CN107079540B - Organic electroluminescent substrate and the display of organic electroluminescence for using it - Google Patents
Organic electroluminescent substrate and the display of organic electroluminescence for using it Download PDFInfo
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- CN107079540B CN107079540B CN201580053559.3A CN201580053559A CN107079540B CN 107079540 B CN107079540 B CN 107079540B CN 201580053559 A CN201580053559 A CN 201580053559A CN 107079540 B CN107079540 B CN 107079540B
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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- H—ELECTRICITY
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- 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
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Organic electroluminescent substrate of the invention is characterized in that the formed body comprising polyimide resin composition, the polyimide resin composition includes at least the polyimides with repetitive unit shown in general formula (1).Formula (I) (in formula, R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl, R3It is indicated for the 4 valence organic groups comprising aromatic rings and by following any structure.) formula (II) substrate is on the basis of the coating by being carried out using solution easily realizes substrate forming, the transparency after substrate forming in visible light region is excellent, and balance has both organic solvent resistance, heat resistance, dimensional stability and mechanical strength well.
Description
Technical field
The present invention relates to organic electroluminescent (hereinafter, sometimes referred to as organic EL) to be shown with substrate and using its organic EL
Device.
Background technique
Organic el display is as having many characteristics, such as that high contrast, high response speed, wide viewing angle, a new generation of low-power consumption are aobvious
Show that device is starting functionization.In order to further widen the purposes of organic el display, carry out the base of organic el display
Plate is replaced with by previous glass to be thinned, the effort of the plastics of lightweight, flexibility.
As performance required by substrate for organic el, the closely related surface of electric leakage with element, short circuit can be enumerated
The heat resistance or solvent resistance for the degree that will not be damaged in flatness, element manufacture craft.In addition, in element manufacture craft,
Since heating and cooling is repeated, it is also required to for preventing lacking by the flexible caused organic layer of substrate or electrode etc.
Fall into dimensional stability generate, to thermal change.It in turn, is that the bottom-emission knot of light is taken out from substrate-side in organic el display
In the case where structure, substrate needs the transparency in visible light region.
It is excellent to study mechanical property, insulating properties and heat resistance for the material of plastic base as organic el display
The application of different polyimides.Such as organic EL element in top lighting structure is described in patent document 1, patent document 2
The middle example using polyimide substrate.
But since the usual dissolubility of polyimides is low, using the state of the polyamic acid as polyimide precursor
It is shaped, the cyclodehydration reaction based on heating is carried out in supporting base material, polyimide substrate is made, therefore propping up
The variation of molecular structure is big on support group material, is easy to produce the defects of shrinkage cavity, recess and crackle, it is not easy to make high equal of flatness
Even substrate.In addition, polyimides in the case where being configured to substrate, is often colored as dark brown, yellow, it is difficult to be applied to
The organic EL device of the bottom-emission structure of the transparency.
On the other hand, dissolubility possessed by polyimides is low, formability is poor, after forming colour the problem of can pass through
Bendability is high, soft aliphatic structure imports main chain backbone, or volume is big, soft substituent group imports side chain to solve
Certainly.But it is described in patent document 3~5：Big, softness the substituent group of the aliphatic structure or volume of such softness
Import become generate heat resistance, that the physical property such as mechanical strength reduce, thermal expansion coefficient (hereinafter, sometimes referred to as CTE) rises etc. is new
The reason of problem, is easy to be not suitable for baseplate material.
In addition, being disclosed in patent document 6~12 with hexafluoroisopropanol base (- C (CF3)2OH, hereinafter, sometimes referred to as
HFIP yl) polyimides.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-026969 bulletin
Patent document 2：Japanese Unexamined Patent Publication 2014-048619 bulletin
Patent document 3：Japanese Unexamined Patent Publication 2012-146905 bulletin
Patent document 4：Japanese Unexamined Patent Publication 2007-169304 bulletin
Patent document 5：Japanese Unexamined Patent Publication 2008-297360 bulletin
Patent document 6：The International Publication pamphlet of WO2012/165455A1
Patent document 7：The International Publication pamphlet of WO2014/084185A1
Patent document 8：The International Publication pamphlet of WO2014/084186A1
Patent document 9：The International Publication pamphlet of WO2014/084187A1
Patent document 10：The International Publication pamphlet of WO2014/084188A1
Patent document 11：The International Publication pamphlet of WO2006/043501A1
Patent document 12：Japanese Unexamined Patent Publication 2006-206879 bulletin
Summary of the invention
Problems to be solved by the invention
It, can not only be by the painting that is carried out using solution the object of the present invention is to provide a kind of substrate for organic el
Cloth and easily realize substrate forming, and after substrate forming visible light region the transparency it is excellent, balance it is simultaneous well
Have organic solvent resistance, heat resistance, dimensional stability and mechanical strength.
The solution to the problem
Status be it has not been found that balance there is substrate for organic el well needed for the shaping processability, transparency, resistance to
The polyimides of hot, organic solvent resistance, dimensional stability and mechanical strength.
The dissolubility for the polyimides recorded in patent document 6, shaping processability are excellent, but not about polyimides at
The record of the organic solvent resistance, heat resistance, thermal expansion coefficient, mechanical properties of body.In addition, recorded in patent document 7~9
The excellent heat resistance of the dissolubility of polyimides, polyimides formed body, but not about organic solvent resistance, heat resistance, heat
The record of the coefficient of expansion, mechanical properties.The polyimides recorded in patent document 10 is not about shaping processability, polyimides
The record of the organic solvent resistance, heat resistance, thermal expansion coefficient, mechanical properties of formed body.The polyamides recorded in patent document 11
The dissolubility of imines, the transparency of polyimides formed body, excellent heat resistance, but not about thermal expansion coefficient, mechanical properties
Record, do not record about the transparency details.The dissolubility for the polyimides recorded in patent document 12, polyamides are sub-
The transparency of amine formed body is excellent, shows low thermal coefficient of expansion, but does not have about mechanical properties, the record of heat resistance
Record the details about the transparency.In addition, about the polyimides recorded in the patent document 6~12, not about
The specific record of organic EL substrate purposes.
As mentioned above, it is known that the polyimides with HFIP base, but do not carry out about the application to organic EL substrate
Research, indefinite whether balance have various physical property required by organic EL substrate well.
The inventors of the present invention have made intensive studies to solve the above-mentioned problems.As a result, it has been found that by using including at least
The polyimide resin composition of polyimides containing following repetitive units, is able to solve the above problem, so as to complete this
Invention.
(in formula, R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl, R3It is organic for 4 valences comprising aromatic rings
It group and is indicated by following any structure.)
That is, the present invention includes each technical solution below.
[technical solution 1]
A kind of organic electroluminescent substrate, it includes the formed body of polyimide resin composition, the polyimides
Resin combination includes at least the polyimides with repetitive unit shown in general formula (1).
(in formula, R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl, R3It is organic for 4 valences comprising aromatic rings
It group and is indicated by following any structure.)
[technical solution 2]
Organic electroluminescent substrate according to technical solution 1, it includes the formings of polyimide resin composition
Body, the polyimide resin composition are only made of the polyimides with repetitive unit shown in general formula (1).
[technical solution 3]
The organic electroluminescent substrate according to technical solution 1 or 2,400~780nm wavelength region it is saturating
Penetrating rate is 60% or more, and the thermal expansion coefficient at 30~250 DEG C is 50ppm/ DEG C or less.
[technical solution 4]
The organic electroluminescent substrate according to any one of technical solution 1~3, wherein R1And R2Respectively first
Base.
[technical solution 5]
According to organic electroluminescent substrate described in technical solution 4, wherein R3For by any one in formula (3)~formula (6)
The group of expression.
[technical solution 6]
A kind of organic electroluminescent device at least has organic electroluminescent described in any one of technical solution 1~5
Use substrate.
[technical solution 7]
A kind of display of organic electroluminescence at least has the hair of organic electroluminescence described in any one of technical solution 1~5
Light substrate.
[technical solution 8]
A kind of bottom emission type display of organic electroluminescence, at least has described in any one of technical solution 1~5
Organic electroluminescent substrate.
[technical solution 9]
A kind of polyimide solution, it includes polyimide resin composition and organic solvent, the polyimide resin
Composition includes at least the polyimides with repetitive unit shown in general formula (1).
(in formula, R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl, R3It is organic for 4 valences comprising aromatic rings
It group and is indicated by following any structure.)
[technical solution 10]
According to polyimide solution described in technical solution 9, wherein R1And R2Respectively methyl.
[technical solution 11]
According to polyimide solution described in technical solution 10, wherein R3To be indicated by any one in formula (3)~formula (6)
Group.
[technical solution 12]
The polyimide solution according to any one of technical solution 9~11, wherein organic solvent is selected from by amide
At least one of series solvent, ether series solvent, aromatic series solvent, halogen-based solvent and group of interior ester series solvent composition.
[technical solution 13]
The polyimide solution according to any one of technical solution 9~12, wherein organic solvent is selected from by N, N-
Dimethylformamide, DMAC N,N' dimethyl acetamide, N-METHYLFORMAMIDE, hexamethylphosphoramide, n-methyl-2-pyrrolidone,
Diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, cyclopentyl methyl ether, diphenyl ether, dimethoxy-ethane, diethoxyethane, four
Hydrogen furans, dioxane, trioxane, benzene, methyl phenyl ethers anisole, nitrobenzene, benzonitrile, chloroform, methylene chloride, 1,2- dichloroethanes, 1,1,
2,2- tetrachloroethanes, gamma-butyrolacton, gamma-valerolactone, ε-valerolactone, ε-valerolactone, γ-hexalactone, 6-caprolactone and α-first
Base-gamma-butyrolacton composition at least one of group.
[technical solution 14]
The polyimide solution according to any one of technical solution 9~13, wherein polyimide resin group in solution
The concentration for closing object is 5~50 mass %.
[technical solution 15]
A kind of manufacturing method of polyimides formed body includes at least following process：
Polyimide solution described in any one of technical solution 9~14 is coated on the process in supporting base material；
The process for keeping be coated with polyimide solution dry and obtaining resin film；And
Heated the process for obtaining polyimides formed body to gained resin film.
[technical solution 16]
A method of the formed body of polyimide resin composition is used as organic electroluminescent substrate, the polyamides
Imide resin composition includes at least the polyimides with repetitive unit shown in general formula (1).
(in formula, R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl, R3It is organic for 4 valences comprising aromatic rings
It group and is indicated by following any structure.)
[technical solution 17]
According to method described in technical solution 16, wherein polyimide resin composition is only as with shown in general formula (1)
The polyimides of repetitive unit forms.
[technical solution 18]
The method according to technical solution 16 or 17, wherein transmission of the formed body in the wavelength region of 400~780nm
Rate is 60% or more, and the thermal expansion coefficient at 30~250 DEG C is 50ppm/ DEG C or less.
[technical solution 19]
The method according to any one of technical solution 16~18, wherein R1And R2Respectively methyl.
[technical solution 20]
According to method described in technical solution 19, wherein R3For the group indicated by any one in formula (3)~formula (6).
[technical solution 22]
According to method described in technical solution 16~20, wherein formed body be will comprising polyimide resin composition and
The polyimide solution of organic solvent is coated in supporting base material, and be coated with polyimide solution is made to be dried to obtain resin film,
Polyimides formed body obtained from heating to the resin film.
[technical solution 22]
According to method described in technical solution 21, wherein organic solvent is selected from by acid amides series solvent, ether series solvent, virtue
At least one of fragrant race's property solvent, halogen-based solvent and group of interior ester series solvent composition.
[technical solution 23]
The method according to technical solution 21 or 22, wherein organic solvent be selected from by n,N-Dimethylformamide, N,
N- dimethyl acetamide, N-METHYLFORMAMIDE, hexamethylphosphoramide, n-methyl-2-pyrrolidone, diethyl ether, dipropyl ether, two
Isopropyl ether, butyl oxide, cyclopentyl methyl ether, diphenyl ether, dimethoxy-ethane, diethoxyethane, tetrahydrofuran, dioxane, three
Oxane, benzene, methyl phenyl ethers anisole, nitrobenzene, benzonitrile, chloroform, methylene chloride, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, γ-
Butyrolactone, gamma-valerolactone, ε-valerolactone, ε-valerolactone, γ-hexalactone, 6-caprolactone and Alpha-Methyl-gamma-butyrolacton composition
At least one of group.
[technical solution 24]
The method according to any one of technical solution 21~23, wherein polyimide resin composition in solution
Concentration is 5~50 mass %.
In the present specification, organic EL refers to that luminous phenomenon and applying voltage to organic matter, organic EL element are
Refer to the organic material for issuing the light of colors such as red, green, blue by combination, the light of all colours including white can be issued
Light-emitting component.In addition, organic el display refers to the display picture device for having used organic EL element.
Polyimide resin composition of the invention is high to the dissolubility of polar organic solvent, can be with polyimide solution
State be coated in supporting base material, shaped in supporting base material.The transparency of polyimides after forming in visible light region
Excellent, balance has both organic solvent resistance, heat resistance, dimensional stability and mechanical strength well, as substrate for organic el
It is useful.
Specific embodiment
Hereinafter, the present invention will be described in more detail, but the present invention is not limited thereto.
[polyimide resin composition]
Polyimide resin composition (hereinafter, sometimes referred to simply as " composition of the invention ") of the invention includes at least tool
There is the polyimides of repetitive unit shown in the following general formula (1).
In general formula (1), R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl.R3For 4 valences comprising aromatic rings
Organic group, such as indicated by following any structure.
Among these, preferably following 4 valence organic groups.
As be described hereinafter, in general formula (1), R1And R2The R being originated from diamine compound shown in general formula (7)1And R2, general formula
(1) in, R3From the R in tetracarboxylic dianhydride shown in general formula (9)3。
In general formula (1), it is preferred that R1And R2Respectively methyl.That is, repetitive unit shown in above-mentioned general formula (1) is preferably
Repetitive unit shown in the following general formula (2).
In general formula (2), R3With the R in general formula (1)3It is synonymous.
As long as polyimides of the invention has repetitive unit shown in above-mentioned general formula (1), to other skeletons without spy
It does not limit.For example, the repetitive unit in addition to can have the repetitive unit shown in above-mentioned general formula (1).Polyamides of the invention is sub-
Amine can have repetitive unit shown in the above-mentioned general formula (1) of 50 moles of % or more, preferably have 75 moles of % or more, more preferably
Only it is made of the repetitive unit.In addition, the repetitive unit of above-mentioned general formula (1) can be regularly arranged in polyimides, it can also
Randomly to exist.As the repetitive unit in addition to the repetitive unit shown in above-mentioned general formula (1), can enumerate it is following any one
The repetitive unit of expression is not limited to these as preferred example.
The weight average molecular weight of polyimides of the invention is not particularly limited, lower limit can for 30000, preferably 40000,
Particularly preferred 50000.The upper limit can be 1000000, preferably 500000, particularly preferred 200000.Polyimides of the invention
Weight average molecular weight can be 30000~1000000, preferably 40000~500000, particularly preferred 50000~200000.If weight is equal
Molecular weight is less than 30000, then the stability of the substrate after shaping is poor, is easy to produce the problems such as substrate crackle, if being more than
1000000, then the viscosity of solution is high, is difficult to shape sometimes.It should be noted that above-mentioned weight average molecular weight is based on gel infiltration
The value of the standard polystyren conversion of chromatography (hereinafter, sometimes referred to as GPC).
Composition of the invention includes at least the polyimides with repetitive unit shown in general formula (1), preferably only by this
Polyimides composition.Composition of the invention can also include other compositions other than the polyimides.Include other compositions
When containing ratio can be for 50 moles of % in composition hereinafter, preferably 25 moles of % or less, further preferably 10 rubbing
You are % or less.The type of other compositions is not particularly limited, it can be for except the polyamides with repetitive unit shown in general formula (1)
Polyimides other than imines.The polyimides is not particularly limited, can be suitable for selecting well known to one or two or more kinds
Polyimides come using.The polyimides can be original for " other diamine compounds " stated, aftermentioned tetracarboxylic dianhydride later
The polyimides expected and synthesized.
[substrate for organic el]
Substrate for organic el (hereinafter, sometimes referred to simply as " substrate of the invention ") of the invention is polyimides of the invention
The formed body of resin combination.The polyimides formed body balance have both well the transparency, organic solvent resistance, heat resistance,
Dimensional stability, mechanical strength, therefore can be adapted to be used as substrate for organic el.
The usual dissolubility of previous polyimides is low, therefore in the production of polyimides formed body, using as polyamides Asia
After the state of the polyamic acid of amine precursor is coated on supporting substrate, pass through the cyclodehydration based on heating in the supporting base material
Reaction carries out polyimides, and polyimides formed body is made.Therefore, the molecule knot caused by heating in supporting base material
The variation of structure is big, easily causes crackle (crack), shrinkage cavity, it is not easy to make the high uniform substrate of flatness.On the other hand,
In the production of substrate of the invention, can be formed in supporting base material with the state of polyimides, therefore in supporting base material
The variation of the molecular structure caused by heating is small, is not easy to cause crackle (crack), shrinkage cavity, is easy to get desired flat
Property high, uniform state polyimides formed body (substrate).The transparency is excellent after forming, has both organic solvent resistance, heat resistance,
The defect of substrate is not easy to produce in device making technics.
Substrate of the invention can be suitably used for organic el display use.It is especially bottom hair in organic el display
In the case where photo structure, substrate for organic el of the invention can be suitably used.In addition, the translucency about visible light region
High situation can be used for bottom emission type organic el display.Technical scope of the invention is related to including that these are organic
The organic EL element and organic el display of EL substrate.
Hereinafter, the preferred physical property and characteristic to the polyimides formed body of substrate of the invention, that is, of the invention are said
It is bright.
<The transparency>
The entire visible light region i.e. 420~780nm of polyimides formed body of the invention in the high wavelength of 420nm or more
The transmissivity (hereinafter, being denoted as T% sometimes) of wavelength region be preferably 60% or more, by polyimides formed body of the invention
In the case where substrate for the bottom-emission mode of organic el display, 400nm or more high wavelength it is entire visible
The transmissivity of the light region i.e. wavelength region of 400~780nm is particularly preferably 60% or more, in the high wavelength of 400nm or more
Entire visible light region is more preferably 70% or more transmissivity.In addition, cutoff frequency is preferably 380nm shortwave below
It is long.
<Thermal expansion coefficient (CTE) and glass transition temperature (Tg)>
To the thermal expansion coefficient (hereinafter, sometimes referred to as CTE) of polyimides formed body of the invention, at 30~250 DEG C
Range, upper limit value are 50ppm/ DEG C preferred, 30ppm/ DEG C more preferable.Lower limit value is not particularly limited, preferably 0.5ppm/ DEG C, more
It is preferred that 1ppm/ DEG C.It is preferred that 0.5ppm/ DEG C or more and 50ppm/ DEG C or less, more preferable 1ppm/ DEG C or more and 30ppm/ DEG C or less.
If more than 50ppm/ DEG C, then poor dimensional stability, becomes crackle (crack) generation or removing of unexpected substrate etc. sometimes
The reason of problem.
From the viewpoint of heat resistance, the glass transition temperature of polyimides formed body of the invention is (hereinafter, sometimes referred to as
For preferably 250 DEG C or more of Tg), from the viewpoint of being coped with technological temperature height, more preferable 300 DEG C or more.Herein,
Glass transition temperature (Tg) refers to value when measuring under conditions of 10 DEG C/min of heating rate.It should be noted that heat is swollen
Swollen coefficient (CTE) and glass transition temperature (Tg) can be measured by thermo-mechanical analysis (TMA) etc..
<Thermal decomposition temperature (Td5)>
The decomposition temperature of polyimides formed body of the invention is with 5% weightless temperature (hereinafter, sometimes referred to as Td5) it is to refer to
Mark, preferably 300 DEG C or more, more preferable 350 DEG C of 5% weightless temperature or more.If 5% weightless temperature is lower than 300 DEG C, become device
The reason of substrate deteriorates in manufacture craft.It should be noted that 5% weightless temperature refers to, thermogravimetric amount is carried out with apparatus for thermal analysis
Measurement, there is the temperature of 5% weight loss relative to initial weight.
<Mechanical properties>
The elasticity modulus (tensile modulus of elasticity) of polyimides formed body of the invention preferably 1.0GPa or more and 6.0GPa
Below, more preferably 1.5GPa or more and 5.0GPa or less.If elasticity modulus is greater than 6.0GPa, there is substrate warp after hardening
Tendency.
Maximum stress (tensile stress) preferably 70MPa or more, more preferable 100MPa or more.If tensile strength is less than 70MPa,
It is then more crisp, it becomes difficult to handle in the case where being used as substrate for organic el.
Elongation at break preferably 5% or more, more preferable 10% or more.If elongation at break is less than 5%, by polyimides
As the bending stress in the case where substrate, weak, substrate reliability can reduce formed body.
It should be noted that the mechanical properties such as tensile modulus of elasticity, tensile stress, elongation at break can pass through foundation
JIS K 7161 (plastics-tensile properties seek method -) carries out tension test to find out.
<Organic solvent resistance>
Substrate for organic el is generally preferably not easy the organic solvent used in the manufacturing process as organic el display
Dimethyl acetamide (DMAc), tetrahydrofuran (THF), acetone (Acetone), ethyl acetate (EtOAc), isopropanol (IPA),
Toluene (Toluene) and hexane (Hexane) equal solvent immerse.It can be defined by aftermentioned embodiment, polyimides of the invention exists
It is excellent to the dissolubility of these organic solvents in the state of before forming, but the state after forming is i.e. in substrate of the invention, it is resistance to
Organic solvent-borne is excellent, is not easy to be immersed by these organic solvents.Polyimides of the invention can be by being carried out using solution as a result,
Coating and easily realize substrate forming, the substrate of the substrate after forming, that is, of the invention has organic solvent resistance.
<Film thickness>
The thickness of polyimides formed body of the invention is not particularly limited, lower limit can be 0.5 μm, preferably 1 μm, spy
Not preferably 10 μm.The upper limit can be 500 μm, preferably 100 μm, 80 μm particularly preferred.It can be 0.5~500 μm, further preferably
1~100 μm, it is 10~80 μm particularly preferred.
[manufacturing method of polyimides]
The manufacturing method of polyimides of the invention is not particularly limited.For example, can be according to being recorded in patent document 6
The polyimides with HFIP base synthetic method, manufacture polyimides of the invention.As concrete example, can enumerate by under
It states tetracarboxylic dianhydride shown in diamines and the following general formula (9) shown in general formula (7) with HFIP base and is used as necessary raw material,
150 DEG C or more the methods mutually melted.As other examples, can enumerate by by these raw material compounds in organic solvent
Carry out the method that polyamic acid obtained from polycondensation carries out cyclodehydration to manufacture polyimides of the invention.The polycondensation reaction is excellent
It is selected at -20~80 DEG C and carries out, aforementioned diamines and aforementioned tetracarboxylic dianhydride is made to be expressed as 1 with molar ratio：1 is reacted.
In general formula (7), R1And R2Respectively with the R in general formula (1)1And R2It is synonymous.
In general formula (9), R3With the R in general formula (1)3It is synonymous.
As long as the organic solvent that can be used in aforementioned polycondensation reaction can be such that raw material compound dissolves, do not limit especially
System, may be exemplified out n,N-Dimethylformamide, n,N-dimethylacetamide, N-METHYLFORMAMIDE, hexamethylphosphoramide, N-
The acid amides series solvents such as N-methyl-2-2-pyrrolidone N；Diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, cyclopentyl methyl ether, diphenyl ether,
The ether series solvents such as dimethoxy-ethane, diethoxyethane, tetrahydrofuran, dioxane, trioxane；Benzene, methyl phenyl ethers anisole, nitrobenzene,
The aromatic series solvent such as benzonitrile；The halogen-based solvents such as chloroform, methylene chloride, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes；
Gamma-butyrolacton, gamma-valerolactone, ε-valerolactone, ε-valerolactone, γ-hexalactone, 6-caprolactone, Alpha-Methyl-gamma-butyrolacton are interior
Ester series solvent.These organic solvents may be used alone, can also be used in combination two or more.
The polyimides of the invention acyl and polyamic acid further progress cyclodehydration for making to be obtained by polycondensation reaction
Imidization obtains.Cyclodehydration reaction carries out under the conditions ofs promoting heating, the chemical method etc. of cyclisation.Heating is will be rigid
The just imidizate under 150~250 DEG C of high-temperature heating of the polyamic acid after polymerization, chemical method are by room temperature (0~50
DEG C) under relative to raw material diamines add 2 molar equivalents respectively more than and less than the alkali such as the pyridine of 10 equivalents or triethylamine and acetic acid
Acid anhydride and carry out imidizate, the solution of polyimides of the invention can be obtained.The concentration of polyimides in the solution preferably 5
Quality % or more and 50 mass % or less.It is industrial impracticable if fewer than 5 mass %.If being difficult to molten more than 50 mass %
Solution.In turn, preferably 10 mass % or more and 40 mass % or less.
The solution for operating obtained polyimides of the invention in this way is used directly for the manufacture of substrate of the invention i.e.
The manufacture of polyimides formed body of the invention.In addition, single for will be remained contained in the solution of polyimides of the invention
The purpose that body, low-molecular weight remove, the solution of polyimides of the invention can be added in the poor solvents such as water or alcohol, make
Polyimides precipitating after isolating and purifying, is dissolved in organic solvent in a manner of becoming afore mentioned concentration again and prepares polyamides
The solution of the preparation is used for the manufacture of polyimides formed body of the invention by the solution of imines.As the organic solvent, as long as
Polyimides of the invention is dissolved, is just not particularly limited, for example, can enumerate and can be used in aforementioned polycondensation reaction
The same kind of organic solvent of the substance enumerated in organic solvent, can be used alone, and two or more mixing also can be used
Solvent.
Hereinafter, raw material used in the manufacture to polyimides of the invention is illustrated in detail.
<Diamines with HFIP base>
In the manufacture of polyimides of the invention, as one of raw material compound, have using shown in general formula (7)
The diamines of HFIP base.
Wherein, from the accessibility of raw material, diamines shown in particularly preferred formula (8) is (hereinafter, sometimes referred to as
HFIP-mTB。)。
Important organic solvent solubility, formability and strong when substrate is made when in order to production substrate for organic el
Degree, surface characteristic (water repellency, oil repellent), patience (weatherability, corrosion resistance etc.), other characteristics (transparency, low refractiveness,
Low-k etc.), heat resistance be adjusted, can be applied in combination shown in general formula (7) with HFIP base diamines and except its
Diamine compound in addition (hereinafter, sometimes referred to as other diamine compounds).As the usage amount of other diamine compounds, relatively
In the weight of whole diamines, 5% or more and 50% is expressed as hereinafter, preferably 10% or more and 30% or less with quality %.Its
In the case that the containing ratio of his diamine compound is less than 5%, the effect of the adjustment of mechanical strength etc. becomes smaller, other two amine compounds
When the containing ratio of object is greater than 50%, has and heat resistance, dimensional stability, mechanical strength or physical property from fluorine atom, resistance to occurs
Hot reduced worry.
If specifically illustrating other diamine compounds that can be applied in combination, it may be exemplified out benzidine, 2,2 '-diformazans
Oxygroup benzidine, 3,3 '-dimethoxy benzidines, 2,2 '-dimethylbenzidines, 3,3 '-dimethylbenzidines, 2,2 '-bis- (three
Methyl fluoride) benzidine, 3,3 '-bis- (trifluoromethyl) benzidine, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2,4- diamino first
Benzene, 2,5- diaminotoluene, 2,4- diamino meta-xylene, 2,4- diaminostilbene, 3,5- trimethylbenzene, 2,3,5,6- tetramethyl
Base -1,4- phenylenediamine, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diaminodiphenyl ethers, 4,4 '-diamino diphenyl sulfones, 4,
Bis- (3- amino-benzene oxygen) benzene of 4 '-diaminobenzophenones, 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,3-, bis- (the 4- amino of 1,4-
Phenoxy group) benzene, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, bis- (4- (3- amino-benzene oxygen) phenyl) sulfones, bis- (4- (4- aminobenzenes
Oxygroup) phenyl) sulfone, bis- (4- (4- amino-benzene oxygen) phenyl) propane of 2,2-, bis- (4- (4- amino-benzene oxygen) phenyl) six of 2,2-
Bis- (4- (3- amino-benzene oxygen) phenyl) propane of fluoro-propane, 2,2-, bis- (4- aminophenyl) hexafluoropropane of 2,2-, the bis- (3- of 2,2-
Aminophenyl) hexafluoropropane, bis- (3- amino-4-hydroxylphenyl) hexafluoropropane of 2,2-, 2,2- bis- (3- amino -4- aminomethyl phenyls)
Hexafluoropropane, 4,4 '-diaminobenzene anilids, 4,4 '-diamino bibenzyls (ethylenedianiline), bis- (the 4- ammonia of 1,1-
Base phenyl) hexamethylene, bis- (4- aminophenyl) fluorenes of 9,9-, 2,7 diamin of luorene, α, bis- (4- the aminophenyl) -1,4- two of α '-are different
Propylbenzene or bis- (1- (4- the aminophenyl) -1- Methylethyl) benzene of 1,3- etc..One of the hydrogen atom of the aromatic rings of above-mentioned diamines
Dividing can be replaced by fluorine atom, chlorine atom, bromine atom, iodine atom, alkyl, fluoroalkyl, carboxyl, HFIP base, hydroxyl or cyano.
In addition, these may be used singly or in combination of two or more.
Among above-mentioned, from the easiness obtained, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2,4- diamino first
It is benzene, 2,5- diaminotoluene, 4- diamino meta-xylene, 2,4- diamino dimethylbenzene, 2,2 '-dimethylbenzidines, 2,2 '-bis-
(trifluoromethyl) benzidine is advisable, 2,2 '-small dimethylbenzidines of the rising of particularly preferred CTE, 2,2 '-bis- (trifluoromethyls)
Benzidine.
<Tetracarboxylic dianhydride>
In the manufacture of polyimides of the invention, as one of raw material compound, tetrabasic carboxylic acid shown in general formula (9) is used
Dianhydride.
Specifically, tetracarboxylic dianhydride below can be enumerated, but it is not limited to these：
Benzene -1,2,4,5- tetracarboxylic dianhydrides (hereinafter, sometimes referred to as PMDA), bis- (trifluoromethyl) benzene -1,2 of 3,6-, 4,5-
Tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydrides (hereinafter, sometimes referred to as BPDA), 4,4 '-(hexafluoroisopropylidenyls)
Diphthalic anhydrides (hereinafter, sometimes referred to as 6FDA), 4,4 '-oxygen diphthalic anhydrides (hereinafter, sometimes referred to as ODPA), thiophene
Pheno -2,3,4,5- tetracarboxylic dianhydride etc..
These tetracarboxylic dianhydrides may be used singly or in combination of two or more.
Wherein, from the easiness obtained, preferably PMDA, BPDA, 6FDA or ODPA, from obtaining as being originated from fluorine atom
The surface characteristic (water repellency, oil repellent) of physical property, patience (weatherability, corrosion resistance etc.), other characteristic (transparencys, low foldings
Penetrating property, low-k etc.) it sets out in terms of high substrate, particularly preferred 6FDA is tough and tensile, with dimensional stability from obtaining
It sets out in terms of substrate, particularly preferred BPDA.
<The manufacturing method of polyimides formed body of the invention>
Polyimides formed body of the invention is obtained and heating to composition of the invention.Specifically
For, it can be obtained through following process：By the solution comprising composition of the invention (before being dissolved in composition of the invention
State solution made of organic solvent) it is coated on the process (painting process) in supporting base material；By solvent removal/drying process
(solvent removing step)；And then the process (heating process) that gained resin film is heated.
Coating method used in painting process is not particularly limited, well known coating method can be used.It can root
It is suitable for using spinner (spin coater), bar coater, knife type coater, air knife according to desired coating thickness, resin viscosity etc.
It applies and arranges known in coating machine, roll coater, spin coater (rotary coater), flow coater, die coating machine, lip coating machine etc.
It sets.
Aforementioned supporting base material is not particularly limited.Such as it may be exemplified out：Glass, Silicon Wafer, stainless steel, aluminium oxide,
The inorganic substrates such as copper, nickel；Polyethylene terephthalate (polyethylene terephthalate), polyethylene glycol are to benzene
Dicarboxylic acid esters (polyethylene glycol terephthalate), polyethylene naphthalate (polyethylene
Glycol naphthalate), polycarbonate, polyimides, polyamidoimide, polyetherimide, polyether-ether-ketone, poly- third
Alkene, polyether sulfone, polyethylene terephthalate (polyethylene terephthalate), polyphenylsulfone, polyphenylene sulfide etc.
Organic substrate., it is preferable to use the inorganic substrates such as glass, Silicon Wafer, stainless steel from the viewpoint of heat resistance.
When being coated in supporting base material, the thickness of the film comprising composition of the invention can be by the inclusion of of the invention
The concentration of polyimide resin ingredient in the solution of composition come carry out be suitable for adjustment, usually 1 μm or more and 1000 μm with
Under, preferably 5 μm or more and 500 μm or less.If film is thinner than 1 μm, enough intensity can not be obtained for the substrate after forming,
If sometimes the defects of the shrinkage cavity of generation substrate, recess, crackle, uniform substrate can not be obtained by becoming than 1000 μ m-thicks
Reason.
After obtaining film by aforementioned painting process, and then solvent removal/drying solvent is removed via from film
Process and heat treatment is carried out to the film (resin film) after drying solidifies it to obtain the heating process of polyimides formed body,
So as to obtain polyimides formed body of the invention.
Temperature when solvent being removed/dried by solvent removing step is according to dissolving composition of the invention
The type of organic solvent and it is different, preferably 50 DEG C or more and 220 DEG C or less, more preferable 80 DEG C or more and 200 DEG C or less.If being lower than
50 DEG C, then drying becomes inadequate, if being higher than 220 DEG C, causes solvent sharply to evaporate, shrinkage cavity, recess, crackle etc. is caused to lack
It falls into, not will form uniform substrate.
In the heating process after solvent removing step, and keep it solid by being heat-treated at high temperature to resin film
Change, polyimides formed body of the invention can be obtained.By the process, can also expect cannot go in solvent removing step
The residual solvent removed removes, improves acid imide rate, improves physical characteristic.
In heating process, preferably 150 DEG C or more and 400 DEG C of temperature when heat treatment solidifies are carried out to resin film
Below, more preferably 200 DEG C or more and 300 DEG C or less.If being lower than 150 DEG C, there is the worry of dissolvent residual, if being higher than 400 DEG C,
It can become the reason of generating the defect of the substrates such as cracking on gained substrate for organic el.
Heating process it is preferable to use inert gas furnace, heating plate, box like dryer or transmit banding pattern drying machine device into
Row, but it is not limited to the use of these devices.
From the viewpoint of preventing the oxidation of resin film, removing solvent, heating process is preferably under non-active gas air-flow
It carries out.As non-active gas, nitrogen, argon gas etc. may be exemplified out.Flow velocity preferred 1L/ minutes or more of non-active gas and
5L/ minutes or less.If the velocity ratio of non-active gas 1L/ minutes are slow, the drying of solvent removal sometimes/resin film is insufficient,
If faster than 5L/ minutes, only surface resin film is dry sometimes, becomes the Producing reasons such as crackle.
Heating time in solvent removing step, heating process is usually 0.5 hour or more and 3 hours hereinafter, each process
It can also continuously or separately carry out.
Substrate of the invention can also be removed and making devices from supporting base material, but in order to be fixed on new supporting substrate
On, the technology of height is needed, process number also increases, therefore preferably not from supporting base material removing and to be directly fixed on supporting base material
On the state of formed body substrate for organic el is made, then making devices.
[organic EL element]
Organic EL element of the invention at least has substrate of the invention, does not limit especially the composition etc. in addition to it
It is fixed.Organic EL element of the invention can be to make in the organic EL element at least having organic luminous layer, electrode layer and substrate
Use substrate of the invention as the organic EL element of the substrate.
As other compositions, organic EL element of the invention can have hole injection layer, hole transmission layer, hole barrier
Layer, electron transfer layer, electron injecting layer, desiccant, sealing material, metal plate, filter layer, color conversion luminescent coating (CCM
Layer), passivation layer, planarization layer etc..
[organic el display]
Organic el display of the invention at least has substrate of the invention, does not limit especially the composition etc. in addition to it
It is fixed.Organic el display of the invention can have organic EL element of the invention.
Embodiment
Hereinafter, by embodiment, the present invention will be described in detail, but the present invention is not limited to the embodiments.
Firstly, the measurement item and its measurement and evaluation method to the evaluation for substrate are illustrated.
[measurement item]
<Thermal expansion coefficient and glass transition temperature>
For thermal expansion coefficient and glass transition temperature (hereinafter, sometimes referred to as Tg), carry out having used Rigaku
Corporation system, the machine name ' tension test of Thermo Plus EvoII TMA8310 ' are found out.
<Thermal decomposition temperature>
For thermal decomposition temperature, with Rigaku Corporation system, machine name ' RIGAKU Thermo Plus
TG8310 ' is measured.
<Mechanical properties>
For mechanical properties such as elasticity modulus, stress, elongation at break, pass through the precision of Shimadzu Scisakusho Ltd
Universal testing machine ' Autograph AG-IS ' carries out tension test to find out.
<The transparency>
For the transparency, Shimadzu Scisakusho Ltd UV, visible light near infrared spectrometer (UV-VIS- is used
NIR SPECTROMETER, machine name ' UV-3150 ') it is measured.In addition, being the maximum of 1% wavelength below by transmissivity
Value is used as cutoff wavelength (nm).
<Solvent solubility>
For solvent solubility, it is used as the machine name ' UNI of the constant temperature oscillation sink of Tokyo Physico-chemical Apparatus Co., Ltd.
THERMO SHAKER NTS-1300 ' carries out the vibration of following times in the constant temperature under water-bath with the hunting speed of 100rpm
After stirring, the presence or absence of solid matter is observed by visual observation to be confirmed.The case where dissolving within 1 hour at 30 DEG C, is remembered
For it is good, will be dissolved within 1 hour at 70 DEG C the case where be denoted as it is solvable, will at 70 DEG C within 1 hour it is undissolved
Situation is denoted as insoluble.
[preparation of polyimide solution and the production of substrate]
By [Examples 1 to 5] below and [comparative example 1~2], to polyimide substrate (formed body of polyimides)
Preparation method be illustrated.It should be noted that in this preparation method, in order to be measured to physical property such as mechanical strengths, by polyamides Asia
Amido plate is removed from supporting base material, but can without removing and directly on substrate making devices.
[embodiment 1]
In the three-necked flask for the capacity 500mL for having nitrogen ingress pipe and stirring blade, show to respective chemical structure
Dimethyl acetamide is added in HFIP-mTB 60.0g (110mmol), BPDA 32.4g (110mmol) in following reaction equations
(hereinafter, sometimes referred to as DMAc) 220g, is stirred in a nitrogen atmosphere, at 20 DEG C, carries out reaction shown in following reaction equations.
Pyridine 34.8g (440mmol), acetic anhydride 44.9g (440mmol) are sequentially added into gained reaction solution, and then are stirred 24 hours,
Carry out imidizate.Then, DMAc 150g is added to be diluted, carries out pressure filtration, so that the polyamides prepared in reaction equation is sub-
The DMAc solution of amine (A).The DMAc solution of polyimides passes through gel permeation chromatography (hereinafter sometimes referred to GPC.TOSOH
CORPORATION system, machine name ' HLC-8320GPC ', column：TSKgel SuperHZM-H, solvent：Tetrahydrofuran is (hereinafter, have
When referred to as THF) the obtained measurement result of molecular weight is Mw=134000, Mw/Mn=1.97.By the DMAc solution of polyimides
A part for solvent solubility test use sample production, remainder is used for polyimide substrate (polyimides (A)
Formed body) production.
Polyimides (A) substrate (formed body of polyimides (A)) is by by the DMAc solution coating of polyimides (A)
It is dried afterwards on the glass substrate, heats and make.Firstly, dripping the DMAc solution of polyimides (A) in glass
On substrate, using spinner after 10 seconds make rotation speed rise to 1200rpm, kept for 10 seconds at rotation speed 1200rpm
Clock is equably coated with the DMAc solution of polyimides (A).In a nitrogen atmosphere, at 180 DEG C dry 30 minutes and remove solvent,
It is cooling and then after carrying out heat treatment in 2 hours at 200 DEG C, polyimide film is removed from glass baseplate, to obtain polyamides Asia
Amine (A) substrate (formed body of polyimides (A)).With film thickness gauge (Nikon Corporation system, machine name ' DIGIMICRO
MH-15 ') after thickness is measured, result is 51 μm.
Solvent solubility test sample (sediment in embodiment 1) such as gets off production：By polyimides above-mentioned (A)
DMAc solution 30g be slowly injected into the mixed solution of water 90g and methanol 30g and precipitate polyimides (A), to thus
The substance arrived in a nitrogen atmosphere, drying in 2 hours is carried out at 100 DEG C.
[embodiment 2]
In the three-necked flask for the capacity 500mL for having nitrogen ingress pipe and stirring blade, respective chemical structure is added
HFIP-mTB 60.0g (110mmol), the 6FDA 48.9g (110mmol), DMAc 220g being shown in following reaction equations, in nitrogen
It is stirred under gas atmosphere, at 20 DEG C, carries out reaction shown in following reaction equations.Pyridine is sequentially added into gained reaction solution
34.8g (440mmol), acetic anhydride 44.9g (440mmol), and then stir 24 hours, carry out imidizate.Then, it pressurizes
Filtering, to make the DMAc solution of polyimides (B).Passing through for the DMAc solution of polyimides (B) in reaction equation is aforementioned
The measurement result for the molecular weight that GPC is obtained is Mw=86000, Mw/Mn=1.78.By the one of the DMAc solution of polyimides (B)
Part uses the production of sample for solvent solubility test, and remainder is used for polyimides (B) substrate (polyimides (B)
Formed body) production.
Polyimides (B) substrate (formed body of polyimides (B)) is by by the DMAc solution coating of polyimides (B)
It is dried afterwards on the glass substrate, heats and make.Firstly, dripping the DMAc solution of polyimides (B) in glass
On substrate, using spinner after 10 seconds make rotation speed rise to 1200rpm, kept for 10 seconds at rotation speed 1200rpm
Clock is equably coated with the DMAc solution of polyimides (B).In a nitrogen atmosphere, at 180 DEG C dry 30 minutes and remove solvent,
It is cooling and then after carrying out heat treatment in 2 hours at 200 DEG C, polyimide film is removed from glass baseplate, to obtain polyimides
(B) substrate (formed body of polyimides (B)).With aforementioned film thickness gauge after thickness is measured, result is 53 μm.
Solvent solubility test sample (sediment in embodiment 2) such as gets off production：By polyimides above-mentioned (B)
DMAc solution 30g be slowly injected into the mixed solution of water 90g and methanol 30g and precipitate polyimides (B), to thus
The substance arrived in a nitrogen atmosphere, drying in 2 hours is carried out at 100 DEG C.
[embodiment 3]
In the three-necked flask for the capacity 500mL for having nitrogen ingress pipe and stirring blade, respective chemical structure is added
HFIP-mTB 60.0g (110mmol), the ODPA 34.1g (110mmol), the DMAc as solvent being shown in following reaction equations
160g is stirred in a nitrogen atmosphere, at 20 DEG C, carries out reaction shown in following reaction equations.Successively into gained reaction solution
Pyridine 34.8g (440mmol), acetic anhydride 44.9g (440mmol) is added, and then stirs 24 hours, carries out imidizate.Then,
Pressure filtration is carried out, to prepare the DMAc solution of the polyimides (C) in reaction equation.The DMAc solution of polyimides (C)
Measurement result by the obtained molecular weight of above-mentioned GPC is Mw=84400, Mw/Mn=2.03.By the DMAc of polyimides (C)
A part of solution uses the production of sample for solvent solubility test, and remainder is used for polyimides (C) substrate (polyamides
The formed body of imines (C)) production.
Polyimides (C) substrate (formed body of polyimides (C)) is by by the DMAc solution coating of polyimides (C)
It after on the glass substrate, is dried, heats and make.Firstly, dripping the DMAc solution of polyimides (C) in glass
On substrate, using spinner after 10 seconds make rotation speed rise to 700rpm, kept for 10 seconds at rotation speed 700rpm,
Equably it is coated with the DMAc solution of polyimides (A).In a nitrogen atmosphere, at 180 DEG C dry 30 minutes and remove solvent, in turn
It is cooling after carrying out heat treatment in 2 hours at 200 DEG C, polyimide film is removed from glass baseplate, to obtain polyimides
(C) substrate (formed body of polyimides (C)).With film thickness gauge after thickness is measured, result is 48 μm.
Solvent solubility test sample (sediment in embodiment 3) such as gets off production：By polyimides above-mentioned (C)
DMAc solution 30g be slowly injected into the mixed solution of water 90g and methanol 30g and precipitate polyimides (C), to thus
The substance arrived in a nitrogen atmosphere, drying in 2 hours is carried out at 100 DEG C.
[comparative example 1]
In the three-necked flask for the capacity 500mL for having nitrogen ingress pipe and stirring blade, show to respective chemical structure
DMAc 220g is added in HFIP-mTB 60.0g (110mmol), DSDA 39.4g (110mmol) in following reaction equations, in nitrogen
It is stirred under gas atmosphere, at 20 DEG C, carries out reaction shown in following reaction equations.Pyridine is sequentially added into gained reaction solution
34.8g (440mmol), acetic anhydride 44.9g (440mmol), and then stir 24 hours, carry out imidizate.Then, it pressurizes
Filtering, to prepare the DMAc solution of the polyimides (D) in reaction equation.The DMAc solution of polyimides (D) is obtained by GPC
The measurement result of the molecular weight arrived is Mw=74900, Mw/Mn=1.63.A part of the DMAc solution of polyimides (D) is used
In the production of solvent solubility test sample, remainder is used for the production of substrate (formed body of polyimides (D)).
Polyimides (D) substrate (formed body of polyimides (D)) is by by the DMAc solution coating of polyimides (D)
It after on the glass substrate, is dried, heats and make.Firstly, dripping the DMAc solution of polyimides (D) in glass
On substrate, using spinner after 10 seconds make rotation speed rise to 350rpm, kept for 10 seconds at rotation speed 350rpm,
The DMAc solution of polyimides (D) is uniformly coated on glass baseplate.In a nitrogen atmosphere, 30 minutes dry at 180 DEG C
And solvent is removed, and then carry out 2 hours after heating at 200 DEG C, and it is cooling, polyimide film is removed from glass baseplate, from
And obtain polyimides (D) substrate (formed body of polyimides (D)).With film thickness gauge after thickness is measured, result is 43 μ
m。
Solvent solubility test sample (sediment in embodiment 4) such as gets off production：By polyimides above-mentioned (D)
DMAc solution 30g be slowly injected into the mixed solution of water 90g and methanol 30g and precipitate polyimides (D), to thus
The substance arrived in a nitrogen atmosphere, drying in 2 hours is carried out at 100 DEG C.
[comparative example 2]
In the three-necked flask for the capacity 500mL for having nitrogen ingress pipe and stirring blade, show to respective chemical structure
It is added in HFIP-mTB 60.0g (110mmol), BTDA 35.4g (110mmol) in following reaction equations as solvent
DMAc 220g is stirred in a nitrogen atmosphere, at 20 DEG C, carries out reaction shown in following reaction equations.Into gained reaction solution
Pyridine 34.8g (440mmol), acetic anhydride 44.9g (440mmol) are sequentially added, and then is stirred 24 hours, imidizate is carried out.
Then, pressure filtration is carried out, to prepare the DMAc solution of the polyimides (E) in reaction equation.The DMAc of polyimides (E) is molten
The measurement result for the molecular weight of liquid obtained by GPC is Mw=74900, Mw/Mn=1.63.By the DMAc of polyimides (E)
A part of solution is used for the production of solvent solubility test sample, remainder is used for polyimides (E) substrate (polyamides
The formed body of imines (E)) production.
Polyimides (E) substrate (formed body of polyimides (E)) is by by the DMAc solution coating of polyimides (E)
It after on the glass substrate, is dried, heats and make.Firstly, the DMAc solution of polyimides (E) is added dropwise, use
Spinner is kept for 10 seconds, by polyimides after 10 seconds make rotation speed rise to 550rpm at rotation speed 550rpm
(E) DMAc solution is uniformly coated on glass baseplate.In a nitrogen atmosphere, at a temperature of 180 DEG C with 30 minutes by solvent
Drying is removed, it is cooling after heat treatment in 2 hours is carried out at 200 DEG C, polyimide film is removed from glass baseplate, to obtain
The substrate comprising above-mentioned polyimides (E) as polyimides formed body.With film thickness gauge after thickness is measured, result is
50μm。
Solvent solubility test sample (sediment in embodiment 1) such as gets off production：By polyimides above-mentioned (E)
DMAc solution 30g be slowly injected into the mixed solution of water 90g and methanol 30g and precipitate polyimides (E), to thus
The substance arrived in a nitrogen atmosphere, drying in 2 hours is carried out at 100 DEG C.
[reference example 1~3]
In table 1, as a reference example, record the physical property measurement of polyimides recorded in the embodiment 1 of patent document 3 and
Evaluation result records the physical property measurement for the polyimides recorded in the embodiment 1 and embodiment 2 of patent document 4 as a reference example 1
And evaluation result is as a reference example 2, reference example 3.
Hereinafter, showing the structural formula of the polyimides (polyimides (F)~polyimides (H)) of reference example 1~3.
The structure of the polyimides of reference example 1：
The structure of the polyimides of reference example 2：
The structure of the polyimides of reference example 3：
[evaluation of physical property of substrate]
It will be as the substrate of the Examples 1 to 3 of the substrate for organic el made in above-described embodiment and comparative example 1~2
Evaluation of physical property result is shown in table 1.
[table 1]
As shown in table 1, compared with the substrate of reference example 1~3, the substrate for organic el of the embodiment of the present invention 1~3
CTE is lower, to the excellent in dimensional stability of temperature change.With the reference example 1 as fluorinated polyimide with similar structure
The CTE of polyimide substrate compare, also show that low-down value.
It is the Tg higher of the substrate for organic el of the embodiment of the present invention 1~3, heat-resisting compared with the substrate of reference example 1~3
Property is excellent.It should be noted that not observing Tg between 30 DEG C~400 DEG C in Examples 1 to 2 and comparative example 1~2.
Compared with the substrate of reference example 1, the Td5 of the substrate for organic el of the embodiment of the present invention 1~3 is poor, but for making
To be enough values for substrate for organic el use, there is heat resistance.
The substrate for organic el of the embodiment of the present invention 1~3 has sufficient elasticity modulus and most in terms of mechanical strength
Big stress.With the elongation at break with reference example 2,3 equal extent of reference example, for being used as substrate for organic el
With sufficient tensile strength.
Compared with the substrate of comparative example 1~2, the light transmission of the substrate for organic el of the embodiment of the present invention 1~3 in 400nm
It is excellent in terms of rate, cutoff wavelength, have for being used as the substrate for organic el of bottom emission type organic el display
There is the sufficient transparency.
[solvent solubility test]
To in polyimides (A)~(E) (Examples 1 to 3 and comparative example 1~2) sediment and Examples 1 to 5 have
Machine EL carries out solvent solubility test with this 10 kinds of test body of substrate.
Solvent shown in test body and table 2 is added in the bottle with threaded cap, as 10 mass %'s after dissolution
The mode of concentration is adjusted, and is tightened, and is stirred with oscillating mixer, is evaluated dissolubility.
The result of solvent solubility test is shown in table 2.The case where by being dissolved within 1 hour under 30 DEG C of bath temperature
Be denoted as it is readily soluble, will under 70 DEG C of bath temperature within 1 hour dissolve the case where be denoted as it is solvable, will be in 70 DEG C of bath temperature
Under within 1 hour undissolved situation be denoted as it is insoluble.
[table 2]
As shown in table 2, the sediment in polyimides (A)~(E) (Examples 1 to 3 and comparative example 1~2) does not dissolve in
Protic polar solvent and nonpolar solvent.Dissolubility is shown to aprotic polar solvent, especially in DMAc, THF
Show good dissolubility.Therefore, the sediment tool in polyimides (A)~(E) (Examples 1 to 3 and comparative example 1~2)
There is excellent shaping processability.
The substrate of polyimides (A)~(E) (Examples 1 to 3 and comparative example 1~2) is to all solvents tested
Insoluble therefore of the invention transparent substrate has the solvent resistance for the degree that will not be damaged in element manufacture craft.
Claims (17)
1. a kind of organic electroluminescent substrate, it includes the formed body of polyimide resin composition, the polyimides tree
Oil/fat composition includes at least the polyimides with repetitive unit shown in general formula (1),
In formula (1), R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl, R3For the 4 valence organic groups comprising aromatic rings
It rolls into a ball and is indicated by following any structure,
2. organic electroluminescent substrate according to claim 1, it includes the formed body of polyimide resin composition,
The polyimide resin composition is only made of the polyimides with repetitive unit shown in general formula (1).
3. organic electroluminescent substrate according to claim 1, in the transmissivity of the wavelength region of 400~780nm
It is 60% or more, the thermal expansion coefficient at 30~250 DEG C is 50ppm/ DEG C or less.
4. organic electroluminescent substrate described in any one of claim 1 to 3, wherein R1And R2Respectively methyl.
5. organic electroluminescent substrate according to claim 4, wherein R3For by any one table in formula (3)~formula (6)
The group shown,
6. a kind of organic electroluminescent device at least has organic electroluminescent according to any one of claims 1 to 5 and uses
Substrate.
7. a kind of display of organic electroluminescence at least has organic electroluminescent according to any one of claims 1 to 5
Use substrate.
8. a kind of bottom emission type display of organic electroluminescence, at least having according to any one of claims 1 to 5 has
Organic electro luminescent substrate.
9. a kind of formed body by polyimide resin composition is used as the method for organic electroluminescent substrate, the polyamides is sub-
Polyimide resin composition includes at least the polyimides with repetitive unit shown in general formula (1),
In formula (1), R1And R2It is each independently hydrogen atom, methyl or trifluoromethyl, R3For the 4 valence organic groups comprising aromatic rings
It rolls into a ball and is indicated by following any structure,
10. according to the method described in claim 9, wherein, polyimide resin composition is only as with weight shown in general formula (1)
The polyimides composition of multiple unit.
11. according to the method described in claim 9, wherein, formed body is in the transmissivity of the wavelength region of 400~780nm
60% or more, the thermal expansion coefficient at 30~250 DEG C is 50ppm/ DEG C or less.
12. the method according to any one of claim 9~11, wherein R1And R2Respectively methyl.
13. according to the method for claim 12, wherein R3For by formula (3)~formula (6) any one indicate group,
14. according to the method described in claim 9, wherein, formed body is will be comprising polyimide resin composition and organic molten
The polyimide solution of agent is coated in supporting base material, and be coated with polyimide solution is made to be dried to obtain resin film, to the tree
Polyimides formed body obtained from adipose membrane is heated.
15. according to the method for claim 14, wherein organic solvent is selected from by acid amides series solvent, ether series solvent, fragrance
At least one of race's property solvent, halogen-based solvent and group of interior ester series solvent composition.
16. according to the method for claim 15, wherein organic solvent is selected from by n,N-Dimethylformamide, N, N- bis-
Methylacetamide, N-METHYLFORMAMIDE, hexamethylphosphoramide, n-methyl-2-pyrrolidone, diethyl ether, dipropyl ether, diisopropyl
Ether, butyl oxide, cyclopentyl methyl ether, diphenyl ether, dimethoxy-ethane, diethoxyethane, tetrahydrofuran, dioxane, trioxane,
Benzene, methyl phenyl ethers anisole, nitrobenzene, benzonitrile, chloroform, methylene chloride, 1,2- dichloroethanes, 1,1,2,2- tetrachloroethanes, γ-Ding Nei
At least one in ester, gamma-valerolactone, ε-valerolactone, γ-hexalactone, 6-caprolactone and Alpha-Methyl-gamma-butyrolacton composition group
Kind.
17. method according to any one of claims 14-16, wherein polyimide resin composition is dense in solution
Degree is 5~50 mass %.
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| JP2014203767 | 2014-10-02 | ||
| JP2014-203767 | 2014-10-02 | ||
| JP2015180595A JP2016076481A (en) | 2014-10-02 | 2015-09-14 | Substrate for organic electroluminescence and organic electroluminescence display arranged by use thereof |
| JP2015-180595 | 2015-09-14 | ||
| PCT/JP2015/077020 WO2016052311A1 (en) | 2014-10-02 | 2015-09-25 | Substrate for organic electroluminescence, and organic electroluminescent display using same |
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| CN110229331A (en) * | 2019-04-28 | 2019-09-13 | 南京岳子化工有限公司 | A kind of thermoplastic polyimide resin powder and preparation method thereof |
| KR20230134903A (en) * | 2022-03-15 | 2023-09-22 | 주식회사 엘지화학 | Polymer resin composition, method of preparing polymer film, polymer film, substrate for display device, and optical device using the same |
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| CN103842409A (en) * | 2011-09-29 | 2014-06-04 | Jsr株式会社 | Resin composition, and film formation method using same |
| CN103930470A (en) * | 2011-09-09 | 2014-07-16 | 宇部兴产株式会社 | Composition of aqueous polyimide precursor solution and method for producing composition of aqueous polyimide precursor solution |
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| JP5825652B2 (en) * | 2012-01-13 | 2015-12-02 | エルジー・ケム・リミテッド | Insulating material for electronic devices |
| WO2013191180A1 (en) * | 2012-06-19 | 2013-12-27 | 新日鉄住金化学株式会社 | Display device, method for manufacturing same, polyimide film for display device supporting bases, and method for producing polyimide film for display device supporting bases |
| JP6225659B2 (en) * | 2012-11-28 | 2017-11-08 | セントラル硝子株式会社 | Diamine containing hexafluoroisopropanol group, polyimide and polyamide using the same, cyclized product thereof, and production method thereof |
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| JP2014125455A (en) * | 2012-12-27 | 2014-07-07 | Central Glass Co Ltd | Polymer compound using fluorine-containing asymmetric diamine compound and its manufacturing method |
| JP6095978B2 (en) * | 2012-12-27 | 2017-03-15 | デンカ株式会社 | Resin composition for organic EL device and organic EL device |
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| CN103930470A (en) * | 2011-09-09 | 2014-07-16 | 宇部兴产株式会社 | Composition of aqueous polyimide precursor solution and method for producing composition of aqueous polyimide precursor solution |
| CN103842409A (en) * | 2011-09-29 | 2014-06-04 | Jsr株式会社 | Resin composition, and film formation method using same |
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