CN103842408B - Polyamic acid resin composition, polyimide resin composition and polyimides azoles resin combination and containing their flexible base board - Google Patents

Abstract

Film after the problem of the present invention is to provide heat treatment has thermostability, light transmission, the polyamic acid resin composition of low birefringence, polyimide resin composition and the polyimides azoles resin combination of excellence and contains their flexible base board.Then, it is provided that a kind of polyamic acid resin composition, it is characterised in that containing (a) using the construction unit represented by formula (1) as the polyamic acid of main constituent and (b) solvent.(in formula (1), X₁、X₂Represent hydrogen atom or 1 valency organic group of carbon number 1～10, R independently of one another₁Represent the 4 valency organic groups of carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the 4 valency organic groups of carbon number 4～40 that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure, R₂Represent the divalent organic group of the carbon number 2～40 with at least 2 hydroxyls.).

Description

Polyamic acid resin composition, polyimide resin composition and polyimides azoles Resin combination and containing their flexible base board

Technical field

The present invention relates to polyamic acid resin composition, polyimide resin composition and polyimidesAzoles resin group Compound and containing their flexible base board.More particularly, it relates to can perform well in flat faced display, touch panel, The polyamic acid resin composition of flexible base board, the flexible printed boards etc. such as Electronic Paper, colour filtering chip basic board, solaode, poly- Imide resin compositions and polyimidesAzoles resin combination and containing their flexible base board.

Background technology

Organic membrane has compared with glass and is rich in bendability, characteristic the most broken, lightweight.Recently, by by flat board The substrate of display is changed to organic membrane, makes the research of display pliability become all the more and enlivens.

When making display over an organic film, generally carry out following operation: by organic membrane film forming on supporting substrates, system After making device, peel off from supporting substrates.Just organic membrane for film forming, there is following methods on supporting substrates.Such as, use viscous Organic membrane is attached method (such as, patent documentation 1) on the glass substrate by condensation materials etc..Or, former using containing as film The solution of the resin etc. of material is coated on supporting substrates, utilizes heat etc. to make it solidify, carries out method (the such as patent documentation made 2).The former needs to arrange jointing material between supporting substrates and film, sometimes due to the thermostability of binding agent causes later adding Work temperature is restricted.On the other hand, the latter do not use binding agent, masking caudacoria the aspects such as surface smoothness is high excellent.

As in organic membrane use resin, can enumerate polyester, polyamide, polyimides, Merlon, polyether sulfone, Acrylic resin, epoxy resin etc..Wherein, polyimides, as high-fire resistance resin, is suitable as display base plate.Especially It is polyimide resin, not only there is high-fire resistance, and have high mechanical properties, abrasion performance, dimensional stability, drug-resistant concurrently Property etc. the excellent electrical characteristics such as excellent mechanical property, insulating properties, thus be widely used in electric and electronic industrial field.Make With above-mentioned rubbing method by the situation of polyimides film forming, it is possible to use the solution containing polyamic acid precursor is coated, The method making it solidify and to become polyimides.Generally polyamic acid can hold by making anhydride and diamine reactant in a solvent Change places synthesis.

Although all aromatic polyimides derived by aromatic acid dianhydride and aromatic diamine has high-fire resistance, but There is the absorption band deriving from the visible wavelength territory that electric charge between Intramolecular moves coordination compound, thus obtained Polyimide film is in yellow～dark brown.Additionally, be generally of bigger birefringence.Cannot function as needing height thoroughly to this end, exist The problem that bright property, the display base plate of low birefringence use.Want to use as the substitution material of glass substrate, typically need Wanting: when thickness 10 microns, the light transmission of 400nm is more than 80%, glass transition temperature (Tg) or thermal decomposition start temperature It it it is more than 300 degree, it is seen that the low birefringence that birefringence is less than 0.01 in optical wavelength territory (400nm～800nm).

Electric charge as suppression polyimides moves interaction, the method improving light transmission, can list as acid Arbitrary composition in dianhydride and diamidogen and the method that uses ester ring type monomer.

Such as patent document 3 discloses that the polyamides obtained by ester ring type acid dianhydride and various aromatic series or ester ring type diamidogen is sub- Amine has high transparent, low birefringence.

Patent Document 4 discloses by 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 2,2 '-bis-(trifluoromethyls) connection The polyimides that aniline (TFMB) obtains has high transparent, high Tg.In addition patent documentation 4 describes use 2,2 '-bis-(4- (4-amino-benzene oxygen) phenyl) HFC-236fa (HFBAPP) replaces the polyimide film of 2,2 '-bis-(trifluoromethyl) benzidine to have There is high transparent.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2006-091822 publication

Patent documentation 2: Japanese Unexamined Patent Application Publication 2007-512568 publication

Patent documentation 3: Japanese Unexamined Patent Publication 11-080350 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2010-085992 publication

Summary of the invention

The problem that invention is to be solved

But the Tg of the polyimides group described in patent documentation 3 is insufficiently high.Additionally, described in patent documentation 4 Polyimides group, Tg and birefringence can not meet and common require characteristic.

So, current present situation is the polyamides that high transparent, high-fire resistance, the required characteristic of low birefringence all meet Imines material is the most not well known.

The present invention is in view of above-mentioned problem, and the film after its problem is to provide heat treatment has the thermostability of excellence, light transmission, low The polyamic acid resin composition of birefringence, polyimide resin composition and polyimidesAzoles resin combination and Flexible base board containing them.

Solve the means of problem

In order to solve the problem being recited above, it is achieved purpose, the polyamic acid resin composition of the present invention, its feature exists In, containing (a) using the construction unit represented by formula (1) as the polyamic acid of main constituent and (b) solvent,

In formula (1), X₁、X₂Represent hydrogen atom or 1 valency organic group of carbon number 1～10, R independently of one another₁Represent There are 4 valency organic groups of the carbon number 4～40 of the alicyclic structure of monocyclic or condensed ring formula, or there is monocyclic alicyclic ring knot 4 valency organic groups of the carbon number 4～40 that the organic group of structure directly or is connected to each other via bridge crosslinking structure, R₂Represent There is the divalent organic group of the carbon number 2～40 of at least 2 hydroxyls.

Additionally, the polyimide resin composition of the present invention, it is characterised in that containing (a ') with represented by formula (2) Construction unit as the polyimides of main constituent and (b) solvent,

(in formula (2), R₁Represent that 4 valencys of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula are organic Group, or the carbon number that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure The 4 valency organic groups of 4～40, R₂Represent the divalent organic group of the carbon number 2～40 with at least 2 hydroxyls.)

Additionally, the polyimides of the present inventionAzoles resin combination, it is characterised in that containing (a ' ') with formula (3) institute The construction unit represented is as the polyimides of main constituentAzoles and (b) solvent,

(in formula (3), R₁Represent that 4 valencys of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula are organic Group, or the carbon number that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure The 4 valency organic groups of 4～40, R₃Represent 4 valency organic groups of carbon number 2～40.)

Invention effect

By means of the invention it is possible to obtain the film after heat treatment have excellence thermostability, the high light transmittance of visible region, The polyamic acid resin composition of low birefringence, polyimide resin composition and polyimidesAzoles resin combination with And the flexible base board containing them.

Detailed description of the invention

Below, the mode implementing the present invention is illustrated.Furthermore, be not intended to limit by embodiments below The present invention.Additionally, each figure of institute's reference in the following description, only with it will be appreciated that the degree of present disclosure is big Cause property illustrates shape, size and position relationship.I.e., shape, size and the position illustrated during the present invention is not limited merely to each figure Put relation.

1st scheme of the present invention is a kind of polyamic acid resin composition, it is characterised in that containing (a) with formula (1) institute The construction unit represented is as the polyamic acid of main constituent and (b) solvent.2nd scheme of the present invention is a kind of polyimides tree Oil/fat composition, it is characterised in that containing (a ') using the construction unit represented by formula (2) as the polyimides of main constituent and (b) solvent.3rd scheme of the present invention is a kind of polyimidesAzoles resin combination, it is characterised in that containing (a ' ') with logical Construction unit represented by formula (3) is as the polyimides of main constituentAzoles and (b) solvent.

X in formula (1)₁、X₂Represent hydrogen atom or 1 valency organic group of carbon number 1～10 independently of one another.Formula (1)～in (3), R₁Represent 4 valency organic groups of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or Person has the carbon number 4～40 that the organic group of monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure 4 valency organic groups.In formula (1), (2), R₂Represent the divalent organic group of the carbon number 2～40 with at least 2 hydroxyls. In formula (3), R₃Represent 4 valency organic groups of carbon number 2～40.

The polyamic acid of the present invention, as long as using the construction unit represented by described formula (1) as main constituent, it is possible to With containing other construction unit.Can list as other construction unit, as acid dianhydride and the condensation polymer of diamine compound Polyamic acid, as dicarboxylic acid derivatives and the polyhydroxyamide of the condensation polymer of hydroxylated diamines, dehydration as polyamic acid The polyimides of closed loop body, polyhydroxyamide dehydration closed-loop body polyphenyl alsoAzoles etc., it is also possible to containing the most described formula (2) construction unit represented by the construction unit represented by, described formula (3), the R in described formula (1)₁For during aromatic rings R in polyamic acid, described formula (2)₁For the R in polyimides, described formula (3) during aromatic rings₁For polyamides during aromatic rings Imines benzoAzoles.Construction unit represented by the most described formula (1) account for entirety more than 50%, more preferably account for 70% with On, and then preferably comprise more than 90%.

Polyamic acid can as described later, synthesize by the reaction of diamine compound and acid dianhydride or derivatives thereof. As derivant, the tetrabasic carboxylic acid of this acid dianhydride, the mono-, di-of this tetrabasic carboxylic acid, three or four esters, acyl chlorides compound etc. can be listed.

The polyimides of the present invention, as long as using the construction unit represented by described formula (2) as main constituent, it is possible to With containing other construction unit.As other construction unit, polyamic acid, polyhydroxyamide, polyimides can be listed, gather BenzoAzoles etc..The construction unit represented by the most described formula (1), the structure represented by described formula (3) can also be contained R in unit, described formula (1)₁For the R in polyamic acid during aromatic rings, described formula (2)₁Sub-for polyamides during aromatic rings R in amine, described formula (3)₁For polyimides benzo during aromatic ringsAzoles.Structure represented by the most described formula (2) Unit accounts for more than the 50% of entirety, more preferably accounts for more than 70%, and then preferably comprises more than 90%.

Polyimides, can be as described later by being synthesized with acid dianhydride or derivatives thereof by diamine compound Polyamic acid carry out thermal dehydration closed loop, chemical dehydration closed-loop reaction synthesize.

The polyimides of the present inventionAs long as azoles using the construction unit represented by described formula (3) as main constituent is Can, it is also possible to containing other construction unit.As other construction unit, polyamic acid, polyhydroxyamide, polyamides can be listed Imines, polyphenyl are alsoAzoles etc., can contain the construction unit represented by the most described formula (1), the knot represented by formula (2) R in structure unit, described formula (1)₁For the R in polyamic acid during aromatic rings, described formula (2)₁For polyamides during aromatic rings R in imines, described formula (3)₁For polyimides benzo during aromatic ringsAzoles.Structure list represented by described formula (3) Unit preferably comprises more than the 50% of entirety, more preferably accounts for more than 70%, and then preferably comprises more than 90%.

PolyimidesAzoles can as described later, by by diamine compound and the acid dianhydride with hydroxy amide base The polyamic acid that or derivatives thereof is synthesized carries out thermal dehydration closed loop, the dehydration closed-loop reaction of chemical synthesizes.Permissible By by havingThe polyamic acid that the diamine compound of azoles ring and acid dianhydride or derivatives thereof are synthesized carries out thermal dehydration The dehydration closed-loop reaction of closed loop or chemical synthesizes.

R in formula (1)～(3)₁Represent that the structure of acid composition, expression have the alicyclic structure of monocyclic or condensed ring formula 4 valency organic groups of carbon number 4～40, or there is the organic group of monocyclic alicyclic structure directly or via bridge crosslinking structure 4 valency organic groups of the carbon number 4～40 being connected to each other.At this, a part of hydrogen atom of described alicyclic structure also may be used To be optionally substituted by halogen.Additionally, these acid compositions can be used alone or multiple combination uses as acid composition.

If illustrating the acid dianhydride with alicyclic structure that can use in the present invention, then can list 1,2,3,4-rings Ethylene-dimalonic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-ring penta Alkane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-ring fourth Alkane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptane tetracarboxylic acid dianhydride, 2, 3,4,5-oxolane tetracarboxylic acid dianhydride, 3,4-dicarboxyl-1-cyclohexyl succinic acid dianhydride, 2,3,5-tricarboxylic cyclopentyl acetic acid Dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, dicyclo ［ 3.3.0 ］ octane-2,4,6,8-tetracarboxylic acid two Acid anhydride, dicyclo ［ 4.3.0 ］ nonane-2,4,7,9-tetracarboxylic acid dianhydride, dicyclo ［ 4.4.0 ］ decane-2,4,7,9-tetracarboxylic acid dianhydride, double Ring ［ 4.4.0 ］ decane-2,4,8,10-tetracarboxylic acid dianhydride, three rings ［ 6.3.0.0 ＜ 2,6 ＞ ］ hendecane-3,5,9,11-tetracarboxylic acid Dianhydride, dicyclo ［ 2.2.2 ］ octane-2,3,5,6-tetracarboxylic acid dianhydride, dicyclo ［ 2.2.2 ］ octyl-7-alkene-2,3,5,6-tetracarboxylic acid two Acid anhydride, dicyclo ［ 2.2.1 ］ heptane tetracarboxylic acid dianhydride, dicyclo ［ 2.2.1 ］ heptane-5-carboxymethyl-2,3,6-tricarboxylic acids dianhydride, 7-oxa- Dicyclo ［ 2.2.1 ］ heptane-2,4,6,8-tetracarboxylic acid dianhydride, octahydro naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, ten tetrahydrochysene anthracene-1,2,8, 9-tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-bicyclohexyl tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-oxygen bicyclohexane tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and " Rikacid " (registered trade mark) BT-100 (being above trade name, New Japan Chem Co., Ltd's system) and their derivant etc..

In said structure, as the R in formula (1)～(3)₁Preferably, can list the most following formula (4)～ (10) structure represented by.

In formula (4)～(10), R₄～R₇₉Represent that hydrogen atom, halogen atom or hydrogen atom can also be by halogen independently of one another 1 valency organic group of the carbon number 1～3 that atom instead of.As formula (4)～the alicyclic structure of (6), can enumerate respectively Go out Tetramethylene., Pentamethylene., hexamethylene etc..X in formula (7)₃Can also be by for oxygen atom, sulphur atom, sulfonyl or hydrogen atom The divalent organic group of the carbon number 1～3 that halogen atom instead of, or the divalent bridging knot more than two of which being formed by connecting Structure.As this alicyclic structure, can list dicyclo ［ 2.2.1 ］ heptane, dicyclo ［ 2.2.1 ］ oct-2-ene, 7-oxabicyclo 2.2.1 heptane etc..As formula (8), the alicyclic structure of (9), decahydronaphthalene, ten tetrahydrochysene anthracenes can be listed respectively.Formula (10) In X₄The carbon number 1 that can also be instead of by halogen atom for Direct Bonding, oxygen atom, sulphur atom, sulfonyl, hydrogen atom～ The arlydene that the divalent organic group of 3 or hydrogen atom can also be instead of by halogen atom, or selected from oxygen atom, sulphur atom, sulphur Divalent organic group and the hydrogen atom of the carbon number 1～3 that acyl group, hydrogen atom can also be instead of by halogen atom can also be by halogen The divalent bridge crosslinking structure that in the arlydene that atom instead of more than 2 are formed by connecting.As this alicyclic structure, can enumerate Go out 1,1-bis cyclohexane, oxygen bicyclohexane etc..

If enumerating above-mentioned acid dianhydride, then can list 1,2,3,4-cyclobutanetetracarboxylic dianhydrides, 1,2,3,4-Pentamethylene. Tetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-cycloheptane tetracarboxylic acid dianhydride, dicyclo ［ 2.2.2 ］ octyl-7-alkene-2,3,5,6-tetracarboxylic acid dianhydride, dicyclo ［ 2.2.1 ］ heptane four Formic acid dianhydride, 7-oxabicyclo ［ 2.2.1 ］ heptane-2,4,6,8-tetracarboxylic acid dianhydride, octahydro naphthalene-1,2,6,7-tetracarboxylic acid dianhydride, Ten tetrahydrochysene anthracene-1,2,8,9-tetracarboxylic acid dianhydrides, 3,3 ', 4,4 '-bicyclohexyl tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-oxygen two hexamethylene Alkane tetracarboxylic acid dianhydride etc..

Among this, based on viewpoint commercially available, that be readily available and the viewpoint of the reactivity with diamine compound, preferred formula (1) R in₁Represent with following chemical formula (11)～(13), 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4,4 '-bicyclohexyl tetracarboxylic acid dianhydride.These acid dianhydrides are by rock paddy gas strain formula meeting Society sells with ProductName " PMDA-HH ", " PMDA-HS ", " BPDA-H ".Furthermore, these acid dianhydrides can be used alone or 2 kinds Combination of the above uses.

Additionally, in not destroying the limit of effect of the present invention, it is also possible to a part for this acid dianhydride is changed into other acid Dianhydride and use.As acid dianhydride, aromatic acid dianhydride or aliphatic acid dianhydride can be listed.Such as aromatic acid two Acid anhydride, can list pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,3,3 ', 4 '-bibenzene tetracarboxylic two The double adjacent benzene two of acid anhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-terphenyl tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-oxygen The double O-phthalic acid dianhydride of formic acid dianhydride, 2,3,3 ', 4 '-oxygen, the double O-phthalic acid dianhydride of 2,3,2 ', 3 '-oxygen, sulfobenzide .- 3,3 ', 4,4 '-tetracarboxylic acid dianhydride, BP-3, double (3,4-dicarboxyphenyi) propane of 3 ', 4,4 '-tetracarboxylic acid dianhydride, 2,2- Double (3,4-dicarboxyphenyi) the ethane dianhydride of double (2,3-dicarboxyphenyi) propane dianhydride of dianhydride, 2,2-, 1,1-, 1,1-double (2, 3-dicarboxyphenyi) ethane dianhydride, double (3,4-dicarboxyphenyi) methane dianhydride, double (2,3-dicarboxyphenyi) methane dianhydride, Double (3,4-dicarboxyphenyi) ether dianhydride, double (1,3-dioxo-1,3-dihydroisobenzofuran-5-formic acid) 1,4-penylene, 2, Double (4-(4-amino-benzene oxygen) phenyl) propane of 2-, 1,2,5,6-naphthalenetetracarbacidic acidic dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 2,3, Double (3,4-dicarboxyphenyi) hexafluoropropane dianhydride of 5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-tetracarboxylic acid dianhydride, 2,2-, Double (4-(3,4-di carboxyl phenyloxy) phenyl) hexafluoropropane dianhydride of 2,2-, the double (4-(3,4-dicarboxyl benzoyloxy) of 2,2- Phenyl) hexafluoropropane dianhydride, 1,6-difluoro pyromellitic acid anhydride, 1-trifluoromethyl pyromellitic acid anhydride, 1,6-bis-trifluoro Methyl pyromellitic acid anhydride, 2,2 '-bis-(trifluoromethyls)-4,4 '-bis-(3,4-di carboxyl phenyloxy) biphenyl dianhydride, The aromatic tetracarboxylic dianhydrides such as " Rikacid " (registered trade mark) TMEG-100 (trade name, New Japan Chem Co., Ltd's system) and Their derivant etc..As aliphatic acid dianhydride, 1,2,3,4-ethylene-dimalonic acid dianhydrides, 1,2,3,4-pentanes can be listed Tetracarboxylic acid dianhydride and their derivant etc., but do not limit to these.Additionally, these other acid dianhydrides can be used alone or 2 Plant combination of the above to use.

R in formula (1), (2)₂It is the divalent organic group of the carbon number 2～40 with at least 2 hydroxyls, Ke Yilie Enumerate the structure represented by such as chemical formula (14)～(23).

Among those, viewpoint based on the transparency, preferably the structure of chemical formula (14), is preferably used following chemical formula (24) diamidogen represented by.

R in formula (3)₃Represent 4 valency organic groups of carbon number 2～40, such as chemical formula (25) can be listed ～the structure represented by (34).Among those, based on transparent viewpoint, the preferably structure of chemical formula (25).

Furthermore, the R in formula (3)₃Polyimides when representing with chemical formula (25)Azoles, is by above-mentioned chemical formula (24) polyamic acid represented by formula (1) of the diamidogen synthesis represented by and the dehydration of the polyimides represented by formula (2) Closed loop body.

Additionally, in not destroying the limit of effect of the present invention, it is also possible to change a part for this diamine compound into it Its diamine compound and use.As other diamine compound, aromatic diamine compound, ester ring type two amination can be listed Compound or aliphatic diamine compound.Such as aromatic diamine compound, 3 can be listed, 4 '-diamino-diphenyl Ether, 4,4 '-diamino-diphenyl ether, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,3 '-diamino Double (4-aminophenyl) HFC-236fa of base sulfobenzide., 4,4 '-diamino diphenyl sulfone, 2,2-, the double (3-amino-4-first of 2,2- Base phenyl) HFC-236fa, double (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-, 3,3 '-diamino diphenyl sulfide, 4,4 '- Double (4-amino-benzene oxygen) benzene of diamino diphenyl sulfide, 1,4-, benzidine, 2,2 '-bis-(trifluoromethyl) benzidine, 3,3 '- Double (trifluoromethyl) benzidine, 2,2 '-dimethylbenzidine, 3,3 '-dimethylbenzidine, 2,2 ', 3,3 '-tetramethyl biphenyl Amine, m-diaminobenzene., p-phenylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, double { 4-(4-aminophenoxy phenyl) } sulfone, double { 4- (3-aminophenoxy phenyl) } sulfone, double (4-amino-benzene oxygen) biphenyl, double { 4-(4-amino-benzene oxygen) phenyl } ether, 1,4-be double Double (4-aminophenyl) fluorenes of (4-amino-benzene oxygen) benzene, 9,9-, double [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, 2,2-are double [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 4,4-diaminobenzene formailide, 3,4-diaminobenzene formailide, 4,4- Diaminobenzophenone, 3,3-diaminobenzophenone or their aromatic ring are replaced by alkyl, alkoxyl, halogen atom etc. Diamine compound, but do not limit to these.

As ester ring type diamine compound, Tetramethylene. diamidogen, isophorone diamine, dicyclo ［ 2.2.1 ］ heptan can be listed Alkane double methylamine, three rings ［ 3.3.1.13,7 ］ decane-1,3-diamidogen, 1,2-cyclohexyl diamine, 1,3-cyclohexyl diamine, 1,4-hexamethylene Base diamidogen, 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 3,3 '-diethyl Base-4,4 '-diamino-dicyclohexyl methane, 3,3 ', 5,5 '-tetramethyl-4,4 '-diamino-dicyclohexyl methane, 3,3 ', 5, 5 '-tetraethyl-4,4 '-diamino-dicyclohexyl methane, 3,5-diethyl-3 ', 5 '-dimethyl-4,4 '-diaminocyclohexyl Methane, 4,4 '-diaminocyclohexyl ether, 3,3 '-dimethyl-4,4 '-diaminocyclohexyl ether, 3,3 '-diethyl-4, 4 '-diaminocyclohexyl ether, 3,3 ', 5,5 '-tetramethyl-4,4 '-diaminocyclohexyl ether, 3,3 ', 5,5 '-tetraethyl- Double (the 4-of 4,4 '-diaminocyclohexyl ether, 3,5-diethyl-3 ', 5 '-dimethyl-4,4 '-diaminocyclohexyl ether, 2,2- Aminocyclohexyl) propane, double (3-methyl-4-aminocyclohexyl) propane of 2,2-, double (the 3-ethyl-4-aminocyclohexyl) third of 2,2- Double (3,5-diethyl-4-aminocyclohexyl) propane of double (3,5-dimethyl-4-aminocyclohexyl) propane of alkane, 2,2-, 2,2-, 2, 2-(3,5-diethyl-3 ', 5 '-dimethyl-4,4 '-diaminocyclohexyl) propane, 2,2 '-bis-(4-aminocyclohexyl) hexafluoros Propane, 2,2 '-dimethyl-4,4 '-diamino bicyclic hexane, 2,2 '-bis-(trifluoromethyls)-4,4 '-diamino bicyclic hexane or The diamine compound that their alicyclic ring be instead of by alkyl, alkoxyl, halogen atom etc., but do not limit to these.

As aliphatic diamine compound, can list ethylenediamine, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1, Alkylenediamine class, double (amino methyl) ether, double (2-amino-ethyl) ether, double (3-aminopropyl) ethers such as 10-diamino decane Deng double (3-aminopropyl) tetramethyl disiloxane of ethylene glycol bisthioglycolate amine and 1,3-, double (4-aminobutyl) tetramethyl two of 1,3- Siloxanes, α, the siloxane diamine class such as ω-bis-(3-aminopropyl) polydimethylsiloxane, but do not limit to these.

These aromatic diamine compounds, ester ring type diamine compound or aliphatic diamine compound can individually or 2 kinds Combination of the above uses.

Among those, following chemical formula (35) represented by 9 are preferably used, double (4-aminophenyl) fluorenediamine of 9-, send out The most so can keep the transparency and the mechanical property bakeing film, improve glass transition temperature, reduce birefringence.

By using the diamidogen represented by chemical formula (35), following formula (36) or following can be imported in strand Construction unit represented by formula (37).

(the X in formula (36)₁、X₂Represent hydrogen atom or 1 valency organic group of carbon number 1～10 independently of one another.Logical In formula (36), (37), R₁Represent 4 valency organic groups of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, Or the carbon number 4～40 that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure 4 valency organic groups.)

Generally, use the polyimide film of the diamidogen represented by chemical formula (35) to have coloring more.(comparative example as described later 8), the starting monomer as clear polyimides uses 4,4 '-(hexafluoroisopropyli,ene base) diphthalic anhydrides and above-mentioned chemistry Polyimide film obtained by diamidogen represented by formula (35) etc., with polyimides and the polyimides of the present inventionAzoles film is compared Relatively, transparency deterioration.Polyimides and polyimides as the present inventionAzoles film, owing to employing ester ring type acid dianhydride institute So that coloring can be suppressed.

Diamidogen represented by described chemical formula (35) preferably comprises the scope of less than more than the 10% 50% of total diamidogen residue, more Preferably comprise the scope of less than more than 30% 50%, and then preferably comprise the scope of less than more than 40% 50%.By so, at this Bright polyamic acid, polyimides and polyimidesIn azoles, the construction unit represented by formula (36) or formula (37) accounts for 10%～50%.

The polyamic acid of the present invention, polyimides and polyimidesAzoles, in order to be transferred to preferred scope, also by molecular weight Two endcappeds can be made with end-capping reagent.As the end-capping reagent that can react with acid dianhydride, monoamine or monovalence can be listed Alcohol etc..Additionally, as the end-capping reagent that can react with diamine compound, anhydride, monocarboxylic acid, single acyl chlorides chemical combination can be listed Thing, single active ester compound etc..Additionally, by reacting with end-capping reagent, it is possible to import various organic group as terminal groups.

The monoamine used as end-capping reagent, can list 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxyl-8-amino naphthalenes, 1-hydroxyl-7-amino naphthalenes, 1-hydroxyl-6-amino naphthalenes, 1-hydroxyl-5-amino naphthalenes, 1-hydroxyl-4-amino Naphthalene, 1-hydroxyl-3-amino naphthalenes, 1-hydroxyl-2-amino naphthalenes, 1-amino-7-hydroxyl naphthalene, 2-hydroxyl-7-amino naphthalenes, 2-hydroxyl-6- Amino naphthalenes, 2-hydroxyl-5-amino naphthalenes, 2-hydroxyl-4-amino naphthalenes, 2-hydroxyl-3-amino naphthalenes, 1-amino-2 hydroxy naphthalene, 1-carboxylic Base-8-amino naphthalenes, 1-carboxyl-7-amino naphthalenes, 1-carboxyl-6-amino naphthalenes, 1-carboxyl-5-amino naphthalenes, 1-carboxyl-4-amino naphthalenes, 1-carboxyl-3-amino naphthalenes, 1-carboxyl-2-amino naphthalenes, 1-amino-7-carboxyl naphthalene, 2-carboxyl-7-amino naphthalenes, 2-carboxyl-6-amino Naphthalene, 2-carboxyl-5-amino naphthalenes, 2-carboxyl-4-amino naphthalenes, 2-carboxyl-3-amino naphthalenes, 1-amino-2-carboxyl naphthalene, 2-amino cigarette Acid, 4-amino-nicotinic acid, 5-amino-nicotinic acid, 6-amino-nicotinic acid, 4-ASA, 5-aminosalicylic acid, 6-aminosallcylic acid, Ameride, 2-amino benzoic Acid, 3-amino benzoic Acid, PABA, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-ammonia Base benzenesulfonic acid, 3-amino-4,6-dihydroxy-pyrimidine, Ortho-Aminophenol, 3-amino-phenol, PAP, 5-amino-8-sulfydryl Quinoline, 4-amino-thiooxine, 1-sulfydryl-8-amino naphthalenes, 1-sulfydryl-7-amino naphthalenes, 1-sulfydryl-6-amino naphthalenes, 1-mercapto Base-5-amino naphthalenes, 1-sulfydryl-4-amino naphthalenes, 1-sulfydryl-3-amino naphthalenes, 1-sulfydryl-2-amino naphthalenes, 1-amino-7-mercaptonaphthalene, 2-sulfydryl-7-amino naphthalenes, 2-sulfydryl-6-amino naphthalenes, 2-sulfydryl-5-amino naphthalenes, 2-sulfydryl-4-amino naphthalenes, 2-sulfydryl-3-amino Naphthalene, 1-amino-2-mercapto phenyl formic naphthalene, 3-amino-4,6-dimercapto pyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminobenzene sulfur Phenol, 2-acetylenylaniline, 3-acetylenylaniline, 4-acetylenylaniline, 2,4-diacetylene aniline, 2,5-diacetylene aniline, 2,6-diacetylene aniline, 3,4-diacetylene aniline, 3,5-diacetylene aniline, 1-acetenyl-2-amino naphthalenes, 1-acetylene Base-3-amino naphthalenes, 1-acetenyl-4-amino naphthalenes, 1-acetenyl-5-amino naphthalenes, 1-acetenyl-6-amino naphthalenes, 1-acetenyl-7- Amino naphthalenes, 1-acetenyl-8-amino naphthalenes, 2-acetenyl-1-amino naphthalenes, 2-acetenyl-3-amino naphthalenes, 2-acetenyl-4-amino Naphthalene, 2-acetenyl-5-amino naphthalenes, 2-acetenyl-6-amino naphthalenes, 2-acetenyl-7-amino naphthalenes, 2-acetenyl-8-amino naphthalenes, 3, 5-diacetylene-1-amino naphthalenes, 3,5-diacetylene-2-amino naphthalenes, 3,6-diacetylene-1-amino naphthalenes, 3,6-diacetylene- 2-amino naphthalenes, 3,7-diacetylene-1-amino naphthalenes, 3,7-diacetylene-2-amino naphthalenes, 4,8-diacetylene-1-amino naphthalenes, 4, 8-diacetylene-2-amino naphthalenes etc., but do not limit to these.

Additionally, the monovalent alcohol used as end-capping reagent, can list methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-butanol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-enanthol, 3-enanthol, 1-capryl alcohol, Sec-n-octyl alcohol, 3-capryl alcohol, 1 nonyl alcohol, 2-nonyl alcohol, 1-decanol, 2-decanol, 1-undecylenic alcohol, 2-undecylenic alcohol, 1-Lauryl Alcohol, 2- Lauryl Alcohol, 1-13 carbon alcohol, 2-13 carbon alcohol, 1-ten four carbon alcohols, 2-ten four carbon alcohols, 1-pentadecanol, 2-pentadecanol, 1- 16 carbon alcohol, 2-16 carbon alcohol, 1-17 carbon alcohol, 2-17 carbon alcohol, 1-octadecanol, 2-octadecanol, 1-19 carbon alcohol, 2- 19 carbon alcohol, 1-eicosanol, 2-methyl isophthalic acid-propanol, 2-methyl-2-propanol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl group-1-amylalcohol, 2-ethyl-1-hexanol, 4-methyl-3-enanthol, 6-methyl- 2-enanthol, 2,4,4-trimethyl-1-hexanol, 2,6-2,6-dimethyl-4-heptanol, different nonyl alcohol, 3,7-dimethyl-3-capryl alcohol, 2,4- Dimethyl-1-heptanol, 2-heptyl-undecylenic alcohol, ethylene glycol monomethyl ether, glycol monoethyl ether, ethylene glycol monobutyl ether, the third two Alcohol 1-methyl ether, carbiphene, diethylene glycol monomethyl ether, diethylene glycol monobutyl ehter, cyclopentanol, Hexalin, Pentamethylene. list Methanol, bicyclopentane list methanol, tristane list methanol, norborneol, terpinol etc., but do not limit to these.

Anhydride, monocarboxylic acid, single chloride compounds and the single active ester compound used as end-capping reagent, can list neighbour Anhydride, the 2-carboxyls such as phthalate anhydride, maleic anhydride, carbic anhydride, cyclohexane cyclohexanedimethanodibasic acid anhydride, 3-hydroxyl phthalic anhydride Phenol, 3-carboxylic phenol, 4-carboxylic phenol, 2-carboxyl phenylmercaptan., 3-carboxyl phenylmercaptan., 4-carboxyl phenylmercaptan., 1-hydroxyl-8-carboxylic Base naphthalene, 1-hydroxyl-7-carboxyl naphthalene, 1-hydroxyl-6-carboxyl naphthalene, 1-hydroxyl-5-carboxyl naphthalene, 1-hydroxyl-4-carboxyl naphthalene, 1-hydroxyl- 3-carboxyl naphthalene, 1-hydroxyl-2-carboxyl naphthalene, 1-sulfydryl-8-carboxyl naphthalene, 1-sulfydryl-7-carboxyl naphthalene, 1-sulfydryl-6-carboxyl naphthalene, 1-mercapto Base-5-carboxyl naphthalene, 1-sulfydryl-4-carboxyl naphthalene, 1-sulfydryl-3-carboxyl naphthalene, 1-sulfydryl-2-carboxyl naphthalene, 2-carboxyl benzenesulfonic acid, 3-carboxylic Base benzenesulfonic acid, 4-carboxyl benzenesulfonic acid, 2-acetylenylbenzene formic acid, 3-acetylenylbenzene formic acid, 4-acetylenylbenzene formic acid, 2,4-diacetylene Yl benzoic acid, 2,5-diacetylene benzoic acid, 2,6-diacetylene benzoic acid, 3,4-diacetylene benzoic acid, 3,5-diacetylene Yl benzoic acid, 2-acetenyl-1-naphthoic acid, 3-acetenyl-1-naphthoic acid, 4-acetenyl-1-naphthoic acid, 5-acetenyl-1-naphthalene Formic acid, 6-acetenyl-1-naphthoic acid, 7-acetenyl-1-naphthoic acid, 8-acetenyl-1-naphthoic acid, 2-acetenyl-2-naphthoic acid, 3-acetenyl-2-naphthoic acid, 4-acetenyl-2-naphthoic acid, 5-acetenyl-2-naphthoic acid, 6-acetenyl-2-naphthoic acid, 7-second The monocarboxylic acid classes such as alkynyl-2-naphthoic acid, 8-acetenyl-2-naphthoic acid and their the carboxyl single acyl chlorides chemical combination by chloride Thing, and p-phthalic acid, phthalic acid, maleic acid, cyclohexane cyclohexanedimethanodibasic, 3-hydroxyl phthalic, 5-norborene- 2,3-dioctyl phthalate, 1,2-dicarboxyl naphthalene, 1,3-dicarboxyl naphthalene, 1,4-dicarboxyl naphthalene, 1,5-dicarboxyl naphthalene, 1,6-dicarboxyl naphthalene, The omega-dicarboxylic acids such as 1,7-dicarboxyl naphthalene, 1,8-dicarboxyl naphthalene, 2,3-dicarboxyl naphthalene, 2,6-dicarboxyl naphthalene, 2,7-dicarboxyl naphthalene Only one carboxyl by chloride single chloride compounds and by single chloride compounds and N-hydroxybenzotriazole or N-hydroxyl- 5-norborene-2,3-dicarboximide reacts the active ester compound obtained.

Monoamine that end-capping reagent is used, the importing ratio of monohydric alcohol, preferably rub in 0.1～60 relative to whole amine components The scope of you %, coating is preferably at 5～50 moles of %.Anhydride, monocarboxylic acid, single chloride compounds and the list used as end-capping reagent Active ester compound imports ratio, and relative to diamine component preferably in the scope of 0.1～100 mole of %, particularly preferred 5～90 rub You are %.Multiple different terminal groups can also be imported by reacting with multiple end-capping reagent.

At polyamic acid, polyimides and polyimidesThe end-capping reagent imported in azoles, it is possible to held by following method Change places and detect.Such as the polymer having imported end-capping reagent is dissolved in an acidic solution, resolve into the composition as polymer The amine component of unit and anhydride composition, be used for gas chromatogram (GC), NMR is measured, it becomes possible to easily detects envelope End agent.In addition it is also possible to by imported the polymer of end-capping reagent directly with Thermal decomposition gas chromatography (PGC), infrared spectrum and¹³CNMR spectrum is measured, it is also possible to easily detect.

The polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination Thing, containing (b) solvent.As solvent, can by METHYLPYRROLIDONE, gamma-butyrolacton, DMF, N, N-dimethyl acetylamide, the non-protonic solvent of dimethyl sulfoxide isopolarity, oxolane, twoThe ether such as alkane, propylene glycol monomethyl ether Ketone, ethyl acetate, propylene glycol methyl ether acetate, the ethyl lactates such as class, acetone, butanone, isobutyrone, diacetone alcohol It is used alone or uses two or more Deng esters, toluene, dimethylbenzene etc. are aromatic hydrocarbon etc..

B the content of () solvent is relative to polyamic acid, polyimides or polyimidesAzoles 100 weight portion is preferably 50 More than weight portion, more than more preferably 100 weight portions, preferably 2, below 000 weight portion, more preferably 1, below 500 weight portions.50 ～2, during the scope of 000 weight portion, it is possible to become the viscosity being suitable to coating, the thickness after easily dimmable coating.

(a) will be given using the construction unit represented by formula (1) as the manufacture method of the polyamic acid of main constituent below With explanation.The reaction method of polyreaction, be only can manufacturing objective polyamic acid, be just not particularly limited, it is possible to use Known reaction method.

As concrete reaction method, can list and all diamine component and the reaction dissolvent of ormal weight are joined instead Answer in device, after making them dissolve, add the acid dianhydride component of ormal weight, stir at room temperature～80 DEG C 0.5～30 hour Method etc..

As by the diamine compound represented by chemical formula (24), and 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, 1R, The structure of the polyamic acid that 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4,4 '-bicyclohexyl tetracarboxylic acid dianhydride obtain Unit, can list following chemical formula (38)～(42).

It follows that to (a ') using the construction unit represented by formula (2) as the manufacture method of the polyimides of main constituent It is explained.As long as the polyamic acid represented by the formula (1) obtained by above-mentioned known reaction method can be made to carry out The manufacture method of imidizate, is just not particularly limited, it is possible to use known reaction method.

As concrete reaction method, can list the aforementioned polyamic acid solution obtained in room temperature～200 The method etc. of 0.5～30 hour is stirred at DEG C.

As by the diamine compound represented by chemical formula (24), and 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4, the structure of the polyimides that 4 '-bicyclohexyl tetracarboxylic acid dianhydride obtains Unit, can list following chemical formula (43)～(45).

It follows that to (a ' ') using the construction unit represented by formula (3) as the polyimides of main constituentThe system of azoles The method of making is explained.As the 1st method, the formula obtained by the known reaction method above told about of sening as an envoy to can be enumerated (2) polyimides represented by carries out dehydration closed-loop.Reaction method is not particularly limited, it is possible to use known reaction side Method.As concrete reaction method, can list: make polyimide powder heat treatment 0.5～30 at 300～400 DEG C little Time method；In polyimide solution, add the acid catalysts such as thermal acid generator, stir 0.5～30 hour room temperature～250 DEG C Method etc..

As the 2nd method, can enumerate and send as an envoy to by containing represented by following formula (46)The diamidogen of azoles ring and acid two The polyamic acid that acid anhydride obtains carries out imidizate.As concrete reaction method, the acid dianhydride adding ormal weight can be listed Composition, stirs 0.5～30 hour room temperature～80 DEG C, then in room temperature～200 DEG C of stirrings method etc. of 0.5～30 hour.

(in formula (46), R₃The 4 valency organic groups for carbon number 2～40.)

Make by the diamine compound represented by chemical formula (24) and 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4, the polyamic acid that 4 '-bicyclohexyl tetracarboxylic acid dianhydride obtains takes off During water blockage ring, or make by the diamidogen represented by chemical formula (47) and 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4, the polyamic acid that 4 '-bicyclohexyl tetracarboxylic acid dianhydride obtains carries out dehydration closed-loop Time, as the polyimides obtainedThe construction unit of azoles, can list following chemical formula (48)～(50).

The polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination Thing can contain surfactant.As surfactant, Off ロ ラ De (trade name, Sumitomo 3M strain formula meeting can be listed Society's system), メ ガ Off ァ ッ Network (trade name, Dainippon Ink Chemicals's system), ス Le Off ロ Application (trade name, Asahi Glass Co., Ltd's system) etc. Fluorine system surfactant.Furthermore, it is possible to list KP341 (trade name, Shin-Etsu Chemial Co., Ltd's system), DBE (commodity Name, チ ッ ソ Co., Ltd. system), POLYFLOW, グ ラ ノ Le (trade name, Kyoeisha Chemical Co., Ltd.'s system), BYK (PVC ッ Network ケ ミ Co., Ltd. system) etc. organosiloxane surfactant.And then POLYFLOW (trade name, common prosperity can be listed KCC of society system) etc. acrylate copolymer surfactant.

Surfactant, preferably with respect to polyamic acid, polyimides or polyimidesAzoles 100 weight portion contains 0.01～10 weight portions.

The polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination Thing, can contain internal mold release.As internal mold release, long-chain fatty acid etc. can be listed.

The polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination Thing, can contain thermal cross-linking agent.As thermal cross-linking agent, preferably epoxide or there is alkoxy methyl or methylol at least 2 Individual compound.By having these groups at least 2, it is possible to make resin and congeneric elements carry out condensation reaction and form crosslinking Structure, makes mechanical strength, resistance to chemical reagents improve.

As the preferred example of epoxide, such as bisphenol A type epoxy resin, bisphenol F type epoxy tree can be listed Fat, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly-methyl (glycydoxy), silicon The siloxanes etc. containing epoxy radicals such as oxygen alkane, but the present invention does not limit to these.Specifically, can list EPICLON850-S、EPICLONHP-4032、EPICLONHP-7200、EPICLONHP-820、EPICLONHP-4700、 EPICLONEXA-4710、EPICLONHP-4770、EPICLONEXA-859CRP、EPICLONEXA-1514、EPICLONEXA- 4880、EPICLONEXA-4850-150、EPICLONEXA-4850-1000、EPICLONEXA-4816、EPICLONEXA-4822 (being trade name, big Japan イ Application キ chemical industry Co., Ltd. system above), リ カ レ ジ Application BEO-60E, リ カ レ ジ Application BPO- 20E, リ カ レ ジ Application HBE-100, リ カ レ ジ Application DME-100 (above trade name, New Japan Chem Co., Ltd), EP- 4003S, EP-4000S (above trade name, Co., Ltd. ア デ カ), PG-100, CG-500, EG-200 (be above trade name, Osaka ガ ス ケ ミ カ Le Co., Ltd.), NC-3000, NC-6000 (being trade name, Nippon Kayaku K. K above), EPOX- MKR508, EPOX-MKR540, EPOX-MKR710, EPOX-MKR1710, VG3101L, VG3101M80 (are trade name, strain above Formula commercial firm プ リ Application テ ッ Network), セ ロ キ サ イ De 2021P, セ ロ キ サ イ De 2081, セ ロ キ サ イ De 2083, セ ロ キ サ イ De 2085 (being trade name, ダ イ セ Le chemical industry Co., Ltd. above) etc..

As having alkoxy methyl or the compound of methylol at least 2, such as DML-PC, DML-can be listed PEP、DML-OC、DML-OEP、DML-34X、DML-PTBP、DML-PCHP、DML-OCHP、DML-PFP、DML-PSBP、DML- POP、DML-MBOC、DML-MBPC、DML-MTrisPC、DML-BisOC-Z、DML-BisOCHP-Z、DML-BPC、DML- BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp- BPF、TML-BPE、TML-BPA、TML-BPAF、TML-BPAP、TMOM-BP、TMOM-BPE、TMOM-BPA、TMOM-BPAF、 TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (are trade name, Honshu chemistry work above Industry Co., Ltd. system), NIKALAC (registered trade mark) MX-290, NIKALACMX-280, NIKALACMX-270, NIKALACMX- 279, NIKALACMW-100LM, NIKALACMX-750LM (being trade name, Sanwa Co., Ltd.'s ケ ミ カ Le system above).Permissible Containing two or more in them.

The polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination Thing can contain coloring agent.By adding coloring agent, it is possible to regulation polyamic acid, polyimides, polyimidesThe color of azoles film Adjust.

As coloring agent, it is possible to use dyestuff, organic pigment, inorganic pigment etc., from the standpoint of thermostability, the transparency, Preferably organic pigment.Wherein preferably clear height, light resistance, thermostability, resistance to chemical reagents are excellent.If by color index (CI) sequence Number represent the concrete example of representative organic pigment, be preferably used following, but do not limit to these.

Example as yellow uitramarine, it is possible to use Pigment yellow (hereinafter referred to as " PY ") 12,13,17,20, 24、83、86、93、95、109、110、117、125、129、137、138、139、147、148、150、153、154、166、168、 185 etc..Additionally, as the example of orange pigment, it is possible to use Pigment orange (hereinafter referred to as " PO ") 13,36,38, 43,51,55,59,61,64,65,71 etc..In addition as the example of red pigment, it is possible to use Pigment red is (hereinafter referred to as For " PR ") 9,48,97,122,123,144,149,166,168,177,179,180,192,209,215,216,217,220, 223,224,226,227,228,240,254 etc..Additionally, as the example of violet pigment, it is possible to use Pigment violet (hereinafter referred to as " PV ") 19,23,29,30,32,37,40,50 etc..Additionally, as the example of blue pigment, it is possible to use Pigment blue (hereinafter referred to as " PB ") 15,15:3,15:4,15:6,22,60,64 etc..Additionally, as viridine green Example, it is possible to use Pigment green (hereinafter referred to as " PG ") 7,10,36,58 etc..These pigment can also be as required Carry out the surfaces such as Colophonium process, acidic groups process, basic treatment to process.

The polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination Thing can contain inorganic filler.As inorganic filler, silicon dioxide microparticle, alumina particulate, titanium dioxide can be listed micro- Grain, zirconium dioxide particle etc..

The shape of inorganic filler is not particularly limited, spherical, elliptical shape, flat can be listed, rot shape, fibre Dimension shape etc..

Contained inorganic filler, in order to prevent scattering of light, preferable particle size is less.Mean diameter 0.5～100nm, Preferably 0.5～the scope of 30nm.

The content of inorganic filler, relative to polyamic acid, polyimides or polyimidesAzoles is preferably 1～50 weights Amount %, more preferably 10～30 weight %.Along with the increase of content, pliability, folding resistance reduce.

As making polyamic acid resin composition, polyimide resin composition or polyimidesAzoles resin combination In containing the method for inorganic filler, it is possible to use various known methods.Can list and such as make organic-inorganic filler colloidal sol With polyamic acid, polyimides or polyimidesAzoles mixes.Organic-inorganic filler colloidal sol, be with 30 weight % about ratio Example makes inorganic filler dispersion in organic solvent, as organic solvent, can list methanol, isopropanol, n-butyl alcohol, Ethylene glycol, butanone, hexone, propyleneglycol monomethyl acetates, propylene glycol monomethyl ether, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, METHYLPYRROLIDONE, 1,3-methylimidazole alkanone, gamma-butyrolacton etc..

In order to improve inorganic filler relative to polyamic acid, polyimides or polyimidesThe dispersibility of azoles, it is also possible to With silane coupler, organic-inorganic filler colloidal sol is processed.When the terminal functional group as silane coupler has epoxy radicals Or during amino, be bonded by the carboxylic acid with polyamic acid, it is possible to make and polyamic acid, polyimides or polyimidesAzoles Affinity improves, it is possible to more effectively disperse.

As having the silane coupler of epoxy radicals, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silicon can be listed Alkane, 3-glycydoxy methyl dimethoxysilane, 3-glycydoxy trimethoxy silane, 3-contract Water glycerin ether epoxide hydroxypropyl methyl diethoxy silane, 3-glycydoxy triethoxysilane etc..

As having the silane coupler of amino, N-2-(amino-ethyl)-3-amino propyl methyl diformazan can be listed TMOS, N-2-(amino-ethyl)-3-TSL 8330,3-TSL 8330,3-amino Propyl-triethoxysilicane, 3-triethoxysilyl-N-(1,3-dimethyl-butane) propylamine, N-phenyl-3-aminopropan Base trimethoxy silane etc..

As the processing method processing organic-inorganic filler colloidal sol with silane coupler, it is possible to use various known sides Method.Such as can add silane coupler in the organic-inorganic filler colloidal sol have adjusted concentration, in room temperature～80 DEG C of stirrings 0.5 ～2 hours and process.

The polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination Thing can contain photoacid generator.By containing photoacid generator, in time describing to have the mask of exposing patterns to irradiate light, exposing Portion produces acid, and exposure portion increases, it is possible to make as positive type photosensitive organic compound relative to the dissolubility of aqueous alkali With.

As in the present invention use photoacid generator, can list diazonium naphtoquinone compounds, sulfonium salt,Salt, diazonium Salt, iodineSalt etc..Wherein, from showing the dissolving damping effect of excellence, obtaining high sensitive and the eurymeric sense of low mistake film amount From the standpoint of photosensitive resin composition, diazonium naphtoquinone compounds is preferably used.In addition it is also possible to containing two or more photoacid generator.Logical Cross in such manner, it is possible to make the ratio of the dissolution velocity in exposure portion and unexposed portion become much larger, obtain high sensitive positive light sensitivity Resin combination.

As diazonium naphtoquinone compounds, the sulfonic acid that can list polyol and diazonium quinone is combined into by ester bond Compound, the compound that the sulfonic acid of multiamino compound and diazonium quinone is combined into by sulfonamide key, polyhydroxy polyamino The compound etc. that the sulfonic acid of compound and diazonium quinone is combined into by ester bond and/or sulfonamide key.These polyols, Multiamino compound, can not be all functional groups and is all replaced by diazonium quinone, but 50 moles of more than % that preferably functional group is all Replaced by diazonium quinone.By using this diazonium naphtoquinone compounds, it is possible to obtaining can be by the mercury lamp as common ultraviolet I line (wavelength 365nm), h line (wavelength 405nm), g line (wavelength 436nm) carry out the positive type photosensitive organic compound that reacts.

In the present invention, diazonium naphtoquinone compounds be preferably used in 5-diazo naphthoquinone sulfonyl, 4-diazo naphthoquinone sulfonyl appoint A kind of.The compound in same a part with both groups can also be used, it is also possible to and with having the change of different group Compound.

Diazonium naphtoquinone compounds used in the present invention, can be synthesized by the following method by specific phenolic compounds.Permissible List the method such as making 5-diazo naphthoquinone sulfonic acid chloride and phenolic compounds react in the presence of triethylamine.The synthesis of phenolic compounds Method, can list the method making α-(hydroxy phenyl) styrene derivative react under an acid catalysis with multivalence phenolic compounds Deng.

The content of photoacid generator, relative to polyamic acid, polyimides or polyimidesAzoles 100 weight portion, is preferably 3～40 weight portions.By making the content of photoacid generator in this scope, it is possible to realize higher sensitivity.And then can also root According to needs containing sensitizer etc..

The pattern of normal Photosensitive resin to be formed, is coated on the varnish of normal Photosensitive resin on substrate so that it is expose Light, then uses developer solution to remove exposure portion.As developer solution, preferably Tetramethylammonium hydroxide, diethanolamine, lignocaine second Alcohol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethyl amino second Ester, dimethylaminoethanol, dimethylamine ethyl ester, cyclohexylamine, ethylenediamine, hexamethylene diamine etc. show The aqueous solution of the compound of alkalescence.Additionally, according to circumstances, it is also possible in these aqueous alkalis, add N-methyl-2-pyrrolidine Ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, gamma-butyrolacton, DMAA isopolarity The esters such as the alcohols such as solvent, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, Ketocyclopentane, Ketohexamethylene, One or more combination independent in the ketone such as isobutyl ketone, hexone etc..Enter with water the most after development Row drip washing processes.Here, can also be by esters etc. such as the alcohols such as ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetates It is added to the water and carries out drip washing process.

Below by using the polyamic acid resin composition of the present invention, polyimide resin composition and polyimidesAzoles resin combination manufactures the method for heat-resistant resin film and is explained.

First by polyamic acid resin composition, polyimide resin composition or polyimidesAzoles resin combination is coated with Cloth is on substrate.As substrate, it is possible to use such as silicon wafer, ceramic-like, GaAs, soda-lime glass, alkali-free glass etc., but also Do not limit to these.Coating process has the methods such as such as slot coating processes, spin-coating method, spraying process, rolling method, stick coating method, it is also possible to These Combination of Methods are coated together.

It follows that by polyamic acid resin composition, polyimide resin composition or polyimides in coatingAzoles The drying substrates of resin combination, obtains polyamic acid resin composition, polyimide resin composition or polyimidesAzoles Resin combination tunicle.Electric hot plate, baking oven, infrared ray, vacuum chamber etc. are used when being dried.When using electric hot plate, the most directly Connect or, keep heated object to heat on the fixtures such as steady pin (proxy pin) onboard arranging.As fixing The material of pin, has the synthetic resin such as aluminum, stainless steel and other metal materials or polyimide resin, " テ Off ロ Application (registered trade mark) ", The steady pin using arbitrary material can.The height of the steady pin size according to substrate, the resin bed as heated object Kind, heating purpose etc. and different, the such as resin bed on to the glass substrate being coated on 300mm × 350mm × 0.7mm adds During heat, the highly preferred of steady pin is 2～about 12mm.Heating-up temperature is different according to kind and the purpose of heated object, excellent The scope being selected in room temperature to 180 DEG C carries out 1 minute～several hours.

It follows that the scope heating of less than 400 DEG C more than 180 DEG C so that it is it is changed into heat-resistant resin tunicle.In order to incite somebody to action This heat-resistant resin tunicle is peeled off from substrate, can list the method in medicinal liquids such as being immersed in Fluohydric acid., to thermostability tree The method etc. of the interface irradiating laser of fat tunicle and substrate, it is possible to use either method.

Furthermore, by will using the construction unit represented by formula (1), (2) as the polyamic acid of the present invention of main constituent, Polyimides carries out heat treatment as above, it is possible to obtain the polyamides using the construction unit represented by formula (2) as main constituent Imines or using the construction unit represented by formula (3) as the polyimides of main constituentAzoles.

The above-mentioned heat-resistant resin film obtained has high transparent, high-fire resistance, low birefringence, pliability, can To be work perfectly well as flexible base board use.It is more than 85% as the absorbance under the transparency, optimal wavelength 400nm, more preferably More than 90%, and then preferably more than 95%.As for glass transition temperature, preferably more than 250 DEG C, more preferably 300 DEG C Above, and then preferably more than 350 DEG C.As for birefringence, preferably less than 0.01, more preferably less than 0.005, Jin Eryou Elect less than 0.003 as.

The flexible base board of the resin combination containing the present invention may be used for liquid crystal display, organic el display, touch In the flexible devices such as sensitive device such as the display device of panel, Electronic Paper, light filter etc, solaode, CMOS.

Following operation is contained in the manufacturing process of flexible device: form display on the heat-resistant resin film being formed on substrate Circuit necessary to device, sensitive device.Such as can form the TFT of non-crystalline silicon on flexible substrates.And then can be thereon Structure necessary to device is formed by known method.By the above solid, shaped thermostability tree that circuit forming surface has waited like that Adipose membrane uses the known methods such as laser irradiation to peel off from substrate, it becomes possible to obtain flexible device.

Embodiment

It is exemplified below embodiment etc. and the present invention is described, but the present invention is not limited by these examples.

(1) making of heat-resistant resin film

Use the coating developing unit Mark-7 of Tokyo エ レ クトロン Co., Ltd. at the minute surface silicon wafer of 6 inches (ミ ラ シ リ U Application ウ ェ Ha) upper rotary coating varnish, its amount can make the thickness after 140 DEG C of prebake 4 minutes be 15 ±0.5μm.Then, the same electric hot plate using Mark-7 carries out 140 DEG C of pre-bake treatment 4 minutes.Prebake film uses inertia Gas baking oven (silver dollar サ モ シ ス テ system Co., Ltd. INH-21CD) (below oxygen concentration 20ppm) under nitrogen flowing with 3.5 DEG C/min is warmed up to 300 DEG C or 350 DEG C, keeps 30 minutes, is cooled to 50 DEG C with 5 DEG C/min and produces heat-resistant resin film. Then impregnate 1～4 minute in Fluohydric acid., from strippable substrate heat-resistant resin film, air-dry and obtain heat-resistant resin film.

(2) making of heat-resistant resin film (on glass substrate)

Use the spin coater MS-A200 of ミ カ サ Co., Ltd. at glass substrate (テ thick for 50mm × 50mm × 1.1mm Application パ ッ Network ス) rotary coating varnish, its amount can make 140 DEG C of prebake thickness after 4 minutes be 15 ± 0.5 μm.Then, make 140 DEG C of pre-bake treatment are carried out 4 minutes with big Japan ス Network リ Application Co., Ltd. heating plate D-SPIN.Prebake film is used Noble gas baking oven (silver dollar サ モ シ ス テ system Co., Ltd. INH-21CD) under nitrogen flowing (oxygen concentration 20ppm with Under) it is warmed up to 300 DEG C or 350 DEG C with 3.5 DEG C/min, keep 30 minutes, produce thermostability so that 5 DEG C/min is cooled to 50 DEG C Resin molding (on glass substrate).

(3) making of heat-resistant resin film (on silicon substrate)

Use rotation coating machine MS-A200 rotary coating on the 4 inches of silicon substrates be cut into 1/4 of ミ カ サ Co., Ltd. Varnish, its amount can make the thickness behind 140 DEG C of prebake × 4 minute be 5 ± 0.5 μm.Then, big Japan ス Network リ Application is used Co., Ltd. heating plate D-SPIN carries out 140 DEG C of pre-bake treatment 4 minutes.Prebake film is used noble gas baking oven (silver dollar サ モ シ ス テ system Co., Ltd. INH-21CD) under nitrogen flowing (below oxygen concentration 20ppm), with 3.5 DEG C/min heat up To 300 DEG C or 350 DEG C, keep 30 minutes, produce heat-resistant resin film (on silicon substrate) so that 5 DEG C/min is cooled to 50 DEG C.

(4) mensuration of light transmission (T)

Ultraviolet-visual spectrometer (Shimadzu Scisakusho Ltd MultiSpec1500) is used to measure the light under 400nm Absorbance.Furthermore, mensuration uses the heat-resistant resin film produced in (2).

(5) mensuration of total light transmittance (Tt)

Use direct-reading haze computer (ス ガ testing machine Co., Ltd. HGM2DP, illuminant-C) to measure in (1) to produce Total light transmittance of heat-resistant resin film.Furthermore, the value measured is used 1 time as Tt.Furthermore, mensuration uses in (1) The heat-resistant resin film produced.

In refractive index, face (6) mensuration of birefringence outside/face

Use prism coupler (METRICON society system, PC2010) measure wavelength 632.8nm TE refractive index (n (TE)) and TM refractive index (n (TM)).N (TE), n (TM) are parallel, the refractive index of vertical direction of polyimides face respectively.According to ((2 ×n(TE)²+ n (TM)²)/3) ^0.5 calculating mean refractive index n (AV), calculate difference (n (the TE)-n of n (TE) and n (TM) (TM)) as in face/face outside birefringence.Furthermore, mensuration uses the heat-resistant resin film produced in (3).

(7) glass transition temperature (Tg), the mensuration of coefficient of linear expansion (CTE)

Use thermo-mechanical analysis device (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ Co., Ltd. system EXSTAR6000TMA/SS6000) it is measured under nitrogen flowing.Temperature-rising method is to carry out by following condition.The 1st stage with 5 DEG C/min of heating rate be warmed up to 150 degree to remove the absorption water on sample, in the 2nd stage with rate of temperature fall 5 DEG C/min air It is cooled to room temperature.Carry out main mensuration in the 3rd stage with 5 DEG C/min of heating rate, obtain glass transition temperature.Further according to The meansigma methods of the coefficient of linear expansion of 50～200 DEG C in 3 stages obtains coefficient of linear expansion (CTE).Furthermore, mensuration uses (1) In the heat-resistant resin film produced.

The mensuration of (8) 1% weightless temperatures (Td1)

Use thermogravimetric amount determining device (Shimadzu Scisakusho Ltd TGA-50), be measured under nitrogen flowing.Rise Temperature method is carried out with following condition.It is warmed up to 350 degree with the absorption removing sample with 3.5 DEG C/min of heating rate in the 1st stage Water, is cooled to room temperature in the 2nd stage with 10 DEG C/min of rate of temperature fall.Main survey is carried out with 10 DEG C/min of heating rate in the 3rd stage Fixed, obtain 1% thermal weight loss temperature.Furthermore, mensuration uses the heat-resistant resin film produced in (1).

(9) mensuration of breaking stress, Breaking elongation, Young's modulus

Pulling force compression test (Tensilon) (Co., Ltd. オ リ エ Application テ ッ Network RTM-100) is used to be measured.Often More than 10 samples of individual sample determination, JIS quantity average (JISK-6301) is used to calculate JIS meansigma methods.Furthermore, in mensuration Use the heat-resistant resin film produced in (1).

(10) mensuration of b* value

The mensuration of the b* value of representational colour space CIELAB uses SM color computer (ス ガ testing machine Co., Ltd. SM-7-CH) carry out.Use illuminant-C as light source, measure and use through optical mode.Furthermore, in CIELAB b* value be yellow and Blue coordinate, corresponding near yellow during b* ＞ 0, corresponding near blue during b* ＜ 0.Furthermore, mensuration uses in (1) The heat-resistant resin film produced.

(11) making of embossing pattern

Photosensitive polymer combination (varnish) rotary coating produced in embodiment, on 8 inch silicon wafer, is connect down Come, use electric hot plate (Tokyo エ レ クトロン Co., Ltd. system, coating developing unit Mark-7), heat treatment at 120 DEG C (prebake) 3 minutes, and produce the prebake film of thickness 2～4 μm.Obtained prebake film is used i line stepper (GCA society system, DSW-8000) is with 20～320mJ/cm²Light exposure, with 10mJ/cm²Stepping exposes.In exposure use line and Space pattern is 1,2,3,4,5,6,7,8,9,10,15,20,30,50,100 μm.With the tetramethyl hydrogen of 2.38 weight % after exposure Amine-oxides (TMAH) aqueous solution (Rhizoma Sparganii ガ ス KCC system, ELM-D) develops 60 seconds, next uses pure water drip washing, Obtain embossing pattern.Furthermore, the thickness after prebake and after development, is to use big Japan ス Network リ Application to manufacture Co., Ltd.'s system Light interference type determining film thickness device ラ system ダ エ ス STM-602, measures with refractive index 1.63.

(12) calculating of film amount is lost in development

Calculate development according to following formula and lose film amount.

The thickness after the thickness-development after film amount (μm)=prebake is lost in development

(13) calculating of sensitivity

By after exposure, development with 1 to 1 formation 10 μm and the line of 20 μm and minimum exposure during space pattern (1L/1S) Amount is as sensitivity.

Describe the abbreviation of the compound used in embodiment below.

PMDA-HH:1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride

PMDA-HS:1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride

BPDA-H:3,3 ', 4,4 '-bicyclohexyl tetracarboxylic acid dianhydride

PMDA: pyromellitic acid anhydride

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

ODPA:3,3 ', the double O-phthalic acid dianhydride of 4,4 '-oxygen

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

Double ［ 3-(the 3-AB)-4-hydroxy phenyl ］ HFC-236fa of HFHA:2,2-

Double (4-aminophenyl) fluorenes of FDA:9,9-

CHDA: anti-form-1,4-diamino-cyclohexane

PDA: p-phenylenediamine

M-TB:2,2 '-dimethyl-4,4 '-benzidine

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

M-BAPS: double ［ 4-(3-amino-benzene oxygen) phenyl ］ sulfone

Double (3-aminopropyl) tetramethyl disiloxane of SiDA:1,3-

MAP: m-aminophenol

NMP:N-N-methyl-2-2-pyrrolidone N

GBL: gamma-butyrolacton

EL: ethyl lactate

DFA: dimethylformamide dimethyl acetal

Embodiment 1

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HH2.7704g (12mmol), HFHA7.4706g (12mmol), NMP50g, 80 DEG C of heated and stirred.After 8 hours, it is cooled into varnish.

Embodiment 2

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS2.7704g (12mmol), HFHA7.4706g (12mmol), NMP50g, 80 DEG C of heated and stirred.After 8 hours, it is cooled into varnish.

Embodiment 3

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add BPDA-H3.4441g (11mmol), HFHA6.7969g (11mmol), NMP50g, 80 DEG C of heated and stirred.After 8 hours, it is cooled into varnish.

Embodiment 4

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HH2.7704g (12mmol), HFHA6.5286g (10.8mmol), FDA0.4181g (1.2mmol) NMP50g, 80 DEG C of heated and stirred.After 8 hours, cool down shape Become varnish.

Embodiment 5

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add BPDA1.0238g (3.48mmol), PMDA- HH1.9099g (8.52mmol), CHDA0.4110g (3.60mmol), HFHA5.0778g (8.40mmol), NMP50g, at 80 DEG C Heated and stirred.After 8 hours, it is cooled into varnish.

Embodiment 6

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS3.4345g (15.3mmol), HFHA8.7985g (14.5mmol), FDA0.2669g (0.8mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, cool down Form varnish.

Embodiment 7

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS3.4893g (15.6mmol), HFHA8.4683g (14.0mmol), FDA0.5424g (1.6mmol), NMP50g, 30 DEG C of heated and stirred.After 8 hours, cool down Form varnish.

Embodiment 8

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS3.6042g (16.1mmol), HFHA7.7753g (12.9mmol), FDA1.1204g (3.2mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, cool down Form varnish.

Embodiment 9

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS3.7270g (16.6mmol), HFHA7.0351g (11.6mmol), FDA1.7379g (5.0mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, cool down Form varnish.

Embodiment 10

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS3.8584g (17.2mmol), HFHA6.2427g (10.3mmol), FDA2.3989g (6.9mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, cool down Form varnish.

Embodiment 11

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS3.9994g (17.8mmol), HFHA5.3924g (8.9mmol), FDA3.1082g (8.9mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, cool down shape Become varnish.

Comparative example 1

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add PMDA2.7154g (12mmol), HFHA7.5255g (12mmol), NMP50g, heated and stirred at 50 DEG C.After 2 hours, it is cooled into varnish.

Comparative example 2

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add BPDA3.3527g (11mmol), HFHA6.8883g (11mmol), NMP50g, heated and stirred at 50 DEG C.After 2 hours, it is cooled into varnish.

Comparative example 3

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add ODPA3.4731g (11mmol), HFHA6.7679g (11mmol), NMP50g, heated and stirred at 50 DEG C.After 2 hours, it is cooled into varnish.

Comparative example 4

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add PMDA-HH5.2599g (23mmol), m- TB4.9811g (23mmol), NMP50g, heated and stirred at 50 DEG C.After 2 hours, it is cooled into varnish.

Comparative example 5

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add 6FDA7.0599g (15.9mmol), HFHA9.6068g (15.9mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, it is cooled into varnish.

Comparative example 6

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add 6FDA7.2639g (16.4mmol), TFMB5.2361g (16.4mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, it is cooled into varnish.

Comparative example 7

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add 6FDA8.4450g (19.0mmol), m- BAPS8.2216g (19.0mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, it is cooled into varnish.

Comparative example 8

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add 6FDA7.824g (17.6mmol), FDA2.4547g (7.0mmol), HFHA6.3879g (10.6mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, it is cooled into varnish.

Comparative example 9

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HH5.1472g (23mmol), TFMB7.3528g (23mmol), NMP50g, heated and stirred at 50 DEG C.After 6 hours, it is cooled into varnish.

Comparative example 10

Flow down at drying nitrogen in the 4 of 100mL mouthfuls of flasks, add PMDA-HS5.6897g (25.4mmol), m- BAPS10.9770g (25.4mmol), NMP50g, heated and stirred at 50 DEG C.After 6 hours, it is cooled into varnish.

Comparative example 11

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add BPDA-H9.2384g (30.2mmol), PDA3.2616g (30.2mmol), NMP50g, heated and stirred at 50 DEG C.After 6 hours, it is cooled into varnish.

Comparative example 12

Drying nitrogen flow down in the 4 of 100mL mouthfuls of flasks add PMDA-HS4.1511g (18.5mmol), HFHA4.4776g (7.4mmol), FDA3.8714g (11.1mmol), NMP50g, 30 DEG C of heated and stirred.After 6 hours, cool down Form varnish.

Embodiment 1～11 and comparative example 1～12 in the composition of varnish of synthesis as shown in table 1.Additionally, to using these Varnish, the heat-resistant resin film obtained through the bakings of 350 DEG C measure light transmission (T), total light transmittance (Tt), TE refraction In rate (n (TE)), TM refractive index (n (TM)), mean refractive index (n (AV)), face/face outside birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), show the result in table 1.

[table 1]

Embodiment 12

Flow down at drying nitrogen and HFHA121.5804g (0.201mol) is dissolved in NMP400g.And then by PMDA- HS45.5372g (0.203mol) is added thereto together with NMP100g, and 30 DEG C are stirred 6 hours.Then, 12 hours it are stirred at room temperature. Then, stirring in 4 hours at 180 DEG C.Solution is put in water 3L after terminating by stirring, and polymer solids is collected by filtration.And then use Water 3L washes 5 times, is dried 72 hours by the polymer solids collected, and obtains polyimide powder in the drying machine of 50 DEG C.To Obtained polyimide powder 15g adds GBL47.5g, and obtains polyimide varnish.

Embodiment 13

Flow down at drying nitrogen and HFHA62.4272g (0.103mol), FDA23.9891g (0.069mol) are dissolved in NMP400g.And then PMDA-HS38.9695g (0.174mol) is added thereto together with NMP100g, 30 DEG C are stirred 6 hours.So After, it is stirred at room temperature 12 hours.Then, 180 DEG C are stirred 4 hours.Solution is put in water 3L after terminating by stirring, is collected by filtration poly- Compound solid.And then wash 5 times with water 3L, the polymer solids collected is dried 72 hours in the drying machine of 50 DEG C, and obtains Polyimide powder.In obtained polyimide powder 15g, add GBL47.5g, and obtain polyimide varnish.

Use the varnish of embodiment 12,13, measure the light transmission of the heat-resistant resin film obtained through the baking of 350 DEG C , in total light transmittance (Tt), TE refractive index (n (TE)), TM refractive index (n (TM)), mean refractive index (n (AV)), face (T)/ Outside face, birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), show the result in Table 2.

[table 2]

Embodiment 14

Flow down at drying nitrogen and HFHA121.5804g (0.201mol) is dissolved in NMP400g.And then by PMDA- HS45.5372g (0.203mol) is added thereto together with NMP100g, and 30 DEG C are stirred 6 hours.Then, 12 hours it are stirred at room temperature. Then, stirring in 4 hours at 180 DEG C.Solution is put in water 3L after terminating by stirring, and polymer solids is collected by filtration.And then use Water 3L washes 5 times, is dried 72 hours by the polymer solids collected, and obtains polyimide powder in the drying machine of 50 DEG C.Will Obtained by the polyimide powder baking oven of 350 DEG C under nitrogen flowing in heat treatment 30 minutes, just obtained polyimidesAzoles Powder.To obtained polyimidesAzoles powder 15g adds NMP47.5g and obtains polyimidesAzoles varnish.

Embodiment 15

Flow down at drying nitrogen and HFHA62.4272g (0.103mol), FDA23.9891g (0.069mol) are dissolved in In NMP400g.Adding together with NMP100g wherein and then by PMDA-HS38.9695g (0.174mol), 30 DEG C of stirrings 6 are little Time.Then 12 hours it are stirred at room temperature.Then stir 4 hours at 180 DEG C.Solution is put in water 3L after terminating by stirring, filters Collected polymer solid.And then wash 5 times with water 3L, the polymer solids collected is dried 72 hours in the drying machine of 50 DEG C, And obtain polyimide powder.By heat treatment 30 minutes in obtained the polyimide powder under nitrogen flowing baking oven of 350 DEG C, Just obtain polyimidesAzoles powder.To obtained polyimidesAzoles powder 15g adds NMP47.5g, just obtains PolyimidesAzoles varnish.

Use the varnish of embodiment 14,15, measure the light transmission of the heat-resistant resin film obtained through the baking of 350 DEG C , in total light transmittance (Tt), TE refractive index (n (TE)), TM refractive index (n (TM)), mean refractive index (n (AV)), face (T)/ Outside face, birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), show the result in Table 3.

[table 3]

Embodiment 16

In the way of varnish 100 weight portion obtained in silicon dioxide microparticle is relative to embodiment 1 is 10 weight portions, Xiang Ju Amic acid varnish adds Organic silica sols (Nissan Chemical Ind Ltd's system, trade name PMA-ST, particle diameter 10- 30nm), polyamic acid-Nano particles of silicon dioxide varnish is obtained.

Embodiment 17

In the way of varnish 100 weight portion obtained in silicon dioxide microparticle is relative to embodiment 1 is 20 weight portions, Xiang Ju Amic acid varnish adds Organic silica sols (Nissan Chemical Ind Ltd's system, trade name PMA-ST, particle diameter 10- 30nm), polyamic acid-Nano particles of silicon dioxide varnish is obtained.

Embodiment 18

In the way of varnish 100 weight portion obtained in silicon dioxide microparticle is relative to embodiment 1 is 30 weight portions, Xiang Ju Amic acid varnish adds Organic silica sols (Nissan Chemical Ind Ltd's system, trade name PMA-ST, particle diameter 10- 30nm), polyamic acid-Nano particles of silicon dioxide varnish is obtained.

The composition of the varnish made in embodiment 16～18 is as shown in table 4.Additionally, use these varnish, measure through 350 DEG C bakee and obtain the light transmission (T) of heat-resistant resin film, total light transmittance (Tt), TE refractive index (n (TE)), TM folding Penetrate in rate (n (TM)), mean refractive index (n (AV)), face/face outside birefringence, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), show the result in table 4.

[table 4]

Embodiment 19

The polyimide powder 4g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.044g, GBL13.47g, and obtain polyimide varnish.

Embodiment 20

The polyimide powder 4g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.044g, EPICLON850-S (trade name, big Japan イ Application キ chemical industry Co., Ltd.) 0.2g, GBL13.47g, and obtain polyimide varnish.

Embodiment 21

The polyimide powder 4g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.044g, EPICLON850-S (trade name, big Japan イ Application キ chemical industry Co., Ltd.) 0.4g, GBL13.47g, and obtain polyimide varnish.

Embodiment 22

The polyimide powder 4g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.044g, EPICLON850-S (trade name, big Japan イ Application キ chemical industry Co., Ltd.) 0.8g, GBL13.47g, and obtain polyimide varnish.

Use the varnish of embodiment 19～22, measure the light transmission of the heat-resistant resin film that the baking at 300 DEG C obtains Rate (T), total light transmittance (Tt), TE refractive index (n (TE)), TM refractive index (n (TM)), mean refractive index (n (AV)), face In/the outer birefringence in face, glass transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), disrumpent feelings answer Power, Breaking elongation, Young's modulus, show the result in table 5.

[table 5]

Reference example 1

With homogenizer (HOMO DISPER) by the PB15:6 (average primary particle diameter 30nm) of 117g, the gourmet powder Off of 140g The propylene glycol methyl ether acetate solution (30 weight %) of ァ イ Application テ Network ノ system " ア ジ ス パ " PB821, the ダ イ セ of 93g Le chemical industry Co., Ltd. system " サ イ Network ロ マ " ACA250 (45 weight % solution) and the propylene glycol monomethyl ether second of 627g Acid esters is bound together and makes slurry.Beaker and circulating bead mill dispersion machine (the ウ イ リ of this slurry is will be equipped with flexible pipe エ バ ッ コフェン society system " ダ イ ノ ミ Le " KDL-A) it is connected, the zirconium dioxide of diameter 0.3mm is used as medium Pearl carries out 3200rpm, the dispersion of 3 hours processes, thus obtains Blue pigment dispersion liquid.To obtained Blue pigment dispersion liquid 0.4167g adds GBL49.5833g, and obtains dilute solution.

Embodiment 23

The polyimide powder 13g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.013g, GBL36.3g, and obtain polyimide varnish.

Embodiment 24

The polyimide powder 13g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.013g, Blue pigment dispersion liquid 0.325g, GBL36.3g of obtaining in reference example 1, and obtain Polyimide varnish.

Embodiment 25

The polyimide powder 13g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.013g, Blue pigment dispersion liquid 0.650g, GBL36.3g of obtaining in reference example 1, and obtain Polyimide varnish.

Embodiment 26

The polyimide powder 13g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, altogether Rong She KCC system) 0.013g, Blue pigment dispersion liquid 0.975g, GBL36.3g of obtaining in reference example 1, and obtain Polyimide varnish.

Embodiment 27

The polyimide powder 13g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, common prosperity KCC of society system) 0.013g, Blue pigment dispersion liquid 1.300g, GBL36.3g of obtaining in reference example 1, and gathered Acid imide varnish.

Embodiment 28

The polyimide powder 13g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, common prosperity KCC of society system) 0.013g, Blue pigment dispersion liquid 1.625g, GBL36.3g of obtaining in reference example 1, and gathered Acid imide varnish.

Embodiment 29

The polyimide powder 13g obtained in embodiment 13 adds surfactant POLYFLOW77 (trade name, common prosperity KCC of society system) 0.013g, Blue pigment dispersion liquid 2.600g, GBL36.3g of obtaining in reference example 1, and gathered Acid imide varnish.

Use the varnish of embodiment 23～29, measure the light transmission of the heat-resistant resin film obtained through the baking of 350 DEG C In rate (T), b* value, TE refractive index (n (TE)), TM refractive index (n (TM)), mean refractive index (n (AV)), face/face outside birefringence Rate, shows the result in table 6.

[table 6]

Embodiment 30

Flow down at drying nitrogen and HFHA22.4g (0.037 mole), SiDA0.58g (0.0023 mole) are dissolved in In NMP105g.Add together with NMP20g wherein and then by ODPA5.75g (0.018 mole), stir 1 hour at 40 DEG C. Then, PMDA-HH6.23g is added together with NMP20g, stir 8 hours at 80 DEG C, be then stirred at room temperature 11 hours.So After, MAP1.011g is added together with NMP15g, stirs 1 hour at 60 DEG C.Then, dropping NMP10g dilutes The solution of DFA4.60g (0.038 mole), after dropping, continues to stir 1 hour at 60 DEG C.Then, carry out 2 times same Operation.Then, add acetic acid 16.69g under room temperature, stir 1 hour.Solution is put in water 2L after terminating by stirring, filters and receives Collection polymer solids.And then wash 5 times with water 2L, the polymer solids collected is dried 72 hours in the drying machine of 50 DEG C, and Obtain poly amic acid ester powder.

(Japan synthesizes Co., Ltd. to add diazonium naphtoquinone compounds TP-250 in obtained poly amic acid ester powder 4g System) 0.455g, HAP-170 (Japan synthesizes Co., Ltd.'s system) 0.455g, dissolution accelerator Tris-HAP (Honshu chemistry strain formula meeting Society's system) 0.421g, thermal cross-linking agent HMOM (Honshu KCC system) 0.682g, surfactant POLYFLOW77 (commodity Name, Kyoeisha Chemical Co., Ltd.'s system) 0.182g, EL9.3g, GBL6.9g, and obtain the varnish of photosensitive polymer combination.Make With obtained varnish, making embossing pattern by the method for above-mentioned (9), carry out photonasty evaluation, result development is lost film amount and is 0.17 μm, less, sensitivity is 300mJ/cm²。

Embodiment 31

(Japan closes to add diazonium naphtoquinone compounds HAP-170 in the polyimide powder 4.646g obtained in embodiment 12 Become Co., Ltd. system) 0.929g, thermal cross-linking agent HMOM (Honshu KCC system) 0.664g, surfactant POLYFLOW77 (trade name, Kyoeisha Chemical Co., Ltd.'s system) 0.011g, GBL18.75g, and obtain photosensitive resin composition The varnish of thing.Using the obtained varnish method of above-mentioned (9) to make embossing pattern and carry out photonasty evaluation, result development is lost Film amount be 1.27 μm, sensitivity be 125mJ/cm²。

Industry utilizability

In accordance with the invention it is possible to the film after offer heat treatment have the thermostability of excellence, light transmission, low birefringence poly- Amic acid resin combination.Film after heat treatment can perform well in flat faced display, touch panel, Electronic Paper, light filter The flexible base board such as substrate, solaode, the surface protection film of semiconductor element, interlayer dielectric, organic electroluminescent device The insulating barrier of (organic EL element) or wall, the planarization film of thin film transistor base plate, the insulating barrier of organic transistor, flexibility Printed base plate etc..

Claims (13)

1. a flexible base board, it is characterised in that sub-as the polyamides of main constituent containing the construction unit represented using formula (2) Amine,

In formula (2), R₁Represent 4 valency organic groups of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, Or the carbon number 4～40 that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure 4 valency organic groups, R₂Represent the divalent organic group of the carbon number 2～40 with at least 2 hydroxyls.

2. flexible base board as claimed in claim 1, it is characterised in that the R in formula (2)₁Be selected from following formula (4)～ (10) more than a kind in,

In formula (4)～(10), R₄～R₇₉Represent that hydrogen atom, halogen atom or hydrogen atom can also be by halogen atoms independently of one another 1 valency organic group of the carbon number 1～3 that instead of, the X in formula (7)₃Represent oxygen atom, sulphur atom, sulfonyl or hydrogen The divalent organic group of the carbon number 1～3 that atom can also be instead of by halogen atom, or more than two of which connect Divalent bridge crosslinking structure, the X in formula (10)₄Represent that Direct Bonding, oxygen atom, sulphur atom, sulfonyl, hydrogen atom also may be used The Asia that can also be instead of by halogen atom with the divalent organic group of carbon number 1～3 that be instead of by halogen atom or hydrogen atom Aryl, or the 2 of the carbon number 1～3 that can also be instead of by halogen atom selected from oxygen atom, sulphur atom, sulfonyl, hydrogen atom More than 2 the divalent bridgings being formed by connecting in the arlydene that valency organic group and hydrogen atom can also be instead of by halogen atom are tied Structure.

3. flexible base board as claimed in claim 1 or 2, it is characterised in that the R in formula (2)₂Represent with following formula (14),

4. flexible base board as claimed in claim 1, it is characterised in that using the construction unit represented by formula (2) as main one-tenth The polyimides divided contains the construction unit 10%～50% represented by formula (37),

In formula (37), R₁Represent 4 valency organic groups of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, Or the carbon number 4～40 that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure 4 valency organic groups.

5. flexible base board as claimed in claim 1, it is characterised in that the birefringence of described polyimides is less than 0.01.

6. flexible base board as claimed in claim 5, it is characterised in that the glass transition temperature of described polyimides is 300 More than DEG C.

7. a flexible base board, it is characterised in that containing using construction unit represented by formula (3) as the polyimides of main constituentAzoles,

In formula (3), R₁Represent 4 valency organic groups of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, Or the carbon number 4～40 that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure 4 valency organic groups, R₃Represent with formula (25) or (34),

8. a flexible base board, it is characterised in that containing using construction unit represented by formula (3) as the polyimides of main constituentAzoles,

In formula (3), R₁Represent 4 valency organic groups of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, Or the carbon number 4～40 that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure 4 valency organic groups,

Using construction unit represented by formula (3) as the polyimides of main constituentAzoles contains the structure list shown in formula (37) Unit 10～50%,

In formula (37), R₁Represent 4 valency organic groups of the carbon number 4～40 of the alicyclic structure with monocyclic or condensed ring formula, Or the carbon number 4～40 that the organic group with monocyclic alicyclic structure directly or is connected to each other via bridge crosslinking structure 4 valency organic groups.

9. flexible base board as claimed in claim 7 or 8, it is characterised in that the R in formula (3)₁Be selected from following formula (4)～ (10) more than a kind in,

In formula (4)～(10), R₄～R₇₉Represent that hydrogen atom, halogen atom or hydrogen atom can also be by halogen atoms independently of one another 1 valency organic group of the carbon number 1～3 that instead of, the X in formula (7)₃Represent oxygen atom, sulphur atom, sulfonyl or hydrogen The divalent organic group of the carbon number 1～3 that atom can also be instead of by halogen atom, or more than two of which connect Divalent bridge crosslinking structure, the X in formula (10)₄Represent that Direct Bonding, oxygen atom, sulphur atom, sulfonyl, hydrogen atom also may be used The Asia that can also be instead of by halogen atom with the divalent organic group of carbon number 1～3 that be instead of by halogen atom or hydrogen atom Aryl, or the 2 of the carbon number 1～3 that can also be instead of by halogen atom selected from oxygen atom, sulphur atom, sulfonyl, hydrogen atom More than 2 the divalent bridgings being formed by connecting in the arlydene that valency organic group and hydrogen atom can also be instead of by halogen atom are tied Structure.

10. flexible base board as claimed in claim 7, it is characterised in that described polyimidesThe birefringence of azoles be 0.01 with Under.

11. flexible base boards as claimed in claim 10, it is characterised in that described polyimidesThe glass transition temperature of azoles Degree is more than 300 DEG C.

12. 1 kinds of display devices, it is characterised in that there is the flexible base board described in any one of described claim 1～11.

13. 1 kinds of sensitive devices, it is characterised in that there is the flexible base board described in any one of described claim 1～11.