CN105764991B

CN105764991B - Polyimide precursor composition, the manufacturing method of polyimides, polyimides, polyimide film and substrate

Info

Publication number: CN105764991B
Application number: CN201480064165.3A
Authority: CN
Inventors: 冈卓也; 小滨幸德; 久野信治
Original assignee: Ube Industries Ltd
Current assignee: Ube Corp
Priority date: 2013-11-27
Filing date: 2014-11-26
Publication date: 2018-10-26
Anticipated expiration: 2034-11-26
Also published as: CN105764991A; KR20160091936A; TWI658069B; KR102257869B1; KR20210063447A; JP2019108552A; CN109535423B; TW201525026A; CN109535423A; JP6721070B2; JPWO2015080158A1; KR102281153B1; JP6485358B2; WO2015080158A1

Abstract

The present invention relates to a kind of polyimide precursor compositions, which is characterized in that containing polyimide precursor and imidazole compound, the content of imidazole compound is less than 4 moles relative to 1 mole of the repetitive unit of polyimide precursor.

Description

Polyimide precursor composition, the manufacturing method of polyimides, polyimides, polyamides Imines film and substrate

Technical field

The present invention relates to comprising that can obtain, thickness direction phase difference (delay) is small, mechanical property is also excellent and transparent The property also liquid composite (polyimide precursor composition) of the polyimide precursor of excellent polyimides and polyimides Manufacturing method.In addition, that the invention further relates to the transparencys is excellent, thickness direction phase difference is small, also excellent polyamides is sub- for mechanical property Amine, polyimide film and substrate.

Background technology

In recent years, along with the arrival of advanced information society, it is aobvious that optical fiber, optical waveguide of optical communication field etc. are being carried out The exploitation of the optical materials such as liquid crystal orientation film, the colored filter protective film in showing device field.Especially led in display device Domain is actively being implemented the research of the light weight of the substitute as glass substrate and flexible excellent plastic base and can be bent Or form the exploitation of circular display.It is therefore desirable to can be used in the optical material of the higher performance of such purposes.

Aromatic polyimide due to intramolecular is conjugated, the formation of charge transfer complex and be substantially colored as yellowish-brown Color.Therefore, as the means for inhibiting to colour, such as following method is proposed：By importing fluorine atom to intramolecular, being assigned to main chain It gives bendability, import bulky group as side chain etc., inhibit the formation of intramolecular conjugation or charge transfer complex, to Make its performance transparency.

In addition, it is also proposed that by using half ester ring type or full-cream ring type for not forming charge transfer complex in principle Polyimides and make its performance the transparency method.

For example, being disclosed in Patent Documents 1 to 3 using aromatic tetracarboxylic acid's dianhydride as tetracarboxylic acid sour component, using fat The ring type diamines half ester ring type polyimides high as the transparency of diamine component.

In addition, for example, being disclosed in patent document 4~7 using ester ring type tetracarboxylic dianhydride as tetracarboxylic acid sour component, being made Half high ester ring type polyimides of the various transparencys of using aromatic diamine as diamine component.

Disclosed in non-patent literature 1 using norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornane -5, Polyimides of 5 ", 6, the 6 "-tetracarboxylic dianhydrides as tetracarboxylic acid sour component.In addition it describes：Norbornane -2- used herein 5,5 ", 6,6 "-tetracarboxylic dianhydride of spiral shell-α-cyclopentanone-α '-spiral shell -2 "-norbornanes-includes 6 kinds of stereoisomers.In patent text Also disclosed that in offering 8 using norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 " 5,5 ", 6,6 "-tetrabasic carboxylic acid two of-norbornane - Polyimides of the acid anhydride as tetracarboxylic acid sour component.

But according to the difference of purposes, especially in the fields such as display device, other than it is expected that the transparency is high, also It is expected that reducing thickness direction phase difference.By the way that through the big film of thickness direction phase difference, will produce sometimes can not correctly show face Fuzzy or visual angle the problems such as narrowing of color, color.Therefore, especially in the fields such as display device, it is desirable that thickness direction phase The small polyimide film of difference.

On the other hand, Patent Document 9 discloses by that will coordinate imidazoles in polyimide precursor (polyamic acid) The polyimides of masking liquid heating and formation made of quinoline based compound and/or imidazole compound.More specifically, in embodiment In 1, into the solution of the polyamic acid obtained by 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides and 4,4 '-benzidine ethers 2,4- methylimidazole quinolines are added to heat 1 hour at 200 DEG C by obtained solution coating to substrate, obtain film thicknessAromatic polyimide overlay film.In example 2, to by pyromellitic acid dianhydride and 4,4 '-diamino connection 2- ethyl imidazol(e)s quinoline and 1,2- methylimidazoles, by obtained solution coating are added in the solution for the polyamic acid that phenylate obtains Onto substrate, is heated 1 hour at 150 DEG C, obtain film thicknessAromatic polyimide overlay film.In patent text It is recorded in offering 9：By adding imidazoline based compound and/or imidazole compound, the notable coloring of sepia, energy are avoided Access the excellent liquid crystal display element of the high transparency of light transmittance.But the polyimides overlay film of embodiment 1 is used The light transmittance of the wavelength 400nm of the liquid crystal display element of (liquid crystal orientation film) is 82% (polyimides film thickness：0.1 μm), make Light transmittance with the wavelength 400nm of the liquid crystal display element of the polyimides overlay film (liquid crystal orientation film) of embodiment 2 is 83% (polyimides film thickness：0.08 μm), which does not simultaneously have the adequately transparency.

In addition, the manufacturing method as transparent low aromatic polyimide, Patent Document 10 discloses one kind The forming method of polyimide resin layer, wherein the polyimides such as polyimide precursor resin and imidazoles, N- methylimidazoles will be made The curing accelerator of precursor resin is dissolved in the solution coating containing polyimide precursor resin obtained from organic polar solvent and arrives On base material, polyimides tree dry and based on imidizate is completed in the range of 280~380 DEG C by subsequent heat treatment The formation of lipid layer, and describe：By using these curing accelerators, thermal linear expansion coefficient can be controlled relatively low. It is also described in patent document 10：It is preferable to use the curing accelerators that boiling point is more than 120 DEG C, preferably select boiling point and are no more than at heat The curing accelerator of the ceiling temperature of reason, and describe：The curing accelerator that boiling point is such as 400 DEG C or more is after amidation Polyimide resin layer in remaining ratio get higher, there is the tendency being had an impact to the function of polyimide resin layer.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2003-192787 bulletins

Patent document 2：Japanese Unexamined Patent Publication 2004-83814 bulletins

Patent document 3：Japanese Unexamined Patent Publication 2008-308550 bulletins

Patent document 4：Japanese Unexamined Patent Publication 2003-168800 bulletins

Patent document 5：International Publication No. 2008/146637

Patent document 6：Japanese Unexamined Patent Publication 2002-69179 bulletins

Patent document 7：Japanese Unexamined Patent Publication 2002-146021 bulletins

Patent document 8：International Publication No. 2011/099518

Patent document 9：Japanese Unexamined Patent Application 61-267030 bulletins

Patent document 10：Japanese Unexamined Patent Publication 2008-115378 bulletins

Non-patent literature

Non-patent literature 1：Macromolecule collection of thesis, Vol.68, No.3, P.127-131 (2011)

Invention content

Problem to be solved by the invention

Even if the present invention has been made in view of the above-described circumstances, and an object thereof is to provide can obtain the transparency it is excellent, Under same composition thickness direction phase difference also smaller polyimides or thickness direction phase difference are small, mechanical property is also excellent, And the polyimide precursor composition (liquid composite containing polyimide precursor) of transparent also excellent polyimides And the manufacturing method of polyimides.

The means used to solve the problem

The present invention relates to items below.

1. a kind of polyimide precursor composition, which is characterized in that

Including poly- containing repetitive unit shown in repetitive unit shown in following chemical formula (1) or following chemical formula (2) Imide precursor and imidazole compound,

The content of imidazole compound is less than 4 moles relative to 1 mole of the repetitive unit of polyimide precursor.

(in formula, X₁For the group of 4 valences with alicyclic structure, Y₁For the group of the divalent with aromatic ring, R₁、R₂Respectively From the aIkylsilyl groups for independently being hydrogen, the alkyl of carbon atom number 1~6 or carbon atom number 3~9)

(in formula, X₂For the group of 4 valences with aromatic ring, Y₂For the group of the divalent with alicyclic structure, R₃、R₄Respectively From the aIkylsilyl groups for independently being hydrogen, the alkyl of carbon atom number 1~6 or carbon atom number 3~9)

2. the polyimide precursor composition as described in above-mentioned item 1, which is characterized in that by the polyimide precursor composition The light transmittance of wavelength 400nm in the film of 10 μm of the thickness of obtained polyimides is 75% or more.

3. the polyimide precursor composition as described in above-mentioned item 1 or 2, which is characterized in that above-mentioned imidazole compound Content is 0.05 mole or more and 2 moles or less relative to 1 mole of the repetitive unit of polyimide precursor.

4. the polyimide precursor composition as described in any one of above-mentioned item 1~3, which is characterized in that above-mentioned imidazoles system The boiling point of compound at 1 atmosphere pressure is less than 340 DEG C.

5. the polyimide precursor composition as described in any one of above-mentioned item 1~4, which is characterized in that above-mentioned imidazoles system Compound is appointing in 1,2- methylimidazoles, 1- methylimidazoles, 2-methylimidazole, 2- phenylimidazoles, imidazoles or benzimidazole Meaning is a kind of.

6. a kind of manufacturing method of polyimides, which is characterized in that the polyamides described in any one of above-mentioned item 1~5 is sub- Amine precursor composition is heated under conditions of maximum heating temperature is more than 350 DEG C, by polyimide precursor acid imide Change.

7. the manufacturing method of the polyimides as described in above-mentioned item 6, which is characterized in that have：

By the polyimide precursor composition described in any one of above-mentioned item 1~5 be applied to process on base material and

Polyimide precursor composition on base material is carried out under conditions of maximum heating temperature is more than 350 DEG C at heating Reason and by the process of polyimide precursor imidizate.

8. the manufacturing method of the polyimides as described in above-mentioned item 6 or 7, which is characterized in that the highest of above-mentioned heat treatment Heating temperature is more than 400 DEG C.

9. a kind of polyimides is manufactured by the method described in any one of above-mentioned item 6~8.

10. the polyimides as described in above-mentioned item 9, which is characterized in that wavelength 400nm's in the film of 10 μm of thickness is saturating Light rate is 75% or more.

11. a kind of polyimide film is manufactured by the method described in any one of above-mentioned item 6~8.

12. a kind of display is used, touch panel is used or substrate used for solar batteries, which is characterized in that include above-mentioned item 9 Or the polyimides described in 10 or the polyimide film described in above-mentioned item 11.

Invention effect

Even if according to the present invention it is possible to provide can obtain the transparency it is excellent, under same composition thickness direction phase difference Also smaller polyimides or thickness direction phase difference are small, also excellent and transparent also excellent polyamides is sub- for mechanical property The polyimide precursor composition (liquid composite containing polyimide precursor) of amine and the manufacturing method of polyimides.

By the transparency for the polyimides (polyimides of the invention) that the polyimide precursor composition of the present invention obtains High and thick degree direction phase difference is small, also, thermal linear expansion coefficient is low, is easy to form fine circuit, can be suitable for shape At the substrate of display applications etc..In addition, the polyimides of the present invention can also be suitable for forming touch panel use, solar energy The substrate of battery.

Specific implementation mode

The polyimide precursor composition of the present invention includes containing repetitive unit or above-mentionedization shown in above-mentioned chemical formula (1) The polyimide precursor and imidazole compound of at least one of repetitive unit shown in formula (2), imidazole compound Content is less than 4 moles relative to 1 mole of the repetitive unit of polyimide precursor.

By containing in repetitive unit shown in repetitive unit or above-mentioned chemical formula (2) shown in above-mentioned chemical formula (1) extremely The transparency of polyimides, i.e. half ester ring type polyimides that a kind of few polyimide precursor obtains is high.Such transparent Property high polyimides in the case of, it is undesirable to the additive of coloring may be led to by using.But by by imidazole compound It is below less than 4 moles, preferably 0.05 mole or more and 2 moles with 1 mole of the repetitive unit relative to polyimide precursor Ratio is added in polyimide precursor composition, and it is small can to obtain thickness direction phase difference in the state of keeping high transparency Polyimides.That is, according to the present invention it is possible to being obtained while maintaining high transparency by the polyimide precursor of same composition The smaller polyimides of thickness direction phase difference.In addition, being less than 340 DEG C of imidazoles system using the boiling point under 1 atmospheric pressure In the case of closing object, the transparency of obtained polyimides further increases sometimes.

Transparent higher polyimides in order to obtain, it is considered that preferably at a lower temperature to polyimide precursor Heated to complete imidizate, but according to the present invention, even if being more than 350 DEG C by maximum heating temperature, especially excellent It selects the heat treatment more than 400 DEG C by polyimide precursor imidizate, can also manufacture the high polyimides of the transparency.It is tied Fruit, the maximum heating temperature that can be used in the heat treatment of imidizate are high temperature more than 350 DEG C, are particularly preferably more than 400 DEG C of high temperature, therefore, the mechanical property of obtained polyimides improve.That is, according to the present invention it is possible to obtaining the transparency It is high, thickness direction phase difference is small, mechanical property also excellent polyimides.

As described above, the polyimide precursor composition of the present invention includes single containing being repeated shown in above-mentioned chemical formula (1) The polyimide precursor of at least one of repetitive unit shown in first or above-mentioned chemical formula (2).

As the X in above-mentioned chemical formula (1)₁, the group for 4 valences with alicyclic structure that preferably carbon atom number is 4~40, As Y₁, the group for the divalent with aromatic ring that preferably carbon atom number is 6~40.

As the tetracarboxylic acid sour component for the repetitive unit for providing above-mentioned chemical formula (1), for example,：1,2,3,4- ring fourth Alkane tetrabasic carboxylic acid, two phenoxy group of isopropylidene double phthalic acid, hexamethylenes -1,2,4,5- tetrabasic carboxylic acids,;1,1 '-bis- (hexamethylenes Alkane) ]- 3,3 ', 4,4 '-tetrabasic carboxylic acid, [1,1 '-bis- (hexamethylene) ]- 2,3,3 ', 4 '-tetrabasic carboxylic acid, [1,1 '-bis- (hexamethylene) ]- 2, 2 ', 3,3 '-tetrabasic carboxylic acids, 4,4 '-di-2-ethylhexylphosphine oxides (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(propane -2,2- diyl) bis- (hexamethylenes Alkane -1,2- dicarboxylic acids), 4,4 '-oxygen bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-sulphur bis- (hexamethylene -1,2- dicarboxylic acids), 4, 4 '-sulfonyls bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(dimethylsilane diyls) bis- (hexamethylene -1,2- dicarboxylic acids), 4, 4 '-(tetrafluoropropane -2,2- diyls) bis- (hexamethylene -1,2- dicarboxylic acids), octahydro pentalene -1,3, it is 4,6- tetrabasic carboxylic acids, bicyclic [2.2.1]Heptane -2,3,5,6- tetrabasic carboxylic acids, 6- (carboxymethyl group) Shuan Huans [2.2.1]Heptane -2,3, it is 5- tricarboxylic acids, bicyclic [2.2.2]Octane -2,3,5,6- tetrabasic carboxylic acids, Shuan Huan [2.2.2]Octyl- 5- alkene -2,3,7,8- tetrabasic carboxylic acids, San Huan [4.2.2.02,5] Decane -3,4,7,8- tetrabasic carboxylic acids, San Huan [4.2.2.02,5]Decyl- 7- alkene -3,4,9,10- tetrabasic carboxylic acids, 9- oxatricyclos [4.2.1.02,5]Nonane -3,4,7,8- tetrabasic carboxylic acids, norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornanes 5,5 ", 6,6 "-tetrabasic carboxylic acids, (4arH, 8acH)-decahydro -1t, 4t：5c, 8c- dimethanonaphthalene -2c, 3c, 6c, 7c- tetrabasic carboxylic acid, (4arH, 8acH)-decahydro -1t, 4t：5c, 8c- dimethanonaphthalene -2t, 3t, 6c, 7c- tetrabasic carboxylic acid or their tetracarboxylic dianhydride, tetrabasic carboxylic acid The derivatives such as silyl ester, tetrabasic ester, four carboxyl acyl chlorides.Tetracarboxylic acid sour component can be used alone, and in addition can also combine makes With a variety of.

As the diamine component for the repetitive unit for providing above-mentioned chemical formula (1), for example,：P-phenylenediamine, isophthalic Diamines, benzidine, 3,3 '-diamino-biphenyl, 2,2 '-bis- (trifluoromethyl) benzidine, 3,3 '-bis- (trifluoromethyl) benzidine, Between tolidine, 4,4 '-diaminobenzene Formanilides, 3,4 '-diaminobenzene Formanilides, N, bis- (the 4- aminobenzenes of N '- Base) terephthalamide, N, N '-TOPOT 2,2′ p phenylenebis (Para Amino Benzamide), 4- amino-benzene oxygen -4- diaminobenzoic acids Ester, bis- (4- aminophenyls) terephthalates, bis- (4- aminophenyls) esters of 4,4 '-dicarboxylic acids of biphenyl-, TOPOT 2,2′ p phenylenebis are (right Aminobenzoate), bis- (4- aminophenyls)-[1,1 '-Lian Ben ]- 4,4 '-dicarboxylic ester, [1,1 '-Lian Ben ]- 4,4 '-diyls Bis- (4-aminobenzoic acid esters), 4,4 '-oxygen diphenylamines, 3,4 '-oxygen diphenylamines, 3,3 '-oxygen diphenylamines, to di-2-ethylhexylphosphine oxide (benzene two Amine), bis- (4- amino-benzene oxygens) benzene of 1,3-, bis- (3- amino-benzene oxygens) benzene of 1,3-, bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae-, 4, 4 '-bis- (4- amino-benzene oxygens) biphenyl, 4, bis- (4- (4- amino-benzene oxygens) benzene of 4 '-bis- (3- amino-benzene oxygens) biphenyl, 2,2- Base) hexafluoropropane, bis- (4- aminophenyls) hexafluoropropane of 2,2-, bis- (4- aminophenyls) sulfones, 3,3 '-bis- (trifluoromethyl) biphenyl Amine, 3,3 '-bis- ((amino-benzene oxygen) phenyl) propane, 2,2 '-bis- (3- amino-4-hydroxylphenyls) hexafluoropropane, bis- (4- (4- Amino-benzene oxygen) diphenyl) sulfone, bis- (4- (3- amino-benzene oxygens) diphenyl) sulfones, octafluorobiphenyl amine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3,3 '-two chloro- 4,4 '-benzidines, 3,3 '-two fluoro- 4, bis- (the 4- ammonia of 4 '-benzidines, 2,4- Base anilino-) -6- amino -1,3,5-triazines, bis- (4- aminobenzenes the amido) -6- methylaminos -1,3,5-triazines of 2,4-, 2,4- be bis- Bis- (4- aminobenzenes the amido) -6- anilino-s -1,3 of (4- aminobenzenes amido) -6- ethylaminos -1,3,5-triazines, 2,4-, 5- tri- Piperazine.Diamine component can be used alone, and in addition can also be applied in combination a variety of.

It should can contain containing the polyimide precursor of at least one of repetitive unit shown in above-mentioned chemical formula (1) upper State other repetitive units other than repetitive unit shown in chemical formula (1).As the tetracarboxylic acid sour component for providing other repetitive units And diamine component, it is not particularly limited, other well known aromatic series or aliphatic tetracarboxylic acid acids, well known aromatic series or aliphatic Diamines can use.Other tetracarboxylic acid sour components can be used alone, and in addition can also be applied in combination a variety of.Other diamines at Divide and can be used alone, in addition can also be applied in combination a variety of.

About the content of other repetitive units other than repetitive unit shown in above-mentioned chemical formula (1), preferably：Relative to complete Portion's repetitive unit is preferably 30 moles of % or less or is less than 30 moles of %, more preferably 20 moles of % or less, is more preferably 10 moles of % or less.

As the X in above-mentioned chemical formula (2)₂, the group for 4 valences with aromatic ring that preferably carbon atom number is 6~40, As Y₂, the group for the divalent with alicyclic structure that preferably carbon atom number is 4~40.

As the tetracarboxylic acid sour component for the repetitive unit for providing above-mentioned chemical formula (2), for example,：2,2- bis- (3,4- Dicarboxyphenyi) hexafluoropropane, 4- (2,5- dioxotetrahydro furans -3- bases) -1,2,3,4- naphthane -1,2- dicarboxylic acids, Benzenetetracarboxylic acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2,3,3 ', 4 '-biphenyltetracarboxyacid acids, 4, 4 '-oxygen, two phthalic acid, bis- (3,4- dicarboxyphenyi) sulfone dianhydrides, meta-terphenyl -3,4,3 ', 4 '-tetracarboxylic dianhydrides, to three Biphenyl -3,4,3 ', 4 '-tetracarboxylic dianhydrides, double carboxyl phenyl dimethylsilanes, double di carboxyl phenyloxy diphenylsulfides, sulphonyl The derivatives such as two phthalic acid of base or their tetracarboxylic dianhydride, tetrabasic carboxylic acid silyl ester, tetrabasic ester, four carboxyl acyl chlorides. Tetracarboxylic acid sour component can be used alone, and in addition can also be applied in combination a variety of.

As the diamine component for the repetitive unit for providing above-mentioned chemical formula (2), for example, Isosorbide-5-Nitrae-diamino hexamethylene Alkane, Isosorbide-5-Nitrae-diamino -2- hexahydrotoluenes, Isosorbide-5-Nitrae-diamino -2- ethyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- n-propyls hexamethylene, Isosorbide-5-Nitrae-diamino -2- isopropyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- n-butyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- isobutyl group hexamethylenes Alkane, Isosorbide-5-Nitrae-diamino -2- sec-butyls hexamethylene, Isosorbide-5-Nitrae-diamino -2- t-butylcyclohexanes, 1,2- diaminocyclohexanes, 1,3- Bis- (amino methyl) hexamethylenes of diamino cyclobutane, Isosorbide-5-Nitrae-, bis- (amino methyl) hexamethylenes of 1,3-, diamino bicyclic heptane, two Amino methyl norbornane, diamino oxygroup norbornane, bis aminomethyl oxygroup norbornane, isophorone diamine, diamino Base tristane, bis aminomethyl tristane, bis- (aminocyclohexyl) methane, bis- (aminocyclohexyl) isopropylidenes 6,6 '- Bis- (3- amino-benzene oxygens) -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindene is full, 6,6 '-bis- (4- amino-benzene oxygens) -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindene are full.Diamine component can be used alone, and in addition can also be applied in combination a variety of.

It should can contain containing the polyimide precursor of at least one of repetitive unit shown in above-mentioned chemical formula (2) upper State other repetitive units other than repetitive unit shown in chemical formula (2).As the tetracarboxylic acid sour component for providing other repetitive units And diamine component, it is not particularly limited, other well known aromatic series or aliphatic tetracarboxylic acid acids, well known aromatic series or aliphatic Diamines can use.Other tetracarboxylic acid sour components can be used alone, and in addition can also be applied in combination a variety of.Other diamines at Divide and can be used alone, in addition can also be applied in combination a variety of.

About the content of other repetitive units other than repetitive unit shown in above-mentioned chemical formula (2), preferably：Relative to complete Portion's repetitive unit is preferably 30 moles of % or less or is less than 30 moles of %, more preferably 20 moles of % hereinafter, further preferably 10 moles of % or less.

Polyimide precursor can contain at least one of repetitive unit and above-mentioned chemistry shown in above-mentioned chemical formula (1) At least one of repetitive unit shown in formula (2).In this case, single about being repeated shown in above-mentioned chemical formula (1) and (2) The content of other repetitive units other than member, it is also preferred that：It is preferably 30 moles of % or less relative to whole repetitive units or is less than 30 moles of %, more preferably 20 moles of % or less, further preferably 10 moles of % or less.

In one embodiment, as polyimide precursor, such as weight shown in following chemical formula (1-1) is preferably comprised Shown in the polyimide precursor of multiple unit, further preferably at least one following chemical formula (1-2) and following chemical formula (1-3) Total content of repetitive unit is relative to whole repetitive units shown in repetitive unit and chemical formula (1-2) and chemical formula (1-3) For the polyimide precursor of 80 moles of % or more.

(in formula, A is the group of the divalent with aromatic ring, R₁、R₂Be each independently hydrogen, carbon atom number 1~6 alkane The aIkylsilyl groups of base or carbon atom number 3~9)

Wherein, above-mentioned chemical formula (1-1), above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3) indicate, two norborneols Alkane ring (Shuan Huan [2.2.1]Heptane) 5 or 6 acidic groups reacted with amino and form amido bond (- CONH-), one A is the-COOR for not formed amido bond₁Shown in group or-COOR₂Shown in group.That is, above-mentioned chemical formula (1-1), above-mentionedization Include whole 4 kinds of constitutional isomers in formula (1-2) and above-mentioned chemical formula (1-3), i.e., (i) 5 is upper with-COOR₁Shown in Group, 6 it is upper on group shown in-CONH-, 5 " positions with-COOR₂Shown in group, there is on 6 " positions-CONH-A- Shown in group isomers；(ii) 6 above have-COOR₁Shown in group, 5 upper there are group, 5 " shown in-CONH- There is-COOR on position₂Shown in group, the isomers with group shown in-CONH-A- on 6 " positions；(iii) 5 it is upper have- COOR₁Shown in group, 6 it is upper on group shown in-CONH-, 6 " positions with-COOR₂Shown in group, have on 5 " positions There is the isomers of group shown in-CONH-A-；(iv) 6 above have-COOR₁Shown in group, 5 upper there is-CONH- institutes There is-COOR on the group that shows, 6 " positions₂Shown in group, the isomers with group shown in-CONH-A- on 5 " positions.

In addition, polyimide precursor preferably comprises the chemical formula that at least one A is group shown in following chemical formula (1-A) Repetitive unit, more preferable A shown in (1-1) are the chemical formula (1-2) and/or chemistry of group shown in following chemical formula (1-A) Repetitive unit shown in formula (1-3).

(in formula, m independently indicates that 0~3 integer, n independently indicate 0~3 integer.V, U, T are each independently represented One kind in the group being made of hydrogen atom, methyl, trifluoromethyl, Z, W each independently represent direct key or selected from by Formula：One kind in-NHCO- ,-CONH- ,-COO-, the group of group composition shown in-OCO-)

In other words, in one embodiment, polyimide precursor is by following tetracarboxylic acid sour components and following diamine components Obtained polyimide precursor, the tetracarboxylic acid sour component contain norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornane - 5,5 ", 6,6 "-tetracarboxylic acid acids etc., more preferably trans--Nei-it is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norborneol 5,5 ", 6,6 "-tetracarboxylic acid acids of alkane-etc. and/or cis--Nei-it is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norborneol 5,5 ", 6,6 "-tetracarboxylic acid acids of alkane-etc. (tetracarboxylic acid acids etc. indicate tetrabasic carboxylic acid and tetracarboxylic dianhydride, tetrabasic carboxylic acid silyl ester, The tetracarboxylic acid derivatives such as tetrabasic ester, four carboxyl acyl chlorides), which contains diamine component with aromatic ring, more preferably The repetition that A is the chemical formula (1-1), chemical formula (1-2) or chemical formula (1-3) of group shown in above-mentioned chemical formula (1-A) is provided The diamine component of unit.

As the tetracarboxylic acid sour component for the repetitive unit for providing above-mentioned chemical formula (1-1), norbornane -2- can be used alone One kind in 5,5 ", 6,6 "-tetracarboxylic acid acids of spiral shell-α-cyclopentanone-α '-spiral shell -2 "-norbornanes-etc., in addition can also be applied in combination It is a variety of.As the tetracarboxylic acid sour component for the repetitive unit for providing above-mentioned chemical formula (1-2), can be used alone trans--Nei-it is interior-drop One kind in 5,5 ", 6,6 "-tetracarboxylic acid acids of bornylane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornanes-etc., can also group It closes using a variety of.As the tetracarboxylic acid sour component for the repetitive unit for providing above-mentioned chemical formula (1-3), can be used alone it is cis--interior- One kind in 5,5 ", 6,6 "-tetracarboxylic acid acids of interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornane-etc., also may be used It is a variety of to be applied in combination.

It should be noted that in the polyimide precursor of more preferable mode, it can be used only and above-mentioned chemical formula (1- is provided 2) repetitive unit tetracarboxylic acid sour component (trans--Nei-is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornane - One or more of 5,5 ", 6,6 "-tetracarboxylic acid acids etc.), the repetitive unit that above-mentioned chemical formula (1-3) is provided can also be used only Tetracarboxylic acid sour component (cis--Nei-is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 " 5,5 ", 6,6 "-tetracarboxylic acid of-norbornane - Acids etc.) one or more of, can also use the repetitive unit that above-mentioned chemical formula (1-2) is provided tetracarboxylic acid sour component (it is trans-- Nei-is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 " 5,5 ", 6,6 "-tetracarboxylic acid acids etc. of-norbornane -) in one kind Above with the tetracarboxylic acid sour component of repetitive unit that above-mentioned chemical formula (1-3) is provided (cis--Nei-is interior-norbornane -2- spiral shells-α-ring 5,5 ", 6,6 "-tetracarboxylic acid acids of pentanone-α '-spiral shell -2 "-norbornane-etc.) one or more of the two.

In polyimide precursor, the total of repetitive unit contains shown in above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3) Amount relative to whole repetitive units is preferably 80 moles of % or more, that is, preferably comprises at least one above-mentioned chemical formula (1-2) and upper It states repetitive unit shown in chemical formula (1-3) and adds up in whole repetitive units containing preferably 80 moles of % or more, more excellent It is selected as the repetitive unit of 90 moles of % or more, further preferably 95 moles of % or more, particularly preferably 99 moles of % or more. By containing repetitive unit shown at least one above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3) and all repeating list Add up in member and subtracts containing the preferably repetitive unit of 80 moles of % or more, the thermal linear expansion coefficient of obtained polyimides It is small.

There is provided above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2), above-mentioned chemical formula (1-3) repetitive unit diamines Ingredient preferably comprises the diamines for providing that A is the repetitive unit of group shown in above-mentioned chemical formula (1-A).

Offer A is the chemical formula (1-1) or chemical formula (1-2), chemical formula (1-3) of the structure of above-mentioned chemical formula (1-A) The diamine component of repetitive unit has aromatic rings, with multiple aromatic rings, each other each independently by aromatic rings It is attached with direct key, amido bond or ester bond.The mutual link position of aromatic rings is not particularly limited, by 4 to ammonia Base or the mutual linker of aromatic rings are bonded and form linear structure, and obtained polyimides is sometimes up to low linear heat Expansion.In addition, can replace on aromatic rings has methyl, trifluoromethyl.It should be noted that the position of substitution does not limit especially It is fixed.

As the chemical formula (1-1) or chemical formula (1-2), chemical formula (1- for providing the structure that A is above-mentioned chemical formula (1-A) 3) diamine component of repetitive unit, is not particularly limited, for example, p-phenylenediamine, m-phenylene diamine (MPD), benzidine, 3, 3 '-diamino-biphenyl, 2,2 '-bis- (trifluoromethyl) benzidine, 3,3 '-bis- (trifluoromethyl) benzidine, tolidine, 4, 4 '-diaminobenzene Formanilides, 3,4 '-diaminobenzene Formanilides, N, bis- (4- aminophenyls) paraphenylene terephthalamides of N '- Amine, N, N '-TOPOT 2,2′ p phenylenebis (Para Amino Benzamide), 4- amino-benzene oxygen -4- diaminobenzoic acids ester, bis- (4- aminobenzenes Base) terephthalate, bis- (4- aminophenyls) esters of 4,4 '-dicarboxylic acids of biphenyl-, TOPOT 2,2′ p phenylenebis (P aminobenzoates), Bis- (4- aminophenyls)-[1,1 '-Lian Ben ]- 4,4 '-dicarboxylic ester, [1,1 '-Lian Ben ]- 4, the 4 '-bis- (4-aminobenzoic acid of diyl Ester) etc., it can be used alone, in addition can also be applied in combination a variety of.Wherein, preferably p-phenylenediamine, tolidine, 4,4 '- Diaminobenzene Formanilide, 4- amino-benzene oxygen -4- diaminobenzoic acids ester, 2,2 '-bis- (trifluoromethyl) benzidine, biphenyl Amine, N, bis- (4- aminophenyls) terephthalamides of N '-, bis- (4- aminophenyls) esters of 4,4 '-dicarboxylic acids of biphenyl-are more preferably right Phenylenediamine, 4,4 '-diaminobenzene Formanilides, 2,2 '-bis- (trifluoromethyl) benzidine.By using p-phenylenediamine, 4,4 '- Diaminobenzene Formanilide, 2, for 2 '-bis- (trifluoromethyl) benzidine as diamine component, obtained polyimides takes into account height Heat resistance and high-transmission rate.These diamines can be used alone, and in addition can also be applied in combination a variety of.It should be noted that adjacent The danger of tolidine is high, therefore not preferably.

As the repetitive unit for providing above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2), above-mentioned chemical formula (1-3) Diamine component, can be applied in combination provide A be above-mentioned chemical formula (1-A) structure group above-mentioned chemical formula (1-1) or on State chemical formula (1-2), above-mentioned chemical formula (1-3) repetitive unit diamine component other than other diamines.As other diamines Ingredient can use other aromatic series or aliphatic diamine class.As other diamine components, such as 4,4 '-oxygen two can be used Aniline, 3, it is 4 '-oxygen diphenylamines, 3,3 '-oxygen diphenylamines, bis- (4- aminophenyls) thioethers, bis- to di-2-ethylhexylphosphine oxide (phenylenediamine), 1,3- Bis- (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) benzene, 1,3-, bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae-, the bis- &#91 of 2,2-;4- (4- ammonia Phenoxyl) Ben Ji ]Bis- (4- aminophenyls) hexafluoropropane of hexafluoropropane, 2,2-, bis- (4- aminophenyls) sulfones, the bis- ((ammonia of 3,3- Phenoxyl) phenyl) propane, bis- (3- amino-4-hydroxylphenyls) hexafluoropropane of 2,2-, bis- (4- (4- amino-benzene oxygens) hexichol Base) sulfone, bis- (4- (3- amino-benzene oxygens) diphenyl) sulfones, octafluorobiphenyl amine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 3,3 '-two chloro- 4,4 '-benzidines, 3,3 '-two fluoro- 4, bis- (4- aminophenyls) fluorenes of 4 '-benzidines, 9,9-, 4, 4 '-bis- (4- amino-benzene oxygens) biphenyl, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, Isosorbide-5-Nitrae-diaminocyclohexane, Isosorbide-5-Nitrae-diamino Base -2- hexahydrotoluenes, Isosorbide-5-Nitrae-diamino -2- ethyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- n-propyls hexamethylene, Isosorbide-5-Nitrae-diamino - 2- isopropyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- n-butyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- isobutyls butylcyclohexane, Isosorbide-5-Nitrae-diamino Base -2- sec-butyls hexamethylene, Isosorbide-5-Nitrae-diamino -2- t-butylcyclohexanes, 1,2- diaminocyclohexanes, Isosorbide-5-Nitrae-diamino hexamethylene Bis- (amino methyl) hexamethylenes of alkane, 1,3- diamino cyclobutane, Isosorbide-5-Nitrae-, bis- (amino methyl) hexamethylenes of 1,3-, diamino bicyclic Heptane, bis aminomethyl norbornane, diamino oxygroup norbornane, bis aminomethyl oxygroup norbornane, isophorone two Amine, diamino tristane, bis aminomethyl tristane, bis- (aminocyclohexyl) methane, bis- (aminocyclohexyls) sub- isopropyl Base 6,6 '-bis- (3- amino-benzene oxygens) -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindene is full, 6,6 '-bis- (4- amino-benzene oxygens) - 3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindene completely waits or their derivative, can be used alone, in addition can also combine makes With a variety of.

It is the upper of structure shown in above-mentioned chemical formula (1-A) that the polyimide precursor of the present invention, which preferably comprises at least one A, The repetitive unit of chemical formula (1-1) is stated, further preferably at least one A is the above-mentioned of structure shown in above-mentioned chemical formula (1-A) The repetitive unit and/or at least one A of chemical formula (1-2) are the above-mentioned chemical formula (1- of structure shown in above-mentioned chemical formula (1-A) 3) repetitive unit.In other words, repetitive unit that above-mentioned chemical formula (1-1) is provided, more preferable above-mentioned chemical formula (1-2) and above-mentioned The diamine component of the repetitive unit of chemical formula (1-3) preferably comprises the above-mentioned chemistry for providing the structure that A is above-mentioned chemical formula (1-A) Formula (1-1) or above-mentioned chemical formula (1-2), above-mentioned chemical formula (1-3) repetitive unit diamine component.By making offer above-mentionedization The repetitive unit of formula (1-1), the more preferably diamine component of above-mentioned chemical formula (1-2) and the A in above-mentioned chemical formula (1-3) are to carry The weight of above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2), above-mentioned chemical formula (1-3) for the structure of above-mentioned chemical formula (1-A) The heat resistance of the diamine component of multiple unit, obtained polyimides improves.

In the polyimide precursor of the present invention, preferably：Provide above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2) and In 100 moles of % of diamine component of A in above-mentioned chemical formula (1-3), the diamine component of the structure of above-mentioned chemical formula (1-A) is provided Total preferably 50 moles of % or more, more preferably 70 moles of % or more, more preferably 80 moles of % or more of ratio, further Preferably 90 moles of % or more, particularly preferably 100 moles of %.In other words, preferably：In above-mentioned chemical formula (1-1) or above-mentionedization In whole repetitive units shown in formula (1-2) and above-mentioned chemical formula (1-3), A is the above-mentioned of the structure of above-mentioned chemical formula (1-A) More than one ratio of chemical formula (1-1) or the repetitive unit of above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3) is total Preferably 50 moles of % or more, more preferably 70 moles of % or more, more preferably 80 moles of % or more, it further preferably 90 rubs You are % or more, particularly preferably 100 moles of %.The ratio for providing the diamine component of the structure of above-mentioned chemical formula (1-A) is less than 50 When mole %, the thermal linear expansion coefficient of obtained polyimides increases sometimes.In one embodiment, from obtained From the viewpoint of the mechanical property of polyimides, it is sometimes preferred to：Above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2) are being provided In 100 moles of % of diamine component of the A in above-mentioned chemical formula (1-3), provide the diamines of the structure of above-mentioned chemical formula (1-A) at It is preferably 80 moles of % or less that the ratio divided is total, is more preferably 90 moles of % or less or is less than 90 moles of %.For example, providing The diamine component 100 of above-mentioned chemical formula (1-1) or the repetitive unit of above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3) rubs In your %, 4 can be used to be preferably shorter than the % of 20 moles of %, more preferably 10 moles of % or less, more preferably less than 10 moles, Other aromatic series such as 4 '-oxygen diphenylamines or aliphatic diamine class.

In one embodiment, the polyimides containing repetitive unit shown in above-mentioned chemical formula (1-1) of the invention Precursor preferably comprises the repetitive unit that at least two A are the chemical formula (1-1) of structure shown in above-mentioned chemical formula (1-A) sometimes. In one embodiment, of the invention to contain repetitive unit and/or above-mentioned chemical formula (1- shown in above-mentioned chemical formula (1-2) 3) it is to be tied shown in above-mentioned chemical formula (1-A) that the polyimide precursor of repetitive unit shown in preferably comprises at least two A sometimes The chemical formula (1-2) of structure or the repetitive unit of chemical formula (1-2).In other words, the repetitive unit of above-mentioned chemical formula (1-1) is provided The diamine component of diamine component or the repetitive unit of the above-mentioned chemical formula (1-2) of offer and above-mentioned chemical formula (1-3) preferably contains sometimes It is the above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2) and upper of the structure of above-mentioned chemical formula (1-A) to have at least two offer A State the diamine component of the repetitive unit of chemical formula (1-3).By making the A or above-mentioned chemical formulas in the above-mentioned chemical formula of offer (1-1) The diamine component of (1-2) and the A in above-mentioned chemical formula (1-3) contain the above-mentioned chemistry for the structure for being provided with above-mentioned chemical formula (1-A) At least two in the diamine component of formula (1-1) or the repetitive unit of above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3), institute The high transparency of obtained polyimides can obtain balance (i.e., it is possible to obtain transparent high and linear with low linear thermal expansion The low polyimides of coefficient of thermal expansion).

It should be noted that it is above-mentioned chemical formula (1-A) that the polyimide precursor of the present invention, which can contain at least two A, The repetitive unit of the above-mentioned chemical formula (1-2) of structure, alternatively, it is also possible to contain the knot that at least two A are above-mentioned chemical formula (1-A) The repetitive unit of the above-mentioned chemical formula (1-3) of structure, furthermore it is also possible to contain the structure that at least one A is above-mentioned chemical formula (1-A) Above-mentioned chemical formula (1-2) repetitive unit and at least one A be above-mentioned chemical formula (1-A) structure above-mentioned chemical formula (1- 3) repetitive unit.

In one embodiment, polyimide precursor of the invention is sometimes more preferable：

(i) contain at least one A be m and/or n for 1~3, Z and/or W be each independently-NHCO- ,-CONH- ,- Above-mentioned chemical formula (1-1), the preferably above-mentioned chemistry of the structure of the above-mentioned chemical formula (1-A) of any one in COO- or-OCO- The repetitive unit (I) of formula (1-2) and above-mentioned chemical formula (1-3)；

(ii) contain at least one A be the structure for the above-mentioned chemical formula (1-A) that m and n is 0 or A be m and/or n be 1~ 3, Z and W be the above-mentioned chemical formula (1-1) of structure of the above-mentioned chemical formula (1-A) of direct key, preferably above-mentioned chemical formula (1-2) and The repetitive unit (II) of above-mentioned chemical formula (1-3).

In the embodiment, as above-mentioned repetitive unit (I), such as preferred A is in following chemical formula (D-1)~(D-3) Any one shown in structure above-mentioned chemical formula (1-1) repetitive unit, more preferable A be following chemical formula (D-1)~(D- 2) repetitive unit of the above-mentioned chemical formula (1-1) of structure shown in any one in.It should be noted that it is following to provide A The diamine component of the repetitive unit of the above-mentioned chemical formula (1-1) of structure shown in chemical formula (D-1) or following chemical formula (D-2) is 4,4 '-diaminobenzene Formanilides provide the weight that A is the above-mentioned chemical formula (1-1) of structure shown in following chemical formula (D-3) The diamine component of multiple unit is bis- (4- aminophenyls) terephthalates, these diamines can be used alone, in addition can also It is applied in combination a variety of.

In the embodiment, as above-mentioned repetitive unit (II), such as preferred A is in following chemical formula (D-4)~(D-6) Any one shown in structure above-mentioned chemical formula (1-1) repetitive unit, more preferable A be following chemical formula (D-4)~(D- 5) repetitive unit of the above-mentioned chemical formula (1-1) of structure shown in any one in.It should be noted that it is following to provide A The diamine component of the repetitive unit of the above-mentioned chemical formula (1-1) of structure shown in chemical formula (D-4) is p-phenylenediamine, and providing A is The diamine component of the repetitive unit of the above-mentioned chemical formula (1-1) of structure shown in following chemical formula (D-5) is 2,2 '-bis- (trifluoros Methyl) benzidine, the diamines that A is the repetitive unit of the above-mentioned chemical formula (1-1) of structure shown in following chemical formula (D-6) is provided Ingredient be between tolidine, these diamines can be used alone, in addition can also be applied in combination a variety of.

In the polyimide precursor of the embodiment, preferably：The ratio of more than one above-mentioned repetitive unit (I) is above-mentioned 30 moles of % or more and 70 mole of % are added up to hereinafter, more than one is upper in whole repetitive units shown in chemical formula (1-1) The ratio for stating repetitive unit (II) all repeats to add up to 30 moles of % or more in single members shown in above-mentioned chemical formula (1-1) And 70 moles of % or less；Particularly preferably：The ratio of more than one above-mentioned repetitive unit (I) is shown in above-mentioned chemical formula (1-1) Whole repetitive units in add up to 40 moles of % or more and 60 mole of % hereinafter, more than one above-mentioned repetitive unit (II) Ratio adds up to 40 moles of % or more and 60 mole of % or less in whole repetitive units shown in above-mentioned chemical formula (1-1). In a certain embodiment, add up in ratio whole repetitive units shown in above-mentioned chemical formula (1-1) of above-mentioned repetitive unit (I) More preferably less than 60 moles of %, more preferably 50 moles of % or less, particularly preferably 40 moles of % or less.In addition, in a certain reality It applies in mode, it is sometimes preferred to：In whole repetitive units shown in above-mentioned chemical formula (1-1), to be preferably shorter than 20 moles of %, more Preferably 10 moles of % or less, especially preferably less than 10 moles of % contain above-mentioned repetitive unit (I) and above-mentioned repetitive unit (II) In addition, repetitive unit shown in other above-mentioned chemical formulas (1-1) (for example, A be with multiple aromatic rings and aromatic rings each other by The structure of ehter bond (- O-) connection).In addition, in one embodiment, also sometimes preferably：More than one above-mentioned repetitive unit (I) ratio added up in whole repetitive units shown in above-mentioned chemical formula (1-1) 20 moles of % or more and 80 mole of % with Under, add up in ratio whole repetitive units shown in above-mentioned chemical formula (1-1) of more than one above-mentioned repetitive unit (II) For 20 moles of % or more and 80 mole of % or less.

In one embodiment, it is of the invention containing above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2) and/or on In the polyimide precursor for stating the repetitive unit of chemical formula (1-3), preferably：Above-mentioned chemical formula (1-1) or above-mentioned chemical formula are provided The diamine component of (1-2) and the A in above-mentioned chemical formula (1-3) (provide the repetitive unit or above-mentionedization of above-mentioned chemical formula (1-1) The diamine component of the repetitive unit of formula (1-2) and above-mentioned chemical formula (1-3)) containing the structure for being provided with above-mentioned chemical formula (1-A) Diamine component at least two, and one such is 4,4 '-diaminobenzene Formanilides.By making offer above-mentionedization Formula (1-1) or the diamine component of above-mentioned chemical formula (1-2) and the A in above-mentioned chemical formula (1-3), which contain, is provided with above-mentioned chemical formula In the diamine component of the structure of (1-A) at least two and it is one such be 4,4 '-diaminobenzene Formanilides, can obtain To the polyimides for also having both high-fire resistance on the basis of high transparency and low linear thermal expansion.

In one embodiment, it is of the invention containing above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2) and/or on In the polyimide precursor for stating the repetitive unit of chemical formula (1-3), particularly preferably：Above-mentioned chemical formula (1-1) or above-mentionedization are provided Formula (1-2) and the A in above-mentioned chemical formula (1-3) diamine component (provide above-mentioned chemical formula (1-1) repetitive unit or on State the diamine component of the repetitive unit of chemical formula (1-2) and above-mentioned chemical formula (1-3)) containing selected from 2,2 '-bis- (trifluoromethyls) At least one of benzidine and p-phenylenediamine and 4,4 '-diaminobenzene Formanilides.By the way that these diamine components are combined, It can obtain having both the polyimides of high transparency and low linear thermal expansion, heat resistance.

In the embodiment, as the above-mentioned chemical formula (1-1) of offer or above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1- 3) diamine component of the A in (provides the repetitive unit or above-mentioned chemical formula (1-2) and above-mentioned chemical formula of above-mentioned chemical formula (1-1) The diamine component of the repetitive unit of (1-3)), preferably contain 4,4 '-diaminobenzenes with 20 moles of % or more and 80 mole of % or less Formanilide and with 20 moles of % or more and 80 mole of % or less contain p-phenylenediamine and 2,2 '-bis- (trifluoromethyls) connection In aniline any one or both, more preferably contain 4,4 '-diaminobenzene first with 30 moles of % or more and 70 mole of % or less Anilid and with 30 moles of % or more and 70 mole of % or less contain p-phenylenediamine and 2,2 '-bis- (trifluoromethyl) biphenyl In amine any one or both, particularly preferably contain 4,4 '-diaminobenzene first with 40 moles of % or more and 60 mole of % or less Anilid and with 40 moles of % or more and 60 mole of % or less contain p-phenylenediamine and 2,2 '-bis- (trifluoromethyl) biphenyl In amine any one or both.As the above-mentioned chemical formula (1-1) of offer or above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1- 3) diamine component of the A in replaces benzene by containing 4,4 '-diaminobenzene formyls with 30 moles of % or more and 70 mole of % or less Amine and contain p-phenylenediamine and 2 with 30 moles of % or more and 70 mole of % or less, in 2 '-bis- (trifluoromethyl) benzidine Any one or both can obtain the polyimides for having both high transparency and low linear thermal expansion, heat resistance.In a certain reality It applies in mode, two as the A provided in above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3) Amine component (provides the repetition of the repetitive unit or above-mentioned chemical formula (1-2) and above-mentioned chemical formula (1-3) of above-mentioned chemical formula (1-1) The diamine component of unit), more preferably contain 4,4 '-diaminobenzene Formanilides to be less than 60 moles of %, more preferably rubs with 50 Your % or less contains, and is particularly preferably contained with 40 moles of % or less.

The polyimide precursor of the present invention can contain above-mentioned chemical formula (1-1) or above-mentioned chemical formula (1-2) and above-mentionedization Other repetitive units other than repetitive unit shown in formula (1-3).

As the tetracarboxylic acid sour component for providing other repetitive units, other aromatic series or aliphatic tetracarboxylic acid acids can be used. For example, 2,2- bis- (3,4- dicarboxyphenyi) hexafluoropropane, 4- (2,5- dioxotetrahydro furans -3- bases) -1,2,3, 4- naphthanes -1,2- dicarboxylic acids, pyromellitic acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acids, 3,3 ', 4,4 '-biphenyltetracarboxyacid acids, 2, 3,3 ', 4 '-biphenyltetracarboxyacid acids, 4,4 '-oxygen, two phthalic acid, bis- (3,4- dicarboxyphenyi) sulfone dianhydrides, meta-terphenyl -3,4, 3 ', 4 '-tetracarboxylic dianhydrides, para-terpheny -3,4,3 ', 4 '-tetracarboxylic dianhydrides, double carboxyl phenyl dimethylsilanes, double dicarboxyls Phenoxy group diphenylsulfide, two phthalic acid of sulfonyl, 1,2,3,4- cyclobutane tetrabasic carboxylic acids, two phenoxy group of isopropylidene are double adjacent Phthalic acid, hexamethylene -1,2,4,5- tetrabasic carboxylic acid, [1,1 '-bis- (hexamethylene) ]- 3,3 ', 4,4 '-tetrabasic carboxylic acid, [1,1 '-bis- (rings Hexane) ]- 2,3,3 ', 4 '-tetrabasic carboxylic acid, [1,1 '-bis- (hexamethylene) ]- 2,2 ', 3,3 '-tetrabasic carboxylic acids, 4,4 '-di-2-ethylhexylphosphine oxide (hexamethylenes Alkane -1,2- dicarboxylic acids), 4,4 '-(propane -2,2- diyls) bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-oxygen it is bis- (hexamethylene -1, 2- dicarboxylic acids), 4,4 '-sulphur bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-sulfonyls bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 ' - (dimethylsilane diyl) bis- (hexamethylene -1,2- dicarboxylic acids), 4,4 '-(tetrafluoropropane -2,2- diyl) bis- (hexamethylenes -1,2- Dicarboxylic acids), octahydro pentalene -1,3,4,6- tetrabasic carboxylic acids, Shuan Huan [2.2.1]Heptane -2,3,5,6- tetrabasic carboxylic acids, 6- (carboxymethyl group) Shuan Huan [2.2.1]Heptane -2,3,5- tricarboxylic acids, Shuan Huan [2.2.2]Octane -2,3,5,6- tetrabasic carboxylic acids, Shuan Huan [2.2.2]Octyl- 5- Alkene -2,3,7,8- tetrabasic carboxylic acids, San Huan [4.2.2.02,5]Decane -3,4,7,8- tetrabasic carboxylic acids, San Huan [4.2.2.02,5]Decyl- 7- Alkene -3,4,9,10- tetrabasic carboxylic acids, 9- Yang Zasanhuans [4.2.1.02,5]Nonane -3,4,7,8- tetrabasic carboxylic acids, (4arH, 8acH)-ten Hydrogen -1t, 4t：5c, 8c- dimethanonaphthalene -2c, 3c, 6c, 7c- tetrabasic carboxylic acid, (4arH, 8acH)-decahydro -1t, 4t：5c, 8c- diformazan Derivatives or their acid dianhydrides such as bridge naphthalene -2t, 3t, 6c, 7c- tetrabasic carboxylic acid, can be used alone, and in addition can also combine makes With a variety of.Wherein, it is easy, from the viewpoint of the excellent heat resistance of obtained polyimides from the manufacture of polyimides, it is more excellent Select Shuan Huan [2.2.1]Heptane -2,3,5,6- tetrabasic carboxylic acids, Shuan Huan [2.2.2]Octane -2,3,5,6- tetrabasic carboxylic acids, (4arH, 8acH) - Decahydro -1t, 4t：5c, 8c- dimethanonaphthalene -2c, 3c, 6c, 7c- tetrabasic carboxylic acid, (4arH, 8acH)-decahydro -1t, 4t：5c, 8c- bis- Derivatives or their acid dianhydrides such as methanonaphthalene -2t, 3t, 6c, 7c- tetrabasic carboxylic acid.These acid dianhydrides can be used alone, in addition It can also be applied in combination a variety of.

In addition, before the polyimides of the repetitive unit containing above-mentioned chemical formula (1-2) and/or above-mentioned chemical formula (1-3) It, can also-norbornane -2- interior using cis--Nei-as the tetracarboxylic acid sour component for providing other repetitive units in the case of body 5,5 ", 6,6 "-tetracarboxylic acid acids of spiral shell-α-cyclopentanone-α '-spiral shell -2 "-norbornanes-etc. and trans--Nei-it is interior-norbornane -2- spiral shells - Other than 5,5 ", 6,6 "-tetracarboxylic acid acids of α-cyclopentanone-α '-spiral shell -2 "-norbornanes-etc., other norbornanes -2- spiral shells-α-ring 5,5 ", 6,6 "-tetracarboxylic acid acids of pentanone-α '-spiral shell -2 "-norbornane-etc. is (for example, norbornane -2- spiral shells-α-cyclopentanone-α ' - Spiral shell -2 "-norbornane -5,5 ", 6,6 "-tetracarboxylic dianhydrides) 4 kinds of stereoisomers.

The diamine component for providing other repetitive units can be the diamine component for the structure for providing above-mentioned chemical formula (1-A). In other words, can be the knot of above-mentioned chemical formula (1-A) used as offer A as the diamine component for providing other repetitive units The repetitive unit or A of the above-mentioned chemical formula (1-1) of structure are the above-mentioned chemical formula (1-2) of structure of above-mentioned chemical formula (1-A) and upper State diamines illustrated by the diamine component of the repetitive unit of chemical formula (1-3).These diamines can be used alone, and in addition can also It is applied in combination a variety of.

As the diamine component for providing other repetitive units, other aromatic series or aliphatic diamine class can be used.Such as Can enumerate 4,4 '-oxygen diphenylamines, 3,4 '-oxygen diphenylamines, 3,3 '-oxygen diphenylamines, bis- (4- aminophenyls) thioethers, to methylene Bis- (4- amino-benzene oxygens) benzene of bis- (phenylenediamines), 1,3-, bis- (3- amino-benzene oxygens) benzene of 1,3-, Isosorbide-5-Nitrae-are bis- (4- amino-benzene oxygens) The bis- &#91 of benzene, 2,2-;4- (4- amino-benzene oxygens) Ben Ji ]Bis- (4- aminophenyls) hexafluoropropane of hexafluoropropane, 2,2-, bis- (4- amino Phenyl) sulfone, bis- ((amino-benzene oxygen) phenyl) propane of 3,3-, bis- (3- amino-4-hydroxylphenyls) hexafluoropropane of 2,2-, bis- (4- (4- amino-benzene oxygens) diphenyl) sulfone, bis- (4- (3- amino-benzene oxygens) diphenyl) sulfones, octafluorobiphenyl amine, 3,3 '-dimethoxies 4,4 '-benzidine of base-, 3,3 '-two chloro- 4,4 '-benzidines, 3,3 '-two fluoro- 4,4 '-benzidines, 9,9- are bis- (4- aminophenyls) fluorenes, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, 4,4 '-bis- (3- amino-benzene oxygens) biphenyl, Isosorbide-5-Nitrae-diamino Hexamethylene, Isosorbide-5-Nitrae-diamino -2- hexahydrotoluenes, Isosorbide-5-Nitrae-diamino -2- ethyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- n-propyl rings Hexane, Isosorbide-5-Nitrae-diamino -2- isopropyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- n-butyl cyclohexanes, Isosorbide-5-Nitrae-diamino -2- isobutyl groups Hexamethylene, Isosorbide-5-Nitrae-diamino -2- sec-butyls hexamethylene, Isosorbide-5-Nitrae-diamino -2- t-butylcyclohexanes, 1,2- diaminocyclohexanes, Bis- (amino methyl) hexamethylenes of Isosorbide-5-Nitrae-diaminocyclohexane, 1,3- diamino cyclobutane, Isosorbide-5-Nitrae-, bis- (amino methyl) hexamethylenes of 1,3- Alkane, diamino bicyclic heptane, bis aminomethyl norbornane, diamino oxygroup norbornane, bis aminomethyl oxygroup bicyclic heptan Alkane, isophorone diamine, diamino tristane, bis aminomethyl tristane, bis- (aminocyclohexyl) methane, bis- (amino Cyclohexyl) isopropylidene 6,6 '-bis- (3- amino-benzene oxygens) -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindene is full, 6, and 6 '-is bis- (4- amino-benzene oxygens) -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobiindene completely waits or their derivative, can be used alone, separately It can also be applied in combination outside a variety of.

It should be noted that norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 " 5,5 ", 6,6 "-tetracarboxylic acid of-norbornane - The synthetic method of acids etc. is not particularly limited, and can be synthesized by method described in Patent Document 8 etc..Such as non-patent literature Also include multiple stereoisomers sometimes according to the difference of synthetic method as 1 is recorded.By using chromatographic column etc. pair 5,5 ", 6,6 "-tetracarboxylic acid acids of norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornanes-etc. or in which mesosome carry out pure Change, can separately divide and take stereoisomer or point mixture for taking stereoisomer a variety of.

For trans--Nei-it is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornane -5,5 ", 6,6 "-four Carboxylic acids etc. and cis--Nei-it is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 " 5,5 ", 6,6 "-tetracarboxylic acid of-norbornane - The single substance of acids etc. or their mixture, can also be by using chromatographic column etc. to norbornane -2- spiral shells-α-ring penta 5,5 ", 6,6 "-tetracarboxylic acid acids of ketone-α '-spiral shell -2 "-norbornane-etc. or in which mesosome are purified to obtain.

In the case where tetracarboxylic acid sour component and diamine component include isomers, it is used to polymerize after the isomers can be detached Deng alternatively, it is also possible to which isomers is used for polymerization etc. with the state of mixture.

In the polyimide precursor of the present invention, the R of above-mentioned chemical formula (1)₁、R₂, above-mentioned chemical formula (2) R₃、R₄Respectively solely It is on the spot in hydrogen, carbon atom number 1~6, the preferably alkyl of carbon atom number 1~3 or the aIkylsilyl groups of carbon atom number 3~9 Any one.R₁And R₂、R₃And R₄The importing of the type and functional group of its functional group can be changed according to aftermentioned manufacturing method Rate.

In R₁And R₂、R₃And R₄In the case of for hydrogen, the manufacture with polyimides is readily inclined to.

In addition, in R₁And R₂、R₃And R₄In the case of for carbon atom number 1~6, the preferably alkyl of carbon atom number 1~3, have The tendency of the excellent storage stability of polyimide precursor.In this case, R₁And R₂、R₃And R₄More preferably methyl or ethyl.

In addition, in R₁And R₂、R₃And R₄In the case of aIkylsilyl groups for carbon atom number 3~9, there is polyimides The excellent tendency of the dissolubility of precursor.In this case, R₁And R₂、R₃And R₄More preferably trimethyl silyl or tertiary butyl Dimetylsilyl.

The Drug delivery rate of functional group is not particularly limited, and in the case where importing alkyl or aIkylsilyl groups, can make R₁ And R₂、R₃And R₄Respective 25% or more, preferably 50% or more, more preferable 75% or more is alkyl or aIkylsilyl groups.

The polyimide precursor of the present invention can be according to R₁And R₂、R₃And R₄The classification of chemical structure taken is：1) polyamide Acid (R₁And R₂、R₃And R₄For hydrogen), 2) poly amic acid ester (R₁And R₂、R₃And R₄In at least part be alkyl), 3) 4) polyamide Sour silyl ester (R₁And R₂、R₃And R₄In at least part be aIkylsilyl groups).Also, the polyimides of the present invention Precursor can be easily manufactured according to the classification by manufacturing method below.But the system of polyimide precursor of the invention The method of making is not limited to manufacturing method below.

1) polyamic acid

The polyimide precursor of the present invention can be fitted by following methods in the form of polyimide precursor solution composition Locality obtains：In a solvent, make the tetracarboxylic dianhydride as tetracarboxylic acid sour component with diamine component with substantially equimolar, preferably diamines Molar ratio of the ingredient relative to tetracarboxylic acid sour component;The molal quantity of the molal quantity of diamine component/tetracarboxylic acid sour component;Preferably 0.90~ 1.10, be more preferably 0.95~1.05 ratio under such as 120 DEG C of lower temperatures below while inhibiting imidizate It is reacted.

It is not defined, more specifically, dissolves diamines in organic solvent, delay while agitating into the solution Tetracarboxylic dianhydride is slowly added, is stirred 1~72 hour in the range of 0~120 DEG C, preferably 5~80 DEG C, polyamides Asia is thus obtained Amine precursor.In the case where being reacted for 80 DEG C or more, molecular weight can depend on temperature history when polymerization and change, and And can imidizate be carried out due to heat, it is thus possible to can not steadily manufacture polyimide precursor.In above-mentioned manufacturing method The order of addition of diamines and tetracarboxylic dianhydride are easy to improve the molecular weight of polyimide precursor, therefore preferably.Alternatively, it is also possible to make The diamines of above-mentioned manufacturing method and the order of addition of tetracarboxylic dianhydride in turn, due to precipitate reduce and it is preferred that.

In addition, be that diamine component is excessive in tetracarboxylic acid sour component and the molar ratio of diamine component, it can be according to need The carboxylic acid derivates for adding the amount for the molar excess number for being roughly equivalent to diamine component make tetracarboxylic acid sour component and diamine component Molar ratio approximately equivalent.As carboxylic acid derivates herein, the viscosity of polyimide precursor solution is not preferably made substantially Increase, the tricarboxylic acids that is substantially not involved in the extended tetrabasic carboxylic acid of strand or plays a role as end terminator and its acid anhydride, Dicarboxylic acids and its acid anhydride etc..

2) poly amic acid ester

Tetracarboxylic dianhydride is set to be reacted with arbitrary alcohol, after obtaining diester dicarboxylic acids, with chlorination reagent (thionyl chloride, oxalyl Chlorine etc.) reaction, obtain diester dicarboxylic acid chloride.By diester dicarboxylic acid chloride and diamines -20~120 DEG C, preferably -5 It is stirred 1~72 hour in the range of~80 DEG C, thus obtains polyimide precursor.In the case where being reacted for 80 DEG C or more, Molecular weight can depend on temperature history when polymerization and change, and can carry out imidizate due to heat, it is thus possible to Polyimide precursor can not steadily be manufactured.In addition, by using phosphorus system condensing agent, carbon imidodicarbonic diamide condensing agent etc. to diester two Carboxylic acid and diamines carry out dehydrating condensation, can also easily obtain polyimide precursor.

It is stable by the polyimide precursor that this method obtains, accordingly it is also possible to which water, alcohol equal solvent is added to carry out The purifying such as reprecipitation.

3) polyamic acid silyl ester (indirect method)

So that diamines is reacted with silylating agent in advance, obtains silylated diamines.As needed, pass through distillation etc. Carry out the purifying of silylated diamines.Then, so that silylated diamines is dissolved in dewatered solvent, stirring While slowly add tetracarboxylic dianhydride, stir 1~72 hour in the range of 0~120 DEG C, preferably 5~80 DEG C, thus To polyimide precursor.In the case where being reacted for 80 DEG C or more, molecular weight can depend on temperature history when polymerization and send out It changes dynamic, and can imidizate be carried out due to heat, it is thus possible to can not steadily manufacture polyimide precursor.

It, need not be to silicyl when using the silylating agent without chlorine as silylating agent used herein The diamines of change is purified, therefore preferably.As the silylating agent without chlorine atom, N, the bis- (trimethyls of O- can be enumerated Silicyl) trifluoroacetamide, N, bis- (trimethyl silyl) acetamides of O-, hexamethyldisilazane.Never contain fluorine atom And it is at low cost from the viewpoint of, bis- (trimethyl silyl) acetamides of particularly preferred N, O-, hexamethyldisilazane.

In addition, in the silylation reactive of diamines, in order to promote to react, the amine such as pyridine, piperidines, triethylamine can be used Series catalysts.The catalyst can directly be used as the polymerization catalyst of polyimide precursor.

4) polyamic acid silyl ester (direct method)

The polyamic acid solution obtained by method 1) is mixed with silylating agent, 0~120 DEG C, preferably 5~ It is stirred 1~72 hour in the range of 80 DEG C, thus obtains polyimide precursor.In the case where being reacted for 80 DEG C or more, point Son amount can depend on temperature history when polymerization and change, and can carry out imidizate due to heat, it is thus possible to nothing Method steadily manufactures polyimide precursor.

It, need not be to silicyl when using the silylating agent without chlorine as silylating agent used herein The polyamic acid of change or obtained polyimides are purified, therefore preferably.As the silylating agent without chlorine atom, N, bis- (trimethyl silyl) trifluoroacetamides of O-, N, bis- (trimethyl silyl) acetamides of O-, hexamethyl can be enumerated Disilazane.Never contain fluorine atom and it is at low cost from the viewpoint of, bis- (trimethyl silyl) acetamides of particularly preferred N, O-, Hexamethyldisilazane.

Above-mentioned manufacturing method can be carried out suitably in organic solvent, therefore, as a result, it is possible to easily obtain To solution or liquid composite containing polyimide precursor.

Prepare for example preferred n,N-Dimethylformamide of the solvent used when polyimide precursor, N, N- dimethylacetamides The non-protonic solvents such as amine, n-methyl-2-pyrrolidone, 1,3-Dimethyl-2-imidazolidinone, dimethyl sulfoxide (DMSO), particularly preferably N,N-dimethylacetamide, but as long as can dissolve the polyimide precursor of starting monomer ingredient and generation, any kind of solvent It can with there is no problem use, therefore, structure is not particularly limited.As solvent, it is preferred to use N, N- dimethyl formyl The amide solvents such as amine, n,N-dimethylacetamide, N-Methyl pyrrolidone, gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ- The carbonic esters such as the ring-type such as caprolactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolacton ester solvent, ethylene carbonate, propylene carbonate are molten Phenol solvents, acetophenone, 1,3- such as the glycolic solvents such as agent, triethylene glycol, metacresol, paracresol, 3- chlorophenols, 4- chlorophenols Dimethyl-2-imidazolinone, sulfolane, dimethyl sulfoxide (DMSO) etc..In addition it is also possible to use other general organic solvents, i.e. benzene Phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetic acid esters, ethyl cellosolve, the molten fibre of butyl Agent, 2- methylcellosolve acetates, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxy second Alkane, diethoxyethane, dibutyl ethers, diethylene glycol dimethyl ether, methyl iso-butyl ketone (MIBK), diisobutyl ketone, cyclopentanone, hexamethylene Ketone, methyl ethyl ketone, acetone, butanol, ethyl alcohol, dimethylbenzene, toluene, chlorobenzene, turpentine oil, mineral spirits, naphtha etc..It needs to illustrate It is that solvent can also be applied in combination a variety of.

In the present invention, the log viscosities of polyimide precursor are not particularly limited, the N, N- of the concentration 0.5g/dL at 30 DEG C Log viscosities in dimethylacetamide solution are preferably 0.2dL/g or more, more preferably 0.3dL/g or more, are particularly preferably 0.4dL/g or more.When log viscosities are 0.2dL/g or more, the molecular weight of polyimide precursor is high, obtained polyimides Mechanical strength and excellent heat resistance.

The polyimide precursor composition of the present invention contains polyimide precursor and imidazole compound, can be by profit Imidazole compound is added in the polyimide precursor solution or liquid composite that are obtained with above-mentioned manufacturing method to prepare.Separately Outside, solvent can be removed or be added as needed, the desired constituents other than imidazole compound can also be added.In addition, also may be used Tetracarboxylic acid sour component (tetracarboxylic dianhydride etc.), diamine component and imidazole compound to be added in a solvent, in imidazole compound In the presence of so that tetracarboxylic acid sour component is reacted with diamine component, the polyimide precursor composition for obtaining the present invention is (sub- containing polyamides The liquid composite of amine precursor and imidazole compound).

As long as there is the imidazole compound used in the present invention the compound of imidazole skeleton to be not particularly limited.It is logical Addition imidazole compound is crossed, the small polyimides of thickness direction phase difference can be obtained.

In one embodiment, as imidazole compound, it is preferable to use boiling point under 1 atmospheric pressure less than 340 DEG C, Preferably 330 DEG C or less, more preferably 300 DEG C or less, particularly preferably 270 DEG C of compounds below.By adding 1 air The boiling point of pressure is less than 340 DEG C, preferably 330 DEG C or less, more preferably 300 DEG C or less, particularly preferably 270 DEG C of miaows below Azole compounds can obtain the higher polyimides of the transparency sometimes.

Imidazole compound used in the present invention, is not particularly limited, and can enumerate 1,2- methylimidazoles, 1- Methylimidazole, 2-methylimidazole, 2- phenylimidazoles, imidazoles, benzimidazole etc..It is preferred that 1,2- methylimidazole is (under 1 atmospheric pressure Boiling point：205 DEG C), the 1- methylimidazoles (boiling point under 1 atmospheric pressure：198 DEG C), the 2-methylimidazole (boiling under 1 atmospheric pressure Point：268 DEG C), the imidazoles (boiling point under 1 atmospheric pressure：256 DEG C etc.), particularly preferred 1,2- methylimidazoles, 1- methylimidazoles. Imidazole compound can be used alone, and can also be applied in combination a variety of.

In the present invention, the weight of the content of the imidazole compound of polyimide precursor composition relative to polyimide precursor 1 mole of multiple unit is less than 4 moles.The content of imidazole compound is rubbed relative to 1 mole of the repetitive unit of polyimide precursor for 4 When you are above, the storage stability of polyimide precursor composition is deteriorated.The content of imidazole compound is relative to polyimides Preferably 0.05 mole or more of 1 mole of the repetitive unit of precursor, in addition, 1 mole of the repetitive unit relative to polyimide precursor Preferably 2 moles or less.It should be noted that herein, 1 mole of the repetitive unit of polyimide precursor corresponds to tetracarboxylic acid sour component 1 mole.

The polyimide precursor composition of the present invention usually contains solvent.Polyimide precursor composition as the present invention The middle solvent used, there is no problem as long as it can dissolve polyimide precursor, and structure is not particularly limited.It is excellent as solvent Choosing is using amide solvents, γ-Ding Nei such as n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone The ring-type such as ester, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolacton ester solvent, carbonic acid are sub- The glycolic solvents such as the carbonate solvents such as ethyl ester, propylene carbonate, triethylene glycol, metacresol, paracresol, 3- chlorophenols, 4- chlorine The phenol solvents such as phenol, acetophenone, 1,3-Dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide (DMSO) etc..In addition it is also possible to make With other general organic solvents, i.e. phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl second Acid esters, ethyl cellosolve, butyl cellosolve, 2- methylcellosolve acetates, ethyl cellosolve acetate, butyl cellosolve acetic acid Ester, tetrahydrofuran, dimethoxy-ethane, diethoxyethane, dibutyl ethers, diethylene glycol dimethyl ether, methyl iso-butyl ketone (MIBK), Diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethyl alcohol, dimethylbenzene, toluene, chlorobenzene, turpentine oil, mineral oil Essence, naphthas solvent etc..Alternatively, it is also possible to which these solvent multiple combinations are used.It should be noted that before polyimides The solvent of body composition can be directly used in the solvent used when preparing polyimide precursor.

In the present invention, the total amount of tetracarboxylic acid sour component and diamine component is relative to solvent, tetracarboxylic acid sour component and diamine component Total amount be 5 mass % or more, preferably 10 mass % or more, the more preferably ratio of 15 mass % or more is appropriate. It should be noted that in general, tetracarboxylic acid sour component and the total amount of diamine component are relative to solvent, tetracarboxylic acid sour component and diamine component Total amount be 60 mass % or less, preferably 50 mass % or less be appropriate.The concentration be with because polyimide precursor produces Raw solid component concentration substantially approximate concentration when the concentration is too low, such as is difficult to control sometimes in manufacture polyimide film When the obtained film thickness of polyimide film.

In the present invention, the viscosity (rotary viscosity) of polyimide precursor composition is not particularly limited, and is rotated using E types viscous Degree meter is in 25 DEG C of temperature, shear velocity 20 seconds^-1The rotary viscosity of lower measurement is preferably 0.01~1000Pa seconds, is more preferably 0.1~100Pa seconds.Alternatively, it is also possible to assign thixotropy as needed.Under the viscosity of above range, it is coated, forms a film When, it is easy to operate, and recess is can inhibit, levelability is excellent, therefore can obtain good overlay film.

The polyimide precursor composition of the present invention can contain the chemical imidization agent (acid such as acetic anhydride as needed The amine compounds such as acid anhydride, pyridine, isoquinolin), antioxidant, filler (inorganic particulates such as silica etc.), dyestuff, pigment, silane The coupling agents such as coupling agent, priming paint, fire proofing, antifoaming agent, levelling agent, rheology control agent (flow promortor), remover etc..

The polyimides of the present invention can be by by polyimide precursor composition acid imide present invention as described above Change (that is, polyimide precursor is made to carry out dehydration closed-loop reaction) to obtain.The method of imidizate is not particularly limited, Ke Yishi When the method using well known hot-imide or chemical imidization.The form of obtained polyimides can be enumerated preferably Laminated body, film, powder, microballon, formed body, the foaming body etc. of film, polyimide film and other base materials.

In the present invention, preferably polyimide precursor composition is carried out under conditions of maximum heating temperature is more than 350 DEG C Heat treatment, by polyimide precursor imidizate.The maximum heating temperature of heat treatment for imidizate is more preferably super 380 DEG C are crossed, particularly preferably more than 400 DEG C.Maximum heating temperature by using the heat treatment in imidizate is more than 350 DEG C temperature, more preferably more than 380 DEG C of temperature, particularly preferably temperature more than 400 DEG C, obtained polyimides Mechanical property improves.The upper limit of the maximum heating temperature of heat treatment is not particularly limited, it is often preferred that 500 DEG C or less.

For example, by the polyimide precursor composition curtain coating of the present invention, be applied on base material, the polyamides on the base material is sub- Amine precursor composition maximum heating temperature be more than 350 DEG C, more preferably above 380 DEG C, particularly preferably more than 400 DEG C at a temperature of Heated, by polyimide precursor imidizate, it is possible thereby to suitably manufacture polyimides.It should be noted that Heating distribution (プロ Off アイ Le) is not particularly limited, and can suitably select, from the viewpoint of productivity, preferably be added The time of heat treatment is short.

In addition, by the polyimide precursor composition curtain coating of the present invention, being applied on base material, at preferably 180 DEG C or less Within the temperature range of be dried, on base material formed polyimide precursor composition film, before obtained polyimides The film of body composition is removed from base material, in the state that the end of the film is fixed, maximum heating temperature be more than 350 DEG C, More preferably above 380 DEG C, particularly preferably more than 400 DEG C at a temperature of heated, by polyimide precursor imidizate, Thus polyimides can also suitably be manufactured.

The system of polyimides (polyimide film/base material laminated body or polyimide film) about the more specific present invention An example of method is made, as described later.

About the polyimides (polyimides of the invention) that the polyimide precursor composition by the present invention obtains, do not have It is particularly limited to, the thermal linear expansion coefficient of 150 when film is made DEG C to 250 DEG C can be preferably 60ppm/K or less, be more preferably 50ppm/K or less, further preferably 45ppm/K or less, further preferably 40ppm/K or less, particularly preferably 35ppm/K Below.It is big with the difference of the thermal linear expansion coefficient of the conductors such as metal when thermal linear expansion coefficient is big, have when forming circuit board When will produce warpage increase a problem that.

About the polyimides (polyimides of the invention) that the polyimide precursor composition by the present invention obtains, do not have It is particularly limited to, the total light transmittance (average transmittance of wavelength 380nm~780nm) in the film of 10 μm of thickness can be preferably 86% or more, it is more preferably 87% or more, particularly preferably 88% or more.In display applications etc. in the case of use, if Total light transmittance is low, needs to reinforce light source, will produce the problem of consumption energy sometimes etc..

Especially in the case where the light such as display applications penetrate the use use on the way of polyimide film, it is expected that polyimides The transparent higher of film.(polyamides of the invention is sub- for the polyimides obtained about the polyimide precursor composition by the present invention Amine), it is not particularly limited, the light transmittance under wavelength 400nm in the film of 10 μm of thickness can be preferably 75% or more, preferably It is 80% or more, more preferably above 80%, further preferably 81% or more, particularly preferably 82% or more.

It should be noted that about polyimides (this hair obtained comprising the polyimide precursor composition by the present invention Bright polyimides) film, although additionally depending on purposes, as the thickness of film, preferably 0.1 μm~250 μm, more preferably 1 μm~150 μm, further preferably 1 μm~50 μm, particularly preferably 1 μm~30 μm.The purposes of polyimide film is penetrated in light In the case of middle use, if polyimide film is blocked up, light transmittance may reduce.

About the polyimides (polyimides of the invention) that the polyimide precursor composition by the present invention obtains, do not have It is particularly limited to, 1% loss of weight temperature of the index of the heat resistance as polyimide film can be preferably 395 DEG C or more, more preferably It is 430 DEG C or more, further preferably 440 DEG C or more, particularly preferably 470 DEG C or more.By being formed on polyimide In the case that transistor etc. forms gas barrier film etc. on polyimide, if heat resistance is low, sometimes due to polyimides Decomposition caused by outgassing and between polyimides and barrier film generate protuberance.

About the polyimides (polyimides of the invention) that the polyimide precursor composition by the present invention obtains, do not have Be particularly limited to, the thickness direction phase difference of polyimide film can be preferably 1000nm or less, more preferably 800nm or less, into One step is preferably 700nm or less, particularly preferably 600nm or less.When the phase difference of thickness direction is big, will produce sometimes can not be just The problems such as really color of display transmitted light, color are fuzzy, visual angle narrows.

Polyimides, the polyimides i.e. of the invention obtained by the polyimide precursor composition of the present invention has film thickness The excellent specific properties such as the phase difference in direction is small, high transparency, buckle resistance, high-fire resistance, and there is extremely low linear thermal expansion Coefficient, therefore, it is possible to be suitble to the use in display transparent substrate, touch panel transparent substrate or substrate used for solar batteries It uses on the way.

Hereinafter, polyimide film/base material the laminated body or polyamides of the polyimide precursor composition to having used the present invention An example of the manufacturing method of imines film illustrates.But it is not limited to the following method.

For example, by the polyimide precursor composition (varnish) of the present invention be cast to ceramic (glass, silicon, aluminium oxide etc.), On the base materials such as metal (copper, aluminium, stainless steel etc.), heat resistant plastice film (polyimide film etc.), in a vacuum, the inert gases such as nitrogen In or air in, using hot wind or infrared ray, be dried within the temperature range of 20~180 DEG C, preferably 20~150 DEG C.It connects It, obtained polyimide precursor film is removed from base material on base material or by polyimide precursor film and should In the state that the end of film is fixed, in a vacuum, in the inert gases such as nitrogen or in air, using hot wind or infrared ray, in example If 200~500 DEG C, preferably up to heating temperature are more than 350 DEG C, more preferably above 380 DEG C, the temperature particularly preferably more than 400 DEG C Heating imidizate is carried out under degree, it is possible thereby to manufacture polyimide film/base material laminated body or polyimide film.It needs to illustrate , in order to prevent obtained polyimide film occur oxidative degradation, heating imidizate is preferably in a vacuum or indifferent gas It is carried out in body.For the transporting of about subsequent process, polyimide film herein is (in the feelings of polyimide film/base material laminated body Be polyimide film under condition) thickness be preferably 1~250 μm, more preferably 1~150 μm.

In addition, instead of the heating imidizate as described above based on heat treatment, the imidizate of polyimide precursor Reaction can also be by making polyimide precursor in the presence of the tertiary amines such as pyridine or triethylamine containing cyclodehydrations such as acetic anhydrides Impregnating is chemically treated to carry out in the solution of reagent.Alternatively, it is also possible to by the way that these cyclodehydration reagents are put into advance In polyimide precursor composition (varnish) and stirs, is cast on base material and dry come after making part imidizate Polyimide precursor further heats it as described above, it is hereby achieved that polyimide film/base material stacking Body or polyimide film.

Electric conductivity is formed in the one or two sides of the polyimide film obtained in this way/base material laminated body or polyimide film Layer, it is hereby achieved that conductive board flexible.

Conductive board flexible can for example be obtained by following methods.That is, as first method, for polyamides Asia Amine film/base material laminated body, does not remove polyimide film from base material, by sputtering, vapor deposition, printing etc. in the polyimide film table The conductive layer of conductive material (metal or metal oxide, conducting organics, conductive carbon etc.) is formed on face, manufacture is conductive The conductive laminate of property layer/polyimide film/base material.Then, conductive layer/polyimides is removed from base material as needed Film laminated body, it is hereby achieved that the transparent and flexible conductive board comprising conductive layer/polyimide film laminated body.

As second method, polyimide film is removed from the base material of polyimide film/base material laminated body, obtains polyamides Asia Amine film, in the same manner as first method on the polyimide film surface formed conductive material (metal or metal oxide, conduction Property organic matter, conductive carbon etc.) conductive layer, can obtain comprising conductive layer/polyimide film laminated body, conductive layer/ The transparent and flexible conductive board of polyimide film laminated body/conductive layer.

It should be noted that in the first, second method, it can be formed and be led on the surface of polyimide film as needed Before electric layer, it is inorganic that gas barrier layer, light regulating course of vapor, oxygen etc. etc. is formed by sputtering, vapor deposition, agglutinating nature yeast etc. Layer.

In addition, conductive layer can be properly formed circuit by the methods of photoetching process, various print processes, ink-jet method.

The substrate of the present invention obtained in this way is on the surface of polyimide film composed of polyimide of the present invention There is across gas barrier layer, inorganic layer the substrate of the circuit of conductive layer as needed.The substrate is flexible, high transparency, bending Property, excellent heat resistance, and extremely low thermal linear expansion coefficient and excellent solvent resistance are had both, therefore be easy to be formed fine Circuit.Therefore, which can be suitable as display use, touch panel is used or substrate used for solar batteries uses.

That is, being further formed transistor (mineral crystal by vapor deposition, various print processes or ink-jet method etc. on the substrate Pipe, organic transistor) and thin film transistor (TFT) flexible is manufactured, moreover, being suitable as the liquid crystal cell of display device, EL members Part, photoelectric cell use.

[Shi Shili ]

Hereinafter, by embodiment and comparative example, further the present invention will be described.It should be noted that the present invention is not It is defined in embodiment below.

In each example below, evaluation is carried out by following methods.

<The Ping Jia &gt of polyimide precursor solution (varnish);

[Bao Cunwendingxing ]

Varnish is preserved at 23 DEG C, if to occur after being denoted as zero, 3 day if with the uniform state of mobility after 3 days Gonorrhoea or gelation be then denoted as ×.

<The Ping Jia &gt of polyimide film;

[400nm light transmittances, Zong Touguangshuai ]

Using ultraviolet-uisible spectrophotometer/V-650DS (Japan's light splitting manufacture), the polyimides of about 10 μm of film thickness is measured Light transmittance and total light transmittance (average transmittance under 380nm~780nm) under the 400nm of film.For under the 400nm that is measured Light transmittance and total light transmittance, reflectivity is set as 10%, use lambert's Bill's formula calculate 10 μ m-thicks 400nm under light transmission Rate and total light transmittance.Calculation formula is as follows.

Log₁₀((T₁+ 10)/100)=10/L × (Log₁₀((T₁’+10)/100))

Log₁₀((T₂+ 10)/100)=10/L × (Log₁₀((T₂’+10)/100))

T₁：Light transmittance (%) under the 400nm of the polyimide film of 10 μ m-thicks when reflectivity is set as 10%

T₁'：Light transmittance (%) under the 400nm measured

T₂：The total light transmittance (%) of the polyimide film of 10 μ m-thicks when reflectivity is set as 10%

T₂'：The total light transmittance (%) measured

L：The film thickness (μm) of the polyimide film measured

[Elasticity modulus, breaking point Shen Changshuai ]

About 10 μm of polyimide film of film thickness is punched into the dumbbell shape of IEC450 specifications, as test film, is used The TENSILON of ORIENTEC companies manufacture, initial stage is measured between collet under conditions of length 30mm, tensile speed 2mm/ minutes Elasticity modulus, breaking point elongation.

[Thermal linear expansion coefficient (CTE)s ]

The strip that about 10 μm of polyimide film of film thickness is cut into width 4mm uses TMA/ as test film SS6100 (manufacture of SII nanosecond science and technology Co., Ltd.), the item of length 15mm, load 2g, 20 DEG C/min of heating rate between collet 500 DEG C are warming up under part.150 DEG C to 250 DEG C of thermal linear expansion coefficient is found out by obtained TMA curves.

[1% loss of weight Wen Du ]

Using the polyimide film of about 10 μm of film thickness as test film, the calorimeter measurement device manufactured using TA instrument companies (Q5000IR), 600 DEG C are warming up to from 25 DEG C with 10 DEG C/min of heating rate in stream of nitrogen gas.By obtained weight song Line finds out 1% loss of weight temperature.

[Thickness direction phase difference (the R of film_th)]

Using the polyimide film of 10 μm of film thickness as test film, the measuring difference of phases dress that uses prince's tester company to manufacture (KOBRA-WR) is set, incidence angle is set as 40 ° to carry out the measuring difference of phases of film.Film thickness 10 is found out by obtained phase difference μm film thickness direction phase difference.

Abbreviation, purity of raw material used in each example below etc. is as described below.

[Er Anchengfen ]

tra-DACH：Anti-form-1,4- Er Anjihuanjiwans [Purity：99.1% (GC analysis)s ]

DABAN：4,4 '-diaminobenzene Jia Xiantibenan [Purity：99.90% (GC analysis)s ]

PPD：Dui Beneran [Purity：99.9% (GC analysis)s ]

4,4 '-ODA：4,4 '-oxygen Er Benan [Purity：99.9% (GC analysis)s ]

BAPB：4,4 '-bis- (4- amino-benzene oxygens) Lian Ben [Purity：99.93% (HPLC analysis)s ]

[Tetracarboxylic acid sour component;

s-BPDA：3,3 ', 4,4 '-Lian Bensisuosuanergan [(H-NMR analyzes) &#93 to purity 99.9%;

a-BPDA：2,3,3 ', 4 '-Lian Bensisuosuanergan [(H-NMR analyzes) &#93 to purity 99.6%;

PMDA-HS：1R, 2S, 4S, 5R- cyclopentanetetracarboxylic's Er Gan [Purity：99.9% (GC analysis)s ]

CpODA-tee：Trans--Nei-is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornane -5, and 5 ", 6, 6 "-tetracarboxylic dianhydrides

CpODA-cee：Cis--Nei-is interior-norbornane -2- spiral shells-α-cyclopentanone-α '-spiral shell -2 "-norbornane -5, and 5 ", 6, 6 "-tetracarboxylic dianhydrides

CpODA：The mixture of CpODA-tee and CpODA-cee

PACDA：N, N '-(Isosorbide-5-Nitrae-phenylene) bis- (1,3- dioxo octahydro isobenzofuran -5- carboxylic acid amides)

[Table 1]

[Imidazoles/Mi Zuolinhuahewu ]

	Boiling point/DEG C
		1- methylimidazoles	198^*1
2-methylimidazole	268^*1
		2- phenylimidazoles	340^*1
Imidazoles	256^*1
		Benzimidazole	> 360^*2
1,2- methylimidazole	205^*1
		2- ethyl -2- imidazolines	120℃/20mmHg^*1
2- methyl -2- imidazolines	130℃/50mmHg^*1
		2- benzylimidazolines	188℃/20mmHg^*1

*1：Tokyo Chemical Industry Co., Ltd

*2：Wako Pure Chemicals Co., Ltd.

[Rong Ji ]

NMP：N-methyl-2-pyrrolidone

The tetracarboxylic acid sour component used in embodiment, comparative example has been recorded in table 1-1, has been recorded embodiment in table 1-2, has been compared The diamine component that uses in example has recorded the structure of the imidazoles/imidazolinium compounds used in embodiment, comparative example in table 1-3 Formula.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Synthesis example 1]

DABAN 90.91g (0.4 mole) and PPD 64.88g are packed into the reaction vessel after being replaced with nitrogen, and (0.6 rubs You), being added makes input monomer gross mass (summation of diamine component and carboxylic acid composition) be the 2835.90g's of the amount of 16 mass % N-methyl-2-pyrrolidone is stirred at room temperature 1 hour.CpODA 384.38g are slowly added into the solution, and (1.0 rub You).It is stirred at room temperature 12 hours, obtains uniform and sticky polyimide precursor solution (varnish A).

[Synthesis example 2]

In the reaction vessel after being replaced with nitrogen be packed into DABAN 90.91g (0.4 mole), (0.5 rubs PPD 54.07g You) and BAPB 36.84g (0.1 mole), being added makes input monomer gross mass (summation of diamine component and carboxylic acid composition) be 16 The n-methyl-2-pyrrolidone of the 2972.56g of the amount of quality % is stirred at room temperature 1 hour.Slowly add in the solution Enter CpODA 384.38g (1.0 moles).It is stirred at room temperature 12 hours, obtains uniform and sticky polyimide precursor solution (varnish B).

[Synthesis example 3]

DABAN 22.73g (0.100 mole) are packed into the reaction vessel after being replaced with nitrogen, addition makes input monomer Gross mass (summation of diamine component and carboxylic acid composition) is the n-methyl-2-pyrrolidone of the 3211.16g of the amount of 16 mass %, It is stirred at room temperature 1 hour.CpODA 38.44g (0.100 mole) are slowly added into the solution.It is stirred at room temperature 12 Hour, obtain uniform and sticky polyimide precursor solution (varnish C).

[Synthesis example 4]

DABAN 15.91g (0.070 mole) and PPD 3.24g are packed into the reaction vessel after being replaced with nitrogen (0.030 mole), being added makes input monomer gross mass (summation of diamine component and carboxylic acid composition) be the amount of 16 mass % The n-methyl-2-pyrrolidone of 302.35g is stirred at room temperature 1 hour.CpODA 38.44g are slowly added into the solution (0.100 mole).It is stirred at room temperature 12 hours, obtains uniform and sticky polyimide precursor solution (varnish D).

[Synthesis example 5]

DABAN 11.36g (0.050 mole), PPD 4.34g (0.040 are packed into the reaction vessel after being replaced with nitrogen Mole) and 4,4 '-ODA 2.00g (0.010 mole), being added makes input monomer gross mass (diamine component and carboxylic acid composition's is total With) be 16 mass % amount 294.74g n-methyl-2-pyrrolidone, be stirred at room temperature 1 hour.Delay in the solution CpODA 38.44g (0.100 mole) are slowly added.It is stirred at room temperature 12 hours, before obtaining uniform and sticky polyimides Liquid solution (varnish E).

[Synthesis example 6]

4,4 '-ODA 20.02g (0.100 mole) are packed into the reaction vessel after being replaced with nitrogen, addition makes input list Body gross mass (summation of diamine component and carboxylic acid composition) is the n-methyl-2-pyrrolidone of the 207.21g of the amount of 17 mass %, It is stirred at room temperature 1 hour.PMDA-HS 22.41g (0.100 mM) are slowly added into the solution.It stirs at room temperature It mixes 12 hours, obtains uniform and sticky polyimide precursor solution (varnish F).

[Synthesis example 7]

DABAN 22.73g (0.100 mole) are packed into the reaction vessel after being replaced with nitrogen, addition makes input monomer Gross mass (summation of diamine component and carboxylic acid composition) is the n-methyl-2-pyrrolidone of the 296.29g of the amount of 20 mass %, It stirs 1 hour at room temperature.PACDA 51.35g (0.100 mole) are slowly added into the solution.It is small to be stirred at room temperature 12 When, obtain uniform and sticky polyimide precursor solution (varnish G).

[Synthesis example 8]

Tra-DACH 10.81g (0.100 mole) are packed into the reaction vessel after being replaced with nitrogen, addition makes input list Body gross mass (summation of diamine component and carboxylic acid composition) is the N- methyl -2- pyrrolidines of the 2950.64g of the amount of 12 mass % Ketone is stirred at room temperature 1 hour.S-BPDA 28.69g (0.0975 mole) and a-BPDA are slowly added into the solution 0.74g (0.0025 mole).It is stirred 12 hours at 50 DEG C, obtains uniform and sticky polyimide precursor solution (varnish H).

[Embodiment 1]

1,2- methylimidazoles 0.05g (0.5 mM) and n-methyl-2-pyrrolidone 0.05g are added to reaction to hold In device, uniform solution is obtained.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative in varnish A The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.05 mole.

The PTFE film filtered polyimide precursor solutions of filter will be utilized to be applied on glass substrate, in nitrogen atmosphere Under (oxygen concentration 200ppm or less), be directly heated to 410 DEG C from room temperature on the glass substrate and carry out hot-imide, obtain nothing Transparent polyimide film/the glass laminate of color.Then, obtained polyimide film/glass laminate is impregnated into water, Then it removes, it is dry, obtain the polyimide film that film thickness is about 10 μm.

The result being measured to the characteristic of the polyimide film is shown in table 2-1.

[Embodiment 2]

1,2- methylimidazoles 0.15g (1.6 mMs) and n-methyl-2-pyrrolidone 0.15g are added to reaction to hold In device, uniform solution is obtained.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative in varnish A The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.16 mole.

[Embodiment 3]

1,2- methylimidazoles 0.19g (2.0 mMs) and n-methyl-2-pyrrolidone 0.19g are added to reaction to hold In device, uniform solution is obtained.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative in varnish A The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.2 mole.

[Embodiment 4]

1,2- methylimidazoles 0.96g (10.0 mMs) and n-methyl-2-pyrrolidone 0.38g are added to reaction to hold In device, uniform solution is obtained.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative in varnish A The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 1.0 moles.

[Embodiment 5]

1,2- methylimidazoles 1.92g (20.0 mMs) and n-methyl-2-pyrrolidone 0.38g are added to reaction to hold In device, uniform solution is obtained.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative in varnish A The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 2.0 moles.

[Embodiment 6]

1- methylimidazoles 0.04g (0.5 mM) and n-methyl-2-pyrrolidone 0.04g are added in reaction vessel, Obtain uniform solution.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative to the polyamides in varnish A The molecular weight of the repetitive unit of imines precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky polyamides Imines precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1- methylimidazoles are 0.05 mole.

[Embodiment 7]

1- methylimidazoles 0.08g (1.0 mMs) and n-methyl-2-pyrrolidone 0.08g are added in reaction vessel, Obtain uniform solution.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative to the polyamides in varnish A The molecular weight of the repetitive unit of imines precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky polyamides Imines precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1- methylimidazoles are 0.1 mole.

[Embodiment 8]

1- methylimidazoles 0.16g (2.0 mMs) and n-methyl-2-pyrrolidone 0.16g are added in reaction vessel, Obtain uniform solution.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative to the polyamides in varnish A The molecular weight of the repetitive unit of imines precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky polyamides Imines precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1- methylimidazoles are 0.2 mole.

[Embodiment 9]

1- methylimidazoles 0.33g (4.0 mMs) and n-methyl-2-pyrrolidone 0.33g are added in reaction vessel, Obtain uniform solution.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative to the polyamides in varnish A The molecular weight of the repetitive unit of imines precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky polyamides Imines precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1- methylimidazoles are 0.4 mole.

[Embodiment 10]

2-methylimidazole 0.16g (2.0 mMs) and n-methyl-2-pyrrolidone 0.16g are added in reaction vessel, Obtain uniform solution.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative to the polyamides in varnish A The molecular weight of the repetitive unit of imines precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky polyamides Imines precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 2-methylimidazole is 0.2 mole.

[Embodiment 11]

Imidazoles 0.14g (2.0 mMs) and n-methyl-2-pyrrolidone 0.14g are added in reaction vessel, obtained Even solution.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (before the polyimides in varnish A The molecular weight of the repetitive unit of body is 10 mMs), it is stirred at room temperature 3 hours, before obtaining uniform and sticky polyimides Liquid solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, imidazoles is 0.2 mole.

[Embodiment 12]

2- phenylimidazoles 0.29g (2.0 mMs) and n-methyl-2-pyrrolidone 0.29g are added in reaction vessel, Obtain uniform solution.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative to the polyamides in varnish A The molecular weight of the repetitive unit of imines precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky polyamides Imines precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 2- phenylimidazoles are 0.2 mole.

[Embodiment 13]

Benzimidazole 0.24g (2.0 mMs) and n-methyl-2-pyrrolidone 0.24g are added in reaction vessel, obtained To uniform solution.It is (sub- relative to the polyamides in varnish A that the varnish A 33.76g obtained in synthesis example 1 are added in the solution The molecular weight of the repetitive unit of amine precursor is 10 mMs), it is stirred at room temperature 3 hours, it is sub- to obtain uniform and sticky polyamides Amine precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, benzimidazole rubs for 0.2 You.

[Comparative example 1]

It will be applied on glass substrate using the varnish A obtained in the filtered synthesis example of PTFE film filters 1, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 410 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Comparative example 2]

1,2- methylimidazoles 1.92g (40.0 mMs) and n-methyl-2-pyrrolidone 0.38g are added to reaction to hold In device, uniform solution is obtained.The varnish A 33.76g obtained in synthesis example 1 are added in the solution (relative in varnish A The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 4.0 moles.When obtained polyimide precursor solution is taken care of at 23 DEG C, by the 3rd day, polyimide precursor Gelation has occurred in solution.

[Reference example 1]

The PTFE film filtered polyimide precursor solutions of filter will be utilized to be applied on glass substrate, in nitrogen atmosphere Under (oxygen concentration 200ppm or less), be directly heated to 350 DEG C from room temperature on the glass substrate and carry out hot-imide, obtain nothing Transparent polyimide film/the glass laminate of color.Then, obtained polyimide film/glass laminate is impregnated into water, Then it removes, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Embodiment 14]

1,2- methylimidazoles 0.05g (0.5 mM) and n-methyl-2-pyrrolidone 0.05g are added to reaction to hold In device, uniform solution is obtained.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative in varnish B The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.05 mole.

The result being measured to the characteristic of the polyimide film is shown in table 2-2.

[Embodiment 15]

1,2- methylimidazoles 0.10g (1.0 mMs) and n-methyl-2-pyrrolidone 0.10g are added to reaction to hold In device, uniform solution is obtained.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative in varnish B The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.1 mole.

[Embodiment 16]

1,2- methylimidazoles 0.19g (2.0 mMs) and n-methyl-2-pyrrolidone 0.19g are added to reaction to hold In device, uniform solution is obtained.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative in varnish B The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.2 mole.

[Embodiment 17]

1- methylimidazoles 0.16g (2.0 mMs) and n-methyl-2-pyrrolidone 0.16g are added in reaction vessel, Obtain uniform solution.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative to the polyamides in varnish B The molecular weight of the repetitive unit of imines precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky polyamides Imines precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1- methylimidazoles are 0.2 mole.

[Comparative example 3]

It will be applied on glass substrate using the varnish B obtained in the filtered synthesis example of PTFE film filters 2, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 410 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Comparative example 4]

2- ethyl -2- imidazolines 0.10g (1.0 mMs) and n-methyl-2-pyrrolidone 0.20g are added to reaction to hold In device, uniform solution is obtained.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative in varnish B The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 2- ethyls -2- Imidazoline is 0.1 mole.

[Comparative example 5]

2- ethyl -2- imidazolines 0.20g (2.0 mMs) and n-methyl-2-pyrrolidone 0.40g are added to reaction to hold In device, uniform solution is obtained.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative in varnish B The molecular weight of the repetitive unit of polyimide precursor is 10 mMs) when, gelation has occurred in varnish.Even if with the state in room The lower stirring of temperature 3 hours, does not obtain uniform polyimide precursor solution yet.It is calculated by input amount, relative to polyamides Asia 1 mole of the repetitive unit of amine precursor, 2- ethyl -2- imidazolines are 0.2 mole.

[Comparative example 6]

2- ethyl -2- imidazolines 0.49g (5.0 mMs) and n-methyl-2-pyrrolidone 0.98g are added to reaction to hold In device, uniform solution is obtained.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative in varnish B The molecular weight of the repetitive unit of polyimide precursor is 10 mMs) when, gelation has occurred in varnish.Even if with the state in room The lower stirring of temperature 3 hours, does not obtain uniform polyimide precursor solution yet.It is calculated by input amount, relative to polyamides Asia 1 mole of the repetitive unit of amine precursor, 2- ethyl -2- imidazolines are 0.5 mole.

[Comparative example 7]

2- methyl -2- imidazolines 0.25g (3.0 mMs) and n-methyl-2-pyrrolidone 0.25g are added to reaction to hold In device, uniform solution is obtained.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative in varnish B The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 2- methyl -2- Imidazoline is 0.3 mole.

[Comparative example 8]

2- benzylimidazolines 0.44g (3.0 mMs) and n-methyl-2-pyrrolidone 0.44g are added to reaction vessel In, obtain uniform solution.The varnish B 35.39g obtained in synthesis example 2 are added in the solution (relative to poly- in varnish B The molecular weight of the repetitive unit of imide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky gather Imide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 2- phenylimidazoles Quinoline is 0.3 mole.

[Embodiment 18]

1,2- methylimidazoles 0.10g (1.0 mMs) and n-methyl-2-pyrrolidone 0.10g are added to reaction to hold In device, uniform solution is obtained.The varnish C 38.23g obtained in synthesis example 3 are added in the solution (relative in varnish C The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.1 mole.

The result being measured to the characteristic of the polyimide film is shown in table 2-3.

[Comparative example 9]

It will be applied on glass substrate using the varnish C obtained in the filtered synthesis example of PTFE film filters 3, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 410 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Embodiment 19]

1,2- methylimidazoles 0.10g (1.0 mMs) and n-methyl-2-pyrrolidone 0.10g are added to reaction to hold In device, uniform solution is obtained.The varnish D 35.99g obtained in synthesis example 4 are added in the solution (relative in varnish D The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.1 mole.

[Comparative example 10]

It will be applied on glass substrate using the varnish D obtained in the filtered synthesis example of PTFE film filters 4, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 410 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Embodiment 20]

1,2- methylimidazoles 0.10g (1.0 mMs) and n-methyl-2-pyrrolidone 0.10g are added to reaction to hold In device, uniform solution is obtained.The varnish E 35.09g obtained in synthesis example 5 are added in the solution (relative in varnish E The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.1 mole.

[Comparative example 11]

It will be applied on glass substrate using the varnish E obtained in the filtered synthesis example of PTFE film filters 5, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 410 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Embodiment 21]

1,2- methylimidazoles 0.19g (2.0 mMs) and n-methyl-2-pyrrolidone 0.19g are added to reaction to hold In device, uniform solution is obtained.The varnish F 24.97g obtained in synthesis example 6 are added in the solution (relative in varnish F The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.2 mole.

The PTFE film filtered polyimide precursor solutions of filter will be utilized to be applied on glass substrate, in nitrogen atmosphere Under (oxygen concentration 200ppm or less), be directly heated to 400 DEG C from room temperature on the glass substrate and carry out hot-imide, obtain nothing Transparent polyimide film/the glass laminate of color.Then, obtained polyimide film/glass laminate is impregnated into water, Then it removes, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Comparative example 12]

It will be applied on glass substrate using the varnish F obtained in the filtered synthesis example of PTFE film filters 6, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 400 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Embodiment 22]

1,2- methylimidazoles 0.19g (2.0 mMs) and n-methyl-2-pyrrolidone 0.19g are added to reaction to hold In device, uniform solution is obtained.The varnish G 37.04g obtained in synthesis example 7 are added in the solution (relative in varnish G The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.2 mole.

[Comparative example 13]

It will be applied on glass substrate using the varnish G obtained in the filtered synthesis example of PTFE film filters 7, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 350 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Embodiment 23]

1,2- methylimidazoles 0.19g (2.0 mMs) and n-methyl-2-pyrrolidone 0.19g are added to reaction to hold In device, uniform solution is obtained.The varnish H 33.53g obtained in synthesis example 8 are added in the solution (relative in varnish H The molecular weight of the repetitive unit of polyimide precursor is 10 mMs), it is stirred at room temperature 3 hours, obtains uniform and sticky Polyimide precursor solution.It is calculated by input amount, relative to 1 mole of the repetitive unit of polyimide precursor, 1,2- diformazan Base imidazoles is 0.2 mole.

The PTFE film filtered polyimide precursor solutions of filter will be utilized to be applied on glass substrate, in nitrogen atmosphere Under (oxygen concentration 200ppm or less), be directly heated to 370 DEG C from room temperature on the glass substrate and carry out hot-imide, obtain nothing Transparent polyimide film/the glass laminate of color.Then, obtained polyimide film/glass laminate is impregnated into water, Then it removes, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Comparative example 14]

It will be applied on glass substrate using the varnish H obtained in the filtered synthesis example of PTFE film filters 8, in nitrogen Under atmosphere (oxygen concentration 200ppm or less), directly 370 DEG C are heated to from room temperature on the glass substrate and carry out hot-imide, obtained To polyimide film/glass laminate of water white transparency.Then, obtained polyimide film/glass laminate is impregnated into In water, then remove, it is dry, obtain the polyimide film that film thickness is about 10 μm.

[Table 2-1]

[Table 2-2]

[Table 2-3]

The result shown in table 2-1~2-3 is it is found that by containing imidazole compound (1,2- methylimidazole, 1- methyl miaows Azoles, 2-methylimidazole, 2- phenylimidazoles, benzimidazole or imidazoles) polyimide precursor composition obtained polyimides Thickness direction phase difference small (embodiment 1~13 and comparative example 1, embodiment 14~17 and comparative example 3, embodiment 18 and comparative example 9, embodiment 19 and comparative example 10, embodiment 20 and comparative example 11, embodiment 21 and comparative example 12, embodiment 22 and comparative example 13, embodiment 23 and comparative example 14).In addition we know, using 1,2- methylimidazoles, 1- methylimidazoles, 2-methylimidazole or In the case of imidazoles, transmissivity also improves (embodiment 1~11 and comparative example 1, embodiment 14~17 and comparative example 3, embodiment 18 With comparative example 9, embodiment 19 and comparative example 10, embodiment 20 and comparative example 11, embodiment 21 and comparative example 12,22 and of embodiment Comparative example 13, embodiment 23 and comparative example 14).In addition it is found that the content of imidazole compound is relative to polyimide precursor When 1 mole of repetitive unit is less than 4 moles, storage stability is also excellent (embodiment 1~13 and comparative example 2).In addition we know, about Mechanical property is set as 410 DEG C by using the maximum heating temperature of the heat treatment in imidizate more than 350 DEG C, breaks Knick point elongation increases (embodiment 3 and reference example 1).

As described above, the thickness direction phase difference of the polyimides obtained by the polyimide precursor composition of the present invention It is small, and with excellent translucency, mechanical property, low coefficient of linear thermal expansion.The polyimide film of the present invention can be suitble to As display applications etc. water white transparency and the transparent substrate of fine circuit can be formed use.

Industrial applicability

Even if according to the present invention it is possible to provide can obtain the transparency it is excellent, under same composition thickness direction phase difference Also smaller polyimides or thickness direction phase difference is small, the excellent, mechanical property of the transparency also excellent polyimides it is poly- The manufacturing method of imide precursor composition (liquid composite containing polyimide precursor) and polyimides.By polyamides Asia The transparent high and thick degree direction phase difference for the polyimides that amine precursor composition obtains is small, also, thermal linear expansion coefficient is low, It is easy to form fine circuit, therefore, it is possible to use particularly suitable for forming display, touch panel is used, used for solar batteries Deng substrate.

Claims

1. a kind of polyimide precursor composition, which is characterized in that

Including containing repetitive unit and chemical formula shown in repetitive unit shown in following chemical formula (1) or following chemical formula (2) (1) content of other repetitive units and other than repetitive unit shown in (2) relative to whole repetitive units be 30 moles of % with Under polyimide precursor and DMIZ 1,2 dimethylimidazole as imidazole compound, 1- methylimidazoles, 2-methylimidazole or Any one in imidazoles,

The content of imidazole compound is 0.05 mole or more and 1 mole relative to 1 mole of the repetitive unit of polyimide precursor Hereinafter,

In formula (1), X₁For the group of 4 valences with alicyclic structure, Y₁For the group of the divalent with aromatic ring, R₁、R₂Respectively solely It is on the spot the aIkylsilyl groups of hydrogen, the alkyl of carbon atom number 1~6 or carbon atom number 3~9,

In formula (2), X₂For the group of 4 valences with aromatic ring, Y₂For the group of the divalent with alicyclic structure, R₃、R₄Respectively solely It is on the spot the aIkylsilyl groups of hydrogen, the alkyl of carbon atom number 1~6 or carbon atom number 3~9.

2. polyimide precursor composition as described in claim 1, which is characterized in that obtained by the polyimide precursor composition To polyimides 10 μm of thickness film in wavelength 400nm light transmittance be 75% or more.

3. polyimide precursor composition as described in claim 1, which is characterized in that the polyimide precursor, chemical The content of other repetitive units other than repetitive unit shown in formula (1) and (2) is 10 moles of % relative to whole repetitive units Below.

4. a kind of manufacturing method of polyimides, which is characterized in that by polyimides according to any one of claims 1 to 3 Precursor composition is heated under conditions of maximum heating temperature is more than 350 DEG C, by polyimide precursor imidizate.

5. the manufacturing method of polyimides as claimed in claim 4, which is characterized in that the highest heating temperature of the heat treatment Degree is more than 400 DEG C.

6. a kind of manufacturing method of polyimides, which is characterized in that have：

By polyimide precursor composition according to any one of claims 1 to 3 be applied to process on base material and

Polyimide precursor composition on base material is heated under conditions of maximum heating temperature is more than 350 DEG C and By the process of polyimide precursor imidizate.

7. a kind of polyimides is manufactured by the method described in claim 4.

8. polyimides as claimed in claim 7, which is characterized in that the light transmission of the wavelength 400nm in the film of 10 μm of thickness Rate is 75% or more.

9. a kind of polyimide film is manufactured by the method described in claim 4.

10. a kind of polyimide film, is manufactured by method of claim 6.

11. a kind of display is used, touch panel is used or substrate used for solar batteries, which is characterized in that include claim 7 institute The polyimides stated.

12. a kind of display is used, touch panel is used or substrate used for solar batteries, which is characterized in that include claim 9 institute The polyimide film stated.