Amphiphilic polyimide precursor and process for preparing the same

Claim 2

An amphiphilic polyimide precursor having the recurring unit of the formula (1): wherein R 1 is a tetravalent group having at least 2 carbon atoms, R 2 is a bivalent group having at least 2 carbon atoms, and R 3 , R 4 , R 5 and R are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of 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, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, provided that at least one of R 3 , R 4 , R 5 and R 6 is not hydrogen atom and the above-mentioned group which has 1 to 11 carbon atoms.

Claim 3

The precursor of Claim 1, wherein at least two of the groups R 3 , R 4 , R 5 and R 6 are not hydrogen atom and a group having 1 to 11 carbon atoms.

Claim 4

The precursor of Claim 1, wherein the groups R 3 , R 4 , Rand R are hydrogen atom or a monovalent group having 1 to 22 carbon atoms, provided that at least two of them are not hydrogen atom and a group having 1 to 15 carbon atoms.

Claim 5

The precursor of Claim 1, wherein either or both of the groups R 1 and R 2 are a group characterized by benzenoid unsaturation having at least 6 carbon atoms.

Claim 6

The precursor of Claim 1, wherein each pair of the four groups, R 3 OCO-, R 4 OCO-, -NR 5 CO- and -CONR 6 -R 2 -, which are attached to the group R 1 , are directly attached to adjacent carbon atoms in the group R 1 to form a 5-membered ring.

Claim 7

The precursor of Claim 1, wherein said recurring unit (1) is represented by the formula (2): wherein R 1 , R 2 , R3 and R 4 are as defined above, provided that R 3 and R 4 are not hydrogen atom and a group having 1 to 11 carbon atoms.

Claim 8

The precursor of Claim 1, wherein the recurring unit (1) is represented by the formula (3): wherein R 1 , R 2 , R 5 and R 6 are as defined above, provided that R 5 and R 6 are not hydrogen atom and a group having 1 to 11 carbon atoms.

Claim 9

A process for preparing an amphiphilic polyimide precursor which comprises reacting a tetracarboxylic acid dianhydride of the formula (4): wherein R 1 is a tetravalent group having at least 2 carbon atoms, with R 3 OH and R 4 0H wherein R 3 and R 4 are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of 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, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, to produce a compound of the formula (5): wherein R 1 , R 3 and R 4 are as defined above, converting the compound (5) into an acid halide in a substantially anhydrous polar organic solvent at a temperature of not lower than -10°C, and reacting the acid halide with a compound of the formula (6): wherein R 2 is a bivalent group having at least 2 carbon atoms, and Rand R are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of 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, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, at a temperature of not lower than -10°C to produce an amphiphilic polyimide precursor having the recurring unit of the formula (l): wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined above, provided that at least one of R 3 , R 4 , R 5 and R 6 is not hydrogen atom and a group having 1 to 11 carbon atoms.

Claim 10

A process for preparing an amphiphilic polyimide precursor which comprises reacting a tetracarboxylic acid dianhydride of the formula (4): wherein R 1 is a tetravalent group having at least 2 carbon atoms, with R 3 OH and R 4 0H wherein R 3 and R 4 are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of 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, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, to produce a compound of the formula (5): wherein R 1 , R 3 and R 4 are as defined above, converting the compound (5) into an acid halide in a substantially anhydrous polar organic solvent at a temperature of not lower than -10°C, and reacting the acid halide with a compound of the formula (6): wherein R 2 is a bivalent group having at least 2 carbon atoms, and Rand R are hydrogen atom or a monovalent group having 1 to 30 carbon atoms selected from the group consisting of 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, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, at a temperature of not lower than -10°C to produce an amphiphilic polyimide precursor having the recurring unit of the formula (l): wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined above, provided that at least one of R 3 , R 4 , R 5 and R 6 is not hydrogen atom and a group having 1 to 11 carbon atoms.

Claim 11

The process of Claim 8, wherein both the groups R 5 and R 6 of the compound (6) are hydrogen atom.

Claim 12

A process for preparing an amphiphilic polyimide precursor which comprises reacting a tetracarboxylic acid dianhydride of the formula (4): wherein R 1 is a tetravalent group having at least 2 carbon atoms, with a compound of the formula (7): wherein R 2 is a bivalent group having at least 2 carbon atoms, and R 7 and R 8 are the same or different and each is a monovalent group having 12 to 30 carbon atoms selected from the group consisting of 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, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, at a temperature of not more than 50°C to produce an amphiphilic polyimide precursor having the recurring unit of the formula (8): wherein R 1 , R 2 , R 7 and R 8 are as defined above.

Claim 13

A process for preparing an amphiphilic polyimide precursor which comprises reacting a tetracarboxylic acid dianhydride of the formula (4): wherein R 1 is a tetravalent group having at least 2 carbon atoms, with a compound of the formula (7): wherein R 2 is a bivalent group having at least 2 carbon atoms, and R 7 and R 8 are the same or different and each is a monovalent group having 12 to 30 carbon atoms selected from the group consisting of 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, and their groups substituted by a halogen atom, nitro group, amino group, cyano group, methoxy group or acetoxyl group, at a temperature of not more than 50°C to produce an amphiphilic polyimide precursor having the recurring unit of the formula (8): wherein R 1 , R 2 , R 7 and R 8 are as defined above.

Claim 14

ll. A thin film of the amphiphilic polyimide precursor of Claim 1.

Claim 15

The thin film of Claim 11, which has a dielectric strength of not less than 1 X 10 6 V/cm.

Claim 16

The thin film of Claim 11, which is a built-up film formed by Langmuir-Blodgett technique.

Claim 17

A thin film of the amphiphilic polyimide precursor of Claim 1 partially converted into polyimide.

Claim 18

The thin film of Claim 14, which has a dielectric strength of not less than 1 X 10 6 V/cm.

Claim 19

The thin film of Claim 14, which has a dielectric strength of not less than 1 X 10 V/cm and a heat resistance of not lower than 200°C.

Claim 20

The thin film of Claim 14, wherein said thin film is formed by building up layers of said amphiphilic polyimide precursor onto a substrate according to Langmuir-Blodgett technique and partially converting said amphiphilic polyimide precursor into polyimide.

Claim 21

A thin film of a polyimide having a thickness of not more than 1,000 A and a dielectric strength of not less than 1 X 10 6 V/cm.

Claim 22

A thin film of a polyimide having a thickness of not more than 1,000 A and a dielectric strength of not less than 1 X 10 6 V/cm.

Claim 23

The thin film of Claim 18, which has a heat resistance of not lower than 400 0 C.

Claim 24

The thin film of Claim 18, wherein said thin film is formed by building up layers of the amphiphilic polyimide precursor of Claim 1 onto a substrate according to Langmuir-Blodgett technique and converting said precursor into polyimide.