Polyimide-siloxanes, method of making and use

Claim 2

Polyimide-siloxane comprising repeat groups selected from the class consisting of, ##STR23## a mixture thereof, and mixtures of such groups with imide groups of the formula ##STR24## wherein R is selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organoterminated polydiorganosiloxane, R 3 is a tetravalent C.sub.(1-14) aromatic organic radical, and n is an integer equal to 5 to about 2000 inclusive.

Claim 3

Polyimide-siloxane having recurring chemically combined imide-siloxane groups comprising the anhydride-amine intercondensation reaction product of (A) a mixture of anhydrides comprising (i) organic dianhydride, and (ii) siloxane anhydride having chemically-combined units of the formula, ##STR25## or such siloxane anhydride units chemically-combined with siloxane units of the formula, ##STR26## intercondensed with (B) diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radical substituted with radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorganosiloxane radical, a is a whole number equal to 0 to 2 inclusive, and b is a whole number equal to 0 to 3 inclusive.

Claim 4

Polyimide-siloxane having recurring chemically combined imide-siloxane groups comprising the anhydride-amine intercondensation reaction product of (A) a mixture of anhydrides comprising (i) organic dianhydride, and (ii) siloxane anhydride having chemically-combined units of the formula, ##STR25## or such siloxane anhydride units chemically-combined with siloxane units of the formula, ##STR26## intercondensed with (B) diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radical substituted with radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorganosiloxane radical, a is a whole number equal to 0 to 2 inclusive, and b is a whole number equal to 0 to 3 inclusive.

Claim 5

Polyimide-siloxane in accordance with claim 2, which comprises by weight, from 5% to 95% of siloxane-imide repeat groups of the formula, ##STR27## chemically-combined with 95% to 5% of imide groups of the formula, ##STR28## where R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorganosiloxane radical, R 3 is a tetravalent C.sub.(6-14) aromatic organic radical, c is an integer equal to 1 to 200 inclusive, and n is an integer equal to 1 to about 2,000 inclusive.

Claim 6

Polyimide siloxane in accordance with claim 2, where the siloxane anhydride has the formula, ##STR29## where R is a C.sub.(1-14) monovalent hydrocarbon radical or a C.sub.(1-14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation.

Claim 7

Polyimide-siloxane in accordance with claim 2, where the siloxane anhydride is ##STR30## R is a member selected from the class consisting of C.sub.(1-14) monoval®nt hydrocarbon radicals, and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, and n is an integer equal to about 1 to about 2,000 inclusive.

Claim 8

Polyimide-siloxane in accordance with claim 2, where the siloxane anhydride is ##STR31## R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, and m is an integer equal to 1 to 3 inclusive.

Claim 9

Polyimide-siloxane in accordance with claim 2, where the organic anhydride is an aromatic bis(etheranhydride).

Claim 10

Polyimide-siloxane in accordance with claim 2, where the organic dianhydride is 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride.

Claim 11

Polyimide-siloxane in accordance with claim 2, where the organic dianhydride is pyromellitic dianhydride.

Claim 12

Polyimide-siloxane in accordance with claim 2, where the organic dianhydride is benzophenone dianhydride.

Claim 13

Polyimide-siloxane in accordance with claim 2, where the organic dianhydride is oxy-bis-(4-phthalic anhydride).

Claim 14

Polyimide-siloxane in accordance with claim 2, where the organic dianhydride is 5,5'-(1,1,3,3-tetramethyl-1,3-disiloxanediyl)-bisnorbornane-2,3 -dicarboxylicanhydride.

Claim 15

Polyimide-siloxane in accordance with claim 2, where the diamine is p-phenylene diamine.

Claim 16

Polyimide-siloxane in accordance with claim 2, where the diamine is 4,4?-oxydianiline.

Claim 17

Polyimide-siloxane in accordance with claim 2, where the diamine is m-phenylene diamine.

Claim 18

Polyimide-siloxane comprising chemically-combined siloxane-imide repeat groups of the formula, ##STR32## where R is selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo-terminated polydiorganosiloxane radical, and n is an integer equal to 5 to about 2000 inclusive.

Claim 19

Polyimide-siloxane comprising chemically-combined siloxane-imide repeat groups of the formula, ##STR32## where R is selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo-terminated polydiorganosiloxane radical, and n is an integer equal to 5 to about 2000 inclusive.

Claim 20

Polyamideacid-siloxane comprising chemically-combined units resulting from the intercondensation of substantially equal molar amounts of amine and anhydride from a mixture of organic dianhydride, siloxane anhydride of the formula, ##STR33## and diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with the same or different radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorganosiloxane radical, and n is an integer equal to 5 to about 2,000 inclusive.

Claim 21

Polyamideacid-siloxane comprising chemically-combined units resulting from the intercondensation of substantially equal molar amounts of amine and anhydride from a mixture of organic dianhydride, siloxane anhydride of the formula, ##STR33## and diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with the same or different radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorganosiloxane radical, and n is an integer equal to 5 to about 2,000 inclusive.

Claim 22

Polyamideacid-siloxane comprising the intercondensation reaction product of substantially equal molar amounts of amine and anhydride resulting from agitating a mixture or organic dianhydride, and siloxane anhydride of the formula, ##STR34## with diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, in the presence of an organic solvent, where R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, and R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorganosiloxane radical.

Claim 23

Polyamideacid-siloxane comprising the intercondensation reaction product of substantially equal molar amounts of amine and anhydride resulting from agitating a mixture or organic dianhydride, and siloxane anhydride of the formula, ##STR34## with diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, in the presence of an organic solvent, where R is a member selected from the class consisting of C.sub.(1-14) monovalent hydrocarbon radicals and C.sub.(1-14) monovalent hydrocarbon radicals substituted with radicals neutral during intercondensation, and R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorganosiloxane radical.

Claim 24

Polyamide acid-siloxane of claim 17, where the organic dianhydride is bisphenol-A dianhydride.

Claim 25

Polyamideacid-siloxane of claim 17, where the organic dianhydride is benzophenone dianhydride.

Claim 26

Polyamideacid-siloxane of claim 17, where the organic dianhydride is oxybisphthalic anhydride.

Claim 27

Polyamideacid-siloxane of claim 17, where the organic dianhydride is pyromellitic dianhydride.

Claim 28

A composite comprising a polyimide layer and a metal layer and an intermediate layer of polyimide siloxane comprising the intercondensation reaction product of (A) siloxane anhydride having chemically combined units of the formula, ##STR35## and or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula, ##STR36## (B) organic diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a C.sub.(1-14) monovalent hydrocarbon radical or a C.sub.(1-14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorgano siloxane radical, a is a whole number equal to 0 to 2 inclusive, and b is a whole number equal to 0 to 3 inclusive.

Claim 29

A composite comprising a polyimide layer and a metal layer and an intermediate layer of polyimide siloxane comprising the intercondensation reaction product of (A) siloxane anhydride having chemically combined units of the formula, ##STR35## and or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula, ##STR36## (B) organic diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a C.sub.(1-14) monovalent hydrocarbon radical or a C.sub.(1-14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorgano siloxane radical, a is a whole number equal to 0 to 2 inclusive, and b is a whole number equal to 0 to 3 inclusive.

Claim 30

A composite comprising glass fiber, carbon fiber, or polyamide fiber and the polyimide siloxane of claim 2.

Claim 31

A composite comprising glass fiber, carbon fiber, or polyamide fiber and the polyimide-siloxane of claim 16.

Claim 32

A polyimide-siloxane film in accordance with claim 2.

Claim 33

A polyimide-siloxane film in accordance with claim 16.

Claim 34

A semiconductor device having a layer of a polyimide-siloxane having recurring chemically combined imidesiloxane groups comprising the intercondensation reaction product of (A) siloxane anhydride having chemically combined units of the formula, ##STR37## or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula ##STR38## (B) organic diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a C.sub.(1-14) monovalent hydrocarbon radical or a C.sub.(1-14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorgano siloxane radical, a is a whole number equal to 0 to 2 inclusive, and b is a whole number equal to 0 to 3 inclusive.

Claim 35

A semiconductor device having a layer of a polyimide-siloxane having recurring chemically combined imidesiloxane groups comprising the intercondensation reaction product of (A) siloxane anhydride having chemically combined units of the formula, ##STR37## or a mixture of such siloxane anhydride units chemically combined with siloxane units of the formula ##STR38## (B) organic diamine of the formula, NH.sub.2 R.sup.2 NH.sub.2, where R is a C.sub.(1-14) monovalent hydrocarbon radical or a C.sub.(1-14) monovalent hydrocarbon radical substituted with the same or different radicals neutral during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorgano siloxane radical, a is a whole number equal to 0 to 2 inclusive, and b is a whole number equal to 0 to 3 inclusive.

Claim 36

A semiconductor device having as a dielectric layer, a polyimide-siloxane comprising chemically combined siloxaneimide repeat groups of the formula, ##STR39## or a mixture of such siloxaneimide repeat groups and imide groups of the formula, ##STR40## where R is selected from the class consisting of a C.sub.(1-14) monovalent hydrocarbon radical and a C.sub.(1-14) monovalent hydrocarbon radical substituted with radicals inert during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorgano siloxane radical, R 3 is a tetravalent C.sub.(6-13) aromatic organic radical, c is an integer equal to 1 to 200 inclusive, and m is an integer equal to 1 to about 3 inclusive.

Claim 37

A semiconductor device having as a dielectric layer, a polyimide-siloxane comprising chemically combined siloxaneimide repeat groups of the formula, ##STR39## or a mixture of such siloxaneimide repeat groups and imide groups of the formula, ##STR40## where R is selected from the class consisting of a C.sub.(1-14) monovalent hydrocarbon radical and a C.sub.(1-14) monovalent hydrocarbon radical substituted with radicals inert during intercondensation, R 1 is a C.sub.(6-14) trivalent aromatic organic radical, R 2 is a member selected from the class consisting of a C.sub.(2-20) divalent organic radical and a C.sub.(2-8) organo terminated polydiorgano siloxane radical, R 3 is a tetravalent C.sub.(6-13) aromatic organic radical, c is an integer equal to 1 to 200 inclusive, and m is an integer equal to 1 to about 3 inclusive.

Claim 38

A semiconductor device in accordance with claim 29, where the polyimide-siloxane layer comprises the intercondensation reaction product of 1,3-bis(3,4-dicarboxyphenyl)-1, 3,3-tetramethyldisiloxane dianhydride and 4,440 -diaminodiphenylether.

Claim 39

A semiconductor device in accordance with claim 29, resulting from the intercondensation of a mixture of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride and oxy-bis(4-phthalicanhydride) and 4,4-diaminodiphenylether.

Claim 40

A semiconductor device in accordance with claim 29, resulting from the intercondensation product of a mixture of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, pyromellitic dianhydride and a mixture of para and meta phenylene diamine.

Claim 41

A semiconductor device in accordance with claim 29 resulting from the intercondensation product of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, benzophenone tetracarboxylic acid anhydride and a mixture of para and meta phenylene diamine.

Claim 42

A semiconductor device in accordance with claim 29 resulting from the intercondensation product of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, oxy-bis(4-phthalicanhydride) and mixture of para and meta phenylene diamine.