CN108026274A - polybenzoxazole and its utilization - Google Patents

polybenzoxazole and its utilization Download PDF

Info

Publication number
CN108026274A
CN108026274A CN201680053831.2A CN201680053831A CN108026274A CN 108026274 A CN108026274 A CN 108026274A CN 201680053831 A CN201680053831 A CN 201680053831A CN 108026274 A CN108026274 A CN 108026274A
Authority
CN
China
Prior art keywords
formula
carbon number
polybenzoxazole
film
changing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201680053831.2A
Other languages
Chinese (zh)
Other versions
CN108026274B (en
Inventor
江原和也
进藤和也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN108026274A publication Critical patent/CN108026274A/en
Application granted granted Critical
Publication of CN108026274B publication Critical patent/CN108026274B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
    • 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
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Thin Film Transistor (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides polymer and its utilization, even if the polymer, without using inorganic constituents, it individually also gives water vapor barrier good film.Polybenzoxazole, it is characterised in that represented by formula (2).(in formula, R1~R13Represent independently of each other hydrogen atom, halogen atom, nitro, cyano group or can be substituted with halogen atoms, the heteroaryl of the alkyl of carbon number 1~20, the alkenyl of carbon number 2~20, the alkynyl of carbon number 2~20, the aryl of carbon number 6~20 or carbon number 2~20, n represents more than 2 integer.)

Description

Polybenzoxazole and its utilization
Technical field
The present invention relates to polybenzoxazole and its utilization.
Background technology
In recent years, with the development of electronic device, its lighting, miniaturization are realized.In its assembling, attempt to replace The glass substrate that used in the past and use lighter and soft resin substrate.
But resin substrate is compared with glass substrate, is that the barrier properties for gases of water vapour etc. is poor mostly.Therefore, for electronics Resin substrate in device it is practical, it is ensured that produced for entering inside element, to electronic circuit, device component parts etc. The barrier properties for gases of dysgenic water vapour etc. is one of problem that should be solved.
As the means of problem as solution, such as report using containing polyimides and the phyllosilicate that organises Composition technology, polyimide film surface formed as barrier layer silicon oxide film technology (reference patent document 1、2)。
But in these techniques, the polyimide resin for lacking barrier properties for gases has been used as principal component, therefore is Raising barrier properties for gases, other inorganic constituents beyond resin component become necessary, its manufacturing engineering becomes miscellaneous, in addition, It is also unfavorable being manufactured into present aspect.
Even if therefore, it is intended that develop using the good resin of barrier properties for gases as principal component, without other inorganic constituents Also the film of sufficient barrier properties for gases can be played.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-245625 publications
Patent document 2：Japanese Unexamined Patent Publication 2012-107178 publications
The content of the invention
The subject that the invention solves
The present invention in view of above-mentioned actual conditions and complete, and it is an object of the present invention to provide even if without using inorganic constituents, its individually Give polymer and its utilization of the good film of water vapor barrier.
Means for solving the problems
The present inventor to achieve these goals, sharp study repeatedly, it turns out that：Polyphenyl with defined structure is simultaneously Oxazole also gives water vapor barrier excellent film even if without using inorganic constituents, completes the present invention.
That is, the present invention provides：
1. polybenzoxazole precursor, it is characterised in that represented by formula (1),
[changing 1]
(in formula, R1~R13Hydrogen atom, halogen atom, nitro, cyano group are represented independently of each other or can use halogen atom Aryl or carbon number 2 of substitution, the alkyl of carbon number 1~20, the alkenyl of carbon number 2~20, the alkynyl of carbon number 2~20, carbon number 6~20 ~20 heteroaryl, n represent more than 2 integer.)
2.1 polybenzoxazole precursor, wherein, above-mentioned R1~R13For hydrogen atom,
3. polybenzoxazole, it is characterised in that represented by formula (2),
[changing 2]
(in formula, R1~R13Hydrogen atom, halogen atom, nitro, cyano group are represented independently of each other or can use halogen atom Aryl or carbon number 2 of substitution, the alkyl of carbon number 1~20, the alkenyl of carbon number 2~20, the alkynyl of carbon number 2~20, carbon number 6~20 ~20 heteroaryl, n represent more than 2 integer.)
4.3 polybenzoxazole, wherein, above-mentioned R1~R13For hydrogen atom,
5. film formation composition, it includes 1 or 2 polybenzoxazole precursor and organic solvent,
6. film formation composition, it includes 3 or 4 polybenzoxazole and organic solvent,
7. film, it includes 3 or 4 polybenzoxazole,
8. the manufacture method of film, it is characterised in that 5 film formation is coated with composition on base material, heats, makes Organic solvent evaporation is stated, while makes above-mentioned polybenzoxazole precursor closed loop,
9. the manufacture method of film, it is characterised in that 6 film formation is coated with composition on base material, makes above-mentioned to have Solvent is evaporated,
10. electronic device, its with 7 film as substrate,
11.10 electronic device, it is organic electroluminescent device,
The manufacture method of 12.1 polybenzoxazole precursor, it is characterised in that formula (3)
[changing 3]
(in formula, R1~R7Represent implication same as described above, X represents halogen atom, hydroxyl, phenoxy group, 2,4,5- trichlorines Phenoxy group, 1H- [1,2,3] triazole epoxide [4,5-b] pyridine radicals, 1H- benzos [d] [1,2,3] triazole epoxide, 2,3- dihydros -2- Thio -3- benzoxazolyls or 4,6- dimethoxy -1,3,5- triazine oxies.)
Shown dicarboxylic acid compound and formula (4)
[changing 4]
(in formula, R8~R13Represent implication same as described above.)
Shown diamine compound reaction,
The manufacture method of 13.3 polybenzoxazole, it is characterised in that heat the polybenzoxazole precursor shown in formula (1) And make its closed loop,
[changing 5]
(in formula, R1~R13Represent implication same as described above.).
The effect of invention
By using the polybenzoxazole of the present invention, even if without using inorganic constituents etc., water vapour barrier can be also made The good film of property.
In addition, the polybenzoxazole of the present invention also has the heat resistance of tolerable TFT manufacture crafts.
Film comprising the polybenzoxazole of the invention having characteristics that can be suitable as (the electricity of electronic device Pole) substrate etc. needs the component of water vapor barrier and heat resistance.
Brief description of the drawings
Fig. 1 is the IR spectrum of precursor [3] and polybenzoxazole [4].
Embodiment
The present invention is described in more detail below.
Polybenzoxazole of the present invention is represented by formula (2), before it can be by the polybenzoxazole shown in formula (1) Body (gather o- hydroxy amide) closed loop and obtain.
[changing 6]
[changing 7]
In formula (1) and (2), R1~R13Hydrogen atom, halogen atom, nitro, cyano group or can be by halogen are represented independently of each other Plain atom substitution, the alkyl of carbon number 1~20, the alkenyl of carbon number 2~20, the alkynyl of carbon number 2~20, the aryl of carbon number 6~20 Or the heteroaryl of carbon number 2~20, n represent more than 2 integer.
As halogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom etc. can be included.
As the alkyl of carbon number 1~20, straight-chain, branch's chain state, cricoid alkyl, such as can include methyl, Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, just The straight chain or branch's chain state alkyl of the carbon numbers such as nonyl, positive decyl 1~20；Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cycloheptyl Base, cyclooctyl, cyclononyl, cyclodecyl, bicyclic butyl, Bicvclopentyl, dicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclic nonyl Cyclic alkyl of the carbon numbers such as base, bicyclodecyl 3~20 etc..
As the concrete example of the alkenyl of carbon number 2~20, vinyl, n- 1- acrylic, n- 2- acrylic, 1- can be included Methyl ethylene, n- 1- cyclobutenyls, n- 2- cyclobutenyls, n- 3- cyclobutenyls, 2- methyl-1-propylenes base, 2- methyl -2- propylene Base, 1- ethyl vinyls, 1- methyl-1-propylenes base, 1- methyl -2- acrylic, n- 1- pentenyls, n- 1- decene base, n- 1- Eicosylene base etc..
As the concrete example of the alkynyl of carbon number 2~20, can include acetenyl, n- 1- propinyls, n- 2-propynyl, N- 1- butynyls, n- 2- butynyls, n- 3- butynyls, 1- methyl -2-propynyl, n- 1- pentynyls, n- valerylene base, N- 3- pentynyls, n- 4- pentynyls, 1- methyl-n- butynyl, 2- methyl-n- butynyl, 3- methyl-n- butynyl, 1, 1- dimethyl-n- propinyl, n- 1- hexin bases, n- 1- decynyls, 15 carbyne bases of n- 1-, 20 carbyne bases of n- 1- etc..
As the concrete example of the aryl of carbon number 6~20, can include phenyl, 1- naphthyls, 2- naphthyls, 1- anthryls, 2- anthryls, 9- anthryls, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl etc..
As the concrete example of the heteroaryl of carbon number 2~20,2- thienyls, 3- thienyls, 2- furyls, 3- furans can be included Mutter the oxygen-containing heteroaryls such as base, 2- oxazolyls, 4- oxazolyls, 5- oxazolyls, 3- isoxazolyls, 4- isoxazolyls, 5- isoxazolyls, The sulfur-bearing heteroaryls such as 2- thiazolyls, 4- thiazolyls, 5- thiazolyls, 3- isothiazolyls, 4- isothiazolyls, 5- isothiazolyls, 2- miaows Oxazolyl, 4- imidazole radicals, 2- pyridine radicals, 3- pyridine radicals, 4- pyridine radicals, 2- pyrazinyls, 3- pyrazinyls, 5- pyrazinyls, 6- pyrazinyls, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- pyrimidine radicals, 6- pyrimidine radicals, 3- pyridazinyls, 4- pyridazinyls, 5- pyridazinyls, 6- pyridazinyls, 1,2, 3- triazine -4- bases, 1,2,3- triazine -5- bases, 1,2,4- triazine -3- bases, 1,2,4- triazine -5- bases, 1,2,4- triazine -6- bases, 1,3,5- triazine -2- bases, 1,2,4,5- tetrazine -3- bases, 1,2,3,4- tetrazine -5- bases, 2- quinolyls, 3- quinolyls, 4- quinoline Base, 5- quinolyls, 6- quinolyls, 7- quinolyls, 8- quinolyls, 1- isoquinolyls, 3- isoquinolyls, 4- isoquinolyls, 5- are different Quinolyl, 6- isoquinolyls, 7- isoquinolyls, 8- isoquinolyls, 2- quinoxalinyls, 5- quinoxalinyls, 6- quinoxalinyls, 2- quinolines Oxazoline base, 4- quinazolyls, 5- quinazolyls, 6- quinazolyls, 7- quinazolyls, 8- quinazolyls, 3- cinnoline bases, 4- cinnolines Nitrogenous heteroaryls such as base, 5- cinnoline bases, 6- cinnoline bases, 7- cinnoline bases, 8- cinnoline bases etc..
In these, preferably R1~R13All hydrogen atoms, by following formula (5) represent polybenzoxazole precursor, under State the polybenzoxazole of formula (6) expression.
[changing 8]
As the molecular weight of the polybenzoxazole of the present invention, it is not particularly limited, if it is considered that obtaining water vapor barrier The good film with heat resistance, weight average molecular weight preferably 1000~200000, more preferably 1500~150000, further preferably 2000~100000.
Therefore, the n in above-mentioned formula (1), (2), (5) and (6) is more than 2 integer, preferably satisfies above-mentioned average molecular weight Integer.
Dicarboxylic acid compound shown in formula (3) and formula (4) institute can be passed through as the polybenzoxazole precursor that formula (1) represents The diamine compound shown is reacted and obtained.
[changing 9]
In formula (3) and (4), R1~R13Representing implication same as described above, X represents halogen atom, hydroxyl, phenoxy group, 2, 4,5- Trichlorophenoxies, 1H- [1,2,3] triazole epoxide [4,5-b] pyridine radicals, 1H- benzos [d] [1,2,3] triazole epoxide, 2,3- Thio -3- the benzoxazolyls of dihydro -2- or 4,6- dimethoxy -1,3,5- triazine oxies.
As the alkoxy of carbon number 1~5, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth oxygen can be included Base, sec-butoxy, n-pentyloxy etc., as halogen atom, can include halogen atom similar to the above, in this case, It is preferred that chlorine atom, bromine atoms, more preferably chlorine atom.
Above-mentioned reaction is reacted for the formation of acid amides, as reaction condition, can use known amidification conditions.
Specifically, can formula (3) and each compound shown in (4) when reacting regulation in organic solvent, under set point of temperature Between.
As organic solvent, as long as not producing harmful effect to reaction, then it is not particularly limited, such as N, N- can be included The amide-types such as dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone；Acetone, methyl ethyl ketone, methyl tert-butyl The ketones such as base ketone, cyclohexanone, isophorone；Gamma-butyrolacton, gamma-valerolactone, δ-valerolactone, γ-hexalactone, 6-caprolactone, α- The esters such as methyl-gamma-butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate；The carbon numbers such as methanol, ethanol, propyl alcohol 1~10 aliphatic alcohols；The phenols such as phenol, cresols；The alcohols containing aromatic group such as benzylalcohol；Ethylene glycol, propane diols etc. two The glycol ethers such as alcohols, ethylene glycol single methyl ether, propylene glycol monomethyl ether；The ring-type ethers such as dioxane, tetrahydrofuran；Carbonic acid is sub- The cyclic carbonates such as ethyl ester, propylene carbonate；The aliphatic hydrocarbons such as pentane, hexane；Toluene, dimethylbenzene etc. are aromatic hydrocarbon； Dimethyl sulfoxide (DMSO) etc., they can a kind be used alone, two or more can be also applied in combination.
For reaction temperature, the fusing point of solvent, boiling point, the dissolubility of the raw material used, reactivity etc. are considered, usually Suitably determined in the range of -20~200 DEG C, be dicarboxylic acids (X in the compound represented by formula (3)：Hydroxyl) in the case of, It is preferred that -20~50 DEG C or so.In this case, preferably by (thio -3- benzoyls of 2,3- dihydro -2-) phosphonic acid diphenyl ester (DBOP), N, N '-dicyclohexylcarbodiimide (DCC), 4- (4,6- dimethoxy -1,3,5- triazine -2- bases) -4- methyl morpholines (DMT-MM) condensing agent as and alkali are used in combination.
In addition, the compound represented by formula (3) is the dihalide (X of dicarboxylic acids：Halogen atom) in the case of, preferably- 20~100 DEG C or so, more preferably -10~80 DEG C or so, in addition, in order to which the hydrogen halides of by-product is neutralized, the preferably presence in alkali Under reacted.
As alkali, amine, sodium hydroxide, the hydrogen-oxygen such as triethylamine, pyridine, N, N- dimethyl -4-aminopyridine can be included Change alkali metal hydroxides such as potassium etc..
When reaction time is 0.1~72 small or so.
The reaction ratio of each compound represented by formula (3) and formula (4), relative to the diamine compound represented by formula (4) Amount of substance (1 mole), by formula (3) represent compound preferably 0.5~1.5 equivalent or so.
By will using the method for the above obtain include by formula (1) represent polybenzoxazole precursor solution heat and Make precursor closed loop, so as to obtain including the solution of the polybenzoxazole represented by formula (2).
Temperature is usually finally brought up to 200~500 DEG C or so and carried out by heating, is preferably as follows method：Exist as needed After being preheated 10 seconds~120 minutes at a temperature of 80~190 DEG C, temperature is brought up to 200~500 DEG C, preferably 250~400 DEG C, is made It is reacted 10~300 minutes.
In the present invention, obtained above include can be directly used as film shape as the solution of the polybenzoxazole shown in formula (2) Into with composition, after also temporarily polybenzoxazole can be isolated, above-mentioned organic solvent is dissolved in again and is formed and used as film Composition.
By the way that these film formation are coated with composition on base material, make evaporation of the solvent, so as to form Ju Ben Bing Evil Azoles film.In this case, temperature during evaporation of the solvent can use room temperature~300 DEG C or so, but usually 80~200 DEG C of left sides It is right.
Composition is used in addition, also can form the solution for including the polybenzoxazole precursor represented by formula (1) as film.
After the film formation composition is coated with base material, by the way that it is finally heated to 200~500 DEG C, make solvent Evaporation, while make precursor closed loop, so as to form the film for including the polybenzoxazole represented by formula (2).In this case, Also described above, preferably using following method, after preheating 10 seconds~120 minutes at a temperature of 80~190 DEG C, temperature is carried Height makes it react about 10 minutes~about 300 minutes to 200~500 DEG C.
In above-mentioned each film formation composition, the solid component concentration of polymer is not particularly limited, according to required Thickness, purposes etc. suitably set, preferably 0.1~80 mass %, more preferably 1~70 mass %, further preferred 5~50 matter Measure %.
The coating method of composition is arbitrary, such as can use spin-coating method, infusion process, flow coat method, ink-jet method, jet stream Distributor method, spraying process, stick coating method, heliogravure rubbing method, slot coated method, rolling method, hectographic printing method, hairbrush coating, Scraper for coating method, air knife coating method etc..
In addition, as base material, it is not particularly limited, can includes and be made of silicon, glass, polyimides, quartz, ceramics etc. Base material etc..
As heating means, be not particularly limited, for example, can be used hot plate, baking oven, the non-active gas such as air, nitrogen, Carried out under the medium appropriate atmosphere of vacuum.
The thickness of film comprising polybenzoxazole is not particularly limited, is suitably set according to purposes of film etc., 0.1~500 μm or so can be defined as, if it is considered that sufficient water vapor barrier is played, preferably more than 5 μm, more preferably 10 μ More than m, further preferred more than 15 μm.
Further more, in above-mentioned film formation composition of the invention, as long as not damaging the effect of the present invention, relative to poly- The others additive such as 100 mass parts of compound, surfactant, silane coupling agent containing 0.0001~5 mass parts or so.
Even if the film of the polybenzoxazole comprising the present invention obtained as described above is without using inorganic constituents, in thickness 15 Also played less than 1g/m under μm2It good water vapor barrier, while there is the heat resistance of tolerable TFT techniques.
The film of the invention having characteristics that can be suitable as making liquid crystal display, organic electroluminescent (EL) display, touch panel, organic EL element, photosemiconductor (LED) element, solid-state imager, organic thin film solar Substrate, the electrode base board of battery, dye-sensitized solar cell, Organic Thin Film Transistors (TFT) when electronic device utilize, special Not, the electrode base board of organic EL element can be suitable as.
Embodiment
Embodiment is exemplified below, the present invention is further illustrated, but the present invention is not limited to following embodiments.Should Explanation is given, the device used is as described below.
(1)FT-IR
Device：Thermo Fisher Scient ific Inc. manufactures, NEXUS 670FTIR
(2) molecular weight determination：Showa electrician (strain) manufacture, room temperature gel permeation chromatography (GPC) device (GPC-101) and Shodex columns (KD-803L)
(determination condition)
Column temperature：40℃
Eluat：Dimethylformamide (DMF), 10mL/L
Flow velocity：1.0mL/ point
Calibration curve, which is made, uses standard sample：Showa electrician (strain) manufacture, SL-105, (molecular weight is about for polystyrene standard 580,2970,7200,19900,52400)
(3) film thickness measuring：Fine shape measuring machine Surfcorder ET-4000 manufactured by (strain) small slope research
(4) water vapour permeability：Small-sized water vapour agar diffusion method (diameter 3cm)
Calcium chloride 4.50g is put into water vapour cup, then, clamping measure film, has made sample.By the sample in constant temperature In constant humidity groove 40 DEG C, 90% time placement 48 of relative humidity it is small when, determine quality.And then quality measurement after 48 hrs, by Quality incrementss have calculated water vapour transit dose.
In addition, the shorthand notation of the compound used in embodiment is as described below.
PDA：P-phenylenediamine
DATP：4,4 '-diaminourea-p- terphenyl
AHPE：3,3 '-diaminourea -4,4 '-dihydroxy diphenyl ether
CBOCA：2- (4- carboxyl phenyl) benzoxazole -5- carboxylic acids
CBOCCl：2- (4- (chlorocarbonyl) phenyl) benzoxazole -5- formyl chlorides
PMDA：Pyromellitic acid anhydride
[1] manufacture of basal substrate polyimide film
[Production Example 1]
PDA20.261g (0.1875mol) and DATP12.206g (0.0469mol) are dissolved in NMP617.4g, cooled down To after 15 DEG C, PMDA50.112g (0.2298mol) is added, when making its reaction 48 small under nitrogen atmosphere, at 50 DEG C.What is obtained is poly- The weight average molecular weight Mw of compound is 82100, molecular weight distribution 2.7.The polyamic acid is applied to glass substrate with bar coater On.The substrate is bakeed 30 minutes on hot plate, at 80 DEG C, so with baking oven, after decompression, at 450 DEG C bakee 1 it is small when, obtain The glass substrate with polyimides of 11 μm of thickness is arrived.
[2] manufacture of polybenzoxazole precursor (film formation composition)
The manufacture of [embodiment 1-1] precursor [3]
[changing 10]
AHPE [2] 0.851g (3.66mmol) is dissolved in NMP18g, then, adds CBOCCl [1] 1.149g (3.59mmol), be stirred at room temperature 24 it is small when.Then, by obtained solution input pure water 500mL.The sediment that will be obtained After being separated by filtration, be dried under reduced pressure at 80 DEG C 24 it is small when, obtained the precursor [3] (yield 95%) of target.Obtained precursor [3] Weight average molecular weight Mw be 142000, molecular weight distribution 8.8.In addition, measured by FTIR, it is thus identified that from phenolic hydroxyl group 3300cm-1Peak and 1651cm from acylamino--1Peak.
The manufacture of [embodiment 1-2] precursor [3]
[changing 11]
AHPE [2] 0.911g (3.92mmol) is dissolved in NMP18g, then, with the addition of CBOCCA [1 '] 1.089g (3.84mmol).And then triethylamine 0.793g (7.85mmol) and DBOP3.01g (7.85mmol) is added, it is stirred at room temperature 24 it is small when.Then, obtained solution is put into the mixed solution 500mL of pure water and 2- propyl alcohol.The sediment that will be obtained After being separated by filtration, be dried under reduced pressure at 80 DEG C 24 it is small when, obtained the precursor [3] (yield 99%) of target.Obtained precursor [3] Weight average molecular weight Mw be 8000, molecular weight distribution 5.6.In addition, measured by FTIR, it is thus identified that from phenolic hydroxyl group 3300cm-1Peak and 1651cm from acylamino--1Peak.
[3] manufacture of polybenzoxazole [4] (film)
[embodiment 2-1]
[changing 12]
Precursor [3] 1g obtained in above-described embodiment 1-1 is dissolved in NMP9g, be stirred at room temperature 24 it is small when.Should Solution is coated with bar coater with 250 μ m thicks on the glass substrate.Then, which is bakeed to 30 points on hot plate, at 80 DEG C Clock, so with baking oven, after decompression, at 450 DEG C bakee 1 it is small when, obtained the film of 15 μm of thickness.The film is measured using FTIR, As a result 3300cm-1Peak and 1651cm-1Peak disappear, newly there is the 1616cm from benzoxazole-1Peak (Fig. 1).Thus Confirmation has obtained polybenzoxazole [4].
In addition, after the glass substrate with polyimides made the solution coating in Production Example 1 of bar coater, together Bakee sample, obtained the polyimide film [4-1] of polybenzoxazole [4] film with 15 μm of thickness.
[embodiment 2-2]
Obtained precursor [3] 1g is dissolved in NMP9g in the same manner as embodiment 2-1, be stirred at room temperature 24 it is small when. With bar coater by the solution on the glass substrate with polyimides with 500 μ m thicks be coated with.Then, by the substrate in hot plate Go up, bakeed 30 minutes at 80 DEG C.And then when baking 1 is small after decompression, at 450 DEG C with baking oven, obtain that there is 30 μm of thickness Polybenzoxazole [4] film polyimide film [4-2].
For [4-2] film obtained in [4-1] and embodiment 2-2 that are obtained in above-described embodiment 2-1, water steaming is determined Vapour transmitance, as a result understands that in embodiment 2-1 be 0.74g/m2My god, it is 0.44g/m in embodiment 2-22My god, it is 1g/m2· My god.Further more, the polyimide film for substrate is 30g/m2My god.Distinguish that the polybenzoxazole of the present invention shows high water by it Vapor barrier property.

Claims (13)

1. polybenzoxazole precursor, it is characterised in that represented by formula (1)：
[changing 1]
In formula, R1~R13Hydrogen atom, halogen atom, nitro, cyano group are represented independently of each other or can be substituted with halogen atoms , the aryl or carbon number 2~20 of the alkyl of carbon number 1~20, the alkenyl of carbon number 2~20, the alkynyl of carbon number 2~20, carbon number 6~20 Heteroaryl, n represent more than 2 integer.
2. polybenzoxazole precursor according to claim 1, wherein, above-mentioned R1~R13For hydrogen atom.
3. polybenzoxazole, it is characterised in that represented by formula (2)：
[changing 2]
In formula, R1~R13Hydrogen atom, halogen atom, nitro, cyano group are represented independently of each other or can be substituted with halogen atoms , the aryl or carbon number 2~20 of the alkyl of carbon number 1~20, the alkenyl of carbon number 2~20, the alkynyl of carbon number 2~20, carbon number 6~20 Heteroaryl, n represent more than 2 integer.
4. polybenzoxazole according to claim 3, wherein, above-mentioned R1~R13For hydrogen atom.
5. film formation composition, it includes polybenzoxazole precursor according to claim 1 or 2 and organic solvent.
6. film formation composition, it includes the polybenzoxazole and organic solvent according to claim 3 or 4.
7. film, it includes the polybenzoxazole according to claim 3 or 4.
8. the manufacture method of film, it is characterised in that apply film formation according to claim 5 on base material with composition Cloth, heating make above-mentioned polybenzoxazole precursor closed loop so that above-mentioned organic solvent evaporation.
9. the manufacture method of film, it is characterised in that apply film formation according to claim 6 on base material with composition Cloth, makes above-mentioned organic solvent evaporation.
10. electronic device, it is with film according to claim 7 as substrate.
11. electronic device according to claim 10, it is organic electroluminescent device.
12. the manufacture method of polybenzoxazole precursor according to claim 1, it is characterised in that two shown in formula (3) Carboxylic acid compound is reacted with the diamine compound shown in formula (4),
[changing 3]
In formula, R1~R7Represent implication same as described above, X represents halogen atom, hydroxyl, phenoxy group, 2,4,5- trichloro-benzenes oxygen Base, 1H- [1,2,3] triazole epoxide [4,5-b] pyridine radicals, 1H- benzos [d] [1,2,3] triazole epoxide, 2,3- dihydros -2- be thio - 3- benzoxazolyls or 4,6- dimethoxy -1,3,5-triazines epoxide,
[changing 4]
In formula, R8~R13Represent implication same as described above.
13. the manufacture method of polybenzoxazole according to claim 3, it is characterised in that by the polyphenyl shown in formula (1) simultaneously Oxazole precursor heats and makes its closed loop：
[changing 5]
In formula, R1~R13Represent implication same as described above.
CN201680053831.2A 2015-09-18 2016-09-13 Polybenzoxazole and use thereof Active CN108026274B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2015-185277 2015-09-18
JP2015185277 2015-09-18
PCT/JP2016/076908 WO2017047561A1 (en) 2015-09-18 2016-09-13 Polybenzoxazole and use thereof

Publications (2)

Publication Number Publication Date
CN108026274A true CN108026274A (en) 2018-05-11
CN108026274B CN108026274B (en) 2020-11-17

Family

ID=58288741

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201680053831.2A Active CN108026274B (en) 2015-09-18 2016-09-13 Polybenzoxazole and use thereof

Country Status (5)

Country Link
JP (1) JP6888549B2 (en)
KR (1) KR102581615B1 (en)
CN (1) CN108026274B (en)
TW (1) TWI709594B (en)
WO (1) WO2017047561A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114790664A (en) * 2021-01-26 2022-07-26 中国科学院化学研究所 High-strength polyphenylene benzobisoxazole paper base material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5549619B2 (en) * 1976-10-18 1980-12-12
JPS5549620B2 (en) * 1976-10-18 1980-12-12
JPS63301224A (en) * 1987-05-31 1988-12-08 Res Inst For Prod Dev Preparation of polybenz(oxy or thio)azole
WO2014163096A1 (en) * 2013-04-05 2014-10-09 味の素株式会社 Polyester compound
WO2014199965A1 (en) * 2013-06-10 2014-12-18 日産化学工業株式会社 Resin composition for display substrates, resin thin film for display substrates, and method for producing resin thin film for display substrates
WO2015060361A1 (en) * 2013-10-23 2015-04-30 味の素株式会社 Polyamide compound

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012107178A (en) 2010-03-31 2012-06-07 Sekisui Chem Co Ltd Polyimide resin composition
JP5598086B2 (en) 2010-05-21 2014-10-01 株式会社カネカ Gas barrier film
JP5549619B2 (en) * 2011-02-17 2014-07-16 富士通株式会社 Air conditioning system and air conditioning method
JP5549620B2 (en) * 2011-02-18 2014-07-16 東洋インキＳｃホールディングス株式会社 Solar cell back surface protection sheet and solar cell module

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5549619B2 (en) * 1976-10-18 1980-12-12
JPS5549620B2 (en) * 1976-10-18 1980-12-12
JPS63301224A (en) * 1987-05-31 1988-12-08 Res Inst For Prod Dev Preparation of polybenz(oxy or thio)azole
WO2014163096A1 (en) * 2013-04-05 2014-10-09 味の素株式会社 Polyester compound
WO2014199965A1 (en) * 2013-06-10 2014-12-18 日産化学工業株式会社 Resin composition for display substrates, resin thin film for display substrates, and method for producing resin thin film for display substrates
WO2015060361A1 (en) * 2013-10-23 2015-04-30 味の素株式会社 Polyamide compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114790664A (en) * 2021-01-26 2022-07-26 中国科学院化学研究所 High-strength polyphenylene benzobisoxazole paper base material
CN114790664B (en) * 2021-01-26 2023-02-24 中国科学院化学研究所 High-strength polyphenylene benzobisoxazole paper base material

Also Published As

Publication number Publication date
TW201723028A (en) 2017-07-01
KR102581615B1 (en) 2023-09-22
JP6888549B2 (en) 2021-06-16
JPWO2017047561A1 (en) 2018-08-09
WO2017047561A1 (en) 2017-03-23
CN108026274B (en) 2020-11-17
TWI709594B (en) 2020-11-11
KR20180055820A (en) 2018-05-25

Similar Documents

Publication Publication Date Title
JP6516048B2 (en) Polyimide precursor and polyimide
JP6123929B2 (en) Copolymer polyimide precursor and copolymer polyimide
CN103459467B (en) Polybenzoxazole resin and precursor thereof
US10513582B2 (en) Tetracarboxylic dianhydride, polyamic acid, polyimide, methods for producing the same, and polyamic acid solution
WO2015053312A1 (en) Polyimide precursor, polyimide, polyimide film, varnish, and substrate
Yu et al. Colorless PI structure design and evaluation for achieving low CTE target
WO2020162411A1 (en) Polyamide acid, polyimide, optical film, display device and production methods of those
WO2018066522A1 (en) Polyimide, polyimide precursor resin, solution of same, method for manufacturing polyimide, and film using polyimide
JP2017119869A (en) Composition for producing polyimide film, production method of the composition, and production method of polyimide film using the composition
US20180171077A1 (en) Polyimide precursor composition and polyimide composition
CN103102488B (en) High dielectric constant polyimide containing bipyrimidine structure and preparation method
JP6461470B2 (en) Polyimide precursor composition, polyimide production method, polyimide, polyimide film, and substrate
WO2006104038A1 (en) Polyamic acids, polyimides, and processes for the production thereof
CN108026274A (en) polybenzoxazole and its utilization
JP7359602B2 (en) Diamine compound and its manufacturing method
US20210230368A1 (en) Polyimide-based polymer film, substrate for display device, and optical device using the same
CN115175955B (en) Polyimide-based polymer film, substrate for display device using same, and optical device
JP2018178121A (en) Poly(amide-imide) copolymer, article including poly(amide-imide) copolymer, and display device
JP6638744B2 (en) Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate
Li et al. Preparation and properties of transparent conductive indium-tin-oxide/polyimide substrates via a sol-gel process
TWI654183B (en) Acid dianhydride and its utilization
US20160237214A1 (en) Composition of preparing poly(imide-benzoxasole) copolymer, poly(imide-benzoxasole) copolymer, article containing poly(imide-benzoxasole) copolymer, and display device including same
JP2011074177A (en) Polyimide material, polyimide resin composition, film, and method of producing the same
KR20220104439A (en) Polyimide precursor composition, and polyimider film, substrate for display device, circuit board, optical device and electronic device using the same
JPH0441530A (en) Highly heat-resistant siloxane polyimide and its manufacture

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant