CN111785857B - Film packaging material, manufacturing method thereof, film packaging structure and electronic device - Google Patents
Film packaging material, manufacturing method thereof, film packaging structure and electronic device Download PDFInfo
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- CN111785857B CN111785857B CN201910271190.3A CN201910271190A CN111785857B CN 111785857 B CN111785857 B CN 111785857B CN 201910271190 A CN201910271190 A CN 201910271190A CN 111785857 B CN111785857 B CN 111785857B
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- 238000004806 packaging method and process Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000005022 packaging material Substances 0.000 title abstract description 20
- 239000010409 thin film Substances 0.000 claims abstract description 48
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012044 organic layer Substances 0.000 claims abstract description 23
- -1 acrylic ester Chemical class 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 229910052732 germanium Inorganic materials 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 22
- 239000012043 crude product Substances 0.000 claims description 20
- 238000005538 encapsulation Methods 0.000 claims description 20
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000010408 film Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- 150000001263 acyl chlorides Chemical class 0.000 claims description 10
- 239000000741 silica gel Substances 0.000 claims description 10
- 229910002027 silica gel Inorganic materials 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000001033 ether group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- KCAOIDNJWQKARC-UHFFFAOYSA-N bromo(phenyl)germanium Chemical compound Br[Ge]C1=CC=CC=C1 KCAOIDNJWQKARC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- RKKOMEIYHHASIN-UHFFFAOYSA-N hydroperoxyboronic acid Chemical compound OOB(O)O RKKOMEIYHHASIN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002834 transmittance Methods 0.000 abstract description 7
- 239000000543 intermediate Substances 0.000 description 29
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 210000002381 plasma Anatomy 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 229910000078 germane Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- CXUWHAIYMDIHBD-UHFFFAOYSA-N phenoxygermanium Chemical compound [Ge]OC1=CC=CC=C1 CXUWHAIYMDIHBD-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Wrappers (AREA)
Abstract
In the thin film packaging material, the manufacturing method thereof, the thin film packaging structure and the electronic device, the germanium group is introduced into the main chain or the side group of the acrylic ester monomer, the structural characteristics of the germanium group compound are utilized to improve the thermal stability and the light transmittance of the organic layer, and meanwhile, the tolerance of the organic layer to plasma is improved, so that the effect of thin film packaging is improved.
Description
Technical Field
The present disclosure relates to the field of display technologies, and in particular, to a thin film packaging material, a manufacturing method thereof, a thin film packaging structure, and an electronic device.
Background
Organic electroluminescent devices (OLEDs) are known as display devices having the most promising applications due to their self-luminescence, high brightness, high contrast, low operating voltage, flexible display, etc. In recent years, with the development of curved screens and foldable display devices, various flexible OLED display devices having flexibility have been developed.
A flexible OLED display device generally includes a substrate, an electroluminescent element on the substrate, and a thin film encapsulation structure on the electroluminescent element. For flexible OLED devices, the packaging effect of the thin film packaging structure directly affects the reliability and lifetime of the device, and therefore, how to efficiently package the flexible OLED device to extend the lifetime of the device is an important problem facing those skilled in the art.
The existing film packaging structure is generally formed by overlapping an inorganic packaging layer and an organic packaging layer, wherein the inorganic packaging layer can block external water vapor and oxygen, and the organic packaging layer can ensure planarization of the surface of the packaging film and release stress. Meanwhile, the organic packaging layer has the function of coating particles, and defects in the inorganic layer are prevented from being diffused.
Currently, the organic layer is generally formed of an acrylic material or an epoxy material. However, these polymeric materials generally exhibit characteristics of poor thermal stability. Meanwhile, as the inorganic layer is deposited by plasma, the plasma can etch the organic layer in the deposition process, so that the packaging performance of the organic layer is damaged, and the OLED device is further deteriorated.
Therefore, how to solve the problems of poor thermal stability and easy damage of the existing film packaging material is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
In view of this, the present application provides a thin film packaging material to solve the problems of poor thermal stability and easy damage of the existing thin film packaging material.
In order to solve the above technical problems, the present invention provides a thin film packaging material, which includes: a photoinitiator and a compound synthesized from germanium groups and acrylate functional groups;
the structure of the compound is shown as a formula I or a formula II:
wherein n is an integer from 0 to 30, and R1 to R7 are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; a3 to A8 are aryl or heteroaryl; l1 to L4 are alkylene or alkylene ether groups.
Optionally, in the film packaging material, the structural formula of the acrylate functional group is:
；
wherein, represents a position combined with L1, L2 or L4, and Y is hydrogen or alkyl.
Optionally, in the film packaging material, the photoinitiator includes any one or any combination of acetophenone, benzophenone, benzoin and phosphorus initiator.
The invention also provides a manufacturing method of the film packaging material, which comprises the following steps:
providing methacryloyl chloride and a germanium-based intermediate having a hydroxyl group;
synthesizing the intermediate of the methacryloyl chloride and the germanium group into a compound through the esterification reaction of the acyl chloride and the hydroxyl, wherein the compound is synthesized by germanium group and acrylic ester functional groups; and
providing a photoinitiator and mixing the compound with the photoinitiator.
Optionally, in the method for manufacturing a thin film encapsulation material, the process of synthesizing the methacryloyl chloride and the germanium-based intermediate into the compound by an esterification reaction of an acyl chloride and a hydroxyl group includes:
placing triethylamine and the germanium-based intermediate with hydroxyl in the same reaction container;
adding methylene dichloride into the reaction vessel to form a first mixed solution;
dissolving the methacryloyl chloride in methylene chloride to form a second mixed solution;
dropwise adding the second mixed solution into the first mixed solution for reaction;
filtering and concentrating to obtain a crude product of the target compound; and
purifying the crude product through a 200-300 mesh silica gel column.
Optionally, in the method for manufacturing a thin film encapsulation material, the manufacturing process of the germanium-based intermediate having a hydroxyl group includes:
under the protection of nitrogen, phenyl bromogermanium and tetraphenylphosphine palladium are placed in the same reaction vessel;
adding a phenyl germanium ethanol solution of hydroxyl borate and a sodium carbonate aqueous solution which are bubbled by nitrogen gas into the reaction vessel to form a mixed solution;
adding degassed toluene into the mixed solution for reflux;
pouring the reaction product into distilled water, and extracting by using methylene dichloride;
washing with saturated salt water to neutrality;
the organic phases were combined and dried over anhydrous magnesium sulfate;
filtering and concentrating to obtain a crude product of the target intermediate; and
purifying the crude product by a 200-300 mesh silica gel column.
Optionally, in the method for manufacturing a thin film encapsulation material, the manufacturing process of the germanium-based intermediate having a hydroxyl group includes:
under the protection of nitrogen, phenoxy germanium bromide and tetraphenylphosphine palladium are placed in the same reaction vessel;
adding a phenyl germanium ethanol solution of hydroxyl borate and a sodium carbonate aqueous solution which are bubbled by nitrogen gas into the reaction vessel to form a mixed solution;
adding degassed toluene into the mixed solution for reflux;
pouring the reaction product into distilled water, and extracting by using methylene dichloride;
washing with saturated salt water to neutrality;
the organic phases were combined and dried over anhydrous magnesium sulfate;
filtering and concentrating to obtain a crude product of the target intermediate; and
purifying the crude product by a 200-300 mesh silica gel column.
The invention also provides a thin film packaging structure, which comprises: laminating alternating inorganic layers and organic layers;
wherein the organic layer adopts the thin film packaging material.
The present invention also provides an electronic device including: a substrate, a functional device, and a thin film package structure as described above;
the functional device and the thin film packaging structure are sequentially formed on the substrate, and the thin film packaging structure is used for packaging the functional device.
According to the thin film packaging material, the manufacturing method thereof, the thin film packaging structure and the electronic device, the germanium group is introduced into the main chain or the side group of the acrylic ester monomer, the structural characteristics of the germanium group compound are utilized to improve the thermal stability and the light transmittance of the organic layer, and meanwhile, the tolerance of the organic layer to plasmas is improved, so that the effect of thin film packaging is improved.
Drawings
The technical scheme of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments so as to make the characteristics and advantages of the present invention more apparent.
FIG. 1 is a schematic structural diagram of a thin film package structure according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the invention.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the example embodiments may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus a repetitive description thereof will be omitted.
The present invention provides a novel thin film encapsulation material comprising: a compound synthesized from germanium groups and acrylate functional groups and a photoinitiator;
the structure of the compound is shown as a formula I or a formula II:
wherein n is an integer from 0 to 30, and R1 to R7 are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; a3 to A8 are aryl or heteroaryl; l1 to L4 are alkylene or alkylene ether groups.
Specifically, in the compound shown in the formula I, the main chain is of a germane structure, and the side chain is of a germane structure. In the compound shown in the formula II, the main chain is of a germane structure, and the side chain is of a germane structure.
In the compound shown in the formula I, R1-R7 are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl, the alkyl base has 1-10 carbon atoms, the cycloalkyl base has 3-30 carbon atoms, the aryl base has 6-30 carbon atoms, and the heteroaryl base has 3-30 carbon atoms. L1-L2 are alkylene or alkylene ether groups, the alkylene radical having 1-30 carbon atoms and the alkylene ether radical having 1-50 carbon atoms. L1-L2 are alkylene or alkylene ether groups, the alkylene radical having 1-30 carbon atoms and the alkylene ether radical having 1-50 carbon atoms. Wherein, L1 and L2 may be the same or different.
In the compound shown in the formula II, A3-A8 are aryl or heteroaryl, wherein the aryl has 6-30 carbon atoms, and the heteroaryl band has 3-30 carbon atoms. R1 and R6 are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl, the alkyl group has 1 to 10 carbon atoms, the cycloalkyl group has 3 to 30 carbon atoms, the aryl group has 6 to 30 carbon atoms, and the heteroaryl group has 3 to 30 carbon atoms. L1 to L4 are alkylene groups or alkylene ether groups, the alkylene groups having 1 to 30 carbon atoms and the alkylene ether groups having 1 to 50 carbon atoms. Wherein A3 to A8 may be the same or different. L1 to L4 may be the same or different.
The acrylic acid ester is the general term for esters of acrylic acid and its homologs, and includes methyl acrylate, ethyl acrylate, methyl 2-methacrylate, ethyl 2-methacrylate, and the like. The acrylate functional groups include methyl acrylate functional groups, ethyl acrylate functional groups, 2-methyl methacrylate functional groups, 2-ethyl methacrylate functional groups, and the like. The structural formula of the acrylate functional group is as follows:
。
wherein, represents a position combined with L1, L2 or L4, and Y is hydrogen or alkyl. In this embodiment, the alkyl groups have 1 to 10 carbon atoms.
The compound is mixed with a photoinitiator, wherein the photoinitiator comprises any one or any combination of acetophenone, benzophenone, benzoin and phosphorus type initiators, and is used for causing a photo-curing reaction.
In the film packaging material, germanium groups and acrylate functional groups cooperate to facilitate light transmission and have higher bond energy, so that the compound has good light transmittance and thermal stability and can resist bombardment of plasmas. Therefore, the thin film packaging material is used as the organic layer of the thin film package, so that the thermal stability and the light transmittance of the organic layer can be improved, and the plasma resistance of the organic layer is improved.
Correspondingly, the invention also provides a manufacturing method of the film packaging material, which comprises the following steps:
step one: providing methacryloyl chloride and a germanium-based intermediate having a hydroxyl (-OH) group;
step two: synthesizing the methacryloyl chloride and the germanium-based intermediate into a compound through esterification reaction of acyl chloride and hydroxyl, wherein the compound is synthesized by germanium-based and acrylate functional groups;
step three: providing a photoinitiator and mixing the compound with the photoinitiator.
Specifically, methacryloyl chloride is an intermediate product that is commercially available directly. The structural formula of the methacryloyl chloride is as follows:
。
in this example, the germanium-based intermediate having a hydroxyl group was prepared from palladium tetraphenylphosphine and phenyl bromogermanium as raw materials. The specific reaction equation is:
。
the preparation process of the germanium-based intermediate with hydroxyl comprises the following steps: first, phenyl bromogermanium (23.61 g,61.2 mmol) and tetrakis triphenylphosphine palladium (6.93 g,6.0 mmol) were placed in the same reaction vessel (e.g., 500mL three-necked flask) under the protection of nitrogen; next, a phenyl germanium ethanol solution of hydroxy borate (36.96 g,122.4 mmol) and an aqueous sodium carbonate solution (100 mL, 2M) in units of M mol/L, which were bubbled with nitrogen gas, were added to the reaction vessel to form a mixed solution; then, degassed toluene (200 mL) was added to the mixed solution, and the mixture was refluxed for 12 hours to effect a reaction; then, the reaction product was poured into 100mL of distilled water, and extracted three times with methylene chloride, 100mL of methylene chloride each time; then, saturated saline is adopted for washing to neutrality; next, the organic phases, which refer to the mixture of reaction product and dichloromethane, are combined; the organic phase was then dried over anhydrous magnesium sulfate; then, obtaining a crude product of the target intermediate through suction filtration and concentration; and finally, purifying the crude product through a 200-300-mesh silica gel column to obtain a target intermediate.
In another embodiment of the invention, the germanium-based intermediate having a hydroxyl group is prepared from palladium tetraphenylphosphine and phenoxygermanium bromide as starting materials. The specific reaction equation is:
。
the preparation process of the germanium-based intermediate with hydroxyl comprises the following steps: first, phenoxy germanium bromide (25.56 g,61.2 mmol) and tetrakis triphenylphosphine palladium (6.93 g,6.0 mmol) were placed in the same reaction vessel (e.g., 500mL three-necked flask) under nitrogen; next, a nitrogen-bubbled phenoxygermanium hydroxyborate ethanol solution (40.97 g,122.4 mmol) and an aqueous sodium carbonate solution (100 mL, 2M) were added to the reaction vessel to form a mixed solution; then, degassed toluene (200 mL) was added to the mixed solution, and the mixture was refluxed for 12 hours to effect a reaction; then, the reaction product was poured into 100mL of distilled water, and extracted three times with methylene chloride, 100mL of methylene chloride each time; then, saturated saline is adopted for washing to neutrality; next, the organic phases, which refer to the mixture of reaction product and dichloromethane, are combined; the organic phase was then dried over anhydrous magnesium sulfate; then, obtaining a crude product of the target intermediate through suction filtration and concentration; and finally, purifying the crude product through a 200-300-mesh silica gel column to obtain a target intermediate.
It should be noted that the above germanium-based intermediate having a hydroxyl group and the preparation method thereof are merely examples and are not limiting, and in other embodiments of the present invention, the germanium-based intermediate having a hydroxyl group may be prepared by other raw materials and other methods.
After obtaining the germanium-based intermediate having a hydroxyl group, methacryloyl chloride and the germanium-based intermediate are synthesized into a compound by an esterification reaction of acyl chloride and hydroxyl group. In this example, the reaction equation for synthesizing methacryloyl chloride and a germanium-based intermediate into a compound by the esterification of an acyl chloride and a hydroxyl group is:
。
specifically, the process for synthesizing the methacryloyl chloride and the germanium-based intermediate into a compound through the esterification reaction of the acyl chloride and the hydroxyl comprises the following steps:
firstly, triethylamine (0.15 g,1.5 mmol) and the germanium-based intermediate (0.78 g,1 mmol) having a hydroxyl group were placed in the same reaction vessel;
subsequently, methylene chloride (10 mL) was added to the reaction vessel to form a first mixed solution;
thereafter, methacryloyl chloride (0.15 g,1.5 mmol) was dissolved in methylene chloride to form a second mixed solution;
then, the second mixed solution is added into the first mixed solution dropwise for reaction, ice bath control is carried out for 30 minutes at the initial time of the reaction, and then room temperature reaction is carried out for 24 hours;
then, obtaining a crude product of the target compound through suction filtration and concentration;
and finally, purifying the crude product through a 200-300 mesh silica gel column to obtain a target compound, wherein the target compound introduces germanium groups into a main chain or a side group of an acrylic monomer.
In another embodiment of the present invention, the reaction equation for synthesizing methacryloyl chloride and germanium based intermediates into a compound by esterification of an acyl chloride and a hydroxyl group is:
。
specifically, the process for synthesizing the methacryloyl chloride and the germanium-based intermediate into a compound through the esterification reaction of the acyl chloride and the hydroxyl comprises the following steps:
first, triethylamine (0.30 g,3 mmol) and the germanium-based intermediate (0.87 g,1 mmol) having a hydroxyl group were placed in the same reaction vessel;
subsequently, methylene chloride (10 mL) was added to the reaction vessel to form a first mixed solution;
thereafter, methacryloyl chloride (0.30 g,3 mmol) was dissolved in methylene chloride to form a second mixed solution;
then, the second mixed solution is added into the first mixed solution dropwise for reaction, ice bath control is carried out for 30 minutes at the initial time of the reaction, and then room temperature reaction is carried out for 24 hours;
then, obtaining a crude product of the target compound through suction filtration and concentration;
and finally, purifying the crude product through a 200-300 mesh silica gel column to obtain a target compound, wherein the target compound introduces germanium groups into a main chain or a side group of an acrylic monomer.
It should be noted that the above-mentioned compounds and the preparation methods thereof are only examples and not limiting, and in other embodiments of the present invention, different germanium-based intermediates and process methods may be used, as long as the compounds synthesized from germanium-based and acrylate-based functional groups can be synthesized by the esterification reaction of acid chloride and hydroxyl groups.
After forming the target compound, the target compound is mixed with a photoinitiator, so that the thin film encapsulation material is obtained. The film packaging material not only has better thermal stability and light transmittance, but also can resist the bombardment of plasma, and avoids the performance degradation of OLED devices caused by the damage of plasma etching to the packaging performance.
Correspondingly, the invention further provides a film packaging structure. Fig. 1 is a schematic structural diagram of a thin film package structure according to an embodiment of the invention. As shown in fig. 1, the thin film encapsulation structure 30 includes: alternating inorganic layers 31 and organic layers 32 are laminated, the organic layers 32 being a thin film encapsulation material as described above.
Correspondingly, the invention further provides an electronic device. Fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the invention. As shown in fig. 2, the electronic device 1 includes a substrate 10, a functional device 20, and a thin film encapsulation structure 30 as described above; the functional device 20 and the thin film encapsulation structure 30 are sequentially formed on the substrate 10, and the thin film encapsulation structure 30 is used for encapsulating the functional device 20.
Specifically, the substrate 10 may be a rigid substrate, or may be a flexible substrate, preferably a flexible substrate, so as to implement a flexible display function. The rigid substrate may be, for example, a glass substrate or a quartz substrate. The flexible substrate may be, for example, an organic polymer substrate such as a polyimide substrate (PI substrate), a polyamide substrate, a polycarbonate substrate, or a polyethersulfone substrate.
The functional device 20 includes, but is not limited to, an electroluminescent element (e.g., OLED), a liquid crystal display device, a solar cell, a thin film battery, an organic sensor, and the like.
The thin film encapsulation structure 30 includes organic layers and inorganic layers alternately stacked, and the thin film at the lowermost layer and/or the uppermost layer may be either an organic layer or an inorganic layer. The organic layer is made of the thin film packaging material, and the thin film packaging material contains a compound synthesized by germanium groups and acrylic functional groups, so that the organic layer has good thermal stability and light transmittance and is more resistant to plasmas. Therefore, in the process of forming the inorganic layer through the plasma deposition process, the organic layer can be prevented or reduced from being damaged, so that the packaging effect of the film packaging structure 30 is ensured, and the problem of performance degradation of the electronic device is avoided.
In summary, the thin film packaging material, the manufacturing method thereof, the thin film packaging structure and the electronic device provided by the invention have the advantages that the germanium group is introduced into the main chain or the side group of the acrylic ester monomer, the structural characteristics of the germanium group compound are utilized to improve the thermal stability and the light transmittance of the organic layer, and meanwhile, the tolerance of the organic layer to plasmas is improved, so that the effect of thin film packaging is improved.
The foregoing is a further detailed description of the present application in connection with the specific preferred embodiments, and it is not intended that the practice of the present application be limited to such description. It should be understood that those skilled in the art to which the present application pertains may make several simple deductions or substitutions without departing from the spirit of the present application, and all such deductions or substitutions should be considered to be within the scope of the present application.
Claims (9)
1. A film encapsulation material, comprising: a photoinitiator and a compound synthesized from germanium groups and acrylate functional groups;
the structure of the compound is shown as a formula I or a formula II:
wherein n is an integer from 0 to 30, and R1 to R7 are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl; a3 to A8 are aryl or heteroaryl; l1 to L4 are alkylene or alkylene ether groups.
2. The film encapsulation material of claim 1, wherein said acrylate functional group has the formula:
wherein, represents a position combined with L1, L2 or L4, and Y is hydrogen or alkyl.
3. The film encapsulation material of claim 1, wherein the photoinitiator comprises any one or any combination of acetophenone, benzophenone, benzoin, and phosphorus-based initiators.
4. A method of manufacturing the film encapsulation material according to claim 1, comprising:
providing methacryloyl chloride and a germanium-based intermediate having a hydroxyl group;
synthesizing the methacryloyl chloride and the germanium-based intermediate into a compound through esterification reaction of acyl chloride and hydroxyl, wherein the compound is synthesized by germanium-based and acrylate functional groups; and
providing a photoinitiator and mixing the compound with the photoinitiator.
5. The method of manufacturing a thin film encapsulation material according to claim 4, wherein the process of synthesizing the methacryloyl chloride and the germanium-based intermediate into a compound by an esterification reaction of an acyl chloride and a hydroxyl group comprises:
placing triethylamine and the germanium-based intermediate with hydroxyl in the same reaction container;
adding methylene dichloride into the reaction vessel to form a first mixed solution;
dissolving the methacryloyl chloride in methylene chloride to form a second mixed solution;
dropwise adding the second mixed solution into the first mixed solution for reaction;
filtering and concentrating to obtain a crude product of the target compound; and
purifying the crude product through a 200-300 mesh silica gel column.
6. The method of manufacturing a thin film encapsulation material of claim 5, wherein said germanium-based intermediate having a hydroxyl group is manufactured by a process comprising:
under the protection of nitrogen, phenyl bromogermanium and tetraphenylphosphine palladium are placed in the same reaction vessel;
adding a phenyl germanium ethanol solution of hydroxyl borate and a sodium carbonate aqueous solution which are bubbled by nitrogen gas into the reaction vessel to form a mixed solution;
adding degassed toluene into the mixed solution for reflux;
pouring the reaction product into distilled water, and extracting by using methylene dichloride;
washing with saturated salt water to neutrality;
the organic phases were combined and dried over anhydrous magnesium sulfate;
filtering and concentrating to obtain a crude product of the target intermediate; and
purifying the crude product by a 200-300 mesh silica gel column.
7. The method of manufacturing a thin film encapsulation material of claim 5, wherein said germanium-based intermediate having a hydroxyl group is manufactured by a process comprising:
under the protection of nitrogen, phenoxy germanium bromide and tetraphenylphosphine palladium are placed in the same reaction vessel;
adding a nitrogen bubbling B monomer ethanol solution and a sodium carbonate aqueous solution into the reaction vessel to form a mixed solution;
adding degassed toluene into the mixed solution for reflux;
pouring the reaction product into distilled water, and extracting by using methylene dichloride;
washing with saturated salt water to neutrality;
the organic phases were combined and dried over anhydrous magnesium sulfate;
filtering and concentrating to obtain a crude product of the target intermediate; and
purifying the crude product by a 200-300 mesh silica gel column.
8. A thin film package structure, comprising: laminating alternating inorganic layers and organic layers; wherein the organic layer employs the thin film encapsulation material according to any one of claims 1 to 3.
9. An electronic device, comprising: a substrate, a functional device, and the thin film package structure of claim 8;
the functional device and the thin film packaging structure are sequentially formed on the substrate, and the thin film packaging structure is used for packaging the functional device.
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