, --SO 2 --, or --CO--; each X is independently hydrogen, an alkyl or an alkoxyl group having suitably from 1 to about 10 carbon atoms or a halogen; and n has a value of zero or 1; (b) component (A-2) is a phenolic hydroxyl-containing compound represented by the following formulas V or VI or a combination of such phenolic hydroxyl-containing compounds ##STR14## wherein each A' is independently a divalent hydrocarbyl group having from 1 to about 10 carbon atoms; each R is as defined above; each R' is independently hydrogen or a hydrocarbyl group having from 1 to about 10 carbon atoms; and m has a value from about 0.1 to about 7; and (c) component (C) is a phosphonium compound, an ammonium compound or an imidazole.

Claim 47

A curing agent composition of claim 42 wherein (a) component (A-1) is a phenolic hydroxyl-containing compound represented by formula IV wherein n has a value of 1; and (b) component (A-2) is a phenolic hydroxyl-containing compound represented by formula V wherein m has a value from about 1.01 to about 7.

Claim 48

A curing agent composition of claim 43 wherein (a) component (A-1) is bisphenol A or tetrabromo bisphenol A; (b) component (A-2) is a phenol-formaldehyde novolac resin; (c) component (B) is acetone; and (d) component (C) is a quaternary phosphonium halide, a quaternary phosphonium acetate·acetic acid complex, an imidazole, the reaction product of a quaternary phosphonium acetate·acetic acid complex and fluoboric acid in a respective molar ratio of from about 1:0.9 to about 1:1.25, or any combination thereof.