CN111757904B - Polyimide precursor, polyimide film, varnish, and substrate - Google Patents

Polyimide precursor, polyimide film, varnish, and substrate Download PDF

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CN111757904B
CN111757904B CN201880089562.4A CN201880089562A CN111757904B CN 111757904 B CN111757904 B CN 111757904B CN 201880089562 A CN201880089562 A CN 201880089562A CN 111757904 B CN111757904 B CN 111757904B
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valent group
polyimide
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CN111757904A (en
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冈卓也
小滨幸德
中川美晴
久野信治
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Ube Corp
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
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    • B32B2457/12—Photovoltaic modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

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Abstract

The present invention provides a polyimide comprising a repeating unit represented by the following general formula (5), wherein A of the general formula (5) 2 Comprises a 4-valent group represented by the formula (A-1), and B of the formula (5) 2 Comprising a 2-valent group represented by the formula (B-1), in addition, A 2 And/or B 2 Containing a 4-valent or 2-valent group having a specific structure in a specific ratio. The polyimide has high transparency and low linear thermal expansion coefficient, and also has small thickness direction phase difference (retardation). (wherein A 2 Is a 4-valent group having an aromatic ring or alicyclic structure, B 2 Is a 2-valent group having an aromatic ring or alicyclic structure. Wherein A is contained in each repeating unit 2 And B 2 May be the same or different. )

Description

Polyimide precursor, polyimide film, varnish, and substrate
Technical Field
The present invention relates to a polyimide having high transparency and a low coefficient of linear thermal expansion and having a small retardation (retardation) in the thickness direction, and a precursor thereof. In addition, the present invention also relates to a polyimide film, a varnish comprising a polyimide precursor or polyimide, and a substrate.
Background
In recent years, with the advent of a highly informative society, development of optical materials such as a liquid crystal alignment film and a protective film for a color filter in the field of display devices such as an optical fiber and an optical waveguide in the field of optical communication has been advanced. In particular, in the field of display devices, as a substitute for a glass substrate, a study of a plastic substrate having light weight and excellent flexibility is being conducted, and development of a flexible or roll-up display is being actively conducted. Therefore, there is a need for higher performance optical materials that can be used for such applications.
Aromatic polyimides are colored in nature yellow brown due to intramolecular conjugation and formation of charge transfer complexes. Therefore, as means for suppressing coloration, for example, a method has been proposed in which fluorine atoms are introduced into a molecule, a main chain is provided with flexibility, a bulky group is introduced as a side chain, and the formation of an intramolecular conjugate or a charge transfer complex is inhibited, thereby making the molecule transparent.
In addition, a method of imparting transparency by using a semi-alicyclic or full-alicyclic polyimide which does not form a charge transfer complex in principle has been proposed. In particular, a variety of semi-alicyclic polyimides having high transparency using an aromatic tetracarboxylic dianhydride as a tetracarboxylic acid component and an alicyclic diamine as a diamine component have been proposed; and a highly transparent semi-alicyclic polyimide using an alicyclic tetracarboxylic dianhydride as the tetracarboxylic acid component and an aromatic diamine as the diamine component.
For example, patent document 1 discloses a polyimide in which norbornane-2-spiro- α -cyclopentanone- α ' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride (abbreviated as CpODA) is used as the tetracarboxylic acid component, and 2,2' -bis (trifluoromethyl) benzidine (abbreviated as TFMB) or TFMB and another aromatic diamine (for example, TFMB:4,4' -diaminobenzanilide: 9, 9-bis (4-aminophenyl) fluorene=5:4:1 (molar ratio)) are used as the diamine component. Patent document 2 discloses a polyimide using CpODA having a specific stereoisomer ratio as a tetracarboxylic acid component, and TFMB and other aromatic diamines (for example, TFMB:4,4' -diaminobenzanilide=5:5 (molar ratio) or the like) as diamine components.
Patent document 3 discloses a polyimide resin containing a structural unit a derived from tetracarboxylic dianhydride and a structural unit B derived from a diamine compound, wherein the structural unit a contains at least one of a structural unit (a-1) derived from CpODA, a structural unit (a-2) derived from pyromellitic dianhydride, and a structural unit (a-3) derived from 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, and the structural unit B contains a structural unit (B-1) derived from 9, 9-bis (4-aminophenyl) fluorene, and the proportion of the structural unit (B-1) in the structural unit B is 60 mol% or more. More specifically, in example 4 of patent document 3, a polyimide resin was produced from CpODA (a-1) and 9, 9-bis (4-aminophenyl) fluorene (B-1). In example 5 of patent document 3, a polyimide resin ((a-1): (a-3) =1:1 (molar ratio)) was produced from CpODA (a-1), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (a-3), and 9, 9-bis (4-aminophenyl) fluorene (B-1). In example 6 of patent document 3, a polyimide resin ((B-1): (B-2) =4:1 (molar ratio)) was produced from CpODA (a-1), 9-bis (4-aminophenyl) fluorene (B-1) and 2,2' -dimethylbenzidine (B-2).
In addition, in example 1 and comparative example 1 of patent document 4, a polyimide obtained from CpODA, 4 '-diamino-2, 2' -dimethylbiphenyl and 9, 9-bis (4-aminophenyl) fluorene (molar ratio: 1/1), and a polyimide obtained from CpODA and 9, 9-bis (4-aminophenyl) fluorene are described.
Prior art literature
Patent literature
Patent document 1: international publication No. 2013/179727
Patent document 2: international publication No. 2014/046064
Patent document 3: international publication No. 2017/191822
Patent document 4: japanese patent laid-open No. 2017-133027
Disclosure of Invention
Problems to be solved by the invention
Polyimide and polyimide films having high transparency and low linear thermal expansion coefficient and small retardation (retardation) in the thickness direction are demanded depending on the application, for example, in display applications and the like. When light passes through a film having a large retardation in the thickness direction, there are some cases where the color of the transmitted light cannot be displayed accurately, the color is blurred, the viewing angle is narrowed, and the like. Therefore, in particular, in display applications and the like, it is desirable to reduce the thickness-direction phase difference.
The present invention provides a polyimide having high transparency and a low linear thermal expansion coefficient and having a small retardation (retardation) in the thickness direction, and a precursor thereof.
Means for solving the problems
The present invention relates to the following.
1. A polyimide precursor comprising a repeating unit represented by the following general formula (1),
a of the following general formula (1) 1 Comprises a 4-valent group represented by the following formula (A-1), and B of the following formula (1) 1 Comprising a 2-valent group represented by the following formula (B-1),
in addition, A of the following general formula (1) 1 And/or B 1 Comprising a 4-valent or 2-valent group having a structure represented by the following formula (2), or A of the following general formula (1) 1 Comprising a 4-valent group represented by the following formula (3) and/or a 4-valent group represented by the following formula (4),
a of the general formula (1) 1 The total content of the 4-valent group represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group represented by the formula (3) and the 4-valent group represented by the formula (4) in 100 mol% is equal to B of the general formula (1) 1 The total content of the 2-valent groups represented by the formula (B-1) and the 2-valent groups having the structure represented by the formula (2) in 100 mol% is 120 mol% or more,
wherein the ratio of the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the formula (4) is 80 mol% or less relative to the total of the 4-valent group having the structure represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the structure represented by the formula (4),
the proportion of the 2-valent group having the structure represented by the formula (2) relative to the total of the 2-valent group having the structure represented by the formula (2) and the 2-valent group having the structure represented by the formula (2) is 80 mol% or less.
[ chemical 1]
Figure BDA0002635458540000031
(wherein A 1 Is a 4-valent group having an aromatic ring or alicyclic structure, B 1 Is a 2-valent group having an aromatic ring or alicyclic structure, R 1 、R 2 Each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. Wherein A is contained in each repeating unit 1 And B 1 May be the same or different. )
[ chemical 2]
Figure BDA0002635458540000041
[ chemical 3]
Figure BDA0002635458540000042
[ chemical 4]
Figure BDA0002635458540000043
[ chemical 5]
Figure BDA0002635458540000044
[ chemical 6]
Figure BDA0002635458540000045
2. A polyimide comprising a repeating unit represented by the following general formula (5),
a of the following general formula (5) 2 Comprises a 4-valent group represented by the following formula (A-1), and B of the following formula (5) 2 Comprising a 2-valent group represented by the following formula (B-1),
in addition, A of the following formula (5) 2 And/or B 2 Comprising a 4-valent or 2-valent group having a structure represented by the following formula (2), or A of the following general formula (5) 2 Comprising a 4-valent group represented by the following formula (3) and/or a 4-valent group represented by the following formula (4),
a of the general formula (5) 2 The total content of the 4-valent group represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group represented by the formula (3) and the 4-valent group represented by the formula (4) in 100 mol% is equal to B of the general formula (5) 2 The total content of the 2-valent groups represented by the formula (B-1) and the 2-valent groups having the structure represented by the formula (2) in 100 mol% is 120 mol% or more,
Wherein the ratio of the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the formula (4) is 80 mol% or less relative to the total of the 4-valent group having the structure represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the structure represented by the formula (4),
the proportion of the 2-valent group having the structure represented by the formula (2) relative to the total of the 2-valent group having the structure represented by the formula (2) and the 2-valent group having the structure represented by the formula (2) is 80 mol% or less.
[ chemical 7]
Figure BDA0002635458540000051
(wherein A 2 Is a 4-valent group having an aromatic ring or alicyclic structure, B 2 Is a 2-valent group having an aromatic ring or alicyclic structure. Wherein each repeating unit comprisesA of (2) 2 And B 2 May be the same or different. )
[ chemical 8]
Figure BDA0002635458540000052
[ chemical 9]
Figure BDA0002635458540000061
[ chemical 10]
Figure BDA0002635458540000062
[ chemical 11]
Figure BDA0002635458540000063
[ chemical 12]
Figure BDA0002635458540000064
3. A polyimide obtained from the polyimide precursor according to item 1 above.
4. A varnish comprising the polyimide precursor according to item 1 above or the polyimide according to item 2 above.
5. A polyimide film obtained by using a varnish comprising the polyimide precursor according to item 1 or the polyimide according to item 2.
6. A laminate comprising a glass substrate and a film comprising the polyimide according to any one of items 2 and 3 or the polyimide film according to item 5.
7. A substrate for a display, a touch panel, or a solar cell, comprising the polyimide according to item 2 or 3, or the polyimide film according to item 5.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polyimide having high transparency and low linear thermal expansion coefficient and having a small retardation (retardation) in the thickness direction and a precursor thereof can be provided.
The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency, low linear thermal expansion coefficient, and small retardation (retardation) in the thickness direction, and thus can be suitably used for forming substrates for display applications and the like. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention can be suitably used for forming substrates for touch panels and solar cells.
Detailed Description
The polyimide precursor of the present invention is a polyimide precursor containing a repeating unit represented by the general formula (1). The total content of the repeating units represented by the general formula (1) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol% or more based on the total of the repeating units. A in the general formula (1) 1 The 4-valent group having an aromatic ring or alicyclic structure is preferably a 4-valent group having an alicyclic structure. B in the general formula (1) 1 The 2-valent group having an aromatic ring or alicyclic structure is preferably a 2-valent group having an aromatic ring.
In the polyimide precursor of the present invention, A in the general formula (1) is 1 Comprises a 4-valent group represented by the above formula (A-1), and B in the above formula (1) 1 Comprises a 2-valent group represented by the above formula (B-1), and A of the above formula (1) 1 And/or B 1 Comprising a 4-valent or 2-valent group having a structure represented by the above formula (2), or A of the above general formula (1) 1 Comprises a 4-valent group represented by the above formula (3) and/or a 4-valent group represented by the above formula (4). It may also be: a is that 1 And/or B 1 Comprising a 4-valent or 2-valent group having a structure represented by the above formula (2), and A 1 Comprises a 4-valent group represented by the above formula (3) and/or a 4-valent group represented by the above formula (4).
Furthermore, in relation to themContent of A of the general formula (1) 1 The total content of the 4-valent group represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group represented by the formula (3) and the 4-valent group represented by the formula (4) in 100 mol% is equal to B of the general formula (1) 1 The total content ratio of the 2-valent group represented by the formula (B-1) and the 2-valent group having the structure represented by the formula (2) in 100 mol% is 120 mol% or more, preferably 160 mol% or more, and more preferably 180 mol% or more. Wherein A of the general formula (1) 1 Wherein the ratio of the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group represented by the formula (4) to the total of the 4-valent group having the structure represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group represented by the formula (4) is 80 mol% or less, and B of the formula (1) 1 Wherein the proportion of the 2-valent group having the structure represented by the formula (2) relative to the total of the 2-valent group having the structure represented by the formula (2) and the 2-valent group having the structure represented by the formula (2) is 80 mol% or less. The sum of these 2 proportions is preferably 125 mol% or less.
The polyimide of the present invention is a polyimide containing a repeating unit represented by the above general formula (5). The total content of the repeating units represented by the general formula (5) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol% or more based on the total of the repeating units. A in the general formula (5) 2 The 4-valent group having an aromatic ring or alicyclic structure is preferably a 4-valent group having an alicyclic structure. B in the general formula (5) 2 The 2-valent group having an aromatic ring or alicyclic structure is preferably a 2-valent group having an aromatic ring.
In the polyimide of the present invention, A in the general formula (5) 2 Comprises a 4-valent group represented by the above formula (A-1), and B in the above formula (5) 2 Comprises a 2-valent group represented by the above formula (B-1), and A of the above formula (5) 2 And/or B 2 Comprising a 4-valent or 2-valent group having a structure represented by the above formula (2), or A of the above formula (5) 2 Comprising a 4-valent group represented by the above formula (3)And/or a 4-valent group represented by the above formula (4). It may also be: a is that 2 And/or B 2 Comprising a 4-valent or 2-valent group having a structure represented by the above formula (2), and A 2 Comprises a 4-valent group represented by the above formula (3) and/or a 4-valent group represented by the above formula (4).
Furthermore, regarding their content, A of the general formula (5) 2 The total content of the 4-valent group represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group represented by the formula (3) and the 4-valent group represented by the formula (4) in 100 mol% is equal to B of the general formula (5) 2 The total content ratio of the 2-valent group represented by the formula (B-1) and the 2-valent group having the structure represented by the formula (2) in 100 mol% is 120 mol% or more, preferably 160 mol% or more, and more preferably 180 mol% or more. Wherein A of the general formula (5) 2 Wherein the ratio of the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group represented by the formula (4) to the total of the 4-valent group having the structure represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group represented by the formula (4) is 80 mol% or less, and B of the general formula (5) 2 Wherein the proportion of the 2-valent group having the structure represented by the formula (2) relative to the total of the 2-valent group having the structure represented by the formula (2) and the 2-valent group having the structure represented by the formula (2) is 80 mol% or less. The sum of these 2 proportions is preferably 125 mol% or less.
In the present specification, the following abbreviations are used as appropriate.
CpODA: norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride
CpODA et al: norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic acids and the like (tetracarboxylic acids and the like represent tetracarboxylic acid derivatives such as tetracarboxylic acid and tetracarboxylic dianhydride, tetracarboxylic silyl ester, tetracarboxylic acid chloride and the like)
TFMB:2,2' -bis (trifluoromethyl) benzidine
The tetracarboxylic acid component providing the 4-valent group represented by the above formula (A-1) is CpODA or the like,the diamine component providing a 2-valent group represented by the above formula (B-1) is TFMB. Polyimides derived from CpODA et al and TFMB (i.e., from A 1 A 4-valent group represented by the above formula (A-1), B 1 Polyimide obtained from polyimide precursor composed of repeating unit of the above general formula (1) which is a 2-valent group represented by the above formula (B-1), and polyimide obtained from A 2 A 4-valent group represented by the above formula (A-1), B 2 The polyimide composed of the repeating unit of the general formula (5) which is a 2-valent group represented by the above formula (B-1) has high transparency and low linear thermal expansion coefficient, but tends to have a relatively large retardation (retardation) in the thickness direction. When the polyimide film is used for a display or the like, as described above, if the retardation in the thickness direction is large, there are some cases where the color of the transmitted light cannot be displayed correctly, the color is blurred, the viewing angle is narrowed, and the like. On the other hand, the content (ratio) of A in the general formula (1) as a structure derived from the tetracarboxylic acid component 1 A of the general formula (5) 2 And/or B of the general formula (1) as a structure derived from a diamine component 1 B of the general formula (5) 2 Introducing a group having a structure represented by the above formula (2) or, in the formula (1) A as a structure derived from a tetracarboxylic acid component 1 A of the general formula (5) 2 The introduction of the 4-valent group represented by the above formula (3) and/or the 4-valent group represented by the above formula (4) can reduce the thickness-direction retardation (retardation) while maintaining high transparency and a low coefficient of linear thermal expansion. As a result, a polyimide having high transparency and a low coefficient of linear thermal expansion and having a small retardation (retardation) in the thickness direction can be obtained.
Here, in the structure represented by the above formula (2), adjacent aromatic rings may be further connected by a direct bond, an ether bond, or the like, and for example, the structure represented by the following formula (2') may be used.
[ chemical 13]
Figure BDA0002635458540000091
(wherein R is a direct bond or an ether bond (-O-))
The aromatic ring contained in the structure represented by the above formula (2) may be substituted with a substituent such as an alkyl group such as a methyl group, a fluoroalkyl group such as a trifluoromethyl group, or a halogen group, but it is usually preferable that the aromatic ring does not have a substituent. The substitution position is not particularly limited.
The tetracarboxylic acid component having a 4-valent group represented by the above formula (2) is a tetracarboxylic acid having a structure represented by the above formula (2), and examples thereof include 9,9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride, other derivatives (tetracarboxylic acid derivatives other than tetracarboxylic acid dianhydrides such as tetracarboxylic silyl ester, tetracarboxylic ester, and tetracarboxylic acid chloride), and the like. The diamine component having a 2-valent group represented by the above formula (2) is a diamine having a structure represented by the above formula (2), and examples thereof include 9, 9-bis (4-aminophenyl) fluorene, 9-bis (4-amino-3-chlorophenyl) fluorene, 9-bis (4-amino-3-fluorophenyl) fluorene, 9-bis (4-amino-3-methylphenyl) fluorene, 4'- (spiro [ fluorene-9, 9' -xanthene ] -3',6' -diylbis (oxy)) diphenylamine, and the like.
The tetracarboxylic acid component having a 4-valent group represented by the above formula (3) is a 1,2,4, 5-cyclohexane tetracarboxylic acid or the like.
The tetracarboxylic acid component providing a 4-valent group represented by the above formula (4) is a 2, 3',4' -biphenyltetracarboxylic acid or the like.
In other words, for the polyimide precursor of the present invention and the polyimide of the present invention,
is obtained from a tetracarboxylic acid component comprising (a-1) CpODA and the like and (a-2) a tetracarboxylic acid having a structure represented by the above formula (2), a 1,2,4, 5-cyclohexane tetracarboxylic acid and the like, or at least one of 2, 3',4' -biphenyl tetracarboxylic acid and the like, and (b) a diamine component comprising TFMB, or a diamine component comprising TFMB and a diamine having a structure represented by the above formula (2), or,
is obtained from (a) a tetracarboxylic acid component containing CpODA or the like and (b) a diamine component containing TFMB and a diamine having a structure represented by the above formula (2).
Among the 6 stereoisomers, the tetracarboxylic acid component CpODA and the like used herein may preferably contain trans-endo-norbornane-2-spiro-alpha-cyclopentanone-alpha '-spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic acids and the like (trans-endo) and/or cis-endo-norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2" -norbornane-5, 5", 6" -tetracarboxylic acids and the like (cis-endo). In one embodiment, the total of the trans-endo form and/or cis-endo form ratio in CpODA or the like is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 99 mol% or more.
Among the 6 stereoisomers, 1R,2S,4S, 5R-cyclohexane tetracarboxylic acids and the like are preferably contained as the tetracarboxylic acid component 1,2,4, 5-cyclohexane tetracarboxylic acids and the like used herein. In one embodiment, the ratio of 1R,2S,4S, 5R-cyclohexane tetracarboxylic acid in the 1,2,4, 5-cyclohexane tetracarboxylic acid is preferably 50 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 95 mol% or more.
CpODA and the like may be used singly or in combination. The tetracarboxylic acids having the structure represented by the above formula (2), 1,2,4, 5-cyclohexane tetracarboxylic acids, and 2, 3',4' -biphenyl tetracarboxylic acids may be used singly or in combination. The diamine having the structure represented by the above formula (2) may be used singly or in combination of two or more.
As the other tetracarboxylic acid component providing the repeating unit represented by the above general formula (1) or the repeating unit represented by the above general formula (5), any of other aromatic or alicyclic tetracarboxylic acids can be used. Examples thereof include, but are not particularly limited to, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, pyromellitic acid, 3',4,4' -benzophenone tetracarboxylic acid, 3',4' -biphenyl tetracarboxylic acid, 4 '-oxydiphthalic acid, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, m-terphenyl-3, 4,3',4 '-tetracarboxylic dianhydride, p-terphenyl-3, 4,3',4 '-tetracarboxylic dianhydride, dicarboxyphenyl dimethylsilane, bisdicarboxyphenoxydiphenyl sulfide, sulfonyl diphthalic acid, 1,2,3, 4-cyclobutane tetracarboxylic acid, isopropylidenediphenoxydiphthalic acid, [1,1' -dicyclohexyl ] -3,3',4,4' -tetracarboxylic acid, [1,1 '-dicyclohexyl ] -2, 3',4 '-tetracarboxylic acid, [1,1' -dicyclohexyl ] -2,2',3,3' -tetracarboxylic acid, 4 '-methylenebis (cyclohexane-1, 2-dicarboxylic acid), 4' - (propane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic acid), 4 '-oxybis (cyclohexane-1, 2-dicarboxylic acid), and 4,4' -thiobis (cyclohexane-1, 2-dicarboxylic acid), 4 '-sulfonylbis (cyclohexane-1, 2-dicarboxylic acid), 4' - (dimethylsilanediyl) bis (cyclohexane-1, 2-dicarboxylic acid), and, 4,4' - (tetrafluoropropane-2, 2-diyl) bis (cyclohexane-1, 2-dicarboxylic acid), octahydropentalene-1, 3,4, 6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2, 3, 5-tricarboxylic acid, bicyclo [2.2.2] octane-2, 3,5, 6-tetracarboxylic acid, bicyclo [2.2.2] oct-5-ene-2, 3,7, 8-tetracarboxylic acid, tricyclo [4.2.2.02,5] decane-3, 4,7, 8-tetracarboxylic acid, tricyclo [ 38325 ] dec-7-ene-3, 4,9, 10-tetracarboxylic acid, 9-oxatricyclo [ 356 ] nonane-3, 4,7, 8-tetracarboxylic acid, (4 arH,8 ach) -decahydro-1 t,4t 5c,8 c-dimethylnaphthalene-c, 6 c-tetracarboxylic acid, 7 c-tetracyclo-8 c-tetracarboxylic acid, 7 c-tetracyclo [ 356 ] naphthalene-3, 4, 8-tetracarboxylic acid, and (4 arH) -decade-1 t,4 c-tetracarboxylic acid. Of these, derivatives such as 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 4' -oxybisphthalic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid, (4 arH,8 ach) -decahydro-1 t,4t:5c,8 c-dimethylnaphthalene-2 c,3c,6c,7 c-tetracarboxylic acid, (4 arH,8 ach) -decahydro-1 t,4t:5c,8 c-dimethylnaphthalene-2 t,3t,6c,7 c-tetracarboxylic acid, and acid dianhydrides thereof are more preferable. These tetracarboxylic acid components may be used alone, or two or more thereof may be used in combination.
As the other diamine component providing the repeating unit of the above general formula (1) or the repeating unit represented by the above general formula (5), any of other aromatic or alicyclic diamines may be used. Examples thereof include, but are not particularly limited to, p-phenylenediamine, m-phenylenediamine, benzidine, 3' -diaminobiphenyl, 3' -bis (trifluoromethyl) benzidine, m-benzidine, 4' -diaminobenzanilide, 3,4' -diaminobenzanilide, N ' -bis (4-aminophenyl) terephthalamide, N, N ' -p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4, 4' -dicarboxylic acid bis (4-aminophenyl) ester, p-phenylenebis (p-aminophenyl) ester, bis (4-aminophenyl) - [1,1' -biphenyl ] -4,4' -dicarboxylate, [1,1' -biphenyl ] -4,4' -diylbis (4-aminobenzoate), 4' -oxydiphenylamine, 3' -oxydiphenylamine, bis (4-aminophenyl) sulfide, p-methylenebis (phenylenediamine), 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, 3, 3-bis ((aminophenoxy) phenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4- (4-aminophenoxy) diphenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfone, octafluorobiphenyl amine 3,3 '-dimethoxy-4, 4' -diaminobiphenyl, 3 '-dichloro-4, 4' -diaminobiphenyl, 3 '-difluoro-4, 4' -diaminobiphenyl, 4 '-bis (4-aminophenoxy) biphenyl, 4' -bis (3-aminophenoxy) biphenyl, 1, 4-diamino-cyclohexane, 1, 4-diamino-2-methylcyclohexane, 1, 4-diamino-2-ethylcyclohexane, 1, 4-diamino-2-n-propylcyclohexane, 1, 4-diamino-2-isopropylcyclohexane, 1, 4-diamino-2-n-butylcyclohexane, 1, 4-diamino-2-isobutylcyclohexane, 1, 4-diamino-2-sec-butylcyclohexane, 1, 4-diamino-2-tert-butylcyclohexane, 1, 2-diamino-cyclohexane, 1, 4-diamino-cyclohexane and the like or derivatives thereof. Among these, p-phenylenediamine, m-tolidine, 4 '-oxydiphenylamine, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl and the like are more preferable. These diamine components may be used alone or in combination of two or more.
The polyimide precursor of the present invention and the polyimide of the present invention may contain one or more other repeating units other than the repeating unit represented by the above general formula (1) or the repeating unit represented by the above general formula (5). The tetracarboxylic acid component and the diamine component that provide the other repeating units are not particularly limited, and any other known tetracarboxylic acids and known diamines may be used. In the case where the diamine component to be combined is not a diamine component providing a repeating unit represented by the above general formula (1) or a repeating unit represented by the above general formula (5), the tetracarboxylic acid component providing another repeating unit may be a tetracarboxylic acid exemplified as a tetracarboxylic acid component providing a repeating unit represented by the above general formula (1) or a repeating unit represented by the above general formula (5) (including CpODA and the like, tetracarboxylic acids and the like having a structure represented by the above general formula (2) and the like, 1,2,4, 5-cyclohexane tetracarboxylic acids and the like, 2, 3',4' -biphenyl tetracarboxylic acids and the like). In the case where the tetracarboxylic acid component to be combined is not a tetracarboxylic acid component providing a repeating unit represented by the above general formula (1) or a repeating unit represented by the above general formula (5), the diamine component providing another repeating unit may be a diamine (including TFMB and a diamine having a structure represented by the above general formula (2)) exemplified as a diamine component providing a repeating unit represented by the above general formula (1) or a repeating unit represented by the above general formula (5).
In the polyimide precursor of the present invention, R in the above general formula (1) 1 、R 2 Each independently represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (particularly preferably methyl or ethyl), and an alkylsilyl group having 3 to 9 carbon atoms (particularly preferably trimethylsilyl or t-butyldimethylsilyl). For R 1 、R 2 The kind of the functional group and the introduction rate of the functional group can be changed by a production method described later.
The introduction rate of the functional group is not particularly limited, and R may be set in the case of introducing an alkyl group or an alkylsilyl group 1 、R 2 More than 25%, preferably more than 50%, more preferably more than 75% of each is alkyl or alkylsilyl. By letting R 1 、R 2 More than 25% of each is alkyl or alkylsilyl, and the polyimide precursor has excellent storage stability.
According to R 1 And R is 2 The chemical structures taken independently of each other, polyimide precursors of the present invention can be classified: 1) Polyamic acid (R) 1 And R is 2 Hydrogen), 2) polyamic acid ester (R) 1 、R 2 At least a part of (a) is an alkaneRadical), 3) 4) polyamic acid silyl ester (R) 1 、R 2 At least a portion of which is an alkylsilyl group). The polyimide precursor of the present invention can be easily produced by the following production method according to the classification. However, the method for producing the polyimide precursor of the present invention is not limited to the following production method.
1) Polyamic acid
The polyimide precursor of the present invention can be suitably obtained as a polyimide precursor solution composition by reacting a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent at a ratio of about equimolar, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [ the number of moles of the diamine component/the number of moles of the tetracarboxylic acid component ] of preferably 0.90 to 1.10, more preferably 0.95 to 1.05, at a relatively low temperature of, for example, 120 ℃ or less, while suppressing imidization.
The method for synthesizing the polyimide precursor of the present invention is not limited, and more specifically, a diamine is dissolved in an organic solvent, a tetracarboxylic dianhydride is slowly added to the solution while stirring, and the solution is stirred at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method is preferable because it is easy to increase the molecular weight of the polyimide precursor. The order of addition of the diamine and the tetracarboxylic dianhydride in the above production method may be reversed, and the precipitate is preferably reduced.
When the molar ratio of the tetracarboxylic acid component to the diamine component is an excess of the diamine component, the molar ratio of the tetracarboxylic acid component to the diamine component may be made approximately equal by adding a carboxylic acid derivative in an amount approximately corresponding to the excess molar number of the diamine component, if necessary. The carboxylic acid derivative is preferably a tetracarboxylic acid which does not substantially increase the viscosity of the polyimide precursor solution, i.e., does not substantially participate in molecular chain extension; or tricarboxylic acids and anhydrides thereof, dicarboxylic acids and anhydrides thereof, and the like, which function as capping agents.
2) Polyamic acid esters
The tetracarboxylic dianhydride is reacted with an arbitrary alcohol to obtain a dicarboxylic acid diester, and then reacted with a chlorinating agent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. The diester dicarboxylic acid chloride and diamine are stirred at a temperature in the range of-20 to 120 ℃, preferably-5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor. Further, a polyimide precursor can be easily obtained by dehydrating condensation of a dicarboxylic acid diester and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.
The polyimide precursor obtained by this method is stable, and therefore, can be purified by adding a solvent such as water or alcohol for reprecipitation.
3) Polyamic acid silyl ester (indirect method)
The diamine is reacted with a silylating agent in advance to give a silylated diamine. Purification of the silylated diamine is carried out by distillation or the like as needed. Then, the silylated diamine is dissolved in the dehydrated solvent, and the tetracarboxylic dianhydride is slowly added while stirring, and stirred at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor.
When a chlorine-free silylating agent is used as the silylating agent used herein, it is not necessary to purify the silylated diamine, and therefore, it is preferable. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable for the reason of no fluorine atom and low cost.
In addition, in the silylation reaction of diamine, amine-based catalysts such as pyridine, piperidine, and triethylamine may be used to promote the reaction. The catalyst can be directly used as a polymerization catalyst of polyimide precursor.
4) Polyamic acid silyl ester (direct method)
The polyamic acid solution obtained in the method of 1) is mixed with a silylating agent and stirred at a temperature ranging from 0 to 120 ℃, preferably from 5 to 80 ℃ for 1 to 72 hours, thereby obtaining a polyimide precursor.
When a chlorine-free silylating agent is used as the silylating agent used herein, it is not necessary to purify the silylated polyamic acid or the obtained polyimide, and therefore it is preferable. Examples of the silylating agent containing no chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferable for the reason of no fluorine atom and low cost.
Since the above production methods can be carried out in an organic solvent, the varnish of the polyimide precursor of the present invention can be easily obtained as a result thereof.
The solvent used in the preparation of the polyimide precursor is preferably an aprotic solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, dimethylsulfoxide, etc., and particularly preferably N, N-dimethylacetamide, N-methyl-2-pyrrolidone, any kind of solvent may be used without any problem as long as the raw material monomer components and the polyimide precursor to be produced can be dissolved, and therefore the structure thereof is not particularly limited. As the solvent, amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, cyclic ester solvents such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, alpha-methyl-gamma-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol, acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably used. In addition, other general organic solvents, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha-based solvents, and the like may also be used. It should be noted that two or more solvents may be used in combination.
In the present invention, the logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5g/dL at 30℃is preferably 0.2dL/g or more, more preferably 0.8dL/g or more, particularly preferably 0.9dL/g or more. When the logarithmic viscosity is 0.2dL/g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide is excellent in mechanical strength and heat resistance.
In the present invention, the varnish of the polyimide precursor (polyimide precursor solution composition) contains at least the polyimide precursor of the present invention and the solvent, and the ratio of the total amount of the tetracarboxylic acid component and the diamine component to the total amount of the solvent, the tetracarboxylic acid component and the diamine component is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more. It is preferable that the content is generally 60% by mass or less, preferably 50% by mass or less. When the concentration is too low, for example, it may be difficult to control the film thickness of the polyimide film obtained when the polyimide film is produced.
The solvent used in the varnish of the polyimide precursor of the present invention is not particularly limited as long as it can dissolve the polyimide precursor. The solvent of the varnish of the polyimide precursor may be the same as the solvent used for preparing the polyimide precursor, and the solvent used for preparing the polyimide precursor may be used as the solvent of the varnish of the polyimide precursor. In addition, the solvent may be removed or added from the polyimide precursor solution prepared as described above, as required.
In the present invention, the viscosity (rotational viscosity) of the varnish of the polyimide precursor is not particularly limited, and the varnish is sheared at a shearing speed of 20sec at a temperature of 25℃using an E-type rotational viscometer -1 The rotational viscosity measured under the conditions of (2) is preferably 0.01 to 1000 Pa-sec, more preferably0.1 to 100 Pa.sec. In addition, thixotropic properties may be imparted as needed. In the above range of viscosity, the film can be easily handled when coating or film formation is performed, shrinkage cavity is suppressed, and leveling property is excellent, so that a good film can be obtained.
The varnish of the polyimide precursor of the present invention may contain, if necessary, a chemical imidizing agent (an acid anhydride such as acetic anhydride, an amine compound such as pyridine or isoquinoline), an antioxidant, a filler (inorganic particles such as silica), a coupling agent such as a dye, a pigment, a silane coupling agent, a primer, a flame retardant material, an antifoaming agent, a leveling agent, a rheology control agent (flow aid), a release agent, and the like.
The polyimide of the present invention can be suitably produced by subjecting the polyimide precursor of the present invention as described above to a dehydration ring-closure reaction (imidization reaction). The method of imidization is not particularly limited, and a known method of thermal imidization or chemical imidization may be suitably applied.
The polyimide thus obtained may be in the form of a film, a laminate of a polyimide film and another substrate, a coating film, a powder, a bead, a molded article, a foam, a varnish, or the like.
Hereinafter, an example of a polyimide film/substrate laminate or a method for producing a polyimide film using the polyimide precursor of the present invention will be described. However, the method is not limited to the following method.
The varnish of the polyimide precursor of the present invention is cast and coated on a substrate, and dried in vacuum, in an inert gas such as nitrogen or in air at a temperature ranging from 20 to 180 ℃, preferably from 20 to 150 ℃ using hot air or infrared rays. Next, the obtained polyimide precursor film is peeled off from the substrate, and the polyimide film/substrate laminate or polyimide film is produced by heating and imidizing the polyimide precursor film obtained on the substrate, or by peeling the polyimide precursor film off from the substrate and fixing the ends of the film in a vacuum, in an inert gas such as nitrogen or in air, using hot air or infrared rays at a temperature of about 200 to 500 ℃, more preferably about 250 to 450 ℃. In order to prevent the obtained polyimide film from being oxidized and deteriorated, the imidization by heating is preferably performed in vacuum or in an inert gas. The imidization may be performed in air as long as the temperature at which the imidization is heated is not excessively high.
The substrate is not particularly limited, and for example, a substrate such as ceramic (glass, silicon, or alumina), metal (copper, aluminum, or stainless steel), or a heat-resistant plastic film (polyimide film) can be used. In one embodiment, the substrate is preferably glass, and the polyimide film/glass substrate laminate having a polyimide film formed on a glass substrate is suitably used for, for example, manufacturing a substrate for a display.
In addition, instead of the above-described thermal imidization by the heat treatment, the imidization reaction of the polyimide precursor may be performed by a chemical treatment such as immersing the polyimide precursor in a solution containing a dehydrative ring-closure reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. Alternatively, a partially imidized polyimide precursor may be produced by pouring these dehydrative ring-closure reagents into a varnish of a polyimide precursor in advance, stirring the mixture, casting the mixture onto a substrate, and drying the mixture, and further subjecting the mixture to the above-described heat treatment, whereby a polyimide film/substrate laminate or a polyimide film can be obtained.
The polyimide of the present invention can be suitably produced by the following method: a solution composition (varnish) containing the polyimide of the present invention is prepared by reacting a tetracarboxylic acid component with a diamine component in a solvent, and the solvent is removed from the prepared polyimide solution composition by heating or the like.
Hereinafter, a method for producing a polyimide solution composition (varnish containing polyimide) according to the present invention and an example of a method for producing a polyimide film/substrate laminate or a polyimide film using the polyimide solution composition will be described. However, the method is not limited to the following method.
The polyimide solution composition of the present invention can be suitably obtained by reacting a tetracarboxylic acid component such as tetracarboxylic dianhydride with a diamine component in a solvent in a ratio of substantially equimolar, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [ the number of moles of the diamine component/the number of moles of the tetracarboxylic acid component ] of preferably 0.90 to 1.10, more preferably 0.95 to 1.05.
More specifically, a diamine component is dissolved in a solvent, a tetracarboxylic acid component such as tetracarboxylic dianhydride is slowly added to the solution while stirring, and if necessary, the solution is stirred at a temperature preferably in the range of room temperature to 80 ℃ for 0.5 to 30 hours, and then the temperature is raised to carry out imidization, thereby obtaining a polyimide solution. After the addition of the tetracarboxylic acid component, the temperature may be raised immediately to effect imidization. The order of addition of the diamine component and the tetracarboxylic acid component may be reversed, and the diamine component and the tetracarboxylic acid component may be added to the solvent at the same time.
The method of imidization is not particularly limited, and a known method of thermal imidization or chemical imidization may be suitably applied. For example, the imidization reaction may be performed by stirring a solution containing a tetracarboxylic acid component such as tetracarboxylic dianhydride and a diamine component at a temperature in the range of 100 ℃ or higher, preferably 120 ℃ or higher, more preferably 150 to 250 ℃ for 0.5 to 72 hours, and reacting the tetracarboxylic acid component with the diamine component. In the case of chemical imidization, a chemical imidizing agent (an acid anhydride such as acetic anhydride, an amine compound such as pyridine, isoquinoline, triethylamine, etc.) is added to the reaction solution to perform a reaction. If necessary, an imidization catalyst or the like may be added to the reaction solution to carry out the reaction.
In addition, the imidization reaction may be performed while removing water generated during the reaction.
When the molar ratio of the tetracarboxylic acid component to the diamine component is excessive, the molar ratio of the tetracarboxylic acid component to the diamine component may be made approximately equal by adding a carboxylic acid derivative in an amount approximately corresponding to the excessive molar number of the diamine component, if necessary. The carboxylic acid derivative is preferably a tetracarboxylic acid which does not substantially increase the viscosity of the polyimide solution, i.e., does not substantially participate in molecular chain extension; or tricarboxylic acids and anhydrides thereof, dicarboxylic acids and anhydrides thereof, and the like, which function as capping agents.
The solvent used in the preparation of the polyimide solution is preferably an aprotic solvent such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, dimethylsulfoxide, etc., and particularly preferably N, N-dimethylacetamide, N-methyl-2-pyrrolidone, any kind of solvent may be used without any problem as long as the raw material monomer components and the polyimide to be produced can be dissolved. As the solvent, amide solvents such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, cyclic ester solvents such as gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, epsilon-caprolactone, alpha-methyl-gamma-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol, acetophenone, 1, 3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably used. In addition, other general organic solvents, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha-based solvents, and the like may also be used. It should be noted that two or more solvents may be used in combination.
After the imidization reaction as described above, the obtained reaction solution may be directly or after being concentrated or diluted, additives described later and the like may be further added as needed to use the polyimide solution composition of the present invention. Alternatively, a soluble polyimide may be separated from the obtained reaction solution, and the separated polyimide may be added to a solvent to obtain the polyimide solution composition (varnish) of the present invention. The polyimide may be separated, for example, by adding dropwise or mixing the obtained reaction solution containing the soluble polyimide to a poor solvent such as water, and precipitating (reprecipitating) the polyimide.
The polyimide solution composition (varnish of polyimide) of the present invention contains at least the polyimide of the present invention and the solvent, and the polyimide is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, particularly preferably 20 mass% or more, based on the total amount of the solvent and the polyimide. When the concentration is too low, for example, it may be difficult to control the film thickness of the polyimide film obtained when the polyimide film is produced. In general, polyimide is preferably 60 mass% or less, more preferably 50 mass% or less.
The solvent of the polyimide solution composition of the present invention is not particularly limited as long as it can dissolve polyimide. The solvent of the polyimide solution composition may be the same as that used in the preparation of the polyimide solution, and the solvent used in the preparation of the polyimide solution may be used as the solvent of the polyimide solution composition. In addition, the solvent may be removed or added from the polyimide solution composition prepared as described above, as required.
In the present invention, the logarithmic viscosity of the polyimide is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5g/dL at 30℃is preferably 0.2dL/g or more, more preferably 0.4dL/g or more, particularly preferably 0.5dL/g or more. When the logarithmic viscosity is 0.2dL/g or more, the obtained polyimide is excellent in mechanical strength and heat resistance.
In the present invention, the viscosity (rotational viscosity) of the polyimide solution composition is not particularly limited, and the polyimide solution composition is subjected to a shearing speed of 20sec at a temperature of 25℃using an E-type rotational viscometer -1 The rotational viscosity measured under the conditions of (a) is preferably 0.01 to 1000 Pa-sec, more preferably 0.1 to 100 Pa-sec. In addition, thixotropic properties may be imparted as needed. In the above range of viscosity, the film can be easily handled when coating or film formation is performed, shrinkage cavity is suppressed, and leveling property is excellent, so that a good film can be obtained.
The polyimide solution composition of the present invention may contain, as required, a filler (inorganic particles such as silica), a dye, a pigment, a coupling agent such as a silane coupling agent, a primer, a flame retardant, a defoaming agent, a leveling agent, a rheology control agent (flow aid), a release agent, and the like.
The polyimide of the present invention can be suitably obtained by removing the solvent from the polyimide solution composition prepared as above. For example, a polyimide film/substrate laminate can be produced by casting and coating a polyimide solution composition onto a substrate, heating the polyimide solution composition on the substrate, and removing the solvent. The temperature of the heat treatment is not particularly limited, but is usually about 80 to 500 ℃, preferably about 100 to 500 ℃, more preferably about 150 to 450 ℃. The heating treatment may be performed in vacuum, in an inert gas such as nitrogen, or in air, and is usually preferably performed in vacuum or in an inert gas. Then, the polyimide film formed on the substrate is peeled off from the substrate, whereby a polyimide film can be produced.
The substrate is not particularly limited, and for example, a substrate such as ceramic (glass, silicon, or alumina), metal (copper, aluminum, or stainless steel), or a heat-resistant plastic film (polyimide film) can be used. In one embodiment, the substrate is preferably glass, and the polyimide film/glass substrate laminate having a polyimide film formed on a glass substrate is suitably used for, for example, manufacturing a substrate for a display.
Further, a polyimide film can be suitably produced by casting and coating a polyimide solution composition on a substrate, drying the polyimide solution composition on the substrate to a degree that the composition is self-supporting, peeling the self-supporting film obtained from the substrate, heating the film in a state where the end portions of the film are fixed, and removing the solvent. The drying conditions in the production of the self-supporting film may be appropriately determined, and for example, the polyimide solution composition may be dried on the substrate at a temperature ranging from about 50 to 300 ℃. The temperature of the heat treatment of the self-supporting film is not particularly limited, but is usually 80 to 500 ℃, preferably 100 to 500 ℃, and more preferably about 150 to 480 ℃. In this method, the heating treatment may be performed in vacuum, in an inert gas such as nitrogen, or in air, and is usually preferably performed in vacuum or in an inert gas.
The form of polyimide obtained from the polyimide solution composition is not limited to a film, a laminate of a polyimide film and other base materials, and may be suitably exemplified by a coating film, a powder, beads, a molded article, a foam, and the like.
The polyimide of the present invention thus obtained has a linear thermal expansion coefficient of 100 to 250℃when measured as a film having a thickness of 10. Mu.m, but is not particularly limited, and is preferably 40ppm/K or less, more preferably 35ppm/K or less, still more preferably 30ppm/K or less, and particularly preferably 25ppm/K or less. When the linear thermal expansion coefficient is large, there is a large difference between the linear thermal expansion coefficient and the linear thermal expansion coefficient of the conductor such as metal, and there is a case where a problem such as an increase in warpage occurs in forming a circuit board.
The polyimide of the present invention has a light transmittance of 400nm, preferably 80% or more, more preferably 83% or more, and particularly preferably 85% or more, when measured as a film having a thickness of 10. Mu.m. When the polyimide film is used for display applications or the like, a strong light source is required when the light transmittance is low, and problems such as energy consumption may occur.
The haze of the polyimide of the present invention when measured as a film having a thickness of 10 μm is not particularly limited, but is preferably 2% or less, more preferably 1.5% or less, and particularly preferably 1% or less. When the polyimide film is used for a display or the like, light is scattered when haze is high, and an image may be blurred.
The polyimide of the present invention is not particularly limited in terms of the thickness-direction retardation (Rth) when measured as a film having a thickness of 10 μm, and is preferably 500nm or less, more preferably 350nm or less, particularly preferably 400nm or less. When the polyimide film is used for a display or the like, if the retardation in the thickness direction is large, there may be a problem that the color of the transmitted light cannot be displayed accurately, the color is blurred, the viewing angle is narrowed, or the like.
The thickness of the film containing the polyimide of the present invention varies depending on the application, but is preferably 1 μm to 250. Mu.m, more preferably 1 μm to 150. Mu.m, still more preferably 1 μm to 100. Mu.m, particularly preferably 1 μm to 80. Mu.m. In the case of using a polyimide film for light transmission, there is a possibility that the light transmittance may be lowered when the polyimide film is too thick.
The polyimide film/base material laminate or polyimide film thus obtained can be provided with a flexible conductive substrate by forming a conductive layer on one or both surfaces thereof.
The flexible conductive substrate can be obtained by, for example, the following method. That is, as a first method, a conductive layer of a conductive substance (metal or metal oxide, conductive organic substance, conductive carbon, or the like) is formed on the surface of a polyimide film by sputtering, vapor deposition, printing, or the like, without peeling the polyimide film from the substrate, to produce a conductive laminate of a conductive layer/polyimide film/substrate. Then, the conductive layer/polyimide film laminate is peeled off from the base material as needed, whereby a transparent and flexible conductive substrate composed of the conductive layer/polyimide film laminate can be obtained.
As a second method, a polyimide film is peeled from a substrate of a polyimide film/substrate laminate to obtain a polyimide film, and a conductive layer of a conductive substance (metal or metal oxide, conductive organic substance, conductive carbon, or the like) is formed on the surface of the polyimide film in the same manner as in the first method, whereby a transparent and flexible conductive substrate composed of the conductive layer/polyimide film laminate or the conductive layer/polyimide film/conductive layer laminate can be obtained.
In the first and second methods, an inorganic layer such as a gas barrier layer of water vapor, oxygen, or the like, or a light adjustment layer may be formed by sputtering, vapor deposition, gel-sol method, or the like before the conductive layer is formed on the surface of the polyimide film, if necessary.
The conductive layer may be formed into a circuit by photolithography, various printing methods, an inkjet method, or the like.
The substrate of the present invention thus obtained is a substrate of a circuit having a conductive layer on the surface of a polyimide film made of the polyimide of the present invention via a gas barrier layer or an inorganic layer as required. The substrate is flexible, has high transparency, excellent bending property and heat resistance, and further has a low linear thermal expansion coefficient, so that a fine circuit is easily formed. Therefore, the substrate is suitable for use as a substrate for a display, a touch panel, or a solar cell.
That is, a transistor (an inorganic transistor, an organic transistor) is further formed over the substrate by vapor deposition, various printing methods, an inkjet method, or the like, and a flexible thin film transistor is manufactured, and is suitably used as a liquid crystal element, an EL element, or a photoelectric element for a display device.
In the first method, the substrate may be peeled off after forming the conductive layer and at least a part of other elements or structures required for the transistor and/or the device on the surface of the polyimide film/substrate laminate.
Examples
The present invention will be further described below with reference to examples and comparative examples. The present invention is not limited to the following examples.
In the following examples, the evaluation was performed by the following methods.
< evaluation of polyimide film >
[ light transmittance at 400nm ]
The transmittance of a polyimide film having a film thickness of 10 μm and a square size of 5cm was measured at a wavelength of 400nm using an ultraviolet-visible spectrophotometer/V-650 DS (manufactured by Japan spectroscopy).
[ haze ]
Haze of a polyimide film having a film thickness of 10 μm and a square size of 5cm was measured according to JIS K7136 using a haze meter/NDH 2000 (manufactured by the electric color industry of Japan).
[ coefficient of Linear thermal expansion (CTE) ]
A polyimide film having a film thickness of 10 μm was cut into a long shape having a width of 4mm, and a test piece was produced, and the temperature was raised to 500℃under conditions of a chuck spacing of 15mm, a tensile load of 2g and a heating rate of 20℃per minute using TMA/SS6100 (manufactured by SII Nanotechnology Co., ltd.). The linear thermal expansion coefficient of 100℃to 250℃was determined from the TMA curve obtained.
[ film thickness-direction phase difference (R) th )]
A polyimide film having a film thickness of 10 μm and a square size of 5cm was used as a test piece, and the retardation of the film was measured by using a retardation measuring apparatus (KOBA-WR) manufactured by prince measuring instruments, and setting the incident angle to 40 ℃. The phase difference in the thickness direction of the film having a film thickness of 10 μm was obtained from the obtained phase difference.
[ tensile elastic modulus, elongation at break point, stress at break point ]
The polyimide film was punched into a dumbbell shape of IEC-540 (S) standard, and test pieces (width: 4 mm) were produced, and the initial tensile modulus of elasticity, elongation at break, and stress at break were measured under conditions of a length between chucks of 30mm and a tensile speed of 2 mm/min using TENSILON manufactured by ORIENTEC Co.
The abbreviations, purities, and the like of the raw materials used in the examples below are as follows.
[ diamine component ]
TFMB:2,2' -bis (trifluoromethyl) benzidine [ purity: 99.83% (GC analysis) ]
BAFL:9, 9-bis (4-aminophenyl) fluorene
4,4' -ODA:4,4' -oxydiphenylamine [ purity: 99.9% (GC analysis) ]
BAPB:4,4' -bis (4-aminophenoxy) biphenyl
SFXO:4,4'- (spiro [ fluorene-9, 9' -xanthene ] -3',6' -diylbis (oxy)) diphenylamine
[ tetracarboxylic acid component ]
CpODA: norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2 "-norbornane-5, 5",6 "-tetracarboxylic dianhydride
PMDA-H:1,2,4, 5-cyclohexane tetracarboxylic dianhydride [ purity: 99.9% (GC analysis) ]
a-BPDA:2, 3',4' -biphenyltetracarboxylic dianhydride
[ solvent ]
GBL: gamma-butyrolactone
DMAc: n, N-dimethylacetamide
The structural formulas of the tetracarboxylic acid component and the diamine component used in examples and comparative examples are shown in Table 1.
TABLE 1
Figure BDA0002635458540000231
Example 1
To a reaction vessel replaced with nitrogen gas, 1.70g (5.3 mmol) of TFMB and 7.40g (21.3 mmol) of BAFL were charged 94.24g of DMAc in an amount of 25 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 10.20g (26.5 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 2
To a reaction vessel replaced with nitrogen gas, 3.00g (9.4 mmol) of TFMB and 6.06g (17.4 mmol) of BAFL6 were charged 94.48g of DMAc in an amount of 17 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 10.29g (26.8 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 3
To a reaction vessel replaced with nitrogen gas were added 7.00g (21.9 mmol) of TFMB and 7.62g (21.9 mmol) of BAFL, 94.26g of DMAc in an amount of 25 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 16.80g (43.7 mmole). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 4
7.00g (21.9 mmol) of TFMB and 6.23g (17.9 mmol) of BAFL were charged into a reaction vessel which had been replaced with nitrogen gas, and 95.44g of a mixed solvent of DMAc and GBL (DMAc: GBL=1:2 (weight ratio)) was added in an amount of 23% by mass based on the total mass of the charged monomers (sum of the diamine component and the carboxylic acid component) (DMAc: 31.81g, GBL: 63.63 g), and stirred at room temperature for 1 hour. To this solution was slowly added CpODA 15.28g (39.7 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 450℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 5
To a reaction vessel replaced with nitrogen gas, 9.00g (28.1 mmol) of TFMB and 6.53g (18.7 mmol) of BAFL were charged 112.26g of DMAc in an amount of 23 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 18.00g (46.8 mmole). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 430℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 6
To a reaction vessel replaced with nitrogen gas, 9.00g (28.1 mmol) of TFMB and 4.20g (12.0 mmol) of BAFL were charged, 95.85g of DMAc in an amount of 23 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component) was added, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 15.43g (40.2 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 7
To a reaction vessel replaced with nitrogen gas, 10.00g (31.2 mmol) of TFMB and 2.72g (7.8 mmol) of BAFL were charged 92.82g of DMAc in an amount of 23 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 15.00g (39.0 mmole). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 8
To a reaction vessel replaced with nitrogen gas, 8.00g (25.0 mmol), 2.90g (8.3 mmol) of BAFL and 1.67g (8.3 mmol) of 4,4' -ODA were charged 95.66g of DMAc in an amount of 23 mass% based on the total mass of the charged monomers (the sum of the diamine component and the carboxylic acid component), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 16.00g (41.6 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 9
To a reaction vessel replaced with nitrogen gas, 8.00g (25.0 mmol), 4.35g (12.5 mmol) of BAFL and 1.53g (4.2 mmol) of BAPB were charged 100.07g of DMAc in an amount to bring the total mass of the charged monomers (sum of diamine component and carboxylic acid component) to 23 mass%, and stirred at room temperature for 1 hour. To this solution was slowly added CpODA 16.00g (41.6 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 10
To a reaction vessel replaced with nitrogen gas, 6.00g (18.7 mmol) of TFMB and 8.38g (15.3 mmol) of SFXO were charged, 82.44g of a mixed solvent of DMAc and GBL (DMAc: gbl=1:2 (weight ratio)) in an amount of 25 mass% based on the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 27.48g, GBL: 54.96 g) were added, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 13.09g (34.1 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-1.
Example 11
To a reaction vessel replaced with nitrogen gas, 11.00g (34.4 mmol) of TFMB and 5.13g (14.7 mmol) of BAFL were added, 87.29g of a mixed solvent of DMAc and GBL (DMAc: gbl=1:2 (weight ratio)) in an amount of 25 mass% based on the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 29.10g, GBL: 58.19 g) were added, and the mixture was stirred at room temperature for 1 hour. To this solution were slowly added CpODA 4.72g (12.3 mmol) and PMDA-H8.25 g (36.8 mmol). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
Example 12
To a reaction vessel replaced with nitrogen gas, 10.00g (31.2 mmol) of TFMB and 4.66g (13.4 mmol) of BAFL were added, 84.71g of a mixed solvent of DMAc and GBL (DMAc: gbl=1:2 (weight ratio)) in an amount of 25 mass% based on the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 28.24g, GBL: 56.47 g) were added, and the mixture was stirred at room temperature for 1 hour. To this solution were slowly added CpODA 8.57g (22.3 mmoles) and PMDA-H5.00 g (22.3 mmoles). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
Example 13
To a reaction vessel replaced with nitrogen gas, 10.00g (31.2 mmol) of TFMB and 4.66g (13.4 mmol) of BAFL were added, 90.06g of a mixed solvent of DMAc and GBL (DMAc: gbl=1:2 (weight ratio)) in an amount of 25 mass% based on the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 30.02g, GBL: 60.04 g) were added, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 12.86g (33.5 mmol) and PMDA-H2.50 g (11.1 mmol). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
Example 14
To a reaction vessel replaced with nitrogen gas, 7.50g (23.4 mmol) of TFMB and 8.16g (23.4 mmol) of BAFL were added, 95.40g of a mixed solvent of DMAc and GBL (DMAc: gbl=1:2 (weight ratio)) in an amount of 25 mass% based on the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 31.80g, GBL: 63.60 g) were added, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 13.50g (35.1 mmol) and PMDA-H2.63 g (11.7 mmol). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
Example 15
To a reaction vessel replaced with nitrogen gas, 8.00g (25.0 mmol) of TFMB and 8.70g (25.0 mmol) of BAFL were added, and 95.73g of a mixed solvent of DMAc and GBL (DMAc: gbl=1:2 (weight ratio)) was added in an amount to achieve 25 mass% of the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 31.91g, GBL: 63.82 g), and stirred at room temperature for 1 hour. To this solution was slowly added CpODA 13.50g (25.0 mmol) and PMDA-H2.63 g (25.0 mmol). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
Example 16
15.00g (46.8 mmol) of TFMB was charged into a reaction vessel replaced with nitrogen, 90.00g of a mixed solvent of DMAc and GBL (DMAc: GBL=1:2 (weight ratio)) was charged in an amount to achieve 25 mass% of the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 30.00g, GBL: 60.00 g), and the mixture was stirred at room temperature for 1 hour. To this solution were slowly added CpODA 10.80g (28.1 mmol) and PMDA-H4.20 g (18.7 mmol). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 370℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
Example 17
15.00g (46.8 mmol) of TFMB was charged into a reaction vessel replaced with nitrogen, 93.95g of a mixed solvent of DMAc and GBL (DMAc: GBL=1:2 (weight ratio)) was charged in an amount to achieve 25% by mass of the total mass of the charged monomers (sum of the diamine component and the carboxylic acid component) (DMAc: 31.32g, GBL: 62.63 g), and the mixture was stirred at room temperature for 1 hour. To this solution were slowly added CpODA 10.80g (28.1 mmole) and a-BPDA 5.51g (18.7 mmole). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
Comparative example 1
To a reaction vessel replaced with nitrogen gas, 40.00g (124.9 mmol) of TFMB was charged, 264.04g of a mixed solvent of DMAc and GBL (DMAc: gbl=1:2 (weight ratio)) was added in an amount to achieve 25 mass% of the total mass of the charged monomers (sum of diamine component and carboxylic acid component) (DMAc: 88.01g, GBL: 176.03 g), and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CpODA 48.01g (124.9 mmol). Stirring was carried out at 70℃for 3 hours and 160℃for 7 hours to give a uniform and viscous polyimide solution. The polyimide solution obtained has an imidization rate of 95% or more.
The polyimide solution was applied to a glass substrate, and the polyimide film/glass laminate was directly heated to 410℃from room temperature on the glass substrate under a nitrogen atmosphere (oxygen concentration: 200ppm or less) to remove the solvent, thereby obtaining a colorless transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, and then peeled off and dried to obtain a polyimide film having a film thickness of 10 μm.
The results of measuring the properties of the polyimide film are shown in Table 2-2.
[ Table 2-1]
Figure BDA0002635458540000311
[ Table 2-2]
Figure BDA0002635458540000312
Industrial applicability
According to the present invention, a polyimide having high transparency and low linear thermal expansion coefficient and having a small retardation (retardation) in the thickness direction and a precursor thereof can be provided. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency and low linear thermal expansion coefficient, are easy to form a fine circuit, and have small retardation (retardation) in the thickness direction, and therefore can be particularly suitably used for forming a substrate for display applications or the like.

Claims (7)

1. A polyimide precursor comprising a repeating unit represented by the following general formula (1),
a of the following general formula (1) 1 Comprises a 4-valent group represented by the following formula (A-1), and B of the following formula (1) 1 Comprising a 2-valent group represented by the following formula (B-1),
in addition, B of the following formula (1) 1 Comprises a 2-valent group having a structure represented by the following formula (2), and A of the following formula (1) as an optional component 1 Comprising a 4-valent group having a structure represented by the following formula (2), a 4-valent group represented by the following formula (3), and/or a 4-valent group represented by the following formula (4),
a of the general formula (1) 1 The total content of the 4-valent group represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group represented by the formula (3) and the 4-valent group represented by the formula (4) in 100 mol% is equal to B of the general formula (1) 1 The total content of the 2-valent groups represented by the formula (B-1) and the 2-valent groups having the structure represented by the formula (2) in 100 mol% is 180 mol% or more,
wherein the ratio of the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the formula (4) is 80 mol% or less relative to the total of the 4-valent group having the structure represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the structure represented by the formula (4),
the proportion of the 2-valent group having the structure represented by the formula (2) is 20 to 80 mol% based on the total of the 2-valent group having the structure represented by the formula (2) and the 2-valent group having the structure represented by the formula (2),
Figure FDA0004156414280000011
Wherein A is 1 Is a 4-valent group having an aromatic ring or alicyclic structure, B 1 Is a 2-valent group having an aromatic ring or alicyclic structure, R 1 、R 2 Each independently is hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms, wherein A is contained in each repeating unit 1 And B 1 May be the same or different from each other,
Figure FDA0004156414280000021
2. a polyimide comprising a repeating unit represented by the following general formula (5),
a of the following general formula (5) 2 Comprises a 4-valent group represented by the following formula (A-1), and B of the following formula (5) 2 Comprising a 2-valent group represented by the following formula (B-1),
in addition, B of the following formula (5) 2 Comprises a 2-valent group having a structure represented by the following formula (2), and A of the following formula (5) as an optional component 2 Comprising a 4-valent group having a structure represented by the following formula (2), a 4-valent group represented by the following formula (3), and/or a 4-valent group represented by the following formula (4),
a of the general formula (5) 2 The total content of the 4-valent group represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group represented by the formula (3) and the 4-valent group represented by the formula (4) in 100 mol% is equal to B of the general formula (5) 2 The total content of the 2-valent groups represented by the formula (B-1) and the 2-valent groups having the structure represented by the formula (2) in 100 mol% is 180 mol% or more,
wherein the ratio of the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the formula (4) is 80 mol% or less relative to the total of the 4-valent group having the structure represented by the formula (A-1), the 4-valent group having the structure represented by the formula (2), the 4-valent group having the structure represented by the formula (3) and the 4-valent group having the structure represented by the formula (4),
the proportion of the 2-valent group having the structure represented by the formula (2) is 20 to 80 mol% based on the total of the 2-valent group having the structure represented by the formula (2) and the 2-valent group having the structure represented by the formula (2),
Figure FDA0004156414280000031
wherein A is 2 Is a 4-valent group having an aromatic ring or alicyclic structure, B 2 Is a 2-valent group having an aromatic ring or alicyclic structure, wherein A is contained in each repeating unit 2 And B 2 May be the same or different from each other,
Figure FDA0004156414280000032
Figure FDA0004156414280000041
3. a polyimide obtained from the polyimide precursor of claim 1.
4. A varnish comprising the polyimide precursor of claim 1 or the polyimide of claim 2.
5. A polyimide film obtained using a varnish comprising the polyimide precursor according to claim 1 or the polyimide according to claim 2.
6. A laminate comprising a glass substrate and a film comprising the polyimide according to claim 2 or 3 formed on the glass substrate.
7. A substrate for a display, a touch panel or a solar cell, comprising the polyimide according to claim 2 or 3.
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