CN110028666A - Polyimide precursor and resin combination containing it - Google Patents

Polyimide precursor and resin combination containing it Download PDF

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Publication number
CN110028666A
CN110028666A CN201910054325.0A CN201910054325A CN110028666A CN 110028666 A CN110028666 A CN 110028666A CN 201910054325 A CN201910054325 A CN 201910054325A CN 110028666 A CN110028666 A CN 110028666A
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tetracarboxylic dianhydride
dianhydride
film
pmda
tfmb
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CN110028666B (en
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宫本佳季
米谷昌树
饭塚康史
金田隆行
奥田敏章
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

This application involves a kind of polyimide precursor and contain its resin combination.A kind of polyimide precursor, which is characterized in that as the structure for deriving from diamines, there is the structure from bis- (trifluoromethyl) benzidine (TFMB) of 2,2'- and other diamines；As the structure for deriving from tetracarboxylic dianhydride, there is the structure from the structure of specific ester ring type tetracarboxylic dianhydride and from aromatic tetracarboxylic dianhydride, the acid imide rate from the amido bond of aforementioned ester ring type tetracarboxylic dianhydride is 10~100%.

Description

Polyimide precursor and resin combination containing it
The application be the applying date be on June 25th, 2014, application No. is 201480065199.4, entitled " polyamides The divisional application of the application of imines precursor and resin combination containing it ".
Technical field
The present invention relates to polyimide precursor and contain its resin combination.The polyimide precursor, which can be used, for example, as, scratches Substrate used in property device.
The present invention also provides Kapton and its manufacturing method and laminated body and its manufacturing methods.
Background technique
Kapton is usually the film formed by polyimide resin.Polyimide resin is by aromatic series tetracarboxylic acid Acid dianhydride and aromatic diamine carry out polymerisation in solution after manufacturing polyimide precursor, carry out hot-imide or chemical acid imide The high heat resistance resin changed and manufactured.Aforementioned hot-imide is carried out by the closed loop dehydration under high temperature, afore mentioned chemical acid imide Change by carrying out closed loop dehydration with catalyst and carries out.
Polyimide resin is insoluble and insoluble super heat-resistant resin, has heatproof oxidation performance, heat-resistant quality, radiation hardness Linearly, the excellent characteristics of lower temperature resistance, chemical reagent resistance etc..Therefore, polyimide resin is for example in insulation coating agent, insulation Film, semiconductor, TFT-LCD electrode protective membrane etc. used in wide range of areas including electronic material.It is also used to liquid recently The display materials such as brilliant alignment films, optical fiber etc..
However, polyimide resin is colored as brown or yellow because of its high aromatic rings density, it is seen that ray regions it is saturating Penetrate that rate is low, accordingly, it is difficult to for requiring the field of the transparency.
It about this point, reports in patent document 1: being come by using the tetracarboxylic dianhydride comprising specific structure and diamines The transparency of manufacture transmissivity and form and aspect is improved and new structural polyimides.
In addition, patent document 2 and patent document 3 individually disclose to assign the transparency and are imported with the poly- of alicyclic structure Imide membrane.
In turn, it is reported in patent document 4: as tetracarboxylic dianhydride, by the way that specific aromatic tetracarboxylic acid is applied in combination Dianhydride and ester ring type tetracarboxylic dianhydride can obtain the low polyimide resin of yellow chromaticity (hereinafter also referred to " YI value ").
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2000-198843 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-336243 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2003-155342 bulletin
Patent document 4: Korean Patent Publication No. 10-2013-0077946
Summary of the invention
Problems to be solved by the invention
However, the mechanical property and thermal characteristics of the polyimides recorded in patent document 1 are insufficiently to serve as such as semiconductor Insulating film, TFT-LCD insulating film, electrode protective membrane and flexible display substrate.
Especially, the polyimides recorded in patent document 1 is characterized in that linear expansion coefficient (is also denoted as below " CTE ") it is high.When being used as film, the expansion of the film generated by temperature change and shrinkage degree become the resin of CTE high Greatly.Thus, for example the inorganic matter film as element material generates damage when using the film of CTE high in TFT process etc., lead Element capability is caused to reduce.Therefore, it forms the substrate of TFT, form substrate, alignment films, the transparent base of flexible display of colour filter Polyimide resin used in plate etc. is necessary for colorless and transparent and CTE is low.
Although there are CTE high and extension at breaks in addition, the polyimides recorded in patent document 2 has the transparency The low disadvantage of rate.In the case where elongation at break is low, when handling flexible device, flexible substrate can generate damage, because This is not used as device.
In the case where the polyimides recorded in patent document 3, toughness is assigned by using polycyclic aromatic diamine. But the CTE of the polyimides is also high, therefore, is not suitable for use in semiconducting insulation film, TFT-LCD insulating film, electrode protective membrane Or flexible display substrate.
Also, in the case where the polyimides recorded in patent document 4, YI value is centainly low.However, people etc. according to the present invention Research, since CTE high, elongation are small, for be applied to display processes for also there is room for improvement (referring to aftermentioned Comparative example 22~24).
The present invention in view of the above description the problem of and carry out, it is intended that provide can manufacture it is colorless and transparent and The polyimide precursor for the Kapton that CTE is low and elongation is excellent and resin combination, polyimides containing it Film and its manufacturing method and laminated body and its manufacturing method.
The solution to the problem
The inventors of the present invention have made intensive studies retrial of laying equal stress in order to solve the above problems and test.It is as a result, it has been found that as follows Opinion, and the present invention is completed based on these opinions.
The excellent storage stability of the resin combination (varnish) of polyimide precursor comprising specific structure；
There is Kapton obtained from the composition is solidified the excellent transparency, low linear expansion coefficient and height to stretch Long rate；And
The Haze for being formed with the laminated body of inoranic membrane on the Kapton is small, moisture-vapor transmission is excellent.
That is, the present invention is as follows.
[1] a kind of polyimide precursor, which is characterized in that its with structure shown in the following general formula (A), also,
As the structure for deriving from diamines, has and derives from selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2, In 2 '-dimethyl diphenyl bases -4,4 '-diamines, 4,4 '-diaminobenzene anilids and 4- aminophenyl -4-aminobenzoic acid ester At least one diamines structure；
As the structure for deriving from tetracarboxylic dianhydride, have from selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydrides (CBDA), 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- are bicyclic Hexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene - 2,3,5,6- tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- furyl)-naphtho- [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- The structure of at least one of tetracarboxylic dianhydride ester ring type tetracarboxylic dianhydride and knot from aromatic tetracarboxylic dianhydride Structure, also,
Acid imide rate from the amido bond of aforementioned ester ring type tetracarboxylic dianhydride is 10~100%.
{X1For from selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl bases -4,4 ' - The structure of at least one of diamines, 4,4 '-diaminobenzene anilids and 4- aminophenyl -4-aminobenzoic acid ester diamines；
X2For from selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- cyclopentanetetracarboxylic's dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane- 2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, tri- carboxyl of 2,3,5- Cyclopenta acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- furyl)-naphtho- At least one of [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride tetrabasic carboxylic acid two The structure of acid anhydride.}
[2] polyimide precursor according to [1], wherein aforementioned polyimide precursor has the knot of the following general formula (B) Structure.
{X1It is identical as the definition in previously described formula (A),
X3For from the structure of aforementioned fragrance race tetracarboxylic dianhydride.}
[3] polyimide precursor according to [1] or [2], wherein from the amido bond of ester ring type tetracarboxylic dianhydride Acid imide rate be 20~100%.
[4] polyimide precursor according to any one of [1]~[3], wherein derive from ester ring type tetracarboxylic dianhydride Amido bond acid imide rate be 30~100%.
[5] polyimide precursor according to any one of [1]~[4], wherein aforementioned fragrance race tetracarboxylic dianhydride packet Contain:
Benzenetetracarboxylic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acids are selected from as aromatic tetracarboxylic dianhydride 1 At least one of dianhydride；And
As aromatic tetracarboxylic dianhydride 2 selected from 4,4 '-oxos double O-phthalic acid dianhydrides (ODPA), 4,4 '-(hexafluoros Isopropylidene) at least one of double phthalic anhydrides (6FDA) and 4,4 '-xenyls bis- (trihemellitic acid monoester anhydrides).
[6] polyimide precursor according to any one of [1]~[5], wherein aforementioned fragrance race tetracarboxylic dianhydride 1 For benzenetetracarboxylic dianhydride (PMDA).
[7] polyimide precursor according to any one of [1]~[5], wherein aforementioned fragrance race tetracarboxylic dianhydride 2 For selected from the double O-phthalic acid dianhydrides (ODPA) of 4,4 '-oxos and 4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides At least one of (6FDA).
[8] polyimide precursor according to any one of [1]~[7], wherein foregoing sources are in the structure of diamines From the structure of 2,2 '-bis- (trifluoromethyl) benzidine (TFMB).
[9] polyimide precursor according to any one of [1]~[8], wherein aforementioned ester ring type tetracarboxylic dianhydride is Selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4- Pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2, At least one of 3:5,6- dianhydride and bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride.
[10] polyimide precursor according to any one of [1]~[9], wherein aforementioned ester ring type tetracarboxylic dianhydride For in 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA) and 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA) extremely Few one.
[11] polyimide precursor according to any one of [1]~[10], wherein all from the structure of diamines In include 60 moles of % or more the structure from aforementioned TFMB,
All amounted in the structure of tetracarboxylic dianhydride comprising 60 moles of % or more from selected from aforementioned PMDA, The structure of at least one of aforementioned ODPA, aforementioned 6FDA, aforementioned CBDA and aforementioned H-PMDA tetracarboxylic dianhydride.
[12] polyimide precursor according to any one of [1]~[11], wherein all from tetracarboxylic dianhydride Structure in include 1~70 mole of % the structure from aforementioned PMDA, and
All aforementioned ODPA and 6FDA is selected from comprising 1~50 mole of deriving from for % in the structure of tetracarboxylic dianhydride At least one of tetracarboxylic dianhydride structure.
[13] polyimide precursor according to any one of [1]~[11], wherein from aforementioned PMDA, aforementioned The sum of molal quantity of each structure of ODPA, aforementioned 6FDA, aforementioned CBDA and aforementioned H-PMDA and the structure for deriving from aforementioned TFMB The ratio between molal quantity { PMDA+ODPA+6FDA+CBDA+H-PMDA)/TFMB } be 100/99.9~100/95.
[14] polyimide precursor according to any one of [1]~[13], wherein be dissolved in solvent and in supporting mass Unfolded surface after, as under nitrogen atmosphere heating carry out imidizate obtained from Kapton yellow chromaticity be 10 Below, linear expansion coefficient is 25ppm or less and film elongation rate when film thickness is 20 μm is 15% or more.
[15] polyimide precursor according to any one of [1]~[14], is used to manufacture flexible device.
[16] a kind of resin combination, which is characterized in that before it contains polyimides described in any one of [1]~[15] Body and solvent.
[17] resin combination according to [16], also contains alkoxysilane compound containing trialkylsilyl group in molecular structure.
[18] resin combination according to [16] or [17], also contains surfactant.
[19] a kind of Kapton, which is characterized in that it is by resin group described in any one of [16]~[18] It closes object to be unfolded on the surface of supporting mass and form film, then heats aforementioned supporting mass and aforementioned film and aforementioned polyamides is sub- Amine precursor carries out imidizate to be formed.
[20] a kind of manufacturing method of Kapton, which is characterized in that it is comprised the following steps:
Resin combination described in any one of [16]~[18] is unfolded on the surface of supporting mass, to form film Film formation process；
It heats aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is subjected to imidizate, to form polyamides The heating process of imines film；And
Aforementioned Kapton is removed from aforementioned supporting mass, to obtain the stripping process of Kapton.
[21] a kind of laminated body, which is characterized in that its polyimide film for having supporting mass and being formed on the supporting mass, And
The laminated body obtains as follows: by resin combination described in any one of [16]~[18] in aforementioned supporting mass It is unfolded on surface and forms film, then heats aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is subjected to acyl Asia Amination is formed obtained from polyimide film.
[22] a kind of manufacturing method of laminated body, the polyamides that the laminated body has supporting mass and is formed on the supporting mass Imines film, this method comprise the following steps:
Resin combination described in any one of [16]~[18] is unfolded on the surface of supporting mass, to form film Film formation process；And
It heats aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is subjected to imidizate, to form polyamides The heating process of imines film.
[23] a kind of Kapton, which is characterized in that it is manufactured by diamines and the copolymer of tetracarboxylic dianhydride Kapton,
Aforementioned diamines is selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl bases -4,4 '-two Amine, 4, at least one of 4 '-diaminobenzene anilids and 4- aminophenyl -4-aminobenzoic acid ester,
Aforementioned tetracarboxylic dianhydride includes:
1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- hexamethylene are selected from as ester ring type tetracarboxylic dianhydride It is alkane tetracarboxylic dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- Furyl) in-naphtho- [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride at least One；
Benzenetetracarboxylic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acids are selected from as aromatic tetracarboxylic dianhydride 1 At least one of dianhydride；And
As aromatic tetracarboxylic dianhydride 2 selected from 4,4 '-oxos double O-phthalic acid dianhydrides (ODPA), 4,4 '-(hexafluoros Isopropylidene) double phthalic anhydrides (6FDA) and 4, at least one of 4 '-xenyls bis- (trihemellitic acid monoester anhydrides),
Using CVD method with 350 DEG C on the Kapton formed inoranic membrane when, use atomic force microscope (AFM) Surface roughness to the inoranic membrane surface measurements is 0.01~50nm.
[24] Kapton according to [23], wherein aforementioned diamines is 2,2 '-bis- (trifluoromethyl) benzidine (TFMB),
Aforementioned tetracarboxylic dianhydride includes:
1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA) and 1,2,4,5- ring are selected from as ester ring type tetracarboxylic dianhydride At least one of hexane tetracarboxylic dianhydride (H-PMDA)；
Benzenetetracarboxylic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acids are selected from as aromatic tetracarboxylic dianhydride 1 At least one of dianhydride；
As aromatic tetracarboxylic dianhydride 2 selected from the double O-phthalic acid dianhydrides (ODPA) and 4,4 '-(six of 4,4 '-oxos At least one of fluorine isopropylidene) double phthalic anhydrides (6FDA).
[25] a kind of flexible device, it includes Kaptons described in [23] or [24].
[26] a kind of manufacturing method of flexible device comprising [20] manufacturing method of the Kapton described in.
[27] a kind of manufacturing method of flexible device comprising [22] manufacturing method of the laminated body described in.
The effect of invention
The excellent storage stability of resin combination (varnish) comprising polyimide precursor of the invention.In addition, by this The Kapton that composition obtains be it is colorless and transparent, linear expansion coefficient is low and elongation is excellent.In the Kapton On be formed with inoranic membrane laminated body Haze is small, moisture-vapor transmission is excellent.
Specific embodiment
Hereinafter, being directed to an embodiment of the invention (hereinafter abbreviated as " embodiment ".) be described in detail.It needs Illustrate, the present invention is not limited to the following embodiments and the accompanying drawings, can carry out within the scope of its subject matter various modifications to implement.
<polyimide precursor>
The polyimide precursor of present embodiment is characterized in that,
With structure shown in the following general formula (A), and
As the structure for deriving from diamines, has and derives from selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2, In 2 '-dimethyl diphenyl bases -4,4 '-diamines and 4,4 '-diaminobenzene anilids, 4- aminophenyl -4-aminobenzoic acid ester At least one diamines structure；
As derive from tetracarboxylic dianhydride structure,
With from selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- cyclopentanetetracarboxylic's dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane- 2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, tri- carboxyl of 2,3,5- Cyclopenta acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- furyl)-naphtho- At least one of [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride ester ring type four The structure of carboxylic acid dianhydride and structure from aromatic tetracarboxylic dianhydride, also,
Acid imide rate from the amido bond of aforementioned ester ring type tetracarboxylic dianhydride is 10~100%.
{X1For from selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl bases -4,4 ' - The structure of at least one of diamines, 4,4 '-diaminobenzene anilids and 4- aminophenyl -4-aminobenzoic acid ester diamines；
X2For from selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- cyclopentanetetracarboxylic's dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane- 2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, tri- carboxyl of 2,3,5- Cyclopenta acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- furyl)-naphtho- At least one of [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride tetrabasic carboxylic acid two The structure of acid anhydride.}
The polyimide precursor of present embodiment preferably has the structure of the following general formula (B).
{X1It is identical as previously described formula (A),
X3For from the structure of aforementioned fragrance race tetracarboxylic dianhydride.}
Also, the polyimide precursor of present embodiment is as it appears from the above, derive from the amido bond of ester ring type tetracarboxylic dianhydride Acid imide rate be 10~100%.That is, at least part amido bond from ester ring type tetracarboxylic dianhydride has carried out acyl Asia The imidizate polyamic acid of amination.
The amido bond from ester ring type tetracarboxylic dianhydride is set to carry out imidizate obtained from imidizate in order to present Polyamic acid structure, such as can be with the following method:
Firstly, carry out ester ring type tetracarboxylic dianhydride and diamines react obtain polyamic acid after or obtaining polyamide Imidizate is carried out to the amido bond of the polyamic acid while sour,
Then, other tetracarboxylic dianhydrides (being aromatic tetracarboxylic dianhydride in the case where present embodiment) and two are persistently carried out The reaction of amine.
From the viewpoint of the transparency of the viewpoint and raising gained Kapton for the molecular weight for increasing polyimide precursor It sets out, preferably reacts first ester ring type tetracarboxylic dianhydride.Also, have to increase from ester ring type tetracarboxylic dianhydride's The molecular weight of the polyimides (precursor) of structure needs from common 60~100 DEG C to improve synthesis temperature to 150~210 DEG C. Like this, by improving synthesis temperature, the imidizate of the amido bond from ester ring type tetracarboxylic dianhydride, source as a result occurs Imide concentration (acid imide rate) in the part of ester ring type acid dianhydride becomes larger.Herein, from including polyimide precursor From the perspective of the storage stability of composition (varnish) and the elongation and YI of gained Kapton, rouge is derived from The acid imide rate of the amido bond of ring type tetracarboxylic dianhydride is preferably 10~100%, is more preferably 20~100%, is further excellent It is selected as 30~100%.
Like this, the reason of making ester ring type tetracarboxylic dianhydride react first, is, while adding ester ring type tetrabasic carboxylic acid Dianhydride and aromatic tetracarboxylic dianhydride or after adding aromatic tetracarboxylic dianhydride add ester ring type tetracarboxylic dianhydride and with When 150~210 DEG C of temperature is synthesized, acid imide sharp occurs for the amido bond of the part from aromatic tetracarboxylic dianhydride Change, polymer is precipitated, therefore not applicable.
The detailed synthetic method of polyimide precursor in present embodiment is seen below.
Hereinafter, being described in detail for each structure.
<from the structure of tetracarboxylic dianhydride>
In the polyimide precursor of present embodiment, as derive from tetracarboxylic dianhydride structure,
With from selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- cyclopentanetetracarboxylic's dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane- 2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, tri- carboxyl of 2,3,5- Cyclopenta acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- furyl)-naphtho- At least one of [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride tetrabasic carboxylic acid two The structure of acid anhydride and structure from aromatic tetracarboxylic dianhydride.
Herein, as aforementioned ester ring type tetracarboxylic dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydrides are preferably selected from (CBDA), 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- are bicyclic Hexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene - 2,3,5,6- tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- furyl)-naphtho- [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- At least one of tetracarboxylic dianhydride.Wherein, from the viewpoint of the CTE of gained Kapton, be preferably selected from CBDA, H-PMDA, 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2, 3,5,6- tetrabasic carboxylic acids 2,3:5,6- dianhydride and bicyclic [2.2.2] octyl- 7- alkene -2,3, at least one of 5,6- tetracarboxylic dianhydrides, Also, from the viewpoint of the YI of cost and gained Kapton and the transparency, more preferably it is selected from CBDA and H-PMDA At least one of, from the viewpoint of cost, further preferably H-PMDA.
Aforementioned 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA) can be following formula (1)~(3) be shown respectively it is different Any one of structure body is also possible to comprising the mixture of more than two kinds in these.
Aforementioned fragrance race tetracarboxylic dianhydride preferably comprises:
Benzenetetracarboxylic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acids are selected from as aromatic tetracarboxylic dianhydride 1 At least one of dianhydride；And
As aromatic tetracarboxylic dianhydride 2 selected from 4,4 '-oxos double O-phthalic acid dianhydrides (ODPA), 4,4 '-(hexafluoros Isopropylidene) at least one of double phthalic anhydrides (6FDA) and 4,4 '-xenyls bis- (trihemellitic acid monoester anhydrides).
Herein, aforementioned fragrance race tetracarboxylic dianhydride 1 is mainly used for improving the thermal characteristics of gained Kapton, mechanical spy Property etc.,
Aforementioned fragrance race tetracarboxylic dianhydride 2 is used to improve the transparency etc. of Kapton.
As aromatic tetracarboxylic dianhydride 1, from the viewpoint of the CTE of gained Kapton, more preferably use PMDA。
As aromatic tetracarboxylic dianhydride 2, from the viewpoint of the YI of gained Kapton and the transparency, more preferably Using at least one of ODPA and 6FDA is selected from, from the viewpoint of the CTE of Kapton, further preferably use 6FDA。
The polyimide precursor of present embodiment is preferably:
All have 5~60 moles of %'s to derive from aforementioned ester ring type tetrabasic carboxylic acid two in the structure of tetracarboxylic dianhydride The structure of acid anhydride,
All have 40~95 moles of %'s to derive from aromatic tetracarboxylic dianhydride in the structure of tetracarboxylic dianhydride Structure；
It is even more preferred that
All have 5~60 moles of %'s to derive from aforementioned ester ring type tetrabasic carboxylic acid two in the structure of tetracarboxylic dianhydride The structure of acid anhydride,
All have 20~80 moles of %'s to derive from aforementioned fragrance race tetrabasic carboxylic acid in the structure of tetracarboxylic dianhydride The structure of dianhydride 1,
All in the structure of tetracarboxylic dianhydride there are 5~60 moles of % to derive from aforementioned fragrance race tetracarboxylic dianhydride 2 structure.
The polyimide precursor of present embodiment is it may further be preferable that all total in the structure of tetracarboxylic dianhydride Meter is selected from aforementioned PMDA, aforementioned ODPA, aforementioned 6FDA, aforementioned CBDA and aforementioned H-PMDA comprising 60 moles of deriving from for % or more At least one of tetracarboxylic dianhydride structure.
Also, from the viewpoint of the suitable yellow chromaticity, CTE and the breaking strength that obtain Kapton,
It is particularly preferred that all equal from benzene with 1~70 mole of % in the structure of tetracarboxylic dianhydride The structure of tetracid dianhydride (PMDA),
All the double neighbours of 4,4 '-oxos are selected from 1~50 mole of deriving from for % in the structure of tetracarboxylic dianhydride The knot of at least one of phthalic acid dianhydride (ODPA) and the double phthalic anhydrides (6FDA) of 4,4 '-(hexafluoroisopropyli,ene bases) Structure.
<from the structure of diamines>
In the polyimide precursor of present embodiment, as the structure for deriving from diamines, have from being selected from 2,2 '-is bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl bases -4,4 '-diamines, 4,4 '-diaminobenzene anilids and 4- The structure of at least one of aminophenyl -4-aminobenzoic acid ester diamines.Wherein, from the YI of gained Kapton and thoroughly From the perspective of bright property, preferably TFMB.
It is particularly preferred that all including 60 moles of % or more in the structure of diamines from aforementioned TFMB's Structure.
<structure from tetracarboxylic dianhydride and the ratio between the structure from diamines>
From the viewpoint of the transparency of Kapton, thermal characteristics and mechanical property, above-mentioned tetrabasic carboxylic acid two is derived from The sum of molal quantity of structure of acid anhydride and the ratio of the sum of the molal quantity of structure from diamines are preferably 100/99.9~100/ 95.More specifically, from the viewpoint of obtaining the Kapton with the yellow chromaticity, CTE and the breaking strength that are more suitable for, Mole of the sum of molal quantity of each structure from PMDA, ODPA, 6FDA, CBDA and H-PMDA and the structure from TFMB The ratio between number { (PMDA+ODPA+6FDA+CBDA+H-PMDA)/TFMB } is preferably 100/99.9~100/95.
<weight average molecular weight of polyimide precursor>
The weight average molecular weight of the polyimide precursor of present embodiment is preferably 5,000 or more and 1,000,000 or less, more It preferably 50,000 or more and 500,000 or less, is more preferably 70,000 or more and 250,000 or less.By keeping weight equal Molecular weight is 5,000 or more, and the intensity of gained Kapton, elongation are improved, and mechanical properties are excellent.Especially from From the perspective of obtaining low CTE and low yellow chromaticity (YI value), molecular weight is more preferably 50,000 or more.By making weight average molecular weight Mw is 1,000,000 hereinafter, desired film can be coated into without exudation for the resin combination containing the polyimide precursor It is thick.
Herein, weight average molecular weight refers to following value: using monodisperse polystyrene as standard and utilize gel infiltration color In the molecular weight distribution for composing measurement, the summation of numerical value obtained from quality of the molecular weight of each molecule multiplied by the molecule is again divided by complete The summation of the quality of part, thus obtained numerical value.
<synthetic method of polyimide precursor>
The polyimide precursor of present embodiment can be by dissolving above-mentioned tetracarboxylic dianhydride's ingredient preferably with diamine component In solvent and make its reaction, to manufacture with the solution form containing polyimide precursor and solvent.Condition when reaction does not have It is particularly limited to, such as the condition that reaction temperature is -20~250 DEG C, the reaction time is 2~48 hours can be exemplified.When reaction Surrounding atmosphere be preferably the inert atmospheres such as argon gas, nitrogen.
Aforementioned solvents are not particularly limited as long as the solvent for dissolving polymer generated.It is molten as well known reaction Agent, such as selected from metacresol, n-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethacetic acid ester, エ Network ア ミ De M100 (trade name: go out the emerging production strain formula meeting of light Society's system) and one or more of エ Network ア ミ De B100 (trade name: Idemitsu Kosen Co., Ltd.'s system) polar solvent be useful. Wherein, it is preferably selected from one or more of NMP, DMAc, エ Network ア ミ De M100 and エ Network ア ミ De B100.In addition to this, Can replace above-mentioned solvent or with above-mentioned solvent use simultaneously tetrahydrofuran (THF), chloroform etc low boiling point solvent or The low absorption solvent of gamma-butyrolacton etc.
Aforementioned polyimide precursor is a part of acyl at least deriving from ester ring type tetracarboxylic dianhydride among polyamic acid Imidizate polyamic acid obtained from amine key is dehydrated through closed loop.
As the process that amido bond is carried out closed loop dehydration, it is not particularly limited, well known method can be applied.For example, Hot-imide or chemical imidization can be used.
Hot-imide more specifically for example can be with the following method.Firstly, diamines is made to dissolve and/or be scattered in suitable When polymer solvent in, add tetracarboxylic dianhydride thereto, add the solvent (such as toluene etc.) of azeotrope with water.Then, it uses Mechanical agitator, heatings stirring 0.5 hour~96 hours, preferred heating stirring 0.5 on one side remove the water azeotropic of by-product while Hour~30 hours.Heating temperature is preferably greater than 100 DEG C and for 250 DEG C hereinafter, preferably 130~230 DEG C, more preferably 150 ~210 DEG C.At this point, monomer concentration is preferably set to 0.5 mass % or more and 95 mass % or less, more preferably 1 mass % or more And 90 below mass %.
Well known imidization catalyst can be used to carry out in chemical imidization.As imidization catalyst, do not have It is particularly limited to, such as can enumerate:
The acid anhydrides of acetic anhydride etc；
Gamma-valerolactone, gamma-butyrolacton, γ-tetronic acid, γ-phthalide, γ-cumarin, γ-phthalide acid etc lactonizes Close object；
The tertiary amine etc. of pyridine, quinoline, N-methylmorpholine, triethylamine etc.
Imidization catalyst can be used only a kind as needed, or be also possible to mixture of more than two kinds.Wherein, Especially from the viewpoint of reactive height, the particularly preferably mixed system of gamma-valerolactone and pyridine.
As the additive amount of imidization catalyst, relative to 100 mass parts of polyamic acid, preferably 50 mass parts with Under, more preferably 30 below the mass.
From the viewpoint of will control to minimum the influence of subsequent reactions, the closed loop dehydration of amido bond is particularly preferably taken The hot-imide carried out under no catalyst.
The polyimide precursor of present embodiment most preferably benefit synthesizes with the following method:
Firstly, carry out reacting for ester ring type tetracarboxylic dianhydride and diamines under conditions of above-mentioned hot-imide, obtain through The polyamic acid of imidizate,
Then, additional addition aromatic tetracarboxylic dianhydride and diamines, preferably at 100 DEG C or less, the reaction was continued.
Operation as above, can obtain the solution containing polyimide precursor.
Can by the solution directly for the preparation of resin combination, or
It can also be by after the polyimide precursor separation and purification contained in the solution, then for the preparation of resin combination.
<other additives>
The resin combination of present embodiment contains polyimide precursor and solvent as described above, as needed can be with Contain other additives.
As this other additives, such as alkoxysilane compound containing trialkylsilyl group in molecular structure, surfactant, levelling agent can be enumerated etc..
(alkoxysilane compound containing trialkylsilyl group in molecular structure)
When forming the elements such as TFT by the polyimides that the resin combination of present embodiment obtains, in order to make itself and bearing Sufficient adaptation is kept between body, resin combination can contain 0.001~2 relative to 100 mass % of polyimide precursor The alkoxysilane compound containing trialkylsilyl group in molecular structure of quality %.
By make alkoxysilane compound containing trialkylsilyl group in molecular structure relative to 100 mass % of polyimide precursor 0.01 mass % of content with On, good adaptation can be obtained with supporting mass.In addition, from the viewpoint of the storage stability of resin combination, alkane The content of oxysilane compound is preferably 2 mass % or less.Before the content of alkoxysilane compound containing trialkylsilyl group in molecular structure is relative to polyimides Body is more preferably 0.02~2 mass %, further preferably 0.05~1 mass %, further preferably 0.05~0.5 matter Measure %, particularly preferably 0.1~0.5 mass %.
As alkoxysilane compound containing trialkylsilyl group in molecular structure, such as 3-mercaptopropyi trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry can be enumerated Co. Ltd. system, trade name KBM803；CHISSO CORPORATION system, trade name サ イ ラ エ ー ス S810), 3- sulfydryl third Ethyl triethoxy silicane alkane (AZMAX Corp., system, trade name SIM6475.0), 3- mercapto propyl methyl dimethoxy silane (letter More chemical industry Co. Ltd. system, trade name LS1375；AZMAX Corp., system, trade name SIM6474.0), mercapto methyl three Methoxy silane (AZMAX Corp., system, trade name SIM6473.5C), mercapto methyl methyl dimethoxysilane (AZMAX Corp., system, trade name SIM6473.0), 3- mercaptopropyi diethoxy methoxy silane, 3- mercaptopropyi ethyoxyl dimethoxy Base silane, 3- mercaptopropyi tripropoxy silane, 3- mercaptopropyi diethoxy npropoxysilane, 3- mercaptopropyi ethyoxyl two Npropoxysilane, 3- mercaptopropyi dimethoxy npropoxysilane, 3- mercaptopropylmethoxy dipropoxy silane, 2- sulfydryl second Base trimethoxy silane, 2- mercaptoethyl diethoxy methoxy silane, 2- mercaptoethyl ethyoxyl dimethoxysilane, 2- mercapto Base ethyl tripropoxy silane, 2- mercaptoethyl tripropoxy silane, 2- mercaptoethyl ethyoxyl dipropoxy silane, 2- sulfydryl Ethyl dimethoxy npropoxysilane, 2- mercaptoethyl methoxyl group dipropoxy silane, 4- mercaptobutyl trimethoxy silane, 4- Mercaptobutyl triethoxysilane, 4- mercaptobutyl tripropoxy silane, N- (3- triethoxysilylpropyltetrasulfide) urea (SHIN-ETSU HANTOTAI Chemical industry Co. Ltd. system, trade name LS3610；AZMAX Corp., system, trade name SIU9055.0), N- (3- trimethoxy Silylpropyl) urea (AZMAX Corp., system, trade name SIU9058.0), N- (3- diethoxy methoxysilyl third Base) urea, N- (3- ethyoxyl dimethoxysilyl propyl) urea, N- (3- tripropoxy-silicane base propyl) urea, N- (3- bis- Ethoxy-c oxygroup silylpropyl) urea, N- (3- ethyoxyl dipropoxy silylpropyl) urea, N- (3- dimethoxy Isopropoxysilyl group propyl) urea, N- (3- methoxyl group dipropoxy silylpropyl) urea, N- (3- trimethyoxysilane Base ethyl) urea, N- (3- ethyoxyl dimethoxysilyl ethyl) urea, N- (3- tripropoxy-silicane base ethyl) urea, N- (3- tripropoxy-silicane base ethyl) urea, N- (3- ethyoxyl dipropoxy silyl ether) urea, N- (3- dimethoxy third Oxygroup silyl ether) urea, N- (3- methoxyl group dipropoxy silyl ether) urea, N- (3- trimethoxysilyl Butyl) urea, N- (3- triethoxysilyl butyl) urea, N- (3- tripropoxy-silicane base butyl) urea, 3- (m-aminophenyl Oxygroup) propyl trimethoxy silicane (AZMAX Corp., system, trade name SLA0598.0), m-aminophenyl base trimethoxy silane (AZMAX Corp., system, trade name SLA0599.0), p-aminophenyl trimethoxy silane (AZMAX Corp., system, trade name SLA0599.1) aminophenyl trimethoxy silane (AZMAX Corp., system, trade name SLA0599.2), 2- (trimethoxy first Silylation ethyl) pyridine (AZMAX Corp., system, trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilyl Methylethyl) pyridine, 2- (diethoxy silyl methyl ethyl) pyridine, (3- triethoxy Silylpropyl) t-butylcarbamate, (3- glycidoxypropyl group) triethoxysilane, tetramethoxy-silicane, four Ethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silanes, tetraisobutoxy-silicane alkane, four tertiary fourths Oxysilane, four (methoxy-ethoxy-silanes), four (methoxy-n-propyloxy silane), four (ethoxyethoxysilanes), four It is (methoxyethoxyethoxy silane), bis- (trimethoxysilyl) ethane, bis- (trimethoxysilyl) hexanes, double It is (triethoxysilyl) methane, bis- (triethoxysilyl) ethane, bis- (triethoxysilyl) ethylene, double (triethoxysilyl) octane, bis- (triethoxysilyl) octadienes, bis- [3- (triethoxysilyl) third Base] disulphide, bis- [3- (triethoxysilyl) propyl] tetrasulfides, ditert-butyldiacetyl oxygen-base silane, two Isobutoxy alumina ethyl triethoxy silicane alkane, bis- bis- (oxoethyl)-aminopropyl triethoxies of (acetylacetone,2,4-pentanedione) titanium-O, O '- Silane, phenyl silane triol, aminomethyl phenyl silane glycol, ethylphenyl silandiol, n-propylbenzene base silane glycol, isopropyl Phenyl silane glycol, n-butylphenyl silandiol, isobutyl phenenyl silandiol, tert-butyl-phenyl silandiol, diphenyl Silandiol, dimethoxydiphenyl silane, diethoxy diphenyl silane, dimethoxy di-p-tolyl silane, ethyl first Base phenyl silane alcohol, n-propyl aminomethyl phenyl silane alcohol, isopropyl methyl phenyl silane alcohol, normal-butyl aminomethyl phenyl silane alcohol, Isobutyl methyl phenyl silane alcohol, tertbutyl methyl phenyl silane alcohol, ethyl n-propylbenzene base silane alcohol, ethylisopropyl base phenyl Silanol, normal-butyl ethylphenyl silanol, isobutyl group ethylphenyl silanol, t-butylethyl phenyl silane alcohol, methyl two Phenyl silane alcohol, ethyl diphenyl silanol, n-propyl diphenyl silane alcohol, isopropyl diphenyl base silane alcohol, normal-butyl hexichol Base silane alcohol, isobutyl diphenyl silanol, t-butyl diphenylsilane alcohol, tri-phenyl-silane alcohol, 3- urea propyl triethoxy Silane, bis- (2- hydroxyethyl) -3-aminopropyltriethoxysilane, 3- glycidoxypropyltrime,hoxysilane, phenyl Trimethoxy silane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, gamma-amino propyl 3 third Oxysilane, three butoxy silane of gamma-amino propyl, gamma-amino ethyl triethoxysilane, gamma-amino ethyl trimethoxy Silane, gamma-amino ethyl tripropoxy silane, three butoxy silane of gamma-amino ethyl, gamma-amino butyl triethoxysilane, Gamma-amino butyl trimethoxy silane, gamma-amino butyl tripropoxy silane, three butoxy silane of gamma-amino butyl etc., but It is not limited to them.They can be used alone, and can also combine a variety of uses.
As silane coupling agent, among aforementioned silane coupling agent, from the sight for the storage stability for ensuring resin combination Point sets out, and is preferably selected from phenyl silane triol, trimethoxy-benzene base silane, trimethoxy (p-methylphenyl) silane, diphenyl Silandiol, dimethoxydiphenyl silane, diethoxy diphenyl silane, dimethoxy di-p-tolyl silane, triphenyl One or more of the silane coupling agent that silanol and following structures are shown respectively.
(surfactant or levelling agent)
In addition, can be improved coating by the way that surfactant or levelling agent are added to resin combination.It is specific and Speech, the contraction after coating can be prevented.
As this surfactant or levelling agent, for example, can enumerate organic siloxane polymer KF-640,642, 643, (the above are trade names, SHIN-ETSU HANTOTAI's chemical industry strain by KP341, X-70-092, X-70-093, KBM303, KBM403, KBM803 Formula commercial firm system), (the above are trade names, east by SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 レ ダ ウ コ ー ニ Application グ シ リ コ ー Application corporation), SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ- 2154, FZ-2164, FZ-2166, L-7604 (the above are trade names, Japan's ユ ニ カ ー corporation), DBE-814, DBE-224, DBE-621、CMS-626、CMS-222、KF-352A、KF-354L、KF-355A、KF-6020、DBE-821、DBE-712 (Gelest), (the above are trade names, ビ ッ Network ケ ミ ー ジ ャ パ Application by BYK-307, BYK-310, BYK-378, BYK-333 System), グ ラ ノ ー Le (trade name, Kyoeisha Chemical Co., Ltd.'s system)；As polyoxyethylene laurel ether, polyoxyethylene stearyl メ ガ Off ァ ッ Network ス F171, F173, R-08 (the big Japanese ink of ether, polyoxyl 10 oleyl ether, polyoxethylene octylphenyl phenol ether etc. Chemical industry Co. Ltd. system, trade name), Off ロ ラ ー De FC430, FC431 (Sumitomo 3M Co., Ltd., trade name) etc..
When using surfactant or levelling agent, total compounding amount is relative to the polyimide precursor in resin combination 100 mass parts are preferably 0.001~5 mass parts, more preferably 0.01~3 mass parts.
<resin combination>
The resin combination of present embodiment can be with molten by aforementioned polyimide precursor and the other ingredients optionally employed (varnish) form of the liquid composite made of solvent uses.
Herein, as solvent, workable solvent when can be used as synthesis of polyimides precursor and it is same as described above Solvent.
The solid component concentration that the dosage of solvent is preferably set to resin combination reaches the amount of 3~50 mass %.
The room temperature preservation excellent in stability of the varnish of the resin combination of present embodiment, when saving for 4 week at room temperature Varnish rate of change in viscosity relative to initial viscosity be 10% or less.When room temperature preservation excellent in stability, without being freezed Keeping, is easily processed.
<laminated body>
The polyimide film that the laminated body of present embodiment has supporting mass and is formed on the supporting mass.In addition, aforementioned Laminated body can also be further equipped with inoranic membrane on aforementioned polyimide film.
Aforementioned laminated body via following process by forming:
The resin combination of present embodiment is unfolded and is formed on the surface of supporting mass the film formation process of film； And
It heats aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is subjected to imidizate, form polyimides The heating process of film.
Aforementioned inorganic film is used as preventing moisture, oxygen from invading organic EL luminescent layer from Kapton of the invention Deng gas barrier layer, can compatibly exemplify silica, aluminium oxide, silicon carbide, Zirconia/silicon carbide, silicon carbide-silicon nitride, silicon nitride, nitrogen The inorganic oxide film of oxide/silica etc..The inoranic membrane is formed a film using plasma CVD method etc..
As above-mentioned supporting mass, for example, inorganic substrate of glass substrates such as alkali-free glass substrate etc, but do not limit especially Due to this.
As above-mentioned method of deploying, such as coating method well known to spin coating, slot coated, blade coating being enumerated etc..
More specifically, by the way that resin combination to be unfolded on supporting mass (or on the adhesive layer formed on its interarea) And after removing solvent, is preferably heated under inert atmosphere and polyimide precursor is subjected to imidizate, it can be in aforementioned branch It holds and forms Kapton on body.
Solvent above-mentioned removal for example can by less than 250 DEG C, preferably 50~200 DEG C at a temperature of be heat-treated 1 Minute~carry out within 300 minutes.Imidizate above-mentioned for example can by 250 DEG C~550 DEG C at a temperature of heat 1 Minute~carry out within 300 minutes.Surrounding atmosphere when imidizate is preferably set under the inert atmospheres such as nitrogen.
The thickness of the Kapton as obtained from present embodiment is not particularly limited, and preferably 10~50 μm Range, more preferably 15~25 μm.
The laminated body is for example for manufacturing flexible device.More specifically, semiconductor device is formed on polyimide film, Thereafter supporting mass is removed, the flexible device for having the flexible transparent substrate formed by polyimide film can be obtained.
<Kapton>
The Kapton of present embodiment is formed via following process:
By the resin combination of the above-mentioned polyimide precursor containing present embodiment and solvent on the surface of supporting mass Expansion, to form the film formation process of film；
It heats aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is subjected to imidizate, to form polyamides The heating process of imines film；And
Aforementioned Kapton is removed from aforementioned supporting mass, to obtain the stripping process of Kapton.
The Kapton is for example for manufacturing flexible device.Specifically, the Kapton can be used for Form the substrate of TFT, the substrate, alignment films, the flexible display transparent substrate that form colour filter etc..
<advantages of the present invention>
As described above, the polyimide precursor of present embodiment is preferably,
(1) it is included as the structure from tetracarboxylic dianhydride
From the structure of at least one kind of ester ring type tetracarboxylic dianhydride in CBDA, H-PMDA etc.,
From the structure of the aromatic tetracarboxylic dianhydride 1 in PMDA etc.,
From the structure of the aromatic tetracarboxylic dianhydride in OPDA, 6FDA etc.,
(2) there is the structure from TFMB etc. as the structure from diamines.
The Kapton manufactured using this polyimide precursor be it is colorless and transparent, CTE is low and elongation is excellent. The surface roughness for being formed with the laminated body of inoranic membrane on the Kapton is small, Haze value is small, moisture-vapor transmission is small, because This, the use being suitble in the transparent substrate of flexible display.
When being further elaborated with, as follows.
When forming flexible display, glass substrate is used as supporting mass, is formed on flexible substrate, further on it Form the inoranic membrane of TFT etc..By inoranic membrane be formed in the process on substrate it is typical for 150~650 DEG C of wide scope temperature Degree is lower to be implemented.In order to play practical desired performance, 250 DEG C~400 DEG C of temperature range is mainly used.As above-mentioned inorganic Film, such as TFT-IGZO (InGaZnO) oxide semiconductor, TFT (a-Si-TFT, poly-Si-TFT) can be enumerated etc..
At this point, the CTE of flexible substrate is higher compared with the CTE of glass substrate, then they form work in the inoranic membrane of high temperature The warpage that glass substrate can more be generated when cooling after expanding in sequence when being shunk and damaged, flexible substrate are from glass substrate The problems such as removing.In general, the thermal expansion coefficient of glass substrate is smaller than resin.Therefore, the linear expansion coefficient of flexible substrate is got over It is small the more preferred.
Kapton about present embodiment, it is contemplated that above-mentioned aspect, it can will be 15~25 μm with film thickness 25.0ppm/ DEG C or less is set as benchmark, the average linear expansion coefficient measured at 100~300 DEG C according to TMA method (CTE).
In addition, the yellow chromaticity (YI value) of the Kapton of present embodiment is 10 hereinafter, and it is possible to will be with film 15~25 μm of thickness as benchmark, measure transmissivity using ultraviolet specrophotometer when 550nm under transmissivity be set as 85% More than.
The surface roughness for being formed with the inoranic membrane of the laminated body of inoranic membrane on the Kapton of this implementation is small, Haze value is small, moisture-vapor transmission is small.
In the case where organic el display, as gas barrier layer, inoranic membrane is formed on Kapton.At this point, nothing When the surface roughness of machine film is big, Haze value is big, laminated body generation is muddy and fuzzy, is not suitable as display.In addition, water steams When vapor permeability is big, the function as gas barrier layer will not be played, therefore be not suitable for.
It is considered that: the surface roughnesses of these laminated bodies, Haze value, moisture-vapor transmission and Kapton it is resistance to It is hot related.This is because: including the Kapton when forming inoranic membrane on Kapton by CVD method High temperature more than solidification (imidizate processing) temperature when laminated body is exposed to form Kapton.The laminated body is excellent Choosing: surface roughness is 25nm or less, Haze is 15 or less, moisture-vapor transmission is 0.1g/ (m2For 24 hours) below.
In addition, elongation of the Kapton of present embodiment using 15~25 μm of film thickness as benchmark is preferably 15% or more.By the way that with this elongation, breaking strength when handling flexible substrate becomes excellent, therefore can be improved finished product Rate.
The Kapton for meeting the present embodiment of above-mentioned physical property can be used for having because of existing Kapton Some yellow and use limited purposes and require the purposes of the transparency.Especially, in addition to being suitable as flexible display with thoroughly Except bright substrate,
Such as it can be also used for scattering sheet in protective film or TFT-LCD and film (for example, the internal layer of TFT-LCD, grid are exhausted Velum and liquid crystal orientation film) etc..When applying the polyimides of present embodiment as liquid crystal orientation film, facilitate aperture opening ratio Increase, the TFT-LCD of high contrast can be manufactured.
The Kapton and laminated body manufactured using the polyimide precursor of present embodiment for example can be compatibly Manufacture for semiconducting insulation film, TFT-LCD insulating film, electrode protective membrane, flexible device.Particularly suitable for manufacturing substrate. Herein, flexible device can for example enumerate flexible display, flexible solar battery, flexible illumination, flexible batteries etc..
Embodiment
Hereinafter, illustrating the present invention based on embodiment.They be in order to illustrate and record, the scope of the present invention is not It is defined in following embodiments.
Various evaluations in embodiment and comparative example are as follows.
(measurement of weight average molecular weight)
Weight average molecular weight is measured under the following conditions using gel permeation chromatography (GPC).For calculating Weight-average molecular The standard curve of amount is made using standard polystyren (TOSOH Co., Ltd's system).
Solvent: it uses n,N-Dimethylformamide (Wako Pure Chemical Industries, Ltd.'s system, high performance liquid chromatography use), shortly Will measurement before addition 24.8mmol/L lithium bromide monohydrate (Wako Pure Chemical Industries, Ltd.'s system, purity 99.5%) and The phosphoric acid (Wako Pure Chemical Industries, Ltd.'s system, high performance liquid chromatography use) of 63.2mmol/L
Column: Shodex KD-806M (Showa Denko K. K's system)
Flow velocity: 1.0mL/ minutes
Column temperature: 40 DEG C
Pump: PU-2080Plus (JASCO corporation)
Detector: RI-2031Plus (RI: differential refractometer, JASCO corporation), UV-2075Plus (UV-VIS: ultraviolet It can be seen that absorptiometer, JASCO corporation)
(from the calculating of the imide concentration of the part of ester ring type tetracarboxylic dianhydride)
Imide concentration from the part of ester ring type acid dianhydride is by for the measurement of polyimide precursor varnish13C- The integrated value of NMR signal calculates.13C-NMR measurement carries out under the following conditions.
Measurement device: Jeol Ltd.'s JNM-GSX400 type
Measuring temperature: 23 DEG C
Measure solvent: deuterated dimethyl sulfoxide solvent (DMSO-d6)
The signal belonged to from each carbon of the imide bond of the part of ester ring type tetracarboxylic dianhydride, amido bond and carboxylic acid Present in following magnetic field strengths:
The signal that imide bond carbon from the part of ester ring type tetracarboxylic dianhydride is belonged to: 177ppm is nearby (A)
The signal that amido bond carbon from the part of ester ring type tetracarboxylic dianhydride is belonged to: 172ppm is nearby (B)
The signal that carboxyl carbon from the part of ester ring type tetracarboxylic dianhydride is belonged to: 177ppm is nearby (C)
Herein, the position about amic acid (not carrying out imidizate), B are identical as the integrated value of C.Imidizate is carried out Position in imide bond carbon integrated value and do not carry out the integrated value of the amido bond carbon in the position of imidizate and use respectively Following formula indicates:
The integrated value of imide bond carbon: the integrated value of the integrated value-B of A
The integrated value of amido bond carbon and carboxyl carbon: integrated value × 2 of B
Thus, imide concentration is indicated with following calculating formulas:
Imide concentration (%)=100 × (integrated value of the integrated value-B of A)/(integrated value+B's of the integrated value-B of A Integrated value × 2)=100 × (integrated value of the integrated value-B of A)/(integrated value of the integrated value+B of A)
(evaluation of varnish storage stability)
The composition varnish prepared respectively in following embodiments and comparative example is stood 3 days at room temperature, by gained sample The viscosimetric analysis at 23 DEG C is carried out as the sample after preparation.Thereafter, it will further stand at room temperature obtained from 4 weeks Sample carries out the viscosimetric analysis at 23 DEG C as the sample after 4 weeks again.
Above-mentioned viscosimetric analysis is come using the viscosimeter (eastern machine industrial machine Co. Ltd. system TV-22) of subsidiary thermoregulator It carries out.
Using said determination value, 4 week of room temperature rate of change in viscosity is calculated according to following mathematical expressions.
4 week of room temperature rate of change in viscosity (%)=[(sample viscosity after 4 weeks)-(sample viscosity after preparation)]/(system Sample viscosity after standby) × 100
4 week of room temperature, rate of change in viscosity evaluated according to following benchmark.Show the result in table 2.
◎: rate of change in viscosity is 5% or less (storage stability " excellent ")
Zero: rate of change in viscosity is 10% or less (storage stability " good ")
×: rate of change in viscosity is greater than 10% (storage stability " bad ")
(production of laminated body and separating film)
The varnish of polyimide precursor obtained in each embodiment and comparative example is coated on alkali-free glass using bar coater On substrate (with a thickness of 0.7mm).Then, after carrying out 5 minutes~10 minutes levellings at room temperature, with 140 in hot-air oven DEG C heating 60 minutes, further in a nitrogen atmosphere with defined temperature heating 60 minutes, have to be produced on aforesaid base plate There is the laminated body of film.Film film thickness in laminated body is set in such a way that the film thickness after solidifying reaches 20 μm.Then, with Defined temperature is solidified (curing process) and carries out imidizate to film.Laminated body after solidification is stood at room temperature After 24 hours, Kapton is removed from glass, to isolate film.
It is poly- by what is had cured under the predetermined temperature in the evaluation of breaking strength below, yellow chromaticity and linear expansion coefficient Imide membrane is used as sample.
(evaluation of elongation)
For the sample of the Kapton for 20 μm of width 5mm, length 50mm, thickness having cured at the specified temperature Product are stretched using cupping machine (A&D Company, Limited system: RTG-1210) with 100mm/ minutes speed Measurement.Elongation at break is evaluated as ◎ (elongation " excellent "), is 15% or more when being 20% or more and less than 20% when is evaluated For zero (elongation " good "), be 10% or more and less than 15% when is evaluated as △ (elongation " bad "), less than 10% news commentary Valence is (elongation " poor ").
(evaluation of yellow chromaticity (YI value))
(Spectrophotometer:SE600) manufactured using Nippon Denshoku Industries Co., Ltd. is measured with D65 light source The Kapton of 20 μm of the thickness having cured at the specified temperature.YI value is evaluated as ◎ when being 8.0 or less, and (yellow chromaticity is " excellent It is good "), be evaluated as zero (yellow chromaticity " good ") more than 8.0 and when being 10.0 or less, be evaluated as more than 10.0 and when being 15.0 or less △ (yellow chromaticity " bad "), more than 15.0 when be evaluated as × (yellow chromaticity " poor ").
(evaluation of linear expansion coefficient (CTE))
For the Kapton having cured at the specified temperature, filled using the thermo-mechanical analysis that Shimadzu Seisakusho Ltd. manufactures (TMA-50) is set, carries out the measurement of test film elongation under the following conditions by thermo-mechanical analysis.
Load-carrying: 5g
Heating rate: 10 DEG C/min
Measure atmosphere: nitrogen atmosphere
Nitrogen flow: 20ml/ minutes)
Measuring temperature range: 50~450 DEG C
The CTE of the Kapton within the temperature range of 100~300 DEG C at this time is found out, CTE is 20ppm/ DEG C or less When be evaluated as ◎ (CTE " excellent "), more than 20ppm/ DEG C and for 25ppm/ DEG C or less when be evaluated as zero (CTE " good "), be more than 25ppm/ DEG C and be 30ppm/ DEG C or less when be evaluated as △ (CTE " bad "), more than 30ppm/ DEG C when be evaluated as × (CTE " poor ").
(measurement of the surface roughness of the inoranic membrane formed on Kapton)
It is following to operate using the composition varnish prepared respectively in above-described embodiment and comparative example, it is formed in surface setting The laminated body chip of Kapton and inoranic membrane is sequentially laminated on the 6 inch silicon wafer substrates for having aluminium-vapour deposition layer.
Firstly, heated 60 minutes with hot-air oven with 140 DEG C on aforesaid substrate after each composition varnish of rotary coating, It is further heated 60 minutes with 320 DEG C in a nitrogen atmosphere, to obtain the chip with 20 μm of film thickness of Kapton.
Thereafter, CVD method is used to be formed using the thickness of 350 DEG C, 100nm as nothing on the Kapton of above-mentioned formation Silicon nitride (the SiN of machine filmx) film.Then, used as 2100 (the SII NANOTECHNOLOGY company of Na ノ ピ Network ス of AFM System, trade name), measurement is formed by the surface roughness of silicon nitride in the range of 100 μm of 100 μ m.Test with N=5 into Row, takes its average value as surface roughness Ra.
Show the result in table 2.
(evaluation of Haze)
By laminated body water immersion obtained above in diluted hydrochloric acid aqueous solution, with this two layers of inoranic membrane and Kapton It is removed from chip as one, to obtain the sample for being formed with the Kapton of inoranic membrane to surface.Use the sample Product, the SC-3H type haze meter manufactured using Suga Test Instruments Co., Ltd., according to JIS K7105 transparency The measurement of test method(s) progress Haze.
Measurement result is evaluated according to following benchmark.
◎: Haze is 5 or less (Haze " excellent ")
Zero: Haze is greater than 5 and is 15 or less (Haze " good ")
×: Haze is greater than 15 (Haze " bad ")
Show the result in table 2.
(evaluation of moisture-vapor transmission)
Moisture-vapor transmission measurement device (the machine name: PERMATRAN (registered trademark) W3/ manufactured using MOCON company 31), 40 DEG C of temperature, humidity 90%RH and measurement area 80mm φ under conditions of measure surface obtained above be formed with it is inorganic The moisture-vapor transmission of the Kapton of film.Measurement number is set as each 5 times, using its average value as moisture-vapor transmission, It is evaluated according to following benchmark.
◎: moisture-vapor transmission is 0.01g/ (m2For 24 hours) below (moisture-vapor transmission " excellent ")
Zero: moisture-vapor transmission is greater than 0.01g/ (m2It for 24 hours) and is 0.1g/ (m2(moisture-vapor transmission below for 24 hours) " good ")
×: moisture-vapor transmission is greater than 0.1g/ (m2(moisture-vapor transmission " bad ") for 24 hours)
Show the result in table 2.
[reference example 1]
In a nitrogen atmosphere, 2,2 '-bis- (trifluoromethyl) benzidine (TFMB) are added into the separable flask of 500ml 15.69g (49.00mmol) and n-methyl-2-pyrrolidone (NMP) 178.95g, dissolves TFMB under stiring.Thereafter, benzene is added Double O-phthalic acid dianhydride (ODPA) 3.10g (10.0mmol) of equal tetracid dianhydride (PMDA) 1.09g (5.0mmol), 4,4 '-oxos With 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA) 6.86g (35.0mmol) are stirred 4 hours at 80 DEG C, to be gathered The nmp solution (hereinafter also referred to " varnish " of amic acid.).The weight average molecular weight (Mw) of gained polyamic acid is 116,500.It will be with CTE, YI value and elongation of 330 DEG C of films having cured are shown in table 2 below.
[reference example 2]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 180.42g, PMDA3.27g (15.0mmol), ODPA 3.10g (10.0mmol) and CBDA 4.90g (25.0mmol), it is in addition to this, same as reference example 1 It operates and obtains varnish.The weight average molecular weight (Mw) of gained polyamic acid is 120,000.By the film being had cured with 330 DEG C CTE, YI value and elongation are shown in table 2 below.
[reference example 3]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 186.58g, PMDA1.09g (5.00mmol), ODPA 6.20g (20.0mmol) and CBDA 4.90g (25.0mmol), it is in addition to this, same as reference example 1 It operates and obtains varnish.The weight average molecular weight (Mw) of gained polyamic acid is 128,000.By the film being had cured with 330 DEG C CTE, YI value and elongation are shown in table 2 below.
[embodiment 4]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.1,2,4,5- hexamethylene is added thereto Tetracarboxylic dianhydride (H-PMDA) 2.24g (10.0mmol) after flowing back 2 hours at 180 DEG C, expends removal in 3 hours as azeotropic The toluene of solvent.Then, after flask contents being cooled to 40 DEG C, TFMB 12.55g (39.2mmol), NMP are added 168.43g, PMDA 6.54g (30.0mmol) and ODPA 3.10g (10.0mmol) are stirred 4 hours at 80 DEG C, to obtain Polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 82,000.CTE, YI value and elongation of the film being had cured with 350 DEG C are shown in table 2 below.
[reference example 5]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 178.14g, PMDA5.45g (25.0mmol), ODPA 1.55g (5.0mmol) and CBDA 3.92g (20mmol) are in addition to this equally operated with reference example 1 And obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 119,000.By the CTE for the film being had cured with 330 DEG C, YI value and elongation are shown in table 2 below.
[reference example 6]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 187.38g, PMDA2.18g (10.0mmol), ODPA 6.20g (20.0mmol) and CBDA 3.92g (20.0mmol), it is in addition to this, same as reference example 1 It operates and obtains varnish.The weight average molecular weight (Mw) of gained polyamic acid is 123,000.By the film being had cured with 330 DEG C CTE, YI value and elongation are shown in table 2 below.
[reference example 7]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 175.19g, PMDA1.09g (5.0mmol), ODPA 1.55g (5.0mmol) and CBDA 7.84g (40.0mmol) are in addition to this equally grasped with reference example 1 Make to obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 123,000.By the film being had cured with 330 DEG C CTE, YI value and elongation are shown in table 2 below.
[reference example 8]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 189.59g, PMDA5.45g (25.0mmol), ODPA 6.20g (20.0mmol) and CBDA 0.98g (5.0mmol) are in addition to this equally grasped with reference example 1 Make to obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 103,000.By the film being had cured with 330 DEG C CTE, YI value and elongation are shown in table 2 below.
[embodiment 9]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 12.55g (39.2mmol), NMP 171.51g, PMDA 5.45g (25.0mmol) and ODPA 4.65g (15.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 123,000.By the film being had cured with 350 DEG C CTE, YI value and elongation are shown in table 2 below.
[embodiment 10]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 12.55g (39.2mmol), NMP 174.59g, PMDA 4.36g (20.0mmol) and ODPA 6.20g (20.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 81,000.By the film being had cured with 350 DEG C CTE, YI value and elongation are shown in table 2 below.
[embodiment 11]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 6.28g (19.6mmol), NMP 32.28g and toluene 50g, dissolve TFMB under stiring.H-PMDA 4.48g is added thereto (20.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 9.42g (29.4mmol), NMP 76.44g, PMDA 5.45g (25.0mmol) and ODPA 1.55g (5.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained is poly- Acid imide-polyamic acid polymeric compositions weight average molecular weight (Mw) is 68,000.By the CTE for the film being had cured with 350 DEG C, YI value and elongation are shown in table 2 below.
[embodiment 12]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 6.28g (19.6mmol), NMP 32.28g and toluene 50g, dissolve TFMB under stiring.H-PMDA 4.48g is added thereto (20.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 9.42g (29.4mmol), NMP 78.28g, PMDA 4.36g (20.0mmol) and ODPA 3.10g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained Polyimides-polyamic acid polymer weight average molecular weight (Mw) is 68,000.By CTE, YI of the film being had cured with 350 DEG C Value and elongation are shown in table 2 below.
[embodiment 13]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 0.63g (1.96mmol), NMP 3.22g and toluene 30g, dissolve TFMB under stiring.H-PMDA 0.45g is added thereto (2.00mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 15.06g (47.0mmol), NMP 186.57g, PMDA 6.33g (29.0mmol) and ODPA 5.89g (19.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 112,000.By the film being had cured with 350 DEG C CTE, YI value and elongation are shown in table 2 below.
[embodiment 14]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 12.55g (39.2mmol), NMP 166.88g, PMDA 7.09g (32.5mmol) and ODPA 2.33g (7.5mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymeric compositions weight average molecular weight (Mw) is 79,000.The film that will be had cured with 350 DEG C CTE, YI value and elongation be shown in table 2 below.
[embodiment 15]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 9.42g (29.4mmol), NMP 48.42g and toluene 50g, dissolve TFMB under stiring.H-PMDA 6.78g is added thereto (30.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 6.28g (19.6mmol), NMP 60.54g, PMDA 3.27g (15.0mmol) and ODPA 1.55g (5.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained is poly- Acid imide-polyamic acid polymeric compositions weight average molecular weight (Mw) is 56,000.By the CTE for the film being had cured with 350 DEG C, YI value and elongation are shown in table 2 below.
[embodiment 16]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.80mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, addition TFMB 12.55g (39.2mmol), NMP 168.43g, PMDA 4.36g (20.0mmol), ODPA 3.10g (10.0mmol) and CBDA 1.96g (10.0mmol) is stirred 4 hours with 80 DEG C, to obtain polyimides- The varnish of polyamic acid polymer.Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 71,000.It will be with CTE, YI value and elongation of 350 DEG C of films having cured are shown in table 2 below.
[reference example 17]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 162.24g, PMDA6.54g (30.0mmol), double phthalic anhydride (6FDA) 4.44g (10.0mmol) of 4,4 '-(hexafluoroisopropyli,ene bases) and CBDA1.96g (10mmol) in addition to this obtains varnish with the equally operation of reference example 1.The weight average molecular weight (Mw) of gained polyamic acid is 159,000.CTE, YI value and elongation of the film being had cured with 330 DEG C are shown in table 2 below.
[embodiment 18]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.1,2,4,5- hexamethylene is added thereto Tetracarboxylic dianhydride (H-PMDA) 2.24g (10.0mmol) after flowing back 2 hours at 180 DEG C, expends removal in 3 hours as azeotropic The toluene of solvent.After the content of flask is cooled to 40 DEG C, addition TFMB 12.55g (39.2mmol), NMP 147.70g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyamides Asia Amine-polyamic acid polymer varnish.Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 85,000. CTE, YI value and elongation of the film being had cured with 350 DEG C are shown in table 2 below.
[embodiment 19]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond by infrared spectroscopic analysis (IR) confirmation-1Neighbouring absorption (C=O) disappears It loses.Thereafter, into flask add TFMB 12.55g (39.2mmol), NMP 153.4g, PMDA 5.45g (25.0mmol) and 6FDA 6.66g (15.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 88,000.By commenting for the film being had cured with 350 DEG C Valence result is shown in table 2.
[embodiment 20]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 159.8g, PMDA 4.36g (20.0mmol) and 6FDA 8.88g (20.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 86,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 21]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 6.28g (19.6mmol), NMP 32.28g and toluene 50g, dissolve TFMB under stiring.H-PMDA 4.48g is added thereto (20.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 9.42g (29.4mmol), NMP 124.9g, PMDA 5.45g (25.0mmol) and 6FDA 2.22g (5.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid is poly- The weight average molecular weight (Mw) for closing object is 76,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 22]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 6.28g (19.6mmol), NMP 32.28g and toluene 50g, dissolve TFMB under stiring.H-PMDA 4.48g is added thereto (20.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 9.42g (29.4mmol), NMP 131.3g, PMDA 4.36g (20.0mmol) and 6FDA 4.44g (10.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid is poly- The weight average molecular weight (Mw) for closing object is 77,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 23]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 0.45g is added thereto (2.00mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 158.3g, PMDA 6.33g (29.0mmol) and 6FDA 8.44g (19.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 89,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 24]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, and the 1650cm of amido bond is derived from using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 143.9g, PMDA 7.09g (32.5mmol) and 6FDA 3.33g (7.5mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid is poly- The weight average molecular weight (Mw) for closing object is 89,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 25]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 9.42g (29.4mmol), NMP 48.42g and toluene 50g, dissolve TFMB under stiring.H-PMDA6.78g is added thereto (30.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 6.28g (19.6mmol), NMP 109.5g, PMDA 3.27g (15.0mmol) and 6FDA2.22g (5.0mmol), 80 It is stirred 4 hours at DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid polymerization The weight average molecular weight (Mw) of object is 75,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 26]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 153.5g, PMDA 3.27g (15.0mmol), BPDA 4.41g (15.0mmol) and 6FDA 4.44g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 87,000.By commenting for the film being had cured with 350 DEG C Valence result is shown in table 2.
[embodiment 27]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 143.3g, PMDA 6.54g (30.0mmol), ODPA 1.55g (5.0mmol) and 6FDA 2.22g (5.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 86,000.By commenting for the film being had cured with 350 DEG C Valence result is shown in table 2.
[embodiment 28]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA1.12g is added thereto (5.0mmol), CBDA0.98g (5.0mmol) after flowing back 2 hours at 180 DEG C, expends removal in 3 hours as azeotropic solvent Toluene.The content of flask is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C= O it) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 146.3g, PMDA6.54g (30.0mmol) and 6FDA4.44g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 90,000.By commenting for the film being had cured with 350 DEG C Valence result is shown in table 2.
[embodiment 29]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA0.34g is added thereto (1.5mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 147g, PMDA6.54g (30.0mmol), 6FDA4.44g (10.0mmol) and H-PMDA1.9g (8.5mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyamides is sub- Amine-polyamic acid polymer weight average molecular weight (Mw) is 71,000.The evaluation result for the film being had cured with 350 DEG C is shown in Table 2.
[embodiment 30]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA0.56g is added thereto (2.5mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 147g, PMDA6.54g (30.0mmol), 6FDA4.44g (10.0mmol) and H- PMDA1.68g (7.5mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Institute Obtaining polyimides-polyamic acid polymer weight average molecular weight (Mw) is 75,000.By the evaluation for the film being had cured with 350 DEG C As a result it is shown in table 2.
[embodiment 31]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA0.78g is added thereto (3.5mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 147g, PMDA 6.54g (30.0mmol), 6FDA 4.44g (10.0mmol) and H-PMDA 1.46g (6.5mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained is poly- Acid imide-polyamic acid polymer weight average molecular weight (Mw) is 78,000.By the evaluation result for the film being had cured with 350 DEG C It is shown in table 2.
[embodiment 32]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 0.62g is added thereto (2.75mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 153.3g, PMDA 6.54g (30.0mmol), 6FDA 6.66g (15.0mmol) and H-PMDA 0.5g (2.25mmol) is stirred 4 hours at 80 DEG C, so that it is clear to obtain polyimides-polyamic acid polymer Paint.Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 80,000.The film that will be had cured with 350 DEG C Evaluation result is shown in table 2.
[embodiment 33]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 1.68g is added thereto (7.5mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 160.1g, PMDA 6.54g (30.0mmol), 6FDA 2.22g (5.0mmol) and H-PMDA 5.1g (22.5mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained is poly- Acid imide-polyamic acid polymer weight average molecular weight (Mw) is 71,000.By the evaluation result for the film being had cured with 350 DEG C It is shown in table 2.
[embodiment 34]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.CBDA 1.96g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 166.5g, PMDA 6.54g (30.0mmol) and ODPA 3.10g (10.0mmol), It is stirred 4 hours with 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid is poly- The weight average molecular weight (Mw) for closing object is 120,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 35]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.CBDA 0.98g is added thereto (5.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 191.3g, PMDA 5.45g (25.0mmol) and 6FDA 8.88g (20.0mmol), at 80 DEG C Lower stirring 4 hours, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid polymer Weight average molecular weight (Mw) be 95,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 36]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.CBDA 1.96g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 175.5g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 100,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 37]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 9.42g (29.4mmol), NMP 48.42g and toluene 50g, dissolve TFMB under stiring.CBDA 5.88g is added thereto (30.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 6.28g (19.6mmol), NMP 169.5g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid is poly- The weight average molecular weight (Mw) for closing object is 100,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 38]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.CBDA 0.29g is added thereto (1.5mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 175.5g, PMDA 6.54g (30.0mmol), 6FDA4.44g (10.0mmol) and CBDA1.67g (8.5mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Institute Obtaining polyimides-polyamic acid polymer weight average molecular weight (Mw) is 95,000.By the evaluation for the film being had cured with 350 DEG C As a result it is shown in table 2.
[embodiment 39]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.CBDA 0.53g is added thereto (2.75mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 183.8g, PMDA 6.54g (30.0mmol), 6FDA 6.66g (15.0mmol) and CBDA 0.45g (2.25mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish. Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 80,000.By commenting for the film being had cured with 350 DEG C Valence result is shown in table 2.
[embodiment 40]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.CBDA 1.47g is added thereto (7.5mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 186.8g, PMDA 6.54g (30.0mmol), 6FDA 2.22g (5.0mmol) and CBDA 4.41g (22.5mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained Polyimides-polyamic acid polymer weight average molecular weight (Mw) is 91,000.By the evaluation knot for the film being had cured with 350 DEG C Fruit is shown in table 2.
[embodiment 41]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 160g, BPDA 8.83g (30.0mmol) and 6FDA 4.44g (10.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid is poly- The weight average molecular weight (Mw) for closing object is 86,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 42]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1After neighbouring absorption (C=O) disappears, TFMB is added 12.55g (39.2mmol), NMP 147.8g, PMDA 6.54g (30.0mmol) and bis- (the trihemellitic acid monoesters of 4,4 '-xenyls Acid anhydrides (TAHQ) 4.58g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer Varnish.Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 84,000.It is thin by being had cured with 350 DEG C Film evaluation result is shown in table 2.
[embodiment 43]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.CPDA 2.1g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 146.3g, PMDA6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid is poly- The weight average molecular weight (Mw) for closing object is 71,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 44]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-BPDA 3.06g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 151.7g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 73,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 45]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.BCDA 2.36g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask Object is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, it adds TFMB 12.55g (39.2mmol), NMP 147.7g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 75,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[embodiment 46]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.Bicyclic [2.2.2] octyl- is added thereto 7- alkene -2,3,5,6- tetracarboxylic dianhydrides (BOTDA) 2.48g (10.0mmol) after flowing back 2 hours at 180 DEG C, expend 3 hours Remove the toluene as azeotropic solvent.The content of flask is cooled to 40 DEG C, derives from the 1 of amido bond using IR confirmation, 650cm-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB 12.55g (39.2mmol), NMP 148.4g, PMDA are added 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamides The varnish of amino acid polymer.Gained polyimides-polyamic acid polymer weight average molecular weight (Mw) is 74,000.It will be with 350 DEG C film having cured evaluation result is shown in table 2.
[embodiment 47]
2,2 '-diformazans are put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere Base xenyl -4,4 '-diamines (mTB) 2.08g (9.8mmol), NMP 16.14g and toluene 50g, dissolve mTB under stiring.To H-PMDA 2.24g (10.0mmol) wherein is added, after flowing back 2 hours at 180 DEG C, expends removal in 3 hours as azeotropic solvent Toluene.The content of flask is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C =O) it disappears.Thereafter, mTB 8.32g (39.2mmol), NMP 117.2g, PMDA 6.54g (30.0mmol) and 6FDA are added 4.44g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained Polyimides-polyamic acid polymer weight average molecular weight (Mw) is 82,000.By the evaluation knot for the film being had cured with 350 DEG C Fruit is shown in table 2.
[embodiment 48]
4,4 '-diaminos are put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere Base benzanilide (DABA) 2.23g (9.8mmol), NMP 16.14g and toluene 50g, dissolve DABA under stiring.Thereto It adds H-PMDA 2.24g (10.0mmol), after flowing back 2 hours at 180 DEG C, expends first of the removal in 3 hours as azeotropic solvent Benzene.The content of flask is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) It disappears.Thereafter, DABA 8.91g (39.2mmol), NMP 121.4g, PMDA 6.54g (30.0mmol) and 6FDA4.44g are added (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyamides is sub- Amine-polyamic acid polymer weight average molecular weight (Mw) is 83,000.The evaluation result for the film being had cured with 350 DEG C is shown in Table 2.
[embodiment 49]
4- aminobenzene is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere Base -4-aminobenzoic acid ester (APAB) 2.24g (9.8mmol), NMP 16.14g and toluene 50g, dissolves APAB under stiring.To H-PMDA2.24g (10.0mmol) wherein is added, after flowing back 2 hours at 180 DEG C, expends removal in 3 hours as azeotropic solvent Toluene.The content of flask is cooled to 40 DEG C, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C =O) it disappears.Thereafter, APAB 8.95g (39.2mmol), NMP 121.6g, PMDA 6.54g (30.0mmol) and 6FDA are added 4.44g (10.0mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained Polyimides-polyamic acid polymer weight average molecular weight (Mw) is 82,000.By the evaluation knot for the film being had cured with 350 DEG C Fruit is shown in table 2.
[embodiment 50]
Into the polyimides-polyamic acid polymer varnish obtained using embodiment 9, dissolution is relative to 100 weight of resin Amount part is scaled the alkoxysilane compound containing trialkylsilyl group in molecular structure 1 (ROSi1) of 0.5 parts by weight, is filtered with 0.1 μm of filter, to make Standby resin combination.The characteristic of the composition and its cured film is measured according to aforementioned evaluation method.Acquired results are shown in table 2.
[embodiment 51]
Into the polyimides-polyamic acid polymer varnish obtained using embodiment 19, dissolution is relative to resin 100 Parts by weight are scaled the alkoxysilane compound containing trialkylsilyl group in molecular structure 1 of 0.5 parts by weight, are filtered with 0.1 μm of filter, to prepare resin Composition.The characteristic of the composition and its cured film is measured according to aforementioned evaluation method.Acquired results are shown in table 2.
[embodiment 52]
Into the polyimides-polyamic acid polymer varnish obtained using embodiment 9, dissolution is relative to 100 weight of resin Amount part is scaled the surfactant 1 (Surf1) of 0.05 parts by weight, is filtered with 0.1 μm of filter, to prepare resin Composition.The characteristic of the composition and its cured film is measured according to aforementioned evaluation method.Acquired results are shown in table 2.
[embodiment 53]
Into the polyimides-polyamic acid polymer varnish obtained using embodiment 19, dissolution is relative to resin 100 Parts by weight are scaled the surfactant 1 of 0.05 parts by weight, are filtered with 0.1 μm of filter, to prepare resin combination Object.The characteristic of the composition and its cured film is measured according to aforementioned evaluation method.Acquired results are shown in table 2.
[comparative example 1]
Feeding intake for raw material is changed to TFMB 14.39g (44.9mmol), NMP 163.23g, PMDA10.0g (45.8mmol), ODPA 0g (0mmol) and CBDA 0g (0mmol) are in addition to this obtained clear with the equally operation of reference example 1 Paint.The weight average molecular weight (Mw) of polyamic acid in gained varnish is 47,000.By CTE, YI of the film being had cured with 350 DEG C Value and elongation are shown in table 2 below.
[comparative example 2]
By raw material feed intake be changed to TFMB 10.12g (31.6mmol), NMP 134.65g, PMDA0g (0mmol), ODPA10.0g (32.2mmol) and CBDA0g (0mmol) in addition to this obtains varnish with the equally operation of reference example 1.Gained The weight average molecular weight (Mw) of polyamic acid in varnish is 65,500.By CTE, YI value for the film being had cured with 350 DEG C and stretch Long rate is shown in table 2 below.
[comparative example 3]
By raw material feed intake be changed to TFMB 16.00g (50.0mmol), NMP 174.00g, PMDA0g (0mmol), ODPA0g (0mmol) and CBDA 10.00g (51.0mmol) in addition to this obtains varnish with the equally operation of reference example 1.Institute The weight average molecular weight (Mw) for obtaining the polyamic acid in varnish is 221,000.By CTE, YI value for the film being had cured with 330 DEG C and Elongation is shown in table 2 below.
[comparative example 4]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 14.00g (43.7mmol), NMP 160.62g and toluene 50g, dissolve TFMB under stiring.H-PMDA is added thereto 10.00g (44.6mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.Thereafter, will The content of flask is cooled to room temperature, to obtain the varnish of polyimides.The Weight-average molecular of polyimides in gained varnish Measuring (Mw) is 50,600.CTE, YI value and elongation of the film being had cured with 350 DEG C are shown in table 2 below.
[comparative example 5]
Feeding intake for raw material is changed to TFMB 8.79g (27.4mmol), NMP 60.6g, PMDA 5.50g (25.2mmol) Varnish in addition to this is obtained with the equally operation of reference example 1 with ODPA 0.87g (2.8mmol).By what is contained in gained varnish The weight average molecular weight (Mw) of polymer is 47,000.CTE, YI value and breaking strength of the film being had cured with 350 DEG C are shown in Table 2 below.
[comparative example 6]
Feeding intake for raw material is changed to TFMB 16.44g (51.3mmol), NMP 184.18g, PMDA8.00g (36.7mmol), ODPA 0g (0mmol) and CBDA 3.08g (15.7mmol), in addition to this, with reference example 1 equally operation and Obtain varnish.It is 121,900 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.By what is had cured with 330 DEG C CTE, YI value and breaking strength of film are shown in table 2 below.
[comparative example 7]
By raw material feed intake be changed to TFMB 14.17g (44.2mmol), NMP 171.31g, PMDA 0g (0mmol), ODPA 7.00g (22.6mmol) and CBDA 4.43g (22.6mmol) is in addition to this obtained clear with the equally operation of reference example 1 Paint.The weight average molecular weight (Mw) of gained varnish is 105,000.CTE, YI value for the film being had cured with 330 DEG C and fracture is strong Degree is shown in table 2 below.
[comparative example 8]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, TFMB 12.55g (39.2mmol), NMP 186.91g and ODPA 12.41g (40.0mmol) are added, It is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 66,700.By CTE, YI value and elongation of the film being had cured with 350 DEG C be shown in Under table 2.
[comparative example 9]
Feeding intake for raw material is changed to TFMB 15.69g (49.0mmol), NMP 175.05g, PMDA6.54g (30.0mmol), ODPA0g (0mmol) and CBDA3.92g (20.0mmol) are in addition to this equally operated with reference example 1 and are obtained To varnish.It is 91,200 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.The film that will be had cured with 330 DEG C CTE, YI value and breaking strength be shown in table 2 below.
[comparative example 10]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 2.24g is added thereto (10.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, TFMB 12.55g (39.2mmol), NMP 162.26g and PMDA8.72g (40.0mmol) are added, with 80 DEG C are stirred 4 hours, to obtain polyimides-polyamic acid polymeric compositions varnish.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymeric compositions is 226,000.CTE, YI value and elongation of the film being had cured with 350 DEG C are shown In table 2 below.
[comparative example 11]
By raw material feed intake be changed to TFMB 15.69g (49.0mmol), NMP 193.54g, PMDA 0g (0mmol), ODPA 9.31g (30.0mmol) and CBDA 3.92g (20.0mmol) is in addition to this obtained clear with the equally operation of reference example 1 Paint.It is 125,100 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.By the film being had cured with 330 DEG C CTE, YI value and breaking strength are shown in table 2 below.
[comparative example 12]
By raw material feed intake be changed to TFMB 15.69g (49.0mmol), NMP 178.27g, PMDA 0g (0mmol), ODPA 3.10g (10.0mmol) and CBDA 7.84g (40.0mmol) is in addition to this obtained clear with the equally operation of reference example 1 Paint.It is 120,900 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.By the film being had cured with 330 DEG C CTE, YI value and breaking strength are shown in table 2 below.
[comparative example 13]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 12.55g (39.2mmol), NMP 64.56g and toluene 50g, dissolve TFMB under stiring.H-PMDA 8.97g is added thereto (40.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask After object is cooled to 40 DEG C, TFMB3.14g (9.8mmol), NMP 46.48g and ODPA 3.1g (10.0mmol) are added, at 80 DEG C Lower stirring 4 hours, to obtain polyimides-polyamic acid polymer varnish.Gained polyimides-polyamic acid polymer Weight average molecular weight (Mw) be 49,800.CTE, YI value and elongation of the film being had cured with 350 DEG C are shown in table below 2。
[comparative example 14]
By raw material feed intake be changed to TFMB 7.06g (22.0mmol), NMP 96.67g, PMDA 0g (0mmol) and 6FDA 10.00g (22.5mmol) in addition to this obtains varnish with the equally operation of reference example 1.Polyamide in gained varnish The weight average molecular weight (Mw) of acid is 110,000.CTE, YI value and elongation of the film being had cured with 350 DEG C are shown in below Table 2.
[comparative example 15]
In a nitrogen atmosphere, TFMB 15.69g (49.00mmol) and NMP are added into the separable flask of 500ml 203.4g dissolves TFMB under stiring.Then, BPDA 14.71g (50.0mmol) is added, is stirred 4 hours at 80 DEG C, thus Obtain the nmp solution (varnish) of polyamic acid.The weight average molecular weight (Mw) of gained polyamic acid is 49,000.It will be solid with 330 DEG C The film changed evaluation result is shown in table 2.
[comparative example 16]
In a nitrogen atmosphere, TFMB 15.69g (49.00mmol) and NMP are added into the separable flask of 500ml 258.4g dissolves TFMB under stiring.Then, TAHQ 22.92g (50.0mmol) is added, is stirred 4 hours at 80 DEG C, thus Obtain the nmp solution (varnish) of polyamic acid.The weight average molecular weight (Mw) of gained polyamic acid is 64,000.It will be solid with 330 DEG C The film changed evaluation result is shown in table 2.
[comparative example 17]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 15.69g (49.0mmol), NMP 175.3g and toluene 50g, dissolve TFMB under stiring.CPDA 10.51g is added thereto (100.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, to obtain the varnish of polyimides.The weight average molecular weight of polyimides in gained varnish It (Mw) is 51,600.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[comparative example 18]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 15.69g (49.0mmol), NMP 175.3g and toluene 50g, dissolve TFMB under stiring.H-BPDA 15.32g is added thereto (100.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, to obtain the varnish of polyimides.The weight average molecular weight of polyimides in gained varnish It (Mw) is 54,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[comparative example 19]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 15.69g (49.0mmol), NMP 175.3g and toluene 50g, dissolve TFMB under stiring.BCDA 11.82g is added thereto (100.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, to obtain the varnish of polyimides.The weight average molecular weight of polyimides in gained varnish It (Mw) is 50,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[comparative example 20]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 15.69g (49.0mmol), NMP 175.3g and toluene 50g, dissolve TFMB under stiring.BOTDA 12.41g is added thereto (100.0mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, to obtain the varnish of polyimides.The weight average molecular weight of polyimides in gained varnish It (Mw) is 54,000.By the film being had cured with 350 DEG C evaluation result is shown in table 2.
[comparative example 21]
TFMB is put into the separable flask for being equipped with Dien Stark apparatus and return channel in a nitrogen atmosphere 3.14g (9.8mmol), NMP 16.14g and toluene 50g, dissolve TFMB under stiring.H-PMDA 0.16g is added thereto (0.7mmol) after flowing back 2 hours at 180 DEG C, expends toluene of the removal in 3 hours as azeotropic solvent.By the content of flask 40 DEG C are cooled to, derives from the 1,650cm of amido bond using IR confirmation-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 147g, PMDA 6.54g (30.0mmol), 6FDA 4.44g (10.0mmol) and H-PMDA 2.08g (9.3mmol) is stirred 4 hours at 80 DEG C, to obtain polyimides-polyamic acid polymer varnish.Gained is poly- Acid imide-polyamic acid polymer weight average molecular weight (Mw) is 51,000.By the evaluation result for the film being had cured with 350 DEG C It is shown in table 2.
[comparative example 22]
According to method described in Korean Patent Publication No. 10-2013-0077946, the preparation of varnish is carried out.
In a nitrogen atmosphere, it is separated to 1,000ml and adds dimethyl acetamide (DMAc) 270ml in flask, in room temperature Under be completely dissolved TFMB 32.02g (100.0mmol).Then, 6FDA 111.1g (25.0mmol), PMDA are successively added 109.1g (50.0mmol) and H-PMDA56.04g (25.0mmol), is stirred at room temperature 12 hours.Thereafter, 120 DEG C are utilized Oil bath heating after twenty minutes, stirs 12 hours, to obtain polyamic acid solution (varnish) at normal temperature.Gained polyamic acid Weight average molecular weight (Mw) is 32,000.
Using above-mentioned varnish, expend 8 hours from 80 DEG C be heated to 250 DEG C after, Slow cooling and obtain Kapton, By it evaluation result is shown in table 2.
[comparative example 23]
According to method described in Korean Patent Publication No. 10-2013-0077946, the preparation of varnish is carried out.
Feeding intake for raw material is changed to 6FDA88.85g (20.0mmol), PMDA87.25g (40.0mmol) and H- PMDA89.67g (40.0mmol) is in addition to this carried out similarly operation with comparative example 22.By commenting for gained Kapton Valence result is shown in table 2.
[comparative example 24]
According to method described in Korean Patent Publication No. 10-2013-0077946, the preparation of varnish is carried out.
Feeding intake for raw material is changed to 6FDA 177.7g (40.0mmol), PMDA 87.25g (40.0mmol) and H-PMDA 44.83g (20.0mmol) is in addition to this carried out similarly operation with comparative example 22.By the evaluation knot of gained Kapton Fruit is shown in table 2.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
The abbreviation of ingredient described in table 1 is respectively following meaning.
[aromatic tetracarboxylic dianhydride 1]
PMDA: benzenetetracarboxylic dianhydride
BPDA:3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides
[aromatic tetracarboxylic dianhydride 2]
The double O-phthalic acid dianhydrides of ODPA:4,4 '-oxo
6FDA:4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides
TAHQ:4,4 '-xenyl is bis- (trihemellitic acid monoester anhydride)
[ester ring type tetracarboxylic dianhydride]
CBDA:1,2,3,4- cyclobutane tetracarboxylic dianhydride
H-PMDA:1,2,4,5- cyclopentanetetracarboxylic's dianhydride
CPDA:1,2,3,4- pentamethylene tetracarboxylic dianhydride
H-BPDA:1,2,4,5- bis cyclohexane tetracarboxylic dianhydride
BCDA: bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride
BOTDA: bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride
[diamines]
Bis- (trifluoromethyl) benzidine of TFMB:2,2 '-
MTB:2,2 '-dimethyl diphenyl base -4,4 '-diamines
DABA:4,4 '-diaminobenzene anilid
APAB:4- aminophenyl -4-aminobenzoic acid ester
[other additives]
ROSi1: the compound of alkoxysilane compound containing trialkylsilyl group in molecular structure 1, following structural formula
Surf1: surfactant 1, organic silicon type nonionic surfactant DBE224 (trade name, Gelest corporation)
It is as shown in the table like that, for comprising having the structure from ester ring type tetracarboxylic dianhydride, deriving from aforementioned fragrance The structure of race tetracarboxylic dianhydride 1 and whole polyimide precursors in the structure of aforementioned fragrance race tetracarboxylic dianhydride 2 Resin combination (varnish), it is thus identified that
Rate of change in viscosity when (0) 4 week room temperature preservation be 10% hereinafter,
The film physical property of Kapton obtained from aforementioned composition is solidified while meeting following condition:
(1) CTE is 25ppm or less
(2) YI value is 10 or less
(3) elongation is 15% or more,
It is formed with the laminated body of inoranic membrane on aforementioned Kapton while meeting:
(4) Haze is 15 or less
(5) moisture-vapor transmission is 0.1g/ (m2For 24 hours) below.
In addition, being confirmed according to the evaluation result of comparative example 1~4,14 and 15~20: having used only has from a kind The Kapton of the polyimide precursor of the structure of tetracarboxylic dianhydride can not meet the whole in above-mentioned (0)~(5) simultaneously Film physical property；
It is confirmed according to the evaluation result of comparative example 5~13: being respectively derived from 2 kinds of tetrabasic carboxylic acids two even with having The Kapton of the polyimide precursor of 2 kinds of structures of acid anhydride is not yet assigned for whole film physical property in above-mentioned (0)~(5) Give sufficient performance.
In turn, it is confirmed according to the evaluation result of comparative example 21~25: being respectively derived from aforementioned 3 kinds even with having The Kapton of the polyimide precursor of 3 kinds of structures of tetracarboxylic dianhydride derives from alicyclic ring in the polyimide precursor In the case that the acid imide rate of the amido bond of formula tetracarboxylic dianhydride is in outside 10~100% ranges, for above-mentioned (0)~(5) In whole film physical property, not yet assign sufficient performance.
It is confirmed according to result as above: as long as there is the knot from ester ring type tetracarboxylic dianhydride in polyimide precursor Structure, from the structure of aforementioned fragrance race tetracarboxylic dianhydride 1 and complete in the structure of aforementioned fragrance race tetracarboxylic dianhydride 2 Portion's structure, and from ester ring type tetracarboxylic dianhydride amido bond acid imide rate be 10~100% ranges in the case where, packet The excellent storage stability of composition containing the polyimide precursor, Kapton obtained from the composition is solidified are Colorless and transparent and linear expansion coefficient is low and then elongation is excellent, and the laminated body of inoranic membrane is formed on the Kapton Haze is small, moisture-vapor transmission is excellent.
Industrial availability
Polyimide precursor of the invention can for example be suitably employed in manufacture semiconducting insulation film, TFT-LCD insulating film, electricity Pole protective film, flexible display, particularly suitablely for manufacturing substrate.

Claims (30)

1. a kind of polyimide precursor, which is characterized in that its with structure shown in the following general formula (A), also,
As the structure for deriving from diamines, have from selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-two In methyl biphenyl -4,4 '-diamines, 4,4 '-diaminobenzene anilids and 4- aminophenyl -4-aminobenzoic acid ester at least A kind of structure of diamines；
As derive from tetracarboxylic dianhydride structure, have from selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydrides (CBDA), 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane four Carboxylic acid dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, alkene -2,3,5 bicyclic [2.2.2] octyl- 7-, 6- tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro - 2,5- dioxa -3- furyl)-naphtho- [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetrabasic carboxylic acid The structure of at least one of dianhydride ester ring type tetracarboxylic dianhydride and structure from aromatic tetracarboxylic dianhydride, also,
Acid imide rate from the amido bond of the ester ring type tetracarboxylic dianhydride is 10~100%,
X1For from be selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl bases -4,4 '-diamines, 4, The structure of at least one of 4 '-diaminobenzene anilids and 4- aminophenyl -4-aminobenzoic acid ester diamines；
X2For from selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- cyclopentanetetracarboxylic's dianhydride (H- PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2, 3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, 2,3,5- tricarboxylic basic ring Amyl acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- furyl)-naphtho- [1, 2-C] at least one of furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride tetracarboxylic dianhydride Structure.
2. polyimide precursor according to claim 1, wherein the polyimide precursor is with the following general formula (B) Structure:
X1It is identical as the definition in the formula (A),
X3For from the structure of the aromatic tetracarboxylic dianhydride.
3. polyimide precursor according to claim 1 or 2, wherein from the amido bond of ester ring type tetracarboxylic dianhydride Acid imide rate be 20~100%.
4. polyimide precursor described in any one of claim 1 to 3, wherein derive from ester ring type tetracarboxylic dianhydride Amido bond acid imide rate be 30~100%.
5. polyimide precursor described in any one of claim 1 to 3, wherein the aromatic tetracarboxylic dianhydride packet It is bis- (trihemellitic acid monoester anhydride) containing 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides or 4,4 '-xenyls.
6. polyimide precursor described in any one of claim 1 to 3, wherein the aromatic tetracarboxylic dianhydride packet Containing 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides.
7. polyimide precursor described in any one of claim 1 to 3, wherein the aromatic tetracarboxylic dianhydride packet It is bis- (trihemellitic acid monoester anhydride) containing 4,4 '-xenyls.
8. polyimide precursor according to any one of claims 1 to 7, wherein the aromatic tetracarboxylic dianhydride packet Contain:
Benzenetetracarboxylic dianhydride (PMDA) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides are selected from as aromatic tetracarboxylic dianhydride 1 At least one of；And
As aromatic tetracarboxylic dianhydride 2 selected from 4,4 '-oxos double O-phthalic acid dianhydrides (ODPA), 4,4 '-(hexafluoro isopropyls Pitch base) at least one of double phthalic anhydrides (6FDA) and 4,4 '-xenyls bis- (trihemellitic acid monoester anhydrides).
9. polyimide precursor described according to claim 1~any one of 8, wherein the aromatic tetracarboxylic dianhydride 1 is Benzenetetracarboxylic dianhydride (PMDA).
10. polyimide precursor described according to claim 1~any one of 8, wherein the aromatic tetracarboxylic dianhydride 2 For selected from the double O-phthalic acid dianhydrides (ODPA) of 4,4 '-oxos and 4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides At least one of (6FDA).
11. polyimide precursor described according to claim 1~any one of 10, wherein the structure from diamines For from the structure of 2,2 '-bis- (trifluoromethyl) benzidine (TFMB).
12. polyimide precursor described according to claim 1~any one of 11, wherein the ester ring type tetracarboxylic dianhydride For selected from 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA), 1,2,3, 4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid At least one of 2,3:5,6- dianhydride and bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride.
13. polyimide precursor described according to claim 1~any one of 12, wherein the ester ring type tetracarboxylic dianhydride For in 1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA) and 1,2,4,5- cyclopentanetetracarboxylic dianhydride (H-PMDA) extremely Few one.
14. polyimide precursor described according to claim 1~any one of 13, wherein all from the structure of diamines In include 60 moles of % or more the structure from the TFMB,
All amounted in the structure of tetracarboxylic dianhydride comprising 60 moles of % or more from selected from PMDA, ODPA, The structure of at least one of 6FDA, the CBDA and H-PMDA tetracarboxylic dianhydride.
15. polyimide precursor described according to claim 1~any one of 14, wherein all from tetracarboxylic dianhydride Structure in include 1~70 mole of % the structure from PMDA, and
It all include deriving from ODPA and 6FDA at least for 1~50 mole of % in the structure of tetracarboxylic dianhydride A kind of structure of tetracarboxylic dianhydride.
16. polyimide precursor described according to claim 1~any one of 14, wherein from PMDA, ODPA, 6FDA, The sum of molal quantity of each structure of the CBDA and H-PMDA and the ratio between the molal quantity of structure for deriving from the TFMB PMDA+ODPA+6FDA+CBDA+H-PMDA) and/TFMB } it is 100/99.9~100/95.
17. polyimide precursor described according to claim 1~any one of 16, wherein be dissolved in solvent and in supporting mass Unfolded surface after, as under nitrogen atmosphere heating carry out imidizate obtained from Kapton yellow chromaticity be 10 Below, linear expansion coefficient is 25ppm or less and film elongation rate when film thickness is 20 μm is 15% or more.
18. polyimide precursor described according to claim 1~any one of 17 is used to manufacture flexible device.
19. a kind of resin combination, which is characterized in that before it contains polyimides described in any one of claim 1~18 Body and solvent.
20. resin combination according to claim 19, also contains alkoxysilane compound containing trialkylsilyl group in molecular structure.
21. resin combination described in 9 or 20 according to claim 1, also contains surfactant.
22. a kind of Kapton, which is characterized in that it is by resin combination described in any one of claim 19~21 Object is unfolded on the surface of supporting mass and forms film, then heats the supporting mass and the film and by the polyimides Precursor carries out imidizate to be formed.
23. a kind of manufacturing method of Kapton, which is characterized in that it is comprised the following steps:
Resin combination described in any one of claim 19~21 is unfolded on the surface of supporting mass, to form film Film formation process；
It heats the supporting mass and the film and the polyimide precursor is subjected to imidizate, to form polyimides The heating process of film；And
The Kapton is removed from the supporting mass, to obtain the stripping process of Kapton.
24. a kind of laminated body, which is characterized in that its polyimide film for having supporting mass and being formed on the supporting mass, and
The laminated body obtains as follows: by resin combination described in any one of claim 19~21 in the supporting mass It is unfolded on surface and forms film, then heats the supporting mass and the film and the polyimide precursor is subjected to acyl Asia Amination is formed obtained from polyimide film.
25. a kind of manufacturing method of laminated body, the polyimides that the laminated body has supporting mass and is formed on the supporting mass Film, this method comprise the following steps:
Resin combination described in any one of claim 19~21 is unfolded on the surface of supporting mass, to form film Film formation process；And
It heats the supporting mass and the film and the polyimide precursor is subjected to imidizate, to form polyimides The heating process of film.
26. a kind of Kapton, which is characterized in that it is the polyamides Asia manufactured by diamines and the copolymer of tetracarboxylic dianhydride Amine film,
The diamines be selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl bases -4,4 '-diamines, At least one of 4,4 '-diaminobenzene anilids and 4- aminophenyl -4-aminobenzoic acid ester,
The tetracarboxylic dianhydride includes:
1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA), 1,2,4,5- hexamethylene four are selected from as ester ring type tetracarboxylic dianhydride It is carboxylic acid dianhydride (H-PMDA), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- bis cyclohexane tetracarboxylic dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetrabasic carboxylic acid 2,3:5,6- dianhydride, bicyclic [2.2.2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid -1,4:2,3- dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxa -3- Furyl) in-naphtho- [1,2-C] furans -1,3- diketone and bicyclic [3,3,0] octane -2,4,6,8- tetracarboxylic dianhydride at least One；
Benzenetetracarboxylic dianhydride (PMDA) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides are selected from as aromatic tetracarboxylic dianhydride 1 At least one of；And
As aromatic tetracarboxylic dianhydride 2 selected from 4,4 '-oxos double O-phthalic acid dianhydrides (ODPA), 4,4 '-(hexafluoro isopropyls Pitch base) double phthalic anhydrides (6FDA) and 4, at least one of 4 '-xenyls bis- (trihemellitic acid monoester anhydrides),
Using CVD method with 350 DEG C on the Kapton formed inoranic membrane when, using atomic force microscope (AFM) to this The surface roughness of inoranic membrane surface measurements is 0.01~50nm.
27. Kapton according to claim 26, wherein the diamines is 2,2 '-bis- (trifluoromethyl) biphenyl Amine (TFMB),
The tetracarboxylic dianhydride includes:
1,2,3,4- cyclobutane tetracarboxylic dianhydride (CBDA) and 1,2,4,5- hexamethylene are selected from as ester ring type tetracarboxylic dianhydride At least one of tetracarboxylic dianhydride (H-PMDA)；
Benzenetetracarboxylic dianhydride (PMDA) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides are selected from as aromatic tetracarboxylic dianhydride 1 At least one of；And
As aromatic tetracarboxylic dianhydride 2 is selected from the double O-phthalic acid dianhydrides (ODPA) of 4,4 '-oxos and 4,4 '-(hexafluoro is different At least one of propylidene base) double phthalic anhydrides (6FDA).
28. a kind of flexible device, it includes the Kaptons described in claim 26 or 27.
29. a kind of manufacturing method of flexible device comprising the manufacturing method of Kapton described in claim 23.
30. a kind of manufacturing method of flexible device comprising the manufacturing method of laminated body described in claim 25.
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