CN103842408A - Polyamic acid resin composition, polyimide resin composition, polyimide oxazole resin composition, and flexible substrate containing same - Google Patents

Polyamic acid resin composition, polyimide resin composition, polyimide oxazole resin composition, and flexible substrate containing same Download PDF

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CN103842408A
CN103842408A CN201280040267.2A CN201280040267A CN103842408A CN 103842408 A CN103842408 A CN 103842408A CN 201280040267 A CN201280040267 A CN 201280040267A CN 103842408 A CN103842408 A CN 103842408A
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carbonatoms
polyimide
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CN103842408B (en
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胁田润史
宫崎大地
三好一登
富川真佐夫
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Toray Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0108—Transparent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Provided are: a polyamic acid resin composition, polyimide resin composition, and polyimide oxazole resin composition of which a post-heat-treatment film has superior heat resistance, transparency, and low birefringence; and a flexible substrate containing same. The polyamic acid resin composition is characterized by containing: (a) a polyamic acid having as the primary component the structural unit represented in general formula (1); and (b) a solvent. (In general formula (1): X1 and X2 each independently represent a hydrogen atom or a monovalent organic group having 1-10 carbon atoms; R1 represents a tetravalent organic group having 4-40 carbon atoms having an alicyclic structure that is a monocycle or a fused polycycle, or a tetravalent organic group having 4-40 carbon atoms wherein organic groups having a monocyclic alicyclic structure are bonded to each other directly or with a cross-linking structure therebetween; and R2 represents a divalent organic group having 2-40 carbon atoms and having at least two hydroxyl groups.)

Description

Polyamic acid resin composition, polyimide resin composition and polyimide * azoles resin combination and the flexible base, board that contains them
Technical field
The flexible base, board that the present invention relates to polyamic acid resin composition, polyimide resin composition and polyimide azoles resin combination and contain them.More particularly, relate to polyamic acid resin composition, polyimide resin composition and the polyimide of flexible base, board, flexible printed boards etc. such as can performing well in flat-panel monitor, touch panel, Electronic Paper, colour filtering chip basic board, solar cell azoles resin combination and the flexible base, board that contains them.
Background technology
Organic membrane has with glassy phase ratio and is rich in bendability, is difficult for fragmentation, lightweight characteristic.Recently, by the substrate of flat-panel monitor is changed to organic membrane, make the research of indicating meter snappiness become active all the more.
When make indicating meter on organic membrane time, conventionally carry out following operation: by organic membrane film forming on supporting substrates, make after device, peel off from supporting substrates.Just organic membrane with regard to film forming, is had to following methods on supporting substrates.For example, use jointing material etc. that organic membrane is attached to the method (for example, patent documentation 1) on glass substrate.Or, using containing solution coat as the resin of the raw material of film etc. on supporting substrates, utilize heat to wait it solidified, the method (for example patent documentation 2) of making.The former need to arrange jointing material between supporting substrates and film, is sometimes restricted because the thermotolerance of tackiness agent causes later processing temperature.On the other hand, the latter is not using the aspect excellences such as the surface smoothness height of tackiness agent, masking caudacoria.
As the resin using in organic membrane, can enumerate polyester, polymeric amide, polyimide, polycarbonate, polyethersulfone, acrylic resin, epoxy resin etc.Wherein, polyimide, as high heat resistance resin, is suitable as display base plate.Particularly polyimide resin, not only has high heat resistance, and has the excellent electrical characteristic such as mechanical characteristics, insulativity that high mechanical strength, wear resistant, dimensional stability, resistance to chemical reagents etc. are excellent concurrently, thereby is widely used in electric and electronic industrial field.The coating method of stating in the use, by the situation of polyimide film forming, can use the solution that contains polyamic acid precursor is coated with, and it is solidified and becomes the method for polyimide.Conventionally polyamic acid can be by making acid anhydrides and diamine reactant easily synthesize in solvent.
Although all aromatic polyimide being derived by aromatic acid dianhydride and aromatic diamine has high heat resistance, but existence derives from intermolecular electric charge in molecule and moves the absorption band in the visible wavelength territory of coordination compound, so the polyimide film obtaining is Huang～dark brown.In addition, conventionally there is larger birefringence.For this reason, existence can not be as the problem that needs the display base plate of high transparent, low-birefringence to use.Want the equivalent material that can serve as glass substrate to use, generally need: in the time of 10 microns of thickness, the optical transmittance of 400nm is more than 80%, it is more than 300 degree that second-order transition temperature (Tg) or thermolysis start temperature, and the double refraction in visible wavelength territory (400nm～800nm) is the low-birefringence below 0.01.
The method that moves interaction, raising light transmission as the electric charge that suppresses polyimide, can list the method that uses ester ring type monomer as at least arbitrary composition in acid dianhydride and diamines.
For example patent documentation 3 discloses the polyimide being obtained by ester ring type acid dianhydride and various aromatic series or ester ring type diamines and has had high transparent, low birefringence.
In patent documentation 4, disclose by 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic acid dianhydride and 2,2 '-polyimide that bis-(trifluoromethyl) p-diaminodiphenyl (TFMB) obtains has high transparent, high Tg.In addition patent documentation 4 has been recorded and has been used 2,2 '-bis-(4-(4-amino-benzene oxygen) phenyl) HFC-236fa (HFBAPP) to replace the polyimide film of 2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl to have high transparent.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2006-091822 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2007-512568 communique
Patent documentation 3: Japanese kokai publication hei 11-080350 communique
Patent documentation 4: TOHKEMY 2010-085992 communique
Summary of the invention
The problem that invention will solve
But the Tg of the polyimide cohort of recording in patent documentation 3 is insufficiently high.In addition, the polyimide group who records in patent documentation 4, Tg and double refraction can not meet the common characteristic that requires.
Like this, current present situation is that high transparent, high heat resistance, all polyimide materials that require characteristic all to meet of low-birefringence are also not known.
The present invention is in view of above-mentioned problem, and its problem is to provide film after thermal treatment and has polyamic acid resin composition, polyimide resin composition and the polyimide of excellent thermotolerance, light transmission, low-birefringence
Figure 2012800402672100002BDA0000466894510000031
azoles resin combination and the flexible base, board that contains them.
Solve the means of problem
In order to solve the problem of telling about above, realize object, polyamic acid resin composition of the present invention, is characterized in that, contain (a) using the represented structural unit of general formula (1) as the polyamic acid of principal constituent and (b) solvent
Figure BDA0000466894510000032
In general formula (1), X 1, X 2represent independently of one another 1 valency organic group of hydrogen atom or carbonatoms 1～10, R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 2represent the divalent organic group of the carbonatoms 2～40 with at least 2 hydroxyls.
In addition, polyimide resin composition of the present invention, is characterized in that, contains (a ') using the represented structural unit of general formula (2) as the polyimide of principal constituent and (b) solvent,
Figure BDA0000466894510000033
(in general formula (2), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 2represent the divalent organic group of the carbonatoms 2～40 with at least 2 hydroxyls.)
In addition polyimide of the present invention,
Figure BDA0000466894510000041
azoles resin combination, is characterized in that, contains (a ' ') polyimide using the represented structural unit of general formula (3) as principal constituent azoles and (b) solvent,
(in general formula (3), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 3represent 4 valency organic groups of carbonatoms 2～40.)
Invention effect
By the present invention, the film that can obtain after thermal treatment has the high light transmittance of excellent thermotolerance, visible region, polyamic acid resin composition, polyimide resin composition and the polyimide of low-birefringence
Figure BDA0000466894510000044
azoles resin combination and the flexible base, board that contains them.
Embodiment
Below, illustrated implementing mode of the present invention with reference to accompanying drawing.Moreover, be not to limit the present invention by following embodiment.In addition, each figure of institute's reference in the following description, be only degree can understand content of the present invention roughly property shape, size and position relationship are shown., the present invention is also not only confined to illustrative shape, size and position relationship in each figure.
The 1st scheme of the present invention is a kind of polyamic acid resin composition, it is characterized in that, contains (a) using the represented structural unit of general formula (1) as the polyamic acid of principal constituent and (b) solvent.The 2nd scheme of the present invention is a kind of polyimide resin composition, it is characterized in that, contains (a ') using the represented structural unit of general formula (2) as the polyimide of principal constituent and (b) solvent.The 3rd scheme of the present invention is a kind of polyimide
Figure BDA0000466894510000045
azoles resin combination, is characterized in that, contains (a ' ') polyimide using the represented structural unit of general formula (3) as principal constituent
Figure BDA0000466894510000046
azoles and (b) solvent.
Figure BDA0000466894510000051
X in general formula (1) 1, X 2represent independently of one another 1 valency organic group of hydrogen atom or carbonatoms 1～10.In general formula (1)～(3), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure.In general formula (1), (2), R 2represent the divalent organic group of the carbonatoms 2～40 with at least 2 hydroxyls.In general formula (3), R 3represent 4 valency organic groups of carbonatoms 2～40.
Polyamic acid of the present invention, as long as using the represented structural unit of described general formula (1) as principal constituent, also can contain other structural unit.Can list as other structural unit, as the polyamic acid of the polycondensate of acid dianhydride and diamine compound, as the polyhydroxyamide of the polycondensate of dicarboxylic acid derivatives and hydroxyl diamines, as the dehydration closed-loop body polyphenyl of the polyimide of the dehydration closed-loop body of polyamic acid, polyhydroxyamide also
Figure BDA0000466894510000052
azoles etc., also can contain the R in the represented structural unit of for example described general formula (2), described general formula (3) represented structural unit, described general formula (1) 1r in polyamic acid during for aromatic nucleus, described general formula (2) 1r during for aromatic nucleus in polyimide, described general formula (3) 1polyimide benzo during for aromatic nucleus
Figure BDA0000466894510000053
azoles.The represented structural unit of preferred described general formula (1) accounts for all more than 50%, more preferably accounts for more than 70%, and then preferably accounts for more than 90%.
Polyamic acid can be as described later, synthesize by the reaction of diamine compound and acid dianhydride or derivatives thereof.As derivative, can list single, two, three or four esters, acyl chlorides compound of tetracarboxylic acid, this tetracarboxylic acid of this acid dianhydride etc.
Polyimide of the present invention, as long as using the represented structural unit of described general formula (2) as principal constituent, also can contain other structural unit.As other structural unit, can list polyamic acid, polyhydroxyamide, polyimide, polyphenyl also azoles etc.Also can contain the R in the represented structural unit of for example described general formula (1), described general formula (3) represented structural unit, described general formula (1) 1r in polyamic acid during for aromatic nucleus, described general formula (2) 1r in polyimide during for aromatic nucleus, described general formula (3) 1polyimide benzo during for aromatic nucleus
Figure BDA0000466894510000062
azoles.The represented structural unit of preferred described general formula (2) accounts for all more than 50%, more preferably accounts for more than 70%, and then preferably accounts for more than 90%.
Polyimide, the dehydration closed-loop reaction of can be as described later carrying out thermal dehydration closed loop, chemical by the polyamic acid that reacts synthetic by diamine compound, with acid dianhydride or derivatives thereof is synthesized.
Polyimide of the present invention
Figure BDA0000466894510000063
azoles, as long as using the represented structural unit of described general formula (3) as principal constituent, also can contain other structural unit.As other structural unit, can list polyamic acid, polyhydroxyamide, polyimide, polyphenyl also
Figure BDA0000466894510000064
azoles etc., can contain the R in the represented structural unit of for example described general formula (1), general formula (2) represented structural unit, described general formula (1) 1r in polyamic acid during for aromatic nucleus, described general formula (2) 1r in polyimide during for aromatic nucleus, described general formula (3) 1polyimide benzo during for aromatic nucleus
Figure BDA0000466894510000065
azoles.The represented structural unit of described general formula (3) preferably accounts for all more than 50%, more preferably accounts for more than 70%, and then preferably accounts for more than 90%.
Polyimide
Figure BDA0000466894510000066
azoles can as described later, synthesize by the dehydration closed-loop reaction of being carried out thermal dehydration closed loop, chemical by the polyamic acid that has the diamine compound of oxyamide base, react synthetic with acid dianhydride or derivatives thereof.Can be by by having
Figure BDA0000466894510000067
the polyamic acid that the diamine compound of azoles ring reacts synthetic with acid dianhydride or derivatives thereof carries out the dehydration closed-loop reaction of thermal dehydration closed loop or chemical and synthesizes.
R in general formula (1)～(3) 1represent the structure of sour composition, represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure.At this, a part of hydrogen atom of described alicyclic structure also can replace by halogen.In addition these sour compositions can be used separately or multiple combination use as sour composition.
If illustrate the acid dianhydride with alicyclic structure that can use in the present invention, can list 1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-hexanaphthene tetracarboxylic acid dianhydride, 1,2,4,5-cyclopentane tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl--1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic acid dianhydride, 1,2,3,4-suberane tetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran (THF) tetracarboxylic acid dianhydride, 3,4-dicarboxyl-1-cyclohexyl succsinic acid dianhydride, 2,3,5-tricarboxylic base NSC 60134 dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene-1-naphthalene succinic dianhydride, dicyclo ［ 3.3.0 ］ octane-2,4,6,8-tetracarboxylic acid dianhydride, dicyclo ［ 4.3.0 ］ nonane-2,4,7,9-tetracarboxylic acid dianhydride, dicyclo ［ 4.4.0 ］ decane-2,4,7,9-tetracarboxylic acid dianhydride, dicyclo ［ 4.4.0 ］ decane-2,4,8,10-tetracarboxylic acid dianhydride, three ring ［ 6.3.0.0 < 2,6 > ］ undecane-3,5,9,11-tetracarboxylic acid dianhydride, dicyclo ［ 2.2.2 ］ octane-2,3,5,6-tetracarboxylic acid dianhydride, dicyclo ［ 2.2.2 ］ is pungent-7-alkene-2, and 3,5,6-tetracarboxylic acid dianhydride, dicyclo ［ 2.2.1 ］ heptane tetracarboxylic acid dianhydride, dicyclo ［ 2.2.1 ］ heptane-5-carboxymethyl-2,3,6-tricarboxylic 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 dianhydride, 3,3 ', 4,4 '-bicyclohexyl tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-oxygen bicyclohexane tetracarboxylic acid dianhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid anhydride, " Rikacid " (registered trademark) BT-100 (is trade(brand)name above, New Japan Chem Co., Ltd's system) and their derivative etc.
In said structure, as the R in general formula (1)～(3) 1preferably, can list for example following general formula (4)～(10) represented structure.
Figure BDA0000466894510000081
Figure BDA0000466894510000091
In general formula (4)～(10), R 4～R 79represent independently of one another 1 valency organic group of the carbonatoms 1～3 that hydrogen atom, halogen atom or hydrogen atom also can replace by halogen atom.As the alicyclic structure of general formula (4)～(6), can list respectively tetramethylene, pentamethylene, hexanaphthene etc.X in general formula (7) 3the divalent organic group of the carbonatoms 1～3 that also can have been replaced by halogen atom for Sauerstoffatom, sulphur atom, alkylsulfonyl or hydrogen atom, or two divalent bridge crosslinking structures that are formed by connecting above in them.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 the alicyclic structure of general formula (8), (9), can list respectively perhydronaphthalene, ten tetrahydrochysene anthracenes.X in general formula (10) 4arylidene that the divalent organic group of the carbonatoms 1～3 that also can have been replaced by halogen atom for Direct Bonding, Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom or hydrogen atom also can have been replaced by halogen atom, or be selected from 2 divalent bridge crosslinking structures that are formed by connecting above in the arylidene that the divalent organic group of the carbonatoms 1～3 that Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom also can replace by halogen atom and hydrogen atom also can replace by halogen atom.As this alicyclic structure, can list 1,1-bis cyclohexane, oxygen bicyclohexane etc.
If enumerate above-mentioned acid dianhydride, can list 1, 2, 3, 4-tetramethylene tetracarboxylic acid dianhydride, 1, 2, 3, 4-cyclopentane tetracarboxylic acid dianhydride, 1, 2, 3, 4-hexanaphthene tetracarboxylic acid dianhydride, 1, 2, 4, 5-cyclopentane tetracarboxylic acid dianhydride, 1, 2, 3, 4-tetramethyl--1, 2, 3, 4-tetramethylene tetracarboxylic acid dianhydride, 1, 2-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dianhydride, 1, 3-dimethyl-1, 2, 3, 4-tetramethylene tetracarboxylic acid dianhydride, 1, 2, 3, 4-suberane tetracarboxylic acid dianhydride, dicyclo ［ 2.2.2 ］ is pungent-7-alkene-2, 3, 5, 6-tetracarboxylic acid dianhydride, dicyclo ［ 2.2.1 ］ heptane tetracarboxylic 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 dianhydride, 3, 3 ', 4, 4 '-bicyclohexyl tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 '-oxygen bicyclohexane tetracarboxylic acid dianhydride etc.
Among this, the viewpoint based on commercially available, easy acquisition and with reactive viewpoint of diamine compound, the R in preferred formula (1) 1represent with following chemical formula (11)～(13), 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-bicyclohexyl tetracarboxylic acid dianhydride.These acid dianhydrides are sold with ProductName " PMDA-HH ", " PMDA-HS ", " BPDA-H " by Yan Gu gas Co., Ltd..Moreover these acid dianhydrides can use separately or two or more is used in combination.
In addition,, not destroying in the limit of effect of the present invention, also can change a part for this acid dianhydride into other acid dianhydride and use.As acid dianhydride, can list aromatic acid dianhydride or aliphatic acid dianhydride.For example, as aromatic acid dianhydride, can list pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-terphenyl tetracarboxylic acid dianhydride, 3,3 ', 4, the two O-phthalic acid dianhydrides of 4 '-oxygen, 2,3, the two O-phthalic acid dianhydrides of 3 ', 4 '-oxygen, 2,3, the two O-phthalic acid dianhydrides of 2 ', 3 '-oxygen, sulfobenzide-3,3 ', 4,4 '-tetracarboxylic acid dianhydride, BP-3,3 ', 4,4 '-tetracarboxylic acid dianhydride, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2,2-, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2,2-, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (2,3-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (3,4-dicarboxyl phenyl) methane dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (1,3-dioxo-1,3-dihydroisobenzofuran-5-formic acid) Isosorbide-5-Nitrae-penylene, two (4-(4-amino-benzene oxygen) phenyl) propane of 2,2-, 1,2,5,6-naphthalenetetracarbacidic acidic dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2,2-, two (4-(3, the 4-di carboxyl phenyloxy) phenyl) hexafluoropropane dianhydrides of 2,2-, two (4-(3, the 4-dicarboxyl benzoyloxy) phenyl) hexafluoropropane dianhydrides of 2,2-, 1,6-difluoro pyromellitic acid anhydride, 1-trifluoromethyl pyromellitic acid anhydride, 1,6-, bis-trifluoromethyl pyromellitic acid anhydrides, 2,2 '-bis-(trifluoromethyl)-4,4 '-bis-(3,4-di carboxyl phenyloxy) biphenyl dianhydride, " Rikacid " (registered trademark) TMEG-100 (trade(brand)name, New Japan Chem Co., Ltd's system) etc. the derivative etc. of aromatic series tetracarboxylic acid dianhydride and they.As aliphatic acid dianhydride, can list 1,2,3,4-ethylene-dimalonic acid dianhydride, 1,2,3,4-pentane tetracarboxylic acid dianhydride and their derivative etc., but do not limit to these.In addition, these other acid dianhydrides can use separately or two or more is used in combination.
R in general formula (1), (2) 2be the divalent organic group with the carbonatoms 2～40 of at least 2 hydroxyls, can list for example chemical formula (14)～(23) represented structure.
Figure BDA0000466894510000121
Among these, based on transparent viewpoint, preferably the structure of chemical formula (14), is preferably used the represented diamines of following chemical formula (24).
Figure BDA0000466894510000122
R in general formula (3) 3the 4 valency organic groups that represent carbonatoms 2～40, can list for example chemical formula (25)～(34) represented structure.Viewpoint among these, based on transparent, the preferably structure of chemical formula (25).
Figure BDA0000466894510000131
Figure BDA0000466894510000141
Moreover, the polyimide when R3 in general formula (3) represents with chemical formula (25)
Figure BDA0000466894510000142
azoles is the dehydration closed-loop body of the represented polyimide of the polyamic acid represented by the synthetic general formula (1) of the represented diamines of above-mentioned chemical formula (24) and general formula (2).
In addition,, not destroying in the limit of effect of the present invention, also can change a part for this diamine compound into other diamine compound and use.As other diamine compound, can list aromatic diamine compound, ester ring type diamine compound or aliphatie diamine compound.For example, as aromatic diamine compound, can list 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, two (4-aminophenyl) HFC-236fa of 2,2-, two (3-amino-4-aminomethyl phenyl) HFC-236fa of 2,2-, two (3-amino-4-hydroxylphenyl) HFC-236fa of 2,2-, 3,3 '-diamino-diphenyl thioether, 4,4 '-diamino-diphenyl thioether, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, p-diaminodiphenyl, 2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl, 3,3 '-bis-(trifluoromethyl) p-diaminodiphenyl, 2,2 '-tolidine, 3,3 '-tolidine, 2,2 ', 3,3 '-tetramethyl benzidine, mphenylenediamine, Ursol D, 1,5-naphthylene diamine, 2,6-naphthylene diamine, two { 4-(4-amino-benzene oxygen phenyl) } sulfone, two { 4-(3-amino-benzene oxygen phenyl) } sulfone, two (4-amino-benzene oxygen) biphenyl, two { 4-(4-amino-benzene oxygen) phenyl } ether, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, 4,4-diaminobenzene formylaniline, 3,4-diaminobenzene formylaniline, 4,4-diaminobenzophenone, 3,3-diaminobenzophenone or their aromatic ring are by alkyl, alkoxyl group, the diamine compound that halogen atom etc. replace, but do not limit to these.
As ester ring type diamine compound, can list tetramethylene diamines, isophorone diamine, the two methylamines of dicyclo ［ 2.2.1 ］ heptane, three ring ［ 3.3.1.13,7 ］ decane-1,3-diamines, 1,2-cyclohexyl diamines, 1,3-cyclohexyl diamines, Isosorbide-5-Nitrae-cyclohexyl diamines, 4,4 '-diamino-dicyclohexyl methane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 3,3 '-diethyl-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 '-diamino-dicyclohexyl methane, 4,4 '-diamino dicyclohexyl ether, 3,3 '-dimethyl-4,4 '-diamino dicyclohexyl ether, 3,3 '-diethyl-4,4 '-diamino dicyclohexyl ether, 3,3 ', 5,5 '-tetramethyl--4,4 '-diamino dicyclohexyl ether, 3,3 ', 5,5 '-tetraethyl--4,4 '-diamino dicyclohexyl ether, 3,5-diethyl-3 ', 5 '-dimethyl-4,4 '-diamino dicyclohexyl ether, two (4-aminocyclohexyl) propane of 2,2-, two (3-methyl-4-aminocyclohexyl) propane of 2,2-, two (3-ethyl-4-aminocyclohexyl) propane of 2,2-, two (3, the 5-dimethyl-4-aminocyclohexyl) propane of 2,2-, two (3, the 5-diethyl-4-aminocyclohexyl) propane of 2,2-, 2,2-(3,5-diethyl-3 ', 5 '-dimethyl-4,4 '-diamino dicyclohexyl) propane, 2,2 '-bis-(4-aminocyclohexyl) HFC-236fa, 2,2 '-dimethyl-4,4 '-diamino bicyclic hexane, 2,2 '-bis-(trifluoromethyl)-4,4 '-diamino bicyclic hexane, or their alicyclic ring is by alkyl, alkoxyl group, the diamine compound that halogen atom etc. have replaced, but do not limit to these.
As aliphatie diamine compound, can list quadrol, 1, 3-diaminopropanes, 1, 4-diaminobutane, 1, 5-1,5-DAP, 1, 6-diamino hexane, 1, 7-diamino heptane, 1, 8-diamino-octane, 1, 9-diamino nonane, 1, the Alkylenediamine classes such as 10-diamino decane, two (amino methyl) ether, two (2-amino-ethyl) ether, the ethylene glycol bisthioglycolate amines such as two (3-aminopropyl) ether, with 1, two (3-aminopropyl) tetramethyl disiloxanes of 3-, 1, two (4-aminobutyl) tetramethyl disiloxanes of 3-, α, the siloxane diamine classes such as ω-bis-(3-aminopropyl) polydimethylsiloxane, but do not limit to these.
These aromatic diamine compounds, ester ring type diamine compound or aliphatie diamine compound can be used singly or two or more kinds in combination.
Among these, preferably use following chemical formula (35) represented 9, two (4-aminophenyl) fluorenediamines of 9-, find the transparency and the mechanical characteristics that can keep like this curing film, improve second-order transition temperature, reduce degree of birefringence.
By using the represented diamines of chemical formula (35), can in molecular chain, import following general formula (36) or the represented structural unit of following general formula (37).
Figure BDA0000466894510000162
(the X in general formula (36) 1, X 2represent independently of one another 1 valency organic group of hydrogen atom or carbonatoms 1～10.In general formula (36), (37), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure.)
Conventionally, use the polyimide film of the represented diamines of chemical formula (35) to have painted more.As described later (comparative example 8), use 4 as the starting monomer of clear polyimides, the diamines that 4 '-(hexafluoroisopropyli,ene base) diphthalic anhydrides and above-mentioned chemical formula (35) are represented etc. and polyimide film, with polyimide of the present invention and polyimide azoles film is compared, transparency deterioration.As for polyimide of the present invention and polyimide
Figure BDA0000466894510000172
azoles film, so owing to having used ester ring type acid dianhydride can suppress painted.
The represented diamines of described chemical formula (35) preferably accounts for more than 10% scope below 50% of total diamines residue, more preferably accounts for more than 30% scope below 50%, and then preferably accounts for more than 40% scope below 50%.By like this, at polyamic acid of the present invention, polyimide and polyimide
Figure BDA0000466894510000173
in azoles, general formula (36) or the represented structural unit of general formula (37) account for 10%～50%.
Polyamic acid of the present invention, polyimide and polyimide azoles, for molecular weight is transferred to preferable range, also can make two end closures with end-capping reagent.As the end-capping reagent that can react with acid dianhydride, can list monoamine or monovalent alcohol etc.In addition,, as the end-capping reagent that can react with diamine compound, can list acid anhydrides, monocarboxylic acid, single chloride compounds, single active ester compound etc.In addition,, by reacting with end-capping reagent, can import various organic groups as terminal group.
The monoamine using 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 naphthalenes, 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-carboxyl-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 naphthalenes, 2-carboxyl-5-amino naphthalenes, 2-carboxyl-4-amino naphthalenes, 2-carboxyl-3-amino naphthalenes, 1-amino-2-carboxyl naphthalene, 2-amino-nicotinic acid, 4-amino-nicotinic acid, 5-amino-nicotinic acid, 6-amino-nicotinic acid, 4-ASA, 5-aminosalicylic acid, 6-aminosallcylic acid, ameride, 2-benzaminic acid, 3-benzaminic acid, PABA, 2-aniline sulfonic acid, 3-aniline sulfonic acid, 4-aniline sulfonic acid, 3-amino-4,6-dihydroxy-pyrimidine, Ortho-Aminophenol, 3-amino-phenol, PAP, 5-amino-thiooxine, 4-amino-thiooxine, 1-sulfydryl-8-amino naphthalenes, 1-sulfydryl-7-amino naphthalenes, 1-sulfydryl-6-amino naphthalenes, 1-sulfydryl-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 naphthalenes, 1-amino-2-mercapto phenyl formic naphthalene, 3-amino-4,6-dimercapto pyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 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-ethynyl-2-amino naphthalenes, 1-ethynyl-3-amino naphthalenes, 1-ethynyl-4-amino naphthalenes, 1-ethynyl-5-amino naphthalenes, 1-ethynyl-6-amino naphthalenes, 1-ethynyl-7-amino naphthalenes, 1-ethynyl-8-amino naphthalenes, 2-ethynyl-1-amino naphthalenes, 2-ethynyl-3-amino naphthalenes, 2-ethynyl-4-amino naphthalenes, 2-ethynyl-5-amino naphthalenes, 2-ethynyl-6-amino naphthalenes, 2-ethynyl-7-amino naphthalenes, 2-ethynyl-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.
In addition, the monovalent alcohol using as end-capping reagent, can list methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-enanthol, 3-enanthol, 1-octanol, sec-n-octyl alcohol, 3-octanol, 1 nonyl alcohol, 2-nonyl alcohol, 1-decanol, 2-decyl alcohol, 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-propyl alcohol, 2-methyl-2-propanol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 2-methyl-2-butanols, 3-methyl-2-butanols, 2-propyl group-1-amylalcohol, 2-ethyl-1-hexanol, 4-methyl-3-enanthol, 6-methyl-2-enanthol, 2,4,4-trimethylammonium-1-hexanol, 2,6-2,6-dimethyl-4-heptanol, different nonyl alcohol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptyl-undecylenic alcohol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, carbiphene, diethylene glycol monomethyl ether, diglycol monotertiary butyl ether, cyclopentanol, hexalin, pentamethylene list methyl alcohol, two pentamethylene list methyl alcohol, tristane list methyl alcohol, norborneol, terpinol etc., but do not limit to these.
The acid anhydrides using as end-capping reagent, monocarboxylic acid, single chloride compounds and single active ester compound, can list Tetra hydro Phthalic anhydride, maleic anhydride, carbic anhydride, cyclohexane cyclohexanedimethanodibasic acid anhydride, the acid anhydrides such as 3-hydroxyl phthalic anhydride, 2-carboxylic phenol, 3-carboxylic phenol, 4-carboxylic phenol, 2-carboxyl thiophenol, 3-carboxyl thiophenol, 4-carboxyl thiophenol, 1-hydroxyl-8-carboxyl 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-sulfydryl-5-carboxyl naphthalene, 1-sulfydryl-4-carboxyl naphthalene, 1-sulfydryl-3-carboxyl naphthalene, 1-sulfydryl-2-carboxyl naphthalene, 2-carboxyl Phenylsulfonic acid, 3-carboxyl Phenylsulfonic acid, 4-carboxyl Phenylsulfonic acid, 2-acetylenylbenzene formic acid, 3-acetylenylbenzene formic acid, 4-acetylenylbenzene formic acid, 2,4-diacetylene phenylformic acid, 2,5-diacetylene phenylformic acid, 2,6-diacetylene phenylformic acid, 3,4-diacetylene phenylformic acid, 3,5-diacetylene phenylformic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, the carboxyl of the monocarboxylic acid classes such as 8-ethynyl-2-naphthoic acid and they by chloride single chloride compounds, and terephthalic acid, phthalic acid, toxilic acid, cyclohexane cyclohexanedimethanodibasic, 3-hydroxyl phthalic, 5-norbornylene-2,3-dioctyl phthalate, 1,2-dicarboxyl naphthalene, 1,3-dicarboxyl naphthalene, Isosorbide-5-Nitrae-dicarboxyl naphthalene, 1,5-dicarboxyl naphthalene, 1,6-dicarboxyl naphthalene, 1,7-dicarboxyl naphthalene, 1,8-dicarboxyl naphthalene, 2,3-dicarboxyl naphthalene, 2,6-dicarboxyl naphthalene, an only carboxyl of the omega-dicarboxylic acids such as 2,7-dicarboxyl naphthalene is by single chloride compounds of chloride, and by single chloride compounds and N-hydroxybenzotriazole or N-hydroxyl-5-norbornylene-2, the active ester compound that 3-dicarboxyl imide reaction obtains.
The monoamine that end-capping reagent uses, the importing ratio of monohydroxy-alcohol, with respect to whole amine components, preferably the scope of 0.1～60 % by mole, coating is preferably at 5～50 % by mole.The acid anhydrides, monocarboxylic acid, single chloride compounds using as end-capping reagent and single active ester compound import ratio, with respect to two amine components preferably the scope of 0.1～100 % by mole, particularly preferably 5～90 % by mole.Can also, by reacting with multiple end-capping reagent, import multiple different terminal group.
At polyamic acid, polyimide and polyimide
Figure BDA0000466894510000191
the end-capping reagent importing in azoles, can easily detect by following method.For example by the polymer dissolution that has imported end-capping reagent in acidic solution, resolve into amine component and acid anhydrides composition as the Component units of polymkeric substance, use gas-chromatography (GC), NMR to measure to it, just can easily detect end-capping reagent.In addition, also the polymkeric substance that has imported end-capping reagent directly can be used Thermal decomposition gas chromatography (PGC), infrared spectra and 13cNMR spectrum is measured, and also can easily detect.
Polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000203
azoles resin combination, contains (b) solvent.As solvent, can be by the non-protonic solvent of METHYLPYRROLIDONE, gamma-butyrolactone, DMF, N,N-dimethylacetamide, methyl-sulphoxide isopolarity, tetrahydrofuran (THF), two
Figure BDA0000466894510000201
ester class, toluene, the dimethylbenzene etc. such as the ketones such as the ethers such as alkane, propylene glycol monomethyl ether, acetone, butanone, valerone, Pyranton, ethyl acetate, propylene glycol methyl ether acetate, ethyl lactate are aromatic hydrocarbon based etc. uses separately or uses two or more.
(b) content of solvent is with respect to polyamic acid, polyimide or polyimide
Figure BDA0000466894510000202
azoles 100 weight parts be preferably 50 weight parts above, more preferably more than 100 weight parts, preferably 2,000 weight parts following, more preferably below 1,500 weight part.50～2, when the scope of 000 weight part, can become the viscosity that is suitable for coating, easily regulate the thickness after coating.
To (a) be explained as the manufacture method of the polyamic acid of principal constituent using the represented structural unit of general formula (1) below.The reaction method of polyreaction, is only can manufacturing objective polyamic acid, is just not particularly limited, and can use known reaction method.
As concrete reaction method, can list all two amine components and the reaction solvent of specified amount are joined in reactor, after their are dissolved, then add the acid dianhydride composition of specified amount, at room temperature～80 DEG C, stir the method etc. of 0.5～30 hour.
As by the represented diamine compound of chemical formula (24), with 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic acid dianhydride, 3,3 ', 4, the structural unit of the polyamic acid that 4 '-bicyclohexyl tetracarboxylic acid dianhydride obtains, can list following chemical formula (38)～(42).
Figure BDA0000466894510000211
Figure BDA0000466894510000231
Next, (a ') is explained as the manufacture method of the polyimide of principal constituent using the represented structural unit of general formula (2).As long as the represented polyamic acid of general formula (1) that can make to obtain by above-mentioned known reaction method carries out the manufacture method of imidization, be just not particularly limited, can use known reaction method.
As concrete reaction method, can list the aforementioned polyamic acid solution obtaining is like that stirred to method of 0.5～30 hour etc. at room temperature～200 DEG C.
As by the represented diamine compound of chemical formula (24), with 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic acid dianhydride, 3,3 ', 4, the structural unit of the polyimide that 4 '-bicyclohexyl tetracarboxylic acid dianhydride obtains, can list following chemical formula (43)～(45).
Figure BDA0000466894510000241
Next, the polyimide using the represented structural unit of general formula (3) as principal constituent to (a ' ')
Figure BDA0000466894510000255
the manufacture method of azoles is explained.As the 1st method, the represented polyimide of general formula (2) that can enumerate sends as an envoy to obtains by the known reaction method of telling about above carries out dehydration closed-loop.Reaction method is not particularly limited, can uses known reaction method.As concrete reaction method, can list: make polyimide powder thermal treatment method of 0.5～30 hour at 300～400 DEG C; In polyimide solution, add the acid catalysts such as hot acidogenic agent, stir the method etc. of 0.5～30 hour in room temperature～250 DEG C.
As the 2nd method, can enumerate and send as an envoy to by represented the containing of following general formula (46)
Figure BDA0000466894510000254
the polyamic acid that the diamines of azoles ring and acid dianhydride obtain carries out imidization.As concrete reaction method, can list the acid dianhydride composition that adds specified amount, stir 0.5～30 hour in room temperature～80 DEG C, then DEG C stir the method etc. of 0.5～30 hour in room temperature～200.
Figure BDA0000466894510000251
(in general formula (46), R 3for 4 valency organic groups of carbonatoms 2～40.)
Make diamine compound and the 1S represented by chemical formula (24), 2S, 4R, 5R-hexanaphthene tetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic acid dianhydride, 3,3 ', 4, when the polyamic acid that 4 '-bicyclohexyl tetracarboxylic acid dianhydride obtains carries out dehydration closed-loop, or make diamines and the 1S represented by chemical formula (47), 2S, 4R, 5R-hexanaphthene tetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic acid dianhydride, 3,3 ', 4, when the polyamic acid that 4 '-bicyclohexyl tetracarboxylic acid dianhydride obtains carries out dehydration closed-loop, as the polyimide obtaining
Figure BDA0000466894510000253
the structural unit of azoles, can list following chemical formula (48)～(50).
Figure BDA0000466894510000252
Figure BDA0000466894510000261
Figure BDA0000466894510000271
Polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000272
azoles resin combination can contain tensio-active agent.As tensio-active agent, can list the fluorine such as Off ロ ラ ー De (trade(brand)name, Sumitomo 3M Co., Ltd. system), メ ガ Off ァ ッ Network (trade(brand)name, Dainippon Ink Chemicals's system), ス Le Off ロ Application (trade(brand)name, Asahi Glass Co., Ltd's system) is tensio-active agent.In addition, can list the organo-siloxane tensio-active agents such as KP341 (trade(brand)name, Shin-Etsu Chemial Co., Ltd's system), DBE (trade(brand)name, チ ッ ソ Co., Ltd. system), POLYFLOW, グ ラ ノ ー Le (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system), BYK (PVC ッ Network ケ ミ ー Co., Ltd. system).And then can list the acrylate copolymer tensio-active agents such as POLYFLOW (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system).
Tensio-active agent, preferably with respect to polyamic acid, polyimide or polyimide
Figure BDA0000466894510000273
azoles 100 weight parts contain 0.01～10 weight part.
Polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000274
azoles resin combination, can contain internal mold release.As internal mold release, can list longer chain fatty acid etc.
Polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000281
azoles resin combination, can contain thermal cross-linking agent.As thermal cross-linking agent, preferably epoxy compounds or there is alkoxy methyl or the compound of at least 2 of methylols.By thering are at least 2 of these groups, can make resin and congeneric elements carry out condensation reaction and form crosslinking structural body, physical strength, resistance to chemical reagents are improved.
As the preferred example of epoxy compounds, can list siloxanes that bisphenol A type epoxy resin such as, bisphenol f type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly-methyl (glycidyl ether oxygen base propyl group), siloxanes etc. contain epoxy group(ing) etc., 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 (is trade(brand)name above, large Japanese イ Application キ chemical industry Co., Ltd. system), 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(brand)name, New Japan Chem Co., Ltd), EP-4003S, EP-4000S (above trade(brand)name, the ア デ カ of Co., Ltd.), PG-100, CG-500, EG-200 (is trade(brand)name above, Osaka ガ ス ケ ミ カ Le Co., Ltd.), NC-3000, NC-6000 (is trade(brand)name above, Nippon Kayaku K. K), EPOX-MKR508, EPOX-MKR540, EPOX-MKR710, EPOX-MKR1710, VG3101L, VG3101M80 (is trade(brand)name above, the プ リ of Co., Ltd. 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 (is trade(brand)name above, ダ イ セ Le chemical industry Co., Ltd.) etc.
As the compound with at least 2 of alkoxy methyl or methylols, can list for example DML-PC, DML-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 (is trade(brand)name above, Honshu Chemical Ind's system), NIKALAC (registered trademark) MX-290, NIKALACMX-280, NIKALACMX-270, NIKALACMX-279, NIKALACMW-100LM, NIKALACMX-750LM (is trade(brand)name above, the ケ ミ カ of Sanwa Co., Ltd. Le system).Can contain two or more in them.
Polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000291
azoles resin combination can contain tinting material.By adding tinting material, can regulate polyamic acid, polyimide, polyimide
Figure BDA0000466894510000292
the tone of azoles film.
As tinting material, can use dyestuff, pigment dyestuff, mineral dye etc., from the viewpoint of thermotolerance, transparent, preferably pigment dyestuff.Wherein high, the photostabilization of preferably transparent, thermotolerance, resistance to chemical reagents excellence.If represent the concrete example of representative pigment dyestuff by color index (CI) sequence number, below preferably using, but do not limit to these.
As the example of yellow ultramarine, can use Pigment yellow (being designated hereinafter simply 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.In addition,, as the example of orange pigments, can use Pigment orange (being designated hereinafter simply as " PO ") 13,36,38,43,51,55,59,61,64,65,71 etc.In addition as the example of red pigment, can use Pigment red (being designated hereinafter simply as " 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.In addition,, as the example of violet pigment, can use Pigment violet (being designated hereinafter simply as " PV ") 19,23,29,30,32,37,40,50 etc.In addition,, as the example of blue pigments, can use Pigment blue (being designated hereinafter simply as " PB ") 15,15:3,15:4,15:6,22,60,64 etc.In addition,, as the example of veridian, can use Pigment green (being designated hereinafter simply as " PG ") 7,10,36,58 etc.These pigment also can carry out the surface treatments such as rosin processing, acidic groups processing, basic treatment as required.
Polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000304
azoles resin combination can contain mineral filler.As mineral filler, can list silicon dioxide microparticle, alumina particulate, titanium dioxide fine particles, zirconium dioxide particle etc.
Shape to mineral filler is not particularly limited, and can list spherical, elliptical shape, flats, the shape that rots, fibrous etc.
Contained mineral filler, in order to prevent scattering of light, preferable particle size is less.Median size is at 0.5～100nm, the preferably scope of 0.5～30nm.
The content of mineral filler, with respect to polyamic acid, polyimide or polyimide
Figure BDA0000466894510000303
azoles is preferably 1～50 % by weight, more preferably 10～30 % by weight.Along with the increase of content, snappiness, folding resistance reduce.
As making polyamic acid resin composition, polyimide resin composition or polyimide
Figure BDA0000466894510000305
in azoles resin combination, contain the method for mineral filler, can use various known methods.Can list and for example make organic-inorganic filler colloidal sol and polyamic acid, polyimide or polyimide azoles mixes.Organic-inorganic filler colloidal sol, with the ratio of 30 % by weight left and right, mineral filler to be dispersed in organic solvent to form, as organic solvent, can list methyl alcohol, Virahol, propyl carbinol, ethylene glycol, butanone, hexone, propyleneglycol monomethyl acetates, propylene glycol monomethyl ether, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, METHYLPYRROLIDONE, 1,3-methylimidazole alkane ketone, gamma-butyrolactone etc.
In order to improve mineral filler with respect to polyamic acid, polyimide or polyimide the dispersiveness of azoles, also can process organic-inorganic filler colloidal sol with silane coupling agent.When the end functional group as silane coupling agent has epoxy group(ing) or when amino, by with the carboxylic acid bonding of polyamic acid, can make and polyamic acid, polyimide or polyimide the affinity of azoles improves, and can more effectively disperse.
As the silane coupling agent with epoxy group(ing), can list 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidyl ether oxygen base propyl group methyl dimethoxysilane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, 3-glycidyl ether oxygen base propyl group methyldiethoxysilane, 3-glycidyl ether oxygen base propyl-triethoxysilicane etc.
As thering is amino silane coupling agent, can list N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(amino-ethyl)-3-TSL 8330,3-TSL 8330, APTES, 3-triethoxysilyl-N-(1,3-dimethyl-Ding pitches base) propylamine, N-phenyl-3-TSL 8330 etc.
As the treatment process of processing organic-inorganic filler colloidal sol with silane coupling agent, can use various known methods.Can be for example add silane coupling agent to having regulated in the organic-inorganic filler colloidal sol of concentration, DEG C stir 0.5～2 hour in room temperature～80 and process.
Polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000311
azoles resin combination can contain light acid producing agent.By containing light acid producing agent, in the time describing the mask light irradiation of exposing patterns, produce acid in exposure portion, exposure portion increases with respect to the solvability of alkali aqueous solution, so can use as positive type photosensitive organic compound.
As the light acid producing agent using in the present invention, can list diazonium naphtoquinone compounds, sulfonium salt,
Figure BDA0000466894510000312
salt, diazonium
Figure BDA0000466894510000313
salt, iodine salt etc.Wherein, from the viewpoint of showing excellent dissolving damping effect, obtain the positive type photosensitive organic compound of high sensitive and low mistake film amount, preferably use diazonium naphtoquinone compounds.In addition, also can contain two or more light acid producing agent.By like this, can make the ratio of the dissolution rate of exposure portion and unexposed portion become larger, obtain high sensitive positive type photosensitive organic compound.
As diazonium naphtoquinone compounds, can list the compound that the sulfonic acid of polyol and diazonium quinone is combined into by ester bond, the compound that the sulfonic acid of multiamino compound and diazonium quinone is combined into by sulphonamide key, the compound that the sulfonic acid of poly-hydroxy multiamino compound and diazonium quinone is combined into by ester bond and/or sulphonamide key etc.These polyols, multiamino compound, can not all functional group all be replaced by diazonium quinone, but preferably all more than 50 % by mole being replaced by diazonium quinone of functional group.By using this diazonium naphtoquinone compounds, can obtain the positive type photosensitive organic compound that can react by the i line as common ultraviolet mercury lamp (wavelength 365nm), h line (wavelength 405nm), g line (wavelength 436nm).
In the present invention, diazonium naphtoquinone compounds preferably uses any in 5-diazo naphthoquinone alkylsulfonyl, 4-diazo naphthoquinone alkylsulfonyl.Also can use the compound in same a part with these two kinds of groups, also can be used together and there is not isoplastic compound.
Diazonium naphtoquinone compounds used in the present invention, can, by specific phenolic compound, synthesize by the following method.Can list the method that for example makes 5-diazo naphthoquinone SULPHURYL CHLORIDE and phenolic compound reaction under triethylamine exists.The synthetic method of phenolic compound, can list and under acid catalyst, make method that α-(hydroxy phenyl) styrene derivatives reacts with multivalence phenolic compound etc.
The content of light acid producing agent, with respect to polyamic acid, polyimide or polyimide
Figure BDA0000466894510000321
azoles 100 weight parts, are preferably 3～40 weight parts.By making the content of light acid producing agent in this scope, can realize higher susceptibility.And then also can contain as required sensitizing agent etc.
Form the pattern of normal Photosensitive resin, the varnish of normal Photosensitive resin is coated on substrate, make its exposure, then use developing solution to remove exposure portion.As developing solution, preferably Tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, triethylamine, diethylamine, methylamine, dimethylamine, acetic acid dimethylamino ethyl ester, dimethylaminoethanol, dimethylaminoethyl acrylate methyl base amino-ethyl ester, hexahydroaniline, quadrol, hexamethylene-diamine etc. show the aqueous solution of alkaline compound.In addition, according to circumstances, also can in these alkali aqueous solutions, add METHYLPYRROLIDONE, N, independent one or more combination in the ketones such as ester class, cyclopentanone, pimelinketone, isobutyl ketone, hexone such as alcohols, ethyl lactate, propylene glycol methyl ether acetate such as dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide, gamma-butyrolactone, DMAA isopolarity solvent, methyl alcohol, ethanol, Virahol etc.Preferably after development, water carries out drip washing processing.At this, also the ester classes such as the alcohols such as ethanol, Virahol, ethyl lactate, propylene glycol methyl ether acetate etc. can be added to the water and carry out drip washing processing.
Below will be to using polyamic acid resin composition of the present invention, polyimide resin composition and polyimide
Figure BDA0000466894510000322
the method that azoles resin combination is manufactured heat-resistant resin film is explained.
First by polyamic acid resin composition, polyimide resin composition or polyimide
Figure BDA0000466894510000323
azoles resin combination is applied on substrate.As substrate, can use such as silicon wafer, ceramic-like, gallium arsenide, soda-lime glass, non-alkali glass etc., but not limit to these.Coating process has the methods such as such as slit die coating method, spin-coating method, spraying method, rolling method, excellent Tu Fa, also these Combination of Methods can be coated with together.
Next, coating has been gone up to polyamic acid resin composition, polyimide resin composition or polyimide the drying substrates of azoles resin combination, obtains polyamic acid resin composition, polyimide resin composition or polyimide
Figure BDA0000466894510000325
azoles resin combination tunicle.When dry, use hot plate, baking oven, infrared rays, vacuum chamber etc.Using when hot plate, onboard directly or, on the fixtures such as tumbler pin (proxy pin) onboard, keep heated object and heat arranging.As the material of tumbler pin, there is the synthetic resins such as aluminium, stainless steel and other metal materials or polyimide resin, " テ Off ロ Application (registered trademark) ", use the tumbler pin of arbitrary material can.The height of tumbler pin is according to the size of substrate, as kind, the heating object etc. of the resin layer of heated object and different, for example, in the time of the resin layer heating on the glass substrate that is coated on 300mm × 350mm × 0.7mm, the height of tumbler pin is preferably 2～12mm left and right.Heating temperature is according to the kind of heated object and object and difference, preferably carries out 1 minute～several hours in the scope of room temperature to 180 DEG C.
Next, the scope heating more than 180 DEG C below 400 DEG C, makes it change heat-resistant resin tunicle into.For this heat-resistant resin tunicle is peeled off from substrate, can list method in liquids such as being immersed in hydrofluoric acid, to method of the interface irradiating laser of heat-resistant resin tunicle and substrate etc., can use either method.
Moreover, by heat-treating as above as polyamic acid of the present invention, the polyimide of principal constituent using general formula (1), (2) represented structural unit, can obtain using the represented structural unit of general formula (2) as the polyimide of principal constituent or polyimide using the represented structural unit of general formula (3) as principal constituent azoles.
The above-mentioned heat-resistant resin film obtaining like that has high transparent, high heat resistance, low-birefringence, snappiness, can use as flexible base, board well.As for the transparency, the transmissivity under optimal wavelength 400nm is more than 85%, more preferably more than 90%, and then is preferably more than 95%.As for second-order transition temperature, be preferably more than 250 DEG C, more preferably more than 300 DEG C, and then be preferably more than 350 DEG C.As for degree of birefringence, be preferably below 0.01, more preferably below 0.005, and then be preferably below 0.003.
The flexible base, board that contains resin combination of the present invention can be in the flexible devices such as sensitive device such as the display device of liquid-crystal display, OLED display, touch panel, Electronic Paper, colour filter and so on, solar cell, CMOS.
Following operation is contained in the manufacturing process of flexible device: on the heat-resistant resin film being formed on substrate, form display device, the necessary circuit of sensitive device.For example can on flexible base, board, form the TFT of non-crystalline silicon.And then can form the necessary structure of device by known method thereon.The solid state heat-resistant resin film that above circuit forming surface has like that been waited uses the known methods such as laser radiation to peel off from substrate, just can obtain flexible device.
Embodiment
Below list embodiment etc. the present invention is described, but the present invention is not limited by these examples.
(1) making of heat-resistant resin film
The coating developing apparatus Mark-7 rotary coating varnish on the minute surface silicon wafer (ミ ラ ー シ リ コ Application ウ ェ Ha ー) of 6 inches that uses Tokyo エ レ クトロン Co., Ltd. system, it is 15 ± 0.5 μ m that its amount can make the thickness after 4 minutes 140 DEG C of prebake.Then, use equally the hot plate of Mark-7 to carry out 140 DEG C of pre-bake treatment 4 minutes.Prebake film uses rare gas element baking oven (the silver dollar サ ー モ シ ス テ system INH-21CD processed of Co., Ltd.) (below oxygen concn 20ppm) under nitrogen gas stream to be warmed up to 300 DEG C or 350 DEG C with 3.5 DEG C/min, keep 30 minutes, be cooled to 50 DEG C to produce heat-resistant resin film with 5 DEG C/min.Then in hydrofluoric acid, flood 1～4 minute, 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. system at the thick glass substrate of 50mm × 50mm × 1.1mm (テ Application パ ッ Network ス) rotary coating varnish, it is 15 ± 0.5 μ m that its amount can make the thickness of 140 DEG C of prebake after 4 minutes.Then, use the large Japanese ス ク リ ー Application heating plate D-SPIN of Co., Ltd. to carry out 140 DEG C of pre-bake treatment 4 minutes.Use rare gas element baking oven (the silver dollar サ ー モ シ ス テ system INH-21CD processed of Co., Ltd.) (below oxygen concentration 20ppm) under nitrogen gas stream to be warmed up to 300 DEG C or 350 DEG C with 3.5 DEG C/min prebake film, keep 30 minutes, be cooled to 50 DEG C and produce heat-resistant resin film (on glass substrate) with 5 DEG C/min.
(3) making of heat-resistant resin film (on silicon substrate)
What use ミ カ サ Co., Ltd. system revolves coating machine MS-A200 rotary coating varnish on 4 inches of silicon substrates that are cut into 1/4, and it is 5 ± 0.5 μ m that its amount can make the thickness behind 140 DEG C of prebake × 4 minute.Then, use the large Japanese ス ク リ ー Application heating plate D-SPIN of Co., Ltd. to carry out 140 DEG C of pre-bake treatment 4 minutes.By prebake film use rare gas element baking oven (the silver dollar サ ー モ シ ス テ system INH-21CD processed of Co., Ltd.) under nitrogen gas stream (below oxygen concn 20ppm), be warmed up to 300 DEG C or 350 DEG C with 3.5 DEG C/min, keep 30 minutes, be cooled to 50 DEG C and produce heat-resistant resin film (on silicon substrate) with 5 DEG C/min.
(4) mensuration of optical transmittance (T)
Use ultraviolet-visual spectrometer (MultiSpec1500 processed of Shimadzu Scisakusho Ltd) to measure the optical transmittance under 400nm.Moreover, in mensuration, use the heat-resistant resin film of producing in (2).
(5) mensuration of total light transmittance (Tt)
Use direct-reading type mist degree computer (the ス ガ trier HGM2DP processed of Co., Ltd., illuminant-C) to measure total light transmittance of the heat-resistant resin film of producing in (1).Moreover, use the value of measuring for 1 time as Tt.Moreover, in mensuration, use the heat-resistant resin film of producing in (1).
In specific refractory power, face (6) mensuration of/outer degree of birefringence of face
Use prism coupler (METRICON society system, PC2010) to measure TE specific refractory power (n (TE)) and the TM specific refractory power (n (TM)) of wavelength 632.8nm.N (TE), n (TM) are respectively the specific refractory poweres of parallel, the vertical direction of polyimide face.According to ((2 × n (TE) 2+ n (TM) 2)/3) ^0.5 calculates mean refractive index n (AV), poor (n (the TE)-n (TM)) that calculates n (TE) and n (TM) as in face/face degree of birefringence outward.Moreover, in mensuration, use the heat-resistant resin film of producing in (3).
(7) mensuration of second-order transition temperature (Tg), coefficient of linear expansion (CTE)
Use thermo-mechanical analysis device (the エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー EXSTAR6000TMA/SS6000 processed of Co., Ltd.) to measure under nitrogen gas stream.Temperature-rising method is to be undertaken by following condition.Be warmed up to 150 planar water of spending to remove on sample in the 1st stage with 5 DEG C/min of temperature rise rate, arrive room temperature in the 2nd stage with 5 DEG C/min of rate of temperature fall air cooling.Carry out main mensuration in the 3rd stage with 5 DEG C/min of temperature rise rate, obtain second-order transition temperature.In addition obtain coefficient of linear expansion (CTE) according to the mean value of the coefficient of linear expansion of 50～200 DEG C in the 3rd stage.Moreover, in mensuration, use the heat-resistant resin film of producing in (1).
The mensuration of (8) 1% weightless temperatures (Td1)
Use thermogravimetric amount determining device (TGA-50 processed of Shimadzu Scisakusho Ltd), under nitrogen gas stream, measure.Temperature-rising method carries out with following condition.Be warmed up to 350 planar water of spending to remove sample in the 1st stage with 3.5 DEG C/min of temperature rise rate, in the 2nd stage with 10 DEG C/min of rate of temperature fall cool to room temperature.Carry out main mensuration in the 3rd stage with 10 DEG C/min of temperature rise rate, obtain 1% thermal weight loss temperature.Moreover, in mensuration, use the heat-resistant resin film of producing in (1).
(9) mensuration of breaking stress, Breaking elongation, Young's modulus
Use pulling force compression testing machine (Tensilon) (the オ リ エ of Co., Ltd. Application テ ッ Network RTM-100) to measure.10 of each sample determinations more than sample, use JIS quantity average (JISK-6301) to calculate JIS mean value.Moreover, in mensuration, use the heat-resistant resin film of producing in (1).
(10) mensuration of b* value
The mensuration of the b* value of representational color space CIELAB is used SM color computer (ス ガ trier SM Co., Ltd.-7-CH) to carry out.Use illuminant-C as light source, measure and use through optical mode.Moreover b* value is yellow and blue coordinate in CIELAB, when b* > 0 corresponding near yellow, when b* < 0 corresponding near blueness.Moreover, in mensuration, use the heat-resistant resin film of producing in (1).
(11) making of embossing pattern
By the photosensitive polymer combination of producing in embodiment (varnish) rotary coating on 8 inches of silicon wafers, next, use hot plate (Tokyo エ レ クトロン Co., Ltd. system, coating developing apparatus Mark-7), thermal treatment at 120 DEG C (prebake) 3 minutes, and produce the prebake film of thickness 2～4 μ m.Use i line stepper (GCA society system, DSW-8000) with 20～320mJ/cm obtained prebake film 2exposure, with 10mJ/cm 2stepping exposure.The line using in exposure and gap pattern are 1,2,3,4,5,6,7,8,9,10,15,20,30,50,100 μ m.Tetramethyl-ammonium (TMAH) aqueous solution (ガ ス KCC of Mitsubishi system, ELM-D) by 2.38 % by weight after exposure developed for 60 seconds, next used pure water drip washing, obtained embossing pattern.Moreover the thickness after prebake and after developing, is to use large Japanese ス ク リ ー Application to manufacture the light interference type determining film thickness processed device ラ of Co., Ltd. system ダ エ ー ス STM-602, measures with specific refractory power 1.63.
(12) develop and lose the calculating of film amount
Calculate to develop according to following formula and lose film amount.
Develop lose film amount (μ m)=thickness after thickness-development after prebake
(13) calculating of susceptibility
By in exposure, develop after minimum exposure amount during using the line of 1 to 1 formation 10 μ m and 20 μ m and gap pattern (1L/1S) as susceptibility.
Record the abbreviation of the compound using in embodiment below.
PMDA-HH:1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic acid dianhydride
PMDA-HS:1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic 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 ', 4, the two O-phthalic acid dianhydrides of 4 '-oxygen
6FDA:4,4 '-(hexafluoroisopropyli,ene base) diphthalic anhydrides
HFHA:2, two ［ 3-(the 3-AB)-4-hydroxy phenyl ］ HFC-236fa of 2-
FDA:9, two (4-aminophenyl) fluorenes of 9-
CHDA: anti-form-1,4-diamino-cyclohexane
PDA: Ursol D
M-TB:2,2 '-dimethyl-4,4 '-benzidine
TFMB:2,2 '-bis-(trifluoromethyl) p-diaminodiphenyl
M-BAPS: two ［ 4-(3-amino-benzene oxygen) phenyl ］ sulfone
SiDA:1, two (3-aminopropyl) tetramethyl disiloxanes of 3-
MAP: Metha Amino Phenon
NMP:N-N-methyl-2-2-pyrrolidone N-
GBL: gamma-butyrolactone
EL: ethyl lactate
DFA: dimethylformamide dimethyl acetal
Embodiment 1
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HH2.7704g (12mmol), HFHA7.4706g (12mmol), NMP50g at drying nitrogen, 80 DEG C of heated and stirred.After 8 hours, cooling formation varnish.
Embodiment 2
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS2.7704g (12mmol), HFHA7.4706g (12mmol), NMP50g at drying nitrogen, 80 DEG C of heated and stirred.After 8 hours, cooling formation varnish.
Embodiment 3
Flow down in 4 mouthfuls of flasks of 100mL and add BPDA-H3.4441g (11mmol), HFHA6.7969g (11mmol), NMP50g at drying nitrogen, 80 DEG C of heated and stirred.After 8 hours, cooling formation varnish.
Embodiment 4
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HH2.7704g (12mmol), HFHA6.5286g (10.8mmol), FDA0.4181g (1.2mmol) NMP50g at drying nitrogen, 80 DEG C of heated and stirred.After 8 hours, cooling formation varnish.
Embodiment 5
Flow down in 4 mouthfuls of flasks of 100mL and add BPDA1.0238g (3.48mmol), PMDA-HH1.9099g (8.52mmol), CHDA0.4110g (3.60mmol), HFHA5.0778g (8.40mmol), NMP50g at drying nitrogen, 80 DEG C of heated and stirred.After 8 hours, cooling formation varnish.
Embodiment 6
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS3.4345g (15.3mmol), HFHA8.7985g (14.5mmol), FDA0.2669g (0.8mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Embodiment 7
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS3.4893g (15.6mmol), HFHA8.4683g (14.0mmol), FDA0.5424g (1.6mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 8 hours, cooling formation varnish.
Embodiment 8
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS3.6042g (16.1mmol), HFHA7.7753g (12.9mmol), FDA1.1204g (3.2mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Embodiment 9
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS 3.7270g (16.6mmol), HFHA7.0351g (11.6mmol), FDA1.7379g (5.0mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Embodiment 10
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS3.8584g (17.2mmol), HFHA6.2427g (10.3mmol), FDA2.3989g (6.9mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Embodiment 11
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS3.9994g (17.8mmol), HFHA5.3924g (8.9mmol), FDA3.1082g (8.9mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Comparative example 1
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA2.7154g (12mmol), HFHA7.5255g (12mmol), NMP50g, heated and stirred at 50 DEG C at drying nitrogen.After 2 hours, cooling formation varnish.
Comparative example 2
Flow down in 4 mouthfuls of flasks of 100mL and add BPDA3.3527g (11mmol), HFHA6.8883g (11mmol), NMP50g, heated and stirred at 50 DEG C at drying nitrogen.After 2 hours, cooling formation varnish.
Comparative example 3
Flow down in 4 mouthfuls of flasks of 100mL and add ODPA3.4731g (11mmol), HFHA6.7679g (11mmol), NMP50g, heated and stirred at 50 DEG C at drying nitrogen.After 2 hours, cooling formation varnish.
Comparative example 4
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HH5.2599g (23mmol), m-TB4.9811g (23mmol), NMP50g, heated and stirred at 50 DEG C at drying nitrogen.After 2 hours, cooling formation varnish.
Comparative example 5
Flow down in 4 mouthfuls of flasks of 100mL and add 6FDA 7.0599g (15.9mmol), HFHA9.6068g (15.9mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Comparative example 6
Flow down in 4 mouthfuls of flasks of 100mL and add 6FDA7.2639g (16.4mmol), TFMB5.2361g (16.4mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Comparative example 7
Flow down in 4 mouthfuls of flasks of 100mL and add 6FDA8.4450g (19.0mmol), m-BAPS8.2216g (19.0mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Comparative example 8
Flow down in 4 mouthfuls of flasks of 100mL and add 6FDA7.824g (17.6mmol), FDA2.4547g (7.0mmol), HFHA6.3879g (10.6mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
Comparative example 9
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HH5.1472g (23mmol), TFMB7.3528g (23mmol), NMP50g, heated and stirred at 50 DEG C at drying nitrogen.After 6 hours, cooling formation varnish.
Comparative example 10
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS5.6897g (25.4mmol), m-BAPS10.9770g (25.4mmol), NMP50g, heated and stirred at 50 DEG C at drying nitrogen.After 6 hours, cooling formation varnish.
Comparative example 11
Flow down in 4 mouthfuls of flasks of 100mL and add BPDA-H9.2384g (30.2mmol), PDA3.2616g (30.2mmol), NMP50g, heated and stirred at 50 DEG C at drying nitrogen.After 6 hours, cooling formation varnish.
Comparative example 12
Flow down in 4 mouthfuls of flasks of 100mL and add PMDA-HS 4.1511g (18.5mmol), HFHA4.4776g (7.4mmol), FDA3.8714g (11.1mmol), NMP50g at drying nitrogen, 30 DEG C of heated and stirred.After 6 hours, cooling formation varnish.
In embodiment 1～11 and comparative example 1～12, the composition of synthetic varnish is as shown in table 1.In addition, to use these varnish, through 350 DEG C cure and the heat-resistant resin film that obtains is measured in optical transmittance (T), total light transmittance (Tt), TE specific refractory power (n (TE)), TM specific refractory power (n (TM)), mean refractive index (n (AV)), face/face outside degree of birefringence, second-order 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 HFHA121.5804g (0.201mol) is dissolved in NMP400g at drying nitrogen.And then PMDA-HS45.5372g (0.203mol) is added wherein together with NMP100g, 30 DEG C are stirred 6 hours.Then, stirring at room temperature 12 hours.Then, within 180 DEG C 4 hours, stir.After stirring finishes, solution is put in water 3L, filtered collected polymer solid.And then water 3L washes 5 times, by the polymer solids of collecting in the drying machine of 50 DEG C dry 72 hours, and obtain polyimide powder.In obtained polyimide powder 15g, add GBL47.5g, and obtain polyimide varnish.
Embodiment 13
Flow down HFHA62.4272g (0.103mol), FDA23.9891g (0.069mol) are dissolved in to NMP400g at drying nitrogen.And then PMDA-HS38.9695g (0.174mol) is added wherein together with NMP100g, 30 DEG C are stirred 6 hours.Then, stirring at room temperature 12 hours.Then, 180 DEG C are stirred 4 hours.After stirring finishes, solution is put in water 3L, filtered collected polymer solid.And then water 3L washes 5 times, by the polymer solids of collecting in the drying machine of 50 DEG C dry 72 hours, and obtain polyimide powder.In obtained polyimide powder 15g, add GBL47.5g, and obtain polyimide varnish.
Use the varnish of embodiment 12,13, measure through 350 DEG C cure and in the optical transmittance (T) of the heat-resistant resin film that obtains, total light transmittance (Tt), TE specific refractory power (n (TE)), TM specific refractory power (n (TM)), mean refractive index (n (AV)), face/face outside degree of birefringence, second-order transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), show the result in table 2.
[table 2]
Figure BDA0000466894510000441
Embodiment 14
Flow down HFHA121.5804g (0.201mol) is dissolved in to NMP400g at drying nitrogen.And then PMDA-HS45.5372g (0.203mol) is added wherein together with NMP100g, 30 DEG C are stirred 6 hours.Then, stirring at room temperature 12 hours.Then, within 180 DEG C 4 hours, stir.After stirring finishes, solution is put in water 3L, filtered collected polymer solid.And then water 3L washes 5 times, by the polymer solids of collecting in the drying machine of 50 DEG C dry 72 hours, and obtain polyimide powder.By the thermal treatment 30 minutes in the baking oven of 350 DEG C under nitrogen gas stream of obtained polyimide powder, just obtain polyimide
Figure BDA0000466894510000451
azoles powder.To obtained polyimide in azoles powder 15g, add NMP47.5g and obtain polyimide
Figure BDA0000466894510000453
azoles varnish.
Embodiment 15
Flow down HFHA62.4272g (0.103mol), FDA23.9891g (0.069mol) are dissolved in NMP400g at drying nitrogen.Add together with NMP100g wherein and then by PMDA-HS38.9695g (0.174mol), 30 DEG C are stirred 6 hours.Then stirring at room temperature 12 hours.Then stir 4 hours at 180 DEG C.After stirring finishes, solution is put in water 3L, filtered collected polymer solid.And then water 3L washes 5 times, by the polymer solids of collecting in the drying machine of 50 DEG C dry 72 hours, and obtain polyimide powder.By the thermal treatment 30 minutes in the baking oven of 350 DEG C under nitrogen gas stream of obtained polyimide powder, just obtain polyimide
Figure BDA0000466894510000454
azoles powder.To obtained polyimide
Figure BDA0000466894510000455
in azoles powder 15g, add NMP47.5g, just obtained polyimide
Figure BDA0000466894510000456
azoles varnish.
Use the varnish of embodiment 14,15, measure through 350 DEG C cure and in the optical transmittance (T) of the heat-resistant resin film that obtains, total light transmittance (Tt), TE specific refractory power (n (TE)), TM specific refractory power (n (TM)), mean refractive index (n (AV)), face/face outside degree of birefringence, second-order transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), show the result in table 3.
[table 3]
Figure BDA0000466894510000461
Embodiment 16
Taking silicon dioxide microparticle with respect to varnish 100 weight parts that obtain in embodiment 1 mode as 10 weight parts, in polyamide acid varnish, add organic silicon dioxide gel (Nissan Chemical Ind Ltd's system, trade(brand)name PMA-ST, particle diameter 10-30nm), and obtain polyamic acid-Nano particles of silicon dioxide varnish.
Embodiment 17
Taking silicon dioxide microparticle with respect to varnish 100 weight parts that obtain in embodiment 1 mode as 20 weight parts, in polyamide acid varnish, add organic silicon dioxide gel (Nissan Chemical Ind Ltd's system, trade(brand)name PMA-ST, particle diameter 10-30nm), and obtain polyamic acid-Nano particles of silicon dioxide varnish.
Embodiment 18
Taking silicon dioxide microparticle with respect to varnish 100 weight parts that obtain in embodiment 1 mode as 30 weight parts, in polyamide acid varnish, add organic silicon dioxide gel (Nissan Chemical Ind Ltd's system, trade(brand)name PMA-ST, particle diameter 10-30nm), and obtain polyamic acid-Nano particles of silicon dioxide varnish.
The composition of the varnish making in embodiment 16～18 is as shown in table 4.In addition, use these varnish, outside measure in the optical transmittance (T) of 350 DEG C of heat-resistant resin films that cure and obtain, total light transmittance (Tt), TE specific refractory power (n (TE)), TM specific refractory power (n (TM)), mean refractive index (n (AV)), face/face, degree of birefringence, second-order transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), show the result in table 4.
[table 4]
Figure BDA0000466894510000481
Embodiment 19
In the polyimide powder 4g obtaining in embodiment 13, add tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.044g, GBL13.47g, and obtain polyimide varnish.
Embodiment 20
To adding tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.044g, EPICLON850-S (trade(brand)name, large Japanese イ Application キ chemical industry Co., Ltd.) 0.2g, GBL13.47g in the polyimide powder 4g obtaining in embodiment 13, and obtain polyimide varnish.
Embodiment 21
To adding tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.044g, EPICLON850-S (trade(brand)name, large Japanese イ Application キ chemical industry Co., Ltd.) 0.4g, GBL13.47g in the polyimide powder 4g obtaining in embodiment 13, and obtain polyimide varnish.
Embodiment 22
To adding tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.044g, EPICLON850-S (trade(brand)name, large Japanese イ Application キ chemical industry Co., Ltd.) 0.8g, GBL13.47g in the polyimide powder 4g obtaining in embodiment 13, and obtain polyimide varnish.
Use the varnish of embodiment 19～22, outside measure in the optical transmittance (T) of the heat-resistant resin film that obtains of curing at 300 DEG C, total light transmittance (Tt), TE specific refractory power (n (TE)), TM specific refractory power (n (TM)), mean refractive index (n (AV)), face/face, degree of birefringence, second-order transition temperature (Tg), coefficient of linear expansion (CTE), 1% thermal weight loss temperature (Td1), breaking stress, Breaking elongation, Young's modulus, show the result in table 5.
[table 5]
Figure BDA0000466894510000501
Reference example 1
With clarifixator (HOMO DISPER), the propylene glycol methyl ether acetate of ダ イ セ Le chemical industry Co., Ltd. system " サ イ Network ロ マ ー " ACA250 (45 % by weight solution) of the propylene glycol methyl ether acetate solution (30 % by weight) of monosodium glutamate Off ァ イ Application テ Network ノ system " the ア ジ ス パ ー " PB821 of the PB15:6 of 117g (average primary particle diameter 30nm), 140g, 93g and 627g be stirred in together and make slurry.With flexible pipe, the beaker that this slurry is housed being ground to dispersion machine (ウ イ リ ー エ バ ッ コ ー Off ェ Application society's system " ダ イ ノ ー ミ Le " KDL-A) with circulating pearl is connected, use the zirconium dioxide pearl of diameter 0.3mm to carry out 3200rpm, the dispersion treatment of 3 hours as medium, thereby obtain blue pigments dispersion liquid.In obtained blue pigments dispersion liquid 0.4167g, add GBL 49.5833g, and obtain diluting soln.
Embodiment 23
In the polyimide powder 13g obtaining in embodiment 13, add tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.013g, GBL36.3g, and obtain polyimide varnish.
Embodiment 24
In the polyimide powder 13g obtaining in embodiment 13, add the blue pigments dispersion liquid 0.325g, the GBL36.3g that in tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.013g, reference example 1, obtain, and obtain polyimide varnish.
Embodiment 25
In the polyimide powder 13g obtaining in embodiment 13, add the blue pigments dispersion liquid 0.650g, the GBL36.3g that in tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.013g, reference example 1, obtain, and obtain polyimide varnish.
Embodiment 26
In the polyimide powder 13g obtaining in embodiment 13, add the blue pigments dispersion liquid 0.975g, the GBL36.3g that in tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.013g, reference example 1, obtain, and obtain polyimide varnish.
Embodiment 27
In the polyimide powder 13g obtaining in embodiment 13, add the blue pigments dispersion liquid 1.300g, the GBL36.3g that in tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.013g, reference example 1, obtain, and obtain polyimide varnish.
Embodiment 28
In the polyimide powder 13g obtaining in embodiment 13, add the blue pigments dispersion liquid 1.625g, the GBL36.3g that in tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.013g, reference example 1, obtain, and obtain polyimide varnish.
Embodiment 29
In the polyimide powder 13g obtaining in embodiment 13, add the blue pigments dispersion liquid 2.600g, the GBL36.3g that in tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.013g, reference example 1, obtain, and obtain polyimide varnish.
Use the varnish of embodiment 23～29, measure through 350 DEG C cure and in the optical transmittance (T) of the heat-resistant resin film that obtains, b* value, TE specific refractory power (n (TE)), TM specific refractory power (n (TM)), mean refractive index (n (AV)), face/face outside degree of birefringence, show the result in table 6.
[table 6]
Figure BDA0000466894510000531
Embodiment 30
Flow down HFHA22.4g (0.037 mole), SiDA0.58g (0.0023 mole) are dissolved in NMP105g at drying nitrogen.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, then stirring at room temperature 11 hours.Then, MAP1.011g is added together with NMP15g, at 60 DEG C, stir 1 hour.Then, dropping dilutes with NMP10g the solution that DFA4.60g (0.038 mole) forms, and dropping is rear, continuation is stirred 1 hour at 60 DEG C.Then, carry out 2 same operations.Then, under room temperature, add acetic acid 16.69g, stir 1 hour.After stirring finishes, solution is put in water 2L, filtered collected polymer solid.And then water 2L washes 5 times, by the polymer solids of collecting in the drying machine of 50 DEG C dry 72 hours, and obtain poly amic acid ester powder.
In obtained poly amic acid ester powder 4g, add diazonium naphtoquinone compounds TP-250 (synthetic Co., Ltd. of Japan system) 0.455g, HAP-170 (synthetic Co., Ltd. of Japan system) 0.455g, dissolution accelerator Tris-HAP (Honshu KCC system) 0.421g, thermal cross-linking agent HMOM (Honshu KCC system) 0.682g, tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.182g, EL9.3g, GBL6.9g, and obtain the varnish of photosensitive polymer combination.Use the varnish obtaining, make embossing pattern by the method for above-mentioned (9), carry out photosensitivity evaluation, result development is lost film amount and is 0.17 μ m, and less, susceptibility is 300mJ/cm 2.
Embodiment 31
In the polyimide powder 4.646g obtaining in embodiment 12, add diazonium naphtoquinone compounds HAP-170 (synthetic Co., Ltd. of Japan system) 0.929g, thermal cross-linking agent HMOM (Honshu KCC system) 0.664g, tensio-active agent POLYFLOW77 (trade(brand)name, Kyoeisha Chemical Co., Ltd.'s system) 0.011g, GBL18.75g, and obtain the varnish of photosensitive polymer combination.Use the varnish obtaining to make embossing pattern by the method for above-mentioned (9) and carry out photosensitivity evaluation, it is that 1.27 μ m, susceptibility are 125mJ/cm that film amount is lost in result development 2.
Industry utilizability
According to the present invention, can provide film after thermal treatment to there is the polyamic acid resin composition of excellent thermotolerance, light transmission, low-birefringence.Film after thermal treatment can perform well in the insulation layer of surface protection film, interlayer dielectric, organic electroluminescent device (organic EL) of the flexible base, boards such as flat-panel monitor, touch panel, Electronic Paper, colour filtering chip basic board, solar cell, semiconductor element or wall, the planarization film of thin film transistor base plate, insulation layer, the flexible printed board etc. of organic transistor.

Claims (17)

1. a polyamic acid resin composition, is characterized in that, contains (a) using the represented structural unit of general formula (1) as the polyamic acid of principal constituent and (b) solvent,
Figure FDA0000466894500000011
In general formula (1), X 1, X 2represent independently of one another 1 valency organic group of hydrogen atom or carbonatoms 1～10, R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 2represent the divalent organic group of the carbonatoms 2～40 with at least 2 hydroxyls.
2. polyamic acid resin composition as claimed in claim 1, is characterized in that, the R in general formula (1) 1be be selected from following general formula (4)～(10) more than a kind,
Figure FDA0000466894500000012
Figure FDA0000466894500000021
In general formula (4)～(10), R 4～R 79represent independently of one another 1 valency organic group of the carbonatoms 1～3 that hydrogen atom, halogen atom or hydrogen atom also can replace by halogen atom, X in general formula (7) 3represent the divalent organic group of the carbonatoms 1～3 that Sauerstoffatom, sulphur atom, alkylsulfonyl or hydrogen atom also can replace by halogen atom, or two divalent bridge crosslinking structures that are formed by connecting above in them, the X in general formula (10) 4represent the arylidene that the divalent organic group of the carbonatoms 1～3 that Direct Bonding, Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom also can replace by halogen atom or hydrogen atom also can have been replaced by halogen atom, or be selected from 2 divalent bridge crosslinking structures that are formed by connecting above in the arylidene that the divalent organic group of the carbonatoms 1～3 that Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom also can replace by halogen atom and hydrogen atom also can replace by halogen atom.
3. polyamic acid resin composition as claimed in claim 1 or 2, is characterized in that, the R in general formula (1) 2represent with following formula (14),
4. the polyamic acid resin composition as described in any one of claim 1～3, it is characterized in that, (a) contain the represented structural unit 10%～50% of general formula (36) using the represented structural unit of general formula (1) as the polyamic acid of principal constituent
In general formula (36), X 1, X 2represent independently of one another 1 valency organic group of hydrogen atom or carbonatoms 1～10, R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure.
5. the polyamic acid resin composition as described in any one of claim 1～4, is characterized in that, in the face of the film obtaining through thermal treatment/face outside double refraction be below 0.01.
6. a polyimide resin composition, is characterized in that, contains (a ') using the represented structural unit of general formula (2) as the polyimide of principal constituent and (b) solvent,
Figure FDA0000466894500000033
In general formula (2), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 2represent the divalent organic group of the carbonatoms 2～40 with at least 2 hydroxyls.
7. polyimide resin composition as claimed in claim 6, is characterized in that, the R in general formula (2) 1be be selected from following general formula (4)～(10) more than a kind,
Figure FDA0000466894500000041
In general formula (4)～(10), R 4～R 79represent independently of one another 1 valency organic group of the carbonatoms 1～3 that hydrogen atom, halogen atom or hydrogen atom also can replace by halogen atom, X in general formula (7) 3represent the divalent organic group of the carbonatoms 1～3 that Sauerstoffatom, sulphur atom, alkylsulfonyl or hydrogen atom also can replace by halogen atom, or two divalent bridge crosslinking structures that are formed by connecting above in them, the X in general formula (10) 4represent the arylidene that the divalent organic group of the carbonatoms 1～3 that Direct Bonding, Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom also can replace by halogen atom or hydrogen atom also can have been replaced by halogen atom, or be selected from 2 divalent bridge crosslinking structures that are formed by connecting above in the arylidene that the divalent organic group of the carbonatoms 1～3 that Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom also can replace by halogen atom and hydrogen atom also can replace by halogen atom.
8. the polyimide resin composition as described in claim 6 or 7, is characterized in that, the R in general formula (2) 2represent with following formula (14),
Figure FDA0000466894500000052
9. the polyimide resin composition as described in any one of claim 6～8, it is characterized in that, (a ') contain the represented structural unit 10%～50% of general formula (37) using the represented structural unit of general formula (2) as the polyimide of principal constituent
Figure FDA0000466894500000053
In general formula (37), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure.
10. the polyimide resin composition as described in any one of claim 6～9, is characterized in that, in the face of the film obtaining through thermal treatment/face outside double refraction be below 0.01.
11. 1 kinds of polyimide
Figure FDA0000466894500000061
azoles resin combination, is characterized in that, contains (a ") polyimide using the represented structural unit of general formula (3) as principal constituent
Figure FDA0000466894500000062
azoles and (b) solvent,
Figure FDA0000466894500000063
In general formula (3), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 3represent 4 valency organic groups of carbonatoms 2～40.
12. polyimide as claimed in claim 11
Figure FDA0000466894500000064
azoles resin combination, is characterized in that, the R in general formula (3) 1be be selected from following general formula (4)～(10) more than a kind,
Figure FDA0000466894500000065
Figure FDA0000466894500000071
In general formula (4)～(10), R 4～R 79represent independently of one another 1 valency organic group of the carbonatoms 1～3 that hydrogen atom, halogen atom or hydrogen atom also can replace by halogen atom, X in general formula (7) 3represent the divalent organic group of the carbonatoms 1～3 that Sauerstoffatom, sulphur atom, alkylsulfonyl or hydrogen atom also can replace by halogen atom, or two divalent bridge crosslinking structures that are formed by connecting above in them, the X in general formula (10) 4represent the arylidene that the divalent organic group of the carbonatoms 1～3 that Direct Bonding, Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom also can replace by halogen atom or hydrogen atom also can have been replaced by halogen atom, or be selected from 2 divalent bridge crosslinking structures that are formed by connecting above in the arylidene that the divalent organic group of the carbonatoms 1～3 that Sauerstoffatom, sulphur atom, alkylsulfonyl, hydrogen atom also can replace by halogen atom and hydrogen atom also can replace by halogen atom.
13. polyimide as described in claim 11 or 12
Figure FDA0000466894500000081
azoles resin combination, is characterized in that, the R in general formula (3) 3represent with following formula (25),
Figure FDA0000466894500000082
14. polyimide as described in any one of claim 11～13
Figure FDA0000466894500000083
azoles resin combination, is characterized in that, (a ' ') polyimide using the represented structural unit of general formula (3) as principal constituent
Figure FDA0000466894500000084
azoles contains the represented structural unit 10%～50% of general formula (37),
In general formula (37), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure.
15. polyimide as described in any one of claim 11～14
Figure FDA0000466894500000086
azoles resin combination, is characterized in that, in the face of the film obtaining through thermal treatment/face outside double refraction be below 0.01.
16. 1 kinds of flexible base, boards, is characterized in that, contain resin combination, and described resin combination contains the represented polyimide of general formula (2),
Figure FDA0000466894500000087
In general formula (2), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 2represent the divalent organic group of the carbonatoms 2～40 with at least 2 hydroxyls.
17. 1 kinds of flexible base, boards, is characterized in that, contain resin combination, and described resin combination contains the represented polyimide of general formula (3)
Figure FDA0000466894500000091
azoles,
Figure FDA0000466894500000092
In general formula (3), R 1represent the 4 valency organic groups of carbonatoms 4～40 of the alicyclic structure with monocyclic or condensed ring formula, or the organic group with monocyclic alicyclic structure directly or be situated between by be connected to each other 4 valency organic groups of the carbonatoms 4～40 forming of bridge crosslinking structure, R 3represent 4 valency organic groups of carbonatoms 2～40.
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