CN110028666B - Polyimide precursor and resin composition containing same - Google Patents

Polyimide precursor and resin composition containing same Download PDF

Info

Publication number
CN110028666B
CN110028666B CN201910054325.0A CN201910054325A CN110028666B CN 110028666 B CN110028666 B CN 110028666B CN 201910054325 A CN201910054325 A CN 201910054325A CN 110028666 B CN110028666 B CN 110028666B
Authority
CN
China
Prior art keywords
dianhydride
polyimide
tetracarboxylic dianhydride
pmda
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910054325.0A
Other languages
Chinese (zh)
Other versions
CN110028666A (en
Inventor
宫本佳季
米谷昌树
饭塚康史
金田隆行
奥田敏章
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Original Assignee
Asahi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp filed Critical Asahi Kasei Corp
Publication of CN110028666A publication Critical patent/CN110028666A/en
Application granted granted Critical
Publication of CN110028666B publication Critical patent/CN110028666B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Abstract

The present application relates to a polyimide precursor and a resin composition containing the same. A polyimide precursor having a structure derived from a diamine, wherein the structure is derived from 2,2' -bis (trifluoromethyl) benzidine (TFMB) or another diamine; the structure derived from a tetracarboxylic dianhydride has a structure derived from a specific alicyclic tetracarboxylic dianhydride and a structure derived from an aromatic tetracarboxylic dianhydride, and the imidization rate of an amide bond derived from the alicyclic tetracarboxylic dianhydride is 10 to 100%.

Description

Polyimide precursor and resin composition containing same
The present application is a divisional application of an application having an application date of 2014 25/6, an application number of 201480065199.4 and an invention name of "polyimide precursor and resin composition containing the same".
Technical Field
The present invention relates to a polyimide precursor and a resin composition containing the same. The polyimide precursor can be used, for example, as a substrate for a flexible device.
The invention also provides a polyimide film and a method for producing the same, and a laminate and a method for producing the same.
Background
The polyimide film is generally a film formed of a polyimide resin. The polyimide resin is a highly heat-resistant resin produced by solution-polymerizing an aromatic tetracarboxylic dianhydride and an aromatic diamine to produce a polyimide precursor, and then thermally imidizing or chemically imidizing the polyimide precursor. The thermal imidization is performed by ring-closing dehydration at a high temperature, and the chemical imidization is performed by ring-closing dehydration with a catalyst.
Polyimide resins are insoluble and infusible super heat-resistant resins, and have excellent properties such as thermal oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, polyimide resins are used in a wide range of fields including electronic materials, such as insulating coating agents, insulating films, semiconductors, and electrode protective films of TFT-LCDs. Recently, the liquid crystal alignment film is used for display materials such as liquid crystal alignment films, optical fibers, and the like.
However, polyimide resins are colored brown or yellow due to their high aromatic ring density, and have low transmittance in the visible light region, and thus are difficult to use in fields requiring transparency.
In this regard, patent document 1 reports: a polyimide having improved transparency and hue and a novel structure is produced by using a tetracarboxylic dianhydride and a diamine having a specific structure.
Further, patent documents 2 and 3 each disclose a polyimide film having an alicyclic structure introduced therein for the purpose of imparting transparency.
Further, patent document 4 reports: by using a specific aromatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride in combination as the tetracarboxylic dianhydride, a polyimide resin having a low yellowness (hereinafter also referred to as "YI value") can be obtained.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2000-198843
Patent document 2: japanese patent laid-open publication No. 2005-336243
Patent document 3: japanese patent laid-open publication No. 2003-155342
Patent document 4: korean patent laid-open publication No. 10-2013-0077946
Disclosure of Invention
Problems to be solved by the invention
However, the polyimide described in patent document 1 is insufficient in mechanical and thermal properties for use as, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible display substrate.
In particular, the polyimide described in patent document 1 is characterized by a high coefficient of linear expansion (hereinafter also referred to as "CTE"). When a resin having a high CTE is used as a film, the degree of expansion and contraction of the film due to temperature change increases. Therefore, when a thin film having a high CTE is used in a TFT process or the like, an inorganic film as an element material is damaged, and the element performance is lowered. Therefore, polyimide resins used for substrates for forming TFTs, substrates for forming color filters, alignment films, transparent substrates for flexible displays, and the like must be colorless and transparent and have a low CTE.
The polyimide described in patent document 2 has transparency, but has disadvantages of high CTE and low elongation at break. When the elongation at break is low, the flexible substrate is damaged when the flexible device is handled, and thus the flexible substrate cannot be used as a device.
In the case of the polyimide described in patent document 3, toughness is imparted by using a polycyclic aromatic diamine. However, since this polyimide also has a high CTE, it is not suitable for use as a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, or a flexible display substrate.
In the case of the polyimide disclosed in patent document 4, the YI value is constantly low. However, according to the studies of the present inventors, since the CTE is high and the elongation is small, there is room for improvement in the process of applying to a display (see comparative examples 22 to 24 described later).
The present invention has been made in view of the above-described problems, and an object thereof is to provide a polyimide precursor capable of producing a transparent polyimide film having a low CTE and an excellent elongation, a resin composition containing the polyimide precursor, a polyimide film and a method for producing the polyimide film, and a laminate and a method for producing the laminate.
Means for solving the problems
The present inventors have conducted extensive studies and repeated experiments to solve the above problems. As a result, the following findings have been found, and the present invention has been completed based on these findings.
The resin composition (varnish) containing the polyimide precursor having a specific structure is excellent in storage stability;
the polyimide film obtained by curing the composition has excellent transparency, low linear expansion coefficient and high elongation; and
the laminate having the inorganic film formed on the polyimide film has a small Haze and an excellent water vapor permeability.
That is, the present invention is as follows.
[1] A polyimide precursor having a structure represented by the following general formula (A),
the diamine-derived structure has a structure derived from at least one diamine selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine (TFMB), 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide, and 4-aminophenyl-4-aminobenzoate;
the structure derived from a tetracarboxylic dianhydride includes a structure derived from a tetracarboxylic dianhydride selected from the group consisting of 1,2,3, 4-cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,4, 5-bicyclohexane tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1, a structure of at least one alicyclic tetracarboxylic dianhydride selected from the group consisting of 2-C furan-1, 3-dione and bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride, and a structure derived from an aromatic tetracarboxylic dianhydride, and,
the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 10 to 100%.
Figure GDA0003184518430000041
{X1Is a structure derived from at least one diamine selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine (TFMB), 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide, and 4-aminophenyl-4-aminobenzoate;
X2is derived from a compound selected from 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexane tetracarboxylic dianhydride, bicyclo [2.2.1] bicyclo]Heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, bicyclo [2.2.2]Oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1,2-C]Furan-1, 3-dione and bicyclo [3,3,0]]Structure of at least one tetracarboxylic dianhydride in octane-2, 4,6, 8-tetracarboxylic dianhydride. }
[2] The polyimide precursor according to [1], wherein the polyimide precursor has a structure represented by the following general formula (B).
Figure GDA0003184518430000042
{X1As defined in the aforementioned formula (A),
X3is derived from the structure of the aromatic tetracarboxylic dianhydride. }
[3] The polyimide precursor according to [1] or [2], wherein the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 20 to 100%.
[4] The polyimide precursor according to any one of [1] to [3], wherein the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 30 to 100%.
[5] The polyimide precursor according to any one of [1] to [4], wherein the aromatic tetracarboxylic dianhydride comprises:
at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride as the aromatic tetracarboxylic dianhydride 1; and
at least one selected from the group consisting of 4,4 ' -Oxybisphthalic Dianhydride (ODPA), 4 ' - (hexafluoroisopropylidene) bisphthalic anhydride (6FDA), and 4,4 ' -biphenylbis (trimellitic acid monoester anhydride) as the aromatic tetracarboxylic dianhydride 2.
[6] The polyimide precursor according to any one of [1] to [5], wherein the aromatic tetracarboxylic dianhydride 1 is pyromellitic dianhydride (PMDA).
[7] The polyimide precursor according to any one of [1] to [5], wherein the aromatic tetracarboxylic dianhydride 2 is at least one selected from the group consisting of 4,4 '-Oxydiphthalic Dianhydride (ODPA) and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA).
[8] The polyimide precursor according to any one of [1] to [7], wherein the diamine-derived structure is a structure derived from 2,2' -bis (trifluoromethyl) benzidine (TFMB).
[9] The polyimide precursor according to any one of [1] to [8], wherein the alicyclic tetracarboxylic dianhydride is at least one selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexaetetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride.
[10] The polyimide precursor according to any one of [1] to [9], wherein the alicyclic tetracarboxylic dianhydride is at least one selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA).
[11] The polyimide precursor according to any one of [1] to [10], wherein the structure derived from TFMB is contained in an amount of 60 mol% or more based on the total structure derived from diamine,
the total of all the structures derived from tetracarboxylic dianhydrides contains 60 mol% or more of a structure derived from at least one tetracarboxylic dianhydride selected from the group consisting of the PMDA, the ODPA, the 6FDA, the CBDA and the H-PMDA.
[12] The polyimide precursor according to any one of [1] to [11], wherein the structure derived from the PMDA is contained in an amount of 1 to 70 mol% based on the total structure derived from the tetracarboxylic dianhydride, and
the total structure derived from the tetracarboxylic dianhydrides contains 1 to 50 mol% of a structure derived from at least one tetracarboxylic dianhydride selected from the group consisting of the ODPA and 6 FDA.
[13] The polyimide precursor according to any one of [1] to [11], wherein a ratio { PMDA + ODPA +6FDA + CBDA + H-PMDA)/TFMB } of a sum of moles of structures derived from the PMDA, the ODPA, the 6FDA, the CBDA, and the H-PMDA to a mole of a structure derived from the TFMB is 100/99.9 to 100/95.
[14] The polyimide precursor according to any one of [1] to [13], wherein a polyimide film obtained by dissolving the polyimide precursor in a solvent, developing the polyimide film on the surface of a support, and then imidating the polyimide film by heating the polyimide film in a nitrogen atmosphere has a yellowness of 10 or less, a linear expansion coefficient of 25ppm or less, and a film elongation of 15% or more at a film thickness of 20 μm.
[15] The polyimide precursor according to any one of [1] to [14], which is used for producing a flexible device.
[16] A resin composition comprising the polyimide precursor according to any one of [1] to [15] and a solvent.
[17] The resin composition according to [16], which further contains an alkoxysilane compound.
[18] The resin composition according to [16] or [17], which further contains a surfactant.
[19] A polyimide film characterized by being formed by developing the resin composition according to any one of [16] to [18] on the surface of a support to form a coating film, and then heating the support and the coating film to imidize the polyimide precursor.
[20] A method for producing a polyimide film, comprising the steps of:
a coating film forming step of forming a coating film by spreading the resin composition according to any one of [16] to [18] on the surface of a support;
a heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film; and
and a peeling step of peeling the polyimide film from the support to obtain a polyimide film.
[21] A laminate comprising a support and a polyimide film formed on the support, wherein the laminate is characterized in that
The laminate is obtained as follows: and (3) a resin composition according to any one of [16] to [18], which is formed by developing a coating film on the surface of the support, and then heating the support and the coating film to imidize the polyimide precursor to form a polyimide film.
[22] A method for producing a laminate provided with a support and a polyimide film formed on the support, the method comprising the steps of:
a coating film forming step of forming a coating film by spreading the resin composition according to any one of [16] to [18] on the surface of a support; and
and a heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film.
[23] A polyimide film produced from a copolymer of a diamine and a tetracarboxylic dianhydride,
the diamine is at least one selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine (TFMB), 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide and 4-aminophenyl-4-aminobenzoate,
the tetracarboxylic dianhydride comprises:
as alicyclic tetracarboxylic acid dianhydride selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic acid dianhydride (H-PMDA), 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4, 5-bicyclohexanetetracarboxylic acid dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1, at least one of 2-C ] furan-1, 3-dione and bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride;
at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride as the aromatic tetracarboxylic dianhydride 1; and
at least one selected from the group consisting of 4,4 ' -Oxybisphthalic Dianhydride (ODPA), 4 ' - (hexafluoroisopropylidene) bisphthalic anhydride (6FDA) and 4,4 ' -biphenylbis (trimellitic acid monoester anhydride) as the aromatic tetracarboxylic dianhydride 2,
when an inorganic film is formed on the polyimide film at 350 ℃ by a CVD method, the surface roughness of the inorganic film surface measured by an Atomic Force Microscope (AFM) is 0.01 to 50 nm.
[24] The polyimide film according to [23], wherein the diamine is 2,2' -bis (trifluoromethyl) benzidine (TFMB),
the tetracarboxylic dianhydride comprises:
at least one selected from 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA) as an alicyclic tetracarboxylic dianhydride;
at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride as the aromatic tetracarboxylic dianhydride 1;
at least one selected from the group consisting of 4,4 '-Oxybisphthalic Dianhydride (ODPA) and 4, 4' - (hexafluoroisopropylidene) bisphthalic anhydride (6FDA) as the aromatic tetracarboxylic dianhydride 2.
[25] A flexible device comprising the polyimide film according to [23] or [24 ].
[26] A method for producing a flexible device, comprising the method for producing a polyimide film according to [20 ].
[27] A method for producing a flexible device, comprising the method for producing a laminate according to [22 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The resin composition (varnish) containing the polyimide precursor of the present invention has excellent storage stability. The polyimide film obtained from the composition is colorless and transparent, and has a low coefficient of linear expansion and excellent elongation. The laminate having the inorganic film formed on the polyimide film has a small Haze and an excellent water vapor permeability.
Detailed Description
Hereinafter, one embodiment (hereinafter, abbreviated as "embodiment") of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.
< polyimide precursor >
The polyimide precursor of the present embodiment is characterized in that,
has a structure represented by the following general formula (A), and
the diamine-derived structure has a structure derived from at least one diamine selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine (TFMB), 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide, and 4-aminophenyl-4-aminobenzoate;
as the structure derived from a tetracarboxylic dianhydride,
having a structure derived from a compound selected from 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexatetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1,2-C ] furan-1, a structure of at least one alicyclic tetracarboxylic dianhydride selected from the group consisting of 3-diketones and bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride, and a structure derived from an aromatic tetracarboxylic dianhydride,
the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 10 to 100%.
Figure GDA0003184518430000101
{X1Is a structure derived from at least one diamine selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine (TFMB), 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide, and 4-aminophenyl-4-aminobenzoate;
X2is derived from a compound selected from 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexane tetracarboxylic dianhydride, bicyclo [2.2.1] bicyclo]Heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, bicyclo [2.2.2]Oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1,2-C]Furan-1, 3-dione and bicyclo [3,3,0]]Structure of at least one tetracarboxylic dianhydride in octane-2, 4,6, 8-tetracarboxylic dianhydride. }
The polyimide precursor of the present embodiment preferably has a structure represented by the following general formula (B).
Figure GDA0003184518430000102
{X1In the same manner as in the above-mentioned formula (A),
X3is derived from the structure of the aromatic tetracarboxylic dianhydride. }
As described above, the polyimide precursor of the present embodiment has an imidization rate of an amide bond derived from an alicyclic tetracarboxylic dianhydride of 10 to 100%. Namely, an imidized polyamic acid in which at least a part of amide bonds derived from an alicyclic tetracarboxylic dianhydride are imidized.
In order to obtain an imidized polyamic acid structure obtained by imidizing an amide bond derived from an alicyclic tetracarboxylic dianhydride, for example, the following method can be employed:
first, after a polyamic acid is obtained by reacting an alicyclic tetracarboxylic dianhydride with a diamine or by imidizing an amide bond of the polyamic acid at the same time as the polyamic acid is obtained,
next, the reaction between the diamine and another tetracarboxylic dianhydride (in the case of the present embodiment, an aromatic tetracarboxylic dianhydride) is continued.
From the viewpoint of increasing the molecular weight of the polyimide precursor and the viewpoint of improving the transparency of the resulting polyimide film, it is preferable to first react an alicyclic tetracarboxylic dianhydride. In order to increase the molecular weight of a polyimide (precursor) having a structure derived from an alicyclic tetracarboxylic dianhydride, the synthesis temperature needs to be increased from 60 to 100 ℃ to 150 to 210 ℃. As a result of increasing the synthesis temperature in this manner, imidization of the amide bond derived from the alicyclic tetracarboxylic dianhydride occurs, and the imide group concentration (imidization rate) of the portion derived from the alicyclic acid dianhydride increases. Here, the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is preferably 10 to 100%, more preferably 20 to 100%, and even more preferably 30 to 100%, from the viewpoints of the storage stability of the composition (varnish) containing the polyimide precursor, and the elongation and YI of the polyimide film to be obtained.
The reason why the alicyclic tetracarboxylic dianhydride is first reacted in this manner is that when the alicyclic tetracarboxylic dianhydride and the aromatic tetracarboxylic dianhydride are added simultaneously or the aromatic tetracarboxylic dianhydride is added and then the alicyclic tetracarboxylic dianhydride is added and the synthesis is carried out at a temperature of 150 to 210 ℃, the amide bond derived from the aromatic tetracarboxylic dianhydride portion is rapidly imidized to precipitate a polymer, which is not suitable.
The detailed synthesis method of the polyimide precursor in the present embodiment will be described later.
Hereinafter, each configuration will be described in detail.
< structure derived from tetracarboxylic dianhydride >
In the polyimide precursor of the present embodiment, as the structure derived from a tetracarboxylic dianhydride,
having a structure derived from a compound selected from 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexatetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1,2-C ] furan-1, a structure of at least one tetracarboxylic dianhydride selected from the group consisting of 3-diketone and bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride, and a structure derived from an aromatic tetracarboxylic dianhydride.
The alicyclic tetracarboxylic acid dianhydride is preferably selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride (CBDA), 1,2,4, 5-cyclohexanetetracarboxylic acid dianhydride (H-PMDA), 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4, 5-bicyclohexaetetracarboxylic acid dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1, at least one of 2-C furan-1, 3-dione and bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride. Among them, from the viewpoint of the CTE of the obtained polyimide film, at least one selected from CBDA, H-PMDA, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexane tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic dianhydride 2,3:5, 6-dianhydride, and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride is preferable, and from the viewpoint of the cost and YI and transparency of the obtained polyimide film, at least one selected from CBDA and H-PMDA is more preferable, and from the viewpoint of the cost, H-PMDA is further preferable.
The 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA) may be any of the isomers represented by the following formulae (1) to (3), respectively, or may be a mixture containing 2 or more of these.
Figure GDA0003184518430000131
The aromatic tetracarboxylic dianhydride preferably comprises:
at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride as the aromatic tetracarboxylic dianhydride 1; and
at least one selected from the group consisting of 4,4 ' -Oxybisphthalic Dianhydride (ODPA), 4 ' - (hexafluoroisopropylidene) bisphthalic anhydride (6FDA), and 4,4 ' -biphenylbis (trimellitic acid monoester anhydride) as the aromatic tetracarboxylic dianhydride 2.
Here, the aromatic tetracarboxylic dianhydride 1 is mainly used for improving the thermal properties, mechanical properties, etc. of the polyimide film to be obtained,
the aromatic tetracarboxylic dianhydride 2 is used for improving the transparency of a polyimide film and the like.
The aromatic tetracarboxylic dianhydride 1 is more preferably PMDA from the viewpoint of CTE of the polyimide film to be obtained.
The aromatic tetracarboxylic dianhydride 2 is more preferably used at least one selected from ODPA and 6FDA from the viewpoint of YI and transparency of the polyimide film to be obtained, and is further preferably used at 6FDA from the viewpoint of CTE of the polyimide film.
The polyimide precursor of the present embodiment is preferably:
the structure derived from the alicyclic tetracarboxylic dianhydride is contained in an amount of 5 to 60 mol% based on the total structure derived from the tetracarboxylic dianhydride,
the total structure derived from the tetracarboxylic dianhydride has a structure derived from an aromatic tetracarboxylic dianhydride in an amount of 40 to 95 mol%;
more preferably:
the structure derived from the alicyclic tetracarboxylic dianhydride is contained in an amount of 5 to 60 mol% based on the total structure derived from the tetracarboxylic dianhydride,
the total structure derived from the tetracarboxylic dianhydride has a structure derived from the aromatic tetracarboxylic dianhydride 1 in an amount of 20 to 80 mol%,
the total structure derived from the tetracarboxylic dianhydride has a structure derived from 5 to 60 mol% of the aromatic tetracarboxylic dianhydride 2.
In the polyimide precursor according to the present embodiment, it is further preferable that the total structure derived from tetracarboxylic dianhydrides comprises 60 mol% or more of a structure derived from at least one tetracarboxylic dianhydride selected from the group consisting of the PMDA, the ODPA, the 6FDA, the CBDA, and the H-PMDA.
Further, from the viewpoint of obtaining a suitable yellowness index, CTE and breaking strength of the polyimide film,
particularly preferably, the structure derived from pyromellitic dianhydride (PMDA) is contained in an amount of 1 to 70 mol% based on the total structure derived from tetracarboxylic dianhydride,
the total structure derived from the tetracarboxylic dianhydride has 1 to 50 mol% of a structure derived from at least one selected from the group consisting of 4,4 '-Oxydiphthalic Dianhydride (ODPA) and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA).
< Structure derived from diamine >
The polyimide precursor of the present embodiment has a structure derived from at least one diamine selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine (TFMB), 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide, and 4-aminophenyl-4-aminobenzoate as a structure derived from a diamine. Among them, TFMB is preferable from the viewpoint of YI and transparency of the polyimide film obtained.
It is particularly preferable that the structure derived from TFMB is contained in an amount of 60 mol% or more of the total diamine-derived structures.
< ratio of structure derived from tetracarboxylic dianhydride to structure derived from diamine >
From the viewpoint of transparency, thermal properties and mechanical properties of the polyimide film, the ratio of the sum of the number of moles of the structure derived from the tetracarboxylic dianhydride to the sum of the number of moles of the structure derived from the diamine is preferably 100/99.9 to 100/95. More specifically, from the viewpoint of obtaining a polyimide film having more suitable yellowness, CTE, and breaking strength, the ratio { (PMDA + ODPA +6FDA + CBDA + H-PMDA)/TFMB } of the sum of the moles of each structure derived from PMDA, ODPA, 6FDA, CBDA, and H-PMDA to the moles of the structure derived from TFMB is preferably 100/99.9 to 100/95.
< weight average molecular weight of polyimide precursor >
The weight average molecular weight of the polyimide precursor of the present embodiment is preferably 5,000 or more and 1,000,000 or less, more preferably 50,000 or more and 500,000 or less, and further preferably 70,000 or more and 250,000 or less. When the weight average molecular weight is 5,000 or more, the strength and elongation of the obtained polyimide film are improved, and the polyimide film has excellent mechanical properties. In particular, the molecular weight is more preferably 50,000 or more from the viewpoint of obtaining a low CTE and a low yellowness (YI value). When the weight average molecular weight Mw is 1,000,000 or less, the resin composition containing the polyimide precursor can be applied to a desired film thickness without bleeding.
Here, the weight average molecular weight means the following value: the molecular weight distribution measured by gel permeation chromatography using monodisperse polystyrene as a standard is a value obtained by dividing the sum of the values obtained by multiplying the molecular weight of each molecule by the mass of the molecule by the sum of the masses of all the molecules.
< method for synthesizing polyimide precursor >
The polyimide precursor of the present embodiment can be produced in the form of a solution containing the polyimide precursor and a solvent by dissolving and reacting the tetracarboxylic dianhydride component and the diamine component in a solvent, preferably. The conditions for the reaction are not particularly limited, and examples thereof include a reaction temperature of-20 to 250 ℃ and a reaction time of 2 to 48 hours. The ambient atmosphere during the reaction is preferably an inert atmosphere such as argon or nitrogen.
The solvent is not particularly limited as long as it dissolves the polymer to be produced. As the known reaction solvent, for example, one or more polar solvents selected from the group consisting of M-cresol, N-methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate, ekuamido (エクアミド) M100 (trade name: manufactured by shinko corporation) and ekuamido B100 (trade name: manufactured by shinko corporation) are useful. Among them, one or more selected from NMP, DMAc, ekuamido M100, and ekuamido B100 are preferable. In addition, a low boiling point solvent such as Tetrahydrofuran (THF) or chloroform, or a low absorption solvent such as γ -butyrolactone may be used instead of or in addition to the above-mentioned solvent.
The polyimide precursor is an imidized polyamic acid obtained by ring-closing dehydration of at least a part of amide bonds derived from an alicyclic tetracarboxylic dianhydride in the polyamic acid.
The step of ring-closing dehydration of an amide bond is not particularly limited, and a known method can be applied. For example, thermal imidization or chemical imidization may be employed.
More specifically, the thermal imidization can be carried out, for example, by the following method. First, a diamine is dissolved and/or dispersed in an appropriate polymerization solvent, a tetracarboxylic dianhydride is added thereto, and a solvent (for example, toluene or the like) azeotropic with water is added. Then, the mixture is heated and stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours, while removing by-product water by azeotropy using a mechanical stirrer. The heating temperature is preferably more than 100 ℃ and 250 ℃ or less, preferably 130 to 230 ℃, and more preferably 150 to 210 ℃. In this case, the monomer concentration is preferably 0.5 mass% or more and 95 mass% or less, more preferably 1 mass% or more and 90 mass% or less.
The chemical imidization can be carried out using a known imidization catalyst. The imidization catalyst is not particularly limited, and examples thereof include:
acid anhydrides such as acetic anhydride;
lactone compounds such as γ -valerolactone, γ -butyrolactone, γ -tetronic acid, γ -phthalide, γ -coumarin, and γ -phthalide;
tertiary amines such as pyridine, quinoline, N-methylmorpholine and triethylamine, and the like.
The imidization catalyst may be used alone in 1 kind or in a mixture of 2 or more kinds as required. Among these, a mixed system of γ -valerolactone and pyridine is particularly preferable from the viewpoint of high reactivity.
The amount of the imidization catalyst added is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the polyamic acid.
The ring-closing dehydration of the amide bond is particularly preferably performed by thermal imidization in the absence of a catalyst from the viewpoint of minimizing the influence on the subsequent reaction.
The polyimide precursor of the present embodiment is most preferably synthesized by the following method:
first, a reaction of alicyclic tetracarboxylic dianhydride and diamine is carried out under the above-mentioned thermal imidization conditions to obtain imidized polyamic acid,
subsequently, the aromatic tetracarboxylic dianhydride and the diamine are added thereto, and the reaction is continued preferably at 100 ℃ or lower.
By the above operation, a solution containing a polyimide precursor can be obtained.
The solution may be directly supplied to the preparation of the resin composition, or
The polyimide precursor contained in the solution may be separated and purified, and then may be used for the preparation of a resin composition.
< other additives >
The resin composition of the present embodiment contains the polyimide precursor and the solvent as described above, and may contain other additives as needed.
Examples of such other additives include alkoxysilane compounds, surfactants, and leveling agents.
(alkoxysilane compound)
When a device such as a TFT is formed from the polyimide obtained from the resin composition of the present embodiment, the resin composition may contain 0.001 to 2 mass% of an alkoxysilane compound with respect to 100 mass% of the polyimide precursor in order to maintain sufficient adhesion between the device and a support.
When the content of the alkoxysilane compound is 0.01% by mass or more based on 100% by mass of the polyimide precursor, good adhesion to the support can be obtained. In addition, the content of the alkoxysilane compound is preferably 2% by mass or less from the viewpoint of storage stability of the resin composition. The content of the alkoxysilane compound is more preferably 0.02 to 2% by mass, still more preferably 0.05 to 1% by mass, still more preferably 0.05 to 0.5% by mass, and particularly preferably 0.1 to 0.5% by mass, based on the polyimide precursor.
Examples of the alkoxysilane compound include 3-mercaptopropyltrimethoxysilane (product name KBM 803; product name: CHISSO CORPORATION, product name: Sila-Ace (サイラエース) S810), 3-mercaptopropyltriethoxysilane (product name: SIM 6475.0; product name: AZMAX Corp.), 3-mercaptopropylmethyldimethoxysilane (product name: LS 1375; product name: AZMAX Corp., product name: SIM 6474.0; product name: AZMAX Corp., product name: SIM6473.5C), mercaptomethyldimethoxysilane (product name: AZMAX Corp., product name: SIM 6473.0; product name: AZMAX Corp., product name: SIM6473.0), 3-mercaptopropyldiethoxymethyloxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropyltrimethoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxy silane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (available from shin-Etsu chemical industries, Ltd., Japan, etc., the trade name, etc., trade name LS 3610; AZMAX Corp., product name SIU9055.0), N- (3-trimethoxysilylpropyl) urea (AZMAX Corp., product name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxypropyloxysilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-methoxysilylpropyl) urea, N- (3-ethoxysilylpropyl) urea, N- (3-urea, N- (3-propy) urea, N- (3-ethoxysilylpropyl) urea, N- (3-bis (3-ethoxysilylpropyl) urea, N- (3-ethoxysilylpropyl) urea, N- (3-urea, N, n- (3-Tripropoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxypropyloxysilylethyl) urea, N- (3-trimethoxysilylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (AZMAX Corp., product, trade name SLA0598.0), m-aminophenyltrimethoxysilane (AZMAX Corp., product, trade name SLA0599.0), p-aminophenyltrimethoxysilane (AZMAX Corp., product, SLA0599.0, N-propoxyethyl) urea, N- (3-methoxypropylsilylethyl) urea, N- (3-trimethoxysilylbutyl) urea, N- (3-methoxybutyl) urea, N- (3-triethoxysilylbutyl) urea, N-methoxybutyl) urea, N- (3-phenoxybutyl) urea, N-trimethoxysilane (AZMAX Corp., product, N-butyl, N-methoxybutyl-urea, N-butyl-urea, N-methoxybutyl-urea, N-butyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-, prepared product, trade name SLA0599.1) aminophenyltrimethoxysilane (AZMAX Corp., manufactured product, trade name SLA0599.2), 2- (trimethoxysilylethyl) pyridine (AZMAX Corp., manufactured product, trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxysilylpropyl) tert-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-tert-butoxysilane, tetra-methoxyethoxysilane, tetra-methoxy-n-propoxysilane), tetra-ethoxyethoxyethoxyethoxysilane, Tetrakis (methoxyethoxyethoxysilane), bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl ] disulfide, bis [3- (triethoxysilyl) propyl ] tetrasulfide, di-t-butoxydiacetoxysilane, diisobutyloxyaluminoxysilane, bis (acetylacetonato) titanium-O, O' -bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilane triol, methylphenylsilane glycol, ethylphenylsilane glycol, n-propylsilanediol, and mixtures thereof, Isopropylphenylsilane diol, n-butylphenylsilane diol, isobutylphenylsilane diol, tert-butylphenylsilane diol, diphenylsilandiol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl-n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butyleethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyl diphenylsilanol, isopropyldiphenylsilanol, n-propyldiphenylsilanol, n-butyldiphenylsilanol, isopropyldiphenylsilanol, n-propyldiphenylsilanol, N-propyldiphenylsilanol, etc, T-butyldiphenylsilanol, triphenylsilanol, 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, γ -aminopropyltripropoxysilane, γ -aminopropyltributoxysilane, γ -aminoethyltriethoxysilane, γ -aminoethyltrimethoxysilane, γ -aminoethyltripropoxysilane, γ -aminobutyltriethoxysilane, γ -aminobutyltrimethoxysilane, γ -aminobutyltripropoxysilane, γ -aminobutyltributoxysilane, etc., but are not limited to them. These may be used alone or in combination of two or more.
Among the silane coupling agents, from the viewpoint of ensuring the storage stability of the resin composition, 1 or more selected from the group consisting of phenylsilane triol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanols, and silane coupling agents having the respective structures shown below are preferable.
Figure GDA0003184518430000211
(surfactant or leveling agent)
In addition, by adding a surfactant or a leveling agent to the resin composition, the coatability can be improved. Specifically, shrinkage after coating can be prevented.
Examples of such a surfactant or leveling agent include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093, KBM303, KBM403, KBM803 (trade name, manufactured by shin-Etsu chemical Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (trade name, manufactured by Toyo Corning Silicone Co., Ltd.), SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (trade name, manufactured by Nikka Co., Ltd.), DBE-814, DBE-224, DBE-621, CMS-352, CMS-222, KF-354L-352A, KF, KF-A, KF-89898L-898, KF-355A, KF-6020, DBE-821, DBE-712(Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (trade name, BYK Japan), guranouru (グラノール) (trade name, Kyowa chemical Co., Ltd.); megafac (メガファックス) F171, F173, R-08 (trade name, manufactured by Dainippon ink chemical Co., Ltd.) as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc., FLUORAD (フロラード) FC430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), etc.
When a surfactant or a leveling agent is used, the total amount of the surfactant or the leveling agent is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the polyimide precursor in the resin composition.
< resin composition >
The resin composition of the present embodiment can be used in the form of a solution composition (varnish) in which the polyimide precursor and other components optionally used are dissolved in a solvent.
Here, as the solvent, the same solvents as those described above as the solvents usable in synthesizing the polyimide precursor can be used.
The amount of the solvent used is preferably such that the solid content concentration of the resin composition is 3 to 50 mass%.
The varnish of the resin composition of the present embodiment has excellent room temperature storage stability, and the rate of change in viscosity of the varnish when stored at room temperature for 4 weeks is 10% or less of the initial viscosity. When the storage stability at room temperature is excellent, the storage by freezing is not necessary, and handling is easy.
< layered product >
The laminate of the present embodiment includes a support and a polyimide film formed on the support. The laminate may further include an inorganic film on the polyimide film.
The laminate is formed by the following steps:
a coating film forming step of spreading the resin composition of the present embodiment on the surface of the support to form a coating film; and
and a heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film.
The inorganic film is used as a gas barrier layer for preventing moisture and oxygen from penetrating into the organic EL light-emitting layer and the like from the polyimide film of the present invention, and inorganic oxide films of silicon oxide, aluminum oxide, silicon carbide oxide, silicon carbide nitride, silicon nitride oxide and the like are suitably exemplified. The inorganic film is formed by a plasma CVD method or the like.
The support is, for example, an inorganic substrate such as a glass substrate such as an alkali-free glass substrate, but is not particularly limited thereto.
Examples of the development method include known coating methods such as spin coating, slit coating, and blade coating.
More specifically, the polyimide film can be formed on the support by spreading the resin composition on the support (or on the adhesive layer formed on the main surface thereof) and removing the solvent, and then heating the spread resin composition in an inert atmosphere to imidize the polyimide precursor.
The solvent removal can be performed by, for example, heat treatment at a temperature of less than 250 ℃ and preferably 50 to 200 ℃ for 1 to 300 minutes. The imidization can be carried out by, for example, heat treatment at a temperature of 250 to 550 ℃ for 1 to 300 minutes. The ambient atmosphere at the time of imidization is preferably an inert atmosphere such as nitrogen.
The thickness of the polyimide film obtained in the present embodiment is not particularly limited, but is preferably in the range of 10 to 50 μm, and more preferably 15 to 25 μm.
The laminate is used for manufacturing a flexible device, for example. More specifically, a flexible device including a flexible transparent substrate formed of a polyimide film can be obtained by forming a semiconductor device on the polyimide film and then peeling off the support.
< polyimide film >
The polyimide film of the present embodiment is formed through the following steps:
a coating film forming step of forming a coating film by spreading the resin composition containing the polyimide precursor of the present embodiment and the solvent on the surface of the support;
a heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film; and
and a peeling step of peeling the polyimide film from the support to obtain a polyimide film.
The polyimide film is used, for example, for manufacturing flexible devices. Specifically, the polyimide film can be used for a substrate for forming a TFT, a substrate for forming a color filter, an alignment film, a transparent substrate for a flexible display, and the like.
< advantages of the present invention >
As described above, the polyimide precursor of the present embodiment is preferably a polyimide precursor,
(1) the structure derived from a tetracarboxylic dianhydride comprises:
derived from at least 1 alicyclic tetracarboxylic dianhydride selected from CBDA, H-PMDA and the like,
derived from the structure of aromatic tetracarboxylic dianhydride 1 selected from PMDA and the like,
a structure derived from an aromatic tetracarboxylic dianhydride selected from OPDA, 6FDA and the like,
(2) the diamine-derived structure may be a structure derived from TFMB or the like.
The polyimide film produced using the polyimide precursor is colorless and transparent, has a low CTE, and has excellent elongation. The laminate having the inorganic film formed on the polyimide film has a small surface roughness, a small Haze value, and a small water vapor transmission rate, and is therefore suitable for use as a transparent substrate for a flexible display.
The following description will be made in detail.
In forming a flexible display, a glass substrate is used as a support, a flexible substrate is formed thereon, and further an inorganic film of a TFT or the like is formed thereon. The step of forming the inorganic film on the substrate is typically performed at a temperature in a wide range of 150 to 650 ℃. In order to exert the actually desired properties, a temperature range of 250 ℃ to 400 ℃ is mainly used. Examples of the inorganic film include a TFT-IGZO (InGaZnO) oxide semiconductor, a TFT (a-Si-TFT, poly-Si-TFT), and the like.
In this case, when the CTE of the flexible substrate is higher than the CTE of the glass substrate, the problem that the glass substrate is warped or damaged and the flexible substrate is peeled off from the glass substrate is more likely to occur when the flexible substrate contracts during cooling after expansion in the high-temperature inorganic film forming step. Generally, the glass substrate has a smaller thermal expansion coefficient than the resin. Therefore, the smaller the linear expansion coefficient of the flexible substrate, the more preferable.
In view of the above, the polyimide film of the present embodiment may have an average coefficient of linear expansion (CTE) of 25.0 ppm/c or less, as measured by TMA method at 100 to 300 c, based on a film thickness of 15 to 25 μm.
The polyimide film of the present embodiment has a yellowness index (YI value) of 10 or less, and the transmittance at 550nm when measured with an ultraviolet spectrophotometer with a film thickness of 15 to 25 μm as a reference can be 85% or more.
The inorganic film of the laminate in which the inorganic film is formed on the polyimide film of this embodiment has a small surface roughness, a small Haze value, and a small water vapor transmission rate.
In the case of an organic EL display, an inorganic film is formed on a polyimide film as a gas barrier layer. In this case, when the inorganic film has a large surface roughness and a large Haze value, the laminate is cloudy or blurred, and is not suitable for a display. Further, when the water vapor permeability is high, the function as a gas barrier layer is not exhibited, and therefore, this is not suitable.
It can be considered that: the surface roughness, Haze value and water vapor transmission rate of these laminates are related to the heat resistance of the polyimide film. This is because: when an inorganic film is formed on a polyimide film by a CVD method, a laminate including the polyimide film is exposed to a high temperature equal to or higher than the curing (imidization) temperature at the time of forming the polyimide film. The laminate is preferably: surface roughness of 25nm or less, Haze of 15 or less, and water vapor permeability of 0.1 g/(m)224h) or less.
The polyimide film of the present embodiment preferably has an elongation of 15% or more based on a film thickness of 15 to 25 μm. By having such an elongation, the breaking strength when the flexible substrate is processed becomes excellent, and therefore the yield can be improved.
The polyimide film of the present embodiment satisfying the above physical properties can be used in applications where the use is limited due to the yellow color of the conventional polyimide film and applications where transparency is required. In particular, in addition to being suitable as a transparent substrate for a flexible display,
for example, it can be used for a protective film or a light-diffusing sheet and a coating film in a TFT-LCD (for example, an inner layer, a gate insulating film and a liquid crystal alignment film of a TFT-LCD), etc. When the polyimide of the present embodiment is applied as a liquid crystal alignment film, it contributes to an increase in aperture ratio, and a TFT-LCD with high contrast can be manufactured.
The polyimide film and the laminate produced using the polyimide precursor of the present embodiment can be suitably used for production of, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible device. Is particularly suitable for manufacturing substrates. Examples of the flexible device include a flexible display, a flexible solar cell, a flexible lighting device, and a flexible battery.
Examples
The present invention will be specifically described below based on examples. These are described for illustrative purposes, and the scope of the present invention is not limited to the following examples.
Various evaluations in examples and comparative examples are as follows.
(measurement of weight average molecular weight)
The weight average molecular weight was measured using Gel Permeation Chromatography (GPC) under the following conditions. A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (available from Tosoh corporation).
Solvent: using N, N-dimethylformamide (manufactured by Wako pure chemical industries, Ltd., for high performance liquid chromatography), 24.8mmol/L of lithium bromide monohydrate (manufactured by Wako pure chemical industries, Ltd., purity 99.5%) and 63.2mmol/L of phosphoric acid (manufactured by Wako pure chemical industries, Ltd., for high performance liquid chromatography) were added immediately before the measurement
Column: shodex KD-806M (made by Showa Denko K.K.)
Flow rate: 1.0 mL/min
Column temperature: 40 deg.C
A pump: PU-2080Plus (JASCO products.)
A detector: RI-2031Plus (RI: differential refractometer, JASCO Co., Ltd.), UV-2075Plus (UV-VIS: ultraviolet-visible absorptiometer, JASCO Co., Ltd.)
(calculation of imide group concentration of moiety derived from alicyclic tetracarboxylic dianhydride)
Imide group concentration of moiety derived from alicyclic acid dianhydride measured with respect to polyimide precursor varnish13The integrated value of the C-NMR signal was calculated.13The C-NMR measurement was carried out under the following conditions.
A measuring device: JNM-GSX400 manufactured by Japan electronic Co., Ltd
Measuring temperature: 23 deg.C
And (3) determination of a solvent: deuterated dimethyl sulfoxide solvent (DMSO-d)6)
Signals attributed to imide bonds, amide bonds, and respective carbons of carboxylic acids derived from the moiety of alicyclic tetracarboxylic dianhydride appear at the following magnetic field strengths:
signal attributed to imide bond carbon derived from alicyclic tetracarboxylic dianhydride moiety: about 177ppm (A)
Signal attributed to amide bond carbon derived from alicyclic tetracarboxylic dianhydride moiety: near 172ppm (B)
Signal attributed to carboxyl carbon derived from part of alicyclic tetracarboxylic dianhydride: about 177ppm (C)
Here, the integral values of B and C are the same for the amic acid (not imidized) site. The integrated value of the imide bond carbons in the imidized portion and the integrated value of the amide bond carbons in the non-imidized portion are represented by the following formulae:
integrated value of imide-bonded carbons: integral value of A-integral value of B
Integral value of amide bond carbon and carboxyl group carbon: integral value of B × 2
Thus, the imide group concentration is represented by the following calculation formula:
imide group concentration (%) (100 × (integrated value of integrated value-B of a)/(integrated value of integrated value-B of a + integrated value of B) × 2) × (integrated value-B of a)/(integrated value of a + integrated value of B) 100 × (integrated value of integrated value-B of a)
(evaluation of storage stability of varnish)
The varnish compositions prepared in examples and comparative examples below were allowed to stand at room temperature for 3 days, and the viscosity at 23 ℃ was measured using the obtained samples as prepared samples. Thereafter, the sample obtained by further standing at room temperature for 4 weeks was regarded as a sample after 4 weeks, and the viscosity measurement at 23 ℃ was performed again.
The viscosity measurement was performed using a viscometer with a temperature controller (TV-22, manufactured by Toyobo Industrial Co., Ltd.).
The viscosity change rate at room temperature for 4 weeks was calculated by the following equation using the above measured values.
Viscosity change rate (%) at room temperature for 4 weeks [ (sample viscosity after 4 weeks) - (sample viscosity after preparation) ]/(sample viscosity after preparation) × 100
The viscosity change rate at room temperature for 4 weeks was evaluated according to the following criteria. The results are shown in Table 2.
Very good: viscosity change rate of 5% or less (Excellent storage stability)
O: viscosity change rate of 10% or less (good storage stability)
X: viscosity change rate of more than 10% (poor storage stability)
(production of laminate and separation film)
The varnish of the polyimide precursor obtained in each of examples and comparative examples was coated on an alkali-free glass substrate (thickness: 0.7mm) using a bar coater. Then, the substrate was leveled at room temperature for 5 to 10 minutes, and then heated in a hot air oven at 140 ℃ for 60 minutes, and further heated in a nitrogen atmosphere at a predetermined temperature for 60 minutes, thereby producing a laminate having a coating film on the substrate. The film thickness of the coating film in the laminate was set so that the film thickness after curing became 20 μm. Then, the coating film is cured (cured) at a predetermined temperature to imidize the coating film. The cured laminate was allowed to stand at room temperature for 24 hours, and then the polyimide film was peeled off from the glass, thereby separating the film.
In the following evaluations of the breaking strength, yellowness and linear expansion coefficient, a polyimide film cured at the predetermined temperature was used as a sample.
(evaluation of elongation)
A sample of a polyimide film cured at a predetermined temperature and having a width of 5mm, a length of 50mm and a thickness of 20 μm was subjected to tensile measurement at a rate of 100 mm/min using a tensile tester (RTG-1210, manufactured by A & D Company, Limited). The steel was evaluated as "excellent" when the elongation at break was 20% or more, as "good" when the elongation at break was 15% or more and less than 20%, as "Δ (poor" elongation ") when the elongation at break was 10% or more and less than 15%, and as" poor "when the elongation at break was less than 10%.
(evaluation of yellowness (YI value))
A polyimide film having a thickness of 20 μm cured at a predetermined temperature was measured with a D65 light source using a Spectrophotometer (SE 600) manufactured by Nippon Denshoku industries Co., Ltd. The YI value was evaluated as | ("good" in yellowness index) when it was 8.0 or less, as | ("good" in yellowness index) when it was more than 8.0 and 10.0 or less, as | ("bad" in yellowness index) when it was more than 10.0 and 15.0 or less, and as × (poor "in yellowness index) when it was more than 15.0.
(evaluation of coefficient of Linear expansion (CTE))
The elongation of the test piece was measured under the following conditions by thermomechanical analysis using a thermomechanical analyzer (TMA-50) manufactured by shimadzu corporation for a polyimide film cured at a predetermined temperature.
Loading: 5g
Temperature rise rate: 10 ℃/min
And (3) measuring atmosphere: atmosphere of nitrogen
Nitrogen flow rate: 20 ml/min)
Measurement temperature range: 50 to 450 DEG C
The CTE of the polyimide film in the temperature range of 100 to 300 ℃ at this time was determined, and the film was evaluated as excellent (CTE "excellent") when the CTE was 20 ppm/c or less, as good (CTE) when the CTE was more than 20 ppm/c and 25 ppm/c or less, as Δ (CTE "poor") when the CTE was more than 25 ppm/c and 30 ppm/c or less, and as x (CTE "poor") when the CTE was more than 30 ppm/c.
(measurement of surface roughness of inorganic film formed on polyimide film)
Using the varnish compositions prepared in the above examples and comparative examples, a laminate wafer was formed by sequentially laminating a polyimide film and an inorganic film on a 6-inch silicon wafer substrate having an aluminum vapor deposition layer provided on the surface thereof in the following manner.
First, the respective varnish compositions were spin-coated on the substrate, and then heated in a hot air oven at 140 ℃ for 60 minutes and further at 320 ℃ for 60 minutes under a nitrogen atmosphere, thereby obtaining a wafer having a polyimide thin film with a film thickness of 20 μm.
Thereafter, a CVD method was used to form a thin film of polyimide on the substrateSilicon nitride (SiN) as an inorganic film was formed at a thickness of 100nm at 350 deg.Cx) And (3) a membrane. Then, the surface roughness of the formed silicon nitride was measured in a range of 100 μm × 100 μm using ナノピクス 2100 (trade name, product of SII nanoechhnology) as an AFM. The test was performed with N being 5, and the average value thereof was taken as the surface roughness Ra.
The results are shown in Table 2.
(evaluation of Haze)
The laminate wafer obtained above was immersed in a dilute hydrochloric acid aqueous solution, and the two layers of the inorganic film and the polyimide film were peeled off from the wafer as a single body, thereby obtaining a sample of a polyimide film having an inorganic film formed on the surface thereof. Haze was measured using this sample by a Haze meter, model SC-3H manufactured by Suga Test Instruments co., ltd., according to the transparency Test method of JIS K7105.
The measurement results were evaluated according to the following criteria.
Very good: haze is 5 or less (Haze is excellent)
O: haze is greater than 5 and less than 15(Haze "good")
X: haze is greater than 15(Haze is bad)
The results are shown in Table 2.
(evaluation of Water vapor Transmission Rate)
The water vapor transmission rate of the polyimide film having an inorganic film formed on the surface thereof obtained above was measured under the conditions of a temperature of 40 ℃, a humidity of 90% RH and a measurement area of 80 mm.phi.using a water vapor transmission rate measuring apparatus (model name: PERMATRAN (registered trademark)) W3/31 manufactured by MOCON. The number of measurements was 5 times each, and the average value thereof was evaluated as the water vapor transmission rate according to the following criteria.
Very good: the water vapor transmission rate is 0.01 g/(m)224h) or less (water vapor transmission rate "excellent")
O: the water vapor transmission rate is more than 0.01 g/(m)224h) and 0.1 g/(m)224h) or less (water vapor transmission rate "good")
X: the water vapor transmission rate is more than 0.1 g/(m)224h) (Water vapor Transmission Rate "poor")
The results are shown in Table 2.
[ reference example 1]
15.69g (49.00mmol) of 2,2' -bis (trifluoromethyl) benzidine (TFMB) and 178.95g of N-methyl-2-pyrrolidone (NMP) were added to a 500ml separable flask under a nitrogen atmosphere, and TFMB was dissolved with stirring. Thereafter, 1.09g (5.0mmol) of pyromellitic dianhydride (PMDA), 3.10g (10.0mmol) of 4, 4' -Oxydiphthalic Dianhydride (ODPA), and 6.86g (35.0mmol) of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride (CBDA) were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain an NMP solution of polyamic acid (hereinafter also referred to as "varnish"). The weight average molecular weight (Mw) of the obtained polyamic acid was 116,500. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ reference example 2]
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 180.42g, PMDA3.27g (15.0mmol), ODPA3.10g (10.0mmol) and CBDA 4.90g (25.0 mmol). The weight average molecular weight (Mw) of the obtained polyamic acid was 120,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ reference example 3]
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 186.58g, PMDA1.09g (5.00mmol), ODPA 6.20g (20.0mmol) and CBDA 4.90g (25.0 mmol). The weight average molecular weight (Mw) of the obtained polyamic acid was 128,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ example 4]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. Subsequently, the flask contents were cooled to 40 ℃ and then 12.55g (39.2mmol) of TFMB, 168.43g of NMP, 6.54g (30.0mmol) of PMDA and 3.10g (10.0mmol) of ODPA3 were added thereto, followed by stirring at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 82,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ reference example 5]
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 178.14g, PMDA5.45g (25.0mmol), ODPA 1.55g (5.0mmol) and CBDA 3.92g (20 mmol). The weight average molecular weight (Mw) of the obtained polyamic acid was 119,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ reference example 6]
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw materials was changed to TFMB 15.69g (49.0mmol), NMP 187.38g, PMDA2.18g (10.0mmol), ODPA 6.20g (20.0mmol) and CBDA 3.92g (20.0 mmol). The weight average molecular weight (Mw) of the obtained polyamic acid was 123,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ reference example 7]
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 175.19g, PMDA1.09g (5.0mmol), ODPA 1.55g (5.0mmol) and CBDA 7.84g (40.0 mmol). The weight average molecular weight (Mw) of the obtained polyamic acid was 123,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ reference example 8]
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 189.59g, PMDA5.45g (25.0mmol), ODPA 6.20g (20.0mmol) and CBDA 0.98g (5.0 mmol). The weight average molecular weight (Mw) of the obtained polyamic acid was 103,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ example 9]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 12.55g (39.2mmol) of TFMB, 171.51g of NMP, 5.45g (25.0mmol) of PMDA and 4.65g (15.0mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 123,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 10]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 12.55g (39.2mmol) of TFMB, 174.59g of NMP, 4.36g (20.0mmol) of PMDA and 6.20g (20.0mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 81,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 11]
A separable flask equipped with a dean stark apparatus and a reflux device was charged with 6.28g (19.6mmol) of TFMB, 32.28g of NMP and 50g of toluene under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 4.48g (20.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 9.42g (29.4mmol) of TFMB, 76.44g of NMP, 5.45g (25.0mmol) of PMDA, and 1.55g (5.0mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymerization composition was 68,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 12]
A separable flask equipped with a dean stark apparatus and a reflux device was charged with 6.28g (19.6mmol) of TFMB, 32.28g of NMP and 50g of toluene under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 4.48g (20.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 9.42g (29.4mmol) of TFMB, 78.28g of NMP, 4.36g (20.0mmol) of PMDA, and 3.10g (10.0mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 68,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 13]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 0.63g (1.96mmol) of TFMB, 3.22g of NMP and 30g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.45g (2.00mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 15.06g (47.0mmol) of TFMB, 186.57g of NMP, 6.33g (29.0mmol) of PMDA and 5.89g (19.0mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 112,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 14]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 12.55g (39.2mmol) of TFMB, 166.88g of NMP, 7.09g (32.5mmol) of PMDA, and 2.33g (7.5mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymeric composition was 79,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 15]
Into a separable flask equipped with a dean stark apparatus and a reflux vessel, 9.42g (29.4mmol) of TFMB, 48.42g of NMP, and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 6.78g (30.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 6.28g (19.6mmol) of TFMB, 60.54g of NMP, 3.27g (15.0mmol) of PMDA and 1.55g (5.0mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymeric composition was 56,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 16]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.80mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 12.55g (39.2mmol) of TFMB, 168.43g of NMP, 4.36g (20.0mmol) of PMDA, 3.10g (10.0mmol) of ODPA and 1.96g (10.0mmol) of CBDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ reference example 17]
Varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to 15.69g (49.0mmol) of TFMB, 162.24g of NMP, 6.54g (30.0mmol) of PMDAD, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4.44g (10.0mmol) of CBDA1.96g (10 mmol). The weight average molecular weight (Mw) of the obtained polyamic acid was 159,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
[ example 18]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 12.55g (39.2mmol) of TFMB, 147.70g of NMP, 6.54g (30.0mmol) of PMDA, and 4.44g (10.0mmol) of 6FDA were added, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 85,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
[ example 19]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by infrared spectroscopic analysis (IR)-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 153.4g of NMP, 5.45g (25.0mmol) of PMDA and 6.66g (15.0mmol) of 6FDA were added to the flask, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 88,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 20]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 deg.CIR analysis was conducted at 1,650cm for confirmation of the amino bond-derived structure-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 159.8g of NMP, 4.36g (20.0mmol) of PMDA and 8.88g (20.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 86,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 21]
A separable flask equipped with a dean stark apparatus and a reflux device was charged with 6.28g (19.6mmol) of TFMB, 32.28g of NMP and 50g of toluene under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 4.48g (20.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 9.42g (29.4mmol) of TFMB, 124.9g of NMP, 5.45g (25.0mmol) of PMDA and 2.22g (5.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 76,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 22]
A separable flask equipped with a dean stark apparatus and a reflux device was charged with 6.28g (19.6mmol) of TFMB, 32.28g of NMP and 50g of toluene under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 4.48g (20.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 9.42g (29.4mmol) of TFMB, 131.3g of NMP, 4.36g (20.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 77,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 23]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.45g (2.00mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 158.3g of NMP, 6.33g (29.0mmol) of PMDA and 8.44g (19.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 89,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 24]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 143.9g of NMP, 7.09g (32.5mmol) of PMDA and 3.33g (7.5mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 89,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 25]
Into a separable flask equipped with a dean stark apparatus and a reflux vessel, 9.42g (29.4mmol) of TFMB, 48.42g of NMP, and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 6.78g (30.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1NearbyAbsorption (C ═ O) disappeared. Thereafter, 6.28g (19.6mmol) of TFMB, 109.5g of NMP, 3.27g (15.0mmol) of PMDA, and 6FDA2.22g (5.0mmol) were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 75,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 26]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 153.5g of NMP, 3.27g (15.0mmol) of PMDA, 4.41g (15.0mmol) of BPDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 87,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 27]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 143.3g of NMP, 6.54g (30.0mmol) of PMDA, 1.55g (5.0mmol) of ODPA and 2.22g (5.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 86,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 28]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 1.12g (5.0mmol) of H-PMDA and 0.98g (5.0mmol) of CBDA were added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 146.3g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 90,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 29]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.34g (1.5mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 147g of NMP, 6.54g (30.0mmol) of PMDA, 4.44g (10.0mmol) of 6FDA and 1.9g (8.5mmol) of H-PMDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 30]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.56g (2.5mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 147g of NMP, 6.54g (30.0mmol) of PMDA, 4.44g (10.0mmol) of 6FDA and 1.68g (7.5mmol) of H-PMDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 75,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 31]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.78g (3.5mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 147g of NMP, 6.54g (30.0mmol) of PMDA, 4.44g (10.0mmol) of 6FDA and 1.46g (6.5mmol) of H-PMDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 78,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 32]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.62g (2.75mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 153.3g of NMP, 6.54g (30.0mmol) of PMDA, 6.66g (15.0mmol) of 6FDA and 0.5g (2.25mmol) of H-PMDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 80,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 33]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 1.68g (7.5mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 160.1g of NMP, 6.54g (30.0mmol) of PMDA, 2.22g (5.0mmol) of 6FDA and 5.1g (22.5mmol) of H-PMDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 34]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. To this, CBDA1.96g (10.0mmol) was added, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 166.5g of NMP, 6.54g (30.0mmol) of PMDA and 3.10g (10.0mmol) of ODPA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 120,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 35]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.98g (5.0mmol) of CBDA was added thereto, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. The contents of the flask were cooled to 40 ℃ and the amide bond-derived compounds were confirmed by IR1,650cm-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 191.3g of NMP, 5.45g (25.0mmol) of PMDA and 8.88g (20.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 95,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 36]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 1.96g (10.0mmol) of CBDA was added thereto, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 175.5g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 100,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 37]
Into a separable flask equipped with a dean stark apparatus and a reflux vessel, 9.42g (29.4mmol) of TFMB, 48.42g of NMP, and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 5.88g (30.0mmol) of CBDA was added thereto, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Then, 6.28g (19.6mmol) of TFMB, 169.5g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 100,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 38]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.29g (1.5mmol) of CBDA was added thereto, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 175.5g of NMP, 6.54g (30.0mmol) of PMDA, 4.44g (10.0mmol) of 6FDA and 1.67g (8.5mmol) of CBDAA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 95,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 39]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.53g (2.75mmol) of CBDA was added thereto, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 183.8g of NMP, 6.54g (30.0mmol) of PMDA, 6.66g (15.0mmol) of FDA and 0.45g (2.25mmol) of CBDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 80,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 40]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 1.47g (7.5mmol) of CBDA was added thereto, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1Nearby suctionThe yield (C ═ O) disappeared. Thereafter, 12.55g (39.2mmol) of TFMB, 186.8g of NMP, 6.54g (30.0mmol) of PMDA, 2.22g (5.0mmol) of 6FDA and 4.41g (22.5mmol) of CBDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 91,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 41]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 160g of NMP, 8.83g (30.0mmol) of BPDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 86,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 42]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1After the absorption (C ═ O) around the cured film disappeared, 12.55g (39.2mmol) of TFMB, 147.8g of NMP, 6.54g (30.0mmol) of PMDA, and 4.58g (10.0mmol) of 4, 4' -biphenylbis (trimellitic acid monoester anhydride (TAHQ) were added, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer, the weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 84,000, and the evaluation results of the film cured at 350 ℃ are shown in table 2.
[ example 43]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. To this was added 2.1g (10.0mmol) of CPDA, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 146.3g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 44]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. To this was added 3.06g (10.0mmol) of H-BPDA, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 151.7g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 73,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 45]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.36g (10.0mmol) of BCDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1Absorption (C ═ O) in the vicinityAnd (6) losing. Thereafter, 12.55g (39.2mmol) of TFMB, 147.7g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 75,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 46]
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. To which bicyclo [2.2.2] is added]2.48g (10.0mmol) of oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride (BOTDA) was refluxed at 180 ℃ for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 148.4g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 74,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 47]
2.08g (9.8mmol) of 2,2 '-dimethylbiphenyl-4, 4' -diamine (mTB), 16.14g of NMP, and 50g of toluene were put into a separable flask equipped with a dean stark apparatus and a reflux device under a nitrogen atmosphere, and the mTB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 8.32g (39.2mmol) of mTB, 117.2g of NMP, 6.54g (30.0mmol) of PMDA, and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 82,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 48]
A separable flask equipped with a dean stark apparatus and a reflux device was charged with 2.23g (9.8mmol) of 4, 4' -Diaminobenzanilide (DABA), 16.14g of NMP and 50g of toluene under a nitrogen atmosphere, and the DABA was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 8.91g (39.2mmol) of DABA, 121.4g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 83,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 49]
A separable flask equipped with a dean stark apparatus and a reflux device was charged with 2.24g (9.8mmol) of 4-aminophenyl-4-aminobenzoate (APAB), 16.14g of NMP, and 50g of toluene under a nitrogen atmosphere, and APAB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 8.95g (39.2mmol) of APAB, 121.6g of NMP, 6.54g (30.0mmol) of PMDA and 4.44g (10.0mmol) of 6FDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 82,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
[ example 50]
A resin composition was prepared by dissolving the alkoxysilane compound 1(ROSi1) in an amount of 0.5 parts by weight per 100 parts by weight of the resin in the varnish of the polyimide-polyamic acid polymer obtained in example 9 and filtering the solution through a 0.1 μm filter. The properties of the composition and the cured film thereof were measured according to the evaluation methods described above. The results are shown in Table 2.
[ example 51]
To the varnish of the polyimide-polyamic acid polymer obtained in example 19, alkoxysilane compound 1 was dissolved in an amount of 0.5 parts by weight in terms of 100 parts by weight of the resin, and the resultant solution was filtered through a 0.1 μm filter to prepare a resin composition. The properties of the composition and the cured film thereof were measured according to the evaluation methods described above. The results are shown in Table 2.
[ example 52]
To the varnish of the polyimide-polyamic acid polymer obtained in example 9, 0.05 part by weight of the surfactant 1(Surf1) in terms of 100 parts by weight of the resin was dissolved, and the resulting solution was filtered through a 0.1 μm filter to prepare a resin composition. The properties of the composition and the cured film thereof were measured according to the evaluation methods described above. The results are shown in Table 2.
[ example 53]
To the varnish of the polyimide-polyamic acid polymer obtained in example 19, 0.05 part by weight of the surfactant 1 was dissolved in terms of 100 parts by weight of the resin, and the resulting solution was filtered through a 0.1 μm filter to prepare a resin composition. The properties of the composition and the cured film thereof were measured according to the evaluation methods described above. The results are shown in Table 2.
Comparative example 1
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to 14.39g (44.9mmol) of TFMB, 163.23g of NMP, 10.0g (45.8mmol) of PMDA, 0g (0mmol) of ODPA and 0g (0mmol) of CBDA. The weight average molecular weight (Mw) of the polyamic acid in the resulting varnish was 47,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 2
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 10.12g (31.6mmol), NMP 134.65g, PMDA 0g (0mmol), ODPA 10.0g (32.2mmol) and CBDA 0g (0 mmol). The weight average molecular weight (Mw) of the polyamic acid in the resulting varnish was 65,500. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 3
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to 16.00g (50.0mmol) of TFMB, 174.00g of NMP, 0g (0mmol) of PMDA, 0g (0mmol) of ODPA and 10.00g (51.0mmol) of CBDA. The weight average molecular weight (Mw) of the polyamic acid in the resulting varnish was 221,000. The CTE, YI value and elongation of the film cured at 330 ℃ are shown in table 2 below.
Comparative example 4
Into a separable flask equipped with a dean stark apparatus and a reflux vessel, 14.00g (43.7mmol) of TFMB, 160.62g of NMP, and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 10.00g (44.6mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature, thereby obtaining a varnish of polyimide. The weight average molecular weight (Mw) of the polyimide in the varnish obtained was 50,600. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 5
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 8.79g (27.4mmol), NMP 60.6g, PMDA 5.50g (25.2mmol) and ODPA 0.87g (2.8 mmol). The weight average molecular weight (Mw) of the polymer contained in the varnish was 47,000. The CTE, YI value and breaking strength of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 6
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to 16.44g (51.3mmol) of TFMB, 184.18g of NMP, 8.00g (36.7mmol) of PMDAA, 0g (0mmol) of ODPA and 3.08g (15.7mmol) of CBDA. The weight average molecular weight (Mw) of the polymer contained in the varnish obtained was 121,900. The CTE, YI value and breaking strength of the film cured at 330 ℃ are shown in table 2 below.
Comparative example 7
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to 14.17g (44.2mmol) of TFMB, 171.31g of NMP, 0g (0mmol) of PMDA, 7.00g (22.6mmol) of ODPA and 4.43g (22.6mmol) of CBDA. The weight average molecular weight (Mw) of the resulting varnish was 105,000. The CTE, YI value and breaking strength of the film cured at 330 ℃ are shown in table 2 below.
Comparative example 8
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 12.55g (39.2mmol) of TFMB, 12.41g (40.0mmol) of NMP 186.91 and ODPA were added, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 66,700. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 9
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 175.05g, PMDA6.54g (30.0mmol), ODPA 0g (0mmol) and CBDA 3.92g (20.0 mmol). The weight average molecular weight (Mw) of the polymer contained in the varnish obtained was 91,200. The CTE, YI value and breaking strength of the film cured at 330 ℃ are shown in table 2 below.
Comparative example 10
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 2.24g (10.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, 12.55g (39.2mmol) of TFMB, 162.26g of NMP, and 8.72g (40.0mmol) of PMDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymerization composition. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymerization composition was 226,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 11
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 193.54g, PMDA 0g (0mmol), ODPA 9.31g (30.0mmol) and CBDA 3.92g (20.0 mmol). The weight average molecular weight (Mw) of the polymer contained in the varnish obtained was 125,100. The CTE, YI value and breaking strength of the film cured at 330 ℃ are shown in table 2 below.
Comparative example 12
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 15.69g (49.0mmol), NMP 178.27g, PMDA 0g (0mmol), ODPA3.10g (10.0mmol) and CBDA 7.84g (40.0 mmol). The weight average molecular weight (Mw) of the polymer contained in the varnish obtained was 120,900. The CTE, YI value and breaking strength of the film cured at 330 ℃ are shown in table 2 below.
Comparative example 13
Into a separable flask equipped with a dean stark apparatus and a reflux device under a nitrogen atmosphere were charged 12.55g (39.2mmol) of TFMB, 64.56g of NMP, and 50g of toluene, and the TFMB was dissolved with stirring. 8.97g (40.0mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After the contents of the flask were cooled to 40 ℃, tfmb3.14g (9.8mmol), NMP 46.48g, and ODPA3.1 g (10.0mmol) were added, and stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 49,800. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 14
A varnish was obtained in the same manner as in reference example 1 except that the charge of the raw material was changed to TFMB 7.06g (22.0mmol), NMP 96.67g, PMDA 0g (0mmol) and 6FDA 10.00g (22.5 mmol). The weight average molecular weight (Mw) of the polyamic acid in the resulting varnish was 110,000. The CTE, YI value and elongation of the film cured at 350 ℃ are shown in table 2 below.
Comparative example 15
15.69g (49.00mmol) of TFMB and 203.4g of NMP were added to a 500ml separable flask under a nitrogen atmosphere, and the TFMB was dissolved with stirring. Then, 14.71g (50.0mmol) of BPDA was added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain an NMP solution (varnish) of polyamic acid. The weight average molecular weight (Mw) of the obtained polyamic acid was 49,000. The evaluation results of the film cured at 330 ℃ are shown in Table 2.
Comparative example 16
15.69g (49.00mmol) of TFMB and 258.4g of NMP were added to a 500ml separable flask under a nitrogen atmosphere, and the TFMB was dissolved with stirring. Subsequently, TAHQ 22.92g (50.0mmol) was added, and the mixture was stirred at 80 ℃ for 4 hours to obtain an NMP solution (varnish) of polyamic acid. The weight average molecular weight (Mw) of the obtained polyamic acid was 64,000. The evaluation results of the film cured at 330 ℃ are shown in Table 2.
Comparative example 17
Into a separable flask equipped with a dean stark apparatus and a reflux device, 15.69g (49.0mmol) of TFMB, 175.3g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 10.51g (100.0mmol) of CPDA was added thereto, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. Thereafter, the contents of the flask were cooled to room temperature, thereby obtaining a varnish of polyimide. The weight average molecular weight (Mw) of the polyimide in the resulting varnish was 51,600. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
Comparative example 18
Into a separable flask equipped with a dean stark apparatus and a reflux device, 15.69g (49.0mmol) of TFMB, 175.3g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 15.32g (100.0mmol) of H-BPDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature, thereby obtaining a varnish of polyimide. The weight average molecular weight (Mw) of the polyimide in the resulting varnish was 54,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
Comparative example 19
Into a separable flask equipped with a dean stark apparatus and a reflux device, 15.69g (49.0mmol) of TFMB, 175.3g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 11.82g (100.0mmol) of BCDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature, thereby obtaining a varnish of polyimide. The weight average molecular weight (Mw) of the polyimide in the varnish obtained was 50,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
Comparative example 20
Into a separable flask equipped with a dean stark apparatus and a reflux device, 15.69g (49.0mmol) of TFMB, 175.3g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. To this was added 12.41g (100.0mmol) of BOTDA, and after refluxing at 180 ℃ for 2 hours, it took 3 hours to remove toluene as an azeotropic solvent. Thereafter, the contents of the flask were cooled to room temperature, thereby obtaining a varnish of polyimide. The weight average molecular weight (Mw) of the polyimide in the resulting varnish was 54,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
Comparative example 21
Into a separable flask equipped with a dean stark apparatus and a reflux device, 3.14g (9.8mmol) of TFMB, 16.14g of NMP and 50g of toluene were charged under a nitrogen atmosphere, and the TFMB was dissolved with stirring. 0.16g (0.7mmol) of H-PMDA was added thereto, and after refluxing at 180 ℃ for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ℃ and 1,650cm derived from the amide bond was confirmed by IR-1The nearby absorption (C ═ O) disappears. Thereafter, 12.55g (39.2mmol) of TFMB, 147g of NMP, 6.54g (30.0mmol) of PMDA, 4.44g (10.0mmol) of 6FDA and 2.08g (9.3mmol) of H-PMDA were added thereto, and the mixture was stirred at 80 ℃ for 4 hours to obtain a varnish of a polyimide-polyamic acid polymer. The weight average molecular weight (Mw) of the resulting polyimide-polyamic acid polymer was 51,000. The evaluation results of the film cured at 350 ℃ are shown in Table 2.
Comparative example 22
The preparation of the varnish was carried out according to the method described in Korean patent laid-open No. 10-2013-0077946.
To a1,000 ml separable flask, 270ml of dimethylacetamide (DMAc) was added under a nitrogen atmosphere, and 32.02g (100.0mmol) of TFMB was completely dissolved at room temperature. Subsequently, 111.1g (25.0mmol) of 6FDA, 109.1g (50.0mmol) of PMDA and 56.04g (25.0mmol) of H-PMDA were added in this order, and the mixture was stirred at room temperature for 12 hours. Thereafter, the mixture was heated in an oil bath at 120 ℃ for 20 minutes, and then stirred at room temperature for 12 hours to obtain a polyamic acid solution (varnish). The weight average molecular weight (Mw) of the obtained polyamic acid was 32,000.
The evaluation results of the polyimide film obtained by heating the varnish from 80 ℃ to 250 ℃ over 8 hours and then slowly cooling the same are shown in table 2.
Comparative example 23
The preparation of the varnish was carried out according to the method described in Korean patent laid-open No. 10-2013-0077946.
The operation was carried out in the same manner as in comparative example 22 except that the charge of the raw material was changed to 6FDA 88.85g (20.0mmol), PMDA 87.25g (40.0mmol) and H-PMDA 89.67g (40.0 mmol). The evaluation results of the obtained polyimide film are shown in table 2.
Comparative example 24
The preparation of the varnish was carried out according to the method described in Korean patent laid-open No. 10-2013-0077946.
The operation was carried out in the same manner as in comparative example 22 except that the charge of the raw material was changed to 6FDA 177.7g (40.0mmol), PMDA 87.25g (40.0mmol) and H-PMDA 44.83g (20.0 mmol). The evaluation results of the obtained polyimide film are shown in table 2.
Figure GDA0003184518430000561
Figure GDA0003184518430000571
Figure GDA0003184518430000581
Figure GDA0003184518430000591
Figure GDA0003184518430000601
Figure GDA0003184518430000611
Figure GDA0003184518430000621
Figure GDA0003184518430000631
The abbreviations for the components shown in Table 1 have the following meanings, respectively.
[ aromatic tetracarboxylic dianhydride 1]
And (3) PMDA: pyromellitic dianhydride
BPDA: 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride
[ aromatic tetracarboxylic dianhydride 2]
ODPA: 4, 4' -oxydiphthalic dianhydride
6 FDA: 4, 4' - (Hexafluoroisopropylidene) diphthalic anhydrides
TAHQ: 4, 4' -Biphenyl bis (trimellitic acid monoester anhydride)
[ alicyclic tetracarboxylic dianhydride ]
CBDA: 1,2,3, 4-cyclobutanetetracarboxylic dianhydride
H-PMDA: 1,2,4, 5-Cyclohexanetetracarboxylic dianhydride
CPDA: 1,2,3, 4-cyclopentanetetracarboxylic dianhydride
H-BPDA: 1,2,4, 5-bicyclohexane tetracarboxylic dianhydride
BCDA: bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid 2,3:5, 6-dianhydride
BOTDA: bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride
[ diamine ]
TFMB: 2,2' -bis (trifluoromethyl) benzidine
mTB: 2,2 '-dimethylbiphenyl-4, 4' -diamine
DABA: 4, 4' -diaminobenzanilides
APAB: 4-aminophenyl-4-aminobenzoic acid ester
[ other additives ]
ROSi 1: alkoxysilane Compound 1, Compound of the following structural formula
Figure GDA0003184518430000651
Surf 1: surfactant 1, Silicone type nonionic surfactant DBE224 (product name, manufactured by Gelest corporation)
As shown in the table, it was confirmed that the resin composition (varnish) containing the polyimide precursor having all of the structure derived from the alicyclic tetracarboxylic dianhydride, the structure derived from the aromatic tetracarboxylic dianhydride 1, and the structure derived from the aromatic tetracarboxylic dianhydride 2 contained
(0) The viscosity change rate at 4 weeks at room temperature is 10% or less,
the polyimide film obtained by curing the composition has film properties satisfying the following conditions:
(1) CTE of 25ppm or less
(2) YI value of 10 or less
(3) The elongation of the steel is more than 15 percent,
the laminate having the inorganic film formed on the polyimide film satisfies both of:
(4) haze is 15 or less
(5) The water vapor transmission rate is 0.1 g/(m)224h) or less.
In addition, according to the evaluation results of comparative examples 1 to 4, 14 and 15 to 20, it was confirmed that: a polyimide film using a polyimide precursor having only a structure derived from 1 tetracarboxylic dianhydride cannot satisfy all of the film properties in the above (0) to (5) at the same time;
according to the evaluation results of comparative examples 5 to 13, it was confirmed that: even in the case of a polyimide film using a polyimide precursor having 2 kinds of structures derived from 2 kinds of tetracarboxylic dianhydrides, sufficient performance has not been imparted to all of the film properties in the above (0) to (5).
Further, according to the evaluation results of comparative examples 21 to 25, it was confirmed that: even when a polyimide film of a polyimide precursor having 3 structures derived from the 3 kinds of tetracarboxylic dianhydrides is used, when the imidization ratio of the amide bond derived from the alicyclic tetracarboxylic dianhydride in the polyimide precursor is out of the range of 10 to 100%, sufficient performance has not been imparted to all of the film properties in the above (0) to (5).
From the above results, it was confirmed that: provided that a polyimide precursor having all of a structure derived from an alicyclic tetracarboxylic dianhydride, a structure derived from an aromatic tetracarboxylic dianhydride 1 and a structure derived from an aromatic tetracarboxylic dianhydride 2 and having an imidization rate of an amide bond derived from the alicyclic tetracarboxylic dianhydride in the range of 10 to 100% has excellent storage stability, a polyimide film obtained by curing the composition is colorless and transparent, has a low linear expansion coefficient and excellent elongation, and a laminate having an inorganic film formed on the polyimide film has a small Haze and excellent water vapor permeability.
Industrial applicability
The polyimide precursor of the present invention can be suitably used for, for example, production of a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, a flexible display, and particularly suitably used for production of a substrate.

Claims (30)

1. A polyimide precursor having a structure represented by the following general formula (A),
the diamine-derived structure has a structure derived from at least one diamine selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine TFMB, 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide, and 4-aminophenyl-4-aminobenzoate;
the structure derived from a tetracarboxylic dianhydride includes a structure derived from a tetracarboxylic dianhydride selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride CBDA, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride H-PMDA, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexatetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid-2, 3:5, 6-dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1, a structure of at least one alicyclic tetracarboxylic dianhydride selected from the group consisting of 2-C furan-1, 3-dione and bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride, and a structure derived from an aromatic tetracarboxylic dianhydride, and,
the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 10 to 100%,
Figure DEST_PATH_IMAGE002
X1is a structure derived from at least one diamine selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine TFMB, 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide, and 4-aminophenyl-4-aminobenzoate;
X2is derived from a compound selected from 1,2,3, 4-cyclobutanetetracarboxylic dianhydride CBDA, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride H-PMDA, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexane tetracarboxylic dianhydride, bicyclo [2.2.1]Heptane-2, 3,5, 6-tetracarboxylic-2, 3:5, 6-dianhydride, bicyclo [2.2.2]Oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1,2-C]Furan-1, 3-dione and bicyclo [3,3,0]]Structure of at least one tetracarboxylic dianhydride in octane-2, 4,6, 8-tetracarboxylic dianhydride.
2. The polyimide precursor according to claim 1, wherein the polyimide precursor has a structure of the following general formula (B):
Figure 909217DEST_PATH_IMAGE003
X1as defined in said formula (A),
X3is derived from the structure of the aromatic tetracarboxylic dianhydride.
3. The polyimide precursor according to claim 1 or 2, wherein the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 20 to 100%.
4. The polyimide precursor according to claim 1 or 2, wherein the imidization rate of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 30 to 100%.
5. The polyimide precursor according to claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride comprises 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride or 4,4 ' -biphenylbis (trimellitic acid monoester anhydride).
6. The polyimide precursor according to claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride comprises 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride.
7. The polyimide precursor according to claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride comprises 4, 4' -biphenylyl bis (trimellitic acid monoester anhydride).
8. The polyimide precursor according to claim 1 or 2, wherein the aromatic tetracarboxylic dianhydride comprises:
at least one selected from pyromellitic dianhydride PMDA and 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride as the aromatic tetracarboxylic dianhydride 1; and
the aromatic tetracarboxylic dianhydride 2 is at least one selected from the group consisting of 4,4 ' -oxybisphthalic dianhydride ODPA, 4 ' - (hexafluoroisopropylidene) bisphthalic anhydride 6FDA and 4,4 ' -biphenylyl bis (trimellitic acid monoester anhydride).
9. The polyimide precursor according to claim 8, wherein the aromatic tetracarboxylic dianhydride 1 is pyromellitic dianhydride PMDA.
10. The polyimide precursor according to claim 8, wherein the aromatic tetracarboxylic dianhydride 2 is at least one selected from 4,4 '-oxydiphthalic dianhydride ODPA and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride 6 FDA.
11. The polyimide precursor according to claim 1 or 2, wherein the diamine-derived structure is a structure derived from 2,2' -bis (trifluoromethyl) benzidine TFMB.
12. The polyimide precursor according to claim 1 or 2, wherein the alicyclic tetracarboxylic dianhydride is at least one selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride CBDA, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride H-PMDA, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-bicyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid-2, 3:5, 6-dianhydride, and bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride.
13. The polyimide precursor according to claim 1 or 2, wherein the alicyclic tetracarboxylic dianhydride is at least one selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride CBDA and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride H-PMDA.
14. The polyimide precursor according to claim 1 or 2, wherein 60 mol% or more of the total diamine-derived structures include structures derived from the TFMB,
the total of all the structures derived from tetracarboxylic dianhydrides contains 60 mol% or more of the structures derived from at least one tetracarboxylic dianhydride selected from the group consisting of PMDA, ODPA, 6FDA, CBDA and H-PMDA.
15. The polyimide precursor according to claim 1 or 2, wherein the structure derived from PMDA is contained in an amount of 1 to 70 mol% based on the total structure derived from the tetracarboxylic dianhydride, and
the total structure derived from the tetracarboxylic dianhydrides contains 1 to 50 mol% of a structure derived from at least one tetracarboxylic dianhydride selected from the group consisting of ODPA and 6 FDA.
16. The polyimide precursor according to claim 14, wherein a ratio of a sum of moles of structures derived from PMDA, ODPA, 6FDA, CBDA, and H-PMDA to a number of moles of structures derived from TFMB (PMDA + ODPA +6FDA + CBDA + H-PMDA)/TFMB is 100/99.9 to 100/95.
17. The polyimide precursor according to claim 1 or 2, wherein a polyimide film obtained by dissolving the polyimide in a solvent, developing the polyimide on the surface of a support, and then imidating the polyimide film by heating in a nitrogen atmosphere has a yellowness index of 10 or less, a linear expansion coefficient of 25ppm/° C or less, and a film elongation of 15% or more at a film thickness of 20 μm.
18. The polyimide precursor according to claim 1 or 2, which is used for manufacturing a flexible device.
19. A resin composition comprising the polyimide precursor according to any one of claims 1 to 18 and a solvent.
20. The resin composition according to claim 19, further comprising an alkoxysilane compound.
21. The resin composition according to claim 19 or 20, further comprising a surfactant.
22. A polyimide film, which is formed by spreading the resin composition according to any one of claims 19 to 21 on the surface of a support to form a coating film, and then heating the support and the coating film to imidize the polyimide precursor.
23. A method for producing a polyimide film, comprising the steps of:
a coating film forming step of forming a coating film by spreading the resin composition according to any one of claims 19 to 21 on a surface of a support;
a heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film; and
and a peeling step of peeling the polyimide film from the support to obtain a polyimide film.
24. A laminate comprising a support and a polyimide film formed on the support, wherein the laminate is characterized in that
The laminate is obtained by: a polyimide film obtained by spreading the resin composition according to any one of claims 19 to 21 on the surface of the support to form a coating film, and then heating the support and the coating film to imidize the polyimide precursor.
25. A method for producing a laminate provided with a support and a polyimide film formed on the support, the method comprising the steps of:
a coating film forming step of forming a coating film by spreading the resin composition according to any one of claims 19 to 21 on a surface of a support; and
and a heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film.
26. A polyimide film produced from a copolymer of a diamine and a tetracarboxylic dianhydride,
the diamine is at least one selected from the group consisting of 2,2 '-bis (trifluoromethyl) benzidine TFMB, 2' -dimethylbiphenyl-4, 4 '-diamine, 4' -diaminobenzanilide and 4-aminophenyl-4-aminobenzoate,
the tetracarboxylic dianhydride comprises:
as alicyclic tetracarboxylic acid dianhydride selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic acid dianhydride CBDA, 1,2,4, 5-cyclohexanetetracarboxylic acid dianhydride H-PMDA, 1,2,3, 4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4, 5-bicyclohexanetetracarboxylic acid dianhydride, bicyclo [2.2.1] heptane-2, 3,5, 6-tetracarboxylic acid-2, 3:5, 6-dianhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid-1, 4:2, 3-dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1, at least one of 2-C ] furan-1, 3-dione and bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic dianhydride;
at least one selected from pyromellitic dianhydride PMDA and 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride as the aromatic tetracarboxylic dianhydride 1; and
at least one selected from the group consisting of 4,4 ' -oxybisphthalic dianhydride ODPA, 4 ' - (hexafluoroisopropylidene) bisphthalic anhydride 6FDA and 4,4 ' -biphenylbis (trimellitic acid monoester anhydride) as the aromatic tetracarboxylic dianhydride 2,
when an inorganic film is formed on the polyimide film at 350 ℃ by a CVD method, the surface roughness of the inorganic film surface measured by an Atomic Force Microscope (AFM) is 0.01 to 50 nm.
27. The polyimide film of claim 26, wherein the diamine is 2,2' -bis (trifluoromethyl) benzidine TFMB,
the tetracarboxylic dianhydride comprises:
at least one selected from the group consisting of 1,2,3, 4-cyclobutanetetracarboxylic dianhydride CBDA and 1,2,4, 5-cyclohexanetetracarboxylic dianhydride H-PMDA as the alicyclic tetracarboxylic dianhydride;
at least one selected from pyromellitic dianhydride PMDA and 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride as the aromatic tetracarboxylic dianhydride 1; and
at least one selected from 4,4 '-oxydiphthalic dianhydride ODPA and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride 6FDA as the aromatic tetracarboxylic dianhydride 2.
28. A flexible device comprising the polyimide film of claim 26 or 27.
29. A method for producing a flexible device, comprising the method for producing a polyimide film according to claim 23.
30. A method of manufacturing a flexible device comprising the method of manufacturing the laminate of claim 25.
CN201910054325.0A 2014-02-14 2014-06-25 Polyimide precursor and resin composition containing same Active CN110028666B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014026601 2014-02-14
JP2014-026601 2014-02-14
CN201480065199.4A CN105916910B (en) 2014-02-14 2014-06-25 Polyimide precursor and resin combination containing it

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201480065199.4A Division CN105916910B (en) 2014-02-14 2014-06-25 Polyimide precursor and resin combination containing it

Publications (2)

Publication Number Publication Date
CN110028666A CN110028666A (en) 2019-07-19
CN110028666B true CN110028666B (en) 2021-11-09

Family

ID=53799791

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201910054325.0A Active CN110028666B (en) 2014-02-14 2014-06-25 Polyimide precursor and resin composition containing same
CN201480065199.4A Active CN105916910B (en) 2014-02-14 2014-06-25 Polyimide precursor and resin combination containing it

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201480065199.4A Active CN105916910B (en) 2014-02-14 2014-06-25 Polyimide precursor and resin combination containing it

Country Status (5)

Country Link
JP (2) JP6254197B2 (en)
KR (2) KR101869173B1 (en)
CN (2) CN110028666B (en)
TW (1) TWI567135B (en)
WO (1) WO2015122032A1 (en)

Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6254197B2 (en) * 2014-02-14 2017-12-27 旭化成株式会社 Polyimide precursor and resin composition containing the same
JP6579110B2 (en) * 2014-10-17 2019-09-25 三菱瓦斯化学株式会社 Polyimide resin composition, polyimide film and laminate
KR102269701B1 (en) * 2015-03-13 2021-06-25 아사히 가세이 가부시키가이샤 Polyimide precursor resin composition
KR102103157B1 (en) * 2015-04-17 2020-04-22 아사히 가세이 가부시키가이샤 Resin composition, polyimide resin film, and method for producing same
KR102133559B1 (en) * 2015-09-24 2020-07-13 아사히 가세이 가부시키가이샤 Polyimide precursor, resin composition, and method for producing resin film
US10968316B2 (en) 2015-09-25 2021-04-06 Mitsubishi Gas Chemical Company, Inc. Polyimide resin and polyimide film
JP6634801B2 (en) * 2015-12-03 2020-01-22 Jsr株式会社 Liquid crystal alignment agent
KR102417428B1 (en) * 2015-12-21 2022-07-06 주식회사 두산 Polyamic acid composition comprising alicyclic monomer and trasparent polyimide film using the same
KR102460588B1 (en) * 2016-03-09 2022-10-28 주식회사 두산 Metal laminate and printed circuit board comprising the same
WO2017191830A1 (en) 2016-05-02 2017-11-09 三菱瓦斯化学株式会社 Polyimide resin, polyimide resin composition, and polyimide film
EP3456757B1 (en) * 2016-05-09 2023-06-07 Mitsubishi Gas Chemical Company, Inc. Polyimide resin and polyimide resin composition
JP6693676B2 (en) * 2016-05-09 2020-05-13 三菱瓦斯化学株式会社 Polyimide and polyimide film
KR102339091B1 (en) * 2016-05-20 2021-12-15 에스케이이노베이션 주식회사 Polyamic acid composition, polyamideimide film thereof and method for preparing the polyamindeimide film
KR102386514B1 (en) * 2016-05-23 2022-04-14 닛산 가가쿠 가부시키가이샤 Composition for forming release layer and release layer
JP6705583B2 (en) * 2016-08-08 2020-06-03 Ｊｘｔｇエネルギー株式会社 Polyimide, polyamic acid, polyamic acid solution, and polyimide film
JP6890999B2 (en) * 2016-08-10 2021-06-18 日鉄ケミカル＆マテリアル株式会社 Polyimide precursor and polyimide
JP7079076B2 (en) * 2016-08-10 2022-06-01 日鉄ケミカル＆マテリアル株式会社 Polyimide precursor and the polyimide resulting from it
KR101899902B1 (en) * 2016-08-23 2018-09-18 주식회사 대림코퍼레이션 Transparent polyimide precursor resin composition improving stability of resin and heat-resistance, method for manufacturing polyimide film using the same, and polyimide film thereof
KR102494637B1 (en) * 2016-09-30 2023-02-02 스미또모 가가꾸 가부시키가이샤 Manufacturing method of polyimide-based polymer varnish, manufacturing method of polyimide-based polymer film, and transparent polyimide-based polymer film
WO2018097142A1 (en) * 2016-11-24 2018-05-31 日産化学工業株式会社 Composition for forming flexible device substrate
JP7011231B2 (en) * 2016-11-24 2022-01-26 日産化学株式会社 Composition for forming a flexible device substrate
JP6944784B2 (en) * 2017-02-03 2021-10-06 東京応化工業株式会社 Laminates, flexible devices and methods for manufacturing laminates
US20200140615A1 (en) * 2017-05-10 2020-05-07 Dupont Electronics, Inc. Low-color polymers for flexible substrates in electronic devices
TW201920364A (en) * 2017-08-11 2019-06-01 美商杜邦股份有限公司 Low-color polymers for flexible substrates in electronic devices
CN111212867A (en) * 2017-10-11 2020-05-29 株式会社钟化 Polyimide resin and method for producing same, polyimide solution, and polyimide film and method for producing same
CN111465634B (en) * 2017-12-15 2023-03-10 三菱瓦斯化学株式会社 Polyimide resin, polyimide varnish, and polyimide film
CN111527150B (en) * 2017-12-26 2023-05-30 株式会社钟化 Polyamic acid composition and method for producing same, polyimide film, laminate and method for producing same, and flexible device
KR102271028B1 (en) * 2017-12-29 2021-06-29 코오롱인더스트리 주식회사 Method of preparing Polyamic acid and Polyamic acid, Polyimide resin and Polyimide film thereby
KR102015769B1 (en) 2018-01-12 2019-08-29 경희대학교 산학협력단 Polyamic acid copolymer, a high heat resistant transparent polyimide film prepared by using the same, and method for preparing the same
WO2019198709A1 (en) * 2018-04-10 2019-10-17 三菱瓦斯化学株式会社 Polyimide resin, polyimide varnish and polyimide film
JP2019215394A (en) 2018-06-11 2019-12-19 株式会社ジャパンディスプレイ Display device
JP7120819B2 (en) * 2018-06-12 2022-08-17 旭化成株式会社 Laminate of polyimide film and flexible glass
JP7158914B2 (en) * 2018-06-26 2022-10-24 株式会社ジャパンディスプレイ Display device
WO2020004236A1 (en) * 2018-06-28 2020-01-02 株式会社カネカ Polyimide resin, production method for polyimide resin, polyimide film, and production method for polyimide film
CN110933949A (en) * 2018-07-18 2020-03-27 住友电气工业株式会社 Resin varnish, insulated wire, and method for producing insulated wire
JP7298141B2 (en) * 2018-11-30 2023-06-27 株式会社リコー CUREABLE COMPOSITION, COMPOSITION CONTAINER, TWO-DIMENSIONAL OR THREE-DIMENSIONAL IMAGE FORMING METHOD AND FORMING APPARATUS, CURED PRODUCT, STRUCTURE, AND MOLDED PROCESSED PRODUCT
CN109824894B (en) * 2019-01-29 2021-08-10 西北工业大学 Preparation method of polyimide film with molecular main chain alternately composed of two acid anhydrides
CN110183851A (en) * 2019-04-13 2019-08-30 复旦大学 A kind of fluorine-containing alicyclic c-polymer polyimide film material and preparation method thereof
TWI764046B (en) * 2019-09-19 2022-05-11 臻鼎科技股份有限公司 Polyamic acid block copolymer and preparation method thereof, polyimide coated copper plate and circuit board thereof
CN112521603B (en) 2019-09-19 2023-06-02 臻鼎科技股份有限公司 Polyamic acid block copolymer, preparation method thereof, polyimide copper-clad plate and circuit board
CN111187414B (en) * 2020-02-14 2022-09-06 吉林奥来德光电材料股份有限公司 High-performance transparent polyimide film and preparation method thereof
CN111363354A (en) * 2020-03-27 2020-07-03 中天电子材料有限公司 Polyimide colorless transparent film, preparation method thereof and optical PI film
WO2021241573A1 (en) * 2020-05-29 2021-12-02 東洋紡株式会社 Polyimide film and method for producing same
JP7103534B2 (en) * 2020-05-29 2022-07-20 東洋紡株式会社 Polyimide film and its manufacturing method
WO2021261177A1 (en) * 2020-06-23 2021-12-30 株式会社カネカ Poly(amic acid), poly(amic acid) solution, polyimide, polyimide film, layered product, method for producing layered product, and electronic device
CN116171222A (en) * 2020-09-29 2023-05-26 东洋纺株式会社 Laminate of inorganic substrate and polyamic acid cured product
CN112375241B (en) * 2020-11-03 2021-05-11 深圳瑞华泰薄膜科技股份有限公司 Colorless transparent polyimide film and preparation method thereof
CN112480672B (en) * 2020-11-27 2022-11-04 桂林电器科学研究院有限公司 Colorless transparent polyimide film and preparation method thereof
WO2022211086A1 (en) * 2021-04-02 2022-10-06 旭化成株式会社 Polyimide, resin composition, polyimide film, and production method therefor
JPWO2022220286A1 (en) * 2021-04-16 2022-10-20
CN113621234B (en) * 2021-08-04 2022-08-30 深圳瑞华泰薄膜科技股份有限公司 Ultrahigh-modulus high-transmittance polyimide film and preparation method and application thereof
CN115141372B (en) * 2022-08-08 2024-01-26 波米科技有限公司 Polyimide substance and application thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043419A (en) * 1987-10-23 1991-08-27 Mitsui Toatsu Chemicals, Inc. Process for preparing a polyimide and a composite material containing the same
TW457273B (en) * 1997-12-29 2001-10-01 Chisso Corp Polyamic acid composition
CN101490607A (en) * 2006-07-21 2009-07-22 东丽株式会社 Resin composition for retardation thin film, color filter substrate for liquid crystal display device, liquid crystal display device, and method for production of color filter substrate for liquid cry
CN101580637A (en) * 2009-06-12 2009-11-18 东华大学 Alicyclic-containing polyimide film and preparation method thereof
CN101959935A (en) * 2008-02-25 2011-01-26 日立化成杜邦微系统股份有限公司 Polyimide precursor composition, polyimide film and transparent flexible film
CN102093558A (en) * 2009-12-14 2011-06-15 辽宁科技大学 Polyimide film material capable of serving as flexible transparent conducting film substrate and preparation method thereof
CN102382303A (en) * 2011-08-16 2012-03-21 中国科学院宁波材料技术与工程研究所 Colorless and transparent polyimide resin material and preparation method thereof
CN102382661A (en) * 2010-08-27 2012-03-21 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film, liquid crystal orientation display element, polyamic acid and polyimide
CN102498155A (en) * 2009-09-16 2012-06-13 Solpit工业株式会社 Organic-solvent-soluble polyimide comprising PMDA, DADE, BPDA, and BCD
CN102597862A (en) * 2009-08-28 2012-07-18 国立大学法人九州大学 Liquid-crystal display element and substrate used in same
CN103319714A (en) * 2013-02-08 2013-09-25 长兴化学工业股份有限公司 Polyimide and coating composition formed therefrom

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3486358B2 (en) 1998-12-28 2004-01-13 日本電信電話株式会社 Optical polyimide substrate
JP2003155342A (en) 2001-11-19 2003-05-27 Nippon Steel Chem Co Ltd Polyimide copolymer having alicyclic structure
JP2004252373A (en) * 2003-02-21 2004-09-09 Kanegafuchi Chem Ind Co Ltd Polyimide resin for liquid crystal orientation film
JP2004307857A (en) * 2003-03-26 2004-11-04 Rikogaku Shinkokai Fluorescent polyimide
JP4678142B2 (en) 2004-05-25 2011-04-27 日産化学工業株式会社 Photosensitive resin composition of poly (amic acid-imide) copolymer having high transparency and cured film thereof
US7550194B2 (en) * 2005-08-03 2009-06-23 E. I. Du Pont De Nemours And Company Low color polyimide compositions useful in optical type applications and methods and compositions relating thereto
JP2007063417A (en) * 2005-08-31 2007-03-15 Fujifilm Corp Film and method for producing film, and film with gas-barrier layer, film with transparent electroconductive layer and image display device
KR101505899B1 (en) * 2007-10-23 2015-03-25 제이엔씨 주식회사 Inkjet ink
WO2009116500A1 (en) * 2008-03-19 2009-09-24 Jsr株式会社 Polyimide material, polyimide film, method for producing the polyimide material and method for producing the polyimide film
JP2013082774A (en) * 2011-10-06 2013-05-09 Kaneka Corp Transparent polyimide film and production process thereof
KR101339663B1 (en) 2011-12-30 2013-12-10 웅진케미칼 주식회사 Transparent polyimide with low coefficient of thermal expansion
KR101339664B1 (en) * 2011-12-30 2013-12-10 웅진케미칼 주식회사 Transparent polyimide with low coefficient of thermal expansion
JP6257302B2 (en) * 2012-12-20 2018-01-10 旭化成株式会社 POLYIMIDE PRECURSOR, RESIN COMPOSITION CONTAINING THE SAME, POLYIMIDE FILM AND ITS MANUFACTURING METHOD, AND LAMINATE AND ITS MANUFACTURING METHOD
EP3018164B1 (en) * 2013-07-05 2019-03-06 Mitsubishi Gas Chemical Company, Inc. Polyimide resin
JP6254197B2 (en) * 2014-02-14 2017-12-27 旭化成株式会社 Polyimide precursor and resin composition containing the same

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5043419A (en) * 1987-10-23 1991-08-27 Mitsui Toatsu Chemicals, Inc. Process for preparing a polyimide and a composite material containing the same
TW457273B (en) * 1997-12-29 2001-10-01 Chisso Corp Polyamic acid composition
CN101490607A (en) * 2006-07-21 2009-07-22 东丽株式会社 Resin composition for retardation thin film, color filter substrate for liquid crystal display device, liquid crystal display device, and method for production of color filter substrate for liquid cry
CN101959935A (en) * 2008-02-25 2011-01-26 日立化成杜邦微系统股份有限公司 Polyimide precursor composition, polyimide film and transparent flexible film
CN101580637A (en) * 2009-06-12 2009-11-18 东华大学 Alicyclic-containing polyimide film and preparation method thereof
CN102597862A (en) * 2009-08-28 2012-07-18 国立大学法人九州大学 Liquid-crystal display element and substrate used in same
CN102498155A (en) * 2009-09-16 2012-06-13 Solpit工业株式会社 Organic-solvent-soluble polyimide comprising PMDA, DADE, BPDA, and BCD
CN102093558A (en) * 2009-12-14 2011-06-15 辽宁科技大学 Polyimide film material capable of serving as flexible transparent conducting film substrate and preparation method thereof
CN102382661A (en) * 2010-08-27 2012-03-21 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film, liquid crystal orientation display element, polyamic acid and polyimide
CN102382303A (en) * 2011-08-16 2012-03-21 中国科学院宁波材料技术与工程研究所 Colorless and transparent polyimide resin material and preparation method thereof
CN103319714A (en) * 2013-02-08 2013-09-25 长兴化学工业股份有限公司 Polyimide and coating composition formed therefrom

Also Published As

Publication number Publication date
KR101980506B1 (en) 2019-05-20
CN105916910B (en) 2019-02-19
CN110028666A (en) 2019-07-19
JP2018031018A (en) 2018-03-01
KR20180069927A (en) 2018-06-25
JPWO2015122032A1 (en) 2017-03-30
TWI567135B (en) 2017-01-21
TW201531526A (en) 2015-08-16
WO2015122032A1 (en) 2015-08-20
KR20160079836A (en) 2016-07-06
CN105916910A (en) 2016-08-31
KR101869173B1 (en) 2018-06-19
JP6254197B2 (en) 2017-12-27

Similar Documents

Publication Publication Date Title
CN110028666B (en) Polyimide precursor and resin composition containing same
CN110684195B (en) Polyimide film, polyimide precursor, and polyimide
KR102312462B1 (en) Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same
CN104854165B (en) Resin precursor, resin composition containing the same, resin film and method for producing the same, and laminate and method for producing the same
KR102213304B1 (en) Polyimide precursor and resin composition containing same
US20180093461A1 (en) Resin composition, polyimide resin film, and method for producing same
CN107108886B (en) Polyimide precursor, polyimide, and polyimide film
JP6257302B2 (en) POLYIMIDE PRECURSOR, RESIN COMPOSITION CONTAINING THE SAME, POLYIMIDE FILM AND ITS MANUFACTURING METHOD, AND LAMINATE AND ITS MANUFACTURING METHOD
KR20230147181A (en) Polyimide, resin composition, polyimide film, and method for producing the same
JPWO2019188380A1 (en) Polyamic acid and its manufacturing method, polyamic acid solution, polyimide, polyimide film, laminate and its manufacturing method, and flexible device and its manufacturing method
KR20230066346A (en) Polymer composition, varnish, and polyimide film
JP2022044020A (en) Polyamide acid, polyamide acid solution, polyimide, polyimide film, laminate and flexible device, and method for producing polyimide film
JP7400948B2 (en) Polyimide precursor composition and polyimide film/base material laminate
WO2024024901A1 (en) Polyimide precursor composition, polyimide film, and polyimide film/substrate layered-product
WO2023190555A1 (en) Polyimide precursor composition, polyimide film, and polyimide film/substrate layered-product
KR20230092934A (en) Polyamic acid, polyamic acid solution, polyimide, polyimide film, laminate, electronic device, and method for producing polyimide film
JP2024018828A (en) Polyimide precursor composition, polyimide film and polyimide film/substrate laminate
JP2023038407A (en) Polyamide acid composition, polyimide, polyimide film, laminate and flexible device, and method for producing laminate
CN117120515A (en) Polyimide precursor composition and polyimide film
CN115667368A (en) Resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant