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US4520075A
Expired / Lapsed
US
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Siloxane-modified polyimide precursor and polyimide
Assignee: Nitto Denko Corp
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Filing: 1984-09-25
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Granted: 1985-05-28
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Expires: 2004-09-25
Abstract
Abstract A siloxane-modified polyimide precursor which can be converted into a polyimide having excellent adhesion and moisture resistance is produced by simultaneously polymerizing a diaminosiloxane and a diamine containing no silicon atoms in its molecule with 3,3',4,4'-biphenyltetracarboxylic dianhydride, wherein the diaminosiloxane is used in an amount of 1 to 4 mole % per mole of the total diamino compounds and such that the silicon content in the final reaction product is 0.5 wt % or less. The thus obtained precursor solution is further heat aged to reduce the molecular weight of the precursor so that solution viscosity is decreased to a proper level suitable for coating operation.
Inventors
- 👤 Kazumasa Igarashi
- 👤 Katsuhiko Yamaguchi
- 👤 Kazuo Iko
- 👤 Kazuyuki Miki
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 21:04
CPC Classifications
C; C08; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/1057; C08G73/106; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31551; Y10T428/31623; Y10T428/31652; Y10T428/31663; Y10T428/31721; Y10T428/31725
Claims Analysis
Total Claims: 31
Claim 1
Independent Claim
166 words
A siloxane-modified polyimide precursor which can be converted into a polyimide having excellent adhesion and moisture resistance, the precursor being a reaction product prepared by simultaneously polymerizing (a) a diaminosiloxane represented by the formula ##STR6## wherein R 1 is a divalent organic group, R' is a monovalent organic group, and n is an integer of 1 to 1,000, and (b) a diamine containing no silicon atoms in its molecule with (c) 3,3',4,4'-biphenyltetracarboxylic dianhydride in an inert organic solvent, wherein the diaminosiloxane is used in an amount of 1 to 4 mole % per mole of the total diamino compounds and such that the silicon content in the reaction product is 0.5 wt. % or less, the precursor having the formula ##STR7## wherein R 1 , R' and n are the same as defined above; R 2 is a divalent organic group containing no silicon atoms; Ar is a tetravalent biphenyl organic group; and l and m are positive integers with the proviso that m/l+m=0.01 to 0.04.
Claim 2
Dependent Claim
166 words
A siloxane-modified polyimide precursor which can be converted into a polyimide having excellent adhesion and moisture resistance, the precursor being a reaction product prepared by simultaneously polymerizing (a) a diaminosiloxane represented by the formula ##STR6## wherein R 1 is a divalent organic group, R' is a monovalent organic group, and n is an integer of 1 to 1,000, and (b) a diamine containing no silicon atoms in its molecule with (c) 3,3',4,4'-biphenyltetracarboxylic dianhydride in an inert organic solvent, wherein the diaminosiloxane is used in an amount of 1 to 4 mole % per mole of the total diamino compounds and such that the silicon content in the reaction product is 0.5 wt. % or less, the precursor having the formula ##STR7## wherein R 1 , R' and n are the same as defined above; R 2 is a divalent organic group containing no silicon atoms; Ar is a tetravalent biphenyl organic group; and l and m are positive integers with the proviso that m/l+m=0.01 to 0.04.
Claim 3
Dependent Claim
25 words
The precursor as claimed in claim 1, wherein the polymerization is conducted at a temperature of 60° C. or less under the nitrogen gas stream.
Claim 4
Dependent Claim
12 words
The precursor as claimed in claim 1, wherein the diaminosiloxane is ##STR8##
Claim 5
Dependent Claim
12 words
The precursor as claimed in claim 1, wherein the diaminosiloxane is ##STR9##
Claim 6
Dependent Claim
47 words
The precursor as claimed in claim 1, wherein the diamine containing no silicon atoms in the molecule is an aromatic diamine, an aliphatic diamine or an alicyclic diamine, represented by the formula H.sub.2 N--R.sub.2 --NH.sub.2 wherein R 2 is a divalent organic group containing no silicon atoms.
Claim 7
Dependent Claim
38 words
The precursor as claimed in claim 5, wherein the diamine is selected from the group consisting of m-phenyleneamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2'-bis(4-aminophenyl)propane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, benzidine-3,3'-dicarboxylic acid, benzidine-3,3'-disulfonic acid, 3,3'-dimethoxybenzidine, p-bis(4-aminophenoxy)benzene, m-bis(4-aminophenoxy)-benzene, m-xylylene diamine, and p-xylylene diamine.
Claim 8
Dependent Claim
25 words
The precursor as claimed in claim 1, wherein the ratio of the diaminosiloxane plus diamine containing no silicon atoms to the 3,3',4,4'-biphenyltetracarboxylic dianhydride is equimolar.
Claim 9
Dependent Claim
29 words
The precursor as claimed in claim 1, wherein the precursor has an inherent viscosity of 1.3 to 3.0 as measured at 30° C. as a 0.5% solution in N-methyl-2-pyrolidone.
Claim 10
Dependent Claim
44 words
The precursor as claimed in claim 1, wherein the reaction product obtained by the polymerization is in solution in the organic solvent and the so obtained solution is heat aged at 40° to 80° C. to reduce the inherent viscosity of the polyimide precursor.
Claim 11
Dependent Claim
33 words
The precursor as claimed in claim 9, wherein the polyimide precursor before heat aging has the inherent viscosity of 1.3 to 3.0 as measured at 30° C. as a 0.5% solution of N-methyl-2-pyrolidene.
Claim 12
Dependent Claim
33 words
The precursor as claimed in claim 9, wherein the polyimide precursor after heat aging has the inherent viscosity of 0.3 to 0.7 as measured at 30° C. as a 0.5% solution in N-methyl-2-pyrolidone.
Claim 13
Dependent Claim
193 words
A coated article comprising a substrate and a polyimide coating on the substrate, the polyimide having excellent adhesion and moisture resistance and being formed as a reaction product by the steps of (1) simultaneously polymerizing (a) a diaminosiloxane represented by the formula ##STR10## wherein R 1 is a divalent organic group, R' is a monovalent organic group, and n is an integer of 1 to 1,000, and (b) a diamine containing no silicon atoms in its molecule, with (c) 3,3',4,4'-biphenyltetracarboxylic dianyhydride in an inert organic solvent, wherein the diaminosiloxane is used in an amount of 1 to 4 mole % per mole of the total diamino compounds and such that the silicon content in the reaction product is 0.5 wt % or less to form a polyimide precursor, and (2) heating the precursor to dehydrate and cyclize it to obtain the polyimide, the polyimide having the formula ##STR11## wherein R 1 , R' and n are the same as defined above; R 2 is a divalent organic group containing no silicon atoms; Ar is a tetravelent biphenyl organic group; and l and m are positive integers with the proviso that m/l+m=0.01 to 0.04.
Claim 14
Dependent Claim
193 words
A coated article comprising a substrate and a polyimide coating on the substrate, the polyimide having excellent adhesion and moisture resistance and being formed as a reaction product by the steps of (1) simultaneously polymerizing (a) a diaminosiloxane represented by the formula ##STR10## wherein R 1 is a divalent organic group, R' is a monovalent organic group, and n is an integer of 1 to 1,000, and (b) a diamine containing no silicon atoms in its molecule, with (c) 3,3',4,4'-biphenyltetracarboxylic dianyhydride in an inert organic solvent, wherein the diaminosiloxane is used in an amount of 1 to 4 mole % per mole of the total diamino compounds and such that the silicon content in the reaction product is 0.5 wt % or less to form a polyimide precursor, and (2) heating the precursor to dehydrate and cyclize it to obtain the polyimide, the polyimide having the formula ##STR11## wherein R 1 , R' and n are the same as defined above; R 2 is a divalent organic group containing no silicon atoms; Ar is a tetravelent biphenyl organic group; and l and m are positive integers with the proviso that m/l+m=0.01 to 0.04.
Claim 15
Dependent Claim
25 words
The article as claimed in claim 12, wherein the polymerization is conducted at a temperature of 60° C. or less under the nitrogen gas stream.
Claim 16
Dependent Claim
12 words
The article as claimed in claim 12, wherein the diaminosiloxane is ##STR12##
Claim 17
Dependent Claim
12 words
The article as claimed in claim 12, wherein the diaminosiloxane is ##STR13##
Claim 18
Dependent Claim
47 words
The article as claimed in claim 12, wherein the diamine containing no silicon atoms in the molecule is an aromatic diamine, an aliphatic diamine or an alicyclic diamine, represented by the formula H.sub.2 N--R.sub.2 --NH.sub.2 wherein R 2 is a divalent organic group containing no silicon atoms.
Claim 19
Dependent Claim
35 words
The article as claimed in claim 12, wherein the diamine is selected from the group consisting of m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2'-bis(4-aminophenyl)propane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine-3-monosulfonic acid, 3,3'-dimethoxybenzidine, p-bis(4-aminophenoxy)benzene, m-bis(4-aminophenoxy)benzene, m-xylylene diamine, and p-xylylene diamine.
Claim 20
Dependent Claim
25 words
The article as claimed in claim 12, wherein the ratio of the diaminosiloxane plus diamine containing no silicon atoms to the 3,3',4,4'-biphenyltetracarboxylic dianhydride is equimolar.
Claim 21
Dependent Claim
50 words
The article as claimed in claim 12, wherein the reaction product obtained by the polymerization is in solution in the organic solvent, and the so-obtained solution is heat aged to reduce the inherent viscosity of the polyimide precursor before the precursor is subjected to the heating which dehydrates and cyclizes.
Claim 22
Dependent Claim
14 words
The article as claimed in claim 12, wherein the substrate is silicon or glass.
Claim 23
Dependent Claim
179 words
A polyimide having excellent adhesion and moisture resistance and being formed as a reaction product by the steps of (1) simultaneously polymerizing (a) a diaminosiloxane represented by the formula ##STR14## wherein R 1 is a divalent organic group, R' is a monovalent organic group, and n is an integer of 1 to 1,000, and (b) a diamine containing no silicon atoms in its molecule, with (c) 3,3',4,4'-biphenyltetracarboxylic dianhydride in an inert organic solvent, wherein diaminosiloxane is used in an amount of 1 to 4 mole % per mole of the total diamino compounds and such that the silicon content in the reaction product is 0.5 wt % or less to form a polyimide precursor, and (2) heating the precursor to dehydrate and cyclize it to obtain the polyimide, the polyimide having the formula ##STR15## wherein R 1 , R' and n are the same as defined above; R 2 is a divalent organic group containing no silicon atoms; Ar is a tetravalent biphenyl organic group; and l and m are positive integers with the proviso that m/l+m=0.01 to 0.04.
Claim 24
Dependent Claim
179 words
A polyimide having excellent adhesion and moisture resistance and being formed as a reaction product by the steps of (1) simultaneously polymerizing (a) a diaminosiloxane represented by the formula ##STR14## wherein R 1 is a divalent organic group, R' is a monovalent organic group, and n is an integer of 1 to 1,000, and (b) a diamine containing no silicon atoms in its molecule, with (c) 3,3',4,4'-biphenyltetracarboxylic dianhydride in an inert organic solvent, wherein diaminosiloxane is used in an amount of 1 to 4 mole % per mole of the total diamino compounds and such that the silicon content in the reaction product is 0.5 wt % or less to form a polyimide precursor, and (2) heating the precursor to dehydrate and cyclize it to obtain the polyimide, the polyimide having the formula ##STR15## wherein R 1 , R' and n are the same as defined above; R 2 is a divalent organic group containing no silicon atoms; Ar is a tetravalent biphenyl organic group; and l and m are positive integers with the proviso that m/l+m=0.01 to 0.04.
Claim 25
Dependent Claim
25 words
The polyimide as claimed in claim 21, wherein the polymerization is conducted at a temperature of 60° C. or less under the nitrogen gas stream.
Claim 26
Dependent Claim
12 words
The polyimide as claimed in claim 21, wherein the diaminosiloxane is ##STR16##
Claim 27
Dependent Claim
12 words
The polyimide as claimed in claim 21, wherein the diaminosiloxane is ##STR17##
Claim 28
Dependent Claim
47 words
The polyimide as claimed in claim 21, wherein the diamine containing no silicon atoms in the molecule is an aromatic diamine, an aliphatic diamine or an alicyclic diamine, represented by the formula H.sub.2 N--R.sub.2 --NH.sub.2 wherein R 2 is a divalent organic group containing no silicon atoms.
Claim 29
Dependent Claim
35 words
The polyimide as claimed in claim 21, wherein the diamine is selected from the group consisting of m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 2,2'-bis(4-aminophenyl)propane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminophenylsulfone, 4,4'-diaminophenylsulfide, benzidine-3-monosulfonic acid, 3,3'-dimethoxybenzidine, p-bis(4-aminophenoxy)benzene, m-bis(4-aminophenoxy)benzene, m-xylylene diamine, and p-xylylene diamine.
Claim 30
Dependent Claim
25 words
The polyimide as claimed in claim 21, wherein the ratio of the diaminosiloxane plus diamine containing no silicon atoms to the 3,3',4,4'-biphenyltetracarboxylic dianhydride is equimolar.
Claim 31
Dependent Claim
50 words
The polyimide as claimed in claim 24, wherein the reaction product obtained by the polymerization is in solution in the organic solvent, and the so-obtained solution is heat aged to reduce the inherent viscosity of the polyimide percursor before the precursor is subjected to the heating which dehydrates and cyclizes.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-05-27 | 1988-11-26 | 1989-05-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-05-27 | 1992-11-26 | 1993-05-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-05-27 | 1996-11-26 | 1997-05-28 | $7700.00 | Window Closed / Lapsed |