CN110317425A - Organic polymer thin film and its application for OLED device thin-film package - Google Patents
Organic polymer thin film and its application for OLED device thin-film package Download PDFInfo
- Publication number
- CN110317425A CN110317425A CN201910478047.1A CN201910478047A CN110317425A CN 110317425 A CN110317425 A CN 110317425A CN 201910478047 A CN201910478047 A CN 201910478047A CN 110317425 A CN110317425 A CN 110317425A
- Authority
- CN
- China
- Prior art keywords
- film
- organic
- thin film
- photo
- organic polymer
- 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 94
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 108
- 238000000016 photochemical curing Methods 0.000 claims abstract description 98
- 239000000758 substrate Substances 0.000 claims abstract description 81
- 239000010408 film Substances 0.000 claims abstract description 59
- 239000010410 layer Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000011241 protective layer Substances 0.000 claims abstract description 14
- 238000005538 encapsulation Methods 0.000 claims abstract description 12
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001723 curing Methods 0.000 claims abstract description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920006254 polymer film Polymers 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000035699 permeability Effects 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 3
- 125000006725 C1-C10 alkenyl group Chemical group 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- -1 carboxylic acid vinyl acetate Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 5
- 150000001335 aliphatic alkanes Chemical group 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 150000001733 carboxylic acid esters Chemical class 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 208000037656 Respiratory Sounds Diseases 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000003999 initiator Substances 0.000 description 79
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 38
- 238000007711 solidification Methods 0.000 description 32
- 230000008023 solidification Effects 0.000 description 32
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 238000007740 vapor deposition Methods 0.000 description 21
- 230000002285 radioactive effect Effects 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004415 heterocyclylalkyl group Chemical group 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 125000005597 hydrazone group Chemical group 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- 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
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a kind of organic polymer thin films for OLED device thin-film package, belong to display panel encapsulation technology field.The organic film in the presence of photoinitiators, is made by ultraviolet light curing reaction, general structure by photo-curing monomer (methyl) acrylate or its oligomer are as follows:The organic polymer thin film solves inorganic layer in existing fexible film encapsulation and is also easy to produce the brittleness problems such as stress concentration even crackle.Be applied on organic light emitting diode device, including substrate, the Organic Light Emitting Diode being deposited on substrate, Organic Light Emitting Diode surface inorganic thin film packaging protection layer, be layered in the organic film protective layer on inorganic thin film surface.Organic polymer thin film used in the present invention, OLED can be stopped not caused by the factors such as oxygen, water in environment, and oxidation, reduction or degradation etc. destroy, and then improve the performance of OLED light-emitting display device, extend its service life.
Description
Technical field
The present invention relates to display panel encapsulation field more particularly to a kind of organic polymers for OLED device thin-film package
Object film.
Background technique
Organic electroluminescence device (Organic Light-Emitting Diode, OLED) is due to having self-luminous, height
Brightness, high contrast, fast-response speed, can a series of advantages such as flexible preparation, low driving voltage, low-power consumption, shown in following
Show, illuminate etc. that fields have boundless application prospect.However, the development of OLED also faces lot of challenges, wherein most closing
Key is to solve the problem of that device is failed due to being exposed in air for a long time by steam and oxygen.Therefore, it is necessary to OLED
Device is packaged, and requires water oxygen transmitance lower than 10-6g/m2d。
OLED encapsulation technology experienced conventional package, inorganic thin film encapsulates, organic film encapsulates, inorganic/organic composite is thin
The technologies such as film encapsulation.Inorganic thin film encapsulated layer can effectively stop H2O/O2Infiltration, but inorganic material is innately enbrittled, curved
Easily cracked and crack propagation during folding, leads to package failure, to lose water oxygen blocking capability;Meanwhile it is inorganic
The pin hole or foreign matter defect that film is likely to occur in forming process also reduce its water oxygen blocking capability.Organic film encapsulation
(essential high molecular resin) can improve surface smoothness, reduce mechanical damage and film defects, alleviate inter-laminar stress, improve anti-
Bending performance.Organic film in moisture-proof, antidetonation, impact resistance, resistance to temperature shock, chemicals corrosion and the excellent properties such as wear-resistant,
But its water oxygen blocking capability is poor.
Therefore, either single inorganic material or organic material cannot all reach the barrier requirement of OLED, and inorganic/
Organic composite material has relatively better barrier property.
Summary of the invention
It is existing for solving the purpose of the present invention is to provide a kind of thin polymer film for OLED device thin-film package
Inorganic layer is also easy to produce stress and concentrates the even brittleness problems such as crackle in the encapsulation of Organic Light Emitting Diode fexible film.
To solve the above problems, the present invention provides a kind of organic polymer thin film for OLED device thin-film package.
The organic polymer thin film is to be existed by photo-curing monomer (methyl) acrylate or its oligomer in photoinitiator
Under, it is made by ultraviolet light curing reaction, photo-curing monomer structure is shown in formula I:
Wherein, R1、R2To be identical or different, and it is each independently selected from hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C1-
C10 alkenyl, C1-C10 alkynyl, C6-C30 arlydene, C3-C20 naphthenic base or C4-C30 heteroaryl, work as R1Or R2For hydrogen Shi Buyu Y
It is connected.
Y is selected from O, S, NR, CR2、SiR2, wherein R is hydrogen, C1-C20 alkyl substituted or unsubstituted, C1- substituted or unsubstituted
C20 alkoxy, C6-C30 aryl or C4-C30 heteroaryl;
N is selected from 1,2,3;F is selected from 0,1,2,3;
Z1Selected from Z1-a、Z1- b or Z1- c, wherein Z1R in-c3Selected from C1-C20 alkyl;R4Selected from C1- substituted or unsubstituted
C30 alkyl, C1-C30 alkoxy substituted or unsubstituted, C6-C30 aryl substituted or unsubstituted, C7-C30 substituted or unsubstituted virtue
Alkyl;X1And X2It is each independently selected from O, S or NR, wherein R is selected from hydrogen, C1-C20 alkyl substituted or unsubstituted.
Expression and R1Or R2It is connected;
Further, photo-curing monomer described in general formula I includes 2-25 vinyl substituted or unsubstituted, is specifically contained
The alkyl of unsaturated double-bond replaces C6-C30 aromatic compound, C1-C20 alkyl, C3-C20 naphthenic base, C6-C20 aryl or hydroxyl
Replace esters of unsaturated carboxylic acids, C1-C20 saturation or unsaturated carboxylic acid vinyl acetate, C1-C20 unsaturated carboxylic acid glyceride, monohydroxy or
Polyhydroxy replaces (methyl) acrylate etc..(methyl) acrylic acid groups indicate methacrylic acid group and/or propylene
Acid groups.
Preferably, photo-curing monomer includes at least 1 (methyl) acrylic acid groups;Y is selected from O or CR2, R indicates hydrogen or to take
Generation or unsubstituted C1-C10 alkyl;R1And R2To be identical or different, independently selected from hydrogen, C1-C20 alkyl, C1-C20 alkoxy,
C1-C10 alkenyl, C1-C10 alkynyl, C6-C30 aryl, C6-C30 arlydene, C3-C20 naphthenic base or C4-C30 heterocycle.
As further preferred, the photo-curing monomer is independently selected from the one or more of having structure, and structural formula is such as
Under:
The purity of photo-curing monomer used in the present invention is greater than 97.5% (HPLC@200nm);At 25 ± 15 DEG C, viscosity
Variation range is 10cPs-50cPs;At 25 DEG C, viscosity is 20 ± 2cPs;Other content of organics are less than 3%;Metal ion contains
Amount is less than 2ppm.
In the present invention, the photoinitiator is selected from the one or more of following compounds, and structural formula is as follows:
Wherein, photoinitiator purity is greater than 99%;With photoinitiator when preparing organic polymer thin-film material, test
As a result substantially quite, consider from common property, photoinitiator preferably is selected from TPO.
Mass fraction in organic polymer thin film of the present invention containing photo-curing monomer is 91%-99.9%, is drawn containing light
The mass fraction for sending out agent is 0.1%-9%.
In the present invention, photocuring reaction ultraviolet irradiation is measured in 100-1000mJ, preferably 500-1000mJ;Radiated time is
1s-900s。
Photo-curing rate is tested by conventional method.For example, by using FT-IR (Fourier infrared spectrograph), photocuring list
The composition of body and initiator applies on the glass substrate, its solidification is made under ultraviolet irradiation, cured film is then cut into sample
Product are tested by IR.
The monomer and initiator of photocuring reaction of the present invention can be deposited on by chemical vapor deposition or ink-jet-printing
On OLED and device substrate, the thin-film package of OLED device is used for after ultra-violet curing;It can also be applied to solar battery etc..
As organic polymer thin film applied to OLED encapsulation with a thickness of 0.03 μm -20 μm, preferably 0.4 μm -10 μm.
The present invention also provides a kind of organic light emitting diode devices, including substrate, the organic light emission being deposited on substrate
Diode, Organic Light Emitting Diode surface inorganic thin film packaging protection layer, be layered in the organic polymer on inorganic thin film surface
Thinfilm protective coating.The organic polymer thin film protective layer can stop OLED not by ring using thin polymer film used in the present invention
Oxidation, reduction caused by the factors such as oxygen, water in border or degradation etc. destroy, and then the performance of raising OLED light-emitting display device,
Extend its service life.
Further, the present invention also provides another organic light emitting diode device, including substrate, it is deposited on substrate
On Organic Light Emitting Diode, Organic Light Emitting Diode surface inorganic thin film packaging protection layer, be layered in inorganic thin film surface
Organic polymer thin film protective layer, in the redeposited one layer of inorganic thin film layer in the surface of above-mentioned organic layer.
Wherein, two layers of inorganic thin film adds the packaged type of one layer of organic polymer thin film that can also carry out repeatedly stacking to guarantee
The packaging effect of device, such as inorganic thin film/organic polymer thin film/inorganic thin film, inorganic thin film/organic polymer thin film/
Inorganic thin film/organic polymer thin film/inorganic thin film, inorganic thin film/organic polymer thin film/inorganic thin film/organic polymer
Film/inorganic thin film/organic polymer thin film/inorganic thin film, each inorganic layer or organic layer are identical or different.
The organic film protective layer of above-mentioned device is using organic polymer thin film used in the present invention.The organic film vapor
Permeability is less than 8.0g/m2.24hr (25 DEG C of test condition, relative humidity 100%, 24 hours, 5 μ m thick directions).Used
Substrate is glass substrate, polymer plastic substrate, silicone resin or metal substrate etc..
Organic polymer thin film of the present invention, photocuring rate are greater than 90%, density polymer 0.80g/cm3-1.20g/cm3。
Stretch modulus is up to 2361MPa, and tensile strength is up to 0.76GPa.Glass transition temperature Tg is at 200 DEG C -300 DEG C.
Inorganic thin film can encapsulate organic electroluminescence device, organic solar batteries etc. as packaging protection layer.It is inorganic
Film can directly overlay device surface as encapsulated layer and be packaged, can not also be with the boundary of device contacts covering device
Region.Oxygen or moisture and device contacts outside the blocking of inorganic thin film protective layer, avoid the damage of device.Inorganic layer used
For metal, intermetallic compound or alloy, metal oxide, metal fluoride, metal chloride, metal nitride, metal carbon
Compound, metal oxynitride, metal boride, metal borohydride, or mixtures thereof one kind in metal silicide.The metal
It is a kind of or more in transition metal, lanthanide series metal, Si, Al, In, Ge, Sn, Sb, Bi, Zn, Se, Cu, Mg, Pb, Ag, Ca, titanium, tantalum
Kind.Inorganic protective layer can be such as co-deposited by vacuum technology or cosputtering, chemical vapor deposition, Metallo-Organic Chemical Vapor
Deposition, pulse laser vapor deposition, evaporation, distillation, Ecr plasma enhancing chemical vapor deposition etc. are made.It is inorganic thin
The thickness of film protective layer is less than 1 micron.
Invention beneficial effect
Device surface flatness is effectively improved provided by the present invention for the organic polymer thin film of OLED encapsulation, is reduced
Mechanical damage and film defects, alleviate inter-laminar stress, improve buckle resistance energy;There is material transparency itself simultaneously
High, moisture-proof, antidetonation, impact resistance, resistance to temperature shock, chemicals corrosion and the excellent properties such as wear-resistant.
Detailed description of the invention:
Fig. 1 is a kind of thin-film packing structure of organic light emitting diode display provided by the invention, wherein 1 indicates base
Plate, 2 indicate inorganic encapsulated film, and 3 indicate organic polymer packaging film.
Fig. 2 is the thin-film packing structure of another kind of organic light emitting diode display provided by the invention, wherein 1 indicates base
Plate, 2-1 indicate the first inorganic encapsulated film, and 3 indicate that organic polymer packaging film, 2-2 indicate the second inorganic encapsulated film.
It should be evident that attached drawing described above is only some schemes of the application, for those skilled in the art
For, without creative efforts, can also according to these attached drawings or the present invention program obtain other accompanying drawings.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Unless otherwise stated, the signified substitution of the present invention be at least one functional group H atom by halogen (F, Cl, Br,
I), hydroxyl, nitro, cyano, imido grpup (=NH ,=NR, R are the alkyl of C1-C8), amino [- NH2,-NHR ,-NRR ", wherein R
Or R " be C1-C10 alkyl], narrow base, hydrazone group, diazanyl, carbonyl, C6-C30 aryl substituted or unsubstituted, C3- substituted or unsubstituted
C30 naphthenic base, C3-C30 heteroaryl substituted or unsubstituted, at least one substitution in C3-C30 Heterocyclylalkyl substituted or unsubstituted.
It is of the present invention it is miscellaneous be that at least one C atom is replaced by N, O, S, P.
Performance characterization:
1, permeability can be tested by moisture-inhibiting analyzer (water vapor transmittance analyzer W413).
2, photocuring rate can be by FT-IR measurement light-curing compounds in 1635cm-1(C=C) and 1720cm-1(C=
O the intensity of absorption peak is measured at).Its calculation formula is as follows: photocuring rate (%)=[1- (A/B)] * 100%
A: for measured by cured film in 1635cm-1(C=C) and 1720cm-1(C=O) absorption peak strength ratio at.
B: light-curing compounds are in 1635cm-1(C=C) and 1720cm-1(C=O) absorption peak strength ratio at.
Prepare sample size: 20cm*20cm*5 μm.
3, photocuring residual monomer content is tested by HPLC.
Take appropriate Product samples dissolution in a solvent, solvent (such as ethyl alcohol) plays dissolution reaction monomers, stirring or ultrasound
After 10min, it is measured with high performance liquid chromatography.Shimadzu high performance liquid chromatograph, HPLC-16, Shimadzu (Suzhou) Co., Ltd.
4, glass transition temperature is tested by DSC: differential scanning calorimetry instrument (DSC-1 plum Teller-support benefit)
Photo-curing monomer used in thin polymer film passes through acrylic acid/methacrylic acid and dihydric alcohol, trihydroxylic alcohol, tetrahydroxylic alcohol etc.
Polyol reaction is made, or replaces C6-C30 aromatic compound, C1-C20 alkyl, C3-C20 using the alkyl containing unsaturated double-bond
Naphthenic base, C6-C20 aryl or hydroxyl substitution esters of unsaturated carboxylic acids, C1-C20 saturation or unsaturated carboxylic acid vinyl acetate, C1-C20 are not
Saturated carboxylic acid glyceride, monohydroxy or polyhydroxy replace (methyl) acrylate etc..
It is 91%- containing photo-curing monomer mass fraction if setting thin polymer film mass fraction as 100%
99.9%, the mass fraction containing photoinitiator is 0.1%-9%;When photo-curing monomer has 2 kinds of groups to be grouped as, then two kinds of monomers
The sum of mass fraction is in 91%-99.9%, such as a kind of component, in 10%-50%, another constituent content is in 49%-89.9%;
When photo-curing monomer has 3 kinds of groups to be grouped as, then the sum of mass fraction of 3 kinds of monomers is in 91%-99.9%.
In the present invention, the monomer and initiator of photocuring reaction are uniformly mixed by chemical vapor deposition or monomer initiator
Ink-jet-printing is deposited on OLED and device substrate afterwards, and the thin-film package of OLED device is used for after ultra-violet curing, can also be applied
In fields such as solar batteries.
As organic film applied to OLED encapsulation with a thickness of 0.03 μm -20 μm, preferably 0.4 μm -10 μm, such as 0.03
μm, 0.4 μm, 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm etc..The vapor permeability of the organic film is less than 8.0g/
m2.24hr (25 DEG C of test condition, relative humidity 100%, 24 hours, 5 μ m thick directions).Substrate used thereof is glass substrate, gathers
Polymer plastics substrate, silicone resin or metal substrate etc..
Inorganic thin film can encapsulate organic electroluminescence device, organic solar batteries etc. as packaging protection layer.It is inorganic
Film can directly overlay device surface as encapsulated layer and be packaged, can not also be with the boundary of device contacts covering device
Region.Inorganic thin film protective layer can stop external oxygen or moisture and device contacts, avoid the damage of device.Nothing used
Machine layer can be metal, intermetallic compound or alloy, metal oxide, metal fluoride, metal chloride, nitride metal
Object, metal carbides, metal oxynitride, metal boride, metal borohydride, a kind of in metal silicide or its mixing
Object.The metal be transition metal, lanthanide series metal, Si, Al, In, Ge, Sn, Sb, Bi, Zn, Se, Cu, Mg, Pb, Ag, Ca, titanium,
It is one or more in tantalum.Inorganic protective layer is such as co-deposited by vacuum technology or cosputtering, chemical vapor deposition, metal are organic
The systems such as chemical vapor deposition, pulse laser vapor deposition, evaporation, distillation, Ecr plasma enhancing chemical vapor deposition
?.
As preferred embodiment of the present application, inorganic thin film used in the present invention is selected from aluminum oxide, silicon nitride, oxidation
Silicon, silicon carbide.One of titanium oxide, magnesia and calcium oxide are a variety of.Wherein the thickness of inorganic thin film protective layer is less than 1 μ
M, preferably 5nm, 50nm, 100nm, 300nm, 500nm, 800nm etc..
The present invention provides a kind of organic light emitting diode devices, including substrate, the organic light emission being deposited on substrate two
Pole pipe, the inorganic thin film packaging protection layer on Organic Light Emitting Diode surface, the organic film protection for being layered in inorganic thin film surface
Layer.The organic film protective layer using thin polymer film used in the present invention, can stop OLED not by oxygen, water in environment etc. because
Oxidation, reduction caused by element or degradation etc. destroy, and then improve the performance of OLED light-emitting display device, extend its service life.
The present invention also provides a kind of organic light emitting diode devices, including substrate, the organic light emission being deposited on substrate
Diode, Organic Light Emitting Diode surface inorganic thin film packaging protection layer, be layered in inorganic thin film surface organic film protect
Sheath, in the redeposited one layer of inorganic thin film layer in the surface of above-mentioned organic layer.Two layers of inorganic thin film adds the encapsulation of one layer of organic film
The packaging effect that mode can be stacked repeatedly to guarantee device, such as inorganic thin film/organic film/inorganic thin film, inorganic thin film/
Organic film/inorganic thin film/organic film/inorganic thin film, inorganic thin film/organic film/inorganic thin film/organic film/inorganic
Film/organic film/inorganic thin film, each inorganic layer or organic layer are identical or different.
Embodiment 1-10 synthesizes organic polymer thin film of the invention by taking monomer A and B, A and C, A and D as an example;Embodiment
11-15 synthesizes organic polymer thin film of the invention by taking monomer A, B, C or D as an example;Embodiment 16-19 is with three kinds of monomers A, C and D
Synthesize thin polymer film of the invention.Monomer A, B, C and D structure is as follows:
Embodiment 1
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer films are deposited in body A, B and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer is total
22%, the IPO that 75%, B of weight accounts for initiator and photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
3%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 100mJ/cm2 again.
Embodiment 2
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer films are deposited in body A, B and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer is total
22%, the TPO that 75%, B of weight accounts for initiator and photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
3%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 500mJ/cm2 again.
Embodiment 3
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, B and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
75%, B of total weight accounts for initiator and 22%, TPO of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
3%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 1000mJ/cm2 again.
Embodiment 4
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, B and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
75%, B of total weight accounts for initiator and 22%, TPO of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
3%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 0mJ/cm2 again.
Organic polymer material after above-described embodiment 1-4 solidification is carried out result to be compared as follows:
Embodiment 5
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, C and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
81%, C of total weight accounts for initiator and 18%, TPO of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
1%.Then solidification 15min makes its solidification under the ultraviolet radioactive of 500mJ/cm2 again, and measuring photocuring rate is 94%.After crosslinking
Residual monomer concentration 1.58%, 258 DEG C of glass transition temperature.
Embodiment 6
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, C and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
49.9%, the TPO that 50.0%, C of total weight accounts for initiator and photo-curing monomer total weight accounts for initiator and photo-curing monomer is total
The 0.1% of weight.Then solidification 10min makes its solidification under the ultraviolet radioactive of 1000mJ/cm2 again, and measuring photocuring rate is 93%.
Embodiment 7
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, D and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
81%, D of total weight accounts for initiator and 10%, TPO of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
9%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 1000mJ/cm2 again, and measuring photocuring rate is 97%.
Embodiment 8
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, B and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
77%, B of total weight accounts for initiator and 22%, TPO of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
1%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 800mJ/cm2 again, and measuring photocuring rate is 93%.
Embodiment 9
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, B and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
75%, B of total weight accounts for initiator and 20%, TPO of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
5%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 1000mJ/cm2 again, and measuring photocuring rate is 98%.After crosslinking
Residual monomer concentration 0.17%, 269 DEG C of glass transition temperature.
Embodiment 10
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 3 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, C and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer
83%, C of total weight accounts for initiator and 12%, TPO of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
5%.Then solidification 10min makes its solidification under the ultraviolet radioactive of 1000mJ/cm2 again, and measuring photocuring rate is 97%.
Embodiment 11
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 2 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A and initiator TPO on substrate, wherein A accounts for initiator and photo-curing monomer is total
97%, TPO of weight accounts for the 3% of initiator and photo-curing monomer total weight.It is then solid under the ultraviolet radioactive of 1000mJ/cm2 again
Changing 10min makes its solidification, and measuring photocuring rate is 98%, residual monomer concentration 0.33% after crosslinking, glass transition temperature 255
℃。
Embodiment 12
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 2 vapor deposition crucibles
Then 8 ± 2 μm of organic monomer film is deposited in body B and initiator TPO on substrate, wherein B accounts for initiator and photo-curing monomer is total
99.9%, TPO of weight accounts for the 0.1% of initiator and photo-curing monomer total weight.The ultraviolet radioactive of subsequent 1000mJ/cm2 again
Lower solidification 10min makes its solidification, and measuring photocuring rate is 91%.
Embodiment 13
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 2 vapor deposition crucibles
Then 8 ± 2 μm of organic monomer film is deposited in body C and initiator TPO on substrate, wherein C accounts for initiator and photo-curing monomer is total
91%, TPO of weight accounts for the 9% of initiator and photo-curing monomer total weight.It is then solid under the ultraviolet radioactive of 1000mJ/cm2 again
Changing 10min makes its solidification, and measuring photocuring rate is 97%.
Embodiment 14
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 2 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body D and initiator TPO on substrate, wherein D accounts for initiator and photo-curing monomer is total
99%, TPO of weight accounts for the 1% of initiator and photo-curing monomer total weight.It is then solid under the ultraviolet radioactive of 1000mJ/cm2 again
Changing 10min makes its solidification, and measuring photocuring rate is 93%.
Embodiment 15
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 2 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A and initiator ITX on substrate, wherein A accounts for initiator and photo-curing monomer is total
95%, ITX of weight accounts for the 5% of initiator and photo-curing monomer total weight.It is then solid under the ultraviolet radioactive of 1000mJ/cm2 again
Changing 10min makes its solidification, and measuring photocuring rate is 98%.
Embodiment 16
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 4 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, C, D and initiator TPO on substrate, wherein A accounts for initiator and photocuring list
6%, the D that 83%, C of body total weight accounts for initiator and photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
6%, TPO account for the 5% of initiator and photo-curing monomer total weight.Then solidify 10min under the ultraviolet radioactive of 1000mJ/cm2 again
Make its solidification, measuring photocuring rate is 97%.
Embodiment 17
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 4 vapor deposition crucibles
Then 10 ± 2 μm of organic monomer film is deposited in body A, C, D and initiator TPO on substrate, wherein A accounts for initiator and photocuring
43%, C of total monomer weight accounts for initiator and 38%, D of photo-curing monomer total weight accounts for initiator and photo-curing monomer gross weight
16%, TPO of amount accounts for the 3% of initiator and photo-curing monomer total weight.Then solidify under the ultraviolet radioactive of 1000mJ/cm2 again
10min makes its solidification, and measuring photocuring rate is 98%, residual monomer concentration 0.55% after crosslinking, glass transition temperature 241
℃。
Embodiment 18
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 4 vapor deposition crucibles
Then 8 ± 2 μm of organic monomer film is deposited in body A, C, D and initiator TPO on substrate, wherein A accounts for initiator and photocuring list
30%, C of body total weight accounts for initiator and 45%, D of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
24%, TPO account for the 1% of initiator and photo-curing monomer total weight.Then solidify under the ultraviolet radioactive of 1000mJ/cm2 again
10min makes its solidification, and measuring photocuring rate is 98%.Residual monomer concentration 0.22% after crosslinking, glass transition temperature 282
℃。
Embodiment 19
Transparent ito substrate is cleaned by ultrasonic 15 minutes, and exposure 30 minutes under ultraviolet light in isopropanol, is then used
Plasma is handled 10 minutes.Then by treated, ito substrate is put into evaporated device.List is respectively put into 4 vapor deposition crucibles
Then 5 ± 2 μm of organic monomer film is deposited in body A, C, D and initiator TPO on substrate, wherein A accounts for initiator and photocuring list
42%, C of body total weight accounts for initiator and 16%, D of photo-curing monomer total weight accounts for initiator and photo-curing monomer total weight
36%, TPO account for the 6% of initiator and photo-curing monomer total weight.Then solidify under the ultraviolet radioactive of 1000mJ/cm2 again
10min makes its solidification, and measuring photocuring rate is 97%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of organic polymer thin film for OLED device thin-film package, including photo-curing monomer, photoinitiator, feature
It is, photo-curing monomer structure is as follows:
Wherein, R1、R2To be identical or different, and it is each independently selected from hydrogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C10 alkene
Base, C1-C10 alkynyl, C6-C30 arlydene, C3-C20 naphthenic base or C4-C30 heteroaryl, work as R1Or R2It is connected for hydrogen Shi Buyu Y;
Y is selected from O, S, NR, CR2、SiR2, wherein R is hydrogen, C1-C20 alkyl substituted or unsubstituted, C1-C20 alkane substituted or unsubstituted
Oxygroup, C6-C30 aryl or C4-C30 heteroaryl;
N is selected from 1,2,3;F is selected from 0,1,2,3;
Z1Selected from Z1-a、Z1- b or Z1- c, wherein Z1R in-c3Selected from C1-C20 alkyl;R4Selected from C1-C30 alkane substituted or unsubstituted
Base, C1-C30 alkoxy substituted or unsubstituted, C6-C30 aryl substituted or unsubstituted, C7-C30 aralkyl substituted or unsubstituted;
X1And X2It is each independently selected from O, S or NR, wherein R is selected from hydrogen, C1-C20 alkyl substituted or unsubstituted;
Expression and R1Or R2It is connected.
2. being used for the organic polymer thin film of OLED device thin-film package according to claim 1, it is characterised in that: the light
Curing monomer includes 1-25 vinyl substituted or unsubstituted;Wherein, vinyl substituted or unsubstituted is selected from unsaturated double-bond
Alkyl replaces C6-C30 aromatic compound, and C1-C20 alkyl, C3-C20 naphthenic base, C6-C20 aryl or hydroxyl replace unsaturated carboxylic
Acid esters, C1-C20 saturation or unsaturated carboxylic acid vinyl acetate, C1-C20 unsaturated carboxylic acid glyceride, monohydroxy or polyhydroxy replace
(methyl) acrylate;Preferably, the photo-curing monomer includes at least 1 (methyl) acrylic acid groups;Y is selected from O or CR2,
R indicates hydrogen or C1-C10 alkyl substituted or unsubstituted;R1And R2To be identical or different, independently selected from hydrogen, C1-C20 alkyl, C1-
C20 alkoxy, C1-C10 alkenyl, C1-C10 alkynyl, C6-C30 aryl, C6-C30 arlydene, C3-C20 naphthenic base or C4-C30
Heterocycle.
3. being used for the organic polymer thin film of OLED device thin-film package according to weighing and require 1, it is characterised in that: the light is solid
Change monomer independently selected from the one or more of having structure:
4. being used for the organic polymer thin film of OLED device thin-film package according to weighing and require 1, it is characterised in that: the light is solid
The purity for changing monomer is greater than 97.5%;At 25 ± 15 DEG C, spread of viscosity 10cPs-50cPs;At 25 DEG C, viscosity is
20±2cPs;Other content of organics are less than 3%;Metal ion content is less than 2ppm.
5. being used for the organic polymer thin film of OLED device thin-film package according to weighing and require 1, it is characterised in that: the light draws
It sends out agent and is selected from the one or more of following compounds:
6. being used for the organic polymer thin film of OLED device thin-film package according to weighing and require 1, it is characterised in that: described organic
Mass fraction in thin polymer film containing photo-curing monomer is 91%-99.9%, and the mass fraction containing photoinitiator is
0.1%-9%.
7. being used for the organic polymer thin film of OLED device thin-film package according to weighing and require 1, it is characterised in that: photocuring is anti-
Answer ultraviolet irradiation metering in 100-1000mJ, radiated time 1s-900s.
8. a kind of organic light emitting diode device, including substrate, the Organic Light Emitting Diode being deposited on substrate, organic light emission two
The inorganic thin film packaging protection layer on pole pipe surface, the organic film protective layer for being layered in inorganic thin film surface, it is characterised in that: should
Organic film protective layer is using organic polymer thin film described in claim 1-7 any one.
9. organic light emitting diode device according to claim 8, it is characterised in that: in the table of above-mentioned organic film protective layer
One layer of inorganic thin film layer of face redeposition;Two layers of inorganic thin film adds the packaged type of one layer of organic polymer thin film using multiple heap
Folded, each inorganic layer or organic layer are identical or different.
10. organic light emitting diode device according to claim 8 or claim 9, it is characterised in that: the monomer of photocuring reaction and draw
Hair agent is deposited on OLED and device substrate by chemical vapor deposition or ink-jet-printing, and OLED device is used for after ultra-violet curing
Thin-film package, encapsulation with a thickness of 0.03 μm -20 μm, organic film vapor permeability is less than 8.0g/m2.24hr。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910478047.1A CN110317425A (en) | 2019-06-03 | 2019-06-03 | Organic polymer thin film and its application for OLED device thin-film package |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910478047.1A CN110317425A (en) | 2019-06-03 | 2019-06-03 | Organic polymer thin film and its application for OLED device thin-film package |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110317425A true CN110317425A (en) | 2019-10-11 |
Family
ID=68119575
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910478047.1A Pending CN110317425A (en) | 2019-06-03 | 2019-06-03 | Organic polymer thin film and its application for OLED device thin-film package |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110317425A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111018745A (en) * | 2019-12-12 | 2020-04-17 | 吉林奥来德光电材料股份有限公司 | Compound for packaging film, organic film packaging material and packaging film |
CN111721815A (en) * | 2020-06-18 | 2020-09-29 | 业成科技(成都)有限公司 | Touch device and curing rate detection method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040164251A1 (en) * | 2003-02-26 | 2004-08-26 | Bergh Rudy Van Den | Storage phosphor panel, radiation image sensor and methods of making the same |
CN103811674A (en) * | 2013-11-06 | 2014-05-21 | 溧阳市江大技术转移中心有限公司 | Manufacturing method for organic light emitting device with electron-transporting layer |
CN103881022A (en) * | 2012-12-20 | 2014-06-25 | 第一毛织株式会社 | Composition for encapsulation and encapsulated apparatus including the same |
CN105981188A (en) * | 2014-01-16 | 2016-09-28 | 胡网加成公司 | Organic electronic device and fabrication method therefor |
-
2019
- 2019-06-03 CN CN201910478047.1A patent/CN110317425A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040164251A1 (en) * | 2003-02-26 | 2004-08-26 | Bergh Rudy Van Den | Storage phosphor panel, radiation image sensor and methods of making the same |
CN103881022A (en) * | 2012-12-20 | 2014-06-25 | 第一毛织株式会社 | Composition for encapsulation and encapsulated apparatus including the same |
CN103811674A (en) * | 2013-11-06 | 2014-05-21 | 溧阳市江大技术转移中心有限公司 | Manufacturing method for organic light emitting device with electron-transporting layer |
CN105981188A (en) * | 2014-01-16 | 2016-09-28 | 胡网加成公司 | Organic electronic device and fabrication method therefor |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111018745A (en) * | 2019-12-12 | 2020-04-17 | 吉林奥来德光电材料股份有限公司 | Compound for packaging film, organic film packaging material and packaging film |
CN111018745B (en) * | 2019-12-12 | 2022-03-15 | 吉林奥来德光电材料股份有限公司 | Compound for packaging film, organic film packaging material and packaging film |
CN111721815A (en) * | 2020-06-18 | 2020-09-29 | 业成科技(成都)有限公司 | Touch device and curing rate detection method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6261737B2 (en) | Adhesive film and organic electronic device manufacturing method using the same | |
KR101642568B1 (en) | Encapsulatn film | |
TWI460197B (en) | Photocurable resin composition for sealing organic el device | |
US10829669B2 (en) | Curable and hygroscopic resin composition for sealing electronic devices, resin cured material, and electronic device | |
TWI276861B (en) | Liquid crystal cell substrate, the method of producing the same and the liquid crystal display using the same | |
JP5763280B2 (en) | Surface sealing agent for organic EL element and cured product thereof | |
JP6195099B2 (en) | SEALING MATERIAL FILM AND ELECTRONIC DEVICE INCLUDING THE SAME | |
US20150252125A1 (en) | Curable resin compositions and barrier stacks including the same | |
TWI422632B (en) | Method for fabricating encapsulant materials | |
TWI622603B (en) | Surface encapsulating agent for organic el element, organic el device using the same and manufacturing method thereof, cured object and organic el panel | |
CN110317425A (en) | Organic polymer thin film and its application for OLED device thin-film package | |
CN105981188A (en) | Organic electronic device and fabrication method therefor | |
US20150280037A1 (en) | Solar cell sealing film and solar cell module using the same | |
CN106029817A (en) | Resin composition for sealing electronic device, and electronic device | |
CN102725863B (en) | Thin plate for photovoltaic cell | |
TWI494699B (en) | Photocurable composition, barrier layer including the same and encapsulated apparatus including the same | |
CN116023886A (en) | Adhesive composition | |
TWI613247B (en) | Photocurable composition, barrier layer including the same, and encapsulated apparatus including the same | |
TWI651358B (en) | Sealing material and hardened material | |
CN110079222A (en) | A kind of encapsulating material, relevant glue film and photovoltaic module and preparation method | |
JP2007299725A (en) | Organic electroluminescent device | |
KR102040456B1 (en) | Organic electronic device for virtual reality display | |
CN109791978A (en) | For the composition of organic electronic element encapsulant, and the encapsulant formed using it | |
JP2013108057A (en) | Thermosetting composition for forming moisture capture body, moisture capture body, and electronic device | |
WO2007026579A1 (en) | Method for producing material for forming protective film for organic electroluminescent device |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191011 |