CN104854165A

CN104854165A - Resin precursor, resin composition containing said resin precursor, resin film, method for producing said resin film, laminate, and method for producing said laminate

Info

Publication number: CN104854165A
Application number: CN201480003496.6A
Authority: CN
Inventors: 金田隆行; 加藤聪; 饭塚康史
Original assignee: Asahi Chemical Co Ltd
Current assignee: Asahi Kasei Corp
Priority date: 2013-03-18
Filing date: 2014-03-17
Publication date: 2015-08-19
Anticipated expiration: 2034-03-17
Also published as: JP2018030994A; KR20170097245A; JPWO2014148441A1; KR102008162B1; JP2021152157A; KR20190093687A; KR101896272B1; JP2017226847A; KR102008160B1; KR20210057221A; JP6648076B2; KR101896271B1; KR20170097242A; JP2017020039A; KR101896885B1; JP6435298B2; TW201446714A; KR20170097244A; KR101896268B1; JP6883640B2

Abstract

Provided is a resin precursor, said resin precursor enabling the production of a transparent cured resin article without requiring a particular combination of solvents, and also enabling the production of a cured resin article which generates a small residual stress between the cured resin article and an inorganic film and has excellent chemical resistance and has a YI value and a total light transmittance that are less affected by the concentration of oxygen during a curing process. A resin precursor which is produced by polymerizing a polymerization component containing an amino group and a group reactive with an amino group, wherein the polymerization component comprises a polyvalent compound having at least two groups independently selected from an amino group and a group reactive with an amino group, the polyvalent compound comprises a compound containing a silicon group, the polyvalent compound contains a diamine represented by formula (1), the structure of the resin precursor is represented by general formula (2), and the amount of the compound containing a silicon group is 6 to 25 mass% relative to the whole mass of the polyvalent compound.

Description

Resin precursor and containing its resin combination, resin film and manufacture method thereof and layered product and manufacture method thereof

Technical field

The present invention relates to such as adopt for the substrate of flexible device, resin precursor and containing its resin combination, resin film and manufacture method thereof and layered product and manufacture method thereof.

Background technology

Generally speaking, require in the purposes of high heat resistance, use the film of polyimide (PI) resin as resin film.General polyimide resin is the following high heat stable resin manufactured, aromatic dianhydride and aromatic diamine are carried out solution polymerization, after manufacturing polyimide precursor, at high temperature carry out closed loop dehydration, hot-imide, or use catalyzer to carry out chemical imidization.

Polyimide resin is insoluble, not molten super heat-resistant resin, and heatproof oxidation performance, heat-resistant quality, radiation resistant, lower temperature resistance, chemical proofing etc. have excellent characteristic.Therefore; polyimide resin is used to comprise the wide region field of the electronic material such as electrode protective membrane of insulation coating agent, insulating film, semi-conductor, TFT-LCD; recently; also studied and utilize that it is frivolous, the application of flexibility in water white transparency flexible base board, to replace the glass substrate used in the field of the display material of liquid crystal orientation film and so in the past.

But, general polyimide resin due to high aromatic ring density with brown or yellow, low in the transmitance of visible region, be difficult to use in require the transparency field.

For the problem of the transparency improving such polyimide, such as, in non-patent literature 1, describe by comprising the acid dianhydride of ad hoc structure and comprising the diamines of ad hoc structure, make the polyimide that the transparency of transmitance and form and aspect improves.And then, describe in patent documentation 1 ~ 4, by using 4, two (diamino-diphenyl) sulfone of 4-(following, to be also denoted as 4,4-DAS), 3, two (diamino-diphenyl) sulfone of 3-is (following, also 3,3-DAS is denoted as) and comprise the acid dianhydride of ad hoc structure, make the polyimide that the transparency of transmitance and form and aspect improves.

In addition, following polyimide precursor is described in the embodiment 9,10 of following patent documentation 6, by specific aromatic tetracarboxylic acid's dianhydride and ester ring type diamines, siliceous diamines are carried out copolymerization, the polyimide realizing high Tg, the transparency, high adhesion, low warpage properties can be generated.

And then; in the embodiment 3 of following patent documentation 7 and the embodiment 3 of patent documentation 8, describe and the polyimide precursor of aromatic tetracarboxylic acid's dianhydride, two (diamino-diphenyl) sulfone and siliceous diamines is used as semiconductor protection resin and photosensitive polymer combination.

Prior art document

Patent documentation

Patent documentation 1: Japanese Laid-Open Patent Publication 61-141732 publication

Patent documentation 2: Japanese Unexamined Patent Publication 06-271670 publication

Patent documentation 3: Japanese Unexamined Patent Publication 09-040774 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2000-313804 publication

Patent documentation 5: International Publication No. 2012/118020 brochure

Patent documentation 6: International Publication No. 2011/122198 brochure

Patent documentation 7: International Publication No. 1991/010699 brochure

Patent documentation 8: Japanese Unexamined Patent Publication 4-224823 publication

Non-patent literature

Non-patent literature 1: up-to-date polyimide (basis and application), Japanese polyimide research association compiles, P152

Summary of the invention

the problem that invention will solve

But the physical property characteristic of known clear polyimides is not enough to be used as such as semiconducting insulation film, TFT-LCD insulating film, electrode protective membrane, touch panel ITO electrode substrate and flexible display thermotolerance water white transparency substrate.

Such as, when polyimide resin is used as flexible display with water white transparency substrate, (following in support glass, also referred to as supporter) on form polyimide film, on this polyimide film, typically, in order to make TFT element, sometimes form mineral membrane.The linear expansivity of polyimide is (following, also be designated as CTE) high time, due to not the mating of CTE of mineral membrane or support glass and polyimide film, unrelieved stress is produced between polyimide film and mineral membrane, as a result, there is the problem of degradation of support glass warpage, TFT element.Therefore, in order to improve the warpage of support glass, there is the problem unrelieved stress of polyimide reduced.The unrelieved stress of the polyimide described in patent documentation 1 ~ 4 is high, when being applied as flexible display water white transparency substrate, there is the problem of support glass warpage.

In addition, in order to make polyimide film, general needs is such as coated with polyimide precursor on glass substrate, is dropped into by the glass substrate being coated with this polyimide precursor and has imported in the stoving oven of nitrogen, be heated to 250 DEG C ~ 400 DEG C (following, to be also designated as curing process).For the polyimide making the transparency of transmitance and form and aspect improve that patent documentation 1 ~ 4, non-patent literature 1 are recorded, during oxygen concn height in stoving oven during solidification, when specifically oxygen concn is more than 100ppm, the dependent problem of oxygen concn having that YI value raises, total light transmittance declines and so on.

In addition, when polyimide resin is used as flexible display with water white transparency substrate, on the top of polyimide film, typically, TFT element is made by the photo-mask process employing photo-resist.(following with the polyimide film of water white transparency substrate as flexible display, also polyimide substrate is designated as), owing to being exposed in the chemical agents such as the photo-resist stripping liquid that uses in the operation of the stripping photo-resist included by this operation, the chemical proofing to these chemical agents therefore must be had.Such by 4 for as described in Patent Document 1,4-DAS, 3, the polyimide that 3-DAS and the acid dianhydride comprising ad hoc structure are formed, when photo-resist stripping process, produce the phenomenon etc. of polyimide substrate gonorrhoea, total light transmittance decline because polyimide substrate produces micro-crackle, have problems in chemical proofing.

In patent documentation 5, describe by the second-order transition temperature maintaining polyimide, Young's modulus reduce for the purpose of unrelieved stress, the siliceous diamines of softness is imported in block copolymerization mode.But, as as described in the comparative example 4 of patent documentation 5, during by siliceous diamines with block fashion copolymerization, if not use the combination of special solvent to make polyimide precursor dissolve, then there is being separated of silicone portion, the structure of the island part in the mutually different island structure of specific refractory power becomes large, and thus film gonorrhoea, total light transmittance decline.In addition, when utilizing the combination of low-boiling special solvent, after polyimide precursor solution is coated substrate, when ambient temperatare puts a few hours, have and produce situation that is muddy, film gonorrhoea, be necessary to control storage period.So, when having the polyimide of siliceous diamines to make transparent heat cured film by block copolymerization, exist and need to use the combination of special solvent that precursor is dissolved, need the storage period after controlling coating precursor solution in addition.

In addition, in the embodiment 9,10 of patent documentation 6, describe the polyimide precursor about aromatic tetracarboxylic acid's dianhydride, ester ring type diamines and organosilicon diamines being obtained, and polyimide therefrom.But after the present inventor etc. confirm, find to exist the problem (with reference to present specification comparative example 25) of the oxygen concn impact when yellowness index of this polymeric amide is high, total light transmittance is low and yellowness index and transmitance are subject to polyimide curing.

In addition, in patent documentation 7,8, describe the polyimide precursor about (diamino-diphenyl) sulfone, aromatic tetracarboxylic acid's dianhydride and organosilicon diamines being obtained, and polyimide therefrom.After but the present inventor etc. confirm, there is following problem in discovery: about relative to the total mass containing silica-based monomer, polycarboxylic acid derivative and diamine compound used during synthesis of polyimides precursor, containing the mass ratio of silica-based monomer, less in patent documentation 7, the unrelieved stress of the polyimide therefore obtained is large, and the technique of indicating meter is inappropriate; On the other hand, more in patent documentation 8, the polyimide generation gonorrhoea therefore obtained is inappropriate (with reference to present specification comparative example 23,24) for transparent display.

The present invention is that problem points is in view of the above description made, to provide for the purpose of following resin precursor, this resin precursor also can obtain transparent resin cured matter without the need to the combination of special solvent, and the unrelieved stress that can obtain producing between mineral membrane is low, chemical proofing is excellent, curing process time the little resin cured matter of the impact of oxygen concn on YI value and total light transmittance.The present invention also aims to the resin combination containing this resin precursor is provided, make the resin film of this resin composition and manufacture method thereof, and layered product and manufacture method thereof.

for the scheme of dealing with problems

The present inventor etc. further investigate repeatedly in order to solve above-mentioned problem, found that, the heat-resistant resin precursor of ad hoc structure also can form transparent resin cured matter without the need to the combination of special solvent, resin cured matter so is in addition that the unrelieved stress produced between mineral membrane is low, chemical proofing is excellent, curing process time the impact of oxygen concn on YI value, total light transmittance little resin cured matter, complete the present invention based on this opinion.That is, the present invention is the following stated.

[1] this resin precursor, it is make to comprise polymeric composition that is amino and amino-reactive base to be polymerized the resin precursor obtained,

This polymeric composition comprises the multivalent compounds being selected from the group of amino and amino-reactive base with more than 2,

This multivalent compounds comprises siliceous compound,

This multivalent compounds comprises the diamines represented with following formula (1),

This resin precursor has the structure represented with following general formula (2),

{ in formula (2), there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, and h is the integer of 3 ~ 200.}，

6 quality % ~ 25 quality % should be counted with the total mass benchmark of this multivalent compounds containing the amount of silica-based compound.

[2] resin precursor Gen Ju [1], wherein, this amino-reactive base comprises more than a kind in the group selecting free carboxyl group, replacement carboxyl and anhydride group composition.

[3] according to [1] or the resin precursor described in [2], wherein, should comprise containing silica-based compound the silicoorganic compound represented with following general formula (3):

{ in formula (3), there is multiple R ₂be the divalent organic group of singly-bound or carbon number 1 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, multiple R can be there is ₅be the monovalent organic group of carbon number 1 ~ 20 independently of one another, L ₁, L ₂and L ₃be amino, isocyanate group, carboxyl, anhydride group, perester radical, acid halide group, hydroxyl, epoxy group(ing) or sulfydryl independently of one another, j is the integer of 3 ~ 200, and k is the integer of 0 ~ 197.}。

[4] resin precursor Gen Ju [3], wherein, in this general formula (3), L ₁and L ₂be amino independently of one another or anhydride group, and k is 0.

[5] resin precursor Gen Ju [4], wherein, in this general formula (3), L ₁and L ₂be amino.

[6] according to the resin precursor according to any one of [1] ~ [5], wherein, this resin precursor contains unit 1 and unit 2,

This unit 1 at least has the structure represented with following general formula (4):

{ in formula (4), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, multiple X can be there is ₁be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and n is the integer of 1 ~ 100.}，

This unit 2 has the structure represented with following general formula (5) or the structure represented with following general formula (6), or has the structure represented with described general formula (5) and both the structures represented with described general formula (6),

{ in formula (5), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₂be bivalent aliphatic hydrocarbon or the O divalent aromatic base of carbon number 3 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, multiple X can be there is ₂be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, l is the integer of 3 ~ 50, and m is the integer of 1 ~ 100.}，

{ in formula (6), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, there is multiple R ₈be the trivalent aliphatic hydrocarbon of carbon number 3 ~ 20 or for trivalent aromatic base, p is the integer of 1 ~ 100, and q is the integer of 3 ~ 50 independently of one another.}。

[7] resin precursor Gen Ju [6], wherein, the total amount of this unit 1 and this unit 2 counts more than 30 quality % with the total mass benchmark of this resin precursor.

[8] according to [6] or the resin precursor described in [7], wherein, this resin precursor is further containing the unit 3 with the structure represented with following general formula (7):

{ in formula (7), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, multiple X can be there is ₃be the divalent organic group of carbon number 4 ~ 32 independently of one another, multiple X can be there is ₄be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and t is the integer of 1 ~ 100.}。

[9] resin precursor Gen Ju [8], wherein, in this general formula (7), X ₃to be structure be eliminates amino residue by 2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl.

[10] according to the resin precursor according to any one of [6] ~ [9], wherein, this unit 1 and this unit 2 comprise the position of more than a kind in the group being derived from and being selected from and being made up of pyromellitic acid anhydride (PMDA) and bibenzene tetracarboxylic dianhydride (BPDA) with the amount that the total amount benchmark at the acid dianhydride position being derived from this unit 1 and this unit 2 counts more than 60 % by mole and are derived from and be selected from by 4, 4 '-oxydiphthalic acid dianhydride (ODPA), 4, 4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides (6FDA), hexanaphthene-1, 2, 4, 5-tetracarboxylic dianhydride (CHDA), 3, 3 ', 4, 4 '-diphenylsulfone acid dianhydride (DSDA), 4, 4 '-xenyl two (trimellitic acid monoester anhydride) (TAHQ) and 9, 9 '-bis-(3, 4-dicarboxyphenyi) position of more than one part combination in the group that forms of fluorenes dianhydride (BPAF).

[11] according to the resin precursor according to any one of [1] ~ [10], wherein, this R ₃with this R ₄be the aromatic hydrocarbyl of the univalent aliphatic series alkyl of carbon number 1 ~ 3 or the monovalence of carbon number 6 ~ 10 independently of one another.

[12] according to the resin precursor according to any one of [1] ~ [11], wherein, this R at least partially ₃with this R ₄for phenyl.

[13] according to the resin precursor according to any one of [1] ~ [12], wherein, this resin precursor is carried out being heating and curing with the condition of 300 ~ 500 DEG C under inert atmosphere and the resin obtained has at least one second-order transition temperature the scope of-150 DEG C ~ 0 DEG C and has at least one second-order transition temperature the scope of 150 DEG C ~ 380 DEG C, and be greater than 0 DEG C and the scope being less than 150 DEG C does not have second-order transition temperature.

[14] according to the resin precursor according to any one of [1] ~ [13], wherein, the position being derived from bibenzene tetracarboxylic dianhydride (BPDA) of more than 20 % by mole is comprised in the total amount benchmark at the acid dianhydride position being derived from this resin precursor.

[15] according to the resin precursor according to any one of [1] ~ [14], wherein, the described resin precursor of part is by imidization.

[16] precursor mixture, it comprises [1] ~ [15] according to any one of resin precursor and there is the resin precursor of the structure represented with following general formula (8),

{ in formula, multiple X can be there is ₃be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, and r is the integer of 1 ~ 100.}。

[17] a flexible device material, it comprises [1] ~ [15] according to any one of resin precursor or precursor mixture described in [16].

[18] resin film, its cured article of resin precursor according to any one of [1] ~ [15] or the cured article of the precursor mixture described in [16].

[19] resin combination, it contains [1] ~ [15] according to any one of resin precursor or precursor mixture described in [16] and solvent.

[20] resin combination Gen Ju [19], wherein, the yellowness index of the resin obtained as follows under 20 μm of thickness is shown as less than 7, described resin is launch this resin combination on the surface of supporter after, is obtained by this resin precursor imidization comprised by being carried out heating with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by this resin combination in this resin combination.

[21] according to [19] or the resin combination described in [20], wherein, the unrelieved stress of the resin obtained as follows under 10 μm of thickness is shown as below 25MPa, described resin is launch this resin combination on the surface of supporter after, is obtained by this resin precursor imidization comprised by being carried out heating with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by this resin combination in this resin combination.

[22] resin film, the cured article of its resin combination according to any one of [19] ~ [21].

[23] manufacture method for resin film, it comprises:

The surface of supporter is launched the operation of the resin combination according to any one of [19] ~ [21];

Heat this supporter and this resin combination and by this resin precursor imidization comprised in this resin combination to form the operation of resin film; And

By the operation that this resin film is peeled off from this supporter.

[24] layered product, its resin molding comprising supporter and formed on the surface of this supporter, the cured article of the resin combination of described resin molding according to any one of [19] ~ [21].

[25] manufacture method for layered product, it comprises:

The surface of supporter is launched the operation of the resin combination according to any one of [19] ~ [21]; And

Heat this supporter and this resin combination and by this resin precursor imidization comprised in this resin combination to form resin molding, obtain comprising the operation of this supporter and the layered product of this resin molding thus.

[26] polyimide resin film, it is the polyimide resin film used in the manufacture of display base plate, and the Rth when thickness 20 μm is 20 ~ 90nm.

[27] manufacture method for display base plate, it comprises:

The surface of supporter is launched the operation comprising the resin combination of polyimide precursor;

Heat this supporter and this resin combination and by polyimide precursor imidization to form the operation of the polyimide resin film described in [26];

The operation of forming element on this polyimide resin film; And

By the operation that this polyimide resin film defining this element is peeled off from this supporter.

the effect of invention

According to the present invention, resin precursor can be provided, its combination without the need to special solvent also can obtain transparent resin cured matter, and the unrelieved stress that can obtain producing between mineral membrane is low, chemical proofing is excellent, curing process time the little resin cured matter of the impact of oxygen concn on YI value and total light transmittance.

Embodiment

Below, the embodiment (following, referred to as " embodiment ") for example of the present invention is described in detail.It should be noted that, the present invention is not limited to following embodiment, can carry out various distortion to implement in the scope of its purport.It should be noted that, the repeat number of the structural unit in formula of the present disclosure unless otherwise specified, but is the number representing this structural unit that can comprise in resin precursor entirety, therefore, should note not referring to the specific bonding pattern such as block structure.In addition, the characteristic value recorded in the disclosure unless otherwise specified, refers to the value of the method recorded in the project of employing [embodiment] or the method can understood for those skilled in the art equal with it mensuration.

< resin precursor >

There is provided a kind of resin precursor, the resin precursor of embodiments of the present invention is make to comprise polymeric composition that is amino and amino-reactive base to be polymerized the resin precursor obtained,

This multivalent compounds comprises containing silica-based compound,

Polymeric composition comprises amino and amino-reactive base.Polymeric composition comprises and has the plural multivalent compounds being selected from the group of amino and amino-reactive base.Such as, polymeric composition can, for having amino multivalent compounds and the mixture of multivalent compounds with amino-reactive base, can, for comprising the multivalent compounds comprising amino and amino-reactive base simultaneously, can be maybe maybe their combination.

In the disclosure, amino-reactive base refers to has reactive group to amino.As amino-reactive base, include, for example out, acidic group (such as carboxyl, anhydride group and replacement carboxyl (such as perester radical, acid halide group etc.) etc.), hydroxyl, epoxy group(ing) and sulfydryl.As the compound comprising acidic group, include, for example out, the acid dianhydride, acid esters compound, acyl chlorides etc. of dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid and these carboxylic acids.Therefore, the resin precursor of present embodiment can be polyimide precursor.In typical way, amino-reactive base comprise select free carboxyl group, replace carboxyl and anhydride group composition group in more than one.In preferred mode, amino-reactive base be select free carboxyl group, replace carboxyl and anhydride group composition group in more than one.

Multivalent compounds at least comprises the diamines represented with general formula (1).The compound represented with general formula (1) can for being selected from by such as 4,4-(diamino-diphenyl) sulfone is (following, also 4 are denoted as, 4-DAS), 3,4-(diamino-diphenyl) sulfone (below, is also denoted as 3,4-DAS) and 3, more than one in the group that 3-(diamino-diphenyl) sulfone (following, be also denoted as 3,3-DAS) forms.

At least one in multivalent compounds is containing silica-based compound.The structure that general formula (2) represents is derived from containing silica-based compound.Amount containing silica-based compound counts 6 quality % ~ 25 quality % (following, to be also called this mass fraction containing silica-based monomer concentration) with the quality criteria of multivalent compounds.Be more than 6 quality % from the viewpoint of the reduction effect of the reduction effect of the stress obtaining fully producing between resin molding and mineral membrane, yellowness index containing silica-based monomer concentration be favourable, be preferably more than 7 quality %, be more preferably more than 8 quality %, more preferably more than 10 quality %.On the other hand, containing silica-based monomer concentration be below 25 quality % from the polyimide obtained not gonorrhoea, the transparency improves, yellowness index reduces viewpoint and the viewpoint that obtains good thermotolerance be favourable, be preferably below 22 quality %, more preferably below 20 quality %.From the view point of making the Oxygen Dependence of chemical proofing, YI value, total light transmittance, degree of birefringence, unrelieved stress and optical characteristics be good, be particularly preferably more than 10 quality % and below 20 quality % containing silica-based monomer concentration.

In general formula (2), there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another.As the monovalent organic group of carbon number 1 ~ 20, the monovalent hydrocarbon of carbon number 1 ~ 20, the amino of carbon number 1 ~ 20, the alkoxyl group, epoxy group(ing) etc. of carbon number 1 ~ 20 can be listed.

As the monovalent hydrocarbon of this carbon number 1 ~ 20, the alkyl of carbon number 1 ~ 20, the cycloalkyl of carbon number 3 ~ 20, the aryl etc. of carbon number 6 ~ 20 can be listed.As the alkyl of this carbon number 1 ~ 20, be preferably the alkyl of carbon number 1 ~ 10 from the viewpoint of thermotolerance and unrelieved stress, specifically, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl etc. can be listed.As the cycloalkyl of this carbon number 3 ~ 20, the cycloalkyl of preferred carbon number 3 ~ 10, specifically, can list cyclopentyl, cyclohexyl etc. from the above point of view.As the aryl of this carbon number 6 ~ 20, the aryl of preferred carbon number 6 ~ 12, specifically, can list phenyl, tolyl, naphthyl etc. from the above point of view.

As the amino of this carbon number 1 ~ 20, the amino (such as, two (trialkylsilkl) is amino) etc. of amino, replacement can be listed.

As the monovalence alkoxyl group of this carbon number 1 ~ 20, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, phenoxy group, propenyloxy group and cyclohexyloxy etc. can be listed.

In general formula (2), have both high heat resistance and low unrelieved stress from the view point of the polyimide film obtained, preferably there is multiple R ₃and R ₄be the univalent aliphatic series alkyl of carbon number 1 ~ 3 or the monovalence aromatic hydrocarbyl of carbon number 6 ~ 10 independently of one another.In this viewpoint, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 3 is preferably methyl, and the aromatic series base of carbon number 6 ~ 10 is preferably phenyl.

H in general formula (2) is the integer of 3 ~ 200, be preferably 10 ~ 200 integer, be more preferably 20 ~ 150 integer, more preferably 30 ~ 100 integer, be particularly preferably 35 ~ 80 integer.When h is less than 2, the unrelieved stress of the polyimide obtained by resin precursor of the present disclosure worsens (namely becoming large) sometimes, when h is more than 200, preparation is when comprising the varnish of resin precursor and solvent, sometimes produces the problem such as physical strength reduction of this varnish gonorrhoea, polyimide.

In the resin precursor of present embodiment, preferably comprise the silicoorganic compound represented with following general formula (3) containing silica-based compound:

{ in formula, there is multiple R ₂be the divalent organic group of singly-bound or carbon number 1 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, multiple R can be there is ₅be the monovalent organic group of carbon number 1 ~ 20 independently of one another, L ₁, L ₂and L ₃be amino, isocyanate group, carboxyl, anhydride group, perester radical, acid halide group, hydroxyl, epoxy group(ing) or sulfydryl independently of one another, j is the integer of 3 ~ 200, and k is the integer of 0 ~ 197.}。In preferred mode, be the silicoorganic compound represented with general formula (3) containing silica-based compound.

As R ₂in the divalent organic group of carbon number 1 ~ 20, methylene radical, the alkylidene group of carbon number 2 ~ 20, the cycloalkylidene of carbon number 3 ~ 20, the arylidene etc. of carbon number 6 ~ 20 can be listed.As the alkylidene group of this carbon number 2 ~ 20, from the view point of thermotolerance, unrelieved stress, cost, the alkylidene group of preferred carbon number 2 ~ 10, can list dimethylene, trimethylene, tetramethylene, pentamethylene, hexa-methylene etc.As the cycloalkylidene of this carbon number 3 ~ 20, the cycloalkylidene of preferred carbon number 3 ~ 10, can list sub-cyclobutyl, cyclopentylidene, cyclohexylidene, sub-suberyl etc. from the above point of view.Wherein from the above point of view, the bivalent aliphatic hydrocarbon of preferred carbon number 3 ~ 20.As the arylidene of this carbon number 6 ~ 20, from the above point of view, the aromatic series base of preferred carbon number 3 ~ 20, can list phenylene, naphthylidene etc.

In general formula (3), R ₃and R ₄with the R in general formula (2) ₃and R ₄synonym, preferably as above for the description of general formula (2).In addition, R ₅for the monovalent organic group of carbon number 1 ~ 20, namely with R ₃and R ₄synonym, preferred mode and R ₃and R ₄identical.

In general formula (3), L ₁, L ₂and L ₃be amino, isocyanate group, carboxyl, anhydride group, perester radical, acid halide group, hydroxyl, epoxy group(ing) or sulfydryl independently of one another.

Amino also can be substituted, and include, for example out two (trialkylsilkl) amino etc.As L ₁, L ₂and L ₃for the concrete example of the compound represented with general formula (3) of amino, two terminal amino group modified methyl phenyl silicones (such as Shin-Etsu Chemical Co. can be listed, Ltd. X22-1660B-3 (the number-average molecular weight 4 made, 400) and X22-9409 (number-average molecular weight 1,300)), two terminal amino group modification dimethyl silscone (such as Shin-Etsu Chemical Co., Ltd. X22-161A (the number-average molecular weight 1 made, 600), X22-161B (number-average molecular weight 3,000) and KF8012 (number-average molecular weight 4,400); The BY16-835U (number-average molecular weight 900) of Dow Corning Toray Co., Ltd.; And the SilaplaneFM3311 of CHISSO CORPORATION (number-average molecular weight 1000)) etc.

As L ₁, L ₂and L ₃for the concrete example of the compound of isocyanate group, the isocyanate-modified silicone etc. that aforementioned two terminal amino group modified silicones and phosgene compound are obtained by reacting can be listed.

As L ₁, L ₂and L ₃for the concrete example of the compound of carboxyl, include, for example out the X22-162C (number-average molecular weight 4,600) of Shin-EtsuChemical Co., Ltd., Dow Corning Toray Co., Ltd. the BY16-880 (number-average molecular weight 6,600) etc. made.

As L ₁, L ₂and L ₃for the concrete example of the compound of anhydride group, the acyl compounds etc. of at least one in the group having and represent with following formula group can be listed.

As L ₁, L ₂and L ₃for the concrete example of the compound of anhydride group, X22-168AS (Shin-Etsu Chemical Co. can be listed, Ltd. make, number-average molecular weight 1,000), X22-168A (Shin-Etsu Chemical Co., Ltd. make, number-average molecular weight 2,000), X22-168B (Shin-Etsu Chemical Co., Ltd. system, number-average molecular weight 3,200), X22-168-P5-8 (Shin-Etsu Chemical Co., Ltd. system, number-average molecular weight 4,200), DMS-Z21 (IPROS CORPORATION system, number-average molecular weight 600 ~ 800) etc.

As L ₁, L ₂and L ₃for the concrete example of the compound of perester radical, aforementioned L can be listed ₁, L ₂and L ₃for the compound etc. that compound and the alcohol of carboxyl or anhydride group are obtained by reacting.

As L ₁, L ₂and L ₃for the concrete example of the compound of acid halide group, carboxylic acid chloride, carboxylic acid fluorochemical, carboxylic acid bromide, carboxylic acid iodide etc. can be listed.

As L ₁, L ₂and L ₃for the concrete example of the compound of hydroxyl, KF-6000 (Shin-EtsuChemical Co., Ltd. system can be listed, number-average molecular weight 900), KF-6001 (Shin-Etsu Chemical Co., Ltd. make, number-average molecular weight 1,800), KF-6002 (Shin-Etsu Chemical Co., Ltd. make, number-average molecular weight 3,200), KF-6003 (Shin-Etsu Chemical Co., Ltd. system, number-average molecular weight 5,000) etc.Think that the compound with hydroxyl reacts with the compound with carboxyl or anhydride group.

As L ₁, L ₂and L ₃for the concrete example of the compound of epoxy group(ing), can list is X22-163 (the Shin-Etsu Chemical Co. of two end epoxy types, Ltd. make, number-average molecular weight 400), KF-105 (Shin-Etsu Chemical Co., Ltd. make, number-average molecular weight 980), X22-163A (Shin-EtsuChemical Co., Ltd. make, number-average molecular weight 2, 000), X22-163B (Shin-Etsu Chemical Co., Ltd. make, number-average molecular weight 3, 500), X22-163C (Shin-Etsu Chemical Co., Ltd. make, number-average molecular weight 5, 400), be the X22-169AS (Shin-Etsu Chemical Co., Ltd. system, number-average molecular weight 1,000) of two end ester ring type epoxy types, X22-169B (Shin-Etsu Chemical Co., Ltd. system, number-average molecular weight 3,400), for the X22-9002 (Shin-Etsu Chemical Co., Ltd. system, functional equivalent 5,000g/mol) etc. of side chain two end epoxy type.Think the compound and diamine reactant with epoxy group(ing).

As L ₁, L ₂and L ₃for the concrete example of the compound of sulfydryl, X22-167B (Shin-Etsu Chemical Co., Ltd. system can be listed, number-average molecular weight 3,400), X22-167C (Shin-Etsu Chemical Co., Ltd. system, number-average molecular weight 4,600) etc.Think that the compound with sulfydryl reacts with the compound with carboxyl or anhydride group.

From the view point of the raising viewpoint of molecular weight of resin precursor or the thermotolerance from the polyimide obtained, preferred L ₁, L ₂and L ₃be amino independently of one another or anhydride group, so from the view point of avoid the varnish comprising resin precursor and solvent gonorrhoea viewpoint or from cost, more preferably be amino independently of one another.

Or from the view point of avoid the varnish comprising resin precursor and solvent gonorrhoea viewpoint or from cost, preferred L ₁and L ₂be amino independently of one another or anhydride group, and k is 0.In this situation, more preferably L ₁and L ₂be amino.

In general formula (3), the optimal way of j is identical with the description about h in general formula (2) above.In general formula (3), k is the integer of 0 ~ 197, be preferably 0 ~ 100, more preferably 0 ~ 50, be particularly preferably 0 ~ 25.When k is more than 197, when preparation comprises the varnish of resin precursor and solvent, sometimes produce the problems such as this varnish generation gonorrhoea.From the view point of the raising viewpoint of molecular weight of resin precursor or the thermotolerance from the polyimide obtained, preferred k is the situation of 0.When k is 0, from the view point of the raising viewpoint of molecular weight of resin precursor or the thermotolerance from the polyimide obtained, j is 3 ~ 200 is favourable.

In preferred mode, from the view point of unrelieved stress, cost, various middle R of the present disclosure ₃and R ₄be the univalent aliphatic series alkyl of carbon number 1 ~ 3 or the monovalence aromatic hydrocarbyl of carbon number 6 ~ 10 independently of one another.Or, from the view point of thermotolerance, unrelieved stress, preferred various middle a part of R of the present disclosure ₃and R ₄for phenyl.

In preferred mode, multivalent compounds comprises tetracarboxylic dianhydride and diamines.In preferred mode, multivalent compounds comprises tetracarboxylic dianhydride, dicarboxylic acid and diamines.

< tetracarboxylic dianhydride >

As the tetracarboxylic dianhydride of the example of the multivalent compounds comprised in polymer raw, specifically, from the view point of reduction and the total light transmittance of YI value, be preferably selected from carbon number be 8 ~ 36 aromatic tetracarboxylic acid's dianhydride and carbon number be the compound of the ester ring type tetracarboxylic dianhydride of 6 ~ 36.

More specifically, can 4 be listed, 4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides (following, to be also denoted as 6FDA), 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-cyclohexyl alkene-1,2 dicarboxylic anhydride, pyromellitic acid anhydride (following, to be also denoted as PMDA), 1,2,3,4-benzene tertacarbonic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (following, to be also denoted as BTDA), 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (following, to be also denoted as BPDA), 3,3 ', 4,4 '-diphenylsulfone acid dianhydride (following, to be also denoted as DSDA), 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, methylene radical-4,4 '-two O-phthalic acid dianhydride, 1,1-ethidine-4,4 '-two O-phthalic acid dianhydride, 2,2-propylidene base-4,4 '-two O-phthalic acid dianhydride, ethylene-4,4 '-two O-phthalic acid dianhydride, 1,3-trimethylene-4,4 '-two O-phthalic acid dianhydride, Isosorbide-5-Nitrae-tetramethylene-4,4 '-two O-phthalic acid dianhydride, 1,5-pentamethylene-4,4 '-two O-phthalic acid dianhydride, 4,4 '-oxydiphthalic acid dianhydride (following, to be also denoted as ODPA), sulfo--4,4 '-two O-phthalic acid dianhydride, alkylsulfonyl-4,4 '-two O-phthalic acid dianhydride, two (3, the 4-dicarboxyphenyi) benzene dianhydride of 1,3-, two (3, the 4-di carboxyl phenyloxy) benzene dianhydride of 1,3-, Isosorbide-5-Nitrae-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride, two [2-(3,4-the dicarboxyphenyi)-2-propyl group] benzene dianhydride of 1,3-, Isosorbide-5-Nitrae-bis-[2-(3,4-dicarboxyphenyi)-2-propyl group] benzene dianhydride, two [3-(3,4-di carboxyl phenyloxy) phenyl] methane dianhydride, two [4-(3,4-di carboxyl phenyloxy) phenyl] methane dianhydride, two [3-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-, two [4-(3,4-di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-(following, to be also denoted as BPADA), two (3,4-di carboxyl phenyloxy) dimethylsilane dianhydride, 1,3-two (3,4-dicarboxyphenyi)-1,1,3,3-tetramethyl disiloxane dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, the luxuriant and rich with fragrance tetracarboxylic dianhydride of 1,2,7,8-, ethene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride (following, to be also denoted as CBDA), pentamethylene tetracarboxylic dianhydride, hexanaphthene-1,2,3,4-tetracarboxylic dianhydride, hexanaphthene-1,2,4,5-tetracarboxylic dianhydride (following, to be denoted as CHDA), 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, carbonyl-4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, methylene radical-4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, ethylene-4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, 1,1-ethidine-4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene base-4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, oxo-4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, sulfo--4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, alkylsulfonyl-4,4 '-bis-(hexanaphthene-1,2-dicarboxylic acid) dianhydride, dicyclo [2,2,2] pungent-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 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-naphthane-1,2-dicarboxylic anhydrides, ethylene glycol-bis--(3,4-dicarboxylic anhydride phenyl) ether, 4,4 '-xenyl two (trimellitic acid monoester anhydride) (hereinafter also referred to as TAHQ), 9,9 '-bis-(3,4-dicarboxyphenyi) fluorenes dianhydride (hereinafter also referred to as BPAF) etc.

Wherein, with the viewpoint of the raising of the reduction of CTE, chemical proofing, the raising of second-order transition temperature (Tg) and the raising of mechanical elongation rate, preferred BTDA and PMDA.In addition, with the viewpoint of the raising of the reduction of the reduction of yellowness index, degree of birefringence and mechanical elongation rate, preferred 6FDA, ODPA and BPADA.In addition, with the viewpoint of the raising of the raising of the raising of the reduction of the reduction of the reduction of unrelieved stress, yellowness index, degree of birefringence, chemical proofing, Tg and mechanical elongation rate, be preferably BPDA.In addition, with the viewpoint of the reduction of the reduction of unrelieved stress and yellowness index, preferred CHDA.Among them, from the view point of high resistance to chemicals medicine, reduce unrelieved stress, reduction yellowness index, the reduction of degree of birefringence and the raising of total light transmittance, preferably combination uses the tetracarboxylic dianhydride be selected from the group be made up of 6FDA, ODPA and CHDA that the BPDA of the stiff structure of embodiment high resistance to chemicals medicine, high Tg and low CTE and yellowness index and degree of birefringence are low.

Wherein, except above-mentioned effect, from the view point of raising and the high Young's modulus of high elongation rate, chemical proofing, preferred source from the position of BPDA be all be derived from more than 20 % by mole of the position of acid dianhydride, be more preferably more than 50 % by mole, more preferably more than 80 % by mole, also can be 100%.

< dicarboxylic acid >

In addition, for the resin precursor in present embodiment, not damaging in the scope of performance, except above-mentioned tetracarboxylic dianhydride, for the purpose of the performance adjusting the raising, the raising of second-order transition temperature, the reduction of yellowness index and so on of mechanical elongation, make dicarboxylic acid copolymerization and import polyamide component, thus heat cured film can be made as polyamide-imide.As such dicarboxylic acid, the dicarboxylic acid and ester ring type dicarboxylic acid with aromatic ring can be listed, especially, from the view point of reduction and the total light transmittance of YI value, be preferably selected from by carbon number be 8 ~ 36 aromatic dicarboxylic acid and carbon number be the compound of at least one in the group that forms of ester ring type dicarboxylic acid of 6 ~ 34.Specifically, m-phthalic acid can be listed, terephthalic acid, 4,4 '-diphenyl dicarboxylic acid, 3,4 '-diphenyl dicarboxylic acid, 3,3 '-diphenyl dicarboxylic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 2,3-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, 4, the two M-nitro benzoic acid of 4 '-alkylsulfonyl, 3, the two M-nitro benzoic acid of 4 '-alkylsulfonyl, 3, the two M-nitro benzoic acid of 3 '-alkylsulfonyl, 4, the two M-nitro benzoic acid of 4 '-oxo, 3, the two M-nitro benzoic acid of 4 '-oxo, 3, the two M-nitro benzoic acid of 3 '-oxo, two (4-carboxyl phenyl) propane of 2,2-, two (3-carboxyl phenyl) propane of 2,2-, 2,2 '-dimethyl-4,4 '-diphenyl dicarboxylic acid, 3,3 '-dimethyl-4,4 '-diphenyl dicarboxylic acid, 2,2 '-dimethyl-3,3 '-diphenyl dicarboxylic acid, two (4-(4-carboxyphenoxy) phenyl) fluorenes of 9,9-, two (4-(3-carboxyphenoxy) phenyl) fluorenes of 9,9-, 4,4 '-bis-(4-carboxyphenoxy) biphenyl, 4,4 '-bis-(3-carboxyphenoxy) biphenyl, 3,4 '-bis-(4-carboxyphenoxy) biphenyl, 3,4 '-bis-(3-carboxyphenoxy) biphenyl, 3,3 '-bis-(4-carboxyphenoxy) biphenyl, 3,3 '-bis-(3-carboxyphenoxy) biphenyl, 4,4 '-bis-(4-carboxyphenoxy)-p-terphenyl, 4,4 '-bis-(4-carboxyphenoxy)-meta-terphenyl, 3,4 '-bis-(4-carboxyphenoxy)-p-terphenyl, 3,3 '-bis-(4-carboxyphenoxy)-p-terphenyl, 3,4 '-bis-(4-carboxyphenoxy)-meta-terphenyl, 3,3 '-bis-(4-carboxyphenoxy)-meta-terphenyl, 4,4 '-bis-(3-carboxyphenoxy)-p-terphenyl, 4,4 '-bis-(3-carboxyphenoxy)-meta-terphenyl, 3,4 '-bis-(3-carboxyphenoxy)-p-terphenyl, 3,3 '-bis-(3-carboxyphenoxy)-p-terphenyl, 3,4 '-bis-(3-carboxyphenoxy)-meta-terphenyl, 3,3 '-bis-(3-carboxyphenoxy)-meta-terphenyl, 1,1-cyclobutane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 4,4 '-benzophenone dicarboxylic acid, 1,3-phenylene-diacetic acid, Isosorbide-5-Nitrae-phenylene-diacetic acid and the 5-amino isophthalic acid derivative etc. of No. 2005/068535th, International Publication described in brochure.Make these dicarboxylic acid practically copolymerization in the polymer when, can be used by the form of the derivative acyl chlorides body such as thionyl chloride or active ester body.

Among them, from the view point of the raising of the reduction of YI value, Tg, particularly preferably terephthalic acid.When using dicarboxylic acid replacement tetracarboxylic acid, overall mole number is added up to be preferably less than 50 % by mole from the viewpoint dicarboxylic acid of chemical proofing relative to dicarboxylic acid and tetracarboxylic acid.

< diamines >

The diamines comprised in polymeric composition comprises the diamines represented with general formula (1).The diamines represented with general formula (1) can configuration example as the position being derived from diamines of unit 1 described later.In resin precursor, from the view point of obtaining the reduction of the unrelieved stress produced between the suitable yellowness index of Kapton, low-birefringence, the raising of total light transmittance and mineral membrane, high Tg and high breaking tenacity, the position being derived from the diamines represented with general formula (1) be preferably all be derived from more than 20 % by mole of the position of diamines, be more preferably more than 50 % by mole, more preferably more than 80 % by mole.

In addition, diamines can comprise the divalence with silicon number 2 ~ 100 containing silica-based diamines (following, to be also merely denoted as siliceous diamines).As siliceous diamines, such as, diamino (gathering) siloxanes represented with following general formula (9) is suitable,

{ in formula, there is multiple R ₂be bivalent aliphatic hydrocarbon or the O divalent aromatic base of carbon number 3 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, l is the integer of 3 ~ 50.}。Such diamines can configuration example as unit 2 described later.

As the R in above-mentioned general formula (9) ₂preferred structure, methylene radical, ethylidene, propylidene, butylidene and phenylene etc. can be listed.In addition, about the R in above-mentioned general formula (9) ₃and R ₄suitable example, can list methyl, ethyl, propyl group, butyl and phenyl etc., be particularly preferably phenyl especially at least partially.

As the compound represented with above-mentioned general formula (9), specifically, two terminal amine modified methyl phenyl silicone oil (Shin-Etsu Chemical Co. can be listed, Ltd. make: X22-1660B-3 (number-average molecular weight 4400), X22-9409 (number-average molecular weight 1300)), two terminal amino group modification dimethyl silscone (Shin-EtsuChemical Co., Ltd. make: X22-161A (number-average molecular weight 1600), X22-161B (number-average molecular weight 3000), KF8021 (number-average molecular weight 4400), Dow Corning Toray Co., Ltd. make: BY16-835U (number-average molecular weight 900), CHISSO CORPORATION system: SilaplaneFM3311 (number-average molecular weight 1000)) etc.Among them, improve and the raising of Tg from the view point of chemical proofing, be particularly preferably two terminal amine modified methyl phenyl silicone oil.

In addition, diamines also can comprise and is selected from by 2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl (following, be also denoted as TFMB), 4,4 '-(or 3,4 '-, 3,3 '-, 2,4 '-) diamino-diphenyl ether, 4,4 '-(or 3,3 '-) diaminodiphenylsulfone(DDS), 4,4 '-(or 3,3 '-) diaminodiphenyl sulfide, 4,4 '-benzophenone diamines, 3,3 '-benzophenone diamines, 4,4 '-two (4-amino-benzene oxygen) benzene sulfone, 4,4 '-two (3-amino-benzene oxygen) benzene sulfone, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, two { 4-(4-amino-benzene oxygen) phenyl } propane of 2,2-, 3,3 ', 5,5 '-tetramethyl--4,4 '-diaminodiphenyl-methane, 2,2 '-bis-(4-aminophenyl) propane, 2,2 ', 6,6 '-tetramethyl--4,4 '-benzidine, 2,2 ', 6,6 '-four trifluoromethyl-4,4 '-benzidine, two { (4-aminophenyl)-2-propyl group } Isosorbide-5-Nitrae-benzene, two (4-aminophenyl) fluorenes of 9,9-, two (4-aminophenoxy phenyl) fluorenes of 9,9-, 3,3 '-tolidine, 3,3 '-dimethoxy benzidine and 3,5-diamino M-nitro benzoic acid etc., DAP, 2,4-diamino-pyridine, two (4-aminophenyl-2-propyl group)-Isosorbide-5-Nitrae-benzene, 3,3 '-bis-(trifluoromethyl)-4,4 '-benzidine base (3,3 '-TFDB), 2,2 '-bis-[3 (3-amino-benzene oxygen) phenyl] HFC-236fa (3-BDAF), 2,2 '-bis-[4 (4-amino-benzene oxygen) phenyl] HFC-236fa (4-BDAF), 2,2 '-bis-(3-aminophenyl) HFC-236fa (3,3 '-6F), and more than one in the group that forms of 2,2 '-bis-(4-aminophenyl) HFC-236fa (4,4 '-6F).These diamines can form the position being derived from diamines of unit 3 described later.Among them, from the view point of the reduction of yellowness index, the reduction of CTE, the reduction of YI value, most preferably be Isosorbide-5-Nitrae-cyclohexane diamine and TFMB.

Resin precursor more preferably comprises following unit 1 and unit 2.

Unit 1 at least has the structure represented with following general formula (4):

{ in formula, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, multiple X can be there is ₁be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and n is the integer of 1 ~ 100.}；

This unit 2 has the structure represented with following general formula (5) or the structure represented with following general formula (6), or has the structure represented with described general formula (5) and both the structures represented with described general formula (6):

{ in formula, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₂be bivalent aliphatic hydrocarbon or the O divalent aromatic base of carbon number 3 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, multiple X can be there is ₂be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, l is the integer of 3 ~ 50, and m is the integer of 1 ~ 100.}，

{ in formula, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, there is multiple R ₈be trivalent aliphatic hydrocarbon or the trivalent aromatic base of carbon number 3 ~ 20 independently of one another, p is the integer of 1 ~ 100, and q is the integer of 3 ~ 50.}。

In general formula (4) and (6), the position being derived from diamines can be derived from and be selected from by such as 4,4-(diamino-diphenyl) sulfone, 3, more than one diamines in the group of 4-(diamino-diphenyl) sulfone and 3,3-(diamino-diphenyl) sulfone composition.In general formula (4) and (5), the position being derived from acid anhydrides is derived from respectively has quadrivalent organic radical group X ₁(X ₁as above-mentioned definition) acid dianhydride and have quadrivalent organic radical group X ₂(X ₂as above-mentioned definition) acid dianhydride.The position being derived from diamines in the structure represented with general formula (5) is derived from diamino (gathering) siloxanes represented with general formula (9).

From thermotolerance, the reduction of YI value and the viewpoint of total light transmittance are set out, unit 1 and unit 2 preferably count more than 60 % by mole with the total amount benchmark being derived from the position of acid dianhydride of unit 1 and unit 2, be more preferably more than 65 % by mole, position more than more preferably the amount of more than 70 % by mole comprises in the group being derived from and being selected from and being made up of pyromellitic acid anhydride (PMDA) and bibenzene tetracarboxylic dianhydride (BPDA) at least one is selected from by 4 with being derived from, 4 '-oxydiphthalic acid dianhydride (ODPA), 4, 4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides (6FDA), hexanaphthene-1, 2, 4, 5-tetracarboxylic dianhydride (CHDA), 3, 3 ', 4, 4 '-diphenylsulfone acid dianhydride (DSDA), 4, 4 '-xenyl two (trimellitic acid monoester anhydride) (TAHQ) and 9, 9 '-bis-(3, 4-dicarboxyphenyi) position of more than at least one in the group that forms of fluorenes dianhydride (BPAF) part combination.

In the resin precursor of present embodiment, from the view point of the reduction of YI value, the reduction of degree of birefringence, the raising of Tg, the total mass of unit 1 and unit 2 is preferably more than 30 quality % in the total mass benchmark of resin precursor, from the view point of the reduction of degree of birefringence, be more preferably more than 70 quality %.Most preferably be 100 quality %.

In addition, the resin precursor of present embodiment as required can further containing the unit 3 with the structure represented with following general formula (7) in the scope not damaging performance:

{ in formula, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, multiple X can be there is ₃be the divalent organic group of carbon number 4 ~ 32 independently of one another, multiple X can be there is ₄be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and t is the integer of 1 ~ 100.}。

The structure of unit 3 is as follows, the position being derived from diamines for be derived from be selected from by 4,4-DAS, 3,4-DAS, 3,3-DAS and the group that forms of siliceous diamines in compound beyond the position of diamines.

In unit 3, R ₁be preferably hydrogen atom.In addition, from the view point of reduction and the total light transmittance of thermotolerance, YI value, X ₃be preferably O divalent aromatic base or ester ring type base.In addition, from the view point of reduction and the total light transmittance of thermotolerance, YI value, X ₄be preferably O divalent aromatic base or ester ring type base.Wherein, X ₃preferably structure is eliminate amino residue by 2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl.Organic group X ₁, X ₂and X ₄can mutually the same also can be different.

From the view point of the reduction of the Oxygen Dependence of YI value and total light transmittance, the mass ratio of the unit 3 in the resin precursor of present embodiment is below 80 quality % in whole resin structure, is preferably below 70 quality %.

With regard to the resin precursor of present embodiment, by this resin precursor, under inert atmosphere, (under the atmosphere of such as nitrogen or argon gas) is heating and curing with 300 ~ 500 DEG C and the resin obtained, is maybe heating and curing with 350 DEG C under inert atmosphere by this resin precursor and the resin obtained preferably has at least one second-order transition temperature the scope of-150 DEG C ~ 0 DEG C and has at least one second-order transition temperature the scope of 150 DEG C ~ 380 DEG C, and is being greater than 0 DEG C and the scope being less than 150 DEG C does not have second-order transition temperature.From the viewpoint making the balance of unrelieved stress and total light transmittance good, preferably-150 DEG C ~ 0 DEG C scope and there is second-order transition temperature the scope of 150 DEG C ~ 380 DEG C.From the view point of thermotolerance, the second-order transition temperature being in the scope of 150 DEG C ~ 380 DEG C is more preferably in the scope of 200 ~ 380 DEG C, is preferably in the scope of 250 ~ 380 DEG C further.Resin precursor has the formation that block 1 described later and block 2 are conducive to such resin precursor.

From the view point of raising thermotolerance, the resin precursor of present embodiment is preferably formed by based on the block 1 of unit 1 with based on the block 2 of unit 2.In addition, aforesaid unit 3 also can be contained in block 1 by resin precursor.These blocks can alternately bonding also can sequentially bonding in macromolecular chain.

Contribute to making it to manifest Tg the scope of 150 ~ 380 DEG C the polyimide that above-mentioned block 1 obtains for being heating and curing by the resin precursor of present embodiment.Therefore, block 1 is preferably and only repeats by said units 1 block that formed, but be not precluded within can manifest target Tg scope in comprise the situation of the unit 3 beyond this unit 1.

Similarly, contribute to making it to manifest Tg the scope of-150 ~ 0 DEG C the polyimide that above-mentioned block 2 obtains for being heating and curing by the resin precursor of present embodiment.Therefore, block 2 is preferably and only repeats by said units 2 block that formed, but be not precluded within can manifest target Tg scope in comprise the situation of the unit beyond this unit 2.

In the resin precursor with block 1 and block 2, the unit 1 in block 1 and the repeat number sum of unit 3 are to be on average preferably 2 ~ 500, to be more preferably 5 ~ 300, most preferably to be 10 ~ 200.In addition, the repeat number of the unit 2 in block 2 in every 1 molecule on average, is preferably 1.1 ~ 300, is more preferably 1.1 ~ 200, most preferably is 1.2 ~ 100.Be less than 500 by the repeat number sum of the unit 1 in block 1 and unit 3, and the repeat number of unit 2 in block 2 is less than 300, the solvability of this resin precursor to solvent becomes good and preferred.

The ratio defined divided by the value of the repeat number of the unit 2 in block 2 by the repeat number sum of the unit 1 in block 1 and unit 3 is (following, also be denoted as unit than) although the kind of raw material, molecular weight and different because using, being preferably 0.5 ~ 100, being more preferably 10 ~ 50.As previously mentioned, the polyimide for having the cured article of the resin precursor of block 1 and block 2 can have the following advantages by tool: the scope A of 150 DEG C ~ 380 DEG C have be derived from block 1 second-order transition temperature, at the scope B of-150 DEG C ~ 0 DEG C, there is the second-order transition temperature, the scope C between this scope A and this scope B that are derived from block 2 and not there is second-order transition temperature.When the value of above-mentioned unit ratio is more than 0.5, the thermotolerance of the polyimide resin after solidification is sufficient, preferably.In addition, when being less than 100, unrelieved stress can be reduced, preferably.

On the other hand, as in polymeric composition containing silica-based compound, use high molecular weight silicone compound (specifically, the silicoorganic compound of molecular-weight average more than 3000) time, even if do not form above-mentioned such segmented copolymer, the polyimide obtained also can maintain high glass-transition temperature, and embodies the low unrelieved stress with mineral membrane.If think the silicoorganic compound using high molecular, silicone units, from as long-chain siloxane structure, can play the effect identical with above-mentioned block structure.Herein, when silicoorganic compound are high molecular, functional group concentration reduces, even if the mole number that therefore feeds intake is few, also can embody above-mentioned high glass-transition temperature and low unrelieved stress.

Such as, when high molecular weight silicone compound is diamines, resin precursor generate except the general formula being derived from (diamino-diphenyl) sulfone (4) unit 1 be derived from organosilicon diamines general formula (5) unit 2 multipolymer except, also have such polyimide precursor mixture, the i.e. blend of the polyimide precursor existence of independent (i.e. unit 2 not copolymerization) unit 1.

Therefore, the disclosure also comprises precursor mixture in addition, its resin precursor comprising above-mentioned present embodiment and the resin precursor (polyimide precursor that unit 1 as escribed above is independent) added.Herein, as the concrete example of the independent polyimide precursor of this unit 1, the resin precursor with the structure represented with following general formula (8) can be listed:

{ in formula, multiple X can be there is ₃be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, there is multiple R ₁be hydrogen atom, the univalent aliphatic series alkyl of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, and r is the integer of 1 ~ 100.}。

On the other hand, example when high molecular weight silicone compound is beyond diamines such as, is the L in general formula (3) ₁, L ₂and L ₃be the silicoorganic compound of anhydride group, carboxyl, perester radical, acid halide group, hydroxyl, epoxy group(ing) or sulfydryl and so on independently of one another.

When in the resin precursor of present embodiment, polymeric composition comprises high molecular weight silicone compound, polyimide for the cured article of this resin precursor still maintains the second-order transition temperature of the higher scope of 150 DEG C ~ 380 DEG C, and can realize the special characteristic significantly reducing the unrelieved stress between mineral membrane.

The number-average molecular weight of the resin precursor of present embodiment is preferably 3000 ~ 1000000, be more preferably 5000 ~ 500000, more preferably 7000 ~ 300000, be particularly preferably 10000 ~ 250000.To obtain the viewpoint of thermotolerance, intensity (such as strong elongation) well, this molecular weight is preferably more than 3000, to obtain deliquescent viewpoint to solvent well, man-hour can be added according to the viewpoint that is coated with of desired thickness ne-leakage ground in coating etc., be preferably less than 1000000.From the view point of obtaining high mechanical elongation rate, molecular weight is preferably more than 50000.In the disclosure, number-average molecular weight is use gel permeation chromatography and be scaled the value that polystyrene standard tries to achieve.

In preferred mode, a part of resin precursor also can by imidization.

The resin precursor of present embodiment can form following such polyimide resin: as possessing the thermotolerance that can tolerate in the display manufacturing operation of TFT component arrangement on transparent polyimide substrate, the second-order transition temperature of high temperature side has 150 DEG C ~ 380 DEG C, and and unrelieved stress between mineral membrane be below 25MPa under 10 μm of thickness.In addition, in preferred mode, it is 240 DEG C that resin precursor can form second-order transition temperature ~ unrelieved stress between 380 DEG C and mineral membrane is polyimide resin that below 20MPa is such under 10 μm of thickness.Polyimide resin, when there is second-order transition temperature for-150 ~ 0 DEG C, because this temperature is below room temperature, does not therefore have an impact to required thermotolerance in the display manufacturing operation of reality.

In addition, in preferred mode, resin precursor has following characteristic.

The yellowness index of the resin obtained as follows under 20 μm of thickness is less than 7, described resin is by by resin precursor at solvent (such as, METHYLPYRROLIDONE) in dissolve after the solution that obtains launches on the surface of supporter, in a nitrogen atmosphere with 300 ~ 500 DEG C (such as 350 DEG C) heating (such as 1 hour) this solution, this resin precursor imidization is obtained.

The unrelieved stress of the resin obtained as follows under 10 μm of thickness is below 25MPa, described resin is by by resin precursor at solvent (such as, METHYLPYRROLIDONE) in dissolve after the solution that obtains launches on the surface of supporter, in a nitrogen atmosphere with 300 ~ 500 DEG C (such as 350 DEG C) heating (such as 1 hour) this solution, this resin precursor imidization is obtained.

The manufacture > of < resin precursor

Then the synthetic method for the resin precursor of present embodiment is described.Such as, when the resin precursor of present embodiment is made up of aforesaid block 1 and these two kinds of blocks of block 2, the polyimide precursor that first preparation is corresponding with each block respectively, afterwards both mixing, by carrying out condensation reaction, the resin precursor of present embodiment can be obtained.Herein, the mol ratio of molar ratio as tetracarboxylic dianhydride and diamines for each raw material regulates, and makes as two blocks can carrying out condensation reaction, making when making the terminal group of the polyimide precursor of a block be carboxylic acid the terminal group of the polyimide precursor of another block for amino etc.The method can synthesize the polyimide precursor with preferred block completely.

On the other hand, for the tetracarboxylic dianhydride of polymer raw is common between block 1 and block 2, raw material as block 1 uses aromatic diamine, when using reactive high siliceous diamines as the raw material of block 2, sometimes utilize the synthesis method of the reactivity difference of two kinds of diamines to become possibility.Such as, in previously prepared tetracarboxylic dianhydride, add aromatic diamine and siliceous diamines simultaneously, carry out condensation reaction, thus the polyimide precursor of the block had to a certain degree can be manufactured.Although the method cannot synthesize the block polyimide precursor with block completely, the polyimide precursor with block can be synthesized.There is block herein refer to, for the polyimide resin after being heating and curing, observe the second-order transition temperature corresponding with each block, such as, polyimide resin respectively illustrates to be derived from aforementioned range A and scope B and is selected from by 4,4-(diamino-diphenyl) sulfone, 3, the second-order transition temperature of the block 1 of more than a kind in the group of 4-(diamino-diphenyl) sulfone and 3,3-(diamino-diphenyl) sulfone composition and the polycondensate of tetracarboxylic anhydride and be derived from the second-order transition temperature of block 2 of polycondensate of siliceous diamines and tetracarboxylic anhydride.

As mentioned above, with regard to the resin precursor of present embodiment, this resin precursor is heating and curing and the block that the polyimide resin obtained has discernible second-order transition temperature degree respectively at the scope A of high temperature side and the scope B of low temperature side is favourable, even if polyimide resin does not have block completely, also this advantage can be obtained.In addition, for the aforementioned advantages that the resin precursor with block 1 and 2 has, if the scope C between this scope A and this scope B is unidentified to second-order transition temperature, then also can containing the unit except block 1 and block 2.

In addition, N is added in above-mentioned such polyamic acid, dinethylformamide dimethyl-acetal or N, dinethylformamide diethyl acetal heats, by by part or all of carboxylic esterification, the viscosity stability of solution when room temperature keeping comprising resin precursor and solvent can be improved.These ester modified polyamic acids also can obtain as follows, after first making above-mentioned tetracarboxylic anhydride and the monohydroxy-alcohol being 1 equivalent relative to anhydride group react, react, then carry out condensation reaction with diamines with the dehydrating condensation agent such as thionyl chloride, dicyclohexyl carbodiimide.

< resin combination >

Alternate manner of the present invention provides the resin combination containing aforesaid resin precursor or precursor mixture and solvent.Resin combination is varnish typically.

As preferred mode, carboxylic acid composition and diamine component can be dissolved in solvent such as organic solvent and make them react by resin combination, manufacture with the form containing the polyamic acid solution of polyamic acid and solvent belonging to a form of resin precursor.Herein, be not particularly limited for condition during reaction, such as, temperature of reaction is-20 ~ 150 DEG C, the reaction times is 2 ~ 48 hours.In order to carry out the reaction containing silica-based compound fully, preferably heating about 30 minutes at 120 DEG C.In addition, the inert atmosphere such as argon gas, nitrogen is preferably during reaction.

In addition, as long as solvent dissolves the solvent of polyamic acid, be just not particularly limited.As known reaction solvent, more than one the polar solvent be selected from dialkylene glycol dimethyl ether (DMDG), meta-cresol, METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO) (DMSO), acetone, diethylacetic acid ester, Equamide M100 (trade(brand)name: Idemitsu RetailMarketing Co.Ltd. system) and Equamide B100 (trade(brand)name: Idemitsu Retail MarketingCo.Ltd. system) is useful.Wherein, NMP, DMAc, Equamide M100 and Equamide B100 is preferably.In addition, the lower boiling solution of tetrahydrofuran (THF) (THF), chloroform and so on can also be used, or the low absorbent solvent of gamma-butyrolactone and so on.

In addition, in resin combination of the present invention, the polyimide obtained, when forming the element such as TFT, in order to give the sufficient adaptation with supporter, preferably contains the such composition of the alkoxysilane compound containing trialkylsilyl group in molecular structure of 0.01 ~ 2 quality % relative to resin precursor 100 quality %.

Relative to resin precursor 100 quality %, be more than 0.01 quality % by making the content of alkoxysilane compound containing trialkylsilyl group in molecular structure, the good adaptation with supporter can be obtained, in addition from the view point of the storage stability of resin combination, the content of alkoxysilane compound containing trialkylsilyl group in molecular structure is preferably below 2 quality %.The content of alkoxysilane compound containing trialkylsilyl group in molecular structure is more preferably 0.02 ~ 2 quality %, more preferably 0.05 ~ 1 quality %, more preferably 0.05 ~ 0.5 quality % relative to resin precursor, is particularly preferably 0.1 ~ 0.5 quality %.

As alkoxysilane compound containing trialkylsilyl group in molecular structure, 3-uride propyl-triethoxysilicane can be listed, two (2-hydroxyethyl)-APTES, 3-glycidoxypropyltrime,hoxysilane, phenyltrimethoxysila,e, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, gamma-amino propyl group tripropoxy silane, gamma-amino propyl group three butoxy silane, gamma-amino ethyl triethoxysilane, gamma-amino ethyl trimethoxy silane, gamma-amino ethyl tripropoxy silane, gamma-amino ethyl three butoxy silane, gamma-amino butyl triethoxyl silane, gamma-amino butyl trimethoxy silane, gamma-amino butyl tripropoxy silane, gamma-amino butyl three butoxy silane etc., in addition, they also can be used together two or more.

After making above-mentioned varnish, also can by by solution with 130 ~ 200 DEG C carry out 5 minutes ~ 2 hours heating, do not cause polymkeric substance to separate out partial polymer is carried out dehydration imidization.By control temperature and time, imide rate can be controlled.By part imidization, the viscosity stability during room temperature keeping of resin precursor solution can be improved.As the scope of imide rate, from the view point of the solvability of the resin precursor in solution and the storage stability of solution, be preferably 5% ~ 70%.

In addition, in preferred mode, resin combination has following characteristic.

The yellowness index of the resin obtained as follows under 20 μm of thickness is shown as less than 7, described resin is on the surface of supporter after tree layout oil/fat composition, by being carried out heating (or by heating with 350 DEG C in a nitrogen atmosphere) thus being obtained by the resin precursor imidization comprised in resin combination with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by this resin combination.

The unrelieved stress of the resin obtained as follows under 10 μm of thickness is shown as below 25MPa, described resin is on the surface of supporter after tree layout oil/fat composition, by being carried out heating (or by heating with 350 DEG C in a nitrogen atmosphere) thus being obtained by the resin precursor imidization comprised in resin combination with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by this resin combination.

< resin film >

Alternate manner of the present invention provides resin film, and this resin film is the cured article of the cured article of aforesaid resin precursor or the cured article of aforesaid precursor mixture or aforesaid resin combination.

In addition, alternate manner of the present invention provides the manufacture method of resin film, and it comprises:

The surface of supporter is launched the operation of aforesaid resin combination;

Heat this supporter and this resin combination, the resin precursor imidization comprised is formed the operation of resin film in this resin combination; And

By the operation that this resin film is peeled off from this supporter.

In the optimal way of the manufacture method of resin film, the polyamic acid solution that acid dianhydride component and diamine component dissolving are made them carry out reacting in organic solvent and obtained can be used as resin combination.

Herein, supporter is such as the inorganic substrate of the glass substrate of alkali-free glass substrate etc. and so on, is not particularly limited.

More specifically, the bonding coat that the interarea of inorganic substrate is formed launch above-mentioned resin combination and carries out drying, being cured with the temperature of 300 ~ 500 DEG C under inert atmosphere, can resin film be formed.Finally resin film is peeled off from supporter.

, as method of deploying, include, for example out, the known coating process of rotary coating, slot coated and blade coating herein.In addition, thermal treatment is as follows, after bonding coat launches polyamic acid solution, mainly carry out thermal treatment in 1 minute ~ 300 minutes using desolventizing as object with the temperature of less than 300 DEG C, under the inert atmosphere such as nitrogen, carry out thermal treatment in 1 minute ~ 300 minutes with the temperature of 300 DEG C ~ 550 DEG C further, thus make resin precursor polyimide.When making colorless transparency Kapton in the past, from the view point of reduction and the total light transmittance of YI value, be necessary the oxygen concn in baking oven to control at below 100ppm, if the resin precursor of present embodiment, then control to be that it is enough for below 500ppm.From the view point of the reduction of YI value and the raising of total light transmittance, oxygen concn is preferably below 1000ppm.

In addition, the thickness of the resin film of present embodiment is not particularly limited, and is preferably the scope of 10 ~ 200 μm, is more preferably 10 ~ 50 μm.

The yellowness index of resin film under 20 μm of thickness of present embodiment is preferably less than 7.In addition, under 10 μm of thickness, unrelieved stress is preferably below 25MPa.Especially, preferred yellowness index under 20 μm of thickness is less than 7 further, and unrelieved stress is below 25MPa under 10 μm of thickness.Such characteristic such as by by resin precursor of the present disclosure in a nitrogen atmosphere, with 300 DEG C ~ 500 DEG C, more particularly carry out imidization with 350 DEG C and realize well.

< layered product >

Alternate manner providing layer laminate of the present invention, its resin molding of cured article for aforementioned resin comprising supporter and formed on the surface of this supporter.

In addition, the manufacture method of alternate manner providing layer laminate of the present invention, it comprises:

The surface of supporter is launched the operation of aforementioned resin; And

Heat this supporter and this resin combination, this resin precursor imidization comprised in this resin combination is formed resin molding, obtain the operation of the layered product comprising this supporter and this resin molding thus.

Such layered product such as can by not peeling off to manufacture from supporter by the resin film formed in the same manner as the manufacture method of aforesaid resin film.

This layered product such as uses in the manufacture of flexible device.More specifically, polyimide film forms semiconductor device, afterwards supporter is peeled off, thus the flexible device possessing the flexible transparent substrate formed by polyimide film can be obtained.

Therefore, alternate manner providing package of the present invention contains the flexible device material of aforementioned resin precursor or aforesaid precursor mixture.

As described above, the resin precursor of present embodiment owing to having ad hoc structure, so can without the need to the resin film being formed in combination not gonorrhoea of special solvent.In addition, the dependence to oxygen concn during solidification of the yellowness index (YI value) of the resin film obtained and total light transmittance is few.In addition, the unrelieved stress produced between resin film and mineral membrane is low, and having can the second-order transition temperature of practicality of tolerant T FT production process, and mechanical properties is excellent, has the chemical proofing that can tolerate photo-mask process.Therefore, this resin precursor is suitable for the transparency carrier of flexible display.

When illustrating in further detail, when forming flexible display, use glass substrate as supporter, form flexible base board thereon, carry out the formation of TFT etc. thereon.The operation that substrate is formed TFT is typically implemented at the temperature of the wide region of 150 ~ 650 DEG C, but in order to realize the performance of actual expectation, main near 250 DEG C ~ 350 DEG C, use inorganic material to form TFT-IGZO (InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly-Si-TFT).

Now, if the unrelieved stress of flexible base board and the intermembranous generation of polyimide is high, then expands in the TFT of high temperature and then shrink when normal temperature cools, produce the warpage of glass substrate, breakage, flexible base board in this process from problems such as glass substrate strippings.Generally speaking, the thermal expansivity of glass substrate is less than resin, therefore between itself and flexible base board, produces unrelieved stress.For the resin film of present embodiment, consider this point, using the thickness 10 μm of film as benchmark, the unrelieved stress produced between resin film and glass is preferably below 25MPa.

In addition, for the resin film of present embodiment, preferably, using the thickness 20 μm of film as benchmark, yellowness index is less than 7, and using the thickness 20 μm of film as benchmark, when measuring transmitance with ultraviolet spectrophotometer, the transmitance under 550nm is more than 85%.In addition, oxygen concn dependency when making thermosetting film in the baking oven that uses is favourable stably obtaining on the low resin film of YI value at least, and under the oxygen concn of below 500ppm, the YI value of thermosetting film is stable, preferred.

In addition, for the resin film of present embodiment, from the view point of operation flexible base board time excellent in fracture strength, thus improve yield rate, it is further preferred that using the thickness 20 μm of film as benchmark, mechanical elongation rate is more than 30%.

In addition, for the resin film of present embodiment, in order to not produce the softening of resin substrate at the temperature making TFT element, preferably, second-order transition temperature is more than 250 DEG C.

In addition, the resin film of present embodiment preferably possesses the chemical proofing of the photo-resist stripping liquid in the photo-mask process that can tolerate and use when making TFT element.

In addition, the light extraction mode of flexible display has and extracts the top light emitting mode of light from the face side of TFT element and extract the bottom-emission mode these two kinds of light from rear side.Top light emitting mode has the feature being easy to improve aperture opening ratio because TFT element has no relations; Bottom-emission mode has the feature being easy to manufacture because position alignment is easy.If TFT element transparent, then for bottom-emission mode, also can improve aperture opening ratio, therefore expect to adopt the bottom-emission mode easily manufacturing large-scale organic EL flexible display.When bottom-emission mode colourless transparent resin substrate used uses resin substrate, because resin substrate appears at depending on recognizing side, therefore from the view point of raising image quality, require optic isotropy, to be namely derived from the path difference (Rth) of the thickness direction of degree of birefringence low.In addition, when using top light emitting mode, do not require that Rth is low, but from the view point of commonly using in two kinds of modes, the material that preferred Rth is low.Specifically, using the thickness 20 μm of film as benchmark, be preferably below 200nm, be more preferably below 90nm, more preferably below 80nm, be particularly preferably below 50nm.If Rth is below 100nm and then is below 90nm, then not only meet and apply required performance in the flexible display transparency carrier of top emission type, also meet and apply required performance in the flexible display transparency carrier, touch panel electrode base board of bottom emission type.

Alternate manner of the present invention provides polyimide resin film, and it is the polyimide resin film used in the manufacture of display base plate, and the Rth when thickness 20 μm is 20 ~ 90nm.

In addition, alternate manner of the present invention provides the manufacture method of display base plate, and it comprises:

Heat this supporter and this resin combination and by polyimide precursor imidization to form the operation of aforementioned polyimide resin film;

The operation of forming element on this polyimide resin film; And

The purposes that the resin film meeting the present embodiment of above-mentioned physical property can be used for the yellow because existing Kapton has and is limited to use, be especially suitable as flexible display water white transparency substrate and use.And then; even if the scattering sheet in such as protective membrane or TFT-LCD etc. and film are (such as; the middle layer of TFT-LCD, gate insulating film and liquid crystal orientation film), the resin substrate etc. of the replacement cover glass of touch panel ito substrate, smart mobile phone requires colorless transparency and also can use in the field of low-birefringence.When using the polyimide of present embodiment as liquid crystal orientation film, contribute to the increase of aperture opening ratio, the TFT-LCD of high-contrast ratio can be manufactured.

Use the resin film manufactured by resin precursor of present embodiment and layered product can utilize in the manufacture of such as semiconducting insulation film, TFT-LCD insulating film, electrode protective membrane and flexible device, be especially suitable as substrate and utilize.Herein, flexible device include, for example out flexible display, flexible solar battery, flexible touch panel electrode substrate, flexible light and flexible battery.

Embodiment

In further detail the present invention is described based on embodiment below, they describe to illustrate, scope of the present invention is not limited to following embodiment.

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

(mensuration of weight-average molecular weight)

Weight-average molecular weight (Mw) uses gel permeation chromatography (GPC) to measure according to following condition.As solvent, use N, dinethylformamide (high-speed liquid chromatography is used for Wako Pure Chemical Industries, Ltd. system), employ lithiumbromide monohydrate (the WakoPure Chemical Industries that with the addition of 24.8mmol/L before the assay, Ltd. make, purity 99.5%) and phosphoric acid (Wako PureChemical Industries, the Ltd. system of 63.2mmol/L, high-speed liquid chromatography with) DMF.In addition, the calibration curve for calculating weight-average molecular weight uses polystyrene standard (TOSOHCORPORATION system) to make.

Post: Shodex KD-806M (SHOWA DENKO K.K. system)

Flow velocity: 1.0mL/ minute

Column temperature: 40 DEG C

Pump: PU-2080Plus (JASCO CORPORATION system)

Detector: RI-2031Plus (RI: differential refractometer, JASCO CORPORATION system) UV-2075Plus (UV-VIS: ultra-violet and visible spectrophotometer, JASCOCORPORATION system).

(monomer concentration containing silica-based)

What use when being being used in synthetic resins precursor containing silica-based monomer concentration is calculated by following formula containing the respective quality of silica-based monomer, polycarboxylic acid or derivatives thereof, diamine compound.

Containing silica-based monomer concentration (%)=containing silica-based monomer mass/(quality+diamine compound quality containing silica-based monomer mass+polycarboxylic acid or derivatives thereof) × 100

(making of layered product and separating film)

Resin combination bar coater is coated on alkali-free glass substrate (thickness 0.7mm), at room temperature carry out 5 minutes ~ 10 minutes levellings, in vertical curing oven (Koyo Lindberg Ltd. system, model VF-2000B) in 140 DEG C of heating 60 minutes, and then within 60 minutes, carry out making layer laminate with 350 DEG C of heating in a nitrogen atmosphere.Now, the oxygen concn in hot-air oven is adjusted to 50ppm, 100ppm, 500ppm respectively, the oxygen concn dependency of investigation YI value and total light transmittance.The thickness of the resin combination of layered product is set to 20 μm.After 350 DEG C of solidifications (solidification treatment), layered product is at room temperature left standstill 24 hours, resin film is peeled off from glass, separating film.Oxygen concn in hot-air oven is adjusted to 100ppm, has carried out the resin film of solidification in 60 minutes using 350 DEG C as sample by the evaluation use beyond following yellowness index, total light transmittance.

(evaluation of tensile elongation)

The resin film of long for the sample solidified with 350 DEG C 5 × 50mm, thickness 20 μm is used tensile testing machine (A & D Company, Limited system: RTG-1210) stretched with speed 100mm/ minute, measure tensile elongation.

(yellowness index, total light transmittance and solidification time oxygen concn dependency)

For the oxygen concn in baking oven is adjusted to respectively 50ppm, 100ppm, 500ppm, with the resin film of 350 DEG C of thickness solidified 20 μm, by NIPPON DENSHOUKUINDUSTRIES Co., Ltd. (Spectrophotometer:SE600) that make uses D65 light source, measures yellowness index (YI value) and total light transmittance.

(evaluation of thickness direction path difference (Rth))

Phase differential double refraction detection device (Oji Scientific Instruments system, KOBRA-WR) is used to measure the resin film of the thickness 20 μm solidified with 350 DEG C.The wavelength measuring light is set to 589nm.

(evaluation of second-order transition temperature, linear expansivity)

About the mensuration of second-order transition temperature (being called Tg (1)) more than room temperature range and linear expansivity (CTE), by the long 5 × 50mm of sample solidified with 350 DEG C, the resin film that thickness is 20 μm uses Shimadzu Corporation to heat mechanical analytical equipment (TMA-50), thermo-mechanical analysis is utilized to carry out at load 5g, heat-up rate 10 DEG C/min, under nitrogen atmosphere (flow 20ml/ minute), the mensuration of the test film elongation under the scope that temperature is 50 ~ 450 DEG C, its flex point is obtained as second-order transition temperature, obtain the CTE of the heat-resistant resin film of 100 ~ 250 DEG C.

About the mensuration of the second-order transition temperature (being called Tg (2)) below room temperature range, impossible with above-mentioned method, therefore above-mentioned resin film is utilized Measurement of Dynamic Viscoelasticity device (ORIENTECCo., LTD. make, RHEOVIBRONMODELRHEO-1021) flex point in the temperature range below the room temperature of scope mensuration E program (E prime) of-150 DEG C ~ 400 DEG C, tries to achieve the second-order transition temperature of this flex point under low temperature.

(evaluation of unrelieved stress)

Use residual stress analysis device (KLA-Tencor Corporation system, model FLX-2320), on the 6 inches of Silicon Wafers of thickness 625 μm ± 25 μm determining " amount of warpage " in advance, utilize bar coater coating resin composition, after carrying out baking and banking up with earth in advance for 60 minutes at 140 DEG C, use vertical curing oven (KoyoLindberg Ltd. system, model VF-2000B), in a nitrogen atmosphere, implement the process that is heating and curing of 350 DEG C, 1 hour, after making solidification, have the Silicon Wafer of the resin molding of thickness 10 μm.Use aforesaid residual stress analysis device to measure the amount of warpage of this wafer, evaluate the unrelieved stress produced between Silicon Wafer and resin molding.

(evaluation of chemical proofing test)

The resin film sheet of the thickness 20 μm solidified with 350 DEG C is immersed in the NMP layer of room temperature, within every 10 minutes, mention, after ion exchanged water cleaning, use microscopic examination film surface, every surface of carrying out heat cured film for 10 minutes occurs that the evaluation of the time of crackle is till 300 minutes.

[embodiment 1]

To possess oil bath with stirring rod the removable flask of 3L in, limit imports nitrogen, the NMP of 1000g is added on limit, add 3 of 232.4g while stirring, 3-(diamino-diphenyl) sulfone (being defined as diamines 1), then add 218.12g pyromellitic acid anhydride (being defined as tetracarboxylic anhydride 1), at room temperature stir 30 minutes.Be warming up to 50 DEG C, stir after 12 hours, by 105.6g two terminal amine modified methyl phenyl silicone oil (Shin-Etsu Chemical Co., Ltd. make: X22-1660B-3 (number-average molecular weight 4400)) (being defined as containing silica-based diamines) is dissolved in the NMP of 298g, use dropping funnel to drip.Be warming up to 80 DEG C, stir after 1 hour, remove oil bath, return to room temperature, obtain the nmp solution (following, to be also denoted as varnish) of transparent polyamic acid.Composition is wherein shown in table 1 with the weight-average molecular weight (Mw) of the polyamic acid obtained.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 4.

[embodiment 2 ~ 33,49 ~ 58]

Similarly to Example 1, diamines 1, tetracarboxylic anhydride 1, kind containing silica-based diamines and their interpolation quality are changed to described in table 1 respectively, carries out operation similarly to Example 1 and obtain varnish.In addition, the NMP addition shown in table 1 and table 2 represents the total amount of the NMP comprised in final varnish, for comprising the quality of the NMP for diluting the 298g containing silica-based diamines.Composition wherein and the weight-average molecular weight (Mw) of the polyamic acid obtained are shown in table 1, table 2, table 7.In addition, the test-results through the film of 350 DEG C of solidifications is shown in table 4, table 5, table 8.Below describe the formal compound title of the abbreviation compound name recorded in table 1 ~ table 6.

3,3-DAS:3,3-(diamino-diphenyl) sulfone

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

3,4-DAS:3,4-(diamino-diphenyl) sulfone

PMDA: pyromellitic acid anhydride

ODPA:4,4 '-oxydiphthalic acid dianhydride

6FDA:4,4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides

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

CHDA: hexanaphthene-1,2,4,5-tetracarboxylic dianhydride

DSDA:3,3 ', 4,4 '-diphenylsulfone acid dianhydride

Two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride of BPADA:2,2-

BPAF:9,9 '-bis-(3,4-dicarboxyphenyi) fluorenes dianhydride

TAHQ:4,4 '-xenyl two (trimellitic acid monoester anhydride)

BTDA:3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride

Two (4-amino-benzene oxygen) benzene of TPE-R:1,3-

CBDA:1,2,3,4-tetramethylene tetracarboxylic dianhydride

FM3311: two terminal amine modification dimethyl silicone oils (CHISSO CORPORATION SilaplaneFM3311 (number-average molecular weight 1000))

TFMB:2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl

TACl: chlorination trimellitic acid 1,2-anhydride

[embodiment 34]

To possess oil bath with stirring rod the removable flask of 3L in, import nitrogen, add the NMP of 1274g, add 4,4 '-oxydiphthalic acid dianhydride is (following, be denoted as ODPA) (being defined as tetracarboxylic anhydride 1), while stirring 105.6g two terminal amine modified methyl phenyl silicone oil (Shin-Etsu Chemical Co., Ltd. system: X22-1660B-3 (number-average molecular weight 4400)) (being defined as containing silica-based diamines) being dissolved in 298g NMP the solution obtained uses dropping funnel to drip.At room temperature stir after 1 hour, add 2 of 149.9g while stirring, 2 '-bis-(trifluoromethyl) p-diaminodiphenyl is (following, be denoted as TFMB) (being defined as diamines 2), then add 3,3-DAS of 116.2g while stirring, at room temperature stir 1 hour.Then, heat to 50 DEG C, add the BPDA (being defined as tetracarboxylic anhydride 2) of 147.1g, stir 12 hours.Be warming up to 80 DEG C, stir after 4 hours, remove oil bath, return to room temperature, obtained the nmp solution (following, to be also denoted as varnish) of transparent polyamic acid.By wherein composition and the weight-average molecular weight (Mw) of polyamic acid that obtains be shown in table 2.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 5.

[embodiment 35,39,40,44,45]

In the same manner as embodiment 34, the kind of diamines 1, diamines 2, tetracarboxylic anhydride 1, tetracarboxylic anhydride 2 and their interpolation quality being changed to respectively as recorded in table 2, carrying out the operation identical with embodiment 34 and obtaining varnish.In addition, the NMP addition shown in table 2 represents the total amount of the NMP comprised in final varnish, for comprising the quality of the NMP for diluting the 298g containing silica-based diamines.The weight-average molecular weight (Mw) of composition wherein with the polyamic acid obtained is shown in table 2.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 5.

[embodiment 36]

To possess oil bath with stirring rod the removable flask of 3L in, limit imports nitrogen, it is (following that 1196gN-methyl-2-pyrrolidone is added on limit, be denoted as NMP), add 232.4g 3,3-(diamino-diphenyl) sulfone (being defined as diamines 1) while stirring, heat after 50 DEG C, add 147.1g BPDA (being defined as tetracarboxylic anhydride 1), stir 30 minutes.Then, add 155.1g ODPA (being defined as tetracarboxylic anhydride 2), stir after 8 hours, by 105.6g two terminal amine modified methyl phenyl silicone oil (Shin-Etsu Chemical Co., Ltd. make: X22-1660B-3 (number-average molecular weight 4400)) (being defined as containing silica-based diamines) dissolves in 298g NMP, use dropping funnel to drip.Be warming up to 80 DEG C, stir after 1 hour, remove oil bath, return to room temperature, obtain the nmp solution (following, to be also denoted as varnish) of transparent polyamic acid.Composition wherein and the weight-average molecular weight (Mw) of the polyamic acid obtained are shown in table 2.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 5.

[embodiment 37,42,43,46,47]

In the same manner as embodiment 36, the kind of diamines 1, tetracarboxylic anhydride 1, tetracarboxylic anhydride 2 and their interpolation quality are changed to described in table 2 respectively, carries out the operation identical with embodiment 36 and obtain varnish.In addition, the NMP addition shown in table 2 represents the total amount of the NMP comprised in final varnish, for comprising the quality of the NMP for diluting the 298g containing silica-based diamines.The weight-average molecular weight (Mw) of composition wherein with the polyamic acid obtained is shown in table 2.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 5.

[embodiment 38]

To possess oil bath with stirring rod the removable flask of 3L in, limit imports nitrogen, 1200gNMP is added on limit, add 232.4g 3 while stirring, 3-(diamino-diphenyl) sulfone (being defined as diamines 1), heat after 50 DEG C, after 40.6g p-phthaloyl chloride (being defined as other monomer component) is dissolved in 200g gamma-butyrolactone, drip and stir 30 minutes.Then 235.4g BPDA (being defined as tetracarboxylic anhydride 1) is added, stir after 8 hours, by 105.6g two terminal amine modified methyl phenyl silicone oil (Shin-Etsu Chemical Co., Ltd. make: X22-1660B-3 (number-average molecular weight 4400)) (being defined as containing silica-based diamines) dissolves in 298g NMP, use dropping funnel to drip.Be warming up to 80 DEG C, stir after 1 hour, remove oil bath, return to room temperature, obtain the solution of transparent polyamic acid.After interpolation 1000g NMP dilutes wherein, feed intake while drip limit in 10L ion exchanged water, after the powder precipitation of polyamide-imide precursor, use filtered on buchner funnel powder.The vacuum-drying 48 hours at 40 DEG C of this powder.Add the NMP of 1403g to the powder so obtained, obtain the nmp solution of polyamide-imide precursor.Composition wherein and the weight-average molecular weight (Mw) of the polyamide-imide precursor obtained are shown in table 2.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 5.

[embodiment 43,48]

In the same manner as embodiment 38, the kind of diamines 1, tetracarboxylic anhydride 1, other monomer component and their interpolation quality are changed to described in table 2 respectively, carries out the operation identical with embodiment 38 and obtain varnish.In addition, the NMP addition shown in table 2 represents the total amount of the NMP comprised in final varnish.Composition wherein and the weight-average molecular weight (Mw) of the polyamide-imide precursor obtained are shown in table 2.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 5.

[embodiment 59]

To possess oil bath with stirring rod the removable flask of 3L in, limit imports nitrogen, the NMP of 1000g is added on limit, add 248.30g 3 while stirring, 3-(diamino-diphenyl) sulfone (being defined as diamines 1), then add 275.13g BPDA (being defined as tetracarboxylic anhydride 1), at room temperature stir 30 minutes.Be warming up to 50 DEG C, stir after 12 hours, by the anhydride modified methyl phenyl silicone oil of 104.58g two end (Shin-EtsuChemical Co., Ltd. make: X22-168-P5-B (number-average molecular weight 4200)) dissolve in 298g NMP, use dropping funnel to drip.Be warming up to 80 DEG C, stir after 1 hour, remove oil bath, return to room temperature, obtain the nmp solution (following, to be also denoted as varnish) of transparent polyamic acid.Composition wherein and the weight-average molecular weight (Mw) of the polyamic acid obtained are shown in table 7.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 8.

[embodiment 60 ~ 66]

In the same manner as embodiment 59, diamines 1, tetracarboxylic anhydride 1, kind containing silica-based diamines and their interpolation quality changed to respectively and records in table 1, carry out the operation identical with embodiment 1 and obtain varnish.In addition, table 1 and the NMP addition shown in table 2 represent the total amount of the NMP comprised in final varnish, for comprising the quality of the NMP for diluting the 298g containing silica-based diamines.Composition wherein and the weight-average molecular weight (Mw) of the polyamic acid obtained are shown in table 7.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 8.

[comparative example 1]

To possess oil bath with stirring rod the removable flask of 3L in, limit imports nitrogen, 1065gNMP is added on limit, add 248.3g 3 while stirring, 3-(diamino-diphenyl) sulfone (being defined as diamines 1), then add 218.12g pyromellitic acid anhydride (being defined as tetracarboxylic anhydride 1), at room temperature stir 30 minutes.Be warming up to 50 DEG C, stir after 12 hours, remove oil bath, return to room temperature, obtained the nmp solution (following, to be also denoted as varnish) of transparent polyamic acid.Composition wherein and the weight-average molecular weight (Mw) of the polyamic acid obtained are shown in table 3.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 6.

[comparative example 2 ~ 21]

In the same manner as comparative example 1, the kind of diamines 1, tetracarboxylic anhydride 1 and their interpolation quality are changed to respectively in table 3 record, carry out the operation identical with comparative example 1 and obtain varnish.Composition wherein and the weight-average molecular weight (Mw) of the polyamic acid obtained are shown in table 3.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 6.

[comparative example 22]

To possess oil bath with stirring rod the removable flask of 3L in, import nitrogen, add 1332gNMP, add 299.8g TFMB (being defined as diamines 2) while stirring, add 294.2g BPDA (being defined as tetracarboxylic anhydride 1), heat to 50 DEG C, stir 12 hours.Wherein 105.6g two terminal amine modified methyl phenyl silicone oil (Shin-Etsu Chemical Co., Ltd. system: X22-1660B-3 (number-average molecular weight 4400)) (being defined as containing silica-based diamines) being dissolved in 298g NMP the solution obtained uses dropping funnel to drip.After dropping terminates, be warming up to 80 DEG C, stir after 1 hour, remove oil bath, return to room temperature, obtained the nmp solution (following, to be also denoted as varnish) of the opaque polyamic acid of a little muddiness.Composition wherein and the weight-average molecular weight (Mw) of the polyamic acid obtained are shown in table 3.In addition, the test-results of the film through 350 DEG C of solidifications is shown in table 6.

[embodiment 23]

Make 4.36g (0.02 mole) pyromellitic dianhydride (PMDA) and 25.78g BTDA dispersion in 240g METHYLPYRROLIDONE (NMP), in 50g diethylene glycol dimethyl ether (Dig), dissolving by making 2.4g ω-ω '-bis--(3-aminopropyl) polydimethylsiloxane (molecular-weight average 480) solution obtained to drip step by step on a small quantity, stirring and making them react in 1 hour.So, after diamino siloxanes and tetracarboxylic dianhydride are reacted, by 1,3-of 14.62g (0.05 mole) two (4-amino-benzene oxygen) benzene (TPE-R), then add 3,3-DAS of 11.17g step by step on a small quantity with Powdered further.

[embodiment 24]

The flask of 1 liter with whipping appts, dropping funnel, thermometer, prolong and nitrogen replaceable equipment is fixed in cold water.By after nitrogen replacement in flask, the METHYLPYRROLIDONE (hereinafter referred to as NMP) of mixing 500g dehydration purification, 3 of 25.11g (0.0779 mole), 3 ', 4,3 of 4 '-benzophenone tetracarboxylic dianhydride (BTDA), 15.48g (0.0623 mole), 3 '-diaminodiphenylsulfone(DDS) (3,3-DAS) and the ω-ω ' of 14.96g (0.0159 mole)-bis--(3-aminopropyl) polydimethylsiloxane (molecular weight 960), polyamic acid solution is obtained according to ordinary method.

[embodiment 25]

To be equipped with thermometer, stirrer, nitrogen ingress pipe, cooling tube 300mL four-hole boiling flask in add the two terminal amino group modified methyl phenyl silicones (X22-1660B-3) of Isosorbide-5-Nitrae-diamino-cyclohexane as the 2.87g (25.1mmol) of diamine compound and 3.42g (0.8mmol).Then, after carrying out nitrogen replacement in flask, add the N,N-dimethylacetamide of 58ml and carry out stirring until evenly.In obtained solution, at room temperature add the phenylbenzene-3 of the 8.71g (25.9mmol) as polycarboxylic acid derivative, 3 ', 4,4 '-tetracarboxylic dianhydride (BPDA), direct Keep agitation at such a temperature 24 hours, obtains composition (polyamic acid solution).

[embodiment 26]

To be equipped with thermometer, stirrer, nitrogen ingress pipe, cooling tube 300mL four-hole boiling flask in add as (B) composition 7.85g (24.5mmol) 4, the two terminal amino group modified methyl phenyl silicones (X22-9409) of 4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl (hereinafter also referred to " TFMB ") and 2.03g (1.6mmol).Then, after carrying out nitrogen replacement in flask, add the N,N-dimethylacetamide of 58ml and carry out stirring until evenly.At room temperature add in obtained solution 5.12g (26.1mmol) as 1 of (A) composition, 2,3,4-tetramethylene tetracarboxylic dianhydride (hereinafter also referred to " CBDA "), directly continue stirring 24 hours at such a temperature, obtain composition (polyamic acid solution).

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

It should be noted that, the YI value shown in table 4 ~ 6, table 8 and total light transmittance represent the result (50ppm/100ppm/500ppm) when the oxygen concn in baking oven being adjusted to respectively 50ppm, 100ppm, 500ppm.

As shown in table 4,5,8, confirm embodiment 1 ~ 66 meet following condition simultaneously in film physical property.

(1) unrelieved stress is below 25MPa

(2) yellowness index is less than 7, and the impact by oxygen concn is little

(3) second-order transition temperature of the temperature range more than ambient temperature is more than 250 DEG C

(4) total light transmittance is more than 88%, and the impact by oxygen concn is little

(5) tensile elongation more than 30%

(6) NMP chemical proofing tests more than 30 minutes

(7) even if independent NMP makes varnish, heat cured film does not also produce gonorrhoea, and therefore total light transmittance is high

They meet the performance needed for flexible display transparency carrier being applicable to top emission type.

In embodiment 1 ~ 33,36,37,41,42,46,47,53 ~ 66, the path difference Rth being derived from birefringent film thickness direction is below 100nm (20 ~ 90nm), not only meet the performance needed for flexible display transparency carrier being applicable to top emission type, also meet and be applicable to the flexible display transparency carrier of bottom emission type, the performance needed for touch panel electrode base board.In addition, about the path difference Rth of thickness direction, using do not use containing silica-based monomer as comonomer polyimide (comparative example 1 ~ 22) with use compare as the polyimide (embodiment 1 ~ 33) of comonomer containing silica-based monomer time, use the Rth of the polyimide containing silica-based monomer less, the known Rth contributing to reduction polyimide containing silica-based monomer.

On the other hand, the unrelieved stress of comparative example 1 ~ 26, chemical proofing, tensile elongation are low, and YI value, total light transmittance worsen by oxygen concn when solidifying affects.

Confirm by this result, the resin obtained by resin precursor of the present invention is water white, and be that the unrelieved stress that produces between mineral membrane is low, and chemical proofing is excellent, the resin film that the impact of oxygen concn during solidification on YI value, total light transmittance is little.

It should be noted that, the present invention is not limited to above-mentioned embodiment, can carry out various change to implement.

utilizability in industry

The present invention can be used in manufacture, the touch panel ITO electrode substrate of such as semiconducting insulation film, TFT-LCD insulating film, electrode protective membrane, flexible display aptly, especially uses as substrate.

Claims

1. a resin precursor, it is make to comprise polymeric composition that is amino and amino-reactive base to be polymerized the resin precursor obtained;

Described polymeric composition comprises the multivalent compounds being selected from the group of amino and amino-reactive base with more than 2;

Described multivalent compounds comprises containing silica-based compound;

Described multivalent compounds comprises the diamines represented with following formula (1);

Described resin precursor has the structure represented with following general formula (2),

In formula (2), there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, and h is the integer of 3 ~ 200;

The described amount containing silica-based compound counts 6 quality % ~ 25 quality % with the total mass benchmark of described multivalent compounds.

2. resin precursor according to claim 1, wherein, described amino-reactive base comprise select free carboxyl group, replace carboxyl and anhydride group composition group in more than one.

3. resin precursor according to claim 1 and 2, wherein, describedly comprises the silicoorganic compound represented with following general formula (3) containing silica-based compound,

In formula, there is multiple R ₂be the divalent organic group of singly-bound or carbon number 1 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, optionally there is multiple R ₅be the monovalent organic group of carbon number 1 ~ 20 independently of one another, L ₁, L ₂, and L ₃be amino, isocyanate group, carboxyl, anhydride group, perester radical, acid halide group, hydroxyl, epoxy group(ing) or sulfydryl independently of one another, j is the integer of 3 ~ 200, and k is the integer of 0 ~ 197.

4. resin precursor according to claim 3, wherein, in described general formula (3), L ₁and L ₂independently of one another for amino or anhydride group and k is 0.

5. resin precursor according to claim 4, wherein, in described general formula (3), L ₁and L ₂be amino.

6. the resin precursor according to any one of Claims 1 to 5, wherein, described resin precursor contains unit 1 and unit 2,

In formula (4), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, optionally there is multiple X ₁be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and n is the integer of 1 ~ 100;

In formula (5), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₂be bivalent aliphatic hydrocarbon or the O divalent aromatic base of carbon number 3 ~ 20 independently of one another, R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, optionally there is multiple X ₂be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, l is the integer of 3 ~ 50, and m is the integer of 1 ~ 100;

In formula (6), there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, there is multiple R ₃and R ₄be the monovalent organic group of carbon number 1 ~ 20 independently of one another, there is multiple R ₈be trivalent aliphatic hydrocarbon or the trivalent aromatic base of carbon number 3 ~ 20 independently of one another, p is the integer of 1 ~ 100, and q is the integer of 3 ~ 50.

7. resin precursor according to claim 6, wherein, the total amount of described unit 1 and described unit 2 counts more than 30 quality % with the total mass benchmark of described resin precursor.

8. the resin precursor according to claim 6 or 7, wherein, described resin precursor is further containing the unit 3 with the structure represented with following general formula (7):

In formula, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, optionally there is multiple X ₃be the divalent organic group of carbon number 4 ~ 32 independently of one another, optionally there is multiple X ₄be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, and t is the integer of 1 ~ 100.

9. resin precursor according to claim 8, wherein, in described general formula (7), X ₃to be structure be eliminates amino residue by 2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl.

10. the resin precursor according to any one of claim 6 ~ 9, wherein, described unit 1 and described unit 2 comprise the position of more than a kind in the group being derived from and being selected from and being made up of pyromellitic acid anhydride (PMDA) and bibenzene tetracarboxylic dianhydride (BPDA) with the amount that the total amount benchmark at the acid dianhydride position being derived from described unit 1 and described unit 2 counts more than 60 % by mole and are selected from by 4 with being derived from, 4 '-oxydiphthalic acid dianhydride (ODPA), 4, 4 '-(hexafluoroisopropylidenyl) diphthalic anhydrides (6FDA), hexanaphthene-1, 2, 4, 5-tetracarboxylic dianhydride (CHDA), 3, 3 ', 4, 4 '-diphenylsulfone acid dianhydride (DSDA), 4, 4 '-xenyl two (trimellitic acid monoester anhydride) (TAHQ) and 9, 9 '-bis-(3, 4-dicarboxyphenyi) position of more than one part combination in the group that forms of fluorenes dianhydride (BPAF).

11. resin precursors according to any one of claim 1 ~ 10, wherein, described R ₃with described R ₄be the univalent aliphatic series alkyl of carbon number 1 ~ 3 or the monovalence aromatic hydrocarbyl of carbon number 6 ~ 10 independently of one another.

12. resin precursors according to any one of claim 1 ~ 11, wherein, described R at least partially ₃with described R ₄for phenyl.

13. resin precursors according to any one of claim 1 ~ 12, wherein, described resin precursor is carried out being heating and curing with the condition of 300 ~ 500 DEG C under inert atmosphere and the resin obtained has at least one second-order transition temperature the scope of-150 DEG C ~ 0 DEG C and has at least one second-order transition temperature the scope of 150 DEG C ~ 380 DEG C, and be greater than 0 DEG C and the scope being less than 150 DEG C does not have second-order transition temperature.

14. resin precursors according to any one of claim 1 ~ 13, wherein, comprise the position being derived from bibenzene tetracarboxylic dianhydride (BPDA) of more than 20 % by mole in the total amount benchmark at the acid dianhydride position being derived from described resin precursor.

15. resin precursors according to any one of claim 1 ~ 14, wherein, the described resin precursor of part is by imidization.

16. 1 kinds of precursor mixtures, it comprises resin precursor according to any one of claim 1 ~ 15 and has the resin precursor of the structure represented with following general formula (8),

In formula, optionally there is multiple X ₃be the quadrivalent organic radical group of carbon number 4 ~ 32 independently of one another, there is multiple R ₁be hydrogen atom, the univalent aliphatic series hydrocarbon of carbon number 1 ~ 20 or monovalence aromatic series base independently of one another, and r is the integer of 1 ~ 100.

17. 1 kinds of flexible device materials, it comprises resin precursor according to any one of claim 1 ~ 15 or precursor mixture according to claim 16.

18. a resin film, its cured article of resin precursor according to any one of claim 1 ~ 15 or the cured article of precursor mixture according to claim 16.

19. a resin combination, it contains resin precursor according to any one of claim 1 ~ 15 or precursor mixture according to claim 16 and solvent.

20. resin combinations according to claim 19, wherein, the yellowness index of the resin obtained as follows under 20 μm of thickness is shown as less than 7, described resin is launch described resin combination on the surface of supporter after, is obtained by the described resin precursor imidization comprised by being carried out heating with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by described resin combination in described resin combination.

21. resin combinations according to claim 19 or 20, wherein, the unrelieved stress of the resin obtained as follows under 10 μm of thickness is shown as below 25MPa, described resin is launch described resin combination on the surface of supporter after, is obtained by the described resin precursor imidization comprised by being carried out heating with 300 DEG C ~ 500 DEG C in a nitrogen atmosphere by described resin combination in described resin combination.

22. 1 kinds of resin films, the cured article of its resin combination according to any one of claim 19 ~ 21.

The manufacture method of 23. 1 kinds of resin films, it comprises:

The surface of supporter is launched the operation of the resin combination according to any one of claim 19 ~ 21;

Heat described supporter and described resin combination and by the described resin precursor imidization comprised in described resin combination to form the operation of resin film; And

By the operation that described resin film is peeled off from described supporter.

24. 1 kinds of layered products, its resin molding comprising supporter and formed on the surface of described supporter, the cured article of the resin combination of described resin molding according to any one of claim 19 ~ 21.

The manufacture method of 25. 1 kinds of layered products, it comprises:

The surface of supporter is launched the operation of the resin combination according to any one of claim 19 ~ 21; And

Heat described supporter and described resin combination and by the described resin precursor imidization comprised in described resin combination to form resin molding, obtain the operation of the layered product comprising described supporter and described resin molding thus.

26. 1 kinds of polyimide resin films, it is the polyimide resin film used in the manufacture of display base plate, and the Rth when thickness 20 μm is 20 ~ 90nm.

The manufacture method of 27. 1 kinds of display base plates, it comprises:

Heat described supporter and described resin combination and by polyimide precursor imidization to form the operation of polyimide resin film according to claim 26;

The operation of forming element on described polyimide resin film; And

By the operation that the described polyimide resin film defining described element is peeled off from described supporter.