CN105916910A - Polyimide precursor and resin composition containing same - Google Patents

Abstract

A polyimide precursor characterized by having a structure derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB) or the like as a diamine-derived structure and also having both a structure derived from a specific alicyclic tetracarboxylic acid dianhydride and a structure derived from an aromatic tetracarboxylic acid dianhydride as structures each derived from a tetracarboxylic acid dianhydride, wherein the degree of imidation of an amide bond derived from the alicyclic tetracarboxylic acid dianhydride is 10 to 100%.

Description

Polyimide precursor and containing its resin combination

Technical field

The present invention relates to polyimide precursor and the resin combination containing it.This polyimide precursor such as can be used as scratching Property substrate used by device.

The present invention also provides for Kapton and manufacture method thereof and duplexer and manufacture method thereof.

Background technology

Kapton is typically the thin film formed by polyimide resin.Polyimide resin is by aromatic series tetracarboxylic acid After acid dianhydride and aromatic diamine carry out polymerisation in solution and manufacture polyimide precursor, carry out hot-imide or chemistry acid imide The high heat stable resin changed and manufacture.Aforementioned hot-imide is dehydrated by the closed loop under high temperature and carries out, afore mentioned chemical acid imide Change is carried out by carrying out closed loop dehydration with catalyst.

Polyimide resin is insoluble and insoluble super heat-resistant resin, has heatproof oxidation performance, heat-resistant quality, radiation hardness Linearly, the excellent specific property of lower temperature resistance, chemical reagent resistance etc..Therefore, polyimide resin is such as in insulation coating agent, insulation Film, quasiconductor, TFT-LCD the wide spectrum including electronic material such as electrode protective membrane in use.It is additionally operable to liquid recently Display material, the optical fiber etc. such as brilliant alignment films.

But, polyimide resin is colored as brown or yellow because of its high aromatic rings density, it is seen that ray regions saturating Rate of penetrating is low, accordingly, it is difficult to for the field requiring the transparency.

About this point, patent documentation 1 reports: the tetracarboxylic dianhydride comprising ad hoc structure by use and diamidogen come The transparency manufacturing absorbance and form and aspect is improved and the polyimides of new structure.

It addition, patent documentation 2 and patent documentation 3 individually disclose is imported with the poly-of alicyclic structure to give the transparency Imide membrane.

And then, patent documentation 4 reports: as tetracarboxylic dianhydride, by being applied in combination specific aromatic tetracarboxylic acid Dianhydride and ester ring type tetracarboxylic dianhydride, it is possible to obtain the polyimide resin that yellow chromaticity (hereinafter also referred to " YI value ") is low.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2000-198843 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2005-336243 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2003-155342 publication

Patent documentation 4: Korean Patent Publication No. 10-2013-0077946

Summary of the invention

The problem that invention is to be solved

But, the mechanical property of the polyimides described in patent documentation 1 and thermal characteristics are insufficiently to serve as such as quasiconductor Dielectric film, TFT-LCD dielectric film, electrode protective membrane and flexible display substrate.

Especially, the polyimides described in patent documentation 1 is characterised by, linear expansion coefficient (is the most also denoted as " CTE ") high.Resin high for CTE is when being used as thin film, and the expansion of the thin film produced because of variations in temperature and shrinkage degree become Greatly.During it is thus possible, for instance use thin film high for CTE in TFT etc., the inorganic matter film as element material produces damage, leads Cause element capability reduces.Therefore, form the substrate of TFT, form the substrate of color filter, alignment films, the transparent base of flexible display The polyimide resin used in plate etc. is necessary for water white transparency and CTE is low.

Although it addition, the polyimides described in patent documentation 2 has the transparency, but there is CTE height and extension at break The shortcoming that rate is low.In the case of elongation at break is low, when processing flexible device, flexible substrate can produce damage, because of This is not used as device.

In the case of polyimides described in patent documentation 3, by using multi-ring aromatic diamine to give toughness. But, the CTE of this polyimides is the highest, therefore, is not suitable for use in semiconducting insulation film, TFT-LCD dielectric film, electrode protective membrane Or flexible display substrate.

Further, in the case of the polyimides described in patent documentation 4, YI value is the lowest.But, according to the present inventor etc. Research, owing to CTE is high, percentage elongation is little, for being applied to display processes, therefore also have the leeway of improvement (with reference to aftermentioned Comparative example 22～24).

The present invention is problem in view of the above description and carries out, and its object is to, it is provided that can manufacture water white transparency and The polyimide precursor of the Kapton that CTE is low and percentage elongation is excellent and containing its resin combination, polyimides Thin film and manufacture method thereof and duplexer and manufacture method thereof.

For solving the scheme of problem

The present inventor etc. conduct in-depth research retrial of laying equal stress on test to solve above-mentioned problem.It is found that as follows Opinion, and complete the present invention based on these opinions.

Comprise the excellent storage stability of the resin combination (varnish) of the polyimide precursor of ad hoc structure；

Kapton said composition solidification obtained has the transparency, low linear expansion coefficient and the height of excellence and stretches Long rate；And

The Haze of the duplexer being formed with inoranic membrane on this Kapton is little, moisture-vapor transmission is excellent.

That is, the present invention is as follows.

[1] a kind of polyimide precursor, it is characterised in that it has the structure shown in following formula (A), and,

As deriving from the structure of diamidogen, have derive from selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2, 2 '-dimethyl diphenyl base-4,4 '-diamidogen, in 4,4 '-diaminobenzene anilid and 4-aminophenyl-PABA ester The structure of at least one diamidogen；

As deriving from the structure of tetracarboxylic dianhydride, have and derive from selected from 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides (CBDA), 1,2,4,5-cyclopentanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 1,2,4,5-dicyclo Hexane tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [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- (tetrahydrochysene-2,5-dioxa-3-furyl)-naphtho-[1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8- The structure of at least one ester ring type tetracarboxylic dianhydride in tetracarboxylic dianhydride and derive from the knot of aromatic tetracarboxylic acid's dianhydride Structure, and,

The acid imide rate of the amido link deriving from aforementioned ester ring type tetracarboxylic dianhydride is 10～100%.

{X₁For deriving from selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl base-4,4 '- The structure of at least one diamidogen in diamidogen, 4,4 '-diaminobenzene anilid and 4-aminophenyl-PABA ester；

X₂For deriving from selected from 1,2,3,4-Tetramethylene. 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, dicyclo [2.2.1] heptane- 2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tri-carboxyl Cyclopenta acetic acid-1,4:2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-dioxa-3-furyl)-naphtho- At least one tetrabasic carboxylic acid two in [1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride The structure of acid anhydride.}

[2] according to the polyimide precursor described in [1], wherein, aforementioned polyimide precursor has the knot of following formula (B) Structure.

{X₁It is identical with the definition in previously described formula (A),

X₃For deriving from the structure of aforementioned fragrance race tetracarboxylic dianhydride.}

[3] according to the polyimide precursor described in [1] or [2], wherein, the amido link of ester ring type tetracarboxylic dianhydride is derived from Acid imide rate be 20～100%.

[4] according to the polyimide precursor according to any one of [1]～[3], wherein, ester ring type tetracarboxylic dianhydride is derived from The acid imide rate of amido link be 30～100%.

[5] according to the polyimide precursor according to any one of [1]～[4], wherein, aforementioned fragrance race tetracarboxylic dianhydride wraps Contain:

As aromatic tetracarboxylic acid's dianhydride 1 selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acid At least one in dianhydride；And

As aromatic tetracarboxylic acid's dianhydride 2 selected from 4,4 '-oxo double O-phthalic acid dianhydride (ODPA), 4,4 '-(hexafluoro Isopropylidene) at least one in double phthalic anhydrides (6FDA) and 4,4 '-xenyl double (trihemellitic acid monoester anhydride).

[6] according to the polyimide precursor according to any one of [1]～[5], wherein, aforementioned fragrance race tetracarboxylic dianhydride 1 For pyromellitic dianhydride (PMDA).

[7] according to the polyimide precursor according to any one of [1]～[5], wherein, aforementioned fragrance race tetracarboxylic dianhydride 2 For selected from the double O-phthalic acid dianhydride (ODPA) of 4,4 '-oxo and 4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides (6FDA) at least one in.

[8] according to the polyimide precursor according to any one of [1]～[7], wherein, foregoing sources in the structure of diamidogen is Derive from the structure of 2,2 '-bis-(trifluoromethyl) benzidine (TFMB).

[9] according to the polyimide precursor according to any one of [1]～[8], wherein, aforementioned ester ring type tetracarboxylic dianhydride is Selected from 1,2,3,4-Tetramethylene. 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, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2, At least one in 3:5,6-dianhydride and dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride.

[10] according to the polyimide precursor according to any one of [1]～[9], wherein, aforementioned ester ring type tetracarboxylic dianhydride For in 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclopentanetetracarboxylic's dianhydride (H-PMDA) extremely Few one.

[11] according to the polyimide precursor according to any one of [1]～[10], wherein, the structure of diamidogen is all derived from In comprise the structure deriving from aforementioned TFMB of 60 moles of more than %,

All derive from the structure of tetracarboxylic dianhydride amount to comprise 60 moles of more than % derive from selected from aforementioned PMDA, The structure of at least one tetracarboxylic dianhydride in aforementioned ODPA, aforementioned 6FDA, aforementioned CBDA and aforementioned H-PMDA.

[12] according to the polyimide precursor according to any one of [1]～[11], wherein, tetracarboxylic dianhydride is all derived from Structure in comprise the structure deriving from aforementioned PMDA of 1～70 mole of %, and

All derive from and the structure of tetracarboxylic dianhydride comprises the deriving from selected from aforementioned ODPA and 6FDA of 1～50 mole of % In the structure of at least one tetracarboxylic dianhydride.

[13] according to polyimide precursor according to any one of [1]～[11], wherein, aforementioned PMDA, aforementioned is derived from The molal quantity sum of each structure of ODPA, aforementioned 6FDA, aforementioned CBDA and aforementioned H-PMDA and the structure deriving from aforementioned TFMB Molal quantity ratio PMDA+ODPA+6FDA+CBDA+H-PMDA)/TFMB} is 100/99.9～100/95.

[14] according to the polyimide precursor according to any one of [1]～[13], wherein, it is dissolved in solvent and at supporting mass Unfolded surface after, carry out imidizate by the heating under nitrogen atmosphere and the yellow chromaticity of Kapton that obtains is 10 Below, linear expansion coefficient be below 25ppm and thickness be film elongation rate during 20 μm be more than 15%.

[15] according to the polyimide precursor according to any one of [1]～[14], it is used for manufacturing flexible device.

[16] a kind of resin combination, it is characterised in that before it contains the polyimides according to any one of [1]～[15] Body and solvent.

[17] according to the resin combination described in [16], it is possibly together with alkoxysilane compound containing trialkylsilyl group in molecular structure.

[18] according to the resin combination described in [16] or [17], it is possibly together with surfactant.

[19] a kind of Kapton, it is characterised in that it is by the resin group according to any one of [16]～[18] Compound launches on the surface of supporting mass and forms film, then heats aforementioned supporting mass and aforementioned film and aforementioned polyamides is sub- Amine precursor carries out imidizate thus is formed.

[20] manufacture method of a kind of Kapton, it is characterised in that it includes following operation:

Resin combination according to any one of [16]～[18] is launched on the surface of supporting mass, thus forms film Film formation process；

Heat aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is carried out imidizate, thus form polyamides The heating process of imines thin film；And

Aforementioned Kapton is peeled off from aforementioned supporting mass, thus obtains the stripping process of Kapton.

[21] a kind of duplexer, it is characterised in that it possesses supporting mass and the polyimide film being formed on this supporting mass, And

Described duplexer is obtained as below: by the resin combination according to any one of [16]～[18] at aforementioned supporting mass Launch on surface and form film, then heat aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is carried out acyl Asia Amination, forms polyimide film and obtains.

[22] manufacture method of a kind of duplexer, described duplexer possesses supporting mass and the polyamides being formed on this supporting mass Imines film, the method includes following operation:

Resin combination according to any one of [16]～[18] is launched on the surface of supporting mass, thus forms film Film formation process；And

Heat aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is carried out imidizate, thus form polyamides The heating process of imines thin film.

[23] a kind of aforementioned Kapton, it is characterised in that it is by the copolymer system of diamidogen Yu tetracarboxylic dianhydride The Kapton made,

Aforementioned diamidogen is selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl base-4,4 '-two Amine, 4, at least one in 4 '-diaminobenzene anilid and 4-aminophenyl-PABA ester,

Aforementioned tetracarboxylic dianhydride comprises:

As ester ring type tetracarboxylic dianhydride selected from 2,3,4-Tetramethylene. tetracarboxylic dianhydride (CBDA), 1,2,4,5-hexamethylene Tetracarboxylic dianhydride (H-PMDA), 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 1,2,4,5-bis cyclohexane tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [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-(tetrahydrochysene-2,5-dioxa-3- Furyl) in-naphtho-[1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride at least One；

As aromatic tetracarboxylic acid's dianhydride 1 selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acid At least one in dianhydride；And

As aromatic tetracarboxylic acid's dianhydride 2 selected from 4,4 '-oxo double O-phthalic acid dianhydride (ODPA), 4,4 '-(hexafluoro Isopropylidene) double phthalic anhydrides (6FDA) and 4, at least one in 4 '-xenyl double (trihemellitic acid monoester anhydride),

When using CVD to form inoranic membrane with 350 DEG C on this Kapton, use atomic force microscope (AFM) Surface roughness to this inoranic membrane surface measurements is 0.01～50nm.

[24] according to the Kapton described in [23], wherein, aforementioned diamidogen is 2,2 '-bis-(trifluoromethyl) benzidine (TFMB),

Aforementioned tetracarboxylic dianhydride comprises:

As ester ring type tetracarboxylic dianhydride selected from 2,3,4-Tetramethylene. tetracarboxylic dianhydride (CBDA) and 1,2,4,5-hexamethylene At least one in alkane tetracarboxylic dianhydride (H-PMDA)；

As aromatic tetracarboxylic acid's dianhydride 1 selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acid At least one in dianhydride；

As aromatic tetracarboxylic acid's dianhydride 2 selected from the double O-phthalic acid dianhydride (ODPA) and 4,4 '-(six of 4,4 '-oxo Fluorine isopropylidene) at least one in double phthalic anhydrides (6FDA).

[25] a kind of flexible device, it comprises the Kapton described in [23] or [24].

[26] manufacture method of a kind of flexible device, it includes the manufacture method of the Kapton described in [20].

[27] manufacture method of a kind of flexible device, it includes the manufacture method of the duplexer described in [22].

The effect of invention

Comprise the excellent storage stability of the resin combination (varnish) of the polyimide precursor of the present invention.It addition, by this The Kapton that compositions obtains is water white transparency, and linear expansion coefficient is low and percentage elongation is excellent.At this Kapton On be formed with inoranic membrane the Haze of duplexer little, moisture-vapor transmission is excellent.

Detailed description of the invention

Hereinafter, for an embodiment of the invention (hereinafter abbreviated as " embodiment ".) be described in detail.Need Illustrating, the present invention is not limited to following embodiment, can carry out various deformation and implement in the range of its purport.

<polyimide precursor>

The polyimide precursor of present embodiment is characterised by,

There is the structure shown in following formula (A), and

As deriving from the structure of diamidogen, have derive from selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2, 2 '-dimethyl diphenyl base-4,4 ' in-diamidogen and 4,4 '-diaminobenzene anilid, 4-aminophenyl-PABA ester The structure of at least one diamidogen；

As deriving from the structure of tetracarboxylic dianhydride,

Have and derive from selected from 1,2,3,4-Tetramethylene. 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, dicyclo [2.2.1] heptane- 2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tri-carboxyl Cyclopenta acetic acid-1,4:2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-dioxa-3-furyl)-naphtho- At least one ester ring type four in [1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride The structure of carboxylic acid dianhydride and derive from the structure of aromatic tetracarboxylic acid's dianhydride, and,

The acid imide rate of the amido link deriving from aforementioned ester ring type tetracarboxylic dianhydride is 10～100%.

{X₁For deriving from selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl base-4,4 '- The structure of at least one diamidogen in diamidogen, 4,4 '-diaminobenzene anilid and 4-aminophenyl-PABA ester；

X₂For deriving from selected from 1,2,3,4-Tetramethylene. 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, dicyclo [2.2.1] heptane- 2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tri-carboxyl Cyclopenta acetic acid-1,4:2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-dioxa-3-furyl)-naphtho- At least one tetrabasic carboxylic acid two in [1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride The structure of acid anhydride.}

The polyimide precursor of present embodiment preferably has the structure of following formula (B).

{X₁It is identical with previously described formula (A),

X₃For deriving from the structure of aforementioned fragrance race tetracarboxylic dianhydride.}

Further, the polyimide precursor of present embodiment is as it appears from the above, derive from the amido link of ester ring type tetracarboxylic dianhydride Acid imide rate be 10～100%.That is, at least some of amido link deriving from ester ring type tetracarboxylic dianhydride has carried out acyl Asia The imidizate polyamic acid of amination.

In order to present the imidizate making the amido link deriving from ester ring type tetracarboxylic dianhydride carry out imidizate and to obtain Polyamic acid structure, such as, can adopt with the following method:

First, carry out the reaction of ester ring type tetracarboxylic dianhydride and diamidogen and after obtaining polyamic acid or obtaining polyamide While acid, the amido link to this polyamic acid carries out imidizate,

Then, other tetracarboxylic dianhydride (for aromatic tetracarboxylic acid's dianhydride in the case of present embodiment) is persistently carried out with two The reaction of amine.

From viewpoint and the transparent viewpoint of raising gained Kapton of the molecular weight of increase polyimide precursor Set out, first make ester ring type tetracarboxylic dianhydride react.Further, derive from ester ring type tetracarboxylic dianhydride's to increase to have The molecular weight of the polyimides (precursor) of structure, needs to improve to 150～210 DEG C synthesis temperature from common 60～100 DEG C. Like this, by improving synthesis temperature, result derives from the imidizate of the amido link of ester ring type tetracarboxylic dianhydride, source Imide concentration (acid imide rate) in the part of ester ring type acid dianhydride becomes big.Herein, from comprising polyimide precursor From the viewpoint of the storage stability of compositions (varnish) and the percentage elongation of gained Kapton and YI, derive from fat The acid imide rate of the amido link of ring type tetracarboxylic dianhydride be preferably 10～100%, more preferably 20～100%, the most excellent Elect 30～100% as.

Like this, the reason first making ester ring type tetracarboxylic dianhydride react is, adds ester ring type tetrabasic carboxylic acid simultaneously Dianhydride and aromatic tetracarboxylic acid's dianhydride or add after adding aromatic tetracarboxylic acid's dianhydride ester ring type tetracarboxylic dianhydride and with When the temperature of 150～210 DEG C synthesizes, there is acid imide in the amido link of the part being derived from aromatic tetracarboxylic acid's dianhydride sharp Changing, polymer separates out, the most inapplicable.

The detailed synthetic method of the polyimide precursor in present embodiment sees below.

Hereinafter, it is described in detail for each structure.

<deriving from the structure of tetracarboxylic dianhydride>

In the polyimide precursor of present embodiment, as deriving from the structure of tetracarboxylic dianhydride,

Have and derive from selected from 1,2,3,4-Tetramethylene. 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, dicyclo [2.2.1] heptane- 2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tri-carboxyl Cyclopenta acetic acid-1,4:2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-dioxa-3-furyl)-naphtho- At least one tetrabasic carboxylic acid two in [1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride The structure of acid anhydride and derive from the structure of aromatic tetracarboxylic acid's dianhydride.

Herein, as aforementioned ester ring type tetracarboxylic dianhydride, it is preferably selected from 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides (CBDA), 1,2,4,5-cyclopentanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 1,2,4,5-dicyclo Hexane tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [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- (tetrahydrochysene-2,5-dioxa-3-furyl)-naphtho-[1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8- At least one in 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, dicyclo [2.2.1] heptane-2, 3,5,6-tetrabasic carboxylic acids 2,3:5,6-dianhydride and dicyclo [2.2.2] octyl-7-alkene-2, at least one in 3,5,6-tetracarboxylic dianhydrides, Further, from the viewpoint of cost and the YI of gained Kapton and the transparency, more preferably selected from CBDA and H-PMDA In at least one, from the viewpoint of cost, more preferably H-PMDA.

Aforementioned 1,2,4,5-cyclopentanetetracarboxylic's dianhydride (H-PMDA) can be following formula (1)～that (3) are shown respectively is different Any one in structure body, it is also possible to be to comprise the mixture of more than two kinds in these.

Aforementioned fragrance race tetracarboxylic dianhydride preferably comprises:

As aromatic tetracarboxylic acid's dianhydride 1 selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4,4 '-xenyl tetrabasic carboxylic acid At least one in dianhydride；And

As aromatic tetracarboxylic acid's dianhydride 2 selected from 4,4 '-oxo double O-phthalic acid dianhydride (ODPA), 4,4 '-(hexafluoro Isopropylidene) at least one in double phthalic anhydrides (6FDA) and 4,4 '-xenyl double (trihemellitic acid monoester anhydride).

Herein, aforementioned fragrance race tetracarboxylic dianhydride 1 is mainly used in improving the thermal characteristics of gained Kapton, machinery spy Property etc.,

Aforementioned fragrance race tetracarboxylic dianhydride 2 is for improving the transparency etc. of Kapton.

As aromatic tetracarboxylic acid's dianhydride 1, from the viewpoint of the CTE of gained Kapton, more preferably use PMDA。

As aromatic tetracarboxylic acid's dianhydride 2, from the viewpoint of the YI and the transparency of gained Kapton, more preferably Use at least one in ODPA and 6FDA, from the viewpoint of the CTE of Kapton, further preferably use 6FDA。

The polyimide precursor of present embodiment is preferably:

All derive from the structure of tetracarboxylic dianhydride has 5～60 moles of % derive from aforementioned ester ring type tetrabasic carboxylic acid two The structure of acid anhydride,

All derive from the structure of tetracarboxylic dianhydride has 40～95 moles of % derive from aromatic tetracarboxylic acid's dianhydride Structure；

It is even more preferred that

All derive from the structure of tetracarboxylic dianhydride has 5～60 moles of % derive from aforementioned ester ring type tetrabasic carboxylic acid two The structure of acid anhydride,

All derive from the structure of tetracarboxylic dianhydride has 20～80 moles of % derive from aforementioned fragrance race tetrabasic carboxylic acid The structure of dianhydride 1,

All derive from and the structure of tetracarboxylic dianhydride has 5～60 moles of % derive from aforementioned fragrance race tetracarboxylic dianhydride The structure of 2.

The polyimide precursor of present embodiment is it may further be preferable that all derive from the structure of tetracarboxylic dianhydride total Meter comprises the deriving from selected from aforementioned PMDA, aforementioned ODPA, aforementioned 6FDA, aforementioned CBDA and aforementioned H-PMDA of 60 moles of more than % In the structure of at least one tetracarboxylic dianhydride.

Further, from the viewpoint of applicable yellow chromaticity, CTE and the fracture strength obtaining Kapton,

It is particularly preferred that all derive from the structure of tetracarboxylic dianhydride has 1～70 mole of % to derive from benzene equal The structure of tetracarboxylic dianhydride (PMDA),

All derive from that to have deriving from selected from 4,4 '-oxo of 1～50 mole of % in the structure of tetracarboxylic dianhydride double adjacent The knot of at least one in phthalic acid dianhydride (ODPA) and 4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides (6FDA) Structure.

<deriving from the structure of diamidogen>

In the polyimide precursor of present embodiment, as deriving from the structure of diamidogen, have derive from selected from 2,2 '-bis- (trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl base-4,4 '-diamidogen, 4,4 '-diaminobenzene anilid and 4- The structure of at least one diamidogen in aminophenyl-PABA ester.Wherein, from the YI of gained Kapton with saturating From the viewpoint of bright property, preferably TFMB.

It is particularly preferred that all derive from the structure of diamidogen comprises 60 moles of more than % derive from aforementioned TFMB's Structure.

The ratio of the structure deriving from diamidogen<structure deriving from tetracarboxylic dianhydride with>

From the viewpoint of the transparency of Kapton, thermal characteristics and mechanical property, derive from above-mentioned tetrabasic carboxylic acid two The molal quantity sum of the structure of acid anhydride is preferably 100/99.9～100/ with the ratio of the molal quantity sum of the structure deriving from diamidogen 95.More specifically, from the viewpoint of obtaining the Kapton with the yellow chromaticity, CTE and the fracture strength that are more suitable for, Derive from PMDA, ODPA, 6FDA, CBDA and H-PMDA each structure molal quantity sum with derive from TFMB structure mole { (PMDA+ODPA+6FDA+CBDA+H-PMDA)/TFMB} is preferably 100/99.9～100/95 to the ratio of number.

<weight average molecular weight of polyimide precursor>

The weight average molecular weight of the polyimide precursor of present embodiment is preferably more than 5,000 and less than 1,000,000, more It is preferably more than 50,000 and less than 500,000, more preferably more than 70,000 and less than 250,000.By making weight average Molecular weight is 5, more than 000, and the intensity of gained Kapton, percentage elongation are improved, and mechanical properties is excellent.Especially from From the viewpoint of obtaining low CTE and low yellow chromaticity (YI value), molecular weight is more preferably 50, and more than 000.By making weight average molecular weight Mw is 1, less than 000,000, it is possible to the resin combination containing this polyimide precursor without oozing out is coated into desired film Thick.

Herein, weight average molecular weight refers to be worth as follows: as standard and utilizing gel infiltration color using monodisperse polystyrene In the molecular weight distribution that spectrum measures, the summation of the numerical value that the molecular weight of each molecule is multiplied by the quality of this molecule and obtains is again divided by entirely The summation of the quality of parton, thus obtained numerical value.

<synthetic method of polyimide precursor>

The polyimide precursor of present embodiment preferably can dissolve with diamine component by making above-mentioned tetracarboxylic dianhydride's composition In solvent and make it react, thus manufacture with the solution form containing polyimide precursor and solvent.Condition during reaction does not has Be particularly limited to, such as can exemplify reaction temperature be-20～250 DEG C, the response time be the condition of 2～48 hours.During reaction Surrounding atmosphere be preferably the inert atmosphere such as argon, nitrogen.

As long as the solvent that aforementioned solvents dissolves the polymer generated just is not particularly limited.Molten as known reaction Agent, is selected from metacresol, METHYLPYRROLIDONE (NMP), dimethylformamide (DMF), dimethyl acetylamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethacetic acid ester, エ Network ア ミ De M100 (trade name: go out light emerging product strain formula meeting Society's system) and エ Network ア ミ De B100 (trade name: Idemitsu Kosen Co., Ltd.'s system) in more than one polar solvents be useful. Wherein, be preferably selected from NMP, DMAc, エ Network ア ミ De M100 and エ Network ア ミ De B100 more than one.In addition, also Can substitute for above-mentioned solvent or with above-mentioned solvent use simultaneously oxolane (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 The imidizate polyamic acid that amine key obtains through closed loop dehydration.

As amido link being carried out the operation of closed loop dehydration, being not particularly limited, known method can be applied.Such as, Hot-imide or chemical imidization can be used.

Hot-imide the most such as can be adopted with the following method.First, make two amine solvents and/or be scattered in suitable When polymer solvent in, be added to tetracarboxylic dianhydride, add the solvent (such as toluene etc.) of azeotrope with water.Then, use Mechanical agitator, removes heated and stirred 0.5 hour～96 hours, preferred heated and stirred 0.5 on one side by the water azeotropic of by-product Hour～30 hours.Heating-up temperature preferably greater than 100 DEG C and be less than 250 DEG C, preferably 130～230 DEG C, more preferably 150 ～210 DEG C.Now, monomer concentration is preferably set to more than below more than 0.5 mass % and 95 mass %, more preferably 1 mass % And 90 below mass %.

Chemical imidization can use known imidization catalyst to carry out.As imidization catalyst, do not have It is particularly limited to, include, for example out:

The anhydride of acetic anhydride etc；

Lactonizing of gamma-valerolactone, gamma-butyrolacton, γ-tetronic acid, γ-Phthalide, γ-coumarin, γ-Phthalide acid etc Compound；

The tertiary amine etc. of pyridine, quinoline, N-methylmorpholine, triethylamine etc.

Imidization catalyst can only use a kind as required, or can also be mixture of more than two kinds.Wherein, Especially from the viewpoint of reactivity height, particularly preferably gamma-valerolactone and the mixed system of pyridine.

As the addition of imidization catalyst, relative to polyamic acid 100 mass parts, preferably 50 mass parts with Under, below more preferably 30 mass parts.

From controlling the impact of subsequent reactions to minimum, the closed loop dehydration of amido link is particularly preferably taked Without the hot-imide carried out under catalyst.

The polyimide precursor of present embodiment most preferably profit synthesizes with the following method:

First, under conditions of above-mentioned hot-imide, carry out the reaction of ester ring type tetracarboxylic dianhydride and diamidogen, obtain through The polyamic acid of imidizate,

Then, add and add aromatic tetracarboxylic acid's dianhydride and diamidogen, below 100 DEG C, preferably continue reaction.

Operate as above, it is possible to obtain the solution containing polyimide precursor.

Can by this solution directly for the preparation of resin combination, or

After the polyimide precursor separation and purification that can also will contain in this solution, then the preparation for resin combination.

<other additive>

The resin combination of present embodiment contains polyimide precursor as described above and solvent, the most all right Containing other additive.

As other additive this, include, for example out alkoxysilane compound containing trialkylsilyl group in molecular structure, surfactant, levelling agent etc..

(alkoxysilane compound containing trialkylsilyl group in molecular structure)

When the polyimides obtained by the resin combination of present embodiment forms the elements such as TFT, in order to make itself and supporting Keeping sufficient adaptation between body, resin combination can be containing 0.001～2 relative to polyimide precursor 100 mass % The alkoxysilane compound containing trialkylsilyl group in molecular structure of quality %.

By make alkoxysilane compound containing trialkylsilyl group in molecular structure relative to the content of polyimide precursor 100 mass % be 0.01 mass % with On, it can obtain good adaptation with supporting mass.It addition, from the viewpoint of the storage stability of resin combination, alkane The content of TMOS compound is preferably below 2 mass %.Before the content of alkoxysilane compound containing trialkylsilyl group in molecular structure is relative to polyimides Body is more preferably 0.02～2 mass %, more preferably 0.05～1 mass %, more preferably 0.05～0.5 matter Amount %, particularly preferably 0.1～0.5 mass %.

As alkoxysilane compound containing trialkylsilyl group in molecular structure, include, for example out 3-mercaptopropyi trimethoxy silane (SHIN-ETSU HANTOTAI's chemical industry Co., Ltd.'s system, trade name KBM803；CHISSO CORPORATION system, trade name サ イ ラ エ ス S810), 3-sulfydryl third Ethyl triethoxy silicane alkane (AZMAX Corp., system, trade name SIM6475.0), 3-mercaptopropyi methyl dimethoxysilane (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 group) urea, N-(3-tripropoxy-silicane base propyl group) urea, N-(3-bis- Ethoxy-c epoxide silylpropyl) urea, N-(3-ethyoxyl dipropoxy silylpropyl) urea, N-(3-dimethoxy Isopropoxysilyl group propyl group) 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 Epoxide 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 Epoxide) 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 silane, tetraisobutoxy-silicane alkane, four tertiary fourths TMOS, four (methoxy-ethoxy-silane), four (methoxy-n-propyloxy silane), four (ethoxyethoxysilane), four (methoxyethoxyethoxy silane), double (trimethoxysilyl) ethane, double (trimethoxysilyl) hexane, double (triethoxysilyl) methane, double (triethoxysilyl) ethane, double (triethoxysilyl) ethylene, double (triethoxysilyl) octane, double (triethoxysilyl) octadiene, double [3-(triethoxysilyl) third Base] disulphide, double [3-(triethoxysilyl) propyl group] tetrasulfide, ditert-butyldiacetyl oxygen-base silane, two Isobutoxy alumina ethyl triethoxy silicane alkane, double (acetylacetone,2,4-pentanedione) titanium-O, O '-bis-(oxoethyl)-aminopropyl triethoxy 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-pro-pyl 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-pro-pyl 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, double (2-hydroxyethyl)-APTES, 3-glycidoxypropyltrime,hoxysilane, phenyl Trimethoxy silane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, gamma-amino propyl group 3 third TMOS, gamma-amino propyl group three butoxy silane, gamma-amino ethyl triethoxysilane, gamma-amino ethyl trimethoxy Silane, gamma-amino ethyl tripropoxy silane, gamma-amino ethyl three butoxy silane, gamma-amino butyl triethoxysilane, Gamma-amino butyl trimethoxy silane, gamma-amino butyl tripropoxy silane, gamma-amino butyl three butoxy silane etc., but It is not limited to them.They can be used alone, it is also possible to combines multiple use.

As silane coupler, among aforementioned silane coupling agent, from the sight of the storage stability guaranteeing 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 In the silane coupler that silanol and following structure are shown respectively more than a kind.

(surfactant or levelling agent)

It addition, by surfactant or levelling agent are added to resin combination, it is possible to increase coating.Concrete and Speech, it is possible to prevent the contraction after coating.

As this surfactant or levelling agent, include, for example out organic siloxane polymer KF-640,642, 643, KP341, X-70-092, X-70-093, KBM303, KBM403, KBM803 (are trade name, SHIN-ETSU HANTOTAI's chemical industry strain above Formula commercial firm system), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (be above trade name, レ ダ ウ conning シ リ コン company system), SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ- 2154, FZ-2164, FZ-2166, L-7604 (being trade name, ユ ニ カ company of Japan system above), DBE-814, DBE-224, DBE-621、CMS-626、CMS-222、KF-352A、KF-354L、KF-355A、KF-6020、DBE-821、DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (are trade name, PVC ッ Network ケ ミ ジ ャ パ Application above System), グ ラ ノ 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 (big Japanese ink of ether, polyoxyl 10 oleyl ether, polyoxethylene octylphenyl phenol ether etc. Chemical industry Co., Ltd. system, trade name), Off ロ ラ De FC430, FC431 (Sumitomo 3M Co., Ltd., trade name) etc..

When using surfactant or levelling agent, its 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 by molten to aforementioned polyimide precursor and other composition optionally employed Liquid composite (varnish) form in solvent uses.

Herein, as solvent, it is possible to use same as described above as spendable solvent during synthesis of polyimides precursor Solvent.

The consumption of solvent is preferably set to the solid component concentration of resin combination and 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 at room temperature preserving for 4 week The viscosity B coefficent rate of varnish be less than 10% relative to initial viscosity.During room temperature preservation excellent in stability, it is not necessary to carry out freezing Keeping, is easily processed.

<duplexer>

The duplexer of present embodiment possesses supporting mass and the polyimide film being formed on this supporting mass.It addition, it is aforementioned Duplexer can also be further equipped with inoranic membrane on aforementioned polyimide film.

Aforementioned layers stack is by being formed via following operation:

The resin combination of present embodiment is launched on the surface of supporting mass and forms the film formation process of film； And

Heat aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is carried out imidizate, form polyimides The heating process of thin film.

Aforementioned inorganic film prevents moisture, oxygen from invading organic EL luminescent layer from the Kapton of the present invention with acting on Deng gas barrier layer, can compatibly exemplify silicon oxide, aluminium oxide, carborundum, Zirconia/silicon carbide, silicon carbide-silicon nitride, silicon nitride, nitrogen The inorganic oxide film of oxide/silica etc..This inoranic membrane uses plasma CVD method etc. to carry out film forming.

As the inorganic substrate of the glass substrates such as above-mentioned supporting mass, for example, alkali-free glass substrate etc, but limit the most especially Due to this.

As above-mentioned method of deploying, include, for example out the known coating process such as spin coating, slot coated, blade coating.

More specifically, by (or on the adhesive linkage formed on its interarea) expansion on supporting mass by resin combination And after removing solvent, preferably heat under inert atmosphere and polyimide precursor is carried out imidizate, it is possible at aforementioned Hold formation Kapton on body.

Aforesaid solvent remove such as can by less than 250 DEG C, preferred heat treatment 1 at a temperature of 50～200 DEG C Minute～within 300 minutes, carry out.Aforesaid imidizate such as can be by heat treated 1 at a temperature of 250 DEG C～550 DEG C Minute～within 300 minutes, carry out.Surrounding atmosphere during imidizate is preferably set under the inert atmosphere such as nitrogen.

The thickness of the Kapton obtained by present embodiment is not particularly limited, preferably 10～50 μm Scope, more preferably 15～25 μm.

This duplexer is such as used for manufacturing flexible device.More specifically, polyimide film forms semiconductor device, Thereafter supporting mass is peeled off, it is possible to obtain the flexible device possessing the flexible transparent substrate formed by polyimide film.

<Kapton>

The Kapton of present embodiment is formed via following operation:

By the resin combination of the above-mentioned polyimide precursor containing present embodiment and solvent on the surface of supporting mass Launch, thus form the film formation process of film；

Heat aforementioned supporting mass and aforementioned film and aforementioned polyimide precursor is carried out imidizate, thus form polyamides The heating process of imines thin film；And

Aforementioned Kapton is peeled off from aforementioned supporting mass, thus obtains the stripping process of Kapton.

This Kapton is such as used for manufacturing flexible device.Specifically, this Kapton can be used for Form the substrate of TFT, form the substrate of color filter, alignment films, flexible display transparency carrier etc..

<advantages of the present invention>

As it has been described above, the polyimide precursor of present embodiment is preferably,

(1) have as the structure deriving from tetracarboxylic dianhydride:

Derive from the structure of at least one ester ring type tetracarboxylic dianhydride in CBDA, H-PMDA etc.,

Derive from the structure of aromatic tetracarboxylic acid's dianhydride 1 in PMDA etc.,

Derive from the structure of aromatic tetracarboxylic acid's dianhydride in OPDA, 6FDA etc.,

(2) there is the structure deriving from TFMB etc. as deriving from the structure of diamidogen.

The Kapton using this polyimide precursor and manufacture is water white transparency, and CTE is low and percentage elongation is excellent. The surface roughness of the duplexer being formed with inoranic membrane on this Kapton is little, Haze value is little, moisture-vapor transmission is little, because of This, the use being suitable in the transparency carrier 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, the most thereon Form the inoranic membrane of TFT etc..In the temperature of the wide scope of 150～650 DEG C for the operation typical case that inoranic membrane is formed on substrate Degree is lower to be implemented.In order to give play to actual desired performance, main employing 250 DEG C～the temperature range of 400 DEG C.As above-mentioned inorganic Film, include, for example out TFT-IGZO (InGaZnO) oxide semiconductor, TFT (a-Si-TFT, poly-Si-TFT) etc..

Now, compared with the CTE of glass substrate, the CTE of flexible substrate is the highest, then they form work at the inoranic membrane of high temperature During cooling after expanding in sequence when shrinking, more can produce the warpage of glass substrate and damaged, flexible substrate from glass substrate The problems such as stripping.In general, the thermal coefficient of expansion of glass substrate is less than resin.Therefore, the linear expansion coefficient of flexible substrate is more Little the most preferred.

Kapton about present embodiment, it is contemplated that above-mentioned aspect, can be by with film thickness 15～25 μm It is set to less than 25.0ppm/ DEG C as benchmark, the average coefficient of linear expansion (CTE) that measures at 100～300 DEG C according to TMA method.

It addition, the yellow chromaticity of the Kapton of present embodiment (YI value) is less than 10, and it is possible to will be with thin film Thickness 15～25 μm as benchmark, utilize ultraviolet spectrophotometer measure absorbance time 550nm under absorbance be set to 85% Above.

The surface roughness of the inoranic membrane being formed with the duplexer of inoranic membrane on this Kapton implemented is little, Haze value is little, moisture-vapor transmission is little.

In the case of organic el display, as gas barrier layer, Kapton forms inoranic membrane.Now, nothing When the surface roughness of machine film is big, Haze value is big, duplexer produces muddy and fuzzy, is not suitable as display.It addition, water steams When vapor permeability is big, the function as gas barrier layer will not be played, be therefore not suitable for.

It is believed that: the surface roughness of these duplexers, Haze value, moisture-vapor transmission are resistance to Kapton Hot relevant.This is because: when forming inoranic membrane by CVD on Kapton, comprise this Kapton Duplexer be exposed to formed Kapton time solidification (imidizate process) temperature more than high temperature.This duplexer is excellent Choosing: surface roughness be below 25nm, Haze be less than 15, moisture-vapor transmission be 0.1g/ (m²24h) below.

It addition, the Kapton of present embodiment is preferably using film thickness 15～25 μm as the percentage elongation of benchmark More than 15%.By having this percentage elongation, fracture strength when processing flexible substrate becomes excellent, therefore, it is possible to improve finished product Rate.

The Kapton of the present embodiment meeting above-mentioned physical property may be used for because existing Kapton has Some yellow and use limited purposes and require the transparency purposes.Especially, except being suitable as flexible display with thoroughly Outside bright substrate,

(such as, the internal layer of TFT-LCD, grid are exhausted such as to can be also used for the scattering sheet in protecting film or TFT-LCD and film Velum and liquid crystal orientation film) etc..When applying the polyimides of present embodiment as liquid crystal orientation film, contribute to aperture opening ratio Increase, it is possible to manufacture the TFT-LCD of high-contrast.

The Kapton and the duplexer that use the polyimide precursor of present embodiment and manufacture such as can be compatibly For semiconducting insulation film, TFT-LCD dielectric film, electrode protective membrane, the manufacture of flexible device.It is particularly suitable for manufacturing substrate. Herein, flexible device include, for example out flexible display, flexible solaode, flexible illumination, flexible batteries etc..

Embodiment

Hereinafter, the present invention is illustrated based on embodiment.They illustrate that and record, and the scope of the present invention is not It is defined in following embodiment.

Various evaluations in embodiment and comparative example are as follows.

(mensuration of weight average molecular weight)

Weight average molecular weight uses gel permeation chromatography (GPC) to be measured under the following conditions.For calculating Weight-average molecular The standard curve of amount uses polystyrene standard (TOSOH Co., Ltd's system) to make.

Solvent: use DMF (Wako Pure Chemical Industries, Ltd.'s system, high performance liquid chromatography are used), shortly Will measure before add 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 are used) of 63.2mmol/L

Post: Shodex KD-806M (Showa Denko K. K's system)

Flow velocity: 1.0mL/ minute

Column temperature: 40 DEG C

Pump: PU-2080Plus (JASCO company system)

Detector: RI-2031Plus (RI: differential refractometer, JASCO company system), UV-2075Plus (UV-VIS: ultraviolet Visible absorptiometer, JASCO company system)

(deriving from the calculating of the imide concentration of the part of ester ring type tetracarboxylic dianhydride)

Derive from the imide concentration of part of ester ring type acid dianhydride by measuring for polyimide precursor varnish¹³C- The integrated value of NMR signal calculates.¹³C-NMR measures and carries out under the following conditions.

Determinator: Jeol Ltd.'s JNM-GSX400 type

Mensuration temperature: 23 DEG C

Mensuration solvent: deuterated dimethyl sulfoxide solvent (DMSO-d₆)

Derive from the signal that each carbon of the imide bond of the part of ester ring type tetracarboxylic dianhydride, amido link and carboxylic acid is belonged to Occur at following magnetic field intensity:

Near the signal that the imide bond carbon of the part deriving from ester ring type tetracarboxylic dianhydride is belonged to: 177ppm (A)

Near the signal that the amido link carbon of the part deriving from ester ring type tetracarboxylic dianhydride is belonged to: 172ppm (B)

Near the signal that the carboxyl carbon of the part deriving from ester ring type tetracarboxylic dianhydride is belonged to: 177ppm (C)

Herein, about the position of amic acid (not carrying out imidizate), the integrated value of B with C is identical.Carry out imidizate Position in the integrated value of imide bond carbon and the integrated value of amido link carbon in not carrying out the position of imidizate use respectively Following formula represents:

The integrated value of the integrated value-B of the integrated value of imide bond carbon: A

Amido link carbon and integrated value × 2 of the integrated value of carboxyl carbon: B

Thus, imide concentration represents by following calculating formula:

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 compositions varnish prepared respectively in following embodiment and comparative example is at room temperature stood 3 days, by gained sample The viscosimetric analysis at 23 DEG C is carried out as the sample after preparation.Thereafter, obtain the most at room temperature standing for 4 weeks Sample, as the sample after 4 weeks, carries out the viscosimetric analysis at 23 DEG C again.

Above-mentioned viscosimetric analysis uses the viscometer (Dong Ji industrial machine Co., Ltd. TV-22) of subsidiary thermoregulator Carry out.

Use said determination value, calculate room temperature 4 week viscosity B coefficent rate according to following mathematical expression.

Room temperature 4 week viscosity B coefficent rate (%)=[(sample viscosity after 4 weeks)-(sample viscosity after preparation)]/(system Sample viscosity after Bei) × 100

Room temperature 4 week viscosity B coefficent rate is evaluated according to following benchmark.Show the result in table 2.

◎: viscosity B coefficent rate is less than 5% (storage stability " excellent ")

Zero: viscosity B coefficent rate is less than 10% (storage stability " well ")

×: viscosity B coefficent rate is more than 10% (storage stability " bad ")

(duplexer and the making of separating film)

Use bar coater that the varnish of the polyimide precursor obtained in each embodiment and comparative example is coated on alkali-free glass On substrate (thickness is 0.7mm).Then, after at room temperature carrying out the levelling of 5 minutes～10 minutes, with 140 in hot-air oven DEG C heating 60 minutes, heats 60 minutes with the temperature of regulation the most in a nitrogen atmosphere, thus is produced on aforesaid base plate tool There is the duplexer of film.The film thickness in duplexer thickness after solidification is set in the way of reaching 20 μm.Then, with The temperature of regulation carries out solidifying (cured) and film being carried out imidizate.Duplexer after solidification is at room temperature stood After 24 hours, Kapton is peeled off from glass, thus isolates thin film.

In the evaluation of following fracture strength, yellow chromaticity and linear expansion coefficient, poly-by have cured under this set point of temperature Imide membrane is used as sample.

(evaluation of percentage elongation)

For the width 5mm that have cured at the specified temperature, length 50mm, the sample of Kapton of thickness 20 μm Product, use cupping machine (A&D Company, Limited system: RTG-1210), stretch with the speed of 100mm/ minute Measure.Elongation at break is to be evaluated as ◎ (percentage elongation " excellent ") when more than 20%, be more than 15% and evaluate during less than 20% It is zero (percentage elongation " well "), is more than 10% and is evaluated as △ (percentage elongation " bad "), less than 10% news commentary during less than 15% Valency is (percentage elongation " poor ").

(evaluation of yellow chromaticity (YI value))

Utilize (Spectrophotometer:SE600) that electricity Se Industrial Co., Ltd of Japan manufactures, measure with D65 light source The Kapton of thickness 20 μm that have cured at the specified temperature.YI value is to be evaluated as ◎ when less than 8.0 (yellow chromaticity is " excellent Good "), more than 8.0 and be to be evaluated as zero (yellow chromaticity " well ") when less than 10.0, more than 10.0 and be to be evaluated as when less than 15.0 △ (yellow chromaticity " bad "), more than 15.0 time be evaluated as × (yellow chromaticity " poor ").

(evaluation of linear expansion coefficient (CTE))

For the Kapton that have cured at the specified temperature, use the thermo-mechanical analysis dress that Shimadzu Seisakusho Ltd. manufactures Put (TMA-50), carried out the mensuration of test film percentage elongation by thermo-mechanical analysis under the following conditions.

Load-carrying: 5g

Programming rate: 10 DEG C/min

Mensuration atmosphere: nitrogen atmosphere

Nitrogen flow: 20ml/ minute)

Mensuration temperature range: 50～450 DEG C

The CTE, CTE that obtain the Kapton within the temperature range of 100～300 DEG C now are less than 20ppm/ DEG C Time be evaluated as ◎ (CTE " excellent "), more than 20ppm/ DEG C and for less than 25ppm/ DEG C time be evaluated as zero (CTE " well "), exceed 25ppm/ DEG C and for less than 30ppm/ DEG C time be evaluated as △ (CTE " bad "), more than 30ppm/ DEG C time be evaluated as × (CTE " poor ").

(mensuration of the surface roughness of the inoranic membrane formed on Kapton)

Use the compositions varnish prepared respectively in above-described embodiment and comparative example, operate as follows, be formed at surface configuration There is the duplexer wafer being sequentially laminated with Kapton and inoranic membrane on 6 inch silicon wafer substrates of aluminium-vapour deposition layer.

First, on aforesaid substrate after rotary coating each compositions varnish, heat 60 minutes with 140 DEG C with hot-air oven, Heat 60 minutes with 320 DEG C the most in a nitrogen atmosphere, thus obtain the wafer with the Kapton of thickness 20 μm.

Thereafter, the CVD thickness using 350 DEG C, 100nm on the Kapton of above-mentioned formation is used to be formed as nothing Silicon nitride (the SiN of machine film_x) film.Then, Na ノ ピ Network ス 2100 as AFM (SII NANOTECHNOLOGY company is used System, trade name), in the range of 100 μ m 100 μm, measure the surface roughness of the silicon nitride formed.Test is entered with N=5 OK, take its meansigma methods and be used as surface roughness Ra.

Show the result in table 2.

(evaluation of Haze)

By duplexer water immersion obtained above in diluted hydrochloric acid aqueous solution, with inoranic membrane and this two-layer of Kapton Peel off from wafer as one, thus the sample that surface is formed with the Kapton of inoranic membrane must be arrived.Use this sample Product, use the SC-3H type haze meter that Suga Test Instruments Co., Ltd. manufactures, according to JIS K7105 transparency Test method(s) carries out the mensuration of Haze.

Measurement result is evaluated according to following benchmark.

◎: Haze is less than 5 (Haze " excellent ")

Zero: Haze more than 5 and is less than 15 (Haze " well ")

×: Haze is more than 15 (Haze " bad ")

Show the result in table 2.

(evaluation of moisture-vapor transmission)

Use moisture-vapor transmission determinator (machine name: PERMATRAN (registered trade mark) W3/ that MOCON company manufactures 31), under conditions of temperature 40 DEG C, humidity 90%RH and mensuration area 80mm φ, measure surface obtained above and be formed inorganic The moisture-vapor transmission of the Kapton of film.Measure number of times to be set to each 5 times, be averaged value as moisture-vapor transmission, Evaluate according to following benchmark.

◎: moisture-vapor transmission is 0.01g/ (m²24h) below (moisture-vapor transmission " excellent ")

Zero: moisture-vapor transmission is more than 0.01g/ (m²24h) and be 0.1g/ (m²24h) (moisture-vapor transmission below " well ")

×: moisture-vapor transmission is more than 0.1g/ (m²24h) (moisture-vapor transmission " bad ")

Show the result in table 2.

[reference example 1]

In a nitrogen atmosphere, in the separable flask of 500ml, 2,2 '-bis-(trifluoromethyl) benzidine (TFMB) are added 15.69g (49.00mmol) and METHYLPYRROLIDONE (NMP) 178.95g, under agitation dissolves TFMB.Thereafter, benzene is added Double O-phthalic acid dianhydride (ODPA) 3.10g (10.0mmol) of all tetracarboxylic dianhydride (PMDA) 1.09g (5.0mmol), 4,4 '-oxo With 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (CBDA) 6.86g (35.0mmol), stir 4 hours at 80 DEG C, thus are gathered The nmp solution of amic acid is (hereinafter also referred to " varnish ".).The weight average molecular weight (Mw) of gained polyamic acid is 116,500.Will be with CTE, YI value of 330 DEG C of thin film that have cured and percentage elongation are shown in table 2 below.

[reference example 2]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 180.42g, PMDA 3.27g (15.0mmol), ODPA 3.10g (10.0mmol) and CBDA 4.90g (25.0mmol), in addition, as reference example 1 Operate and obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 120,000.By with 330 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[reference example 3]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 186.58g, PMDA 1.09g (5.00mmol), ODPA 6.20g (20.0mmol) and CBDA 4.90g (25.0mmol), in addition, as reference example 1 Operate and obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 128,000.By with 330 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[embodiment 4]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to 1,2,4,5-hexamethylene Tetracarboxylic dianhydride (H-PMDA) 2.24g (10.0mmol), after refluxing 2 hours, expends 3 hours and removes as azeotropic at 180 DEG C The toluene of solvent.Then, after flask contents is 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), stirs 4 hours at 80 DEG C, thus obtains The varnish of polyimides-polyamic acid polymer.The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 82,000.CTE, YI value and percentage elongation with 350 DEG C of thin film that have cured is shown in table 2 below.

[reference example 5]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 178.14g, PMDA 5.45g (25.0mmol), ODPA 1.55g (5.0mmol) and CBDA 3.92g (20mmol), in addition, operate as reference example 1 And obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 119,000.By with the CTE of 330 DEG C of thin film that have cured, YI value and percentage elongation are shown in table 2 below.

[reference example 6]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 187.38g, PMDA 2.18g (10.0mmol), ODPA 6.20g (20.0mmol) and CBDA 3.92g (20.0mmol), in addition, as reference example 1 Operate and obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 123,000.By with 330 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[reference example 7]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 175.19g, PMDA 1.09g (5.0mmol), ODPA 1.55g (5.0mmol) and CBDA 7.84g (40.0mmol), in addition, grasp as reference example 1 Make and obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 123,000.By with 330 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[reference example 8]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 189.59g, PMDA 5.45g (25.0mmol), ODPA 6.20g (20.0mmol) and CBDA 0.98g (5.0mmol), in addition, grasp as reference example 1 Make and obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 103,000.By with 330 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[embodiment 9]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 12.55g (39.2mmol), NMP 171.51g, PMDA 5.45g (25.0mmol) and ODPA 4.65g (15.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 123,000.By with 350 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[embodiment 10]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 12.55g (39.2mmol), NMP 174.59g, PMDA 4.36g (20.0mmol) and ODPA 6.20g (20.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 81,000.By with 350 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[embodiment 11]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 6.28g (19.6mmol), NMP 32.28g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 4.48g (20.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 9.42g (29.4mmol), NMP 76.44g, PMDA 5.45g (25.0mmol) and ODPA 1.55g (5.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained gathers The weight average molecular weight (Mw) of acid imide-polyamic acid polymeric compositions is 68,000.By with the CTE of 350 DEG C of thin film that have cured, YI value and percentage elongation are shown in table 2 below.

[embodiment 12]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 6.28g (19.6mmol), NMP 32.28g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 4.48g (20.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 9.42g (29.4mmol), NMP 78.28g, PMDA 4.36g (20.0mmol) and ODPA 3.10g (10.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained The weight average molecular weight (Mw) of polyimides-polyamic acid polymer is 68,000.By CTE, YI with 350 DEG C of thin film that have cured Value and percentage elongation are shown in table 2 below.

[embodiment 13]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 0.63g (1.96mmol), NMP 3.22g and toluene 30g, under agitation dissolve TFMB.It is added to H-PMDA 0.45g (2.00mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 15.06g (47.0mmol), NMP 186.57g, PMDA 6.33g (29.0mmol) and ODPA 5.89g (19.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 112,000.By with 350 DEG C of thin film that have cured CTE, YI value and percentage elongation are shown in table 2 below.

[embodiment 14]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 12.55g (39.2mmol), NMP 166.88g, PMDA 7.09g (32.5mmol) and ODPA 2.33g (7.5mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymeric compositions is 79,000.By with 350 DEG C of thin film that have cured CTE, YI value and percentage elongation be shown in table 2 below.

[embodiment 15]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 9.42g (29.4mmol), NMP 48.42g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 6.78g (30.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 6.28g (19.6mmol), NMP 60.54g, PMDA 3.27g (15.0mmol) and ODPA 1.55g (5.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained gathers The weight average molecular weight (Mw) of acid imide-polyamic acid polymeric compositions is 56,000.By with the CTE of 350 DEG C of thin film that have cured, YI value and percentage elongation are shown in table 2 below.

[embodiment 16]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.80mmol), NMP 16.14g and toluene 50g, TFMB is under agitation dissolved.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 12.55g (39.2mmol), NMP 168.43g, PMDA 4.36g (20.0mmol), ODPA 3.10g (10.0mmol) and CBDA 1.96g (10.0mmol), with 80 DEG C stir 4 hours, thus obtain polyimides- The varnish of polyamic acid polymer.The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 71,000.Will be with CTE, YI value of 350 DEG C of thin film that have cured and percentage elongation are shown in table 2 below.

[reference example 17]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 162.24g, PMDA6.54g (30.0mmol), 4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides (6FDA) 4.44g (10.0mmol) and CBDA1.96g (10mmol), in addition, operate as reference example 1 and obtain varnish.The weight average molecular weight (Mw) of gained polyamic acid is 159,000.CTE, YI value and percentage elongation with 330 DEG C of thin film that have cured is shown in table 2 below.

[embodiment 18]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to 1,2,4,5-hexamethylene Tetracarboxylic dianhydride (H-PMDA) 2.24g (10.0mmol), after refluxing 2 hours, expends 3 hours and removes as azeotropic at 180 DEG C The toluene of solvent.After the content of flask is cooled to 40 DEG C, add TFMB 12.55g (39.2mmol), NMP 147.70g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), stirs 4 hours at 80 DEG C, thus it is sub-to obtain polyamides The varnish of amine-polyamic acid polymer.The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 85,000. CTE, YI value and percentage elongation with 350 DEG C of thin film that have cured is shown in table 2 below.

[embodiment 19]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, confirms to derive from the 1,650cm of amido link by infrared spectroscopic analysis (IR)^-1Neighbouring absorption (C=O) disappears Lose.Thereafter, in flask add TFMB 12.55g (39.2mmol), NMP 153.4g, PMDA 5.45g (25.0mmol) and 6FDA 6.66g (15.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 88,000.By commenting with 350 DEG C of thin film that have cured Valency result is shown in table 2.

[embodiment 20]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 159.8g, PMDA 4.36g (20.0mmol) and 6FDA 8.88g (20.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 86,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 21]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 6.28g (19.6mmol), NMP 32.28g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 4.48g (20.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 9.42g (29.4mmol), NMP 124.9g, PMDA 5.45g (25.0mmol) and 6FDA 2.22g (5.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid gathers The weight average molecular weight (Mw) of compound is 76,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 22]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 6.28g (19.6mmol), NMP 32.28g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 4.48g (20.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 9.42g (29.4mmol), NMP 131.3g, PMDA 4.36g (20.0mmol) and 6FDA 4.44g (10.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid gathers The weight average molecular weight (Mw) of compound is 77,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 23]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 0.45g (2.00mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 158.3g, PMDA 6.33g (29.0mmol) and 6FDA 8.44g (19.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 89,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 24]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 143.9g, PMDA 7.09g (32.5mmol) and 6FDA 3.33g (7.5mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid gathers The weight average molecular weight (Mw) of compound is 89,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 25]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 9.42g (29.4mmol), NMP 48.42g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 6.78g (30.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 6.28g (19.6mmol), NMP 109.5g, PMDA 3.27g (15.0mmol) and 6FDA2.22g (5.0mmol), 80 Stir 4 hours at DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid polymerization The weight average molecular weight (Mw) of thing is 75,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 26]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 153.5g, PMDA 3.27g (15.0mmol), BPDA 4.41g (15.0mmol) and 6FDA 4.44g (10.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 87,000.By commenting with 350 DEG C of thin film that have cured Valency result is shown in table 2.

[embodiment 27]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 143.3g, PMDA 6.54g (30.0mmol), ODPA 1.55g (5.0mmol) and 6FDA 2.22g (5.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 86,000.By commenting with 350 DEG C of thin film that have cured Valency result is shown in table 2.

[embodiment 28]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 1.12g (5.0mmol), CBDA 0.98g (5.0mmol), reflux after 2 hours at 180 DEG C, expend removal in 3 hours as azeotropic solvent Toluene.The content of flask is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C =O) disappear.Thereafter, TFMB 12.55g (39.2mmol), NMP 146.3g, PMDA 6.54g (30.0mmol) and 6FDA are added 4.44g (10.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained The weight average molecular weight (Mw) of polyimides-polyamic acid polymer is 90,000.Evaluation with 350 DEG C of thin film that have cured is tied Fruit is shown in table 2.

[embodiment 29]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 0.34g (1.5mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-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 1.9g (8.5mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained gathers The weight average molecular weight (Mw) of acid imide-polyamic acid polymer is 71,000.By the evaluation result with 350 DEG C of thin film that have cured It is shown in table 2.

[embodiment 30]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 0.56g (2.5mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-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 1.68g (7.5mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained gathers The weight average molecular weight (Mw) of acid imide-polyamic acid polymer is 75,000.By the evaluation result with 350 DEG C of thin film that have cured It is shown in table 2.

[embodiment 31]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 0.78g (3.5mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-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), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained gathers The weight average molecular weight (Mw) of acid imide-polyamic acid polymer is 78,000.By the evaluation result with 350 DEG C of thin film that have cured It is shown in table 2.

[embodiment 32]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 0.62g (2.75mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add 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), stirs 4 hours at 80 DEG C, thus obtains the clear of polyimides-polyamic acid polymer Paint.The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 80,000.By with 350 DEG C of thin film that have cured Evaluation result be shown in table 2.

[embodiment 33]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 1.68g (7.5mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-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), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained gathers The weight average molecular weight (Mw) of acid imide-polyamic acid polymer is 71,000.By the evaluation result with 350 DEG C of thin film that have cured It is shown in table 2.

[embodiment 34]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to CBDA 1.96g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 166.5g, PMDA 6.54g (30.0mmol) and ODPA 3.10g (10.0mmol), Stir 4 hours with 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid gathers The weight average molecular weight (Mw) of compound is 120,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 35]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to CBDA 0.98g (5.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-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, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid polymer Weight average molecular weight (Mw) be 95,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 36]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to CBDA 1.96g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 175.5g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 100,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 37]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 9.42g (29.4mmol), NMP 48.42g and toluene 50g, under agitation dissolve TFMB.It is added to CBDA 5.88g (30.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 6.28g (19.6mmol), NMP 169.5g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid gathers The weight average molecular weight (Mw) of compound is 100,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 38]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to CBDA 0.29g (1.5mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, TFMB is added 12.55g (39.2mmol), NMP 175.5g, PMDA 6.54g (30.0mmol), 6FDA 4.44g (10.0mmol) and CBDA1.67g (8.5mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Institute The weight average molecular weight (Mw) obtaining polyimides-polyamic acid polymer is 95,000.By the evaluation with 350 DEG C of thin film that have cured Result is shown in table 2.

[embodiment 39]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to CBDA 0.53g (2.75mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 183.8g, PMDA 6.54g (30.0mmol), 6FDA 6.66g (15.0mmol) and CBDA 0.45g (2.25mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer. The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 80,000.By commenting with 350 DEG C of thin film that have cured Valency result is shown in table 2.

[embodiment 40]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to CBDA 1.47g (7.5mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-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), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained The weight average molecular weight (Mw) of polyimides-polyamic acid polymer is 91,000.Evaluation with 350 DEG C of thin film that have cured is tied Fruit is shown in table 2.

[embodiment 41]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 160g, BPDA 8.83g (30.0mmol) and 6FDA 4.44g (10.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid gathers The weight average molecular weight (Mw) of compound is 86,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 42]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1After neighbouring absorption (C=O) disappears, add TFMB Double (the trihemellitic acid monoesters of 12.55g (39.2mmol), NMP 147.8g, PMDA 6.54g (30.0mmol) and 4,4 '-xenyl Anhydride (TAHQ) 4.58g (10.0mmol), stirs 4 hours at 80 DEG C, thus obtains polyimides-polyamic acid polymer Varnish.The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 84,000.By with 350 DEG C have cured thin The evaluation result of film is shown in table 2.

[embodiment 43]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to CPDA 2.1g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 146.3g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 71,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 44]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-BPDA 3.06g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 151.7g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 73,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 45]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to BCDA 2.36g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask Thing is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) disappears.Thereafter, add TFMB 12.55g (39.2mmol), NMP 147.7g, PMDA 6.54g (30.0mmol) and 6FDA 4.44g (10.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 75,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[embodiment 46]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to dicyclo [2.2.2] octyl- 7-alkene-2,3,5,6-tetracarboxylic dianhydrides (BOTDA) 2.48g (10.0mmol), after refluxing 2 hours, expends 3 hours at 180 DEG C Remove the toluene as azeotropic solvent.The content of flask is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1 of amido link, 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), stirs 4 hours at 80 DEG C, thus obtains polyimides-polyamides The varnish of amino acid polymer.The weight average molecular weight (Mw) of gained polyimides-polyamic acid polymer is 74,000.Will be with 350 The evaluation result of DEG C thin film that have cured is shown in table 2.

[embodiment 47]

2,2 '-diformazan is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel Base xenyl-4,4 '-diamidogen (mTB) 2.08g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve mTB.To Wherein add H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove as azeotropic solvent Toluene.The content of flask is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C =O) disappear.Thereafter, mTB 8.32g (39.2mmol), NMP 117.2g, PMDA 6.54g (30.0mmol) and 6FDA are added 4.44g (10.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained The weight average molecular weight (Mw) of polyimides-polyamic acid polymer is 82,000.Evaluation with 350 DEG C of thin film that have cured is tied Fruit is shown in table 2.

[embodiment 48]

4,4 '-diamino is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel Base benzanilide (DABA) 2.23g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve DABA.Wherein Add H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the first as azeotropic solvent Benzene.The content of flask is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C=O) Disappear.Thereafter, DABA 8.91g (39.2mmol), NMP 121.4g, PMDA 6.54g (30.0mmol) and 6FDA are added 4.44g (10.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained The weight average molecular weight (Mw) of polyimides-polyamic acid polymer is 83,000.Evaluation with 350 DEG C of thin film that have cured is tied Fruit is shown in table 2.

[embodiment 49]

4-aminobenzene is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel Base-PABA ester (APAB) 2.24g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolves APAB.To Wherein add H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove as azeotropic solvent Toluene.The content of flask is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-1Neighbouring absorption (C =O) disappear.Thereafter, APAB 8.95g (39.2mmol), NMP 121.6g, PMDA 6.54g (30.0mmol) and 6FDA are added 4.44g (10.0mmol), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained The weight average molecular weight (Mw) of polyimides-polyamic acid polymer is 82,000.Evaluation with 350 DEG C of thin film that have cured is tied Fruit is shown in table 2.

[embodiment 50]

Dissolve relative to resin 100 weight in the varnish of the polyimides-polyamic acid polymer utilizing embodiment 9 to obtain Amount part is scaled the alkoxysilane compound containing trialkylsilyl group in molecular structure 1 (ROSi1) of 0.5 weight portion, filters with the filter of 0.1 μm, thus makes Standby resin combination.Said composition and the characteristic of cured film thereof is measured according to aforementioned evaluation methodology.Acquired results is shown in table 2.

[embodiment 51]

Dissolve relative to resin 100 in the varnish of the polyimides-polyamic acid polymer utilizing embodiment 19 to obtain Weight portion is scaled the alkoxysilane compound containing trialkylsilyl group in molecular structure 1 of 0.5 weight portion, filters with the filter of 0.1 μm, thus prepares resin Compositions.Said composition and the characteristic of cured film thereof is measured according to aforementioned evaluation methodology.Acquired results is shown in table 2.

[embodiment 52]

Dissolve relative to resin 100 weight in the varnish of the polyimides-polyamic acid polymer utilizing embodiment 9 to obtain Amount part is scaled the surfactant 1 (Surf1) of 0.05 weight portion, filters with the filter of 0.1 μm, thus prepares resin Compositions.Said composition and the characteristic of cured film thereof is measured according to aforementioned evaluation methodology.Acquired results is shown in table 2.

[embodiment 53]

Dissolve relative to resin 100 in the varnish of the polyimides-polyamic acid polymer utilizing embodiment 19 to obtain Weight portion is scaled the surfactant 1 of 0.05 weight portion, filters with the filter of 0.1 μm, thus prepares resin combination Thing.Said composition and the characteristic of cured film thereof is measured according to aforementioned evaluation methodology.Acquired results is shown in table 2.

[comparative example 1]

Feeding intake of raw material is changed to TFMB 14.39g (44.9mmol), NMP 163.23g, PMDA 10.0g (45.8mmol), ODPA 0g (0mmol) and CBDA 0g (0mmol), in addition, operate as reference example 1 and obtain clear Paint.The weight average molecular weight (Mw) of the polyamic acid in gained varnish is 47,000.By CTE, YI with 350 DEG C of thin film that have cured Value and percentage 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, PMDA 0g (0mmol), ODPA 10.0g (32.2mmol) and CBDA 0g (0mmol), in addition, operates as reference example 1 and obtains varnish.Institute The weight average molecular weight (Mw) obtaining the polyamic acid in varnish is 65,500.By with CTE, YI value of 350 DEG C of thin film that have cured and Percentage elongation 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, PMDA 0g (0mmol), ODPA 0g (0mmol) and CBDA 10.00g (51.0mmol), in addition, operates as reference example 1 and obtains varnish.Institute The weight average molecular weight (Mw) obtaining the polyamic acid in varnish is 221,000.By with CTE, YI value of 330 DEG C of thin film that have cured and Percentage elongation is shown in table 2 below.

[comparative example 4]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 14.00g (43.7mmol), NMP 160.62g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 10.00g (44.6mmol), after refluxing 2 hours, expends 3 hours and removes the toluene as azeotropic solvent at 180 DEG C.Thereafter, will The content of flask is cooled to room temperature, thus obtains the varnish of polyimides.The Weight-average molecular of the polyimides in gained varnish Amount (Mw) is 50,600.CTE, YI value and percentage elongation with 350 DEG C of thin film that have cured is shown in table 2 below.

[comparative example 5]

Feeding intake of raw material is changed to TFMB 8.79g (27.4mmol), NMP 60.6g, PMDA 5.50g (25.2mmol) With ODPA 0.87g (2.8mmol), in addition, operate as reference example 1 and obtain varnish.By what gained varnish contained The weight average molecular weight (Mw) of polymer is 47,000.CTE, YI value and fracture strength with 350 DEG C of thin film that have cured is shown in Table 2 below.

[comparative example 6]

Feeding intake of raw material is changed to TFMB 16.44g (51.3mmol), NMP 184.18g, PMDA 8.00g (36.7mmol), ODPA 0g (0mmol) and CBDA 3.08g (15.7mmol), in addition, as reference example 1 operation and Obtain varnish.It is 121,900 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.To have cured with 330 DEG C CTE, YI value of thin film and fracture strength 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), in addition, operates as reference example 1 and obtains clear Paint.The weight average molecular weight (Mw) of gained varnish is 105,000.By strong for CTE, YI value and the fracture with 330 DEG C of thin film that have cured Degree is shown in table 2 below.

[comparative example 8]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 12.55g (39.2mmol), NMP 186.91g and ODPA 12.41g (40.0mmol), Stir 4 hours at 80 DEG C, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymer is 66,700.By with CTE, YI value of 350 DEG C of thin film that have cured and percentage elongation be shown in Under table 2.

[comparative example 9]

Feeding intake of raw material is changed to TFMB 15.69g (49.0mmol), NMP 175.05g, PMDA 6.54g (30.0mmol), ODPA 0g (0mmol) and CBDA 3.92g (20.0mmol), in addition, as reference example 1 operation and Obtain varnish.It is 91,200 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.By with 330 DEG C have cured thin CTE, YI value of film and fracture strength are shown in table 2 below.

[comparative example 10]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 2.24g (10.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB 12.55g (39.2mmol), NMP 162.26g and PMDA 8.72g (40.0mmol), with 80 DEG C are stirred 4 hours, thus obtain the varnish of polyimides-polyamic acid polymeric compositions.Gained polyimides-polyamic acid The weight average molecular weight (Mw) of polymeric compositions is 226,000.CTE, YI value and percentage elongation with 350 DEG C of thin film that have cured is 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), in addition, operates as reference example 1 and obtains clear Paint.It is 125,100 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.By with 330 DEG C of thin film that have cured CTE, YI value and fracture 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), in addition, operates as reference example 1 and obtains clear Paint.It is 120,900 by the weight average molecular weight (Mw) of the polymer contained in gained varnish.By with 330 DEG C of thin film that have cured CTE, YI value and fracture strength are shown in table 2 below.

[comparative example 13]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 12.55g (39.2mmol), NMP 64.56g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 8.97g (40.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask After thing is cooled to 40 DEG C, add TFMB3.14g (9.8mmol), NMP 46.48g and ODPA 3.1g (10.0mmol), at 80 DEG C Lower stirring 4 hours, thus obtain the varnish of polyimides-polyamic acid polymer.Gained polyimides-polyamic acid polymer Weight average molecular weight (Mw) be 49,800.CTE, YI value and percentage elongation with 350 DEG C of thin film that have cured is shown in following table 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, operates as reference example 1 and obtains varnish.Polyamide in gained varnish The weight average molecular weight (Mw) of acid is 110,000.CTE, YI value and percentage elongation with 350 DEG C of thin film that have cured is shown in following Table 2.

[comparative example 15]

In a nitrogen atmosphere, in the separable flask of 500ml, TFMB 15.69g (49.00mmol) and NMP is added 203.4g, under agitation dissolves TFMB.Then, add BPDA 14.71g (50.0mmol), stir 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.Will be solid with 330 DEG C The evaluation result of the thin film changed is shown in table 2.

[comparative example 16]

In a nitrogen atmosphere, in the separable flask of 500ml, TFMB 15.69g (49.00mmol) and NMP is added 258.4g, under agitation dissolves TFMB.Then, add TAHQ 22.92g (50.0mmol), stir 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.Will be solid with 330 DEG C The evaluation result of the thin film changed is shown in table 2.

[comparative example 17]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 15.69g (49.0mmol), NMP 175.3g and toluene 50g, under agitation dissolve TFMB.It is added to CPDA 10.51g (100.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, thus obtain the varnish of polyimides.The weight average molecular weight of the polyimides in gained varnish (Mw) it is 51,600.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[comparative example 18]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 15.69g (49.0mmol), NMP 175.3g and toluene 50g, under agitation dissolve TFMB.It is added to H-BPDA 15.32g (100.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, thus obtain the varnish of polyimides.The weight average molecular weight of the polyimides in gained varnish (Mw) it is 54,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[comparative example 19]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 15.69g (49.0mmol), NMP 175.3g and toluene 50g, under agitation dissolve TFMB.It is added to BCDA 11.82g (100.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, thus obtain the varnish of polyimides.The weight average molecular weight of the polyimides in gained varnish (Mw) it is 50,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[comparative example 20]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 15.69g (49.0mmol), NMP 175.3g and toluene 50g, under agitation dissolve TFMB.It is added to BOTDA 12.41g (100.0mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.Thereafter, by flask Content be cooled to room temperature, thus obtain the varnish of polyimides.The weight average molecular weight of the polyimides in gained varnish (Mw) it is 54,000.Table 2 will be shown in the evaluation result of 350 DEG C of thin film that have cured.

[comparative example 21]

TFMB is put in a nitrogen atmosphere in the separable flask being equipped with Dien Stark apparatus and return channel 3.14g (9.8mmol), NMP 16.14g and toluene 50g, under agitation dissolve TFMB.It is added to H-PMDA 0.16g (0.7mmol), after refluxing 2 hours at 180 DEG C, expend 3 hours and remove the toluene as azeotropic solvent.By the content of flask It is cooled to 40 DEG C, utilizes IR to confirm to derive from the 1,650cm of amido link^-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), stirs 4 hours at 80 DEG C, thus obtains the varnish of polyimides-polyamic acid polymer.Gained gathers The weight average molecular weight (Mw) of acid imide-polyamic acid polymer is 51,000.By the evaluation result with 350 DEG C of thin film that have cured It is shown in table 2.

[comparative example 22]

According to No. 10-2013-0077946 described method of Korean Patent Publication No., carry out the preparation of varnish.

In a nitrogen atmosphere, to 1, the separable flask of 000ml adds dimethyl acetylamide (DMAc) 270ml, in room temperature Under make TFMB 32.02g (100.0mmol) be completely dissolved.Then, 6FDA 111.1g (25.0mmol), PMDA are added successively 109.1g (50.0mmol) and H-PMDA 56.04g (25.0mmol), is stirred at room temperature 12 hours.Thereafter, 120 DEG C are utilized After oil bath is heated 20 minutes, stirring 12 hours at normal temperatures, thus obtain polyamic acid solution (varnish).Gained polyamic acid Weight average molecular weight (Mw) is 32,000.

Use above-mentioned varnish, expend 8 hours from 80 DEG C be heated to 250 DEG C after, Slow cooling and obtain Kapton, Its evaluation result is shown in table 2.

[comparative example 23]

According to No. 10-2013-0077946 described method of Korean Patent Publication No., carry out the preparation of varnish.

Feeding intake of raw material is changed to 6FDA 88.85g (20.0mmol), PMDA 87.25g (40.0mmol) and H-PMDA 89.67g (40.0mmol), in addition, operates in the same manner as comparative example 22.The evaluation of gained Kapton is tied Fruit is shown in table 2.

[comparative example 24]

According to No. 10-2013-0077946 described method of Korean Patent Publication No., carry out the preparation of varnish.

Feeding intake of raw material is changed to 6FDA 177.7g (40.0mmol), PMDA 87.25g (40.0mmol) and H-PMDA 44.83g (20.0mmol), in addition, operates in the same manner as comparative example 22.The evaluation of gained Kapton is tied 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 the composition described in table 1 is respectively following meaning.

[aromatic tetracarboxylic acid's dianhydride 1]

PMDA: pyromellitic dianhydride

BPDA:3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride

[aromatic tetracarboxylic acid's dianhydride 2]

The double O-phthalic acid dianhydride of ODPA:4,4 '-oxo

6FDA:4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides

TAHQ:4,4 '-xenyl is double (trihemellitic acid monoester anhydride)

[ester ring type tetracarboxylic dianhydride]

CBDA:1,2,3,4-Tetramethylene. 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: dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride

BOTDA: dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride

[diamidogen]

TFMB:2,2 ' double (trifluoromethyl) benzidine

MTB:2,2 '-dimethyl diphenyl base-4,4 '-diamidogen

DABA:4,4 '-diaminobenzene anilid

APAB:4-aminophenyl-PABA ester

[other additive]

ROSi1: alkoxysilane compound containing trialkylsilyl group in molecular structure 1, the compound of following structural formula

Surf1: surfactant 1, organic silicon type nonionic surfactant DBE224 (trade name, Gelest company system)

It is as shown in the table like that, derives from the structure of ester ring type tetracarboxylic dianhydride for comprising to have, derives from aforementioned fragrance The structure of race tetracarboxylic dianhydride 1 and the whole polyimide precursor in deriving from the structure of aforementioned fragrance race tetracarboxylic dianhydride 2 Resin combination (varnish), it is thus identified that

Viscosity B coefficent rate during (0) 4 week room temperature preservation is less than 10%,

The film physical property of Kapton foregoing solidification obtained meets following condition simultaneously:

(1) CTE is below 25ppm

(2) YI value is less than 10

(3) percentage elongation is more than 15%,

The duplexer being formed with inoranic membrane on aforementioned Kapton meets simultaneously:

(4) Haze is less than 15

(5) moisture-vapor transmission is 0.1g/ (m²24h) below.

It addition, confirm according to the evaluation result of comparative example 1～4,14 and 15～20: employ only to have and derive from a kind It is whole that the Kapton of the polyimide precursor of the structure of tetracarboxylic dianhydride cannot meet in above-mentioned (0)～(5) simultaneously Film physical property；

Evaluation result according to comparative example 5～13 confirms: be 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, for the whole film physical property in above-mentioned (0)～(5), not yet composes Give sufficient performance.

And then, confirm according to the evaluation result of comparative example 21～25: be 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 at this polyimide precursor The acid imide rate of the amido link of formula tetracarboxylic dianhydride be in 10～100% extraneous in the case of, for above-mentioned (0)～(5) In whole film physical property, not yet give sufficient performance.

According to results verification as above to: as long as have the knot deriving from ester ring type tetracarboxylic dianhydride at polyimide precursor Structure, derive from the structure of aforementioned fragrance race tetracarboxylic dianhydride 1 and derive from the structure of aforementioned fragrance race tetracarboxylic dianhydride 2 in complete Portion's structure, and the acid imide rate deriving from the amido link of ester ring type tetracarboxylic dianhydride is 10～100% in the case of scope, bag The excellent storage stability of the compositions containing this polyimide precursor, Kapton said composition solidification obtained is Water white transparency and linear expansion coefficient is low and then percentage elongation is excellent, this Kapton is formed the duplexer of inoranic membrane Haze is little, moisture-vapor transmission is excellent.

Industrial applicability

The polyimide precursor of the present invention such as can be suitably employed in manufacture semiconducting insulation film, TFT-LCD dielectric film, electricity Pole protecting film, flexible display, be particularly suitable for for manufacturing substrate.

Claims (27)

1. a polyimide precursor, it is characterised in that it has the structure shown in following formula (A), and,

As deriving from the structure of diamidogen, have derive from selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2,2 '-two Methyl biphenyl-4,4 '-diamidogen, in 4,4 '-diaminobenzene anilid and 4-aminophenyl-PABA ester at least A kind of structure of diamidogen；

As deriving from the structure of tetracarboxylic dianhydride, have and derive from selected from 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides (CBDA), 1,2,4,5-cyclopentanetetracarboxylic's dianhydride (H-PMDA), 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 1,2,4,5-bis cyclohexane four Carboxylic acid dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [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-(tetrahydrochysene- 2,5-dioxa-3-furyl)-naphtho-[1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetrabasic carboxylic acid The structure of at least one ester ring type tetracarboxylic dianhydride in dianhydride and derive from the structure of aromatic tetracarboxylic acid's dianhydride, and,

The acid imide rate of the amido link deriving from described ester ring type tetracarboxylic dianhydride is 10～100%,

X₁For deriving from selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl base-4,4 '-diamidogen, 4, The structure of at least one diamidogen in 4 '-diaminobenzene anilid and 4-aminophenyl-PABA ester；

X₂For deriving from selected from 1,2,3,4-Tetramethylene. 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, dicyclo [2.2.1] heptane-2, 3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring Amyl group acetic acid-1,4:2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-dioxa-3-furyl)-naphtho-[1, 2-C] at least one tetracarboxylic dianhydride in furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride Structure.

Polyimide precursor the most according to claim 1, wherein, described polyimide precursor has following formula (B) Structure:

X₁It is identical with the definition in described formula (A),

X₃For deriving from the structure of described aromatic tetracarboxylic acid's dianhydride.

Polyimide precursor the most according to claim 1 and 2, wherein, derives from the amido link of ester ring type tetracarboxylic dianhydride Acid imide rate be 20～100%.

4. according to the polyimide precursor according to any one of claims 1 to 3, wherein, derive from ester ring type tetracarboxylic dianhydride The acid imide rate of amido link be 30～100%.

5. according to the polyimide precursor according to any one of Claims 1 to 4, wherein, described aromatic tetracarboxylic acid's dianhydride bag Contain:

As aromatic tetracarboxylic acid's dianhydride 1 selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride In at least one；And

As aromatic tetracarboxylic acid's dianhydride 2 selected from 4,4 '-oxo double O-phthalic acid dianhydride (ODPA), 4,4 '-(hexafluoro isopropyl Fork base) at least one in double phthalic anhydrides (6FDA) and 4,4 '-xenyl pair (trihemellitic acid monoester anhydride).

6. according to the polyimide precursor according to any one of Claims 1 to 5, wherein, described aromatic tetracarboxylic acid's dianhydride 1 is Pyromellitic dianhydride (PMDA).

7. according to the polyimide precursor according to any one of Claims 1 to 5, wherein, described aromatic tetracarboxylic acid's dianhydride 2 is Selected from the double O-phthalic acid dianhydride (ODPA) of 4,4 '-oxo and 4,4 '-(hexafluoroisopropyli,ene base) double phthalic anhydrides (6FDA) In at least one.

8. the structure deriving from diamidogen described according to the polyimide precursor according to any one of claim 1～7, wherein, is Derive from the structure of 2,2 '-bis-(trifluoromethyl) benzidine (TFMB).

9. according to the polyimide precursor according to any one of claim 1～8, wherein, described ester ring type tetracarboxylic dianhydride is Selected from 1,2,3,4-Tetramethylene. 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, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2, At least one in 3:5,6-dianhydride and dicyclo [2.2.2] octyl-7-alkene-2,3,5,6-tetracarboxylic dianhydride.

10. according to the polyimide precursor according to any one of claim 1～9, wherein, described ester ring type tetracarboxylic dianhydride is In 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclopentanetetracarboxylic's dianhydride (H-PMDA) at least One.

11., according to the polyimide precursor according to any one of claim 1～10, wherein, all derive from the structure of diamidogen In comprise the structure deriving from described TFMB of 60 moles of more than %,

All derive from the structure of tetracarboxylic dianhydride amounts to and comprise the deriving from selected from described PMDA, described of 60 moles of more than % The structure of at least one tetracarboxylic dianhydride in ODPA, described 6FDA, described CBDA and described H-PMDA.

12., according to the polyimide precursor according to any one of claim 1～11, wherein, all derive from tetracarboxylic dianhydride Structure in comprise the structure deriving from described PMDA of 1～70 mole of %, and

All derive from and the structure of tetracarboxylic dianhydride comprises the deriving from described ODPA and 6FDA of 1～50 mole of % The structure of at least one tetracarboxylic dianhydride.

13. according to the polyimide precursor according to any one of claim 1～11, wherein, derives from described PMDA, described The molal quantity sum of each structure of ODPA, described 6FDA, described CBDA and described H-PMDA and the structure deriving from described TFMB Molal quantity ratio PMDA+ODPA+6FDA+CBDA+H-PMDA)/TFMB} is 100/99.9～100/95.

14., according to the polyimide precursor according to any one of claim 1～13, wherein, are dissolved in solvent and at supporting mass Unfolded surface after, carry out imidizate by the heating under nitrogen atmosphere and the yellow chromaticity of Kapton that obtains is 10 Below, linear expansion coefficient be below 25ppm and thickness be film elongation rate during 20 μm be more than 15%.

15. according to the polyimide precursor according to any one of claim 1～14, and it is used for manufacturing flexible device.

16. 1 kinds of resin combinations, it is characterised in that before it contains the polyimides according to any one of claim 1～15 Body and solvent.

17. resin combinations according to claim 16, it is possibly together with alkoxysilane compound containing trialkylsilyl group in molecular structure.

18. according to the resin combination described in claim 16 or 17, and it is possibly together with surfactant.

19. 1 kinds of Kaptons, it is characterised in that it is by the resin combination according to any one of claim 16～18 Thing launches on the surface of supporting mass and forms film, then heats described supporting mass and described film and by described polyimides Precursor carries out imidizate thus is formed.

The manufacture method of 20. 1 kinds of Kaptons, it is characterised in that it includes following operation:

Resin combination according to any one of claim 16～18 is launched on the surface of supporting mass, thus forms film Film formation process；

Heat described supporting mass and described film and described polyimide precursor is carried out imidizate, thus form polyimides The heating process of thin film；And

Described Kapton is peeled off from described supporting mass, thus obtains the stripping process of Kapton.

21. 1 kinds of duplexers, it is characterised in that it possesses supporting mass and the polyimide film being formed on this supporting mass, and

Described duplexer is obtained as below: by the resin combination according to any one of claim 16～18 at described supporting mass Launch on surface and form film, then heat described supporting mass and described film and described polyimide precursor is carried out acyl Asia Amination, forms polyimide film and obtains.

The manufacture method of 22. 1 kinds of duplexers, described duplexer possesses supporting mass and the polyimides being formed on this supporting mass Film, the method includes following operation:

Resin combination according to any one of claim 16～18 is launched on the surface of supporting mass, thus forms film Film formation process；And

Heat described supporting mass and described film and described polyimide precursor is carried out imidizate, thus form polyimides The heating process of thin film.

23. 1 kinds of described Kaptons, it is characterised in that it is poly-with what the copolymer of tetracarboxylic dianhydride manufactured by diamidogen Imide membrane,

Described diamidogen is selected from 2,2 '-bis-(trifluoromethyl) benzidine (TFMB), 2,2 '-dimethyl diphenyl base-4,4 '-diamidogen, 4, at least one in 4 '-diaminobenzene anilid and 4-aminophenyl-PABA ester,

Described tetracarboxylic dianhydride comprises:

As ester ring type tetracarboxylic dianhydride selected from 2,3,4-Tetramethylene. tetracarboxylic dianhydride (CBDA), 1,2,4,5-hexamethylene tetracarboxylic acid Acid dianhydride (H-PMDA), 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 1,2,4,5-bis cyclohexane tetracarboxylic dianhydride, dicyclo [2.2.1] heptane-2,3,5,6-tetrabasic carboxylic acid 2,3:5,6-dianhydride, dicyclo [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-(tetrahydrochysene-2,5-dioxa-3- Furyl) in-naphtho-[1,2-C] furan-1,3-diketone and dicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride at least One；

As aromatic tetracarboxylic acid's dianhydride 1 selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride In at least one；And

As aromatic tetracarboxylic acid's dianhydride 2 selected from 4,4 '-oxo double O-phthalic acid dianhydride (ODPA), 4,4 '-(hexafluoro isopropyl Fork base) double phthalic anhydrides (6FDA) and 4, at least one in 4 '-xenyl double (trihemellitic acid monoester anhydride),

When using CVD to form inoranic membrane with 350 DEG C on this Kapton, use atomic force microscope (AFM) to this The surface roughness of inoranic membrane surface measurements is 0.01～50nm.

24. Kaptons according to claim 23, wherein, described diamidogen is 2,2 '-bis-(trifluoromethyl) biphenyl Amine (TFMB),

Described tetracarboxylic dianhydride comprises:

As ester ring type tetracarboxylic dianhydride selected from 2,3,4-Tetramethylene. tetracarboxylic dianhydride (CBDA) and 1,2,4,5-hexamethylene four At least one in carboxylic acid dianhydride (H-PMDA)；

As aromatic tetracarboxylic acid's dianhydride 1 selected from pyromellitic dianhydride (PMDA) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride In at least one；And

As aromatic tetracarboxylic acid's dianhydride 2 selected from the double O-phthalic acid dianhydride (ODPA) of 4,4 '-oxo and 4,4 '-(hexafluoro is different Propylidene base) at least one in double phthalic anhydrides (6FDA).

25. 1 kinds of flexible devices, it comprises the Kapton described in claim 23 or 24.

The manufacture method of 26. 1 kinds of flexible devices, it includes the manufacture method of the Kapton described in claim 20.

The manufacture method of 27. 1 kinds of flexible devices, it includes the manufacture method of the duplexer described in claim 22.