Copolymerized polyamic acid salts and process of producing them

Claim 2

The copolymerized polyamic acid salt as claimed in claim l, wherein R 31 , R32, R33, R 41 , R 42 , R43, R 5 , and R 6 each is a monovalent group having I to 22 carbon atoms or a hydrogen atom and at least two of said R 31, R32, R33, R 41 , R 4 2, R 4 3, R 5 , and R do not take a group having I to 15 carbon atoms or a hydrogen atom.

Claim 3

The copolymerized polyamic acid salt as claimed in claim I, wherein at least one of R 1 and R 2 represents a group comprising a benzenoid unsaturation having at least 6 carbon atoms.

Claim 4

The copolymerized polyamic acid salt as claimed in claim I, wherein each two of four groups of -NR 5 -CO-. and -CO-NR 6 -R 2 bonded to R 1 are bonded to adjoining two carbon atoms constituting R 1 to form a 5-membered ring.

Claim 5

The polymerized polyamic acid salt as claimed in claim 1, wherein are selected to have a different structure.

Claim 6

The polymerized polyamic acid salt as claimed in claim I, wherein the recurring unit is represented by formula wherein, and each represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; R 31 , R 32 , R33, R 41 , R 42 , R 4 3, R 5 , R 6 , x and y are as defined above.

Claim 7

The copolymerized polyamic acid salt as claimed in claim I, wherein the recurring unit is represented by formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms; and each represents a divalent group having at least 2 carbon atoms; R 31 , R 32 , R33, R 41 , R 4 2, R 4 3, R 5 , R 6 , x and y are as defined above.

Claim 8

The copolymerized polyamic acid salt as claimed in claim I, wherein R 5 and R 6 in formula (1) are a hydrogen atom.

Claim 9

A copolymerized polyamic acid salt having a recurring unit represented by formula wherein (A') represents a subunit of the formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; and R3 1 , R 32 , R 33 , R 41 , R 42 , R 4 3, R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetoxy group; at least one of said R31, R 32 , R33, R41 , R 42 , R 43, R5 , and R 6 does not represent a group having I to II carbons atoms or a hydrogen atom; and (B') represents one or more subunits of the formula wherein R 1 , R2 , R 31 , R 32, R 33, R 41 , R 4 2, R 4 3, R 5 , and R 6 are as defined in (A); a part of at least one of R 1 and R 2 is substituted by a group having a different valence; and x and y represent a ratio which satisfies O<x<l, 0<y<l and x+y= I.

Claim 10

The copolymerized polyamic acid salt as claimed in claim 9, wherein the recurring unit of formula (I) in which a part of R 1 is substituted by a divalent group R 7 having at least 2 carbon atoms is represented by formula wherein, R1 , R 2 , R31 , R 32 , R 33, R 41 , R42, R43, R5, R 6 , x and y are as defined in claim 9; and R 7 represents a divalent group having at least 2 carbon atoms.

Claim 11

II. The copolymerized polyamic acid salt as claimed in claim 9, wherein the recurring unit of formula (I) in which a part of R 1 is substituted by a trivalent group R 8 having at least 2 carbon atoms is represented by formula wherein R1 , R2 , R31 , R3 2, R 33, R 4 1 , R42, R43, R5 and R6 are as defined in claim 9, and R 8 represents a trivalent group having at least 2 carbon atoms.

Claim 12

The copolymerized polyamic acid salt as claimed in claim 9, wherein the recurring unit of formula (I) in which a part of R 2 is substituted by a trivalent group R 9 having at least 2 carbon atoms is represented by formula wherein, R 1 , R2 , R31 , R32 , R33, R 4 1 , R 4 2, R 4 3, R5 and R 6 are as defined in claim 9; R 9 represents a trivalent group having at least 2 carbon atoms; and X represents a substituent for R 9 .

Claim 13

The copolymerized polyamic acid salt as claimed in claim 9, wherein the recurring unit of formula (I) in which a part of R 2 is substituted by a tetravalent group R 10 having at least 2 carbon atoms is represented by formula wherein, R 1 , R2 , R31 , R32 , R 33, R 4 1 , R 4 2, R 4 3, R 5 and R 6 are as defined in claim 9; R 10 represents a tetravalent group having at least 2 carbon atoms, ; and X and Y represent substituents for R 10 .

Claim 14

The copolymerized polyamic acid salt as claimed in claim 9, wherein said R31, R32, R 33, R 4 1 , R 4 2 , R 4 3 , R 5 , and R 6 each is a monovalent group having I to 22 carbon atoms or hydrogen atom and at least two of said R 31 , R32 , R33, R 41 , R 42 , R 4 3, R5, and R6 do not take a group having I to 15 carbon atoms or a hydrogen atom.

Claim 15

The copolymerized polyamic acid salt as claimed in claim 9, wherein at least one of R 1 and R 2 in formula (1) is a group of a benzenoid unsaturation having at least 6 carbon atoms.

Claim 16

The copolymerized polyamic acid salt as claimed in claim 9, wherein each two of four groups, -NR- 5- CO-, and -CO-NR 6 -R 2 -bonded to R 1 in formula (1) are bonded to adjoining two carbon atoms constituting R 1 to form a 5-membered ring or a 6-membered ring

Claim 17

The copolymerized polyamic acid salt as claimed in claim II, wherein two of three groups bonded to R 8 are bonded to adjoining two carbon atoms constituting R 8 to form a 5-membered ring or a 6- membered ring.

Claim 18

The copolymerized polyamic acid salt as claimed in claim 12, wherein two of three groups and X bonded to R 9 in formula (104) are bonded to adjoining two carbon atoms constituting R 9 to form a 5 membered ring or a 6-membered ring.

Claim 19

The copolymerized polyamic acid salt as claimed in claim 13, wherein two of four groups X, and Y bonded to R 10 in formula (105) are bonded to adjoining two carbon atoms constituting R 10 to form a 5-membered ring or a 6-membered ring.

Claim 20

The polymerized polyamic acid salt as claimed in claim 9, wherein the recurring unit is represented by formula wherein, R1 , R2 , R3 1 , R 32, R33, R 4 1, R 4 2, R 4 3, x and y are as defined in claim 9; provided that one of said R 31 , R3 2 , and R 33 and one of said R 41 , R 42 , and R 43 do not take a group having I to II carbon atoms or a hydrogen atom; R 7 represents a divalent group having at least 2 carbon atoms.

Claim 21

The polymerized polyamic acid salt as claimed in claim 3, wherein the recurring unit is represented by formula wherein, R 1 , R 2, R31 , R 32, R33, R 4 1 , R 4 2, R 4 3, x and y are as defined in claim 9, provided that one of said R 31 , R32, and R33 and one of said R 41 , R 42 , and R 43 do not take a group having I to II carbon atoms or a hydrogen atom; R 8 represents a trivalent group having at least 2 carbon atoms.

Claim 22

The polymerized polyamic acid salt as claimed in claim 12, wherein the recurring unit is represented by formula wherein, R 1 , R2, R3 1 , R32, R33, R 41 , R 42 , R 4 3, x and y are as defined in claim 9, one of said R 31 , R 32 , and R 33 and one of said R 41 , R 42 , and R 43 do not take a group having I to II carbon atoms or a hydrogen atom; R 9 represents a trivalent group having at least 2 carbon atoms and X represents a substituent for R 9 .

Claim 23

The polymerized polyamic acid salt as claimed in claim 13, wherein the recurring unit is represented by formula wherein, R 1 , R2, R 31 , R32, R33, R 41 , R 4 2, R 4 3, x and y are as defined in claim 9, one of said R3 1 , R 32 , and R 33 and oneof said R 41 , R 42 , and R 43 do not take a group having I to II carbon atoms or a hydrogen atom; R 10 represents a trivalent group having I to II carbon atoms; and X and Y represent substituents for R 10 .

Claim 24

A process of producing a copolymerized polyamic acid salt having a recurring unit represented by formula (1) wherein, R 1 represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; and R31 , R32 , R33 , R 41, R 42, R 4 3, R5 and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetoxy group; at least one of said R31, R32, R 33 , R 41 , R42, R43, R5 and R 6 does not represent a group having I to II carbon atoms or a hydrogen atom; and are selected to have a different structure which comprises reacting a tetracarboxylic acid dianhydride represented by formula (4) wherein, R 1 represents a tetravalent group having at least 2 carbon atoms with a compound represented by formula (6) wherein, R 2 represents a divalent group having at least 2 carbon atoms and R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetoxy group; to provide a polyamic acid having a recurring unit represented by formula wherein, R 1 , R 2 , R 5 , and R 6 are as defined above and reacting the polyamic acid thus obtained with wherein R 31 , R 32 , R 33 , R 41 , R 42 , and R 43 are as defined above for R 5 and R 6 ; and are selected to have a different structure.

Claim 25

A process of producing a copolymerized polyamic acid salt having a recurrirrg unit represented by formula wherein, Rq and Rb 'each represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; and R 31 , R 32 , R 33 , R 41 , R 42 , R 43 , R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetoxy group; at least one of said R 31 , R 32 , R33, R 41 , R 4 2, R 4 3, R 5 and Redoes not represent a group having I to II carbon atoms or a hydrogen atom; which comprises reacting at least two kinds of tetracarboxylic acid dianhydride represented by formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms with a compound represented by formula wherein, R 2 , R 5 and R 6 are as defined above, to provide a polyamic acid having a recurring unit represented by formula wherein, R 2 , R 5 , and R 6 are as defined above; and are as defined above for R 1 ; and x and y represent a ratio which satisfied 0<x<I, 0<y<l, and x+y=l and then reacting the polyamic acid thus obtained with wherein, R 31 , R32, R33, R 41 , R42, and R 4 3 are as defined above for R 5 and R 6.

Claim 26

A process of producing a copolymerized polyamic acid salt having a recurring unit represented by formula (12) wherein, R 1 , represents a tetravalent group having at least 2 carbon atoms; and each represents a divalent group having at least 2 carbon atoms; R 31 , R 32 , R3 3 , R 41 , R 42 , R 43 , R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetoxy group; at least one of said R3 1 , R3 2 , R33, R 41 , R 4 2, R 4 3, R 5 and R 6 does not represent a group having I to II carbon atoms or a hydrogen atom; which comprises reacting a tetracarboxylic acid di-anhydride represented by formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms with at least two kinds of compounds represented by formula wherein, R 2 , R 5 and R 6 are as defined above to provide a polyamic acid having a recurring unit represented by formula wherein, R 1 , R 5 , and R 6 are as defined above; and are as defined above for R 2 ; and x and y represent a ratio which satisfies 0<x<I, 0<y<l, and x+y=l and then reacting the polyamic acid thus obtained with wherein, R3 1 , R3 2 , R33, R 41 , R 42 , and R 4 3 are as defined above for R 5 and R 6 .

Claim 27

A process of producing a copolymerized polyamic acid salt having a recurring unit represented by formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; R 7 represents a divalent group having at least 2 carbon atoms; R 31 , R 32 , R 33 , R 41 , R 42 , R 43 , R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, and amino group, a cyano group, a methoxy group, or an acetoxy group; at least one of said R 31 , R 32 , R 33 , R 41 , R 42 , R 42 , R 5 and Redoes not represent a group having I to II carbon atoms or a hydrogen atom; and x and y represent a ratio which satisfies 0<x<I, 0<y<l, and x+y=l, which comprises reacting a tetracarboxylic acid dianhydride represented by formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms, with an acid halide formed in a substantially water free polar organic solvent from a compound represented by formula wherein, R 7 is as defined above, and with a compound represented by formula wherein, R 2 , R 5 and R 6 are as defined above to provide a compound represented by the formula wherein, R 1 , R 2 , R 5 , R 6 , R 7 , x and y are as defined above, and then reacting the compound thus obtained with wherein, R 31 , R 32 , R 33 , R 41 , R 42 , and R 43 are as defined above.

Claim 28

A process of producing a copolymerized polyamic acid salt having a recurring unit represented by formula wherein R 1 represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; R 8 represents a trivalent group having at least 2 carbon atoms; R 31 , R 32 , R 33 , R 41 , R 42 , R 43 , R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetox y group; at least one of said R31 , R32 , R33 , R 4 1 , R 4 2, R 43, R5 and R 6 does not represent a group having I to II carbon atoms or a hydrogen atom; and x and y represent a ratio which satisfies 0<x<I, 0<y<l and x+y=1, which comprises reacting a tetracarboxylic acid dianhydride represented by formula wherein, R 1 is same as defined above, with an acid halide formed in a substantially water free polar organic solvent from a compound represented by formula wherein, R 8 is as defined above, and with a compound represented by formula R 5 -NH - R2 -NH - R 6 (6) wherein, R 2 , R 5 , and R 6 are as defined above to provide a compound represented by the following formula wherein, R 1 , R 2 , R 5 , R 6 , R 8 , x and y are as defined above, and then reacting the compound thus obtained with wherein, R 31 , R 32 , R 33 , R 41 , R 42 , R 43 , R 5 , and R 6 are as defined above.

Claim 29

A process of producing a copolymerized polyamic acid salt having a recurring unit represented by formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; R 9 represents a trivalent group having at least 2 carbon atoms; R3 1 , R 32 , R33, R 41 , R 42 , R 43 , R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetox y group; at least one of said R31 , R32 , R 33, R 4 1 , R 4 2, R 4 3, R 5 and R 6 does not represent a group having 1 to 11 carbon atoms or a hydrogen atom; X represents a substituent for R 9 and x and y represent a ratio which satisfies 0<x<1, 0<y<I, and x + y = which comprises reacting a tetracarboxylic acid dianhydride represented by a formula wherein, R 1 is as defined above, with a compound represented by formula wherein, R 2 , R 5 , and R 6 are as defined above, and with a compound represented by formula wherein, R 5 , R 6 , R 9 and X are as defined above, to provide a compound represented by the formula wherein, R 1 , R 2 , R 5 , R 6 , R 9 , R , x and y are same as defined above and then reacting the compound thus obtained with wherein, R 31 , R 32 , R 33 , R 41 , R 42 , and R 43 are as defined above.

Claim 30

A process of producing a copolymerized polyamic acid salt having a recurring unit represented by formula wherein, R 1 represents a tetravalent group having at least 2 carbon atoms; R 2 represents a divalent group having at least 2 carbon atoms; R 10 represents a tetravalent group having at least 2 carbon atoms; R 31 , R3 2 , R33, R 41 , R 42 ,R 43 , R 5 , and R 6 each represents a hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from an aliphatic group, an alicyclic group, an aromatic group, a group in which an aliphatic group is combined with an alicyclic group or an aromatic group, wherein each of these groups may be substituted by a halogen atom, a nitro atom, an amino group, a cyano group, a methoxy group, or an acetoxy group; at least one of said R 31 , R 32 , R 33 , R 41 , R 42 , R 43 , R 5 and R 6 does not represent a group having 1 to 11 carbon atoms or a hydrogen atom; X and Y represent substitutes for R 10 and x and y represent a ratio which satisfies 0<x<I, 0<y<I, and x+y=1, which comprises reacting a tetracarboxylic acid dianhydride represented by formula wherein, R 1 is as defined above, with a compound represented by formula wherein, R 2 , R 5 , and R 6 are as defined above, and with a compound represented by formula (15) wherein, R 5 , R 6 , R 10 , X and Y are as defined above, to provide a compound represented by the following formula wherein, R 1 , R 2 , R 5 , R 6 , R 10 , X, Y, x and y are as defined above, and then reacting the compound thus obtained with wherein, R 31 , R 32 , R 33 , R 41 , R 42 , and R 43 are as defined above.