CN106029743A

CN106029743A - Polyimide precursor and/or polyimide-containing composition, and polyimide film

Info

Publication number: CN106029743A
Application number: CN201580009667.0A
Authority: CN
Inventors: 山口美香; 杉山二郎; 野口浩; 古贺智子; 石窪章; 加藤刚司
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2014-02-21
Filing date: 2015-02-19
Publication date: 2016-10-12
Anticipated expiration: 2035-02-19
Also published as: TW201538572A; KR102268406B1; CN106029743B; JP2016128555A; WO2015125895A1; TWI660980B; JP5888472B2; JPWO2015125895A1; JP6540382B2; KR20160125377A

Abstract

The purpose of the present invention is to provide a polyimide material which exhibits excellent heat resistance and transmissivity, a low coefficient of linear expansion, and low retardation. The present invention pertains to a polyimide film containing a tetracarboxylic acid residue and a diamine residue, and characterized in that the tetracarboxylic acid residue and/or the diamine residue has a curved section, the coefficient of linear expansion is 60 ppm/K or less, and the retardation is 200nm or less.

Description

Containing polyimide precursor and/or the compositions of polyimides, and polyimide film

Technical field

The present invention relates to a kind of polyimide precursor with specific structure division and/or polyimide compositions, The polyimide precursor compositions of film generation albefaction when suppression forms film, there is specific structure division and thermostability, pass through Rate, low linear expansion coefficient and the polyimides of low delayed excellence and polyimide film.

Background technology

In recent years, in the fields such as electric, electronic unit, transportation machines, universe and aviation machine, the thin of equipment is gradually required Type or lightweight and then flexibleization.In these equipment, it is to form the electricity such as thin type transistor or transparency electrode on the glass substrate Sub-element, but seek flexibleization of panel self, slimming, lightweight for plastic material by being changed by this glass substrate.

Owing to there is high-temperature process in the manufacturing process of this equipment, so to setting standby baseboard requirement high-fire resistance.Cause This, develop the polyimide material as one of high heat resistant plastice.If additionally, setting standby baseboard in heating process etc. Change in size relatively big, then the parts such as electronic component or color filter can be caused to rupture, deformation etc., quality stability can become Difference.

Additionally, it is just also excellent to the electrical insulating property in addition to thermostability, abrasion performance, chemical-resistant and mechanical property etc. Polyimide material develop.

Patent documentation 1 there are there is thermostability, the polyimide material of change in size few (linear expansion coefficient is little). Also, patent documentation 2 proposes have the amide imide material with amido link.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2012-144603 publication

Patent documentation 2: Japanese Patent Laid-Open 2013-028688 publication

Summary of the invention

Invent problem to be solved

But, as patent documentation 1 proposes, when the monomer constituting polyimides is only aromatic compound, take in face Xiang Bianqiang and delayed higher, produce phase contrast.If using this kind can produce the material of phase contrast, then have such as that display is being just The tendency that face or oblique visual field property are deteriorated.

During additionally, have the situation of amido link as the amide imide material that patent documentation 2 is proposed, due to amido link Water absorption, solvent affinity higher, therefore there is the water-disintegrable tendency uprised of polyimide resin obtained.

As it has been described above, not yet propose to have to meet to be applicable to set characteristic necessary to lay-by material, i.e. thermostability, pass through simultaneously Rate, low linear expansion coefficient and low delayed material.

The present invention completes in view of above-mentioned problem, its object is to provide a kind of thermostability, transmitance, low linear expansion Coefficient and the polyimide material of low delayed excellence.

Means for solving the above

The present invention has following composition.

[1] a kind of polyimide film, it is characterised in that it is the polyimides comprising tetrabasic carboxylic acid residue with diamidogen residue Film, in above-mentioned tetrabasic carboxylic acid residue and diamidogen residue at least any one has crooked position, linear expansion coefficient be 60ppm/K with Under, and delayed for below 200nm.

[2] polyimide film described in above-mentioned [1], wherein, the thickness of film be yellow colour index during 10 μm for more than-10, Less than 20.

[3] a kind of compositions, it is characterised in that it is to comprise arbitrary with polyimides of polyimide precursor The compositions of person, above-mentioned polyimide precursor and polyimides contain tetrabasic carboxylic acid residue and diamidogen residue, and above-mentioned tetrabasic carboxylic acid is residual Base has the structure division represented by the structure division represented by following formula (1 '), following formula (2) and following formula (4 ') is represented Structure division, above-mentioned diamidogen residue has a structure division represented by following formula (5), and then above-mentioned tetrabasic carboxylic acid residue and diamidogen In residue at least any one has crooked position.

[changing 1]

Wherein, the symbol in formula represents following meanings.

X²For the key of Direct Bonding (not via other elements herein between the Jian Zhi functional group (being aromatic rings) of Direct Bonding And Direct Bonding), there is the secondary or key of tertiary carbon atom or ehter bond.

R³And R⁴It is each independently the functional group in the group selecting free alkyl, alkoxyl, amino and hydroxyl to be formed.

[4] compositions as described in above-mentioned [3], wherein, having represented by above-mentioned formula (4 ') in above-mentioned tetrabasic carboxylic acid residue The ratio of tetrabasic carboxylic acid residue of structure division be more than 2mol%, below 95mol%.

[5] compositions as described in above-mentioned [3] or [4], wherein, has above-mentioned formula (1 ') institute in above-mentioned tetrabasic carboxylic acid residue The tetrabasic carboxylic acid residue of the structure division represented and the ratio of the tetrabasic carboxylic acid residue sum of the structure division having represented by above-mentioned formula (2) Example is more than 5mol%, below 95mol%.

[6] as above-mentioned [3] are to the compositions according to any one of [5], and wherein, above-mentioned crooked position is relative to above-mentioned tetracarboxylic acid Acid residue is more than 0.1mol%, below 150mol% with the ratio of diamidogen residue sum.

The effect of invention

According to the present invention, it is possible to provide a kind of thermostability, transmitance, low linear expansion coefficient and the polyimides of low delayed excellence Presoma and/or polyimide compositions, polyimides and polyimide film.

Detailed description of the invention

Embodiments of the present invention described further below, thing illustrated below or method etc. are embodiments of the present invention An example (typical example), as long as the present invention is without departing from its purport, be just not only restricted to these contents.

Herein, " weight % " is identical with the implication of " quality % ".

[compositions]

The compositions of the present invention, it is characterised in that it is to comprise polyimide precursor and at least appointing in polyimides The compositions of one, above-mentioned polyimide precursor and/or polyimides comprise tetrabasic carboxylic acid residue and diamidogen residue, above-mentioned tetracarboxylic acid Acid residue have the structure division of more than a kind in the I group shown in following and a kind in following shown II group with On structure division, above-mentioned diamidogen residue has the structure division represented by following formula (5).

[changing 2]

I group: the structure division represented by following formula (1) and the structure division represented by following formula (2)

II group: the structure division represented by following formula (3) and the structure division represented by following formula (4)

Wherein, the symbol in formula represents following meanings.

X represent the key (refer between functional group not the Direct Bonding via other elements) of Direct Bonding, alkylidene, carbonyl, Ehter bond or sulfonyl.

N and m represents 0 or 1 independently of one another.

R¹And R²Represent alkylidene, alkenylene or aromatic rings independently of one another.R¹And R²Can also be mutually bonded and be formed Ring.

Y represents key (refer between functional group not the Direct Bonding via other elements) or the divalent organic group of Direct Bonding.

R³And R⁴Represent alkyl, alkoxyl, amino or hydroxyl independently of one another.

Think by having the structure division of more than a kind in I group and the structural portion of more than a kind in II group It is allocated as tetrabasic carboxylic acid residue and there is the structure division represented by formula (5) as diamidogen residue thus plays the present application Effect, its reason is speculated as follows.

By having tetrabasic carboxylic acid residue in I group and the diamidogen residue represented by formula (5), thus obtain thermostability and Mechanical property improves, and reduces the effect of linear expansion coefficient.But, if only aromatic cycle compound, deposit the most as described above In face, orientation becomes the strong and delayed tendency uprised, but by having the tetrabasic carboxylic acid residue in II group, thus can not only obtain Obtain these effects and control delayed.Additionally, speculate by having the tetrabasic carboxylic acid residue in II group, and then obtain high saturating Cross rate, but also obtain low-refraction, effect that dissolubility in organic solvent, the pliability of molded body improve.

Furthermore, in the present invention, so-called tetrabasic carboxylic acid residue represents the 4 valency groups derived from tetracarboxylic dianhydride.Additionally, the present invention In, so-called diamidogen residue represents from the divalent group that diamine compound or diisocyanate cpd are derivative.

The compositions related to of the present invention is preferably: above-mentioned structure division in I group is following formula (1 ') institute table Structure division represented by the structure division shown and formula (2), above-mentioned structure division in II group is following formula (4 ') institute table The structure division shown, the structure division of diamidogen residue is the structure division represented by following formula (5), and its reason is to be readily available Linear expansion coefficient and the balance of optical characteristics, be more preferably tetrabasic carboxylic acid residue and at least one tool in diamidogen residue the most further There is crooked position.

About each structure division and crooked position, see below in detail.

[changing 3]

Wherein, the symbol in formula represents following meanings.

X²For Direct Bonding key, there is the secondary or key of tertiary carbon atom, or ehter bond.

The compositions of the present invention can also comprise other in addition to above-mentioned polyimide precursor and/or polyimides Point.Such as in order to improve acid imide rate further when film forming, acid imide agent can be added.

[polyimide precursor contained in compositions and/or polyimides]

Polyimide precursor and/or polyimides contained by the compositions of the present invention are to comprise tetrabasic carboxylic acid residue and diamidogen The material of residue.As long as the structure division of more than have in I group a kind and the structure of in the II group more than a kind Part is as above-mentioned tetrabasic carboxylic acid residue and has the material as above-mentioned diamidogen residue of the structure division represented by formula (5), the most also It is not particularly limited.Additionally, these materials preferably dissolve in the compound of solvent.

In the compositions of the present invention, as polyimide precursor and/or polyimides, can containing do not have I group and The structure division of II group is as the material of tetrabasic carboxylic acid residue.In addition it is also possible to containing not having the structure division represented by formula (5) Material as diamidogen residue.

In the present invention, so-called " dissolving in solvent ", refer to make polyimide precursor and/or polyimides in room temperature Situation about being completely dissolved when dissolving 0.5 mass % in the solvent constituting compositions under (25 DEG C).

As the concentration being completely dissolved, usually more than 0.5 mass %, more than preferably 1 mass %, more preferably 10 matter Amount more than %.

The so-called solvent constituting compositions, before can enumerating polyimides contained in the compositions of the acquisition present invention described later The solvent that used when driving body and polyimides, carry out the solvent etc. of use during reprecipitation.

Polyimide precursor and/or the concentration of polyimides in compositions can use in itself previously known method the most true Recognize.The methods such as drying under reduced pressure such as can be used to be distilled the solvent of compositions remove, and the mass ratio before and after being removed by distillation is asked Go out.

When the concentration of compositions is less than 0.5 mass %, decompression distillation can be used to remove the methods such as solvent compositions is dense Contracting, it may be judged whether dissolve in solvent.When the concentration of compositions is higher, can by use compositions solvent be diluted thus Concentration is made to become 0.5 mass %.Additionally, when not knowing the solvent of compositions, such as DMF, N can be used, The amide series solvents such as N-dimethyl acetylamide, METHYLPYRROLIDONE；The non-proton series solvent such as dimethyl sulfoxide；Methyl phenyl ethers anisole, Aromatic series series solvent, glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, the diethyls such as phenyl methylcarbamate, dimethylbenzene, toluene The glycol series solvent such as glycol dimethyl ether, propylene glycol methyl ether acetate etc. is diluted.

As tetrabasic carboxylic acid residue, the structure division of I group and II group can be enumerated.As tetrabasic carboxylic acid residue, as long as having selected from I The structure division of the structure division of more than a kind in Qun and in II group more than a kind is then not particularly limited, such as, can have There are the multiple structure divisions from I group, it is possible to have the structure division represented by multiple formulas (1).

Among I group, preferably there is the structure division represented by formula (1), because its effect reducing linear expansion coefficient is higher； More preferably there is the structure division represented by formula (1) and the structure division represented by formula (2), because it is resistance to there is acquisition Hot raising, mechanical property improve and reduce the tendency of the effect of linear expansion coefficient.

Furthermore it is preferred that have the structure division represented by formula (4) among II group, because optical characteristics can improve.

In tetrabasic carboxylic acid residue contained in the compositions of the present invention, there is the structure division in I group with each group of II group The ratio shared by tetrabasic carboxylic acid residue there is no particular restriction, usually more than 10mol%, preferably more than 30mol%, more preferably For more than 50mol%.By being in this scope, the polyimide precursor that optical characteristics is good, linear expansion coefficient is low can be obtained And/or polyimide compositions.

There is the tetrabasic carboxylic acid residue of the structure division in I group and the tetrabasic carboxylic acid of the structure division having in II group There is no particular restriction for the ratio of residue.

In tetrabasic carboxylic acid residue contained in the compositions of the present invention, the tetrabasic carboxylic acid with structure division in I group is residual Ratio shared by base is usually more than 5mol%, preferably more than 10mol%, more preferably more than 15mol%, usually Below 95mol%, preferably below 90mol%, more preferably below 85mol%.By being in this scope, optics can be obtained special Property is good, linear expansion coefficient is low polyimide precursor and/or polyimide compositions.

There are the tetrabasic carboxylic acid residue of the structure division in I group and four Suan acid of the structure division having in II group There is no particular restriction for the ratio of residue, by II faciation for the ratio of I group in terms of, usually more than 5mol%, preferably 10mol% Above, more preferably more than 15mol%, usually below 500mol%, preferably below 300mol%, more preferably Below 200mol%, more preferably below 150mol%.

In tetrabasic carboxylic acid residue contained in the compositions of the present invention, there is the tetrabasic carboxylic acid of structure division represented by formula (1 ') Residue, there is the tetrabasic carboxylic acid residue of structure division represented by formula (2) and there is the tetracarboxylic acid of structure division represented by formula (4 ') There is no particular restriction for acid total ratio shared by residue, usually more than 10mol%, preferably more than 30mol%, more preferably More than 50mol%.By being in this scope, can obtain optical characteristics is good, linear expansion coefficient is low polyimide precursor and/ Or polyimide compositions.

There is the tetrabasic carboxylic acid residue of the structure division represented by formula (1 ') and there is four of structure division represented by formula (2) Carboxylic acid residues and there is the ratio of tetrabasic carboxylic acid residue of structure division represented by formula (4 ') there is no particular restriction.

In tetrabasic carboxylic acid residue contained in the compositions of the present invention, there is the tetrabasic carboxylic acid of structure division represented by formula (1 ') Residue and there is the total ratio shared by tetrabasic carboxylic acid residue of structure division represented by formula (2), usually more than 5mol%, excellent Elect more than 10mol% as, more preferably more than 15mol%, usually below 95mol%, preferably below 90mol%, more excellent Elect below 85mol% as.By being in this scope, the polyimides forerunner that optical characteristics is good, linear expansion coefficient is low can be obtained Body and/or polyimide compositions.Additionally, in the polyimide film obtained by said composition, for Laser Processing Absorption near 308nm, 355nm can increase, it is possible to reply Laser Processing.

There is the tetrabasic carboxylic acid residue of the structure division represented by formula (1 ') and there is four of structure division represented by formula (2) Carboxylic acid residues and there is the ratio of tetrabasic carboxylic acid residue of structure division represented by formula (4 ') there is no particular restriction, to have formula The tetrabasic carboxylic acid residue of the structure division represented by (4 ') is relative to the tetrabasic carboxylic acid residue of the structure division having represented by formula (1 ') With the ratio meter of the tetrabasic carboxylic acid residue sum of the structure division having represented by formula (2), usually more than 5mol%, it is preferably More than 10mol%, more preferably more than 15mol%, usually below 500mol%, preferably below 300mol%, more preferably For below 200mol%, more preferably below 150mol%.By being in this scope, can obtain that optical characteristics is good, line Polyimide precursor that the coefficient of expansion is low and/or polyimide compositions.

In tetrabasic carboxylic acid residue contained in the compositions of the present invention, there is the tetrabasic carboxylic acid of structure division represented by formula (4 ') Ratio shared by residue is usually more than 2mol%, preferably more than 5mol%, more preferably more than 8mol%, usually Below 95mol%, preferably below 90mol%, more preferably below 85mol%.By being in this scope, optics can be obtained special Property is good, linear expansion coefficient is low polyimide precursor and/or polyimide compositions.

There is the tetrabasic carboxylic acid residue of structure division represented by formula (2) relative to the structure division having represented by formula (1 ') The ratio of tetrabasic carboxylic acid residue there is no particular restriction, usually more than 0.5mol%, preferably more than 1mol%, more preferably More than 3mol%, usually below 500mol%, preferably below 400mol%, more preferably below 300mol%.By place In this scope, optical characteristics is good, linear expansion coefficient is low polyimide precursor and/or polyimide compositions can be obtained.

There is the tetrabasic carboxylic acid residue of structure division represented by formula (2) relative to the structure division having represented by formula (1 ') The ratio of tetrabasic carboxylic acid residue and the tetrabasic carboxylic acid residue sum of the structure division having represented by formula (2) there is no particular restriction, logical It is often more than 1mol%, preferably more than 3mol%, more preferably more than 5mol%, usually below 95mol%, is preferably Below 90mol%, more preferably below 85mol%.By being in this scope, can obtain that optical characteristics is good, linear expansion coefficient Low polyimide precursor and/or polyimide compositions.

The ratio of tetrabasic carboxylic acid residue can solve by utilizing NMR (nuclear magnetic resonance, NMR), solid NMR, IR (infrared spectrum) etc. Analyse the composition of starting monomer and obtain.Additionally, can by with utilize after alkali dissolution gas chromatography (GC),¹H-NMR、¹³C-NMR、 Two-dimentional NMR and mass spectral analysis etc. and obtain.

There is the diamidogen residue of the structure division represented by formula (5) ratio shared in diamidogen residue and there is no limit especially System, usually more than 0.1mol%, preferably more than 1mol%, more preferably more than 5mol%, more preferably 7mol% Above, more preferably more than 20mol%, more preferably more than 30mol%, more preferably more than 40mol%, More preferably more than 50mol%.Additionally, there is no the special upper limit, can be 100mol%.By diamidogen residue contains The diamidogen residue with the structure division represented by formula (5) more than specified quantitative, can obtain linear expansion coefficient low The polyimide precursor of polyimides and/or polyimide compositions.

About the amount of the diamine compound of derivative diamidogen residue, relative to tetracarboxylic dianhydride 1mol, usually 0.7mol with On, preferably more than 0.8mol, usually below 1.3mol, preferably below 1.2mol.By the amount of diamine compound is set For this scope, the suitable polyimide precursor of molecular weight ranges and/or polyimides can be obtained.

(I group and II group)

I group: represent following formula (1) and formula (2).

[changing 4]

[in formula (1),

X represents the key of Direct Bonding, alkylidene, carbonyl, ehter bond or sulfonyl.]

[changing 5]

II group: represent following formula (3) and formula (4).

[changing 6]

[in formula (3),

N, m represent 0 or 1 independently of one another,

R¹And R²Represent alkylidene, alkenylene or aromatic rings independently of one another.

R¹And R²May be the same or different, the most also can form ring.]

[changing 7]

[in formula (4),

Y represents key (refer between functional group not the Direct Bonding via other elements) or the divalent organic group of Direct Bonding Group.]

(I group)

(there is the tetrabasic carboxylic acid residue of structure division represented by formula (1))

In formula (1), X represents the key of Direct Bonding, alkylidene, carbonyl, ehter bond or sulfonyl.Among above-mentioned, owing to reducing The effect of linear expansion coefficient is higher, it is advantageous to the key of the key of Direct Bonding, carbonyl or sulfonyl, more preferably Direct Bonding.

As above-mentioned alkylidene, it is not particularly limited, preferably carbon number more than 1, more preferably more than 2.The opposing party Face, preferably carbon number less than 8, more preferably less than 5.Additionally, above-mentioned alkylidene can also have substituent group, such as, can arrange Lift amino, hydroxyl, halogen atom etc..

The tetrabasic carboxylic acid residue with the structure division represented by formula (1) is not particularly limited, and can enumerate from following tetrabasic carboxylic acid The tetrabasic carboxylic acid residue that dianhydride is derivative, such as 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 2, The X such as 2 ', 3,3 '-biphenyl tetracarboxylic dianhydride are the tetracarboxylic dianhydride of the key of Direct Bonding；Double (3,4-dicarboxyphenyi) methane two Double (the 3,4-dicarboxyl of acid anhydride, double (2,3-dicarboxyphenyi) methane dianhydride, 2,3,3 ', 4 '-tetracarboxylic phenylmethane dianhydride, 2,2- Phenyl) propane dianhydride, 2,2-double (2,3-dicarboxyphenyi) propane dianhydride, 2,2-(2,3,3 ', 4 '-tetracarboxylic phenyl) propane two The X such as double (3,4-dicarboxyphenyi) the 1,1,1,3,3,3-hexafluoropropane dianhydrides of acid anhydride, 2,2-are the tetracarboxylic dianhydride of alkylidene；3, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone four The X such as carboxylic acid dianhydride are the tetracarboxylic dianhydride of carbonyl；4,4 '-oxygen diphthalic anhydrides, 3,4 '-oxygen diphthalic anhydrides, 3, The X such as 3 '-oxygen diphthalic anhydrides are the tetracarboxylic dianhydride of ehter bond；3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 2,3,3 ', The X such as 4 '-sulfobenzide. tetracarboxylic dianhydride, 2,2 ', 3,3 '-sulfobenzide. tetracarboxylic dianhydride are the tetracarboxylic dianhydride etc. of sulfonyl.

The structure division represented by formula (1) of tetrabasic carboxylic acid residue is preferably the structure division represented by following formula (1 '), its Reason is to there is acquisition thermostability and mechanical property improves, and reduces the tendency of the effect of linear expansion coefficient.

[changing 8]

In formula (1 '), X²For Direct Bonding key, there is the secondary or key of tertiary carbon atom, or ehter bond, be wherein preferably straight Connecing the key of bonding, its reason is that mechanical property can improve.Furthermore it is preferred that reason be, by said composition obtained poly- In acid imide film, the absorption near 308nm, 355nm of Laser Processing increases and can tackle Laser Processing.

What is called has the secondary or key of tertiary carbon atom, represents X²For the secondary of carbon number 1 or tertiary carbon atom.X²Carbon atom remove Beyond being connected with the phenyl ring in formula (1 '), also it is connected with hydrogen atom and/or substituent group.As with X²Carbon atom connect take Dai Ji, can enumerate halogen atom, cyano group, nitro, sulfo group etc..

(there is the tetrabasic carboxylic acid residue of structure division represented by formula (2))

As the tetracarboxylic dianhydride of the tetrabasic carboxylic acid residue of the derivative structure division having represented by formula (2), equal benzene can be enumerated Tetracarboxylic acid dianhydride etc..

(II group)

(there is the tetrabasic carboxylic acid residue of structure division represented by formula (3))

In formula (3), n and m represents 0 or 1 independently of one another.N and m is not particularly limited, reactive with regard to imidizate For aspect, at least one in preferably n or m is 1.R¹And R²Represent alkyl, thiazolinyl or aromatic rings independently of one another.R¹And R²Can identical can also be different, it is also possible to form ring.Additionally, alkyl, thiazolinyl and aromatic rings can have substituent group.

As alkyl and thiazolinyl, preferably carbon number is more than 1 independently of one another.On the other hand, preferably carbon number Less than 10, more preferably less than 8.By for this scope, there is the tendency that dissolubility in organic solvent uprises.

As aromatic rings, can be any number of in monocycle and condensed ring.Specifically, phenyl ring, naphthalene nucleus, anthracene nucleus can be enumerated Deng.Especially preferably phenyl ring, its reason is the tendency having dissolubility in organic solvent to uprise.

The tetrabasic carboxylic acid residue with the structure division represented by formula (3) is not particularly limited, as enumerated by following tetracarboxylic acid The tetrabasic carboxylic acid residue that acid dianhydride is derivative, i.e. 1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides, 1,2,3,4-Pentamethylene. tetracarboxylic dianhydrides, 1, 2,4,5-cyclopentanetetracarboxylic's dianhydride, 1,2,3,4-cyclopentanetetracarboxylic's dianhydride, dicyclo [2,2,2]-7-octene-2,3,4,6-four Carboxylic acid dianhydride, three rings [6,4,0,0^2.7] dodecane-1,8:2,7-tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-ring fourth Alkane tetracarboxylic dianhydride, 4-(2,5-dioxotetrahydro furan-3-base)-1,2,3,4-naphthane-1,2-dicarboxylic anhydride etc..

(there is the tetrabasic carboxylic acid residue of structure division represented by formula (4))

Y represents key or the divalent organic group of Direct Bonding.As divalent organic group, it is not particularly limited, such as, can arrange Lift alkylidene, carbonyl, ehter bond, sulfonyl etc..Wherein, Y is preferably the key of Direct Bonding, and its reason is that there is optical characteristics carries High tendency.

The preferred scope synonym of the alkylidene of the X of above-mentioned alkylidene and formula (1), the substituent group that can have also synonym.

The tetrabasic carboxylic acid residue with the structure division represented by formula (4) is not particularly limited, and include, for example by following four The tetrabasic carboxylic acid residue etc. that carboxylic acid dianhydride is derivative, i.e. joins hexamethylene-3,3 ', 4,4 '-tetracarboxylic dianhydride, connection hexamethylene-2, and 3,3 ', 4 '-tetracarboxylic dianhydride, connection hexamethylene-2,2 ', 3,3 '-tetracarboxylic dianhydride etc..

Among these, it is preferably by joining hexamethylene-3,3 ', 4, the tetrabasic carboxylic acid residue that 4 '-tetracarboxylic dianhydride derives, its reason It is to there is the tendency that optical characteristics improves.

It is the structure division represented by following formula (4 ') by the structure division represented by the formula (4) of tetrabasic carboxylic acid residue, from And optical characteristics improves, the most preferably.

[changing 9]

(diamidogen residue)

As diamidogen residue, can structure division represented by enumerative (5).

[changing 10]

[in formula (5), R³And R⁴Represent alkyl, alkoxyl, amino or hydroxyl independently of one another.]

(there is the tetrabasic carboxylic acid residue of structure division represented by formula (5))

Alkyl and alkoxyl are preferably each independently carbon number more than 1.On the other hand, preferably carbon number 10 Hereinafter, more preferably less than 8, especially preferably less than 6.By for this scope, there is the tendency of linear expansion coefficient step-down, therefore Preferably.

Additionally, alkyl and alkoxyl can be respectively provided with substituent group.The substituent group can having as alkyl, can enumerate halogen former Son, cyano group, nitro, sulfo group etc..Among these, preferably there is halogen atom, especially preferably fluorine atom.By for this scope, Thus there is the tendency of linear expansion coefficient step-down.

The substituent group can having as alkoxyl, can enumerate the alkyl of carbon number more than 1, less than 6, halogen atom, cyanogen Base, nitro, sulfo group, pi-allyl etc..

Wherein, R³And R⁴Being preferably alkyl or alkoxyl, its reason is that optical characteristics can improve with linear expansion coefficient, more Being preferably the alkyl further with halogen atom alternatively base, its reason is to exist the tendency of linear expansion coefficient step-down. Additionally, R³And R⁴May be the same or different, for the aspect of produceability, the most identical.

The diamidogen residue with the structure division represented by formula (5) is not particularly limited.Include, for example from following diamidogen The diamidogen residue that compound is derivative, i.e. 4,4 '-diaminourea-2,2 '-dimethyl diphenyl, 4,4 '-diaminourea-2,2 '-diethyl joins Benzene, 4,4 '-diaminourea-2,2 ' R of-dipropyl biphenyl etc.³And R⁴There is the diamine compound of alkyl；4,4 '-diaminourea-2,2 '- Double (trifluoromethyl) biphenyl, 4,4 '-diaminourea-2-methyl-2 ' R such as-trifluoromethyl-biphenyl³And R⁴There is the diamidogen of haloalkyl Compound；4,4 '-diaminourea-2,2 '-dimethoxy-biphenyl, 4,4'-diaminourea-2,2 '-diethoxy biphenyl, there is amino 2,2 ', 4,4 '-tetra-amino-biphenyl, there is the 4,4 '-diaminourea-2,2 of hydroxyl ' R such as-dihydroxybiphenyl³And R⁴There is alkoxyl Diamine compound etc..

(tetrabasic carboxylic acid with structure division beyond formula (1), formula (2), formula (3) and the structure division represented by formula (4) is residual Base, and the tetrabasic carboxylic acid with structure division beyond formula (1 '), formula (2), formula (4 ') and the structure division represented by formula (5) is residual Base)

Can use from by following shown aromatic tetracarboxylic acid's dianhydride and fat in the range of without departing from the purport of the present invention The tetrabasic carboxylic acid residue that the tetracarboxylic dianhydrides such as fat race tetracarboxylic dianhydride derive, as having (1), formula (2), formula (3) and formula (4) institute table The tetrabasic carboxylic acid residue of the structure division beyond structure division shown.

Additionally, when compositions involved in the present invention has formula (1 '), formula (2), formula (4 ') and the structure represented by formula (5) When at least one partly and in tetrabasic carboxylic acid residue and diamidogen residue has crooked position described later, as having formula (1 '), formula (2) the tetrabasic carboxylic acid residue of the structure division, beyond formula (4 ') and the structure division represented by formula (5), can enumerate from by following institute The tetrabasic carboxylic acid residue that the tetracarboxylic dianhydrides such as the aromatic tetracarboxylic acid's dianhydride shown and aliphatic tetracarboxylic dianhydride derive, and there is formula (3) the tetrabasic carboxylic acid residue of the structure division beyond structure division represented by.

(aromatic tetracarboxylic acid's dianhydride)

As aromatic tetracarboxylic acid's dianhydride, include, for example: virtue contained in 1,2,3,4-PMDA equimolecular Fragrant ring is the tetracarboxylic dianhydride of 1；Double (the 3,4-dicarboxyphenyi)-1,1,1 of 2,2 ', 6,6 '-biphenyl tetracarboxylic dianhydride, 2,2-, Double (2,3-the dicarboxyphenyi)-1,1,1,3,3,3-hexafluoropropane dianhydride of 3,3,3-hexafluoropropane dianhydride, 2,2-, 2,2 '-bis-(three Methyl fluoride)-4,4 ', 5,5 '-biphenyl tetracarboxylic dianhydride, 4,4 '-(hexafluoro trimethylene)-two O-phthalic acid dianhydride, 4,4 '- (octafluoro tetramethylene)-two O-phthalic acid dianhydride etc. has the tetracarboxylic dianhydride of more than 2 independent aromatic rings；1,2,5,6-naphthalene Dioctyl phthalate dianhydride, 1,4,5,8-naphthalenedicarboxylic acid dianhydride, 2,3,6,7-naphthalenedicarboxylic acid dianhydride, 3,4,9,10-tetracarboxylic acid dianhydride, 2, 3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride etc. have the tetracarboxylic dianhydride etc. of condensed aromatic ring.

(aliphatic tetracarboxylic dianhydride)

As aliphatic tetracarboxylic dianhydride, include, for example 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-hexamethylene The ester ring type tetracarboxylic dianhydrides such as alkene-1,2-dicarboxylic anhydride；Ethylene tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride, meso-butane- The chain fatty race tetracarboxylic dianhydrides etc. such as 1,2,3,4-tetracarboxylic dianhydride.

(there is the diamidogen residue of structure division beyond the structure division represented by formula (5))

The diamidogen by following shown diamine compound is derivative can be used residual in the range of without departing from the purport of the present invention Base, as the diamidogen residue of the structure division beyond the structure division having represented by formula (5).

As these other diamine compounds, include, for example Isosorbide-5-Nitrae-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine equimolecular The diamine compound that aromatic rings is 1 contained by；Double (the 4-of 4,4 '-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 1,4- Amino-benzene oxygen) benzene, double (4-amino-benzene oxygen) benzene of 1,3-, 2,2-double (4-(4-amino-benzene oxygen) phenyl) propane, double (4- (4-amino-benzene oxygen) phenyl) sulfone, double (4-(3-amino-benzene oxygen) phenyl) sulfone, double (4-amino-benzene oxygen) neopentane of 1,3-, Double (4-amino-3-carboxyl phenyl) methane, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminodiphenyl sulfide, N-(4-aminobenzene Epoxide)-4-amino-benzylamine (benzamine), 2,2 '-bis-(trifluoromethyls)-4,4 '-benzidine, double (3-aminophenyls) Sulfone, norbornane diamidogen, 4,4 '-diaminourea-2-(trifluoromethyl) diphenyl ether, 5-Trifluoromethyl-1,3-phenylenediamine, 2,2-is double (4-(4-amino-benzene oxygen) phenyl) hexafluoro third institute, 4,4 '-diaminourea-2,2 '-bis-(trifluoromethyl) biphenyl, the double [4-{4-of 2,2- Amino-2-(trifluoromethyl) phenoxy group } phenyl] HFC-236fa, 2-trifluoromethyl-p-phenylenediamine, the double (3-amino-4-first of 2,2- Base phenyl) HFC-236fa, double (4-aminophenyl) acetylene etc. has the diamine compound of more than 2 independent aromatic rings；4,4’- (9-fluorenylidene) diphenylamines, 2,7 diamin of luorene, 1,5-diaminonaphthalene, 3,7-diaminourea-2,8-dimethyl Dibenzothiophene-5, 5-dioxide etc. has the diamine compound etc. of condensed aromatic ring.

Have in the diamidogen residue of the structure beyond the structure division represented by formula (5), preferably comprise and there is formula (6) institute table The diamidogen residue of the structure division shown, its reason is that optical characteristics can improve.

[changing 11]

[in formula (6),

Z represents that the key of Direct Bonding is (not via other between the Jian Zhi functional group (herein for aromatic rings) of this Direct Bonding Element and Direct Bonding), sulfonyl, alkylidene, carbonyl or ehter bond, A and B represents the key of Direct Bonding, divalent virtue independently of one another Fragrant ring, divalent heterocycle or phenylate base.]

Among Z, preferably sulfonyl, ehter bond or carbonyl, more preferably sulfonyl, it is special that its reason is to improve optics further Property.

As the alkylidene of Z, it is not particularly limited, preferably carbon number more than 1, more preferably more than 2.The opposing party Face, preferably carbon number less than 8, more preferably less than 5.

A and B represents the key of Direct Bonding, divalent aromatic rings, divalent heterocycle or phenylate base independently of one another.Divalent aromatic rings and 2 Valency heterocycle can have substituent group.

Wherein preferred phenylate base, its reason is the tendency having dissolubility in a solvent to uprise.A and B can identical also may be used Difference is for produceability aspect, the most identical.

As the divalent aromatic rings of A and B, specifically can enumerate: phenyl ring, naphthalene nucleus, anthracene nucleus etc..Wherein, preferably phenyl ring, Its reason is the tendency having dissolubility in a solvent to uprise.As the divalent heterocycle of A and B, specifically can enumerate furan, Thiophene, pyrroles, imidazoles, pyridine, pyrimidine, pyrazine, azoles, benzimidazole, benzothiazole etc..

As the diamidogen residue of the structure division having represented by formula (6), include, for example and spread out by following diamine compound Raw diamidogen residue, i.e. 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, 3,3 '-bis-(4- Amino-benzene oxygen) diamine compound of the key that Z is Direct Bonding such as biphenyl, 3,4 '-bis-(4-amino-benzene oxygen) biphenyl；3,3’- Diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 2,3 '-diamino diphenyl sulfone, 2, The Z such as 4 '-diamino diphenyl sulfone, double (4-(4-amino-benzene oxygen) phenyl) sulfone, double (4-(3-amino-benzene oxygen) phenyl) sulfone are The diamine compound of sulfonyl；Double (4-(4-amino-benzene oxygen) phenyl) propane of 2,2-, double (4-(3-amino-benzene oxygen) benzene of 2,2- Base) propane, the double Z such as (4-amino-benzene oxygen) neopentane, double (4-amino-3-carboxyl phenyl) methane of 1,3-be the diamidogen of alkylidene Compound；4,4 '-diamino-diphenyl ketone, 3,4 '-diamino-diphenyl ketone, 2,3 '-diamino-diphenyl ketone, 2,4 '-diamino The Z such as base diphenylketone are the diamine compound of carbonyl；3,3 ', 4,4 '-tetramino diphenylketone, 4,4 '-bis-(4-aminobenzene oxygen Base) Z such as benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone is the diamine compound etc. of ehter bond.

(there is tetrabasic carboxylic acid residue and/or the diamidogen residue of crooked position)

Polyimide precursor and/or polyimides in the compositions of the present invention are preferably containing having crooked position Tetrabasic carboxylic acid residue and/or diamidogen residue, its reason is to there is the tendency improving optical characteristics.

In the present invention, so-called crooked position is to deform repressed crooked position, refers to that suppression is centered by crooked position Ring bonding angle, be bonded to the ring of crooked position face angle, rotate, vibration etc. comprises tetrabasic carboxylic acid residue and/or diamidogen The structure of the motion of the molecule of residue.Wherein, the bonding angle of suppression ring centered by crooked position and rotation it are preferably The structure of motion.

That is, so-called crooked position, is preferably bonded directly to circulus and circulus and circulus to each other Bonding angle is preferably less than 160 degree less than the group more than trivalent of 180 degree, bonding angle, more preferably less than 130 degree.Lower limit is also Without special, usually more than 90 degree.

Above-mentioned angle may utilize the computational methods in the past both known and obtains.Include, for example: shock that method, extension shock that The empirical molecular orbital methods such as method (Extended Hiickel method), breathe out Cui-Fo Kefa, method of Configuration Interaction Singlet The non-experience such as (Configuration Interaction method), multiconfiguration SCF (Self-Consistent Field) method Molecular orbital method, PPP (Pariser-Parr-Pople, Pa Lise-Paar-Popper's) approximation, CNDO/2 (Complete Neglect of Differential Overlap, complete neglect of differential overlap), INDO (Intermediate Neglect of Differential Overlap, slightly divides overlap), MNDO (Modified Neglect of Differential Overlap, improves that to ignore diatomic differential overlapping), AM1 (Austin Model 1, Austin's model 1), PM3 Semiempirical molecular orbital methods such as (Parameterized Model 3, parameterized models 3), MM (Molecular mechanics, Molecular mechanics) 2 equimolecular KINETIC METHOD, BLYP (Becke Lee-Yang-Parr), B3LYP (Becke three- Parameter Lee-Yang-Parr) isodensity functional method etc..

In the present invention, there is suppression polyimide precursor by having crooked position and/or polyimides chain is overall Thermal vibration, improve the tendency of linear expansion coefficient.And then, by between suppression polyimide precursor and/or polyimides chain Interaction and exist the optical characteristics such as transmitance, YI improve tendency, be disturbed by the rule orientating of same chain and exist The tendency of delayed improvement.

Also, increased, with the fragrant circular rector increasing in chain by polyimide precursor and/or being wound around of polyimide molecule chain Many and there is the tendency that thermostability improves.

Polyimide precursor and/or polyimides in the compositions of the present invention generally can be containing having crooked position Tetrabasic carboxylic acid residue and diamidogen residue, it is also possible to containing tetrabasic carboxylic acid residue or the diamidogen residue with crooked position.These it In, preferably diamidogen residue has crooked position, and its reason is to there is the tendency that optical characteristics easily improves.Additionally, it is the most excellent Electing tetrabasic carboxylic acid residue as and be respectively provided with crooked position with diamidogen residue, its reason is to there is the tendency that optical characteristics easily improves.

In the present invention, tetrabasic carboxylic acid residue and/or diamidogen residue crooked position can comprise multiple crooked position, but be preferably Multiple crooked positions do not link.Do not linked by crooked position and there is the tendency that can maintain and improve polymerism.

In the present invention, preferably on crooked position, Direct Bonding has circulus.By making circulus Direct Bonding, can enter The face angle of the one step suppression bonding ring that is bonded with crooked position of angle, rotate, the deformation such as vibration.It is bonded directly to bending The circulus at position may originate from the tetrabasic carboxylic acid residue/diamidogen residue identical with crooked position, it is also possible to different.When being derived from curved During the situation of tetrabasic carboxylic acid residue/diamidogen residue that pars convoluta position is identical, circulus can become tetrabasic carboxylic acid monomer/diamine monomer to be had Some structures.When being not originate from the situation of the tetrabasic carboxylic acid residue/diamidogen residue identical with crooked position, circulus is ring-type Imide structure.

The tetrabasic carboxylic acid residue with crooked position can be to have represented by above-mentioned formula (1), formula (2), formula (3) and formula (4) The tetrabasic carboxylic acid residue of structure division, it is also possible to be have formula (1), formula (2), formula (3) and the structure division represented by formula (4) with The tetrabasic carboxylic acid residue of outer structure.

For having low linear expansion coefficient and low delayed two aspects concurrently, the tetrabasic carboxylic acid residue preferably with crooked position is tool There is the tetrabasic carboxylic acid residue of structure beyond formula (1), formula (2), formula (3) and the structure division represented by formula (4).And then, just have concurrently For low linear expansion coefficient and low delayed two aspects, there is the tetrabasic carboxylic acid residue of crooked position for having above-mentioned formula (1 '), formula (2) And the tetrabasic carboxylic acid residue of the structure beyond the structure division represented by formula (4 ').

Furthermore, it is possible to containing multiple tetrabasic carboxylic acid residues with crooked position.

The diamidogen residue with crooked position can be the structure beyond the structure division represented by above-mentioned formula (5), permissible Containing multiple.

There is no particular restriction for the content of crooked position, with relative to the tetrabasic carboxylic acid residue in compositions and diamidogen residue sum Ratio meter, usually more than 0.1mol%, preferably more than 0.5mol%, more preferably more than 1mol%, further preferably For more than 5mol%.Additionally, usually below 150mol%, preferably below 100mol%, more preferably below 50mol%. Good, the tendency of mechanical properties raising is become by there is optical characteristics for these scopes.

As crooked position, that preferably close with ring key and composition main chain element has being bonded of more than trivalent.More than trivalent Bonding in, be preferably selected from least one in quaternary carbon atom, 6 valency sulphur atoms, tertiary amine, phenyl ring.There is the tetracarboxylic acid of crooked position Acid residue and/or diamidogen residue are especially preferably the aromatic rings being had more than 2 by quaternary carbon atom and/or 6 valency sulfur atom linkages Structure, its reason be exist improve optical characteristics tendency.

As long as having the structure purport without departing from the present invention of the bonding of more than trivalent, then it is not particularly limited, such as may be used Enumerate the structure represented by following formula (30).

[changing 12]

In above-mentioned formula (30), Z¹Represent quaternary carbon atom, 6 valency sulphur atoms, tertiary amine or phenyl ring.Y¹And Y²Represent independently of one another Circulus.

As quaternary carbon, preferably HFC-236fa, propane, fluorenes etc., its reason is that optical characteristics improves.As 6 valency sulfur, excellent Electing sulfonyl as, its reason is that optical characteristics improves.As tertiary amine, preferably Trimethylamine.

So-called Y¹And Y²Circulus, represent aromatic compound, alicyclic series compound or imide ring.

So-called aromatic compound, the first prime number wherein forming 1 ring is more than 5, less than 8, can be monocycle or 2 rings It is condensed.Specifically phenyl ring, condensed aromatic ring or heterocycle.

The number of rings of condensed aromatic ring is not particularly limited, and preferably more than 2, less than 5, it is resistance to that its reason is that existence can have concurrently The hot tendency with optical characteristics.

Heterocycle is not particularly limited, specifically, can enumerate furan, thiophene, pyrroles, imidazoles, pyridine, pyrimidine, pyrazine, Azoles, benzimidazole, benzothiazole etc..

The substituent group can having as aromatic compound, can enumerate the alkyl of carbon number more than 1, less than 6, carbon atom Several alkoxyls of more than 1, less than 6, amino, hydroxyl etc..

The alkyl of carbon number more than 1, less than 6 and the alkoxyl of carbon number more than 1, less than 6 can also have replacement Base.

The substituent group can having as the alkyl of carbon number more than 1, less than 6, can enumerate halogen atom, hydroxyl etc..

The substituent group can having as the alkoxyl of carbon number more than 1, less than 6, can enumerate halogen atom, hydroxyl Deng.

So-called alicyclic series compound, the carbon number wherein forming 1 ring is more than 4, less than 8, can be monocycle or 2 Ring is condensed.Additionally, ring can have unsaturated bond.

Specifically, can enumerate Tetramethylene., cyclobutadiene, Pentamethylene., cyclopentenes, hexamethylene, cyclohexene, cyclohexadiene, Cycloheptane, cycloheptene, cyclooctane etc..

Alicyclic series compound can have substituent group, as the substituent group that can have, can enumerate carbon number more than 1, less than 6 Alkyl, the alkoxyl of carbon number more than 1, less than 6, amino, hydroxyl etc..The alkyl of carbon number more than 1, less than 6 and carbon The alkoxyl of atomic number more than 1, less than 6 also can have substituent group, as the substituent group that can have, with above-mentioned aromatic compound Synonym cited by.

So-called imide ring is the ring with imide bond, and its first prime number forming 1 ring is more than 4, less than 6, permissible It is only imide ring, it is also possible to be condensed with other rings.The ring that can be condensed, be can have substituent group aromatic compound, Can have the alicyclic series compound of substituent group.Number of rings when being condensed is not particularly limited, and preferably more than 2, less than 4, its Reason is to there is the tendency that can have thermostability concurrently with optical characteristics.

In structure represented by formula (30), for optical characteristics raising aspect, be preferably selected from following formula (31)～ (35) structure position represented by.

[changing 13]

In formula (31), R¹⁰、R¹¹Represent alkyl, amino or hydroxyl, Y independently of one another¹And Y²Represent fragrance independently of one another Race's hydrocarbon, alicyclic series compound or imide ring.

R¹⁰、R¹¹Alkyl be preferably carbon number more than 1.On the other hand, preferably carbon number less than 10, more preferably It is less than 8, especially preferably less than 6.By for this scope, there is the tendency of linear expansion coefficient step-down, the most preferably.Additionally, Alkyl can have substituent group.The substituent group can having as alkyl, can enumerate halogen atom, cyano group, nitro, sulfo group etc..These Among, the most unsubstituted or there is halogen atom, especially preferably fluorine atom.By for this scope, there is linear expansion coefficient The tendency of step-down.

Y¹And Y²Respectively with the Y of formula (30)¹And Y²Synonym, concrete example, preferred scope and the substituent group that can have are also same Justice.

[changing 14]

In formula (32), R¹²～R¹⁵Represent alkyl or hydroxyl independently of one another.

R¹²～R¹⁵Alkyl independently of one another be preferably carbon number more than 1.On the other hand, preferably carbon number 10 Hereinafter, more preferably less than 8, especially preferably less than 6.By for this scope, there is the tendency of linear expansion coefficient step-down, therefore Preferably.Additionally, alkyl can have substituent group.The substituent group can having as alkyl, can enumerate halogen atom, cyano group, nitro, sulphur Base etc..Among these, it is however preferred to have halogen atom, especially preferably fluorine atom.By for this scope, there is linear expansion coefficient The tendency of step-down.

[changing 15]

In formula (33), Y¹And Y²Respectively with the Y of formula (30)¹And Y²Synonym, concrete example, preferred scope and taking of can having Dai Ji also synonym.

[changing 16]

In formula (34), R¹⁶Represent alkyl or aromatic compound.Y¹And Y²Respectively with the Y of formula (30)¹And Y²Synonym, specifically Example, preferred scope and the substituent group also synonym that can have.

R¹⁶Alkyl be preferably carbon number more than 1.On the other hand, preferably carbon number less than 10, more preferably 8 with Under, especially preferably less than 6.By for this scope, there is the tendency of linear expansion coefficient step-down, the most preferably.Additionally, alkyl can There is substituent group.The substituent group can having as alkyl, can enumerate halogen atom, cyano group, nitro, sulfo group etc..Among these, excellent Elect as and there is halogen atom, especially preferably fluorine atom.By for this scope, there is the tendency of linear expansion coefficient step-down.

About R¹⁶Aromatic compound, the first prime number forming 1 ring is more than 5, less than 8, it is also possible to be monocycle or 2 Ring is condensed.Specifically, it is phenyl ring, condensed aromatic ring or heterocycle.Among these, preferably monocycle phenyl ring, phenyl ring contracts The condensed aromatic ring closed, its reason is to exist the tendency of linear expansion coefficient step-down.

Heterocycle is not particularly limited, and specifically, can enumerate: furan, thiophene, pyrroles, imidazoles, pyridine, pyrimidine, pyrrole, Purine azoles, benzimidazole, benzo purine azoles etc..

The alkyl of carbon number more than 1, less than 6 and the alkoxyl of carbon number more than 1, less than 6 also can have substituent group.

The substituent group can having as the alkoxyl of carbon number more than 1, less than 6, can enumerate halogen atom, hydroxyl etc..

[changing 17]

In formula (35), R represents alkyl, nitro, amino, hydroxyl or halogen atom.

As abovementioned alkyl, it is not particularly limited, preferably carbon number more than 1.On the other hand, preferably carbon number Less than 8, more preferably less than 5.By for these scopes, there is the tendency that the intermiscibility with solvent becomes good.

Alkyl can also have substituent group, include, for example amino, hydroxyl, nitro, halogen atom etc..

As the diamidogen residue of the structure having represented by formula (35), include, for example derivative from following diamine compound Diamidogen residue, i.e. 2,6-diaminotoluene, 2,5-diaminotoluene, 2,4 di amino toluene, 3,4-diaminotoluene, 2,3-bis- Amino toluene, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 4-nitro-1,2-phenylenediamine, 4-nitro-1,3-phenylenediamine, 2-nitro-1,2-phenylenediamine, 3-Trifluoromethyl-1,5-phenylenediamine, 4-Trifluoromethyl-1,5-phenylenediamine, 4-Trifluoromethyl-1,2- Phenylenediamine, 3-hydroxyl-1,5-phenylenediamine, 4-hydroxyl-1,5-phenylenediamine, 4-hydroxyl-1,2-phenylenediamine etc..

As the tetrabasic carboxylic acid residue of the aromatic rings being bonded with more than 2 by quaternary carbon atom, include, for example from following The tetrabasic carboxylic acid residue that tetracarboxylic dianhydride derives, double (3,4-dicarboxyphenyi) fluorenes dianhydride of i.e. 9,9-, 4, the adjacent benzene of 4 '-isopropylidene two Double (3,4-the dicarboxyphenyi)-1,1,1,3,3,3-hexafluoropropane dianhydride of dicarboxylic acid anhydride, 2,2-, double (the 2,3-dicarboxyl benzene of 2,2- Base)-1,1,1,3,3,3-hexafluoropropane dianhydride etc..

As the tetrabasic carboxylic acid residue of the aromatic rings being had more than 2 by 6 valency sulfur atom linkages, include, for example from following The tetrabasic carboxylic acid residue that tetracarboxylic dianhydride derives, i.e. 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 2,3,3 ', 4 '-sulfobenzide. Tetracarboxylic dianhydride, 2,2 ', 3,3 '-sulfobenzide. tetracarboxylic dianhydride, the adjacent benzene two of 4,4 '-[double (phenylene sulfenyl) to sulfonyl] two Formic anhydride, 3,3 '-[double (phenylene sulfenyl) to sulfonyl] diphthalic anhydrides etc..

As the diamidogen residue of the aromatic rings being bonded with more than 2 by quaternary carbon atom, include, for example from following two The diamidogen residue that amines is derivative, double (4-aminophenyl) HFC-236fa of i.e. 2,2-, 2, double (3-aminophenyl) hexafluoro third of 2- Double (4-aminophenyl) propane of alkane, 2,2-, double (3-aminophenyl) propane of 2,2-, double [2-(4-the aminophenyl)-2-third of 1,3- Base] benzene, double [2-(4-the aminophenyl)-2-propyl group] benzene of 1,4-, 2,2-double (3-amino-4-hydroxylphenyl) HFC-236fa, 2,2- Double (4-aminophenyl) fluorenes of double (3-amino-4-hydroxylphenyl) propane, 9,9-, double (3-aminophenyl) fluorenes of 9,9-, the double (2-of 9,9- Aminophenyl) fluorenes, double [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, double [4-(4-amino-benzene oxygen) phenyl] hexafluoro of 2,2- Propane, 2,2-double [4-{4-amino-2-(trifluoromethyl) phenoxy group } phenyl] HFC-236fa, double [4-(the 4-aminobenzene oxygen of 2,2- Base)-3,5-dibromo phenyl } HFC-236fa etc..

As the diamidogen residue of the aromatic rings being had more than 2 by 6 valency sulfur atom linkages, include, for example from following two The diamidogen residue that amines is derivative, i.e. 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diaminourea Sulfobenzide., 4,4 '-bis-(4-amino phenylene sulfenyl) sulfobenzide .s, 3,3 '-bis-(4-amino phenylene sulfenyl) sulfobenzide .s, Double (the 3-amino-4-hydroxy benzene of double [4-(4-amino-benzene oxygen) phenyl] sulfone, double [4-(3-amino-benzene oxygen) phenyl] sulfone, 2,2- Base) sulfone, 3,3 ', 4,4 '-tetramino sulfobenzide. etc..

(polyimide precursor contained by compositions and/or the physical property of polyimides)

There is no particular restriction for polyimide precursor contained by compositions and/or the weight average molecular weight (Mw) of polyimides, With the Weight-average molecular gauge of polystyrene conversion, usually more than 1000, preferably more than 3000, more preferably more than 5000, More preferably more than 10000.Additionally, usually less than 200000, preferably less than 180000, more preferably 150000 with Under.By becoming this scope, dissolubility, solution viscosity, composition viscosity, melt viscosity etc. become with common manufacture equipment appearance Tractable scope, the most preferably.Furthermore, the weight average molecular weight of polystyrene conversion can pass through gel permeation chromatography (GPC) Obtain.

Polyimide precursor and/or the number-average molecular weight (Mn) of polyimides contained by compositions are not particularly limited, In terms of the number-average molecular weight of polystyrene conversion, usually more than 500, preferably more than 1000, more preferably more than 2500, enter One step is preferably more than 5000.Additionally, usually less than 100000, preferably less than 90000, more preferably less than 80000.Logical Crossing and become this scope, dissolubility, solution viscosity, composition viscosity, melt viscosity etc. become easily to be located with common manufacture equipment The scope of reason, the most preferably.The number-average molecular weight of polyimide precursor and/or polyimides may utilize and above-mentioned Weight-average molecular Measure identical method to be measured.

The molecular weight distribution of polyimide precursor contained by compositions and/or polyimides (PDI, (weight average molecular weight/ Number-average molecular weight (Mw/Mn)) usually more than 1, preferably more than 1.1, more preferably more than 1.2, also, usually less than 10, It is preferably less than 9, more preferably less than 8.For existing for the tendency aspect of the higher compositions of acquisition uniformity, it is preferably and divides Son amount distribution is in this scope.Additionally, for the anti-albefaction aspect of film, exist by being in above-mentioned scope in acquisition film The tendency of the film of the flatness excellence of the uniformity, suppression albefaction and the film that divide.Furthermore, polyimide precursor and/or polyamides are sub- The molecular weight distribution of amine can be obtained by the value of above-mentioned weight average molecular weight with number-average molecular weight.

There is no particular restriction for the acid imide rate of the polyimide precursor contained by polyimide precursor compositions.Generally Less than 100%, preferably less than 80%, more preferably less than 60%, more preferably less than 50%, there is no lower limit, acyl is sub- Amination rate can also be 0%.Become this scope by acid imide rate, have in polyimide precursor compositions use molten The tendency that dissolubility in agent uprises, the stability of polyimide precursor compositions increases, the most preferably.Polyimides forerunner The acid imide rate of the polyimide precursor contained by body compositions may utilize in itself previously known method, such as NMR method, IR method and Titrimetrys etc. are obtained.

(other compositions of polyimide precursor and/or polyimide compositions)

The polyimide precursor of the present invention and/or polyimide compositions, except comprise above-mentioned polyimide precursor and/ Or beyond polyimides and solvent, as long as the effect of the lossless present invention, then can also comprise other compositions.Become as other Point, include, for example surfactant, solvent, antioxidant, lubricant, coloring agent, stabilizer, UV absorbent, anti-quiet Electricity agent, fire retardant, plasticizer, releasing agent, levelling agent, defoamer etc..Additionally, according further to needs, it is also possible in lossless invention Inorganic system filler or the organic system filler such as mixing powdery, granular, tabular and threadiness in the range of purpose.These add Composition can add in manufacturing any stage of any operation of polyimide precursor and/or polyimide compositions.

Among these compositions, preferably comprising levelling agent, its reason is to there is the tendency that the flatness of film improves.As Levelling agent, include, for example silicon-type compound etc..Silicon-type compound is not particularly limited, and include, for example polyethers and changes Property siloxanes, polyether-modified polydimethylsiloxane, the polydimethylsiloxane containing polyether-modified hydroxyl, polyether-modified poly-methyl Alkylsiloxane, polyester modification polydimethylsiloxane, the polydimethylsiloxane containing polyester modification hydroxyl, the poly-first of polyester modification Base alkylsiloxane, aralkyl modified poly-methyl alkyl siloxane, high polymerizing silicone, amino modified silicone, aminoderivative silicon Ketone, phenyl modified silicone and polyether modified silicone etc..

(manufacture of the polyimide precursor contained by compositions)

By the reaction of tetracarboxylic dianhydride with diamine compound acquisition polyimide precursor, can be the most in the past with regard to known bar Carry out under part.Tetracarboxylic dianhydride is not particularly limited with order of addition or the adding method of diamine compound.The most in a solvent Put into tetracarboxylic dianhydride and diamine compound successively, and stir at a suitable temperature, be derived from polyimide precursor.

About the amount of diamine compound, relative to tetracarboxylic dianhydride 1mol, usually more than 0.7mol, preferably 0.8mol Above, also, usually below 1.3mol, preferably below 1.2mol.By diamine compound being set to above-mentioned scope, existing and obtaining The tendency that the productivity of the polyimide precursor obtained improves.

Be in this scope by the amount making diamine compound, exist the viscosity of compositions easily become be suitable to coating scope, And easily obtain the tendency of tough film.

The concentration of the tetracarboxylic dianhydride in solvent and diamine compound can be according to reaction condition or polyimide precursor Viscosity and suitably set.There is no particular restriction, relative to total liquid for total quality % of such as tetracarboxylic dianhydride and diamine compound Amount, usually more than 1 mass %, more than preferably 5 mass %, additionally, usually below 70 mass %, preferably 50 mass % Hereinafter, below more preferably 40 mass %.By response matrix being set to this scope, can obtain poly-with low cost and high productivity Acid imide presoma.And then there is the tendency that molecular weight easily extends, there is also viscosity and will not become too high and easy agitating solution Tendency.

As long as reaction temperature can make the temperature that reaction is carried out, then there is no particular restriction, usually more than 0 DEG C, is preferably More than 20 DEG C, additionally, usually less than 120 DEG C, preferably less than 100 DEG C.Response time is usually more than 1 hour, and preferably 2 More than hour, additionally, usually less than 100 hours, preferably less than 42 hours, more preferably less than 24 hours.By upper React under the conditions of stating, polyimide precursor can be obtained with low cost and high productivity.

Pressure during reaction can be normal pressure, pressurize or reduce pressure in any person.

Environment can be under air, it is also possible to is under non-reactive gas ambient.

The solvent used as this reaction, is not particularly limited, and include, for example hexane, hexamethylene, heptane, benzene, first The hydrocarbon system solvents such as benzene, dimethylbenzene, sym-trimethylbenzene., methyl phenyl ethers anisole；Carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethanes, chlorobenzene, The halogenated hydrocaron solvent such as dichloro-benzenes, fluorobenzene；The ether series solvents such as diethyl ether, oxolane, 1,4-dioxane, methoxybenzene；Acetone, The ketone series solvents such as methyl ethyl ketone, Ketohexamethylene, methyl iso-butyl ketone (MIBK)；Glycol monoethyl ether, ethylene glycol monoethyl ether, glycol dinitrate The glycol series solvents such as ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate；DMF, N, N-dimethyl The amide series solvents such as acetamide, N-methyl-2-Pyrrolizidine ketone；The non-proton system such as dimethyl sulfoxide polar solvent；Pyridine, methyl pyrrole The heterocycle series solvents such as pyridine, lutidines, quinoline, isoquinolin；The phenol series solvent such as phenol, phenyl methylcarbamate；In gamma-butyrolacton, γ-penta The lactone series solvent such as ester, δ-valerolactone etc..These solvents can be used alone a kind, it is possible to by two or more with arbitrary ratio and combination Use.

The polyimide precursor obtained can be used directly, the most also can be by being added in poor solvent in solid Shape is re-dissolved in other solvents after separating out and obtains with the form of polyimide precursor compositions.

There is no particular restriction for poor solvent now, suitably can select according to the kind of polyimide precursor, can arrange Lift the ether series solvent such as diethyl ether or diisopropyl ether；The ketone series solvents such as acetone, methyl ethyl ketone, isobutyl ketone, methyl iso-butyl ketone (MIBK)； The alcohol series solvents etc. such as methanol, ethanol, isopropanol.Wherein, so that it may efficiency obtains precipitate well, boiling point is relatively low and is easily dried For aspect, the preferably alcohol series solvent such as isopropanol.These solvents can be used alone a kind, it is also possible to by two or more with arbitrarily than Rate and being applied in combination.

The solvent making polyimide precursor dissolve is not particularly limited, include, for example hexane, hexamethylene, heptane, benzene, The hydrocarbon system solvents such as toluene, dimethylbenzene, sym-trimethylbenzene., methyl phenyl ethers anisole；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-first The amide series solvents such as base-2-Pyrrolizidine ketone；The non-proton series solvent such as dimethyl sulfoxide；Glycol monoethyl ether, ethylene glycol monoethyl ether, The glycol series solvents etc. such as glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate.Wherein, especially preferably Methyl phenyl ethers anisole, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-methyl-2-Pyrrolizidine ketone, glycol dimethyl ether and second two Alcohol monomethyl ether.These solvents can be used alone a kind, also can two or more with arbitrary ratio and be applied in combination.

As long as the compositions of the present invention is without departing from the purport of the present invention, it is possible to comprise other solvents.Its kind there is no spy Not limiting, preferably alcohol, its reason is that coating becomes good.

As alcohol, there is no particular restriction.There is no particular restriction for vapour pressure at 20 DEG C, preferably below 50000Pa, more excellent Elect below 20000Pa as, more preferably below 10000Pa, more preferably below 5000Pa.Additionally, there is no lower limit, The lowest more preferred, for example, more than 1Pa.Be this scope by vapour pressure, exist obtain the uniformity of composition in compositions and film, Suppression albefaction, and the tendency of the film of flatness excellence.

There is no particular restriction to make an addition to the boiling point of alcohol of compositions, preferably more than 60 DEG C, more preferably more than 100 DEG C, More preferably more than 120 DEG C.Also, preferably less than 300 DEG C, more preferably less than 280 DEG C, more preferably 250 DEG C Below.

Being this scope by boiling point, the concentration change of the polyimide precursor compositions when film of coating etc. is formed becomes Little, therefore there is the tendency of the film of the flatness excellence obtaining the uniformity of composition in film, suppression albefaction and film.Exist further The tendency that residual solvent after drying or in heating caudacoria tails off.

There is no particular restriction to make an addition to the Octanol/water Partition Coefficients (log ρ) of the alcohol of compositions, and preferably more than 0, more preferably It is more than 0.5, and then preferably more than 1.Additionally, and no maximum, the biggest more preferred.It is this scope by log ρ, there is moisture The impact of film is diminished, the downtrod tendency of albefaction time film is formed.

There is no particular restriction to make an addition to the alcohol of the compositions ratio in whole solvents, below preferably 50 mass %, more excellent Elect below 30 mass % as, more preferably below 20 mass %.Furthermore it is preferred that be more than 0.1 mass %, more preferably More than 0.5 mass %, more preferably more than 1.0 mass %.By for this scope, exist polyimide precursor and/or The downtrod tendency of albefaction when the dissolubility of polyimides uprises and film is formed.

Make an addition to the group that the alcohol of compositions is preferably selected from being made up of aromatic alcohols, aliphatic alcohol and glycol monoethers system alcohol In more than a kind.These solvents can be used alone, it is also possible to arbitrary ratio is also used.

Wherein, preferably aliphatic alcohol or glycol monoethers system alcohol, especially preferably aliphatic alcohol, its reason is that polyamides is sub- The dissolubility of amine presoma and/or polyimides uprises.

Among aliphatic alcohol, preferably carbon number more than 4, more preferably carbon number more than 5.Furthermore it is preferred that be carbon Atomic number less than 20, more preferably carbon number less than 15.

Additionally, among aliphatic alcohol, the most ring-type and there is side chain, when having the situation of side chain, especially preferably Branched positional is β and/or γ position.

There is suitable carbon number and/or the position of substitution as described above, exist polyimide precursor and/or The tendency that the dissolubility of polyimides uprises.

The alcohol making an addition to compositions is not particularly limited, and specifically, can enumerate following.

(aromatic alcohols)

As aromatic alcohols, benzylalcohol, saligenin, benzohydrol and cephrol etc. can be enumerated.

(aliphatic alcohol)

As aliphatic alcohol, include, for example the methanol of carbon number 1；The ethanol of carbon number 2；The 1-of carbon number 3 Propanol and 2-propanol；The n-butyl alcohol of carbon number 4,2-butanol, isobutanol and the tert-butyl alcohol；The 1-amylalcohol of carbon number 5,2-penta Alcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol and 2-ethyl-1-propanol；The 1-hexanol of carbon number 6,2-are own Alcohol, 3-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 2-ethyl-fourth Alcohol, 3-ethyl-2-butanol, 2,3-dimethyl-1-butanol and Hexalin；The 1-heptanol of carbon number 7,2-enanthol, 3-enanthol, 4- Enanthol, 2-methyl isophthalic acid-hexanol, 2-methyl-3-hexanol, 2-methyl-4-hexanol, 3-methyl isophthalic acid-hexanol, 3-methyl-2-hexanol, 3- Methyl-4-hexanol, 2-ethyl-1-amylalcohol, 2-ethyl-3-amylalcohol, 2,2-dimethyl-1-amylalcohol, 2,3-dimethyl-1-amylalcohol and 2,4-dimethyl-1-amylalcohol；The 1-capryl alcohol of carbon number 8, sec-n-octyl alcohol, 3-capryl alcohol, 4-capryl alcohol, 2-methyl isophthalic acid-enanthol, 2-first Base-3-enanthol, 2-methyl-4-enanthol, 2-ethyl-1-hexanol, 2-ethyl-3-hexanol, 2-ethyl-4-hexanol, 2-propyl group-1-penta Alcohol, 2-propyl group-3-amylalcohol, 2-propyl group-4-amylalcohol, 2,3-dimethyl-1-hexanol and 2,4-dimethyl-1-hexanol；Carbon number 9 1 nonyl alcohol, 2-nonyl alcohol, 3-nonyl alcohol, 4-nonyl alcohol, 5-nonyl alcohol, 2-methyl isophthalic acid-capryl alcohol, 2-methyl-3-capryl alcohol, 2-methyl-4-pungent Alcohol, 2-methyl-5-capryl alcohol, 2-methyl-6-capryl alcohol, 2-ethyl-1-heptanol, 2-ethyl-3-enanthol, 2-ethyl-4-enanthol, 2-second Base-5-enanthol, 2,6-dimethyl-1-heptanol, 2,6-2,6-dimethyl-4-heptanol, 3,5,5-trimethyl-1-hexanol, 3,5,5-front three Base-2-hexanol and 2,2,4-trimethyl-1-hexanol；The 1-decanol of carbon number 10,2-decanol, 3-decanol, 4-decanol, 5-last of the ten Heavenly stems Alcohol, 2-methyl isophthalic acid-nonyl alcohol, 2-methyl-3-nonyl alcohol, 2-methyl-4-nonyl alcohol, 2-methyl-5-nonyl alcohol, 2-ethyl-1-capryl alcohol, 2-second Base-3-capryl alcohol, 2-ethyl-4-capryl alcohol and 2-ethyl-5-capryl alcohol；The 1-tip-nip of carbon number 11,2-tip-nip, 3-ten One alkanol, 4-tip-nip, 2-methyl isophthalic acid-decanol, 2-ethyl-1 nonyl alcohol and 2-propyl group-1-capryl alcohol；The 1-ten of carbon number 12 Dialkanol, 2-dodecanol, 3-dodecanol, 1-ethyl-1-decanol, 2-ethyl-1-decanol, 3-ethyl-1-decanol and 2-fourth Base-1-capryl alcohol；The 1-tridecyl alcohol of carbon number 13,2-tridecyl alcohol, 3-tridecyl alcohol, 1-ethyl-1-tip-nip, 2-second Base-1-tip-nip, 3-ethyl-1-tip-nip and 2-butyl-1 nonyl alcohol；The 1-tetradecanol of carbon number 14,2-14 Alkanol, 3-tetradecanol, 2-methyl isophthalic acid-tridecyl alcohol, 2-ethyl-DODECANOL, 1-and 2-propyl group-1-tip-nip；Carbon atom The 1-pentadecanol of several 15,2-pentadecanol, 3-pentadecanol, 2-methyl isophthalic acid-tetradecanol, 2-ethyl-1-tridecyl alcohol and 2-propyl group-DODECANOL, 1-；The 1-hexadecanol of carbon number 16,2-hexadecanol, 3-hexadecanol, 2-methyl isophthalic acid-ten five Alkanol, 2-ethyl-1-tetradecanol and 2-propyl group-1-tridecyl alcohol；The 1-heptadecanol of carbon number 17,2-heptadecanol, 3-heptadecanol, 2-methyl isophthalic acid-hexadecanol, 2-ethyl-1-pentadecanol and 2-propyl group-1-tetradecanol；Carbon number 18 1-octadecanol, 2-octadecanol, 3-octadecanol, 2-methyl isophthalic acid-heptadecanol, 2-ethyl-1-hexadecanol and 2-third Base-1-pentadecanol；The 1-nonadecanol of carbon number 19,2-nonadecanol, 3-nonadecanol, 2-methyl isophthalic acid-octadecanol, 2-ethyl-1-heptadecanol and 2-propyl group-1-hexadecanol；The 1-EICOSANOL of carbon number 20,2-EICOSANOL, 3-20 Alkanol, 2-methyl isophthalic acid-nonadecanol, 2-ethyl-1-octadecanol and 2-propyl group-1-heptadecanol etc..

(glycol monoethers system alcohol)

As glycol monoethers system alcohol, include, for example glycol monoethyl ether, ethylene glycol monoethyl ether etc..

When by matrix coating being contained polyimide precursor or the compositions of polyimides and heating and/or dry Dry and when obtaining film, there is the tendency of the impact of environment when films such as being vulnerable to coating is formed in the film obtained.Especially in humidity When being coated in the environment of higher waiting, exist and cause the decreased solubility of compositions, polyimides because of the moisture absorption before being dried The situation that presoma or polyimides separate out, film bleaches (albefaction).Even if additionally, the film that albefaction occurs being dried or adds Heat, there is also the problem that cannot obtain original characteristic such as the polyimides of thermostability and mechanical property etc..Ask to solve these Topic, can use choosing free ether series solvent, ketone series solvent, amide series solvent, sulfone series solvent, heterocycle series solvent, phenol as solvent The vapour pressure at more than a kind and 20 DEG C in the group that series solvent, lactone series solvent and ester series solvent are formed be 50000Pa with Under solvent (hereinafter sometimes referred to solvent orange 2 A), and alcohol (hereinafter sometimes referred to solvent B).Speculate by comprising solvent orange 2 A and solvent B can suppress the reason of albefaction to be, and the hydrophobicity of compositions entirety improves, moisture absorption is suppressed.

Be preferably selected from the group being made up of aromatic alcohols, aliphatic alcohol and glycol monoethers system alcohol a kind of solvent B with On.These solvents can be used alone, it is also possible to arbitrary ratio is also used.

Wherein, preferably aliphatic alcohol or glycol monoethers system alcohol, especially preferably aliphatic alcohol, its reason is that polyamides is sub- The dissolubility of amine presoma uprises.

There is suitable carbon number and/or the position of substitution as described above, there is the molten of polyimide precursor The tendency that solution property uprises.

There is no particular restriction for the steam pressure difference of solvent orange 2 A and solvent B, especially preferably below 10000Pa, more preferably Below 5000Pa, more preferably below 1000Pa.Additionally, there is no lower limit, steam pressure difference can be zero.And then, solvent orange 2 A is with molten Any one Gao Junke of the vapour pressure of agent B.

It is particular range by steam pressure difference, thus the concentration of polyimide precursor compositions when the films such as coating are formed Change diminishes, and therefore there is the tendency of the film of the uniformity of composition in acquisition suppression albefaction, film and the flatness excellence of film.And then There is the tendency that the residual solvent in the film after the dried of film or heating tails off.

There is no particular restriction for the boiling-point difference of solvent orange 2 A and solvent B, preferably less than 100 DEG C, more preferably less than 80 DEG C, enters One step is preferably less than 50 DEG C.Additionally, there is no lower limit, boiling-point difference can be zero.And then, any one is high for solvent orange 2 A and the boiling point of solvent B ?.

It is particular range by boiling-point difference and the concentration change of polyimide precursor compositions diminishes when film is formed, because of The tendency of the film of the flatness excellence of this uniformity that there is composition in acquisition suppression albefaction, film and film.And then there is the dry of film The tendency that residual solvent after dry or in heating caudacoria tails off.

There is no particular restriction for the ratio of solvent orange 2 A and solvent B ratio in whole solvents, and relative to solvent orange 2 A, solvent B is preferred It is below 50 mass %, below more preferably 30 mass %, more preferably below 20 mass %.Furthermore it is preferred that be 0.1 matter Amount more than %, more than more preferably 0.5 mass %, more preferably more than 1.0 mass %.By the ratio of solvent orange 2 A with molten The ratio of the ratio of agent B is this scope, there is the dissolubility maintaining polyimide precursor and the tendency obtaining albefaction inhibition.

The film using above-mentioned solvent to be formed is the most transparent or less colored property excellent, therefore may be suitably used to be coated with material Material, sealer, adhesive agent, set the purposes of standby baseboard and dielectric film etc..

(concentration of compositions)

There is no particular restriction for the viscosity of the compositions of the present invention, with the viscometer of the concentration 20% in 25 DEG C, usual 200cP Above, preferably more than 300cP, more preferably more than 500cP, usually below 200000cP, preferably below 100000cP, More preferably below 80000cP.It is this scope by the viscosity of compositions, deposits process transfiguration during fabrication easily and during masking Thickness easily becomes to be inclined to uniformly.

The viscosity of compositions the most known available method is measured.Such as can use above-mentioned vibrating type viscometer, E Type viscometer etc..

(concentration of compositions)

There is no particular restriction for polyimide precursor contained by the compositions of the present invention and/or the concentration of polyimides, logical It is often more than 3 mass %, more than preferably 5 mass %, more than more preferably 7 mass %, usually below 60 mass %, preferably It is below 50 mass %, below more preferably 45 mass %.It is this scope by concentration, film when there is easily fabricated and masking Thickness easily becomes to be inclined to uniformly.

The concentration of compositions the most known available method is measured.Such as can obtain in aforementioned manners.

(manufacture of the polyimides contained by compositions)

There is no particular restriction for the manufacture method of the polyimides contained by compositions.Such as can use manufacture polyimides forerunner Obtain the method for polyimides after body, directly manufactured the method etc. of polyimides by tetracarboxylic dianhydride and diamine compound.

(method manufactured by polyimide precursor)

Can be by making the polyimide precursor obtained by said method etc. carry out cyclodehydration in the presence of solvent And obtain polyimides.Imidizate can use the most known any means to carry out, and include, for example the heating acyl of thermal cyclization Imidization, the chemical imidization etc. of chemical imidization.These imidization reaction can individually be carried out, it is possible to makes multiple reaction combination Carry out.

(adding hot-imide)

Solvent when carrying out imidizate as making polyimide precursor, can enumerate and above-mentioned acquisition polyimides forerunner The solvent phase used during the reaction of body with solvent.Solvent when polyimides manufactures can use and polyimide precursor system Solvent same solvent when making, it is possible to use different solvents.

Now, imidizate the water produced, owing to can hinder ring-closure reaction, therefore can discharge it to outside system.Acyl is sub- There is no particular restriction for the concentration of polyimide precursor during aminating reaction, usually more than 1 mass %, and preferably 5 mass % Above, usually below 70 mass %, below preferably 40 mass %.By carrying out within the range, there is production efficiency relatively High and can carry out, with easily fabricated solution viscosity, the tendency that manufactures.

There is no particular restriction for imidization reaction temperature, usually more than 50 DEG C, preferably more than 80 DEG C, further preferably It is more than 100 DEG C, usually less than 300 DEG C, preferably less than 280 DEG C, more preferably less than 250 DEG C.By within the range Carry out, there is the tendency that imidization reaction efficiency carries out well and suppresses reaction beyond imidization reaction, the most excellent Choosing.

Pressure during reaction can be normal pressure, pressurize and reduce pressure in any person.Environment can be under air, it is also possible to is for non- Active gas environment.

Additionally, as the imidizate accelerator promoting imidizate, it is possible to add and there is raising nucleophilicity, electrophilicity The compound of effect.Specifically, include, for example Trimethylamine, triethylamine, tripropylamine, tri-butylamine, three ethanol Amine, N, N-dimethylethanolamine, N, N-diethyl ethylene diamine, triethylenediamine, N-crassitude, N-ethyl pyrazole, pyrrole The tertiary amine compounds such as alkane, N-methyl piperidine, N-ethylpiperidine, imidazoles, pyridine, quinoline, isoquinolin；4-hydroxyphenyl acetic acid, 3- The carboxylic acid compounds such as hydroxy benzoic acid, N-acetyl-glycine, N-benzoylglycine；3,5-resacetophenone, 3,5- The polyphenolic substances such as methyl dihydroxy benzoate, 1,2,3,-thrihydroxy-benzene, gallicin, progallin A, naphthalene-1,6-glycol； 2 hydroxy pyrimidine, 3-pyridone, 4-pyridone, 4-piconol, N, N-dimethyl aminopyridine, nicotine aldehyde, nicotimine Aldehyde, picolinic aldehyde, picoline aldoxime, nicotine aldoxime, nicotimine aldoxime, pyridine carboxylic acid ethyl ester, niacin ethyl ester, nicotimine Acetoacetic ester, nicotianamine, nicotimine amide, 2-hydroxyl niacin, 2,2 '-two pyridines, 4,4 '-two pyridines, 3-methyl pyridazine, quinoline The heterocyclic compounds etc. such as quinoline, isoquinolin, phenanthroline, 1,10-phenanthroline, imidazoles, benzimidazole, 1,2,4-triazole.

Among these, preferably tertiary amine compound or heterocyclic compound, more preferably triethylamine, imidazoles or pyridine, its Reason is to exist the tendency of acid imide rate easy to control.These compounds can be used alone a kind, it is possible to by two or more to appoint Meaning ratio and being applied in combination.

About the usage amount of imidizate accelerator, relative to carboxyl or ester group, usually more than 0.01mol%, preferably For more than 0.1mol%, more preferably more than 1mol%.Furthermore it is preferred that be below 50mol%, more preferably below 10mol%. It is in above-mentioned scope by the usage amount of catalyst, there is imidization reaction efficiency and carry out well and acid imide can be obtained Rate obtains the tendency of the polyimides controlled.

Additionally, the opportunity adding imidizate accelerator suitably can adjust according to required acid imide rate, can add Before heat starts, it is possible to hanker adding.In addition, it is possible to add several times.

(chemical imidization)

By making polyimide precursor use dehydrating condensation agent to carry out chemical imidization in the presence of solvent, thus may be used Obtain polyimides.

The solvent used during as chemical imidization, can enumerate the reaction time institute with above-mentioned acquisition polyimide precursor The solvent that the solvent phase used is same.

As dehydrating condensation agent, include, for example N, N-dicyclohexylcarbodiimide, N, N-diphenyl carbon imidodicarbonic diamide Deng N, N-bis-replacement carbon imidodicarbonic diamide；The anhydride such as acetic anhydride, trifluoroacetic anhydride；The chloride such as thionyl chloride, toluene sulfochloride；Second Acyl chlorides, acetyl bromide, propionyl iodide, acetylfluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyl acylbromide, isobutyl Acyl iodides, isobutyl acyl fluorides, n-butyryl chloride, positive butyryl bromide, positive butyryl iodine, positive butyryl fluorine, monochloro chloroacetic chloride, dichloroacetyl chloride, trichlorine Chloroacetic chloride, single bromoacetyl chloride, two bromoacetyl chlorides, tribromo-acetyl chloride, single iodacetyl chloride, two iodacetyl chlorides, triiodoacetyl chloride, single fluorine Chloroacetic chloride, difluoroacetic acid chloride, trifluoro-acetyl chloride, monochloroacetic acid anhydride, phenyl phosphonyl chloride, thionyl chloride, thionyl bromide, thionyl The halogenated compound such as iodine, thionyl fluoride；The phosphorus compounds etc. such as Phosphorous chloride., triphenyl phosphite, cyaniding diethyl phosphate.

Among these, preferably anhydride and halogenated compound, the most more preferably anhydride, there is imidizate because being in it Reaction efficiency carries out and can obtain acid imide rate obtaining the tendency of the polyimides controlled well.These compounds can be single Solely use a kind, it is possible to two or more with arbitrary ratio and be applied in combination.

The usage amount of these dehydrating condensation agents, relative to polyimide precursor 1mol, usually more than 0.1mol, preferably For more than 0.2mol, usually below 1.0mol, preferably below 0.9mol.By dehydrating condensation agent being set to this scope, can To control acid imide rate.

There is no particular restriction for the concentration of polyimide precursor during imidization reaction, usually more than 1 mass %, excellent Elect more than 5 mass % as, usually below 70 mass %, below preferably 40 mass %.By being set to this scope, exist controlled Acid imide rate processed, production efficiency are higher and can manufacture the tendency that easily fabricated solution viscosity carries out manufacturing.

There is no particular restriction for imidization reaction temperature, usually more than 0 DEG C, preferably more than 10 DEG C, and more preferably 20 More than DEG C, usually less than 150 DEG C, preferably less than 130 DEG C, more preferably less than 100 DEG C.By carrying out within the range, There is imidization reaction efficiency to carry out well and acid imide rate can be obtained obtaining the tendency of the polyimides controlled, because of This is preferred.And then the side reaction beyond suppression imidization reaction, the most preferably.

Pressure during reaction can be normal pressure, pressurize or reduce pressure in any person.Environment can be under air, it is possible to for nonactive Under gaseous environment.

In addition, it is possible to add above-mentioned tertiary amines etc. in the same manner as adding hot-imide as the catalysis promoting imidizate Agent.

(method being manufactured polyimides with diamine compound by tetracarboxylic dianhydride)

The most known method can be used to be directly obtained polyimides by tetracarboxylic dianhydride with diamine compound.The method is Start the stopping without reaction or the isolation of presoma from polyimides precursor synthesis and carry out imidizate until realizing Method till imidizate.

Tetracarboxylic dianhydride is not particularly limited with order of addition or the adding method of diamine compound, depends on the most in a solvent Sequence puts into tetracarboxylic dianhydride and diamine compound, persistently carries out until realizing stirring at a temperature of imidizate making reaction Mix, thus obtain polyimides.

The amount of diamine compound, relative to tetracarboxylic dianhydride 1mol, usually more than 0.7mol, preferably 0.8mol with On, usually below 1.3mol, preferably below 1.2mol.By the amount of diamine compound is set to above-mentioned scope, existing can The tendency that the productivity of polyimide compositions obtain polyimides that acid imide rate obtains controlling, being obtained improves.

Tetracarboxylic dianhydride in solvent and the concentration of diamine compound can according to each condition or the viscosity in being polymerized and suitable Setting, tetracarboxylic dianhydride there is no setting especially, relative to total liquid measure, usually 1 mass % with the total quality of diamine compound Above, more than preferably 5 mass %, usually below 70 mass %, below preferably 40 mass %.By the concentration in solvent For proper range, there is molecular weight and easily extend and stir the tendency the most easily carried out.

As the solvent used in this reaction, used when can enumerate the reaction with above-mentioned acquisition polyimide precursor The solvent that solvent phase is same.

Additionally, also obtained with by polyimide precursor by the situation of tetracarboxylic dianhydride with diamine compound acquisition polyimides The situation of polyimides similarly can use and adds hot-imide and/or chemical imidization.Heating acyl during this situation is sub- The reaction conditions of amination or chemical imidization etc. are same as described above.

(the reprecipitation re-dissolved of the polyimides contained by compositions)

The polyimides obtained can use directly as polyimide compositions, or can also be bad by making an addition to Making polyimides in solvent is to be re-dissolved in other solvents after solid, shaped separates out and use as polyimide compositions.

There is no particular restriction for poor solvent now, can suitably select according to polyimides kind, include, for example two The ether series solvent such as ether, diisopropyl ether；The ketone series solvents such as acetone, methyl ethyl ketone, isobutyl ketone, methyl iso-butyl ketone (MIBK)；Methanol, The alcohol series solvent such as ethanol, isopropanol etc..Wherein be preferably the alcohol series solvent such as isopropanol, its reason be existence can efficiency well Obtain precipitate, boiling point relatively low and be prone to dry tendency.These solvents can be used alone a kind, it is also possible to by two or more to appoint Meaning ratio and being applied in combination.

Additionally, as making the solvent of polyimides re-dissolved, include, for example hexane, hexamethylene, heptane, benzene, toluene, two The hydrocarbon system solvents such as toluene, sym-trimethylbenzene., methyl phenyl ethers anisole；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-methyl-2-pyrrole The amide series solvents such as pyrrolidone；The non-proton series solvent such as dimethyl sulfoxide；Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol The glycol series solvents etc. such as dimethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate.Wherein, especially preferably methyl phenyl ethers anisole, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, METHYLPYRROLIDONE, glycol dimethyl ether and ethylene glycol list first Ether.These solvents can be used alone a kind, it is possible to two or more with arbitrary ratio and is applied in combination.

As long as the compositions of the present invention is without departing from the purport of the present invention, other solvents the most also can be comprised.Its kind there is no spy Not limiting, preferably alcohol, its reason is that coating becomes good.Preferably alcohol is same as described above.

In the compositions of the present invention, the coupling agent such as silane coupler, titanium coupling agent can be added, with regulation with body to be coated it Between adhesiveness.

As silane coupler, include, for example γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy Silane, 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, γ-ammonia Base butyl triethoxysilane, gamma-amino butyl trimethoxy silane, gamma-amino butyl tripropoxy silane, gamma-amino fourth Base three butoxy silane etc..

As titanium coupling agent, include, for example gamma-amino propyl triethoxy titanium, gamma-amino propyl trimethoxy titanium, Gamma-amino propyl group tripropoxy titanium, gamma-amino propyl group three titanium butoxide, gamma-amino ethyl triethoxy titanium, gamma-amino ethyl Trimethoxy titanium, gamma-amino ethyl tripropoxy titanium, gamma-amino ethyl three titanium butoxide, gamma-amino butyl triethoxy titanium, Gamma-amino butyl trimethoxy titanium, gamma-amino butyl tripropoxy titanium, gamma-amino butyl three titanium butoxide etc..

These coupling agents can be used alone a kind, it is possible to two or more with arbitrary ratio and is applied in combination.Use now Amount, being preferably relative to polyimides is below more than 0.1 mass %, 3 mass %.

It addition, various additive the most also can be mixed.Such as can mix it in the range of lossless effect of the present invention His powder, granular, the inorganic system filler of tabular, threadiness etc. or organic system filler.

These filleies can use non-woven fabrics etc. to be such as processed into flat filler, it is possible to is used in mixed way multiple.Enter And the most also can mix be generally used in resin combination various and add agent, such as lubricant, coloring agent, stabilizer, anti- Oxidant, UV absorbent, antistatic additive, fire retardant, plasticizer, releasing agent etc..These various filleies and adding ingredients Can add in manufacturing the either phase of either step of polyimides.

(polyimides)

The polyimides of the present invention comprises tetrabasic carboxylic acid residue and diamidogen residue, and tetrabasic carboxylic acid residue has in III group 1 Planting the structure division of above structure division and more than a kind in IV group, diamidogen residue has the knot represented by formula (11) Structure part.

III group: represent following formula (7) and formula (8).

[changing 18]

[in formula (7),

X¹Represent the key of Direct Bonding, alkylidene, carbonyl, ehter bond or sulfonyl.]

[changing 19]

IV group: represent following formula (9) and formula (10).

[changing 20]

[in formula (9),

N ' and m ' represents 0 or 1 independently of one another,

R⁵And R⁶Represent alkyl, thiazolinyl or aromatic rings independently of one another.R⁵And R⁶May be the same or different, or also can shape Cyclization.]

[changing 21]

[in formula (10),

Y ' represents key or the divalent organic group of Direct Bonding.]

[changing 22]

[in formula (11),

R⁷And R⁸Represent alkyl, alkoxyl, amino or hydroxyl independently of one another.]

The X of formula (7)¹With the X synonym of formula (1), preferred scope and the substituent group also synonym that can have.

The n ' and m ' of formula (9) respectively with n and the m synonym of formula (3), preferred scope also synonym.Also, R⁵And R⁶Respectively with formula (3) R¹And R²Synonym, preferred scope and the substituent group also synonym that can have.

The Y ' of formula (10) and the Y synonym of formula (4), preferred scope and the substituent group also synonym that can have.

The R of formula (11)⁷And R⁸Respectively with the R of formula (5)³And R⁴Synonym, preferred scope and the substituent group that can have are also same Justice.

The polyimides of the present invention also can contain without departing from the spirit and scope of the invention and has above-mentioned formula (7), formula (8), formula (9) and the structure division represented by formula (10) are with the tetrabasic carboxylic acid residue of epigenesist.Additionally, also can be containing having formula (11) institute The structure division of expression is with the diamidogen residue of epigenesist.

Residual with the tetrabasic carboxylic acid of epigenesist as the structure division that there is above-mentioned formula (7), formula (8), formula (9) and formula (10) represented Base, can enumerate as having above-mentioned formula (1), formula (2), formula (3) and the structure division represented by formula (4) residual with the tetrabasic carboxylic acid of epigenesist The tetrabasic carboxylic acid residue derived by tetracarboxylic dianhydrides such as aromatic tetracarboxylic acid's dianhydride and aliphatic tetracarboxylic dianhydrides cited by base.

As having the diamidogen residue with epigenesist of the structure division represented by above-mentioned formula (11), can enumerate as having above-mentioned Structure division represented by formula (5) is with the diamidogen residue derived by diamine compound cited by the diamidogen residue of epigenesist.

The polyimides of the present invention is preferably containing tetrabasic carboxylic acid residue and/or the diamidogen residue with crooked position, and it is former Because being to exist the tendency of raising optical characteristics.

As having tetrabasic carboxylic acid and/or the diamidogen residue of crooked position, sub-with the polyamides in the compositions of the invention described above The tetrabasic carboxylic acid with crooked position that amine presoma and/or polyimides can contain and/or diamidogen residue synonym, preferably scope is also Synonym.

There is the structure division represented by formula (11) with in the diamidogen residue of epigenesist, it is however preferred to have represented by formula (12) The diamidogen residue of structure division, its reason is that optical characteristics improves.

[changing 23]

[in formula (12),

Z ' represents the key (refer between functional group not the Direct Bonding via other elements) of Direct Bonding, sulfonyl, alkylene Base, carbonyl or ehter bond,

A ' and B ' represents the key of Direct Bonding, divalent aromatic rings, divalent heterocycle or phenylate base independently of one another.]

Z ', A ' and the B ' of formula (12) is respectively with Z, A and B synonym of formula (6), preferred scope and the substituent group that can have also Synonym respectively.

Structure division contained by polyimides can resolve the composition of starting monomer by solid NMR, IR etc. and obtain.

Additionally, can by with utilize after alkali dissolution gas chromatography (GC),¹H-NMR、¹³C-NMR, two-dimentional NMR and mass spectrum divide Analyse and wait and obtain.

The shape of the polyimides of the present invention is not particularly limited, such as, can be made into powder, graininess, membranaceous etc. various Form.

The polyimides of the present invention preferably dissolves in solvent.What is called dissolves in solvent, as defined above, is used molten Agent also synonym.By dissolving in solvent, it is thus possible to carry out casting or the processing such as coating, now anti-owing to being not accompanied by imidizate Should, therefore can be processed in a mild condition.Additionally, the storage stability of solution can be improved.

(character of polyimides)

Character and the character of the polyimides of the present invention obtain purport without departing from the present invention, then there is no particular restriction.

There is no particular restriction for the hot strength of the polyimides of the present invention, usually more than 50MPa, preferably 70MPa with On, usually below 400MPa, preferably below 300Mpa.

There is no particular restriction for tensile modulus of elasticity, usually more than 1000MPa, preferably more than 1500MPa, usually Below 20GPa, preferably below 10GPa.

There is no particular restriction for tensile elongation, usually more than 5%GL, preferably more than 10%GL, more preferably More than 20GL%, usually below 300%GL, preferably below 200GL%.

By being in scope as above, thus there is intensity, especially useful when making film.These hot strengths, Tensile modulus of elasticity and tensile elongation, such as, can obtain by being measured membranaceous polyimides with cupping machine.

There is no particular restriction for the glass transition temperature of the polyimides of the present invention, usually more than 100 DEG C, and preferably 150 More than DEG C, more preferably more than 200 DEG C.It is this scope by glass transition temperature, thermostability can be obtained.Glass transition temperature example It is measured such as by using differential scanning calorimetry mensuration, determination of viscoelasticity, TG-DTA Synchronization Analysis etc..

The linear expansion coefficient of the polyimides of the present invention in the scope of 100 DEG C to 150 DEG C, usually below 60ppm/K, Be preferably below 50ppm/K, more preferably below 45ppm/K, more preferably 40ppm/K, especially preferably 30ppm/K with Under.By for this scope, such as, when using polyimides as film production equipment, dimensional stability is higher, electronic component or filter The components such as color device are not susceptible to fracture, deformation etc., the most preferably.Assay method is not particularly limited, such as, can use membranaceous poly- The method of acid imide embodiment is measured.

About the transmitance of the polyimides of the present invention, making film and during situation that its thickness is 1～100 μm, right The transmitance of the light of 500nm is usually more than 55%, and preferably more than 60%, more preferably more than 70%.By becoming this Scope, can be efficiently used the luminous efficiency of equipment.Transmitance may utilize the method that JIS K 7361-1 (1997) records and enters Row measures.

The delayed when polyimides of the present invention makes film, if at the wavelength used, such as equipment purposes then 400 ～under any wavelength between 800nm, delayed (Rth) in film thickness direction usually below 300nm, preferably below 200nm, More preferably below 170nm, more preferably below 150nm, more preferably below 140nm, especially preferably 120nm Below.In the face of film, delayed (RO) in direction usually below 10nm, preferably below 5nm, more preferably below 3nm, enters one Step is preferably below 1nm.By becoming this scope, the visual field property of equipment improves, the most preferably.

The polyimides of the present invention is useful to film purposes.Additionally, be not limited only to film purposes, it is possible to be applied to extensive use. Such as can be used for manufacture pliability solar cell component, display component, liquid crystal display carrier, high temperature insulation adhesive tape, Heat-resisting adherent zone, or capacitor or pliability printed base plate film etc..Additionally, such as can also be used for manufacturing through glass fibre or The structural elements of the reinforcement such as carbon fiber, the spool of small coil or the formed products etc. of end insulation pipe.

Additionally, can be used for manufacturing the stacking materials such as insulation spacer, magnetic head pad or transformer cushion block.Also, can be used for manufacturing electricity The enamel-cover materials such as the insulation-coated material of line cable, cryopreservation tank, the heat insulation material in universe or integrated circuit.Can be additionally used in manufacture to have The line of thermostability, spin cloth or non-woven fabrics etc..

(polyimide film)

In addition to using the polyimide film of polyimides having the present invention, it also may be preferable for ground uses has following characteristics Polyimide film.

That is, the present invention also relates to a kind of polyimide film, it is the polyimides comprising tetrabasic carboxylic acid residue with diamidogen residue Film, it is characterised in that in above-mentioned tetrabasic carboxylic acid residue and diamidogen residue at least any one has crooked position, polyimide film Linear expansion coefficient is below 60ppm/K, and delayed for below 200nm.

The definition of at least any one crooked position being had in tetrabasic carboxylic acid residue and diamidogen residue and above-mentioned bending section Position is identical, and preferred structure is the most identical.

As long as the linear expansion coefficient of polyimide film is below 60ppm/K, preferably below 50ppm/K, more preferably For below 45ppm/K, more preferably 40ppm/K, especially preferably below 30ppm/K.Also, there is no lower limit, the lowest more good. By for this scope, such as, when using polyimides making apparatus as film, dimensional stability is higher, electronic component or filter The components such as color device are not susceptible to fracture, deformation etc., the most preferably.Assay method is not particularly limited, such as, can use membranaceous poly- Acid imide utilizes the method for embodiment to be measured.

The linear expansion coefficient making polyimide film becomes the method for below 60ppm/K and is not particularly limited, such as, make With comprising the above-mentioned polyimide precursor method with at least compositions of any one in polyimides, adding filler etc. These are suitably adjusted by method, the method etc. stretched by film, thus can make on the linear expansion coefficient of polyimide film becomes In the range of stating.

Filleies etc. are not particularly limited, and include, for example powder, granular, the inorganic system filling of tabular, threadiness etc. Agent or organic system filler etc..

As inorganic system filler, include, for example in silicon dioxide, kieselguhr, barium ferrite, beryllium oxide, Pumex, Pumex The oxides such as empty ball；The hydroxide such as aluminium hydroxide, magnesium hydroxide, alkaline magnesium carbonate；Calcium carbonate, magnesium carbonate, dolomite, carbon sodium The carbonate such as aluminum stone；Sulfate and the sulphite such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite；Talcum, clay, Muscovitum, The silicate such as asbestos, glass fibre, glass hollow ball, glass beads, calcium silicates, montmorillonite, bentonite；Carbon fiber, carbon black, stone The carbons such as ink, carbon hollow ball；Powder, granular, the plates such as molybdenum sulfide, Firebrake ZB, barium metaborate, Calcium pyroborate, sodium borate, boron fibre Shape, fibrous inanimate matter filler；The powders such as metallic element, metallic compound, alloy, granular, fibrous, crystal whisker-shaped Metal filler；Powder, granular, fibrous, the whiskers such as carborundum, silicon nitride, zirconium oxide, aluminium nitride, titanium carbide, potassium titanate The ceramic filler etc. of shape.

On the other hand, as organic system filler, include, for example CNT, fullerene, aromatic polyamide fibre, Cellulose fibre, nylon fiber, polyester fiber, polypropylene fibre, thermosetting powders, rubber etc..

As filler, it is possible to use non-woven fabrics etc. are processed into flat filler, it is possible to be used in mixed way by multiple material.

Linear expansion coefficient can be measured by thermomechanical device.

As long as polyimide film delayed be below 200nm, preferably below 170nm, more preferably 150nm with Under, more preferably below 140nm, especially preferably below 120nm.In the face of film, delayed (RO) in direction is usually 10nm Above, preferably below 5nm, more preferably below 3nm, more preferably below 1nm.By becoming this scope, equipment Visual field property improves, the most preferably.

The method making delayed below the 200nm of becoming of polyimide film is not particularly limited, such as by using use bag Method containing above-mentioned polyimide precursor and at least compositions of any one in polyimides, mix there is negative delayed change Compound or the method for resin, use the method etc. that the base material that linear expansion coefficient is identical with polyimides is filmed, polyamides can be made The delayed of imines film becomes in above-mentioned scope.

There is negative delayed compound or resin is not particularly limited, include, for example styrenic, acrylic acid Based compound, phenylethylene resin series, acrylic resin etc..

As the base material that linear expansion coefficient is identical with polyimides, metal forming, resin substrate etc. can be enumerated.

Delayed phase retardation film-the optical material that passes through checks that device etc. is measured.

The transmitance of the polyimide film of the present invention, when the situation that its thickness is 1～100, saturating to the light of 500nm The rate of mistake is usually more than 55%, and preferably more than 60%, more preferably more than 70%.By becoming this scope, can effectively make By the luminous efficiency of equipment.Transmitance may utilize the method that JIS K 7361-1 (1997) records and is measured.

About the polyimide film of the present invention, the yellow chromaticity (yellow colour index: YI) during thickness 10 μm is usually more than-10, It is preferably more than-5, more preferably more than-1.On the other hand, usually less than 20, preferably less than 15, more preferably 10 with Under.By becoming this scope, when polyimides being made element of installation and using, luminous efficiency can be efficiently used.Yellow refers to Numerical example is measured such as by use spectral photometric colour measuring meter etc..

There is no particular restriction for the thickness of polyimide film, usually more than 1 μm, more than preferably 2 μm, on the other hand, logical It is often below 200 μm, below preferably 100 μm.Suitable by the thickness of film, abundant patience can be kept, and flexible setting can be realized Standby slimming.

(manufacture method of polyimide film)

There is no particular restriction the manufacture method of the polyimide film of the present invention, such as can be by being obtained by said method Compositions containing polyimide precursor and/or polyimides makes solvent volatilization obtain after coating on carrier substrate.Coating As long as method can form the method for layer in uniform thickness, then there is no particular restriction, include, for example die coating, rotates painting Cloth, screen painting, spray, use applicator casting method, use the method for coating machine, spray attachment method, infusion process, rolling process, stream Prolong method etc..These methods suitably can select according to shape of spreading area and applied etc..

As the substrate of applied material, such as, can use the glass such as float glass, soda-lime glass, poly terephthalic acid second two The substrate that the plastics such as ester, Merlon, polyolefin are constituted.When aforesaid substrate is coated, it is possible in advance substrate surface is coated to Compound containing functional silanes, the compound containing functionality titanium.Again, it is possible to carry out UV treatment, Cement Composite Treated by Plasma etc..

Also there is no particular restriction to make the method that the solvent of polyimide precursor and/or polyimide compositions volatilizees.Logical Heat usually through the method making solvent under reduced pressure volatilize and/or to the applied material being coated with, solvent can be made to volatilize. Heating means are not particularly limited, can enumerate Hot-blast Heating, heating in vacuum, infrared heating, microwave heating, use heating plate or The heating etc. carried out by contact of heating roller etc..

Heating-up temperature when making solvent volatilize can use suitable temperature according to solvent species, usually more than 20 DEG C, It is preferably more than 40 DEG C, more preferably more than 50 DEG C, more preferably more than 60 DEG C.Additionally, usually less than 400 DEG C, excellent Elect less than 380 DEG C as, more preferably less than 350 DEG C, more preferably less than 300 DEG C.It is more than above-mentioned lower limit by temperature, Residual solvent can be reduced, be allowed to dry fully.Additionally, by below for the above-mentioned upper limit, can suppress because drastically volatilization is produced Bubble etc., keep outward appearance or quality well.

Heating environment can be under air, it is possible to under non-reactive gas ambient, there is no particular restriction, polyimide film When seeking colorless transparency, in order to suppress coloring, it is preferably and heats under the non-reactive gas ambient such as nitrogen.

By through above-mentioned coating, be dried and method that the polyimide film that is formed on carrier is peeled off there is no particular restriction, Include, for example laser lift-off, mechanical stripping, by impregnated in stripping etc. in water or hot water.

Employ the film of polyimide precursor compositions and/or the method for polyimide film as manufacturing, can enumerate and make The method that above-mentioned polyimide precursor resin and/or polyimide resin melt postforming, such as injection molding molding method, squeeze Go out forming process, hollow forming method, compression forming method, stratification method, roll-in processing method, stretch process method, punch process method, heat Platen press, T modulus method etc..

Embodiment

It is exemplified below embodiment and comparative example illustrates in greater detail the present invention.Furthermore, below example is in order in detail Illustrate that the present invention illustrates, as long as the present invention does not runs counter to its purport, be then not limited to below example.Furthermore, below It is excellent that various conditions in embodiment or the value of assessment result also have as the upper limit in embodiments of the present invention or lower limit The implication of the value of choosing, preferred scope can be according between the above-mentioned upper limit or the value of lower limit and the value of embodiment or embodiment Value combination defined scope.

Embodiment 1

3,3 ', 4,4 '-biphenyl tetracarboxylic acid is added in the four-hole boiling flask possessing nitrogen reflux ingress pipe, condenser and blender Acid dianhydride (BPDA) 5.7g (0.019mol), 3,3 ', 4,4 '-bicyclohexane tetracarboxylic dianhydride (H-BPDA) 2.6g (0.009mol), pyromellitic dianhydride (PMDA) 1.4g (0.006mol), 2,2 '-bis-(trifluoromethyl) benzidine (6F-m-TB) 5.6g (0.018mol), 4,4 '-DADPS 4.3g (0.018mol) and METHYLPYRROLIDONE (NMP) 73g.Limit Stir this mixture limit to heat up, react 6 hours at 80 DEG C, it is thus achieved that the compositions 1 containing polyimide precursor.

(making of polyimide film)

The compositions 1 obtained is coated on glass substrate by the applicator using 100 μm, heats 30 minutes at 350 DEG C, It is derived from the polyimide film 1 of thickness 10 μm.

(mensuration of linear expansion coefficient (CTE))

Utilize width 4mm, the straight knife cutter (Super Straight Cutter) of length 40mm is punched in temperature 25 DEG C, in the thermostatic constant wet chamber of humidity 50% through the polyimide film 1 of an above damping in evening, use SII Nano The TMA/SS6100 that Technology company manufactures is measured.By the jaw separation at membrane sample from 10mm, nitrogen 120mL/ Min, it is recorded in table 2 with the CTE between in time being warming up to 210 DEG C for 30 DEG C 100 DEG C and 150 DEG C of 10 DEG C/min programming rate.

(mensuration of delayed (Rth) value of the thickness direction of film)

Use and measure phase retardation film-optical material inspection device (" RETS100 " that great Zhong electronics corporation manufactures), measure also Calculate delayed (Rth) value of the film thickness direction of polyimide film 1.Measurement result is shown in table 2.The thickness of the film this time used Delayed (Rth) value in direction is value when wavelength 460nm, film thickness 10 μm.

(mensuration of yellow colour index (YI) value)

The SM color computer SM5 using Suga Test Instruments (strain) to manufacture measures polyimides Yellow colour index (YI) value of film 1.The YI value this time used is the value that the YI value as every 10 μm thickness is calculated.

[embodiment 2]

The BPAD of embodiment 1 is changed to 1.7g (0.006mol), H-BPDA is changed to 1.8g (0.006mol), PMDA change Be changed to 5.5g (0.017mol) for 3.9g (0.018mol), 6F-m-TB, 4,4 '-diamino diphenyl sulfone is changed to 3.2g (0.013mol), NMP is changed to 65g, in addition, by method acquisition polyimide precursor compositions 2 same as in Example 1 And polyimide film 2.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.Show the result in table 2.

[embodiment 3]

The BPAD of embodiment 1 is changed to 5.3g (0.018mol), H-BPDA is changed to 2.5g (0.008mol), PMDA and becomes More 1.3g (0.006mol), 6F-m-TB are changed to 7.9g (0.025mol), 4,4 '-diamino diphenyl sulfone is changed to 2.0g (0.008mol), NMP changes 71g, in addition, by method acquisition polyimide precursor compositions 3 same as in Example 1 And polyimide film 3.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.Show the result in table 2.

[embodiment 4]

The BPAD of embodiment 1 is changed to 5.4g (0.018mol), H-BPDA is changed to 2.5g (0.008mol), PMDA change Be changed to 9.5g (0.03mol) for 1.3g (0.006mol), 6F-m-TB, 4,4 '-diamino diphenyl sulfone is changed to 0.8g (0.003mol), NMP is changed to 78g, in addition, by method acquisition polyimide precursor compositions 4 same as in Example 1 And polyimide film 4.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.Show the result in table 2.

[embodiment 5]

To possess nitrogen reflux ingress pipe, condenser, fill toluene Dean-Stark (Dean-Stark) agglomerator and BPDA4.9g (0.017mol), H-BPDA2.3g (0.007mol), PMDA1.2g is added in the four-hole boiling flask of blender (0.006mol), 6F-m-TB 8.6g (0.027mol), 4,4 '-diamino diphenyl sulfone 0.7g (0.003mol), NMP 71g and Toluene 14g.It is heated to reflux at 200 DEG C 13 hours while stir this mixture limit, it is thus achieved that polyimide compositions 5.

[embodiment 6]

The BPAD of embodiment 1 is changed to 4.1g (0.014mol), H-BPDA is changed to 2.1g (0.007mol), PMDA and becomes More 1.9g (0.009mol), 6F-m-TB are changed to 8.4g (0.026mol), 4,4 '-diamino diphenyl sulfone is changed to 2.2g (0.009mol), NMP be changed to 82g, and add 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride 1.9g (0.005mol), except this In addition, polyimide precursor compositions 6 and polyimide film 6 are obtained by method same as in Example 1.With embodiment 1 phase Carry out together the mensuration of CTE, Rth and YI of polyimide film.Show the result in table 2.

[embodiment 7]

The BPDA of embodiment 6 is changed to 5.4g (0.018mol), H-BPDA is changed to 1.2g (0.004mol), PMDA and becomes More 1.3g (0.006mol), 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride are changed to 1.5g (0.004mol), 6F-m-TB and become More 7.9g (0.025mol), 4,4 '-diamino diphenyl sulfone is changed to 2.0g (0.008mol), NMP is changed to 78g, except this In addition, polyimide precursor compositions 7 and polyimide film 7 are obtained by method same as in Example 6.With embodiment 1 phase Carry out together the mensuration of CTE, Rth and YI of polyimide film.Show the result in table 2.

[embodiment 8]

The BPDA of embodiment 6 is changed to 5.4g (0.018mol), H-BPDA is changed to 2.0g (0.007mol), PMDA and becomes More 1.3g (0.006mol), 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride are changed to 0.6g (0.002mol), 6F-m-TB and become More 7.9g (0.025mol), 4,4 '-diamino diphenyl sulfone is changed to 2.0g (0.008mol), NMP is changed to 77g, except this In addition, polyimide precursor compositions 8 and polyimide film 8 are obtained by method same as in Example 6.With embodiment 1 phase Carry out together the mensuration of CTE, Rth and YI of polyimide film.Show the result in table 2.

[embodiment 9]

The BPDA of embodiment 6 is changed to 5.9g (0.019mol), H-BPDA is changed to 1.9g (0.006mol), PMDA and becomes More 1.4g (0.006mol), 6F-m-TB are changed to 7.7g (0.024mol), 4,4 '-diamino diphenyl sulfone is changed to 1.2g (0.005mol), NMP be changed to 76g, and by 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride is changed to 9, double (the 4-aminobenzene of 9- Base) fluorenes 1.1g (0.003mol), in addition, with method same as in Example 6 obtain polyimide precursor compositions 9 and Polyimide film 9.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.Show the result in table 2.

[embodiment 10]

The BPDA of embodiment 6 is changed to 9.8g (0.033mol), H-BPDA is changed to 2.3g (0.007mol), PMDA and becomes More 2.4g (0.011mol), 6F-m-TB are changed to 18.0g (0.056mol), 4,4'-diamino diphenyl sulfone is changed to 4.7g (0.019mol), NMP be changed to 141g, and by 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride is changed to 2,2-double (3,4-bis- Carboxyl phenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride 9.9g (0.022mol), in addition, with side same as in Example 6 Method obtains polyimide precursor compositions 10 and polyimide film 10.Carry out polyimide film same as in Example 1ly The mensuration of CTE, Rth and YI.Show the result in table 2.

[embodiment 11]

The BPDA of embodiment 10 is changed to 3.8g (0.013mol), H-BPDA is changed to 2.0g (0.007mol), PMDA It is changed to double (3,4-the dicarboxyphenyi)-1,1,1,3,3,3-hexafluoropropane dianhydride of 1.7g (0.008mol), 2,2-be changed to 2.1g (0.005mol), 6F-m-TB are changed to 7.9g (0.025mol), 4,4 '-diamino diphenyl sulfone is changed to 2.0g (0.008mol), NMP is changed to 79g, in addition, with method acquisition polyimide precursor combination same as in Example 10 Thing 11 and polyimide film 11.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.Result is shown In table 2.

[embodiment 12]

The BPDA of embodiment 10 is changed to 6.6g (0.022mol), H-BPDA is changed to 2.2g (0.007mol), PMDA Be changed to 4.9g (0.022mol), NMP is changed to 139g, in addition, obtains polyamides by method same as in Example 10 sub- Amine precursor composition 12 and polyimide film 12.Carry out the survey of CTE, Rth and YI of polyimide film same as in Example 1ly Fixed.Show the result in table 2.

[embodiment 13]

The BPDA of embodiment 9 is changed to 5.2g (0.018mol), H-BPDA is changed to 1.8g (0.006mol), PMDA and becomes More 1.3g (0.006mol), 6F-m-TB are changed to 6.2g (0.020mol), 4,4 '-diamino diphenyl sulfone is changed to 1.9g (0.008mol), NMP be changed to 53g, and by 9, double (4-aminophenyl) fluorenes of 9-is changed to 2, double (the 3-amino-4-hydroxy benzene of 2- Base)-HFC-236fa 1.1g (0.003mol), in addition, obtain polyimide precursor group by method the same as in Example 9 Compound 13 and polyimide film 13.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.By result It is shown in table 2.

[embodiment 14]

The BPAD of embodiment 1 is changed to 6.6g (0.022mol), H-BPDA is changed to 3.0g (0.010mol), PMDA and becomes More 1.6g (0.007mol), 6F-m-TB are changed to 9.6g (0.030mol), NMP is changed to 73g, and by 4,4 '-diaminourea two Phenylsulfone is changed to Isosorbide-5-Nitrae-bis-[2-(4-aminophenyl)-2-propyl group] benzene 3.4g (0.010mol), in addition, uses and embodiment 1 identical method obtains polyimide precursor compositions 14 and polyimide film 14.Carry out polyamides sub-same as in Example 1ly The mensuration of CTE, Rth and YI of amine film.Show the result in table 2.

[embodiment 15]

Double for the 1,4-of embodiment 14 [2-(4-aminophenyl)-2-propyl group] benzene are changed to double [2-(the 4-aminobenzene of 1,3- Base)-2-propyl group] benzene, in addition, obtain polyimide precursor compositions 14 and polyamides by the method identical with embodiment 13 Imines film 14.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.Show the result in table 2.

[comparative example 1]

BPDA 4.4g is added in the four-hole boiling flask possessing nitrogen reflux ingress pipe, condenser and blender (0.015mol)、H-BPDA 2.3g(0.008mol)、PMDA 3.3g(0.015mol)、6F-m-TB 12.2g(0.038mol) And NMP76g.Heat up while whisk this mixture limit, react 6 hours at 80 DEG C, it is thus achieved that containing the combination of polyimide precursor Thing 16.From the compositions 16 obtained, obtain polyimide film 16 same as in Example 1ly.Gather same as in Example 1ly The mensuration of CTE, Rth and YI of acid imide film.Show the result in table 2.

[comparative example 2]

H-BPDA 1.8g is added in the four-hole boiling flask possessing backflow nitrogen ingress pipe, condenser and blender (0.006mol), PMDA 5.2g (0.024mol), 6F-m-TB 7.2g (0.023mol), 4,4 '-diamino diphenyl sulfone 1.9g (0.008mol) and NMP 64g.Heat up while stir this mixture limit, react 6 hours at 80 DEG C, it is thus achieved that before polyimides Drive the compositions 17 of body.Obtained polyimide film 17 by the compositions 17 obtained same as in Example 1ly.With embodiment 1 phase Carry out together the mensuration of CTE, Rth and YI of polyimide film.Show the result in table 2.

[comparative example 3]

To possessing backflow nitrogen ingress pipe, condenser, filling the Dean-Stark agglomerator and the four of blender of methyl phenyl ethers anisole BPDA 14.6g (0.050mol), H-BPDA 15.2g (0.050mol), 6F-m-TB 16.0g is added in mouth flask (0.05mol), 4,4 '-diamino diphenyl sulfone 9.9g (0.04mol), 3,3 '-diamino diphenyl sulfone 2.5g (0.01mol), NMP 87g and methyl phenyl ethers anisole 87g.It is heated to reflux at 200 DEG C 13 hours while stir this mixture limit, it is thus achieved that polyimide compositions 18.Obtained polyimide film 18 by the compositions 18 obtained same as in Example 1ly.Carry out polyamides same as in Example 1ly The mensuration of CTE, Rth and YI of imines film.Show the result in table 2.

[comparative example 4]

The BPAD of embodiment 1 is changed to 5.6g (0.019mol), PMDA is changed to 1.4g (0.006mol), 6F-m-TB Be changed to 7.7g (0.024mol), 4,4 '-diamino diphenyl sulfone is changed to 2.0g (0.008mol), NMP is changed to 76g, and H-BPDA is changed to 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride 2.3g (0.006mol), in addition, with embodiment 1 Identical method obtains polyimide precursor compositions 19 and polyimide film 19.Carry out polyamides sub-same as in Example 1ly The mensuration of CTE, Rth and YI of amine film.Show the result in table 2.

[comparative example 5]

BPDA 3.6g is added in the four-hole boiling flask possessing nitrogen reflux ingress pipe, condenser and blender (0.012mol), H-BPDA3.8g (0.012mol), 2,2 '-dimethylbenzidine (m-TB) 5.3g (0.025mol) and N, N-bis- Methylacetamide (DMAc) 38g.Heat up while stir this mixture limit, react 6 hours at 80 DEG C, it is thus achieved that before polyimides Drive the compositions 21 of body.Obtained polyimide film 21 by the compositions 21 obtained same as in Example 1ly.With embodiment 1 phase Carry out together the mensuration of CTE, Rth and YI of polyimide film.Show the result in table 2.

[comparative example 6]

BPDA 5.8g is added in the four-hole boiling flask possessing nitrogen reflux ingress pipe, condenser and blender (0.02mol), 6F-m-TB 6.4g (0.020mol) and DMAC N,N' dimethyl acetamide (DMAc) 37g.While stir this mixture limit Heat up, react 6 hours at 80 DEG C, it is thus achieved that the compositions 22 containing polyimide precursor.Same as in Example 1ly by being obtained The compositions 22 obtained obtains polyimide film 22.Carry out the survey of CTE, Rth and YI of polyimide film same as in Example 1ly Fixed.Show the result in table 2.

[comparative example 7]

H-BPDA 21.2g is added in the four-hole boiling flask possessing nitrogen reflux ingress pipe, condenser and blender (0.069mol), m-TB 14.7g (0.070mol) and DMAc 108g.Heat up while stir this mixture limit, at 80 DEG C, react 6 Hour, it is thus achieved that the compositions 23 containing polyimide precursor.Gathered by the compositions 23 obtained same as in Example 1ly Acid imide film 23.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.Show the result in table 2.

[comparative example 8]

The H-BPDA of comparative example 7 is changed to 6.8g (0.022mol), m-TB is changed to 4,4 '-diamino diphenyl sulfone 5.9g (0.023mol), DMAc are changed to NMP 37g, in addition, before obtaining polyimides by the method identical with comparative example 7 Drive body compositions 24 and polyimide film 24.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly. Show the result in table 2.

[comparative example 9]

The PMDA of comparative example 2 is changed to 3.2g (0.015mol), 6F-m-TB is changed to 8.8g (0.027mol), NMP and becomes More 69g, and H-BPDA is changed to BPDA4.4g (0.015mol), 4,4 '-diamino diphenyl sulfone is changed to 9, the double (4-of 9- Aminophenyl) fluorenes 0.9g (0.003mol), in addition, obtain polyimide precursor group by the method identical with comparative example 2 Compound 25 and polyimide film 25.Carry out the mensuration of CTE, Rth and YI of polyimide film same as in Example 1ly.By result It is shown in table 2.

[reference example 1]

The BPDA of comparative example 6 is changed to double (3,4-the dicarboxyphenyi)-1,1,1,3,3,3-hexafluoropropane dianhydride of 2,2- 8.7g (0.020mol), 6F-m-TB are changed to 6.4g (0.02mol), DMAc is changed to 46g, in addition, with comparative example 6 Identical method obtains polyimide precursor compositions 26 and polyimide film 26.Carry out polyamides sub-same as in Example 1ly The mensuration of CTE, Rth and YI of amine film.Show the result in table 2.

[reference example 2]

Interpolation BPDA2.9g (0.01mol) in the four-hole boiling flask possessing nitrogen reflux ingress pipe, condenser and blender, H-BPDA 3.0g (0.01mol), 6F-m-TB 6.4g (0.020mol) and DMAC N,N' dimethyl acetamide (DMAc) 37g.Limit is stirred Heating up in this mixture limit, reacts 6 hours, it is thus achieved that the compositions 20 containing polyimide precursor at 80 DEG C.With with embodiment 1 Polyimide film 20 is obtained in the same manner by the compositions 20 obtained.Carry out same as in Example 1ly polyimide film CTE, The mensuration of Rth and YI.Show the result in table 2.Additionally, in above-mentioned raw materials, become the side of 200～600cP with composition viscosity Formula adjusts tetracarboxylic dianhydride and obtains compositions 27 relative to the ratio of diamine compound.This ratio is shown in table 3.

Compositions 27 coated on glass substrate same as in Example 1ly and heat.Produce when peeling off the film obtained Be full of cracks, it is impossible to obtain film.

On the other hand, in the way of composition viscosity becomes 200～600cP, adjust the raw material tetracarboxylic acid used in embodiment 7 Acid dianhydride obtains compositions 28 relative to the ratio of diamine compound.This ratio is shown in table 3.

Compositions 28 coated on glass substrate same as in Example 1ly and heat.The film obtained does not produces be full of cracks Deng, can peel off.

[table 1]

[table 2]

[table 3]

As shown in table 2, to have low linear expansion coefficient concurrently delayed with low for the polyimide film 1～15 of the present invention.On the other hand, than Low linear expansion coefficient cannot be had concurrently delayed with low compared with the polyimide film shown in example.

As shown in reference example 2 and table 3, have in the compositions 28 of crooked position, even if it is such to carry out 200～600cP Lowering viscousity also can carry out membranization, and does not have in the compositions 27 of crooked position, if carrying out lowering viscousity, is difficult to membranization, by This demonstrates can obtain the compositions that range of viscosities is wide by having crooked position, is applicable to various coating processes.

Illustrate the present invention in detail and with reference to specific embodiment, but as those skilled in the art for, permissible In the case of without departing from spirit and scope of the invention, apply various change or correction is apparent from.The application be based on Japanese patent application (Japan Patent Patent 2014-032147), on June 26th, 2014 that on February 21st, 2014 files an application carry The Japanese patent application (Japan Patent Patent 2014-131668) going out application and the Japan Patent filed an application on January 6th, 2015 The application of application (Japan Patent Patent 2015-000993), includes in its content in this specification with the form of reference.

[industrial applicability]

The polyimide precursor compositions of the present invention can be used for being coated with cloth material, sealer, adhesive agent, equipment base Plate and dielectric film etc..

Claims

1. a polyimide film, it is characterised in that it is the polyimide film comprising tetrabasic carboxylic acid residue with diamidogen residue,

In described tetrabasic carboxylic acid residue and diamidogen residue at least any one has crooked position,

The linear expansion coefficient of described polyimide film is below 60ppm/K, and delayed for below 200nm.

Polyimide film the most according to claim 1, wherein, the thickness of film be yellow colour index during 10 μm for more than-10, Less than 20.

3. a compositions, it is characterised in that its be comprise in polyimide precursor and polyimides at least any one Compositions,

Described polyimide precursor and polyimides contain tetrabasic carboxylic acid residue and diamidogen residue,

Described tetrabasic carboxylic acid residue have the structure division represented by the structure division represented by following formula (1 '), following formula (2) and Structure division represented by following formula (4 '),

Described diamidogen residue has the structure division represented by following formula (5),

In tetrabasic carboxylic acid residue described further and diamidogen residue at least any one has crooked position,

[changing 1]

Wherein, the symbol in formula represents following meanings,

X²For Direct Bonding key, there is the secondary or key of tertiary carbon atom, or ehter bond,

Compositions the most according to claim 3, wherein, in described tetrabasic carboxylic acid residue, has represented by described formula (4 ') The ratio of the tetrabasic carboxylic acid residue of structure division is more than 2mol%, below 95mol%.

5., according to the compositions described in claim 3 or 4, wherein, in described tetrabasic carboxylic acid residue, there is described formula (1 ') represented The tetrabasic carboxylic acid residue of structure division with the ratio of the tetrabasic carboxylic acid residue sum of the structure division having represented by described formula (2) be More than 5mol%, below 95mol%.

6., according to the compositions described in any one in claim 3～5, wherein, described crooked position is relative to described tetracarboxylic acid Acid residue is more than 0.1mol%, below 150mol% with the ratio of diamidogen residue sum.