CN110256671A - The manufacturing method and display base plate resin film formation composition of display base plate resin film - Google Patents

The manufacturing method and display base plate resin film formation composition of display base plate resin film Download PDF

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CN110256671A
CN110256671A CN201910439446.7A CN201910439446A CN110256671A CN 110256671 A CN110256671 A CN 110256671A CN 201910439446 A CN201910439446 A CN 201910439446A CN 110256671 A CN110256671 A CN 110256671A
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formula
indicate
resin film
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base plate
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田村隆行
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Nissan Chemical Corp
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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
    • C08G73/1003—Preparatory processes
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The subject of the invention is to provide a kind of manufacturing methods of resin film for assigning substrate that have the good fissility of high heat resistance and good flexibility, display and glass, suitable for flexible display.Solution is, a kind of manufacturing method of display base plate resin film, it is characterized in that, including following process: the resin film for the polyamic acid that coating is 5000 or more containing weight average molecular weight shown in following formula (1-1) on matrix, which is formed, uses composition, and is heated.(in formula, Ar1And Ar2Indicate that such as 3,3 ', 4,4 '-four base of biphenyl-, m indicate the number of repetitive unit, the integer that m is positive.)

Description

The manufacturing method and display base plate resin film of display base plate resin film Formation composition
The present application is that application No. is 201480004765.0, entitled " display base plate resin films Manufacturing method and display base plate resin film formation composition ", the applying date be on January 16th, 2014 application division Application.
Technical field
The present invention relates to a kind of manufacturing method of display base plate resin film and display base plate resin film shapes At with composition.
Background technique
In recent years, in organic electroluminescent (hereinafter also referred to as organic EL.) display devices such as display or liquid crystal display Field in, ultrathin, lightweight require increasingly to increase as flexibility, as baseplate material, soft resin material It is concerned.
On the other hand, the panel that active matrix drive is used in fine display removes matrix in its manufacturing process Except the pixel electrode of shape, in order to form the active matrix layer containing film active element, need to carry out 200 DEG C or more of high temperature Processing, the high-temperature process for according to circumstances needing to carry out 300 DEG C or more.
Therefore, when replacing glass to use baseplate material of the resin material as display, which is required high Heat resistance.
In this respect, it is known that polyphenyl is simultaneouslyAzoles has high heat resistance, it was recently reported that have studied suitable for baseplate material by Polyphenyl is simultaneouslyThe film and its manufacturing method (Patent Documents 1 to 4) that azoles is constituted.
Existing technical literature
Patent document
Patent document 1: No. 2001/34679 pamphlet of International Publication
Patent document 2: Japanese Unexamined Patent Publication 2001-348428 bulletin
Patent document 3: No. 2006/126454 pamphlet of International Publication
Patent document 4: Japanese Unexamined Patent Publication 2004-231875 bulletin
Summary of the invention
Subject to be solved by the invention
But especially with regard to the batch production technique for being suitable for flexible display, using the raw material that can easily prepare The manufacturing method of film towards display substrate etc. or such raw material, are not reported adequately.
The present invention is to complete in light of this situation, it is intended that providing a kind of using can easily prepare Resin film formation composition assign have be resistant in the manufacturing process of flexible display high-temperature process heat resistance, Flexibility appropriate and manufacturing method and such resin film from the resin film of the good fissility of glass substrate Formation composition.
In addition, flexibility appropriate said here refer to it is with self-supporting and not broken with 90 degree of bendings Degree high flexibility.In addition, fissility refers to, resin film itself will not be certainly from the matrix for be formed with resin film So fall off but can by the degree being easily peeled off from external power, have for for mass production processes For adequately with the adaptation of matrix.
Means for solving the problems
The present inventor in order to achieve the above object, has been repeated and has careful studied, as a result, it has been found that, by that will include containing extremely The tree of the polyamic acid of the skeleton derived from specific aromatic dianhydride and specific aromatic diamine of few 60 moles of % or more Membrane of lipoprotein formation is coated on glass substrate and is heated with composition, can be manufactured and is particularly suited for use as display base plate Resin film, so as to complete the present invention.
In addition, in patent document 4, the manufacturing method for having used the film of polyimides is disclosed, but about containing this hair The display base plate of bright defined polyamic acid resin film formation composition uses its manufacturing method, by the system In terms of the resin film that the method for making obtains has the characteristic for being particularly suitable for display base plate, without any disclosure.
That is, the present invention provides:
1. a kind of manufacturing method of display base plate resin film, which is characterized in that include following processes: on matrix The resin film for the polyamic acid that coating is 5000 or more containing weight average molecular weight shown in following formula (1-1) is formed with combination Object, and heated,
[in formula (1-1), Ar1Indicate that 4 valence groups shown in following formula (2) or formula (3), m indicate that the number of repetitive unit, m are Positive integer,
(in formula (2) and formula (3), asterisk and wave symbol indicate associative key, 1 in 2 keys with asterisk and with wave 1 and carboxylic-bond in 2 keys of unrestrained line symbol.),
Ar24 valence groups shown in expression following formula (4-1), formula (4-2) or formula (5),
(in formula (4-1), formula (4-2) and formula (5), asterisk and wave symbol indicate associative key, in 2 keys with asterisk 1 and 2 keys with wave symbol in 1 be bonded with hydroxyl.]；
2. the manufacturing method according to 1, the polyamic acid is indicated with following formula (1-2),
{ in formula (1-2), X indicates divalent group shown in any of following formula (6)~formula (8), Ar1、Ar2With m indicate with Above-mentioned identical meaning.
[in formula (6)~formula (8), R1~R4Separately indicate that the alkyl of hydrogen atom or carbon atom number 1~20, Y indicate 1 valence group shown in following formula (9) or formula (10), n indicate the number for being bonded to the Y of aromatic rings, the integer that n is 1~3, asterisk table Show associative key.
(in formula (9) and formula (10), R5~R8Separately indicate the aryl of hydrogen atom or carbon atom number 6~20, asterisk Indicate associative key.)]}；
3. described matrix is glass matrix according to manufacturing method described in 1 or 2；
4. the manufacturing method according to any one of 1~3, which is characterized in that the heating is so that the heating temperature stage The mode risen to property carries out；
5. the manufacturing method according to 4, the step of periodically increase heating temperature, carries out in the following sequence: 50 DEG C~100 DEG C heat 5 minutes~2 hours, be greater than 100 DEG C and be less than or equal to 200 DEG C heat 5 minutes~2 hours, be greater than 200 DEG C and be less than or equal to 375 DEG C heat 5 minutes~2 hours, then be greater than 375 DEG C and be less than or equal to 500 DEG C heat 30 minutes ~4 hours；
6. a kind of display base plate resin film is that the manufacturing method as described in any one of 1~5 obtains；
7. a kind of flexible display substrate includes display base plate resin film described in 6；
8. a kind of display base plate resin film formation composition, contains Weight-average molecular shown in following formula (1-1) The polyamic acid that amount is 5000 or more；
[in formula (1-1), Ar1Indicate that 4 valence groups shown in following formula (2) or formula (3), m indicate that the number of repetitive unit, m are Positive integer,
(in formula (2) and formula (3), asterisk and wave symbol indicate associative key, 1 in 2 keys with asterisk and with wave 1 and carboxylic-bond in 2 keys of unrestrained line symbol.),
Ar24 valence groups shown in expression following formula (4-1), formula (4-2) or formula (5),
(in formula (4-1), formula (4-2) and formula (5), asterisk and wave symbol indicate associative key, in 2 keys with asterisk 1 and 2 keys with wave symbol in 1 be bonded with hydroxyl.]
9. the resin film formation composition of the display base plate according to 8., the polyamic acid following formula (1-2) is indicated,
{ in formula (1-2), X indicates divalent group shown in any of following formula (6)~formula (8), Ar1、Ar2With m indicate with Above-mentioned identical meaning.
[in formula (6)~formula (8), R1~R4Separately indicate that the alkyl of hydrogen atom or carbon atom number 1~20, Y indicate 1 valence group shown in following formula (9) or formula (10), n indicate the number for being bonded to the Y of aromatic rings, the integer that n is 1~3, asterisk table Show associative key.
(in formula (9) and formula (10), R5~R8Separately indicate the aryl of hydrogen atom or carbon atom number 6~20, asterisk Indicate associative key.)]}.
Invention effect
Resin film is used to manufacture as the flexible display of substrate by following process: excellent in terms of as heat resistance The process of resin film is formed on the glass matrix of different material；Active square is sequentially formed under high-temperature on the resin film The process of battle array layer etc.；Then, the process resin film for being formed with the active matrix layer etc. removed from glass matrix.
Manufacturing method according to the invention can be manufactured with high heat resistance and good flexibility, display and glass Good fissility resin film, the resin film of the invention in addition used in this manufacturing method formed with combination Object can contribute to cost effective, manufacturing process simplification, yield rate raising etc. in the manufacture of flexible display.
Specific embodiment
In the following, the present invention is described in detail.
It in the manufacturing method of the present invention, the use of containing weight average molecular weight shown in following formula (1-1) is 5000 or more Composition is used in the resin film formation of polyamic acid.
In above-mentioned formula (1-1), m indicates number of repeat unit, is positive integer.
In addition, Ar1Indicate 4 valence groups shown in following formula (2) or formula (3).
In formula (2) and formula (3), asterisk and wave symbol indicate that associative key, the singly-bound between each phenyl ring refer to position In any position of phenyl ring.For example, 4 valence groups shown in formula (2) include 2 phenyl ring with either one in formula (2-1)~formula (2-3) Group made of formula bonding.
In addition, in formula (2) and formula (3), 1 in 2 associative keys with asterisk and 2 knots with wave symbol Close key in 1 with the Ar in the formula that is bonded to (1-1)1Carboxylic-bond.For example, Ar1The case where for group shown in formula (2-1) Under, the carboxyl in formula (1-1) is bonded to Ar with either type in formula (A)~formula (C)1。
As the example of group shown in formula (2) or formula (3), formula (2-1)~formula (2-3), formula (3-1) or formula can be enumerated Group shown in (3-2) etc..
Especially if it is considered that reproducibility manufactures the resin film with high flexibility well, then Ar1Preferably formula Group shown in (2-1) or formula (3-1), if it is considered that the accessibility of the acid dianhydride as raw material, then more preferably formula (2- 1) group shown in.
In above-mentioned formula (1-1), Ar24 valence groups shown in expression following formula (4-1), formula (4-2) or formula (5).
In formula (4-1), formula (4-2) and formula (5), asterisk and wave symbol indicate associative key, in formula (5), are located at 2 benzene Singly-bound between ring, it is same as described above, refer to positioned at any position of phenyl ring.
In formula (4-1), formula (4-2) and formula (5), 1 in 2 associative keys with asterisk and 2 with wave symbol 1 in associative key with the Ar in the formula that is bonded to (1-1)2Hydroxyl bonding.For example, Ar2For the feelings of group shown in formula (4-2) Under condition, the hydroxyl of formula (1-1) is bonded to Ar with either type in formula (D)~formula (F)2。
Especially if it is considered that the accessibility of the diamines as raw material, then Ar2Preferably shown in following formula (4-1) Group shown in base or following formula (5-1), if it is considered that reproducibility manufactures the resin film with high flexibility well, then More preferably group shown in formula (5-1).
In the present invention, as polyamic acid shown in above-mentioned formula (1-1), there is unsaturated bond by using two ends , polyamic acid shown in following formula (1-2), it is thin that the resin with higher flexibility and higher heat resistance can be manufactured Film.
In formula (1-2), X indicates divalent group shown in any of following formula (6)~formula (8), Ar1、Ar2And m indicate with Above-mentioned identical meaning.
In formula (6), Y indicates that 1 valence group shown in following formula (9) or formula (10), asterisk indicate associative key.
In formula (9) and formula (10), R5~R8Separately indicate the aryl of hydrogen atom or carbon atom number 6~20.
It as the aryl of carbon atom number 6~20, can enumerate: phenyl, 1- naphthalene, 2- naphthalene, 1- anthryl, 2- anthryl, 9- anthracene Base, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl etc..
As for R5~R8, if it is considered that improving polyamic acid to the dissolubility of organic solvent, then preferably hydrogen atom or carbon are former The aryl below of subnumber 14, more preferably hydrogen atom or the aryl below of carbon atom number 10, further preferably hydrogen atom or benzene Base.Additionally, it is preferred that R5~R7In at least one be hydrogen atom, more preferable 2 groups be hydrogen atom.
In formula (6), n indicate be bonded to aromatic rings Y number, n be 1~3 integer, preferably 1 or 2.In addition, n be 2 with In the case where upper, multiple Y can be all identical, can also be different.
In formula (7) and formula (8), R1~R4Separately indicate the alkyl of hydrogen atom or carbon atom number 1~20.
As the alkyl of carbon atom number 1~20, it can be any one of straight-chain, branched, ring-type, example can be enumerated Such as: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, The straight or branched alkyl of the carbon atom numbers such as n-octyl, n-nonyl, positive decyl 1~20；Cyclopropyl, cyclobutyl, cyclopenta, ring It is hexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclic butyl, Bicvclopentyl, dicyclohexyl, bicycloheptyl, bicyclic pungent The cyclic alkyl etc. of the carbon atom numbers such as base, bicyclononyl, bicyclodecyl 3~20.
As for R1~R4, if it is considered that improve dissolubility of the polyamic acid into organic solvent, then preferably hydrogen atom or carbon The alkyl below of atomicity 10, more preferably hydrogen atom or the alkyl below of carbon atom number 4, further preferably hydrogen atom or first Base.Additionally, it is preferred that R1And R2In 1 group and R3And R4In 1 group be hydrogen atom.
Polyamic acid used in the present invention is rubbed based on the entirety for the repetitive unit for constituting polyamic acid containing at least 60 Repetitive unit, preferably 70 moles of % or more shown in your % following formula (1), more preferable 80 moles of % or more, further preferred 90 Mole %.By using such polyamic acid, can be manufactured well with reproducibility with the high heat resistance suitable for display base plate The resin film of property.
(in formula, Ar1、Ar2And m indicates meaning same as described above.)
As for the lower limit value of the weight average molecular weight of polyamic acid, if it is considered that maintain the heat resistance of obtained film, then for 5000 or more, preferably 10000 or more, more preferably 15000 or more, further preferably 20000 or more.On the other hand, originally But if the upper limit value of the weight average molecular weight of polyamic acid used in invention is usually 2000000 hereinafter, considering to inhibit paint It increases to excess stickiness or reproducibility manufactures the high resin film etc. of flexibility well, then preferably 1000000 hereinafter, more excellent It is selected as 200000 or less.
In addition to the repetitive unit shown in above-mentioned formula (1) of polyamic acid used in the present invention, other repetitions can be contained The content of unit, such repetitive unit is needed based on the entirety for the repetitive unit for constituting polyamic acid lower than 40 moles of %, excellent Choosing is lower than 30 moles of %, more preferably less than 20 moles of %, even more preferably below 10 moles of %.
Polyamic acid shown in above-mentioned formula (1-1) used in the present invention can be by making diamines shown in following formula (11) It is reacted with acid dianhydride shown in following formula (12) to obtain.
(in formula, Ar1And Ar2Indicate meaning same as described above.)
Commercially available product can be used in acid dianhydride shown in diamines shown in formula (11) and formula (12), also can be used known in utilization Method synthesis substance.
As diamines shown in formula (11), 4,6-diaminoresorcinol, 3,3 '-dihydroxybiphenyl amine, 3,3 '-can be enumerated 4,4 '-dihydroxybiphenyl of diamino-etc., but it is not limited to these.
As acid dianhydride shown in formula (12), 4,4 '-connection phthalic anhydrides, 3 can be enumerated, 3 '-connection phthalic anhydrides, 3,4 '-connection phthalic anhydrides, 1,1 ': 4 ', 1 "-terphenyl -3,3 ", 4,4 "-tetracarboxylic dianhydrides, 1,1 ': 3 ', 1 "-terphenyl - 3,4,3 ", 4 "-tetracarboxylic dianhydrides etc., but it is not limited to these.
In addition, polyamic acid shown in above-mentioned formula (1-2) used in the present invention can be by making shown in above-mentioned formula (11) Diamines, acid anhydrides shown in any of acid dianhydride and above-mentioned formula (13)~formula (15) shown in above-mentioned formula (12) (hereinafter, Referred to as capped material) it reacts to obtain.
(in formula, R1~R4, Y and n indicate meaning same as described above.)
Commercially available product can be used in acid anhydrides shown in formula (13)~formula (15), also can be used and utilizes the synthesis of well known method Acid anhydrides.
As acid anhydrides shown in formula (13), can enumerate 3- vinylphthalic acid acid anhydride, 4- vinylphthalic acid acid anhydride, 4- phenylene-ethynylene phthalic anhydride, 4- acetenyl phthalic anhydride, but it is not limited to these.
As acid anhydrides shown in formula (14), 5- norbornene -2,3- dicarboxylic acid anhydride, norbornene -2 methyl -5- can be enumerated, 3- dicarboxylic acid anhydride, but it is not limited to these.
As acid anhydrides shown in formula (15), maleic anhydride, citraconic anhydride etc. can be enumerated, but be not limited to these.
In above-mentioned reaction, for acid anhydrides shown in diamines shown in above-mentioned formula (11) and above-mentioned formula (12)~formula (15) The addition of (acid dianhydride and acid anhydrides) considers molecular weight for the polyamic acid to be synthesized etc. and suitably sets, relatively than (molar ratio) In diamines 1, acid anhydrides 0.6~1.4 or so usually can be set to, preferably 0.8~1.2 or so.
Above-mentioned reaction preferably carries out in a solvent, in the case where using used solvent, as its type, as long as to anti- Adverse effect should not be generated, then various solvents can be used.
It as concrete example, can enumerate: metacresol, 2-Pyrrolidone, n-methyl-2-pyrrolidone, N- ethyl -2- pyrrolidines Ketone, n-vinyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, 3- methoxyl group-N, N- dimethyl Propionamide, 3- ethyoxyl-N, N- dimethylpropionamide, 3- propoxyl group-N, N- dimethylpropionamide, 3- isopropoxy-N, N- bis- Methyl propanamide, 3- butoxy-N, N- dimethylpropionamide, 3- sec-butoxy-N, N- dimethylpropionamide, 3- t-butoxy- Protonic solvents such as N, N- dimethylpropionamide, gamma-butyrolacton etc..These solvents can be used alone or be applied in combination 2 kinds with On.
As for reaction temperature, suitably set in the range of from the fusing point of the solvent used to boiling point, usually 0~ 100 DEG C or so, but the imidizate of the polyamic acid obtained in order to prevent and maintain the high-content of polyamic acid unit, preferably 0~70 DEG C or so, more preferably 0~60 DEG C or so, further preferably 0~50 DEG C or so.
It cannot be provided, be led to without exception due to the reactivity dependent on reaction temperature or raw material as the reaction time It is often 1~100 hour or so.
After reaction, it is conventionally post-processed, isolates target polyamic acid.
It in the manufacturing method of the present invention, will be as obtained from the polyamic acid isolated be made to be dissolved or dispersed in solvent Qi Zuowei resin film formation is used with composition.In particular, if it is considered that reproducibility manufactures the high film of flatness well, Polyamic acid is preferably then dissolved in solvent.
In addition, the reaction solution containing polyamic acid obtained in above-mentioned reaction can also directly or be diluted or dense Contracting, and be that resin film formation composition is used for the manufacturing method of the present invention as paint.
As long as the solvent that the solvent for diluting, dissolving or disperse makes polyamic acid dissolve or disperse, just without special It limits.As such solvent, the same solvent of concrete example with the above-mentioned reaction dissolvent reacted can be enumerated, these solvents can be with It is used singly or in combination two or more.
Wherein, if it is considered that reproducibility obtains the high resin film of flatness well, then preferred N, N- dimethyl formyl Amine, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, 1,3- dimethyl -2- imidazolinedione.
As for polyamic acid, relative to the concentration of the gross mass of varnish (resin film formed use composition), (solid component is dense Degree), consider thickness or varnish viscosity of the film of production etc. and suitably set, usually 0.5~30 mass % or so, preferably 5~25 mass % or so.
In addition, the viscosity of varnish also considers thickness of film of production etc. and suitably sets, it is especially good with reproducibility It is 500~50000mPa usually at 25 DEG C in the case that ground obtains for the purpose of the resin film of 5~50 μm or so of thickness S or so, preferably 1000~20000mPas or so.
Resin film formation composition used in the manufacturing method of the present invention can be containing crosslinking agent (hereinafter, also referred to as For cross-linked compound.).The content of crosslinking agent is 20 below the mass usually relative to 100 mass parts of polyamic acid.
As the cross-linked compound, it can be mentioned, for example the compound of the epoxy group containing 2 or more, with amino Hydrogen atom by methylol, alkoxy methyl or both instead of group, melamine derivative, benzoguanamine derivative Or glycoluril etc., but it is not limited to these.
Hereinafter, enumerating the concrete example of cross-linked compound, but not limited to this.
It as the compound of the epoxy group containing 2 or more, can enumerate: エ ポ リ ー De GT-401, エ ポ リ ー De GT- 403, エ ポ リ ー De GT-301, エ ポ リ ー De GT-302, セ ロ キ サ イ De 2021, セ ロ キ サ イ De 3000 (more than, (strain) ダ イ セ Le system) etc. with cyclohexene epoxide；エピコート1001,エピコート1002,エピ コート1003、エピコート1004、エピコート1007、エピコート1009、エピコート1010、エピコート 828 (more than, ジ ャ パ Application エ Port キ シ レ ジ Application (strain) system (existing: Mitsubishi Chemical's (strain) system, jER (registered trademark) series)) etc. Bisphenol A type epoxy compound；The bisphenol F type epoxies chemical combination such as エ ピ コ ー ト 807 (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) system) Object；エ ピ コ ー ト 152, エ ピ コ ー ト 154 (more than, ジ ャ パ Application エ Port キ シ レ ジ Application (strain) system is (existing: Mitsubishi Chemical (strain) system, jER (registered trademark) series)), the novolaks type ring such as EPPN201, EPPN202 (more than, Japanese chemical drug (strain) system) Oxygen compound；ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (more than, Japan Chemical drug (strain) system), (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) is (existing: Mitsubishi Chemical's (strain) system, jER by エ ピ コ ー ト 180S75 (registered trademark) series) system) and etc. cresol novolak type epoxies compound；The oxidation of the naphthalenes type rings such as V8000-C7 (DIC (strain) system) Close object；デ ナ コ ー Le EX-252 (Na ガ セ ケ system テ ッ Network ス (strain) system), CY175, CY177, CY179, ア ラ Le ダ イ ト CY-182, ア ラ Le ダ イ ト CY-192, ア ラ Le ダ イ ト CY-184 (more than, BASF society system), エ ピ Network ロ Application 200, エ ピ Network ロ Application 400 (more than, DIC (strain) system), エ ピ コ ー ト 871, エ ピ コ ー ト 872 (more than, ジ ャ パ Application エ Port キ シ レ ジ Application (strain) system (existing: Mitsubishi Chemical's (strain) system, jER (registered trademark) series)), ED-5661, ED-5662 (more than, セ ラ ニ ー ズ コ ー テ ィ Application グ (strain) system) etc. cycloaliphatic epoxies；デナコールEX-611,デナコールEX-612,デナ コールEX-614、デナコールEX-622、デナコールEX-411、デナコールEX-512、デナコールEX- 522, デ ナ コ ー Le EX-421, デ ナ コ ー Le EX-313, デ ナ コ ー Le EX-314, デ ナ コ ー Le EX-312 (more than, Na ガ セ ケ system テ ッ Network ス (strain) system) etc. aliphatic polyglycidyl ether compounds.
As the hydrogen atom with amino by methylol, alkoxy methyl or both instead of group, melamine Amine derivative, benzoguanamine derivative or glycoluril, can enumerate: every 1 triazine ring is averaged what 3.7 methoxies replaced MX-750, every 1 triazine ring be averaged 5.8 methoxies substitution MW-30 (more than, (strain) three and chemistry system)；サイ メル300、サイメル301、サイメル303、サイメル350、サイメル370、サイメル771、サイメル 325, the methoxymethylated melamine such as サ イ メ Le 327, サ イ メ Le 703, サ イ メ Le 712；サイメル235,サ The methoxymethylated butoxy such as イ メ Le 236, サ イ メ Le 238, サ イ メ Le 212, サ イ メ Le 253, サ イ メ Le 254 Methylated melamine；The butoxymethyls melamines such as サ イ メ Le 506, サ イ メ Le 508；サ イ メ Le 1141 etc Carboxylic methoxymethylated isobutoxymethyl melamine；The methoxymethylated second of サ イ メ Le 1123 etc Oxygroup methylation benzoguanamine；The methoxymethylated butoxymethyl benzoguanamine of サ イ メ Le 1123-10 etc；サイ The butoxymethyl benzoguanamine of メ Le 1128 etc；サ イ メ Le 1125-80's etc is carboxylic methoxymethylated Ethoxyl methyl benzoguanamine；The butoxymethyl glycoluril of サ イ メ Le 1170 etc；The hydroxyl of サ イ メ Le 1172 etc Methylation glycoluril (more than, three well イ ア Na ミ ッ De (strain) system (existing: Japanese サ イ テ ッ Network イ Application ダ ス ト リ ー ズ (strain)) etc..
In addition, the resin film formation composition containing polyamic acid shown in above-mentioned formula (1-1) is particularly suitable for manufacture Resin film as display base plate, which is also object of the invention.
In the manufacturing method of the present invention, above explained resin film formation is coated on matrix with composition.
As matrix, it can be mentioned, for example plastics (polycarbonate, polymethacrylates, polystyrene, polyester, polyolefin, Epoxy resin, melamine, Triafol T, ABS, AS, norbornene resin etc.), metal, timber, paper, glass, stone Plate etc., but from the aspect of showing good fissility from obtained resin film, most preferably glass matrix.
For used glass matrix, as long as all or part of of the face of coating resin film formation composition is Glass, but from obtained film show good fissility from the aspect of, it is preferable to use entire coated face is the glass of glass The glass matrix such as glass substrate.
The method of coating is not particularly limited, it can be mentioned, for example: cast coating method, spin coating, scraper for coating method, dip coating, Rolling method, stick coating method, die coating method, ink-jet method, print process (relief printing plate, intaglio plate, lithographic plate, silk-screen printing etc.) etc..
In the manufacturing method of the present invention, comprising being heated with composition to the resin film formation for being coated on matrix Stage.It can be mentioned, for example heating plate, baking ovens etc. for utensil for heating.
Heating temperature is needed at 500 DEG C or less.If heating temperature reaches 500 DEG C or more, obtained resin film becomes It is crisp, the resin film suitable for display base plate purposes cannot be manufactured.
In addition, if it is considered that the heat resistance for the resin film that raising obtains, then form the resin film of coating and use The heating temperature of composition is risen with stage, such as after heating 5 minutes~2 hours at 50 DEG C~100 DEG C, the direct stage Property increase heating temperature, finally be greater than 375 DEG C and 500 DEG C or less heating 30 minutes~4 hours.
Particularly preferably by the resin film formation composition of coating by periodically making heating temperature in the following order The step of rising, is heated: after heating 5 minutes~2 hours at 50 DEG C~100 DEG C, being greater than 100 DEG C and 200 DEG C or less Heating 5 minutes~2 hours, then be greater than 200 DEG C and 375 DEG C or less heat 5 minutes~2 hours, finally greater than 375 DEG C and 500 DEG C or less heat 30 minutes~4 hours, more preferably by periodically increase heating temperature in the following order the step of into Row heating: after heating 5 minutes~2 hours at 50 DEG C~100 DEG C, it is being greater than 100 DEG C and 200 DEG C or less heating 5 minutes~2 Hour is then being greater than 200 DEG C and 375 DEG C or less heating 5 minutes~2 hours, is further being greater than 375 DEG C and 425 DEG C or less It heats 15 minutes~2 hours, be finally greater than 425 DEG C and 500 DEG C or less heating 15 minutes~2 hours.
Atmosphere when heating can be under air, or, can also be with furthermore it is possible under normal pressure under inert gas For under decompression.
As for the thickness of resin film, especially in the case where the substrate as flexible display, usually 1~60 μm Left and right, preferably 5~50 μm or so, the thickness of the film before adjustment heating and form the resin film of desired thickness.
Manufacturing method described above meets each condition of needs particularly suitable for manufacturing as the Ranvier's membrane of display base plate Resin film, the basement membrane (i.e. flexible display substrate) of display base plate is most suitable as with the resin film that this method obtains It uses.
Embodiment
In the following, enumerating embodiment, the present invention is more specifically illustrated, but the present invention is not limited to following implementations Example.In addition, the substance that acid dianhydride, diamines and capped material (acid anhydrides) are all made using Tokyo chemical conversion industry (strain).
[1] it abridges used in embodiment
< acid dianhydride >
PMDA: pyromellitic dianhydride
BPDA:4,4 '-joins phthalic anhydride
BzDA:3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides
ODPA:4,4 '-oxygroup diphthalic anhydrides
PSDA:3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic acid dianhydrides
< diamines >
HAB:3,3 '-dihydroxybiphenyl amine
PDA: p-phenylenediamine
< end-capping reagent >
PEPA:4- phenylene-ethynylene phthalic anhydride
4EPA:4- acetenyl phthalic anhydride
< solvent >
NMP:N- N-methyl-2-2-pyrrolidone N
[2] measurement of number-average molecular weight and weight average molecular weight
For weight average molecular weight (the hreinafter referred to as Mw of polymer.) and molecular weight distribution, it is made using Japan's light splitting (strain) GPC device (Shodex [registered trademark] column SB803HQ and SB804HQ), will flow as the dimethylformamide of eluting solvent Amount is measured under conditions of 0.9mL/ minutes, 40 DEG C of column temperature.In addition, Mw is polystyrene scaled value.
[3] resin film forms the manufacture for using composition
1 > of < embodiment
HAB 34.3g (0.16 mole) is dissolved in NMP 720g, after addition BPDA 45.7g (0.16 mole), in nitrogen It is reacted 24 hours under atmosphere, at 23 DEG C.The Mw of obtained polymer is 151800, molecular weight distribution 2.5.The reaction is molten Liquid is used for the manufacture of resin film directly as resin film formation with composition.
2 > of < embodiment
HAB 1.58g (0.0073 mole) is dissolved in NMP 21.3g, addition BPDA 2.10g (0.0071 mole) it Afterwards, under nitrogen atmosphere, stirred 1 hour at 23 DEG C after, add PEPA 0.0724g (0.00029 mole), further react 23 Hour.The Mw of obtained polymer is 94800, molecular weight distribution 2.1.The reaction solution is formed directly as resin film The manufacture of resin film is used for composition.
3 > of < embodiment
HAB 2.08g (0.0096 mole) is dissolved in NMP 20.0g, addition BPDA 2.69g (0.0091 mole) it Afterwards, under nitrogen atmosphere, stirred 1 hour at 23 DEG C after, add PEPA 0.238g (0.00096 mole), further reaction is 23 small When.The Mw of obtained polymer is 38500, molecular weight distribution 1.9.The reaction solution is formed directly as resin film and is used Composition is used for the manufacture of resin film.
4 > of < embodiment
HAB 2.11g (0.0097 mole) is dissolved in NMP 20.0g, addition BPDA 2.72g (0.0093 mole) it Afterwards, under nitrogen atmosphere, stirred 1 hour at 23 DEG C after, add 4EPA 0.168g (0.00097 mole), further reaction is 23 small When.The Mw of obtained polymer is 38100, molecular weight distribution 1.9.The reaction solution is formed directly as resin film and is used Composition is used for the manufacture of resin film.
1 > of < comparative example
PDA 0.955g (0.0088 mole) is dissolved in NMP 21.5g, addition BPDA 2.55g (0.0086 mole) it Afterwards, it is reacted 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of obtained polymer is 37000, molecular weight distribution 2.8.It should Reaction solution is used for the manufacture of resin film directly as resin film formation with composition.
2 > of < comparative example
HAB 1.26g (0.0058 mole) is dissolved in NMP 22.5g, addition PMDA 1.24g (0.0057 mole) it Afterwards, it is reacted 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of obtained polymer is 146300, molecular weight distribution 2.7.It will The reaction solution is used for the manufacture of resin film directly as resin film formation with composition.
3 > of < comparative example
HAB 1.52g (0.0070 mole) is dissolved in NMP 21.3g, addition BzDA 2.23g (0.0069 mole) it Afterwards, it is reacted 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of obtained polymer is 126000, molecular weight distribution 2.6.It will The reaction solution is used for the manufacture of resin film directly as resin film formation with composition.
4 > of < comparative example
HAB 1.56g (0.0072 mole) is dissolved in NMP 21.3g, addition ODPA 2.19g (0.0071 mole) it Afterwards, it is reacted 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of obtained polymer is 54800, molecular weight distribution 3.5.It should Reaction solution is used for the manufacture of resin film directly as resin film formation with composition.
5 > of < comparative example
HAB 1.43g (0.0066 mole) is dissolved in NMP 21.3g, addition PSDA 2.32g (0.0065 mole) it Afterwards, it is reacted 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of obtained polymer is 65400, molecular weight distribution 2.8.It should Reaction solution is used for the manufacture of resin film directly as resin film formation with composition.
6 > of < comparative example
By resin film formation obtained in embodiment 1 with composition (paint) under nitrogen atmosphere, at 170 DEG C heating it is 3 small When, as a result, insoluble matter is precipitated, and cannot obtain and be suitable for obtaining the uniform paint of the high film of flatness.
[4] manufacture of resin film
5 > of < embodiment
Resin film formation obtained in embodiment 1 is coated on glass substrate with composition with scraper plate, according to such as It is baked in the case where elevating the temperature to lower sequential stages, to make resin film: being roasted in air at 90 DEG C It is 20 minutes roasting, it then bakes 20 minutes, is then baked at 180 DEG C 20 minutes, then 240 at 120 DEG C under nitrogen atmosphere It is baked at DEG C 20 minutes, then bakes 20 minutes, then baked at 400 DEG C 60 minutes at 300 DEG C.
6~8 > of < embodiment
In addition to use resin film formation obtained in embodiment 2~4 with composition replace embodiment 1 obtained in resin Except film-forming composition, resin film is made with method similarly to Example 5.
9~12 > of < embodiment
After carrying out heat treatment in 60 minutes at 400 DEG C, further carried out at 450 DEG C at heating in 60 minutes In addition to this reason makes resin film with method same as embodiment 5~8.
7~11 > of < comparative example
In addition to use resin film formation obtained in the Comparative Examples 1 to 5 with composition replace embodiment 1 obtained in resin Except film-forming composition, resin film is made with method similarly to Example 5.
12 > of < comparative example
After carrying out heat treatment in 60 minutes at 400 DEG C, further carried out at 450 DEG C at heating in 60 minutes In addition to this reason makes resin film with method same as comparative example 7.
[5] evaluation of the heat resistance of resin film, fissility and flexibility
The evaluation of the resin film of embodiment 5~12 and comparative example 7~12 is carried out with the following method.For each evaluation Film is made respectively.
Show the result in table 1.In addition, for film thickness, for the resin film for fissility and flexible appraisal.In addition, About the resin film of comparative example 8, fissility evaluation and the evaluation of flexibility are only carried out.
< fissility and flexible appraisal >
Removing easy degree when removing each resin film from glass substrate is evaluated.The evaluation of fissility passes through As under type carries out: cutting indentation using cutter on the resin film being formed on glass substrate with rectangle, be confirmed whether It can be easily peeled off the rectangular film from glass substrate, knife will be inserted between film and glass substrate, can not led Even the case where stripping film, is set as good, and by other than it the case where is set as bad.
In addition, evaluating the flexibility of the resin film of removing.Evaluation for flexibility, by with visual confirmation Broken easy degree (crack, chap, rupture etc.) Lai Jinhang of film when the resin film of removing is bent or is stretched with hand, Will be i.e. using hand with 90 degree bendings, non-destructive situation be set as well stretching, by it in addition the case where is set as bad.
<Evaluation of Heat Tolerance>
Measure the 5% Mass lost temperature (Td5% (DEG C)) of each resin film.Use TG-DTA (Block ル カ ー エ イ エ Star Network ス エ ス society system, TG/D TA2000 SA) it is measured and (heating rate: is warming up to 800 with 10 DEG C from 50 DEG C per minute ℃)。
[table 1]
Fissility evaluation Flexible appraisal Td5% [DEG C]
Embodiment 5 Well Well 609
Embodiment 6 Well Well 609
Embodiment 7 Well Well 607
Embodiment 8 Well Well 603
Embodiment 9 Well Well 618
Embodiment 10 Well Well 619
Embodiment 11 Well Well 621
Embodiment 12 Well Well 620
Comparative example 7 It is bad Well 590
Comparative example 8 Well It is bad -
Comparative example 9 Well It is bad 566
Comparative example 10 Well It is bad 569
Comparative example 11 Well It is bad 537
Comparative example 12 It is bad It is bad 582
As shown in table 1, the resin film of comparative example 7 and 12 does not have the adaptation appropriate with glass substrate, is removing Property evaluation in cannot obtain good result.The especially resin film of comparative example 7, peels naturally from glass substrate, no The substrate resin film being suitable as in the manufacturing process of display.
In addition, although the resin film of comparative example 8~11 shows good fissility, but it is easy and being bent with hand Ground is crushed, in addition, the resin film of comparative example 7,9~12 is compared with the resin film of embodiment 5~12, poor heat resistance.
On the other hand, the resin film of embodiment 5~12 not only shows good fissility and flexibility appropriate, but also With high heat resistance.It is 620 DEG C or so that especially 5% weight of the resin film of embodiment 9~12, which reduces temperature, be can be obtained These films have the result of high heat resistance.
It is learnt as the result of above embodiment: being containing weight average molecular weight shown in above-mentioned formula (1-1) according to having used The resin film of 5000 or more polyamic acid forms the manufacturing method of the present invention for using composition, it is available particularly suitable for In the resin film of display base plate, in addition, such resin film formation is particularly suited for use as display base plate with composition Resin film manufacture.

Claims (9)

1. a kind of manufacturing method of display base plate resin film, which is characterized in that include following processes: being coated on matrix Resin film formation composition containing the polyamic acid that weight average molecular weight shown in following formula (1-1) is 5000 or more, and It is heated,
In formula (1-1), Ar1Indicate that 4 valence groups shown in following formula (2) or formula (3), m indicate the number of repetitive unit, m is positive whole Number,
In formula (2) and formula (3), asterisk and wave symbol indicate associative key, 1 in 2 keys with asterisk and with wave 1 and carboxylic-bond in 2 keys of symbol,
Ar24 valence groups shown in expression following formula (4-1), formula (4-2) or formula (5),
In formula (4-1), formula (4-2) and formula (5), asterisk and wave symbol indicate associative key, 1 in 2 keys with asterisk It is bonded with 1 in 2 keys with wave symbol with hydroxyl.
2. the manufacturing method according to claim 1, the polyamic acid is indicated with following formula (1-2),
In formula (1-2), X indicates divalent group shown in any of following formula (6)~formula (8), Ar1、Ar2With m indicate with it is above-mentioned Identical meaning,
In formula (6)~formula (8), R1~R4Separately indicate that the alkyl of hydrogen atom or carbon atom number 1~20, Y indicate following 1 valence group shown in formula (9) or formula (10), n indicate that the number for being bonded to the Y of aromatic rings, the integer that n is 1~3, asterisk indicate knot Key is closed,
In formula (9) and formula (10), R5~R8Separately indicate that the aryl of hydrogen atom or carbon atom number 6~20, asterisk indicate Associative key.
3. manufacturing method according to claim 1 or 2, described matrix is glass matrix.
4. manufacturing method described in any one of claim 1 to 3, which is characterized in that the heating is so that heating temperature The mode periodically risen carries out.
5. manufacturing method according to claim 4, the step of periodically increase heating temperature, carries out in the following sequence: 5 minutes~2 hours are heated at 50 DEG C~100 DEG C, are being greater than 100 DEG C and are being less than or equal to 200 DEG C of heating 5 minutes~2 hours, big In 200 DEG C and it is less than or equal to 375 DEG C of heating 5 minutes~2 hours, is then being greater than 375 DEG C and is heating 30 points less than or equal to 500 DEG C Clock~4 hour.
6. a kind of display base plate resin film is obtained by manufacturing method according to any one of claims 1 to 5.
7. a kind of flexible display substrate includes display base plate resin film as claimed in claim 6.
8. a kind of display base plate resin film formation composition is containing weight average molecular weight shown in following formula (1-1) 5000 or more polyamic acid,
In formula (1-1), Ar1Indicate that 4 valence groups shown in following formula (2) or formula (3), m indicate the number of repetitive unit, m is positive whole Number,
In formula (2) and formula (3), asterisk and wave symbol indicate associative key, 1 in 2 keys with asterisk and with wave 1 and carboxylic-bond in 2 keys of symbol,
Ar24 valence groups shown in expression following formula (4-1), formula (4-2) or formula (5),
In formula (4-1), formula (4-2) and formula (5), asterisk and wave symbol indicate associative key, 1 in 2 keys with asterisk It is bonded with 1 in 2 keys with wave symbol with hydroxyl.
9. display base plate according to claim 8 resin film formation composition, the polyamic acid is with following Formula (1-2) expression,
In formula (1-2), X indicates divalent group shown in any of following formula (6)~formula (8), Ar1、Ar2With m indicate with it is above-mentioned Identical meaning,
In formula (6)~formula (8), R1~R4Separately indicate that the alkyl of hydrogen atom or carbon atom number 1~20, Y indicate following 1 valence group shown in formula (9) or formula (10), n indicate that the number for being bonded to the Y of aromatic rings, the integer that n is 1~3, asterisk indicate knot Key is closed,
In formula (9) and formula (10), R5~R8Separately indicate that the aryl of hydrogen atom or carbon atom number 6~20, asterisk indicate Associative key.
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