CN104918983A - Method for producing resin thin film for display substrates and composition for forming resin thin film for display substrates - Google Patents
Method for producing resin thin film for display substrates and composition for forming resin thin film for display substrates Download PDFInfo
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- CN104918983A CN104918983A CN201480004765.0A CN201480004765A CN104918983A CN 104918983 A CN104918983 A CN 104918983A CN 201480004765 A CN201480004765 A CN 201480004765A CN 104918983 A CN104918983 A CN 104918983A
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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
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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
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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
- C08G73/1057—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
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Polymers & Plastics (AREA)
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- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
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- Optics & Photonics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
To provide a production method which provides a resin thin film that is suitable for a substrate for flexible displays, said resin thin film having high heat resistance, good flexibility and good separability from glass. [Solution] A method for producing a resin thin film for display substrates, which is characterized by comprising a step wherein a composition for forming a resin thin film, said composition containing a polyamic acid that is represented by formula (1-1) and has a weight average molecular weight of 5,000 or more, is applied to a base and heated thereon. (In the formula, each of Ar1 and Ar2 represents, for example, a biphenyl-3,3',4,4'-tetrayl group; and m represents the number of repeating units, which is a positive integer.)
Description
Technical field
The present invention relates to a kind of manufacture method and display base plate resin film formation composition of display base plate resin film.
Background technology
In recent years, at organic electroluminescent (hereinafter also referred to as organic EL.) display unit such as indicating meter or liquid-crystal display field in, the such requirement of ultrathin, lightweight, flexibility more and more raises, and as baseplate material, soft resin material receives much concern.
On the other hand, the panel of driven with active matrix is used in fine indicating meter, in its manufacturing process, except rectangular pixel electrode, in order to form the active matrix layer containing film active element, needing to carry out the pyroprocessing of more than 200 DEG C, according to circumstances needing to carry out the pyroprocessing of more than 300 DEG C.
Therefore, when replacing the baseplate material that glass uses resin material as indicating meter, high thermotolerance is required to this resin material.
In this respect, known polyphenyl also
azoles has high thermotolerance, report have studied be applicable to baseplate material by polyphenyl also
the film that azoles is formed and manufacture method (patent documentation 1 ~ 4) thereof.
Prior art document
Patent documentation
Patent documentation 1: International Publication No. 2001/34679 brochure
Patent documentation 2: Japanese Unexamined Patent Publication 2001-348428 publication
Patent documentation 3: International Publication No. 2006/126454 brochure
Patent documentation 4: Japanese Unexamined Patent Publication 2004-231875 publication
Summary of the invention
The problem that invention will solve
But, particularly about be suitable for flexible display batch production technique, use the manufacture method of the film towards display substrate of raw material that can prepare easily etc. or such raw material, do not report fully.
The present invention completes in light of this situation, its object is to, the resin film formation composition that provides a kind of use to prepare easily is given has the thermotolerance of the pyroprocessing that can tolerate in the manufacturing process of flexible display, suitable flexibility and from the manufacture method of the resin film of the good separability of glass substrate and such resin film formation composition.
In addition, even if refer to there is self-supporting and the high flexibility bending the degree also do not ruptured with 90 degree in this said suitable flexibility.In addition, separability refers to, but from the matrix being formed with resin film resin film self can not naturally come off can by the degree easily peeled off from the power of outside, have for for mass production processes fully and the adaptation of matrix.
For solving the means of problem
The present inventor in order to achieve the above object, repeatedly carry out concentrated research, found that, by the resin film formation composition of the polyamic acid comprised containing the skeleton derived from specific aromatic dianhydride and specific aromatic diamine of more than at least 60 % by mole to be coated on glass substrate and to heat, the resin film being particularly suitable for being used as display base plate can be manufactured, thus complete the present invention.
In addition, in patent documentation 4, disclose the manufacture method of the film employing polyimide, but about the polyamic acid containing regulation of the present invention display base plate resin film formation composition or use its manufacture method, the resin film that obtained by this manufacture method has in the characteristic that is particularly suitable for for display base plate, without any open.
That is, the invention provides:
1. the manufacture method of a display base plate resin film, it is characterized in that, comprise following operation: coating is the resin film formation composition of the polyamic acid of more than 5000 containing the weight-average molecular weight shown in following formula (1-1) on matrix, and heats
[in formula (1-1), Ar
1represent following formula (2) or 4 valency groups shown in formula (3), m represents the number of repeating unit, and m is positive integer,
(in formula (2) and formula (3), asterisk and wavy line symbol represent associative key, 1 and carboxylic-bond in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol.)，
Ar
2represent following formula (4-1), formula (4-2) or 4 valency groups shown in formula (5),
(in formula (4-1), formula (4-2) and formula (5), asterisk and wavy line symbol represent associative key, 1 in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol with hydroxyl bonding.]；
2. the manufacture method according to 1, described polyamic acid following formula (1-2) represents,
{ in formula (1-2), X represents the divalent group shown in any one in following formula (6) ~ formula (8), Ar
1, Ar
2implication same as described above is represented with m.
[in formula (6) ~ formula (8), R
1~ R
4separately represent the alkyl of hydrogen atom or carbonatoms 1 ~ 20, Y represents following formula (9) or 1 valency group shown in formula (10), and n represents the number of the Y being bonded to aromatic nucleus, and n is the integer of 1 ~ 3, and asterisk represents associative key.
(in formula (9) and formula (10), R
5~ R
8separately represent the aryl of hydrogen atom or carbonatoms 6 ~ 20, asterisk represents associative key.)]}；
3. the manufacture method according to 1 or 2, described matrix is glass basis;
4. the manufacture method according to any one of 1 ~ 3, is characterized in that, described heating is carried out in the mode making Heating temperature periodically increase;
5. the manufacture method according to 4, the step making Heating temperature periodically increase is carried out in the following sequence: 50 DEG C ~ 100 DEG C heating 5 minutes ~ 2 hours, be greater than 100 DEG C and be less than or equal to 200 DEG C heating 5 minutes ~ 2 hours, be greater than 200 DEG C and be less than or equal to 375 DEG C heating 5 minutes ~ 2 hours, then be greater than 375 DEG C and be less than or equal to 500 DEG C heating 30 minutes ~ 4 hours;
6. a display base plate resin film is that the manufacture method according to any one of 1 ~ 5 obtains;
7. a flexible display substrate, comprises the display base plate resin film described in 6;
8. a display base plate resin film formation composition is the polyamic acid of more than 5000 containing the weight-average molecular weight shown in following formula (1-1);
[in formula (1-1), Ar
1represent following formula (2) or 4 valency groups shown in formula (3), m represents the number of repeating unit, and m is positive integer,
(in formula (2) and formula (3), asterisk and wavy line symbol represent associative key, 1 and carboxylic-bond in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol.)，
Ar
2represent following formula (4-1), formula (4-2) or 4 valency groups shown in formula (5),
(in formula (4-1), formula (4-2) and formula (5), asterisk and wavy line symbol represent associative key, 1 in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol with hydroxyl bonding.]
9. the resin film formation composition of the display base plate according to 8., described polyamic acid following formula (1-2) represents,
{ in formula (1-2), X represents the divalent group shown in any one in following formula (6) ~ formula (8), Ar
1, Ar
2implication same as described above is represented with m.
[in formula (6) ~ formula (8), R
1~ R
4separately represent the alkyl of hydrogen atom or carbonatoms 1 ~ 20, Y represents following formula (9) or 1 valency group shown in formula (10), and n represents the number of the Y being bonded to aromatic nucleus, and n is the integer of 1 ~ 3, and asterisk represents associative key.
(in formula (9) and formula (10), R
5~ R
8separately represent the aryl of hydrogen atom or carbonatoms 6 ~ 20, asterisk represents associative key.)]}。
Invention effect
Resin film is used to be manufactured by following operation as the flexible display of substrate: the operation forming resin film on the glass basis of the material as excellence in thermotolerance; This resin film is formed successively the operation of active matrix layer etc. under high-temperature; Then, by operation that the resin film being formed with this active matrix layer etc. is peeled off from glass basis.
Manufacturing method according to the invention, the resin film of good separability with high thermotolerance and good flexibility, display and glass can be manufactured, the resin film formation composition of the present invention used in this manufacture method in addition, can contribute to the simplification, yield rate raising etc. of the cost degradation in the manufacture of flexible display, manufacturing process.
Embodiment
Below, the present invention is described in detail.
In manufacture method of the present invention, use and contain the resin film formation composition that the weight-average molecular weight shown in following formula (1-1) is the polyamic acid of more than 5000.
In above-mentioned formula (1-1), m represents number of repeat unit, is positive integer.
In addition, Ar
1represent following formula (2) or 4 valency groups shown in formula (3).
In formula (2) and formula (3), asterisk and wavy line symbol represent associative key, and the singly-bound between each phenyl ring refers to the optional position being positioned at phenyl ring.Such as, 4 valency groups shown in formula (2) comprise 2 phenyl ring with the group of either type bonding in formula (2-1) ~ formula (2-3).
In addition, in formula (2) and formula (3), 1 in 2 associative keys of 1 in 2 associative keys of band asterisk and band wavy line symbol with the Ar be bonded in formula (1-1)
1carboxylic-bond.Such as, Ar
1when for group shown in formula (2-1), the carboxyl in formula (1-1) is bonded to Ar with either type in formula (A) ~ formula (C)
1.
As the example of the group shown in formula (2) or formula (3), can enumerative (2-1) ~ formula (2-3), formula (3-1) or the group etc. shown in formula (3-2).
If especially consider that reproducibility manufactures the resin film with high flexibility, then Ar well
1be preferably formula (2-1) or the group shown in formula (3-1), if be considered as the acquisition easiness of the acid dianhydride of raw material, be then more preferably the group shown in formula (2-1).
In above-mentioned formula (1-1), Ar
2represent following formula (4-1), formula (4-2) or 4 valency groups shown in formula (5).
In formula (4-1), formula (4-2) and formula (5), asterisk and wavy line symbol represent associative key, in formula (5), and the singly-bound between 2 phenyl ring, same as described above, refer to the optional position being positioned at phenyl ring.
In formula (4-1), formula (4-2) and formula (5), 1 in 2 associative keys of 1 in 2 associative keys of band asterisk and band wavy line symbol with the Ar be bonded in formula (1-1)
2hydroxyl bonding.Such as, Ar
2when for group shown in formula (4-2), the hydroxyl of formula (1-1) is bonded to Ar with either type in formula (D) ~ formula (F)
2.
If be especially considered as the acquisition easiness of the diamines of raw material, then Ar
2be preferably the base shown in following formula (4-1) or the group shown in following formula (5-1), if consider that reproducibility manufactures the resin film with high flexibility well, be then more preferably the group shown in formula (5-1).
In the present invention, as the polyamic acid shown in above-mentioned formula (1-1), by use two ends have unsaturated link(age), the polyamic acid shown in following formula (1-2), the resin film of the thermotolerance with higher flexibility and Geng Gao can be manufactured.
In formula (1-2), X represents the divalent group shown in any one in following formula (6) ~ formula (8), Ar
1, Ar
2and m represents implication same as described above.
In formula (6), Y represents following formula (9) or 1 valency group shown in formula (10), and asterisk represents associative key.
In formula (9) and formula (10), R
5~ R
8separately represent the aryl of hydrogen atom or carbonatoms 6 ~ 20.
As the aryl of carbonatoms 6 ~ 20, can enumerate: phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl etc.
As for R
5~ R
8if consider to improve polyamic acid to the solvability of organic solvent, be then preferably the aryl of hydrogen atom or carbonatoms less than 14, be more preferably the aryl of hydrogen atom or carbonatoms less than 10, more preferably hydrogen atom or phenyl.In addition, preferred R
5~ R
7in at least 1 be hydrogen atom, more preferably 2 groups are hydrogen atom.
In formula (6), n represents the number of the Y being bonded to aromatic nucleus, and n is the integer of 1 ~ 3, is preferably 1 or 2.In addition, when n is more than 2, multiple Y can be all identical, also can be different.
In formula (7) and formula (8), R
1~ R
4separately represent the alkyl of hydrogen atom or carbonatoms 1 ~ 20.
As the alkyl of carbonatoms 1 ~ 20, can be any one in straight-chain, branched, ring-type, can enumerate such as: the straight or branched alkyl of the carbonatomss 1 ~ 20 such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl; The cyclic alkyl etc. of the carbonatomss 3 ~ 20 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, dicyclo butyl, Bicvclopentyl, dicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl.
As for R
1~ R
4if consider to improve polyamic acid to the solvability in organic solvent, be then preferably the alkyl of hydrogen atom or carbonatoms less than 10, be more preferably the alkyl of hydrogen atom or carbonatoms less than 4, more preferably hydrogen atom or methyl.In addition, preferred R
1and R
2in 1 group and R
3and R
4in 1 group be hydrogen atom.
The polyamic acid used in the present invention, based on the entirety of the repeating unit of formation polyamic acid, containing the repeating unit shown at least 60 % by mole of following formula (1), preferably more than 70 % by mole, more preferably more than 80 % by mole, further preferably 90 % by mole.By using such polyamic acid, reproducibility the resin film with the high heat resistance being suitable for display base plate can be manufactured well.
(in formula, Ar
1, Ar
2and m represents implication same as described above.)
As for the lower value of the weight-average molecular weight of polyamic acid, if consider to maintain the thermotolerance of film obtained, be then more than 5000, be preferably more than 10000, be more preferably more than 15000, more preferably more than 20000.On the other hand, the higher limit of the weight-average molecular weight of the polyamic acid used in the present invention is generally less than 2000000, if but consider to suppress the rising of the excess stickiness of paint ground or reproducibility to manufacture the high resin film etc. of flexibility well, then be preferably less than 1000000, be more preferably less than 200000.
The polyamic acid used in the present invention is except the repeating unit shown in above-mentioned formula (1), other repeating unit can be contained, the content of such repeating unit needs lower than 40 % by mole based on the entirety of the repeating unit forming polyamic acid, preferably lower than 30 % by mole, more preferably less than 20 % by mole, preferred lower than 10 % by mole further.
The polyamic acid shown in above-mentioned formula (1-1) used in the present invention can react to obtain by making the acid dianhydride shown in the diamines shown in following formula (11) and following formula (12).
(in formula, Ar
1and Ar
2represent implication same as described above.)
Diamines shown in formula (11) and the acid dianhydride shown in formula (12) can use commercially available product, also can use the material utilizing known method to synthesize.
As the diamines shown in formula (11), 4,6-diaminoresorcinol, 3 can be enumerated, 3 '-dihydroxybiphenyl amine, 3,3 '-diamino-4,4 '-dihydroxybiphenyl etc., but be not limited to these.
As the acid dianhydride shown in formula (12), can 4 be enumerated, 4 '-Lian Tetra hydro Phthalic anhydride, 3,3 '-Lian Tetra hydro Phthalic anhydride, 3,4 '-Lian Tetra hydro Phthalic anhydride, 1,1 ': 4 '; 1 "-terphenyl-3,3 ", 4; 4 "-tetracarboxylic dianhydride, 1,1 ': 3 ', 1 "-terphenyl-3; 4; 3 ", 4 "-tetracarboxylic dianhydride etc., but be not limited to these.
In addition, the polyamic acid shown in above-mentioned formula (1-2) used in the present invention can obtain by making the acid anhydrides (hereinafter also referred to as capped material) shown in any one in the acid dianhydride shown in the diamines shown in above-mentioned formula (11), above-mentioned formula (12) and above-mentioned formula (13) ~ formula (15) react.
(in formula, R
1~ R
4, Y and n represent implication same as described above.)
Acid anhydrides shown in formula (13) ~ formula (15) can use commercially available product, also can use the acid anhydrides utilizing known method to synthesize.
As the acid anhydrides shown in formula (13), 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 4-phenylene-ethynylene Tetra hydro Phthalic anhydride, 4-ethynyl Tetra hydro Phthalic anhydride can be enumerated, but be not limited to these.
As the acid anhydrides shown in formula (14), 5-norbornylene-2,3-dicarboxylic acid anhydride, methyl-5-norbornylene-2,3-dicarboxylic acid anhydride can be enumerated, but be not limited to these.
As the acid anhydrides shown in formula (15), can maleic anhydride, citraconic anhydride etc. be enumerated, but be not limited to these.
In above-mentioned reaction, add than (mol ratio) for the acid anhydrides (acid dianhydride and acid anhydrides) shown in the diamines shown in above-mentioned formula (11) and above-mentioned formula (12) ~ formula (15), molecular weight of the polyamic acid that consideration will be synthesized etc. and suitably setting, relative to diamines 1, usually can be set to acid anhydrides about 0.6 ~ 1.4, be preferably about 0.8 ~ 1.2.
Above-mentioned reaction is preferably carried out in a solvent, when the solvent used, as its kind, as long as do not produce detrimentally affect to reaction, then can use all kinds of SOLVENTS.
As concrete example, can enumerate: meta-cresol, 2-Pyrrolidone, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, NVP, N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, 3-methoxyl group-N, N-dimethylpropionamide, 3-oxyethyl group-N, N-dimethylpropionamide, 3-propoxy--N, N-dimethylpropionamide, 3-isopropoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 3-sec-butoxy-N, N-dimethylpropionamide, uncle 3--butoxy-N, N-dimethylpropionamide, the protic solvents etc. such as gamma-butyrolactone.These solvents can be used alone or combinationally use two or more.
As for temperature of reaction, suitably set to the scope of boiling point at the fusing point of the solvent from use, be generally about 0 ~ 100 DEG C, but in order to the high-content preventing the imidization of the polyamic acid obtained from maintaining polyamic acid unit, be preferably about 0 ~ 70 DEG C, be more preferably about 0 ~ 60 DEG C, more preferably about 0 ~ 50 DEG C.
As for the reaction times, owing to depending on the reactivity of temperature of reaction or raw material, therefore can not specify without exception, be generally 1 ~ 100 hours.
After reaction terminates, conventionally carry out aftertreatment, isolate target polyamic acid.
In manufacture method of the present invention, the paint obtained by making isolated polyamic acid be dissolved or dispersed in solvent is used as resin film formation composition.Particularly, if consider that reproducibility manufactures the high film of flatness well, then preferred polyamic acid is dissolved in solvent.
In addition, the reaction soln containing the polyamic acid obtained in above-mentioned reaction also can directly or carry out diluting or concentrating, and is used for manufacture method of the present invention as paint and resin film formation composition.
As long as the solvent for diluting, dissolving or disperse makes polyamic acid dissolve or the solvent of dispersion, be just not particularly limited.As such solvent, can enumerate the solvent same with the concrete example of the reaction solvent of above-mentioned reaction, these solvents can be used alone or combinationally use two or more.
Wherein, if consider that reproducibility obtains the high resin film of flatness well, then preferred DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolinedione.
As for the concentration (solid component concentration) of polyamic acid relative to the total mass of varnish (resin film formation composition), consider the thickness of film that makes or varnish viscosity etc. and suitably set, be generally about 0.5 ~ 30 quality %, be preferably about 5 ~ 25 quality %.
In addition, the viscosity of varnish is also considered the thickness of the film made etc. and suitably sets, when for the purpose of the resin film particularly obtaining the thickness of about 5 ~ 50 μm by reproducibility well, be about 500 ~ 50000mPas usually at 25 DEG C, be preferably about 1000 ~ 20000mPas.
The resin film formation composition used in manufacture method of the present invention can containing linking agent (hereinafter also referred to as cross-linked compound.)。The content of linking agent is below 20 mass parts relative to polyamic acid 100 mass parts usually.
As described cross-linked compound, the compound such as containing the epoxy group(ing) of more than 2 can be enumerated, have the hydrogen atom of amino by methylol, alkoxy methyl or the group that instead of both it, melamine derivative, benzoguanamine derivative or glycoluril etc., but be not limited to these.
Below, enumerate the concrete example of cross-linked compound, but be not limited thereto.
As the compound containing the epoxy group(ing) of more than 2, 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. have the epoxy compounds of cyclohexene, the bisphenol A type epoxy compound such as 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)), the bisphenol F type epoxy compounds such as エ ピ コ ー ト 807 (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) system), 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 (existing: Mitsubishi Chemical's (strain) system, jER (registered trademark) series)), the novolak type epoxy compounds such as EPPN201, EPPN202 (more than, Japanese chemical drug (strain) is made), the cresol novolak type epoxy compounds such as ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (more than, Japanese chemical drug (strain) make), エ ピ コ ー ト 180S75 (ジ ャ パ Application エ Port キ シ レ ジ Application (strain) (existing: Mitsubishi Chemical's (strain) system, jER (registered trademark) series) system), the naphthalene type epoxy compoundss such as V8000-C7 (DIC (strain) system), 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) makes), 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 is (existing: Mitsubishi Chemical's (strain) makes, jER (registered trademark) series)), ED-5661, ED-5662 (more than, セ ラ ニ ー ズ コ ー テ ィ Application グ (strain) make) etc. cycloaliphatic epoxy, the aliphatic polyglycidyl ether compounds such as デ ナ コ ー Le EX-611, デ ナ コ ー Le EX-612, デ ナ コ ー Le EX-614, デ ナ コ ー Le EX-622, デ ナ コ ー Le EX-411, デ ナ コ ー Le EX-512, デ ナ コ ー Le 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) make).
As have amino hydrogen atom by methylol, alkoxy methyl or the group that instead of both it, melamine derivative, benzoguanamine derivative or glycoluril, can enumerate: MW-30 that the MX-750 that every 1 triazine ring is replaced by average 3.7 methoxymethyies, every 1 triazine ring are replaced by average 5.8 methoxymethyies (more than, (strain) three and chemistry system); The methoxymethylated trimeric cyanamides such as サ イ メ Le 300, サ イ メ Le 301, サ イ メ Le 303, サ イ メ Le 350, サ イ メ Le 370, サ イ メ Le 771, サ イ メ Le 325, サ イ メ Le 327, サ イ メ Le 703, サ イ メ Le 712; The methoxymethylated butoxymethyl trimeric cyanamides such as サ イ メ Le 235, サ イ メ Le 236, サ イ メ Le 238, サ イ メ Le 212, サ イ メ Le 253, サ イ メ Le 254; The butoxymethyl trimeric cyanamides such as サ イ メ Le 506, サ イ メ Le 508; The carboxylic methoxymethylated isobutoxymethyl trimeric cyanamide of サ イ メ Le 1141 and so on; The methoxymethylated ethoxyl methyl benzoguanamine of サ イ メ Le 1123 and so on; The methoxymethylated butoxymethyl benzoguanamine of サ イ メ Le 1123-10 and so on; The butoxymethyl benzoguanamine of サ イ メ Le 1128 and so on; The carboxylic methoxymethylated ethoxyl methyl benzoguanamine of サ イ メ Le 1125-80 and so on; The butoxymethyl glycoluril of サ イ メ Le 1170 and so on; The methylolation glycoluril of サ イ メ Le 1172 and so on (more than, Mitsui 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 the polyamic acid shown in above-mentioned formula (1-1) is particularly suitable for manufacturing the resin film being used as display base plate, and this resin film formation composition is also object of the present invention.
In manufacture method of the present invention, the resin film formation composition of above-mentioned explanation is coated matrix.
As matrix, such as plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefine, epoxy resin, trimeric cyanamide, cellulosetri-acetate, ABS, AS, norbornene resin etc.), metal, timber, paper, glass, slabstone etc. can be enumerated, but show good separability from the viewpoint of the resin film obtained, most preferably glass basis.
For used glass basis, as long as all or part of of the face of coating resin film-forming composition is glass, but show good separability from the viewpoint of the film obtained, preferably use the glass basiss such as the glass substrate that whole coated face is glass.
The method of coating is not particularly limited, and can enumerate such as: cast coating method, spin coating, scraper for coating method, dip coating, rolling method, stick coating method, mouth mould coating method, ink jet method, print process (relief printing plate, intaglio plate, lithographic plate, silk screen printing etc.) etc.
In manufacture method of the present invention, comprise the stage that the resin film formation composition coating matrix is heated.Utensil for heating can enumerate such as hot-plate, baking oven etc.
Heating temperature needs below 500 DEG C.If Heating temperature reaches more than 500 DEG C, then the resin film obtained becomes fragile, and can not manufacture the resin film being suitable for display base plate purposes.
In addition, if consider the thermotolerance improving the resin film obtained, the Heating temperature of the resin film formation composition of coating is then preferably made to increase with stage, such as, after heating 5 minutes ~ 2 hours at 50 DEG C ~ 100 DEG C, directly periodically make Heating temperature increase, finally be greater than 375 DEG C and less than 500 DEG C heating 30 minutes ~ 4 hours.
Particularly preferably the resin film formation composition of coating is heated by the step periodically making Heating temperature increase in the following order: after heating 5 minutes ~ 2 hours at 50 DEG C ~ 100 DEG C, be greater than 100 DEG C and less than 200 DEG C heating 5 minutes ~ 2 hours, then be greater than 200 DEG C and less than 375 DEG C heating 5 minutes ~ 2 hours, finally be greater than 375 DEG C and 500 DEG C below heat 30 minutes ~ 4 hours, heat more particularly by the step periodically making Heating temperature increase in the following order: after heating 5 minutes ~ 2 hours at 50 DEG C ~ 100 DEG C, be greater than 100 DEG C and less than 200 DEG C heating 5 minutes ~ 2 hours, then be greater than 200 DEG C and less than 375 DEG C heating 5 minutes ~ 2 hours, further be greater than 375 DEG C and less than 425 DEG C heating 15 minutes ~ 2 hours, finally be greater than 425 DEG C and 500 DEG C below heat 15 minutes ~ 2 hours.
Atmosphere during heating can be under air, also can be under rare gas element, in addition, can be under normal pressure, also can under decompression.
As for the thickness of resin film, when in particular as the substrate of flexible display, be generally about 1 ~ 60 μm, be preferably about 5 ~ 50 μm, the thickness of the film before adjustment heating and form the resin film of desired thickness.
Manufacture method described above is particularly suitable for the resin film manufacturing each condition of satisfying the demand as the Ranvier's membrane of display base plate, is most suitable for using as the basement membrane (i.e. flexible display substrate) of display base plate with the resin film that the method obtains.
Embodiment
, enumerate embodiment below, the present invention is more specifically described, but the present invention is not limited to following embodiment.In addition, acid dianhydride, diamines and capped material (acid anhydrides) whole use Tokyo changes into the material that industry (strain) is made.
[1] abbreviation used in embodiment
< acid dianhydride >
PMDA: pyromellitic dianhydride
BPDA:4,4 '-Lian Tetra hydro Phthalic anhydride
BzDA:3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride
ODPA:4,4 '-oxygen base diphthalic anhydrides
PSDA:3,3 ', 4,4 '-sulfobenzide tetracarboxylic acid dianhydride
< diamines >
HAB:3,3 '-dihydroxybiphenyl amine
PDA: Ursol D
< end-capping reagent >
PEPA:4-phenylene-ethynylene Tetra hydro Phthalic anhydride
4EPA:4-ethynyl Tetra hydro Phthalic anhydride
< solvent >
NMP:N-N-methyl-2-2-pyrrolidone N-
[2] mensuration of number-average molecular weight and weight-average molecular weight
For the weight-average molecular weight of polymkeric substance (hreinafter referred to as Mw.) and molecular weight distribution, use Japanese light splitting (strain) GPC device processed (Shodex [registered trademark] post SB803HQ and SB804HQ), using as eluting solvent dimethyl formamide flow 0.9mL/ minute, measure under the condition of column temperature 40 DEG C.In addition, Mw is polystyrene conversion value.
[3] manufacture of resin film formation composition
< embodiment 1 >
HAB 34.3g (0.16 mole) is dissolved in NMP 720g, after adding BPDA 45.7g (0.16 mole), reacts 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of the polymkeric substance obtained is 151800, and molecular weight distribution is 2.5.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< embodiment 2 >
HAB 1.58g (0.0073 mole) is dissolved in NMP 21.3g, after adding BPDA 2.10g (0.0071 mole), under nitrogen atmosphere, stir at 23 DEG C after 1 hour, add PEPA0.0724g (0.00029 mole), further reaction 23 hours.The Mw of the polymkeric substance obtained is 94800, molecular weight distribution is 2.1.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< embodiment 3 >
HAB 2.08g (0.0096 mole) is dissolved in NMP 20.0g, after adding BPDA 2.69g (0.0091 mole), under nitrogen atmosphere, stir at 23 DEG C after 1 hour, add PEPA 0.238g (0.00096 mole), further reaction 23 hours.The Mw of the polymkeric substance obtained is 38500, and molecular weight distribution is 1.9.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< embodiment 4 >
HAB 2.11g (0.0097 mole) is dissolved in NMP 20.0g, after adding BPDA 2.72g (0.0093 mole), under nitrogen atmosphere, stir at 23 DEG C after 1 hour, add 4EPA 0.168g (0.00097 mole), further reaction 23 hours.The Mw of the polymkeric substance obtained is 38100, and molecular weight distribution is 1.9.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< comparative example 1 >
PDA 0.955g (0.0088 mole) is dissolved in NMP 21.5g, after adding BPDA2.55g (0.0086 mole), reacts 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of the polymkeric substance obtained is 37000, and molecular weight distribution is 2.8.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< comparative example 2 >
HAB 1.26g (0.0058 mole) is dissolved in NMP 22.5g, after adding PMDA1.24g (0.0057 mole), reacts 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of the polymkeric substance obtained is 146300, and molecular weight distribution is 2.7.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< comparative example 3 >
HAB 1.52g (0.0070 mole) is dissolved in NMP 21.3g, after adding BzDA 2.23g (0.0069 mole), reacts 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of the polymkeric substance obtained is 126000, and molecular weight distribution is 2.6.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< comparative example 4 >
HAB 1.56g (0.0072 mole) is dissolved in NMP 21.3g, after adding ODPA2.19g (0.0071 mole), reacts 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of the polymkeric substance obtained is 54800, and molecular weight distribution is 3.5.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< comparative example 5 >
HAB 1.43g (0.0066 mole) is dissolved in NMP 21.3g, after adding PSDA 2.32g (0.0065 mole), reacts 24 hours under nitrogen atmosphere, at 23 DEG C.The Mw of the polymkeric substance obtained is 65400, and molecular weight distribution is 2.8.This reaction soln is directly used for the manufacture of resin film as resin film formation composition.
< comparative example 6 >
Heated 3 hours under nitrogen atmosphere, at 170 DEG C by the resin film formation composition (paint) obtained in embodiment 1, result, insolubles is separated out, and can not obtain the uniform paint being suitable for obtaining the high film of flatness.
[4] manufacture of resin film
< embodiment 5 >
The resin film formation composition scraper plate obtained in embodiment 1 is coated on glass substrate, bake when periodically elevating the temperature in the following order, thus making resin film: at 90 DEG C, bake 20 minutes in atmosphere, then at 120 DEG C, 20 minutes are baked under nitrogen atmosphere, then at 180 DEG C, 20 minutes are baked, then at 240 DEG C, bake 20 minutes, then at 300 DEG C, bake 20 minutes, then at 400 DEG C, bake 60 minutes.
< embodiment 6 ~ 8 >
Except the resin film formation composition replacing obtaining in embodiment 1 except using the resin film formation composition obtained in embodiment 2 ~ 4, make resin film by method similarly to Example 5.
< embodiment 9 ~ 12 >
Carry out the heat treated of 60 minutes at 400 DEG C after, at 450 DEG C, carry out the heat treated of 60 minutes further, in addition, make resin film by the method same with embodiment 5 ~ 8.
< comparative example 7 ~ 11 >
Except the resin film formation composition replacing obtaining in embodiment 1 except using the resin film formation composition obtained in comparative example 1 ~ 5, make resin film by method similarly to Example 5.
< comparative example 12 >
Carry out the heat treated of 60 minutes at 400 DEG C after, at 450 DEG C, carry out the heat treated of 60 minutes further, in addition, make resin film by the method same with comparative example 7.
[5] evaluation of the thermotolerance of resin film, separability and flexibility
The evaluation of the resin film of embodiment 5 ~ 12 and comparative example 7 ~ 12 is carried out by following method.Film is made respectively in order to each evaluation.
Show the result in table 1.In addition, for thickness, it is the resin film for separability and flexible appraisal.In addition, about the resin film of comparative example 8, only carry out the evaluation of separability evaluation and flexibility.
< separability and flexible appraisal >
The easy degree of stripping when peeling off each resin film from glass substrate is evaluated.The evaluation of separability is carried out in the following way: the resin film on glass substrate uses cutting knife to cut indentation with rectangle, be confirmed whether can easily peel off this rectangular film from glass substrate being formed at, by insert between film and glass substrate cutter, can not involve ground stripping film situation be set to well, the situation beyond it is set to bad.
In addition, the flexibility of the resin film peeled off is evaluated.For the evaluation of flexibility, the easy degree of fragmentation of film during by the resin film hand of stripping being bent or stretched with visual confirmation (crack, chap, break) is carried out, even if will namely use hand to be set to well with 90 degree of bending also non-destructive situations that stretch, the situation beyond it will be set to bad.
< Evaluation of Heat Tolerance >
Measure the 5% Mass lost temperature (Td5% (DEG C)) of each resin film.TG-DTA (Block ル カ ー エ イ エ ッ Network ス エ ス society system, TG/D TA2000SA) is used to carry out measuring (heat-up rate: be warming up to 800 DEG C from 50 DEG C with per minute 10 DEG C).
[table 1]
| Separability is evaluated | Flexible appraisal | Td5％[℃] | |
| 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 | Bad | Well | 590 |
| Comparative example 8 | Well | Bad | - |
| Comparative example 9 | Well | Bad | 566 |
| Comparative example 10 | Well | Bad | 569 |
| Comparative example 11 | Well | Bad | 537 |
| Comparative example 12 | Bad | Bad | 582 |
As shown in table 1, the resin film of comparative example 7 and 12 does not have the suitable adaptation with glass substrate, can not obtain good result in separability evaluation.The particularly resin film of comparative example 7, naturally peels from glass substrate, is not suitable for use in the substrate resin film in the manufacturing process of indicating meter.
In addition, although the resin film of comparative example 8 ~ 11 shows good separability, by bending with hand and easily broken, in addition, the resin film of comparative example 7,9 ~ 12 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 separability and suitable flexibility, and has high thermotolerance.Particularly 5% weight of the resin film of embodiment 9 ~ 12 reduces temperature is about 620 DEG C, can obtain the result that these films have high thermotolerance.
Learnt by the result of above embodiment: form the manufacture method of the present invention with composition according to the use resin film that to have containing the weight-average molecular weight shown in above-mentioned formula (1-1) be the polyamic acid of more than 5000, can obtain being particularly suitable for the resin film for display base plate, in addition, such resin film formation composition is particularly suitable for the manufacture of the resin film being used as display base plate.
Claims (9)
1. the manufacture method of a display base plate resin film, it is characterized in that, comprise following operation: coating is the resin film formation composition of the polyamic acid of more than 5000 containing the weight-average molecular weight shown in following formula (1-1) on matrix, and heats
In formula (1-1), Ar
1represent following formula (2) or 4 valency groups shown in formula (3), m represents the number of repeating unit, and m is positive integer,
In formula (2) and formula (3), asterisk and wavy line symbol represent associative key, 1 and carboxylic-bond in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol,
Ar
2represent following formula (4-1), formula (4-2) or 4 valency groups shown in formula (5),
In formula (4-1), formula (4-2) and formula (5), asterisk and wavy line symbol represent associative key, 1 in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol with hydroxyl bonding.
2. manufacture method according to claim 1, described polyamic acid following formula (1-2) represents,
In formula (1-2), X represents the divalent group shown in any one in following formula (6) ~ formula (8), Ar
1, Ar
2implication same as described above is represented with m,
In formula (6) ~ formula (8), R
1~ R
4separately represent the alkyl of hydrogen atom or carbonatoms 1 ~ 20, Y represents following formula (9) or 1 valency group shown in formula (10), and n represents the number of the Y being bonded to aromatic nucleus, and n is the integer of 1 ~ 3, and asterisk represents associative key,
In formula (9) and formula (10), R
5~ R
8separately represent the aryl of hydrogen atom or carbonatoms 6 ~ 20, asterisk represents associative key.
3. manufacture method according to claim 1 and 2, described matrix is glass basis.
4. the manufacture method according to any one of claims 1 to 3, is characterized in that, described heating is carried out in the mode making Heating temperature periodically increase.
5. manufacture method according to claim 4, the step making Heating temperature periodically increase is carried out in the following sequence: 50 DEG C ~ 100 DEG C heating 5 minutes ~ 2 hours, be greater than 100 DEG C and be less than or equal to 200 DEG C heating 5 minutes ~ 2 hours, be greater than 200 DEG C and be less than or equal to 375 DEG C heating 5 minutes ~ 2 hours, then be greater than 375 DEG C and be less than or equal to 500 DEG C heating 30 minutes ~ 4 hours.
6. a display base plate resin film is that the manufacture method according to any one of Claims 1 to 5 obtains.
7. a flexible display substrate, comprises display base plate resin film according to claim 6.
8. a display base plate resin film formation composition is the polyamic acid of more than 5000 containing the weight-average molecular weight shown in following formula (1-1),
In formula (1-1), Ar
1represent following formula (2) or 4 valency groups shown in formula (3), m represents the number of repeating unit, and m is positive integer,
In formula (2) and formula (3), asterisk and wavy line symbol represent associative key, 1 and carboxylic-bond in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol,
Ar
2represent following formula (4-1), formula (4-2) or 4 valency groups shown in formula (5),
In formula (4-1), formula (4-2) and formula (5), asterisk and wavy line symbol represent associative key, 1 in 2 keys of 1 in 2 keys of band asterisk and band wavy line symbol with hydroxyl bonding.
9. display base plate resin film formation composition according to claim 8, described polyamic acid following formula (1-2) represents,
In formula (1-2), X represents the divalent group shown in any one in following formula (6) ~ formula (8), Ar
1, Ar
2implication same as described above is represented with m,
In formula (6) ~ formula (8), R
1~ R
4separately represent the alkyl of hydrogen atom or carbonatoms 1 ~ 20, Y represents following formula (9) or 1 valency group shown in formula (10), and n represents the number of the Y being bonded to aromatic nucleus, and n is the integer of 1 ~ 3, and asterisk represents associative key,
In formula (9) and formula (10), R
5~ R
8separately represent the aryl of hydrogen atom or carbonatoms 6 ~ 20, asterisk represents associative key.
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| CN107103841A (en) * | 2016-02-19 | 2017-08-29 | 三星显示有限公司 | Flexible display apparatus, the method and hard coating composition for manufacturing form component |
| CN109476951A (en) * | 2016-08-03 | 2019-03-15 | 日产化学株式会社 | Peeling layer, which is formed, uses composition and peeling layer |
| CN110050013A (en) * | 2016-12-08 | 2019-07-23 | 日产化学株式会社 | The manufacturing method of peeling layer |
| CN110062784A (en) * | 2016-12-08 | 2019-07-26 | 日产化学株式会社 | The manufacturing method of peeling layer |
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| JP6479404B2 (en) * | 2014-10-17 | 2019-03-06 | エルジー ディスプレイ カンパニー リミテッド | Flexible display substrate and flexible display |
| US10510993B1 (en) | 2017-02-27 | 2019-12-17 | Sharp Kabushiki Kaisha | Production method for EL device |
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| CN107103841A (en) * | 2016-02-19 | 2017-08-29 | 三星显示有限公司 | Flexible display apparatus, the method and hard coating composition for manufacturing form component |
| CN107103841B (en) * | 2016-02-19 | 2021-05-14 | 三星显示有限公司 | Flexible display device, method for manufacturing window member, and hard coating composition |
| CN109476951A (en) * | 2016-08-03 | 2019-03-15 | 日产化学株式会社 | Peeling layer, which is formed, uses composition and peeling layer |
| CN109476951B (en) * | 2016-08-03 | 2022-07-29 | 日产化学株式会社 | Composition for forming release layer and release layer |
| CN110050013A (en) * | 2016-12-08 | 2019-07-23 | 日产化学株式会社 | The manufacturing method of peeling layer |
| CN110062784A (en) * | 2016-12-08 | 2019-07-26 | 日产化学株式会社 | The manufacturing method of peeling layer |
| KR20190089208A (en) * | 2016-12-08 | 2019-07-30 | 닛산 가가쿠 가부시키가이샤 | Manufacturing method of release layer |
| KR102481072B1 (en) | 2016-12-08 | 2022-12-27 | 닛산 가가쿠 가부시키가이샤 | Manufacturing method of release layer |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201443155A (en) | 2014-11-16 |
| CN110256671A (en) | 2019-09-20 |
| WO2014112558A1 (en) | 2014-07-24 |
| JP6388125B2 (en) | 2018-09-12 |
| JPWO2014112558A1 (en) | 2017-01-19 |
| KR20150107765A (en) | 2015-09-23 |
| TWI657114B (en) | 2019-04-21 |
| CN107254046A (en) | 2017-10-17 |
| KR20190112183A (en) | 2019-10-02 |
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