CN106414575A

CN106414575A - Polyimide film having pores and method for producing same

Info

Publication number: CN106414575A
Application number: CN201580033079.0A
Authority: CN
Inventors: 宫本佳季; 饭塚康史; 加藤聪; 金田隆行
Original assignee: Asahi Kasei Kogyo KK
Current assignee: Asahi Kasei Corp
Priority date: 2014-06-25
Filing date: 2015-06-18
Publication date: 2017-02-15
Anticipated expiration: 2035-06-18
Also published as: JP7033171B2; JP2020128522A; CN106414575B; TWI689532B; JP6820827B2; TW201835165A; JP2018048344A; KR102305617B1; WO2015198970A1; TW201605978A; JP7037534B2; CN112961382A; JPWO2015198970A1; TWI670327B; KR102139455B1; CN112080026B; JP6254274B2; JP2020183539A; CN112080026A; KR20200091953A

Abstract

A polyimide film characterized by having pores of 100 nm or less and being used in the production of a flexible device.

Description

There is Kapton and its manufacture method of hole

Technical field

The present invention relates to being for example used for flexible device substrate, the Kapton with hole and its manufacturer Method.

Aforementioned Kapton preferably has high transparent.

Background technology

Typically for the purposes requiring high-fire resistance, use, as resin film, the thin film being formed by polyimides (PI). Common polyimides are that aromatic tetracarboxylic acid's dianhydride and aromatic diamine polymerisation in solution are manufactured polyimide precursor (polyamides Amino acid) after, by being allowed to the hot-imide of closed loop dehydration at high temperature or being allowed to closed loop dehydration under using catalyst Chemical imidization and manufacture.

Polyimides are insoluble, insoluble super heat-resistant resins, have heatproof oxidation performance, heat-resistant quality, radiation resistance, resistance to The excellent characteristic such as low temperature properties, chemical reagent resistance.Therefore, polyimides be used for insulating properties smearss, dielectric film etc. and The protecting film of quasiconductor, electrode protective membrane of TFT-LCD etc. comprise the wide field of electronic material.Recently, also carried out and replaced In generation, is used as the glass substrate of base plate for displaying all the time and adopts transparent, light using it and flexibility work Kapton for flexible base board.

With regard to the Kapton as flexible base board, for example, report research example as patent documentation 1 and 2.

Prior art literature

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication 2011-74384 publication

Patent documentation 2：No. 2012/118020 pamphlet of International Publication No.

Non-patent literature

Non-patent literature 1：J.L.Hendrik et al.Nanoporous Polyimide in Advances in Polymer Science,141,Progress in Polyimide Chemistry II,PP.1-43,1998,Springer

Content of the invention

Problems to be solved by the invention

It is well known, however, that clear polyimides physical characteristics be used for example as semiconducting insulation film, TFT-LCD dielectric film, It is insufficient when electrode protective membrane, touch panel ITO electrode substrate and flexible display heat resistant substrate.

For example, when Kapton is used as flexible display substrate, generally go through following operation.

First, the polyamic acid as polyimide precursor is coated with the glass substrate as supporting substrate, then Heat cure is carried out to it, thus Kapton is formed on supporting glass.Then, shape above this Kapton Become inoranic membrane.Then, after this inoranic membrane forming display element, finally will there is the polyamides of TFT element and inoranic membrane Imines film is peeled off from aforementioned supporting glass, thus obtaining flexible display.

Herein, when Kapton low for the transparency being applied on flexible display, need color correction.Especially, When using transparent low-down thin film, correction becomes difficult.Therefore, the thin film being applied to flexible display needs it transparent Property high.

As the index of the transparency of thin film, it is widely used yellowness YI.Sub- as the polyamides reducing this yellowness Amine, for example, have the report of patent documentation 1.The extremely low polyimides of yellowness are disclosed in this publication.Generally, yellowness is low There is the high tendency of residual stress in polyimides.In addition, thin film is being shelled by the low polyimides of yellowness from above-mentioned supporting glass From when the wavelength (308nm and 355nm) of laser that used under there is no absorption.Therefore, should by such Kapton During for flexible display, the energy quantitative change needed for laser lift-off is big, or there is the tendency of easily generation flue dust when peeling off.

However, Patent Document 2 discloses in the glass transition temperature keeping polyimides and tensile modulus of elasticity In the state of reduce residual stress technology.The purpose of this patent documentation is, maintain Kapton and glass substrate it Between cementability, and reduce stripping vestige when being mechanically ripped Kapton.Illustrate in patent documentation 2 by The block with the structure from soft siliceous diamidogen is imported in the polymer chain of polyimides, it is achieved thereby that above-mentioned mesh 's.Following main points have been recorded in the paragraph 55 and 151 of this patent documentation：Organosilicon formed have a size of 1nm～1 μm about, The micro phase separation structure of homogeneous texture, thus reduce residual stress.Record in paragraph 31 and measured to confirm organosilicon by TEM The main points of the size in region.

The present inventor etc. carried out confirming as a result, have the Kapton of the micro phase separation structure of organosilicon due to There are the bone lattice of softness in thin film, therefore there is the tendency of glass transition temperature reduction.In addition we know, patent documentation 2 is poly- Although imide membrane yellowness is high, when being applied to laser lift-off, it is impossible to incite somebody to action in the case that the irradiation energy of laser is little This Kapton is peeled off from glass substrate.Herein, when the irradiation energy improving laser is to attempt peeling off, there are polyimides Thin film burns and produces the problem of microgranule.

The present invention is problem in view of the above description and makes.

That is, it is an object of the invention to, a kind of Kapton and its manufacture method are provided,

The residual stress producing between described Kapton and glass substrate and inoranic membrane is low；

Excellent in adhesion with glass substrate；And

Preferably there is high transparent；

Also good stripping can be carried out in the case that irradiation energy is low in laser lift-off operation, do not cause burn with micro- The generation of grain.

For solution to problem

The present inventor etc., in order to solve above-mentioned problem, have been repeated further investigation.It is it was found that YI is low, have spy The Kapton of the hole of fixed structure has high Tg, shows high adhesiveness and glass substrate and inoranic membrane between, and, In laser lift-off operation, fissility excellent and do not produce burn, the situation of microgranule, the present invention is completed based on this opinion.That is, The present invention is as follows.

[1] a kind of Kapton is it is characterised in that it has the hole of below 100nm, and is used for flexible device Manufacture.

[2] Kapton according to [1], wherein, the yellowness in 20 μm of thickness is less than 7.

[3] Kapton according to [1] or [2], wherein, tensile elongation is more than 30%.

[4] Kapton according to any one of [1]～[3], it has organosilicon residue.

[5] Kapton according to any one of [1]～[4], wherein, porosity is 3 volume %～15 bodies The scope of long-pending %.

[6] according to the Kapton any one of [1]～[5], wherein, aforementioned hole be shaped as the long diameter of axle The flattened oval spheroid of average 30nm～60nm.

[7] Kapton according to any one of [1]～[6], wherein, aforementioned hole is in aforementioned polyimides Equably exist on the film thickness direction of thin film.

[8] it is used for manufacturing the resin precursor of the Kapton any one of [1]～[7] it is characterised in that setting There is in fat skeleton the unit 1 shown in following formulas (1) and the unit 2 shown in following formula (2).

In aforementioned formula (1) and aforementioned formula (2), R₁It is each independently the fat of 1 valency of hydrogen atom, carbon number 1～20 Race's hydrocarbon or the aromatic series base of carbon number 6～10；

R₂And R₃It is each independently the aliphatic hydrocarbon of 1 valency of carbon number 1～3 or the aromatic series base of carbon number 6～10；

X₁Organic group for 4 valencys of carbon number 4～32；And,

X₂Organic group for the divalent of carbon number 4～32.}

[9] according to the resin precursor described in [8], it is tetracarboxylic dianhydride, diamidogen and the change shown in following formula (3) The copolymer of compound.

In aforementioned formula (3), multiple R₄It is each independently the organic group of the divalent of singly-bound or carbon number 1～20 Group；

R₅And R₆It is each independently the organic group of 1 valency of carbon number 1～20；

R₇When having multiple, it is each independently the organic group of 1 valency of carbon number 1～20；L₁、L₂And L₃Each independent Ground is amino, NCO, carboxyl, anhydride group, perester radical, acid halide, hydroxyl, epoxy radicals or sulfydryl；

J is 3～200 integer；And,

K is 0～197 integer.}

[10] according to the resin precursor described in [9], wherein, tetracarboxylic dianhydride be selected from pyromellitic acid anhydride, 3,3 ', Double (the trimellitic acid monoesters of 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and 4,4 '-biphenyl Anhydride) in the group that forms more than a kind of tetracarboxylic dianhydride.

[11] according to the resin precursor described in [9] or [10], wherein, the aforementioned formula (3) using during synthetic resin precursor The quality of shown compound is 6 matter of tetracarboxylic dianhydride, diamidogen and the summation of compound shown in aforementioned formula (3) Amount %～25 mass %.

[12] a kind of resin combination it is characterised in that its contain resin precursor any one of [8]～[11] and Solvent.

[13] Kapton according to any one of [1]～[7], it is following manufacture：In supporting mass Launch the resin combination described in [12] on surface and form film, then,

By aforementioned supporting mass and aforementioned film below oxygen concentration 23 mass % and under conditions of more than 250 DEG C of temperature Heating, thus carrying out imidizate and forming hole in aforementioned film to the resin precursor in aforementioned film.

[14] according to the Kapton described in [13], wherein, oxygen concentration during aforementioned heating be 2000ppm with Under.

[15] a kind of manufacture method of Kapton is it is characterised in that it has following operation：

Film formation process, launches the resin combination described in [12] on the surface of supporting mass and forms film；

Heating process, by aforementioned supporting mass and aforementioned film below oxygen concentration 2000ppm and more than 250 DEG C of temperature Under conditions of heat, thus the resin precursor in aforementioned film is carried out imidizate and in aforementioned film formed hole, Thus obtain the Kapton with hole；And

Stripping process, the aforementioned Kapton with hole is peeled off from aforementioned supporting mass.

[16] a kind of flexible display is it is characterised in that its polyimides of having any one of [1]～[7] is thin Film, inoranic membrane and TFT.

It should be noted that as the method making the Kapton with hole it is known that remembering in non-patent literature 1 The method carrying.

Disclose the polyimide precursor using having imported poly(propylene oxide) in main chain or side chain in non-patent literature 1 to make The method making there is the Kapton of hole.If forming the film of the polyimide precursor with poly(propylene oxide) position, Then become the membrane structure that poly(propylene oxide) occurs microphase-separated.When heat treatment is carried out to this film, by there is acid imide simultaneously Change the thermal decomposition with poly(propylene oxide), thus obtaining the Kapton with hole.If however, importing polycyclic oxygen in main chain Propane, then cause the reduction of the thin film physical property such as the reduction of the transparency.In addition, it is numerous and diverse to import poly(propylene oxide) presence synthesis in side chain Problem.

The present invention, by easy method, provides in the case of the reduction not leading to thin film physical property and realizes above-mentioned purpose Kapton and its manufacture method.

The effect of invention

In accordance with the invention it is possible to it is low, with glass substrate to form the residual stress producing and glass substrate, inoranic membrane between Excellent in adhesion, preferably there is high transparent, and also can peel off in the case that in laser lift-off operation, irradiation energy is low, Do not cause the burning of polyimide film, the Kapton of the generation of microgranule.

Brief description

Fig. 1 is STEM image (left) and the SEM image (right) of embodiment 1.

Fig. 2 is the ATR spectrum of the thin film being obtained by embodiment 1,2 and reference example.

Fig. 3 is the SEM image of embodiment 7.

Specific embodiment

Below, an embodiment of the invention (hreinafter referred to as " embodiment ") is explained.Need explanation , the invention is not restricted to implementation below, various modifications can be carried out in the range of its purport and implement.

The Kapton with hole of present embodiment be have below size 100nm pore structure by gathering The thin film that acid imide is formed.The shape of hole can be chondritic, flattened oval spheroid etc., preferably flattened oval spheroid.

Hole be flattened oval spheroid when, its maximum long diameter of axle be preferably average below 100nm, more preferably 80nm with Under, the more preferably scope of 10～70nm, the most preferably scope of 30nm～60nm.Hole is the size more than 100nm When, polyimide film produces mist degree.During for below 1nm, cannot ensure sufficient fissility in laser lift-off, because laser shines Penetrate, polyimide film burns, result produces microgranule.

The model of porosity preferably 3 volume %～15 volume % of the Kapton with hole of present embodiment Enclose, the scope of more preferably 6 volume %～12 volumes %.When porosity is more than 3 volumes %, there is being easily peeled during laser lift-off Property improve, can suppress Kapton the generation burning, can suppressing microgranule tendency.For when below 15% volume, There is the tendency that thin film embodies excellent physical property.

When this porosity can be observed by scanning transmission electron microscope (STEM) or scanning electron microscope (SEM) Image analysis being calculated.

It is overall that hole in Kapton is preferably uniformly present in thin film.Equably there are the polyimides of hole There is the tendency that tensile elongation is high, birefringence (Rth) is low in thin film, be preferred.Especially, preferably hole is in Kapton Film thickness direction on be uniform.

The section of the Kapton that the uniformity on the film thickness direction of hole can be carried out by using STEM or SEM Image analysis during observation and know.Specifically, as follows：

The Electronic Speculum obtaining imaging is divided into each 2 μm of region along film thickness direction, obtains the porosity in each region.Obtain this The difference of the maxima and minima of a little porositys.Then, difference (the Δ porosity (%)=porosity of aforementioned maxima and minima Maximum (%)-porosity minima (%)) for less than 5% when, can be evaluated as uniform on the film thickness direction of hole Property high, be preferred.This value more preferably less than 3%, more preferably less than 1%, particularly preferably less than 0.5%.

From with glass substrate and with inorganic intermembranous adaptation and excellent in adhesion, the polyimides of the present invention are thin Film preferably comprises a part of organosilicon structures.As aforementioned inorganic film, can enumerate for example：The cvd film of silicon nitride, silicon oxide etc. And sputtered film.

The content (mass ratio) of the organosilicon residue comprising in Kapton is preferably the scope of 3～15 mass %, More preferably 6～12 mass %.When the content of organosilicon residue is more than 15 mass %, sometimes cannot ensure during laser lift-off fully Fissility, polyimide film because laser irradiate and burn, finally produce microgranule.On the other hand, this value is below 3 mass % When it is impossible to fully guarantee the cementability with glass substrate.

Below, the method for the Kapton with pore structure specifically making present embodiment is said Bright.

Specifically, the resin combination that is unfolded as follows on substrate and form film, then,

For aforementioned supporting mass and aforementioned film, oxygen concentration and heating-up temperature is controlled to carry out heat treated, so as to Enough formation has the Kapton of the hole of structure as described above, and it is (poly- that described resin combination comprises resin precursor Amic acid) and solvent, the resin matrix of described resin precursor (polyamic acid) have the unit 1 shown in following formulas (1) and under State the unit 2 shown in formula (2)：

X₁Organic group for 4 valencys of carbon number 4～32；And

X₂Organic group for the divalent of carbon number 4～32.}

In above-mentioned resin precursor, the cellular construction 1 shown in formula (1) is to make obtained from tetracarboxylic dianhydride and diamine reactant Structure.X₁From tetracarboxylic dianhydride, X₂From diamidogen.

Cellular construction 2 shown in formula (2) is the structure from organic silicon monomer.

X in the resin precursor of present embodiment, in formula (1)₂It is preferably and be derived from 2,2 '-bis- (trifluoromethyl) biphenyl Amine, 4,4- (diamino-diphenyl) sulfone, the residue of 3,3- (diamino-diphenyl) sulfone.

R in formula (2)₂And R₃A part be preferably phenyl.

In the resin precursor of the present invention, the gross mass of resin structure comprising foregoing units 1 and foregoing units 2 is with respect to total Resin precursor is preferably more than 30 mass %.

＜ tetracarboxylic dianhydride>

Then, the organic group X to 4 valencys comprising in import unit 1₁Tetracarboxylic dianhydride illustrate.

As above-mentioned tetracarboxylic dianhydride, specifically, be preferably selected from aromatic tetracarboxylic acid's dianhydride that carbon number is 8～36, Carbon number be 6～50 aliphatic tetracarboxylic dianhydride and ester ring type tetracarboxylic dianhydride that carbon number is 6～36 in compound.This Locate the number of the carbon that so-called carbon number also includes comprising in carboxyl.

More specifically, the aromatic tetracarboxylic acid's dianhydride being 8～36 as carbon number, can enumerate for example：4,4 '-(hexafluoro Isopropylidene) two phthalate anhydrides (hereinafter also referred to as 6FDA), 5- (2,5- dioxotetrahydro -3- furyl) -3- methyl-ring Hexene -1,2- dicarboxylic anhydride, pyromellitic acid anhydride (hereinafter also referred to as PMDA), 1,2,3,4- benzene tertacarbonic acid's dianhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (hereinafter also referred to as BTDA), 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride (hereinafter also referred to as DSDA), 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, methylene -4,4 '-two phthalic acid dianhydride, 1,1- ethylidene -4,4 '-two Phthalic acid dianhydride, 2,2- propylidene -4,4 '-two phthalic acid dianhydride, 1,2- ethylidene -4,4 '-two phthalic acid dianhydride, 1, 3- trimethylene -4,4 '-two phthalic acid dianhydride, 1,4- tetramethylene -4,4 '-two phthalic acid dianhydride, 1,5- pentamethylene - 4,4 '-two phthalic acid dianhydrides, 4,4 '-epoxide two phthalic acid dianhydride (hereinafter also referred to as ODPA), thio -4,4 '-hexichol two Double (3,4- dicarboxyphenyi) benzene dianhydride of formic acid dianhydride, sulfonyl -4,4 '-two phthalic acid dianhydride, 1,3-, the double (3,4- of 1,3- Di carboxyl phenyloxy) benzene dianhydride, double (3,4- di carboxyl phenyloxy) benzene dianhydride of 1,4-, 1,3- double [2- (3,4- dicarboxyphenyi)- 2- propyl group] benzene dianhydride, 1,4- double [2- (3,4- dicarboxyphenyi) -2- propyl group] benzene dianhydride, double [3- (3,4- di carboxyl phenyloxy) Phenyl] methane dianhydride, double [4- (3,4- di carboxyl phenyloxy) phenyl] methane dianhydride, double [3- (the 3,4- dicarboxyl benzene oxygen of 2,2- Base) phenyl] propane dianhydride, double [4- (3, the 4- di carboxyl phenyloxy) phenyl] propane dianhydride (hereinafter also referred to as BPADA) of 2,2-, Double (3,4- dicarboxyphenyi) -1,1,3,3- tetramethyl two silicon of double (3,4- di carboxyl phenyloxy) dimethylsilane dianhydride, 1,3- Oxygen alkane dianhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydride, 3,4, 9,10- tetracarboxylic dianhydride, 2,3,6,7- anthracene tetracarboxylic dianhydride, 1,2,7,8- phenanthrene tetracarboxylic dianhydride etc.；

The aliphatic tetracarboxylic dianhydride being 6～50 as carbon number, can enumerate for example：Ethylidene tetracarboxylic dianhydride, 1,2, 3,4- butane tetracarboxylic acid dianhydride etc.；

The ester ring type tetracarboxylic dianhydride being 6～36 as carbon number, can enumerate such as 1,2,3,4- Tetramethylene. tetrabasic carboxylic acids two Acid anhydride (hereinafter also referred to as CBDA), Pentamethylene. tetracarboxylic dianhydride, hexamethylene -1,2,3,4- tetracarboxylic dianhydrides, hexamethylene -1,2,4, 5- tetracarboxylic dianhydride (hereinafter also referred to as CHDA), 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, carbonyl -4,4 '-bis- (hexamethylenes Alkane -1,2- dicarboxylic acids) dianhydride, methylene -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydride, 1,2- ethylidene -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydride, 1,1- ethylidene -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydride, 2,2- propylidene - 4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydrides, oxygen -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydride, thio -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydride, sulfonyl -4,4 '-bis- (hexamethylene -1,2- dicarboxylic acids) dianhydride, bicyclo- [2,2,2] octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride, rel- [1S, 5R, 6R] -3- oxabicyclo [3,2,1] octane -2,4- diketone -6- spiral shell - 3 '-(oxolane -2 ', 5 '-diketone), 4- (2,5- dioxotetrahydro furan -3- base) -1,2,3,4- naphthane -1,2- dicarboxyl Anhydride, ethylene glycol-bis--(3,4- dicarboxylic anhydride phenyl) ether, 4,4 '-biphenyl double (trimellitic acid monoester anhydride) (hereinafter also referred to as TAHQ) etc..

Wherein, from the reduction of CTE, the raising of chemical reagent resistance, glass transition temperature (Tg) improves and machinery is stretched From the viewpoint of long rate improves, preferably use selected from more than a kind in the group of BTDA, PMDA, BPDA and TAHQ composition. In addition it is desirable to when obtaining the higher thin film of the transparency, from the reduction of yellowness, the reduction of birefringence and mechanical elongation rate From the viewpoint of raising, preferably use selected from more than a kind in the group of 6FDA, ODPA and BPADA composition.In addition, from residual The reduction, the reduction of yellowness, the reduction of birefringence, the raising of chemical reagent resistance, Tg raising and the machinery that stay stress are stretched From the viewpoint of long rate improves, preferably BPDA.In addition, from the viewpoint of the reduction of residual stress and the reduction of yellowness, Preferably CHDA.Wherein, from high resistance to chemicals is agents, residual stress reduction, yellowness reduction, the reduction of birefringence, Yi Jizong From the viewpoint of the raising of light transmittance, preferably by selected from embodying, high resistance to chemicals is agents, high Tg and low CTE firm knot In the group of PMDA and BPDA composition of structure more than a kind and be selected from yellowness and low 6FDA, the ODPA of birefringence and CHDA composition group in a kind of combination of the above and use.

In the resin precursor of the present invention, preferably 20 the rubbing of the composition all being from tetracarboxylic dianhydride of aforementioned resin precursor That % composition from biphenyltetracarboxyacid acid (BPDA) contained above.

The resin precursor of present embodiment not damaging in the range of its performance, by using above-mentioned tetracarboxylic dianhydride and Dicarboxylic acids, are also used as polyamidoimide precursor.By using such precursor, for gained thin film, can adjust each Performance is as improved mechanical elongation rate, improving glass transition temperature, reduce yellowness etc..As such dicarboxylic acids, Ke Yiju Go out to have dicarboxylic acids and the ester ring type dicarboxylic acids of aromatic ring.Particularly preferably selected from carbon number be 8～36 aromatic dicarboxylic acid and Carbon number is at least one compound in 6～34 group of ester ring type dicarboxylic acids composition.So-called carbon number is also included in carboxyl herein The number of the carbon comprising.

Wherein, preferably there are the dicarboxylic acids of aromatic ring.

Specifically, can enumerate for example：M-phthalic acid, p-phthalic acid, 4,4 '-diphenyl dicarboxylic acid, 3,4 '-biphenyl Dicarboxylic acids, 3,3 '-diphenyl dicarboxylic acid, 1,4- naphthalenedicarboxylic acid, 2,3- naphthalenedicarboxylic acid, 1,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 4, The double benzoic acid of the double benzoic acid of 4 '-sulfonyl, 3,4 '-sulfonyl, the double benzoic acid of 3,3 '-sulfonyl, the double benzoic acid of 4,4 '-oxo, The double benzoic acid of 3,4 '-oxo, the double benzoic acid of 3,3 '-oxo, double (4- carboxyl phenyl) propane of 2,2-, 2,2- are double (3- carboxyl phenyl) Propane, 2,2 '-dimethyl -4,4 '-diphenyl dicarboxylic acid, 3,3 '-dimethyl -4,4 '-diphenyl dicarboxylic acid, 2,2 '-dimethyl -3, Double (4- (3- carboxyphenoxy) phenyl) fluorenes of double (4- (4- carboxyphenoxy) phenyl) fluorenes of 3 '-diphenyl dicarboxylic acid, 9,9-, 9,9-, 4,4 '-bis- (4- carboxyphenoxy) biphenyl, 4,4 '-bis- (3- carboxyphenoxy) biphenyl, 3,4 '-bis- (4- carboxyphenoxy) connection Benzene, 3,4 '-bis- (3- carboxyphenoxy) biphenyl, 3,3 '-bis- (4- carboxyphenoxy) biphenyl, 3,3 '-bis- (3- carboxyphenoxies) Biphenyl, 4,4 '-bis- (4- carboxyphenoxy)-para-terpheny, 4,4 '-bis- (4- carboxyphenoxy)-meta-terphenyls, 3,4 '-bis- (4- Carboxyphenoxy)-para-terpheny, 3,3 '-bis- (4- carboxyphenoxy)-para-terpheny, 3,4 '-bis- (4- carboxyphenoxies)- Terphenyl, 3,3 '-bis- (4- carboxyphenoxy)-meta-terphenyls, 4,4 '-bis- (3- carboxyphenoxy)-para-terpheny, 4,4 '-bis- (3- carboxyphenoxy)-meta-terphenyl, 3,4 '-bis- (3- carboxyphenoxy)-para-terpheny, 3,3 '-bis- (3- carboxyphenoxies)- Para-terpheny, 3,4 '-bis- (3- carboxyphenoxy)-meta-terphenyls, 3,3 '-bis- (3- carboxyphenoxy)-meta-terphenyls, 1,1- ring Butane dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid, 1,2- cyclohexane dicarboxylic acid, 4,4 '-benzophenone dicarboxylic acids, 1,3- benzene diethyl Acid, 1,4- phenylenediacetic Acid etc.；And the 5- amino isophthalic acid described in No. 2005/068535 pamphlet of International Publication No. spreads out Biology etc..During actual these dicarboxylic acids of copolymerization in the polymer it is also possible to be derived from thionyl chloride etc. acyl chlorides body, The forms such as active ester body use.

Wherein, from the viewpoint of the reduction of YI value and the raising of Tg, particularly preferred p-phthalic acid.By dicarboxylic acids When being used together with tetracarboxylic dianhydride, from the viewpoint of the chemical reagent resistance of gained thin film, with respect to by dicarboxylic acids and four The overall molal quantity that carboxylic acid dianhydride is added together, preferred dicarboxylic is 50 moles of below %.

＜ diamidogen>

As the diamidogen of the X2 in the unit 1 of the resin precursor deriving present embodiment, specifically, example can be enumerated As：4,4- (diamino-diphenyl) sulfone (hereinafter also referred to as 4,4-DAS), 3,4- (diamino-diphenyl) sulfone and 3,3- (diaminourea Diphenyl) sulfone (hereinafter also referred to as 3,3-DAS), 2,2 '-bis- (trifluoromethyl) benzidine (hereinafter also referred to as TFMB), 2,2 '- Dimethyl -4,4 '-benzidine (hereinafter also referred to as m-TB), Isosorbide-5-Nitrae-diaminobenzene (hereinafter also referred to as p-PD), 1,3- bis- Aminobenzene (hereinafter also referred to as m-PD), 4- aminophenyl -4 '-Aminobenzoate (hereinafter also referred to as APAB), 4,4 '-diamino Yl benzoic acid ester (hereinafter also referred to as DABA), 4,4 '-(or 3,4 '-, 3,3 '-, 2,4 ' -) diaminodiphenyl ether, 4,4 '-(or 3, 3 ' -) diamino diphenyl sulfone, 4,4 '-(or 3,3 ' -) diamino diphenyl sulfide, 4,4 '-benzophenone diamidogen, 3,3 '-hexichol Ketone diamidogen, 4,4 '-two (4- amino-benzene oxygen) phenylsulfone, 4,4 '-two (3- amino-benzene oxygen) phenylsulfone, 4,4 '-bis- (4- ammonia Phenoxyl) biphenyl, double (4- amino-benzene oxygen) benzene of 1,4-, double (4- amino-benzene oxygen) benzene of 1,3-, double { 4- (the 4- amino of 2,2- Phenoxy group) phenyl propane, 3,3 ', 5,5 '-tetramethyl -4,4 '-diaminodiphenyl-methane, 2,2 '-bis- (4- aminophenyls) third Alkane, 2,2 ', 6,6 '-tetramethyl -4,4 '-benzidine, 2,2 ', 6,6 '-four trifluoromethyls -4,4 '-benzidine, double Double (4- aminophenoxy phenyl) fluorenes of double (4- aminophenyl) fluorenes of { (4- aminophenyl) -2- propyl group } -1,4- benzene, 9,9-, 9,9-, 3,3 '-dimethylbenzidine, 3,3 '-dimethoxy benzidine and 3,5- diaminobenzoic acid, 2,6- diamino-pyridine, 2,4- bis- Aminopyridine, double (4- aminophenyl -2- propyl group) -1,4- benzene, 3,3 '-bis- (trifluoromethyl) -4,4 '-benzidines (3,3 ' - TFDB), 2,2 '-bis- [3 (3- amino-benzene oxygen) phenyl] HFC-236fa (3-BDAF), 2,2 '-bis- [4 (4- amino-benzene oxygen) benzene Base] HFC-236fa (4-BDAF), 2,2 '-bis- (3- aminophenyl) HFC-236fa (3,3 ' -6F), 2,2 '-bis- (4- aminophenyls) The aromatic diamines such as HFC-236fa (4,4 ' -6F).Wherein, from the viewpoint of the reduction of yellowness, the reduction of CTE, high Tg, excellent Choosing is using selected from more than a kind in 4,4-DAS, 3,3-DAS, 1,4- cyclohexane diamine, the group of TFMB and APAB composition.

The importing of ＜ silicon compound>

Structure shown in above-mentioned formula (2) is derived from organic silicon monomer.The organic silicon monomer being used during synthetic resin precursor Amount on the basis of the quality of resin precursor, preferably 6 mass %～25 mass %.Sub- from being fully reduced gained polyamides From the viewpoint of the effect of stress producing between amine thin film and inoranic membrane and the effect reducing yellowness, organic silicon monomer Usage amount is more than 6 mass % is favourable.This value is more preferably more than 8 mass %, more than more preferably 10 mass %. On the other hand, by making the usage amount of organic silicon monomer for, below 25 mass %, gained Kapton does not have nebulousurine, from saturating Bright property is favourable from the viewpoint of improving and obtaining good thermostability.This value is more preferably below 22 mass %, enters one Step is preferably below 20 mass %.From the cementability of chemical reagent resistance, total light transmittance, residual stress and glass substrate and From the viewpoint of the easiness of laser lift-off, the usage amount of organic silicon monomer is particularly preferably more than 10 mass % and 20 mass % Below.Think, as described later, when heat cure being carried out to the film of resin precursor under the control of oxygen concentration, be absorbed into A part for organosilicon in resin precursor is volatilized with forms such as cyclic trimer, ring-type tetramers.After preferably with this volatilization Surplus organosilicon mass ratio be 4～18 mass % with respect to the quality of whole Kaptons the mode of scope adjust The import volume of organic silicon monomer during resin precursor.

As the aliphatic alkyl of 1 valency of the carbon number 1～20 in aforementioned formula (2), such as carbon number 1～20 can be enumerated Alkyl, cycloalkyl of carbon number 3～20 etc.；

As the aromatic series base of carbon number 6～10, such as aryl etc. can be enumerated.Go out from the viewpoint of thermostability and residual stress Send out, the alkyl of the preferred carbon number of alkyl 1～10 of aforementioned carbon number 1～20, specifically, can enumerate for example methyl, ethyl, third Base, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, hexyl etc..From the above point of view, the cycloalkyl of this carbon number 3～20 is excellent Elect the cycloalkyl of carbon number 3～10 as, specifically, such as cyclopenta, cyclohexyl etc. can be enumerated.From the above point of view, make For the aryl of this carbon number 6～10, specifically, such as phenyl, tolyl, naphthyl etc. can be enumerated.

As the organic silicon monomer of the unit 2 derived as described above, preferably use having shown in for example following formulas (3) Organic silicon compound：

R₇When having multiple, it is each independently the organic group of 1 valency of carbon number 1～20；

L₁、L₂And L₃It is each independently amino, NCO, carboxyl, anhydride group, perester radical, acid halide, hydroxyl Base, epoxy radicals or sulfydryl；

J is 3～200 integer, and

K is 0～197 integer }.

As R₄In the divalent of carbon number 1～20 organic group, such as methylene, the alkylene of carbon number 2～20 can be enumerated Base, the ring alkylidene of carbon number 3～20, arlydene of carbon number 6～20 etc..Go out from the viewpoint of thermostability, residual stress and cost Send out, the alkylidene of this carbon number 2～20 is preferably the alkylidene of carbon number 2～10, specifically can enumerate for example dimethylene, three Methylene, tetramethylene, pentamethylene, hexa-methylene etc..From the above point of view, the ring alkylidene of this carbon number 3～20 is preferred The ring alkylidene of carbon number 3～10.Specifically, such as ring butylidene, ring pentylidene, cyclohexylene, ring heptamethylene can be enumerated Deng.Wherein, from the above point of view, the aliphatic hydrocarbon of the preferred divalent of carbon number 3～20.From the above point of view, this carbon number 6～ The aromatic series base of the 20 preferred carbon number of arlydene 3～20, specifically, can enumerate such as phenylene, naphthylene etc..

In formula (3), R₅And R₆With the R in formula (2)₂And R₃For identical meanings, preferred scheme such as mutual-through type (2) institute State like that.And, R₇Preferred scheme and R₂And R₃Identical.

In formula (3), j is 3～200 integer, preferably 10～200 integer, more preferably 20～150 integer, More preferably 30～100 integer, particularly preferably 35～80 integer.In formula (3), k is 0～197 integer, excellent Elect 0～100, more preferably 0～50, particularly preferably 0～25 as.K be more than 197 when, preparation comprise resin precursor and During the resin combination of solvent, sometimes produce said composition the problems such as nebulousurine occurs.When k is 0, carry from the molecular weight of resin precursor It is preferred from the viewpoint of the thermostability of high viewpoint and gained polyimides.When k is 0, from the molecular weight of resin precursor From the viewpoint of the viewpoint improving and the thermostability of gained polyimides, j is 3～200 to be favourable.

In formula (3), L₁、L₂, and L₃Be each independently amino, NCO, carboxyl, anhydride group, perester radical, Acid halide, hydroxyl, epoxy radicals or sulfydryl.

Amino is optionally substituted.As substituted amino, for example double (trialkyl silyl) amino etc. can be enumerated.Formula (3) in, as L₁、L₂, and L₃For the specific example of the compound of amino, two terminal amino group modified methyl phenyl can be enumerated Organosilicon (X22-1660B-3 (number-average molecular weight 4400) and X22-9409 (number-average molecular weight that for example SHIN-ETSU HANTOTAI's chemistry society manufactures 1300))；The two terminal amino group modification dimethyl organosilicon (X22-161A (number-average molecular weights that for example SHIN-ETSU HANTOTAI's chemistry society manufactures 1600), X22-161B (number-average molecular weight 3000) and KF8012 (number-average molecular weight 4400)；レダウ conning The BY16-835U (number-average molecular weight 900) manufacturing；And サイラプレ Application FM3311 (the equal molecule of number that チッソ society manufactures Amount 1000)) etc..

As L₁、L₂And L₃For the specific example of the compound of NCO, can enumerate aforementioned makes two terminal amino groups change Property organosilicon and isocyanate-modified organosilicon etc. obtained from phosgene compound reaction.

As L₁、L₂And L₃For the specific example of the compound of carboxyl, the X22-162C of such as SHIN-ETSU HANTOTAI's chemistry society can be enumerated BY16-880 (number-average molecular weight 6600) that (number-average molecular weight 4600), レダウ conning manufacture etc..

As L₁、L₂, and L₃For example during anhydride group,

Acyl compounds of at least one for example having in the group that following formula group represents respectively etc. can be enumerated.

As L₁、L₂And L₃For the specific example of the compound of anhydride group, such as X22-168AS (SHIN-ETSU HANTOTAI's chemistry can be enumerated System, number-average molecular weight 1000), X22-168A (SHIN-ETSU HANTOTAI chemistry system, number-average molecular weight 2000), X22-168B (SHIN-ETSU HANTOTAI's chemistry system, number Average molecular weight 3200), X22-168-P5-8 (SHIN-ETSU HANTOTAI chemistry system, number-average molecular weight 4200), DMS-Z21 (ゲレスト society system, number Average molecular weight 600～800) etc..

As L₁、L₂And L₃For the specific example of the compound of perester radical, can enumerate aforementioned makes L₁、L₂And L₃For carboxyl or The compound of anhydride group and compound etc. obtained from alcohol reaction.

As L₁、L₂And L₃For example during acid halide, such as carboxylic acid chloride, carboxylic acid fluoride, carboxylic acid can be enumerated Bromide, carboxylic acid iodide etc..

As L₁、L₂And L₃For the specific example of the compound of hydroxyl, can enumerate such as KF-6000 (SHIN-ETSU HANTOTAI's chemistry system, Number-average molecular weight 900), KF-6001 (SHIN-ETSU HANTOTAI chemistry system, number-average molecular weight 1800), KF-6002 (SHIN-ETSU HANTOTAI's chemistry system, the equal molecule of number Amount 3200), KF-6003 (SHIN-ETSU HANTOTAI chemistry system, number-average molecular weight 5000) etc..Think there is the compound of hydroxyl with there is carboxyl or The compound reaction of anhydride group.

As L₁、L₂And L₃For the specific example of the compound of epoxy radicals, the X22- that two ends are epoxy type can be enumerated 163 (SHIN-ETSU HANTOTAI's chemistry system, number-average molecular weights 400), KF-105 (SHIN-ETSU HANTOTAI's chemistry system, number-average molecular weight 980), X22-163A (SHIN-ETSU HANTOTAI Chemistry system, number-average molecular weight 2000), X22-163B (SHIN-ETSU HANTOTAI chemistry system, number-average molecular weight 3500), X22-163C (SHIN-ETSU HANTOTAI's chemistry System, number-average molecular weight 5400)；Two ends are X22-169AS (SHIN-ETSU HANTOTAI's chemistry system, the number-average molecular weight of ester ring type epoxy type 1000), X22-169B (SHIN-ETSU HANTOTAI's chemistry system, number-average molecular weight 3400)；Side chain two end is the X22-9002 (SHIN-ETSU HANTOTAI of epoxy type Chemistry system, functional equivalent 5000g/mol)；Deng.Think the compound and diamine reactant with epoxy radicals.

As L₁、L₂And L₃For the specific example of the compound of sulfydryl, can enumerate such as X22-167B (SHIN-ETSU HANTOTAI's chemistry system, Number-average molecular weight 3400), X22-167C (SHIN-ETSU HANTOTAI chemistry system, number-average molecular weight 4600) etc..Think have the compound of sulfydryl with There is the compound reaction of carboxyl or anhydride group.

From the viewpoint of the viewpoint of molecular weight improving resin precursor or the thermostability of gained polyimides, L₁、L₂With L₃Preferably it is each independently amino or anhydride group, and from avoiding the nebulousurine of the resin combination comprising resin precursor and solvent Viewpoint and cost from the viewpoint of, preferably

L₁、L₂And L₃It is amino；Or

L₁And L₂It is each independently amino or anhydride group, and k is 0.In the latter case, more preferably L₁And L₂All For amino.

The number-average molecular weight of the resin precursor of present embodiment be preferably 3000～1000000, more preferably 5000～ 500000, more preferably 7000～300000, particularly preferably 10000～250000.From obtain well thermostability and From the viewpoint of intensity (such as retractility (stretch)), preferably this molecular weight is more than 3000, obtains to solvent from well Deliquescent viewpoint, coating etc. processing when can be coated with no oozing out with desired thickness from the viewpoint of, excellent Elect less than 1000000 as.From the viewpoint of obtaining high mechanical elongation rate, molecular weight is preferably more than 50000.In the disclosure, Aforementioned number-average molecular weight is the value obtained using chromatograph of gel permeation and according to polystyrene standard conversion.

A part for the resin precursor of present embodiment can also be by imidizate.The imidizate of resin precursor can pass through The amidatioon of known chemistry or hot amidatioon are carrying out.Wherein, preferred hot-imide.As specific method, it is preferably as follows Method：After resin combination is made by aftermentioned method, solution is heated 5 minutes～2 hours at 130～200 DEG C.Logical Cross the method, can be not cause the degree that resin precursor separates out a part for polymer to be carried out be dehydrated imidizate.Herein, By controlling heating-up temperature and heat time heating time, acid imide rate can be controlled.By carrying out part imidizate, it is possible to increase tree The viscosity stability in room temperature keeping for the oil/fat composition.As the scope of acid imide rate, from the dissolubility to solution and preservation From the viewpoint of stability, preferably 5%～70%.

Alternatively, it is also possible to add DMF dimethylacetal, N, N- dimethyl in above-mentioned resin precursor Methanamide diethyl acetal etc. and heated, by carboxylic acid part or all esterification.Thereby, it is possible to improve resin combination Viscosity stability in room temperature keeping.

＜ resin combination>

The resin precursor of present embodiment as described above is (clear preferably as the resin combination being dissolved in solvent Paint) using.

By this composition can be special the combination of solvent and make transparent Kapton.

For preferred scheme, the resin combination of present embodiment can be by tetracarboxylic dianhydride, diamidogen and organic Silicon monomer is dissolved in solvent such as organic solvent and is allowed to react, thus using containing as one of resin precursor polyamic acid and The form of the polyamic acid solution of solvent is manufacturing.Herein, condition during reaction is not particularly limited, for example, can exemplify - 20～150 DEG C of reaction temperature, the condition in 2～48 hours response time.In order that fully entering with the reaction of organic silicon monomer OK, in synthetic reaction, preferably more than 120 DEG C at a temperature of carry out above heating in 30 minutes about.In addition, reaction preferably exists Carry out under the inert atmosphere such as argon, nitrogen.

For aforementioned solvents, as long as the solvent that can dissolve polyamic acid is just not particularly limited.As known anti- Answer solvent, be selected from diformazan glycol dimethyl ether (DMDG), metacresol, METHYLPYRROLIDONE (NMP), dimethyl formyl Amine (DMF), dimethyl acetylamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethacetic acid ester, エ Network アミ De M100 (business The name of an article：Chu Guangxingchan society system) and エ Network アミ De B100 (trade name：Chu Guangxingchan society system) in more than a kind of polar solvent It is useful.Wherein, it is preferably selected from more than a kind in NMP, DMAc, エ Network アミ De M100 and エ Network アミ De B100. In addition it is also possible to will as oxolane (THF), chloroform low boiling solution or as gamma-butyrolacton low absorption Property solvent is used together with above-mentioned solvent or replaces above-mentioned solvent to use.

For the resin combination of present embodiment, sufficient with supporting mass in order to give to gained Kapton Adaptation is it is also possible to contain alkoxysilane compound containing trialkylsilyl group in molecular structure 0.01～2 mass % with respect to resin precursor 100 mass %.

With respect to resin precursor 100 mass %, the content of alkoxysilane compound containing trialkylsilyl group in molecular structure is more than 0.01 mass %, so as to Access and supporting mass good adaptation, and from the viewpoint of the storage stability of resin combination, preferably alcoxyl The content of base silane compound is below 2 mass %.With respect to resin precursor, the content of alkoxysilane compound containing trialkylsilyl group in molecular structure is more preferably 0.02～2 mass %, more preferably 0.05～1 mass %, particularly preferably 0.05～0.5 mass %, especially preferably 0.1～0.5 mass %.

As alkoxysilane compound containing trialkylsilyl group in molecular structure, can enumerate such as 3- ureidopropyltriethoxysilane, double (2- ethoxys)- APTES, 3- glycidoxypropyltrime,hoxysilane, phenyltrimethoxysila,e, gamma-amino Propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, gamma-amino propyl group tripropoxy silane, gamma-amino propyl group Three butoxy silanes, gamma-amino ethyl triethoxysilane, gamma-amino ethyl trimethoxy silane, gamma-amino ethyl 3 third TMOS, gamma-amino ethyl three butoxy silane, gamma-amino butyl triethoxysilane, gamma-amino butyl trimethoxy Silane, gamma-amino butyl tripropoxy silane, gamma-amino butyl three butoxy silane etc..They can also be by two or more group Close and use.

＜ has the making of the Kapton of hole>

The polyimide resin film with pore structure of present embodiment can make as follows：Surface in supporting mass Upper expansion above-mentioned resin combination and form film, then,

By aforementioned supporting mass and aforementioned film below oxygen concentration 23 mass % and under conditions of more than 250 DEG C of temperature Heating.

In this specification, the unit " quality % " with regard to oxygen concentration is the percentage rate of volume reference, with regard to aftermentioned oxygen The unit " ppm " of concentration is the PPM of volume reference.

Herein, for aforementioned supporting mass, inorganic substrate for example, as the glass substrates such as alkali-free glass substrate, do not have Especially limit.

As polyimide precursor to the method for deploying of base material, such as spin coating, slot coated and scraper can be enumerated The known painting method of coating.

Then, it is heated to 80 DEG C～200 DEG C using hot plate, baking oven etc. and so that solvent is evaporated, thus making film (prebake Film).Now, become the silicone portion of resin precursor and polyimide portion forms the film of micro phase separation structure.

Then, this supporting mass and film are put in the baking oven of below oxygen concentration 23 mass %, be heated to 250 DEG C with On, thus carrying out to resin precursor being dehydrated imidizate, the part decomposition of the silicone portion of microphase-separated will occur simultaneously Remove and form hole such that it is able to make the polyimide film of present embodiment.Think, by more than 250 DEG C heating, set Silicone portion in fat precursor occurs thermal decomposition to generate cyclic trimer and/or ring-type tetramer, thus by evaporative removal. Prebake film can not also be made, and the supporting mass after coating is direct plungeed in the baking oven controlling oxygen concentration, be heated to More than 250 DEG C.

The size of hole and porosity can by for example by the silicone content in polymer, solidification temperature, hardening time, Oxygen concentration etc. is set as suitable scope to be controlled.

Specifically, for example increase resin precursor in the import volume of silicone portion shown in above-mentioned formula (2) and The area size of the organosilicon in prebake film becomes big.The size of the regional structure of this organosilicon becomes and controls the one of pore structure Individual key element.If silicone portion is thermally decomposed completely, the area size in prebake film becomes in gained polyimide film Hole full-size.Therefore, by controlling the area size of the organosilicon in prebake film, gained polyamides can be controlled sub- Pore-size (average major axis footpath) in amine film.In order to by the area size of the organosilicon in prebake film be controlled to 100nm with Under, make the mass ratio of the silicone portion shown in above-mentioned formula (2) in resin precursor become 25 overall matter of resin precursor Amount below %.Herein, by one or more of oxygen concentration when controlling solidification temperature, hardening time and solidifying Key element, can be by the magnitude relationship of the area size of the organosilicon in the size of the hole in polyimide film and prebake film It is adjusted to arbitrary degree.

The oxygen concentration during heating of present embodiment is preferably below 2000ppm.By oxygen concentration during heating it is , there is the tendency producing uniform hole in thin film in this scope.Therefore, tensile elongation height, the birefringence (Rth) of thin film are tended to Also low, therefore preferably.On the other hand, if more than 2000ppm and the oxygen concentration below 23 mass % is heated, there is hole The somewhat impaired tendency of uniformity on the film thickness direction of gap.

Speculate that this phenomenon is for being difficult to the heat of the silicone portion that resin precursor occurs during more than 2000ppm by oxygen concentration Decomposition reaction causes.Although its reason is failed to understand, the present inventor etc. speculates, under conditions of there is the oxygen of significant quantity, organic Organic group on the silicon atom of silicon is aoxidized by oxygen, generates such as formaldehyde, formic acid, hydrogen, carbon dioxide etc., is changed into height and hands over The gel heat resistant polymer of connection.

However, by oxygen concentration is controlled to below 2000ppm, Kapton starts equably to produce hole knot Structure.If being compared with identical heating-up temperature, can confirm that oxygen concentration is lower, the size of hole is bigger.

In addition, when oxygen concentration is below 2000ppm, if oxygen concentration is identical, heating-up temperature is higher, more can increase The size of the hole of Kapton.

The present inventor through confirmation, result from the viewpoint of the size Control of hole, preferably by oxygen during heat treated Gas concentration controls in below 1000ppm.Heating-up temperature is preferably 250 DEG C～480 DEG C of scope, from the sight of the size Control of hole Point sets out, more preferably 280 DEG C～450 DEG C of scope.

Particularly preferably oxygen concentration is controlled in below 100ppm, by heating and temperature control in 280 DEG C～450 DEG C of scope Interior.

As controlling the non-active gas using during oxygen concentration, such as nitrogen gas, Ar gas etc. can be enumerated, from warp From the viewpoint of Ji, preferably nitrogen gas.In addition, in order to control oxygen concentration, it is possible to use vacuum drying oven etc. is under reduced pressure Heated.

The thickness of the Kapton of present embodiment is not particularly limited, preferably 1～200 μm of scope, more It is preferably 5～50 μm.

And, the Kapton of the present embodiment residual stress in 10 μm of thickness is preferably below 25MPa.

The yellowness (YI) in 20 μm of thickness for the Kapton of the scheme of present embodiment is preferably less than 7.Right It is in the Kapton of this scope in YI value, when using it for flexible display substrate, color correction can not be carried out And use.The YI value in 20 μm of thickness for the Kapton more preferably less than 6, particularly preferably less than 5.

It should be noted that when the thickness of resin film is not 20 μm, changed by thickness is carried out to the measured value of this thin film Calculate, yellowness during 20 μm of thickness can be known.

＜ duplexer>

The present invention also provides the duplexer including supporting mass and the polyimide film being formed on this supporting mass.This stacking Body can obtain as follows：Above-mentioned resin combination is launched on the surface of supporting mass and forms film, then,

This duplexer is for example used for the manufacture of flexible device.

More specifically, the Kapton that duplexer has forms semiconductor device, thereafter, by supporting mass Peel off and obtain the flexible device including Kapton and the semiconductor device being formed on.

As described above, the Kapton of present embodiment is by having specific pore structure, with The residual stress producing between glass substrate or inoranic membrane is low, excellent in adhesion with glass substrate, even and if in laser stripping Stripping that yet can be good in the case that irradiation energy is low in operation, does not cause the generation burnt with microgranule.Therefore, this enforcement The extremely suitable substrate as flexible display of Kapton of mode.

Below, to by the Kapton of present embodiment be used as flexible display substrate when preferred scheme Illustrate.

When forming flexible display, glass substrate is used as supporting mass, is formed on the polyamides as flexible base board Imines thin film, and then it is formed on TFT etc..The operation forming TFT can be typically in the temperature of 150～650 DEG C of wide scope Lower enforcement.In order to practically embody desired performance, mainly it is formed about TFT-IGZO (InGaZnO) at 250 DEG C～450 DEG C Oxide semiconductor, TFT (a-Si-TFT, LTPS-TFT).

Now, if the residual stress producing between flexible base board and Kapton is high, formed in the TFT of high temperature After operation expands, when shrinking when room temperature cools down, produce the warpage of glass substrate and breakage, flexible base board are shelled from glass substrate From the problems such as.Generally, the thermal coefficient of expansion of glass substrate is less than resin, produces residual therefore between flexible base board and resin film Stay stress.In view of this point, the Kapton of present embodiment, on the basis of 10 μm of the thickness of thin film, produces and between glass Residual stress be preferably below 25MPa.

In addition, the Kapton of present embodiment is due to excellent in fracture strength when using as flexible base board, because , from the viewpoint of improving yield rate, on the basis of 20 μm of the thickness of thin film, tensile elongation is preferably more than 30% for this.Especially Its, if tensile elongation be more than 33%, configure Kapton on inoranic membrane when, exist be less prone to stripping, The tendency of the crackle of thin film.Wherein, particularly preferred more than 40%.

The Kapton of present embodiment has in -150 DEG C～0 DEG C of region and 150 DEG C～380 DEG C of region respectively There is at least each a kind of glass transition temperature, preferably more than 0 DEG C and the region less than 150 DEG C does not have glass transition temperature.

In addition, in order to do not produce TFT element formed at a temperature of softening, the Kapton of present embodiment above-mentioned Glass transition temperature under high-temperature area is preferably in more than 250 DEG C.

And, the Kapton of present embodiment is preferably provided with being resistant to make the photoetching using during TFT element The chemical reagent resistance of the photoresist stripper in operation.

Light extraction mode for flexible display it is known that extract the top light emitting mode of light from the face side of TFT element And this 2 kinds of the bottom-emission mode of light is extracted from rear side.For top light emitting mode, because TFT element does not become obstruction, Therefore there is the easy feature improving aperture opening ratio.Another bottom-emission mode has positioning feature easy and easy to manufacture.If TFT element transparent, then also can improve aperture opening ratio even for bottom-emission mode, therefore for large-scale organic EL Flexible Displays Device, expects using bottom-emission mode easy to manufacture.Colourless transparent resin substrate for bottom-emission mode is used The situation of resin substrate, in identification side configuration resin substrate.Accordingly, as resin substrate, go out from the viewpoint improving picture quality Send out, especially require that yellowness (YI value) is low, total light transmittance is high.

The Kapton of present embodiment and duplexer can be in such as semiconducting insulation film, TFT-LCD dielectric film, electricity It is used as substrate in the manufacture of pole protecting film, flexible device etc. particularly suitablely.Herein, flexible device be, for example, flexible display, Flexible solar battery, flexible touch panel electrode substrate, flexible light, flexible battery etc..Meet this reality of above-mentioned each physical property The Kapton applying mode be used especially for the yellow because existing Kapton has and use limited purposes, Especially flexible display water white transparency substrate purposes.

In addition, the Kapton of present embodiment can be additionally used in the diffusion in such as protecting film, TFT-LCD etc. Mating plate and film (for example, the interlayer of TFT-LCD, gate insulating film, liquid crystal orientation film etc.), touch panel ito substrate, intelligence Mobile phone substitutes the field that resin substrate of protective glass etc. requires colorless transparency and low-birefringence.Present embodiment is poly- When acid imide is used as liquid crystal orientation film, contributes to the increase of aperture opening ratio, realize the manufacture of the TFT-LCD of high-contrast.

Embodiment

Below, according to embodiment, the present invention is illustrated in greater detail.However, these illustrate that and record, this Bright scope is not limited to following embodiments.

Various evaluations in embodiment and comparative example are carried out as follows.

(mensure of number-average molecular weight)

For number-average molecular weight (Mn), it is measured using chromatograph of gel permeation (GPC) and according to following conditions.

Solvent：For DMF (Wako Pure Chemical Industries, Ltd.'s system, high performance liquid chromatograph use), will survey Lithium bromide monohydrate (Wako Pure Chemical Industries, Ltd.'s system, purity 99.5%) and the 63.2mmol/L of 24.8mmol/L is added before fixed Phosphoric acid (Wako Pure Chemical Industries, Ltd.'s system, high performance liquid chromatograph use).

Calibration trace：Made using polystyrene standard (ソ society system)

Post：Shodex KD-806M (Showa electrician society system)

Flow velocity：1.0mL/ minute

Column temperature：40℃

Pump：PU-2080Plus (JASCO society system)

Detector：RI-2031Plus(RI：Differential refractometer, JASCO society system) and UV-2075Plus (UV-VIS：Purple Outer visible ray absorptiometer, JASCO society system)

(making of duplexer and separating film)

The resin precursor composition bar coater obtaining in each synthesis example is coated in alkali-free glass substrate (thickness 0.7mm) On, after carrying out 5 minutes～10 minutes levellings at room temperature, using vertical curing oven (silver dollar リ Application De バグ society system, model Name VF-2000B) heating (prebake) 60 minutes at 140 DEG C, and then heat 60 points in hot-air oven in a nitrogen atmosphere Clock, thus make the duplexer on glass substrate with the Kapton that thickness is 20 μm.

Herein, the oxygen concentration in hot-air oven and solidification temperature are set as described in table 1.Oxygen concentration Zirconium oxide formula LC-750L that meter is manufactured using レエ Application ジニアリ Application グ society.Duplexer after solidification be impregnated in water, Kapton is peeled off, for following evaluation by standing for 24 hours afterwards from glass.Wherein, for laser lift-off Evaluation and the mensure of adhesive strength, for evaluating in the state of not peeling off from glass substrate, for the evaluation of residual stress And infrared analysis, form polyimide film respectively.

(evaluation of tensile elongation)

Kapton after solidification is cut into the size of 5mm × 50mm, using cupping machine (エア Application De ディ Co. Ltd. system：RTG-1210) stretched with speed 100mm/ minute, measured tensile elongation.

(evaluation of glass transition temperature and linear expansion coefficient)

Glass transition temperature for region more than room temperature and the mensure of linear expansion coefficient (CTE), after solidifying Kapton be cut into the size of 5mm × 50mm as test film, carried out by thermodynamic analysis.As mensure device, The thermodynamic analysis device (TMA-50) being manufactured using Shimadzu Seisakusho Ltd., in load 5g, 10 DEG C/min of programming rate and nitrogen Under conditions of gas air-flow (flow 20ml/ minute), enter the mensure of the test film percentage elongation under the scope of 50～450 DEG C of trip temperature. The flex point of the chart obtaining is obtained as glass transition temperature, and obtains the Kapton at 100～250 DEG C CTE.

(evaluation of laser lift-off)

Using Nd：3rd higher hamonic wave (355nm) of Yag laser increases on one side step by step from duplexer obtained above The irradiation energy that glass substrate side is irradiated, is irradiated, polyimides is peeled off.

Herein, the polyimides table peeled off with the minimum irradiation energy that can peel off using observation by light microscope Face, the presence or absence of burning on investigation polyimide surface and microgranule generation.The almost whole face of thin film is produced their situation It is evaluated as fissility " bad ", only minimum their situation of part generation in thin film is evaluated as fissility "available", then, Do not produced their situation and be evaluated as fissility " good ".

(evaluation of residual stress)

Using residual stress measure device (テンコ Le society system, model name FLX-2320) measure thickness be 625 μm ± " amount of warpage " of 25 μm of 6 inch silicon wafer.The resin precursor composition obtaining in each synthesis example is coated on this using bar coater On silicon chip, after carrying out 60 minutes prebake at 140 DEG C, in vertical curing oven (silver dollar リ Application De バグ society system, model name VF-2000B in), heat treated is implemented with the oxygen concentration described in table 1 and solidification temperature, make that to have thickness be 10 μm poly- The silicon chip of acid imide film.

Using aforementioned residual stress measure device measure this carry polyimides chip amount of warpage, by with aforementioned silicon The comparison of the amount of warpage of piece, evaluates the residual stress producing between silicon chip and resin film.

(using the observation of the hole of ultramicroscope)

Kapton is embedded in epoxy resin, makes ultrathin section using microtome (LEICA EM UC6), As microscopy sample.Using transmission electron microscope (Hitachi's system：S-5500) under accelerating potential 30kV with SEM and STEM pattern carries out the observation from film sections direction.

Using image processing software, by using STEM image viewing to pore structure state obtain respectively porosity with And the meansigma methodss of maximum long axis length.

And then, obtain the uniformity on the film thickness direction of the hole in Kapton as follows.By each polyimides The Electronic Speculum imaging of thin film is divided into every 2 μm of region along film thickness direction, carries out image procossing to each region, then obtains hole Rate.Then, for these porositys, obtain the difference (maximum of Δ porosity (%)=porosity of maxima and minima (%) minima (%) of-porosity).Then, using the value of this Δ porosity as the uniformity on the film thickness direction of hole Index.

When this value is less than 5%, can be evaluated high for the uniformity on the film thickness direction of hole.This value more preferably 3% with Under, more preferably less than 1%, particularly preferably less than 0.5%.

(measuring interregional distance and the electron density of the pore structure of (SAXS) using small angle X ray scattering)

Carry out under the following conditions small angle X ray scattering (SAXS) measure, estimation pore structure interregional distance and The electron density of island structure.

Device：The NanoViewer that リガ Network manufactures

Optical system：Collimation mark point (point collimation, 1st slit：0.4mm φ, 2nd slit：0.2mm φ, guard slit：0.8mmφ)

Incident X-rays wavelength X：0.154nm

X-ray incident direction：It is vertical direction (though view) with respect to pellicular front

Detector：PILATUS100K

Camera bellows length (camera length)：842mm

Minute：900 seconds

Sample：By each film overlay, 10 to be measured

With regard to electron density, calculate invariant Q, estimation electron density difference Δ ρ according to following numerical expressions (1), by with polyamides The electron density difference of imines is come to judge the island areas in island structure be organosilicon or hole.

[numerical expression 1]

Q=∫ q²I (q) dq=2 π²VΔρ²φ(1-φ) (1)

{ in above-mentioned numerical expression (1), Q is invariant；

Q is scattering wave-number vector (wave number ベ Network ト Le at random)；

I (q) is scattering strength；

V is irradiated volume；

ρ is electron density；And

φ is the volume fraction that divides of island portion of phase separation structure.}

Herein, in 0.1 ＜ q ＜ 2.0 (nm^-1) in the range of to scattering wave-number vector q calculated.To scattering strength I Q () has been carried out absolute intensity correction, therefore do not consider volume V.For volume fraction it is assumed that being φ=0.1.And, calculate Go out Q/2 π²=13580 (2.7 ° of 0.1 ＜, 2 θ ＜).

(using the estimation of the silicone content in the Kapton of infrared absorption spectroscopy (ATR))

With bar coater, resin precursor composition is coated on alkali-free glass substrate (thickness 0.7mm), carries out 5 at room temperature Minute～levelling of 10 minutes after, using vertical curing oven (silver dollar リ Application De バグ society system, model name VF-2000B) 95 Heating (prebake) 60 minutes at DEG C.Obtain the ATR spectrum of this prebake film, using the 1500cm of the absorption as phenyl ring^-1Place The area standard at peak turns to 1, obtains the 1100cm of the absorption as SiO key^-1The absorbance at place.

For under the oxygen concentration recorded in Table 1 and solidification temperature heat after Kapton be also carried out with front State same mensure, obtain the 1100cm of the absorption as SiO key^-1The absorbance at place.

For 1100cm^-1The absorbance at place, by the value of prebake film with solidify after the value of Kapton be compared, Thus estimating the residual rate of organosilicon residue.Then, by organic silicon monomer during synthesis of polyimides precursor input amount with The residual rate of the organosilicon residue of the polyimide film after solidification calculates the silicone content in gained Kapton.

As the mensure device of ATR, manufactured using サモ Off ィッシャサイエ Application ティフィック society： “Nicolet Continium”.

Fig. 2 illustrates the ATR spectrum of thin film obtaining in embodiment 1,2 and reference example.The chart of Fig. 2 is to be in turn from upper The spectrum of the thin film being obtained by reference example 1, embodiment 2 and embodiment 1.

(adhesive strength with glass substrate)

Using cutter to the Kapton incision width 10mm being had by duplexer obtained above, length 100mm 2 road otch, by end peel off and be clipped in chuck, carry out the mensure of 180 ° of peel strengths with draw speed 100mm/ minute.

As cupping machine, manufactured using エア Application De ディ Co., Ltd.：RTG-1210.

(mensure of birefringence (Rth))

Using the Kapton of 15 μm of thickness as sample, and (prince measures using phase difference double refraction detection device Machine society system, KOBRA-WR) it is measured.The wavelength measuring light is set to 589nm.

(assay method of yellowness (YI))

Using the Kapton of 20 μm of thickness as sample, and using Japan's electricity color industry (strain) system (Spectrophotometer：SE600) it is measured.Light source uses D65 light source.

The preparation of ＜ resin precursor composition and evaluation>

[synthesis example 1]

Import nitrogen gas while putting into NMP in the removable flask of the 3L with stirring rod possessing oil bath 1000g, adds 4,4- (diamino-diphenyl) the sulfone 239.6g (0.965 mole) as diamidogen to stir on one side, then plus Enter 3 as tetracarboxylic dianhydride, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride 294.22g (1.0 moles), be stirred at room temperature 30 points Clock.It is warming up to 50 DEG C, stirred 12 hours.Thereafter, will be organic for the two terminal amine modified methyl phenyl as organic silicon monomer Silicone oil (chemistry society of SHIN-ETSU HANTOTAI system：X22-1660B-3 (number-average molecular weight 4400)) 109.3g (with respect to resin precursor be generally 17 matter Amount %) it is dissolved in NMP298g and obtain organic silicon monomer solution, this organic silicon monomer solution is added from Dropping funnel Deca Plus.Then, response system is warming up to 80 DEG C, stirring is taken off oil bath and recovered to room temperature, thus obtaining transparent for 1 hour afterwards Resin precursor (polyamic acid) nmp solution (resin precursor composition).The number-average molecular weight of the polyamic acid herein obtaining (Mn) it is about 33000.

[synthesis example 2～6 and 9]

The content of the species of the diamidogen in above-mentioned synthesis example 1 and tetracarboxylic dianhydride and amount and organic silicon monomer solution is divided Do not changed as described in table 1, in addition, respectively obtained transparent resin precursor (polyamides in the same manner as synthesis example 1 Amino acid) nmp solution (resin precursor composition).

The number-average molecular weight (Mn) of the polyamic acid obtaining is shown in table 1 in the lump.

[synthesis example 7]

Import nitrogen gas while putting into NMP in the removable flask of the 10L with stirring rod possessing oil bath 5502g, adds 2,2 '-bis- (trifluoromethyl) the benzidine 308.8g (0.96 mole) as diamidogen while stirring, then Sequentially add pyromellitic acid anhydride 185.4g (0.85 mole) and 4,4 '-(hexafluoroisopropylidenyl) as tetracarboxylic dianhydride Two phthalate anhydride 66.64g (0.15 mole).Further to it while being stirred, by 113.64g organic silicon monomer X22- 1660B-3 (being generally 17 mass % with respect to resin precursor) is dissolved in NMP568g and obtains organic silicon monomer solution, This organic silicon monomer solution is carried out Deca from Dropping funnel.Drip after end, be stirred at room temperature 1 hour, then heat to 80 DEG C, stirring is taken off oil bath and is recovered to room temperature, thus obtaining the polyamic acid containing mean molecule quantity 62000 for 4 hours afterwards Transparent nmp solution (resin precursor composition).

[synthesis example 8]

The addition of TFMB is set to 317.02g (0.99 mole), without organic silicon monomer solution, in addition, with Synthesis example 7 is similarly operated, thus obtaining the transparent nmp solution (tree of the polyamic acid containing number-average molecular weight 58000 Fat precursor composition).

[table 1]

The abbreviation of each composition in table 1 represents following meanings respectively.

(diamidogen)

4,4-DAS：4,4- (diamino-diphenyl) sulfone

TFMB：2,2 '-bis- (trifluoromethyl) benzidine

(tetracarboxylic dianhydride)

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

PMDA：Pyromellitic acid anhydride

6FDA：4,4 '-(hexafluoroisopropylidenyl) two phthalate anhydrides

(organic silicon monomer)

1660B：Chemistry society of SHIN-ETSU HANTOTAI system, trade name " X22-1660B-3 ", two terminal amine modified methyl phenyl organic silicone oils, Number-average molecular weight 4400

FM3311：チッソ society system, trade name " サイラプレ Application FM3311 ", two terminal amine modification dimethyl are organic Silicone oil, number-average molecular weight 1000

[embodiment 1～18 and comparative example 1～3]

Using the resin precursor composition of synthesis in aforementioned synthesis example, dense according to the oxygen that said method is recorded in Table 1 Manufacture Kapton under conditions of degree and solidification temperature, carry out various evaluations.

Evaluation result is shown in table 2 and table 3.

The STEM image (left) shown in Fig. 1, the Kapton obtaining in embodiment 1 being shot and SEM image (right)；

The SEM image of the Kapton obtaining in embodiment 7 shown in Fig. 3.

Reference example 1

This reference example is in order to when verifying reduction solidification temperature, silicone ingredients all residue in thin film, do not form hole And carry out.

Using the resin precursor composition obtaining in aforementioned synthesis example 1, condition of cure is set to oxygen concentration 50ppm and consolidates Change 95 DEG C of temperature, in addition, thin film is formed by preceding method, carries out ATR mensure and electron microscope observation.

Result is shown in table 2.

[table 2]

[table 3]

[table 4]

Table 3. evaluation result 2

	The difference of porosity	Rth
			Embodiment 1	0.1%	35nm
Embodiment 4	0.1%	35nm
			Embodiment 5	0.2%	35nm
Embodiment 6	0.2%	35nm
			Embodiment 7	2.5%	50nm
Embodiment 8	5.0%	60nm

By SAXS observe obtained from electron density between regional structure in island structure difference,

In an embodiment, for the value of approximate polyimides and the difference of the electron density of air, therefore, it is possible to confirm in thin film Define hole；

And in a comparative example, for the value of approximate polyimides and the difference of the electron density of organosilicon, therefore, it is possible to confirm not Form hole.In addition, with reference to the film thickness direction of embodiment 1 section STEM image when it is thus identified that it is white that island portion is divided.By this The fact also can distinguish that island portion is divided into hole.Similarly confirming that island portion is divided by SEM image is depression, therefore, it is possible to distinguish This part is hole.

Confirm as shown in table 2, in embodiment 1～18, for thin film physical property, meet following condition simultaneously.

(1) residual stress is below 25MPa；

(2) after laser lift-off, Kapton does not burn；

(3) do not produce microgranule after laser lift-off；

(4) glass transition temperature and the polymer phase ratio having imported organosilicon do not reduce；

(5) tensile elongation is more than 30%；And

(6) excellent in adhesion with glass substrate.

As shown in Table 3, for solidification when oxygen concentration be 2000ppm below example 1,4,5 and 6, shape The uniformity on the film thickness direction of hole becoming is high, and the value of birefringence (Rth) is minimum.

Therefore, the Kapton obtaining in these embodiments is satisfied by being applied to needed for flexible display substrate Performance.

On the other hand, for the Kapton obtaining in comparative example 1～3, in laser lift-off, polyimides burn And colour, finally produce microgranule.

Confirmed by result above, the Kapton being obtained by the resin precursor of the present invention and glass substrate and inorganic Produce between film residual stress is low and glass substrate excellent in adhesion, in laser lift-off operation the low feelings of irradiation energy Also good stripping be can carry out under condition, and the burning of Kapton, the generation of microgranule do not caused when peeling off.

It should be noted that the invention is not restricted to above-mentioned embodiment, various changes can be carried out and implement.

Industrial applicability

The Kapton of the present invention can be suitably used for such as semiconducting insulation film, TFT-LCD dielectric film, electrode Protecting film, flexible display substrate, touch panel ITO electrode substrate etc..Especially, it is useful as various substrates.

Claims

1. a kind of Kapton is it is characterised in that it has a hole of below 100nm, and the system for flexible device Make.

2. Kapton according to claim 1, wherein, the yellowness in 20 μm of thickness is less than 7.

3. Kapton according to claim 1 and 2, wherein, tensile elongation is more than 30%.

4. the Kapton according to any one of claims 1 to 3, it has organosilicon residue.

5. the Kapton according to any one of Claims 1 to 4, wherein, porosity is 3 volume %～15 bodies The scope of long-pending %.

6. the Kapton according to any one of Claims 1 to 5, wherein, described hole be shaped as the long diameter of axle The flattened oval spheroid of average 30nm～60nm.

7. the Kapton according to any one of claim 1～6, wherein, described hole is in described polyimides Equably exist on the film thickness direction of thin film.

8. it is used for the resin precursor of the Kapton any one of manufacturing claims 1～7 it is characterised in that setting There is in fat skeleton the unit 1 shown in following formulas (1) and the unit 2 shown in following formula (2)：

In described formula (1) and described formula (2), R₁Be each independently hydrogen atom, the aliphatic hydrocarbon of 1 valency of carbon number 1～20, Or the aromatic series base of carbon number 6～10；

X₁Organic group for 4 valencys of carbon number 4～32；And,

X₂Organic group for the divalent of carbon number 4～32.

9. resin precursor according to claim 8, it is tetracarboxylic dianhydride, diamidogen and the change shown in following formula (3) The copolymer of compound：

In described formula (3), multiple R₄It is each independently the organic group of the divalent of singly-bound or carbon number 1～20；

L₁、L₂And L₃It is each independently amino, NCO, carboxyl, anhydride group, perester radical, acid halide, hydroxyl, ring Epoxide or sulfydryl；

J is 3～200 integer；And,

K is 0～197 integer.

10. resin precursor according to claim 9, wherein, tetracarboxylic dianhydride be selected from pyromellitic acid anhydride, 3, Double (the trimellitic acid of 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and 4,4 '-biphenyl Monoester anhydride) in the group that forms more than a kind of tetracarboxylic dianhydride.

11. resin precursors according to claim 9 or 10, wherein, described formula (3) institute that uses during synthetic resin precursor The quality of the compound showing is 6 mass % of tetracarboxylic dianhydride, diamidogen and the summation of compound shown in described formula (3) ～25 mass %.

A kind of 12. resin combinations it is characterised in that its contain resin precursor any one of claim 8～11 and Solvent.

13. Kaptons according to any one of claim 1～7, it is following manufacture：Table in supporting mass Launch the resin combination described in claim 12 on face and form film, then,

By described supporting mass and described film below oxygen concentration 23 mass % and under conditions of more than 250 DEG C of temperature plus Heat, thus carrying out imidizate and forming hole in described film to the resin precursor in described film.

14. Kaptons according to claim 13, wherein, described heating when oxygen concentration be 2000ppm with Under.

A kind of 15. manufacture methods of Kapton are it is characterised in that it has following operation：

Film formation process, launches the resin combination described in claim 12 on the surface of supporting mass and forms film；

Heating process, by described supporting mass and described film below oxygen concentration 2000ppm and more than 250 DEG C of temperature bar Heat under part, thus the resin precursor in described film being carried out with imidizate and forming hole in described film, thus Obtain the Kapton with hole；And

Stripping process, the described Kapton with hole is peeled off from described supporting mass.

A kind of 16. flexible displays are it is characterised in that its polyimides of having any one of claim 1～7 is thin Film, inoranic membrane and TFT.