CN114874255A - Silicon-containing epoxy compound and composition thereof - Google Patents
Silicon-containing epoxy compound and composition thereof Download PDFInfo
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- CN114874255A CN114874255A CN202210399835.3A CN202210399835A CN114874255A CN 114874255 A CN114874255 A CN 114874255A CN 202210399835 A CN202210399835 A CN 202210399835A CN 114874255 A CN114874255 A CN 114874255A
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 150000001875 compounds Chemical class 0.000 title claims abstract description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 26
- 239000010703 silicon Substances 0.000 title claims abstract description 26
- 239000004593 Epoxy Substances 0.000 title claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 239000012954 diazonium Substances 0.000 claims description 6
- 150000001989 diazonium salts Chemical class 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 150000004714 phosphonium salts Chemical class 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 238000005538 encapsulation Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000001450 anions Chemical group 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- 239000011342 resin composition Substances 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 14
- 238000004806 packaging method and process Methods 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000002834 transmittance Methods 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000005022 packaging material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- DMHSCCFHYJAXNG-UHFFFAOYSA-N sodium;bis(trimethylsilyl)azanide;oxolane Chemical compound [Na+].C1CCOC1.C[Si](C)(C)[N-][Si](C)(C)C DMHSCCFHYJAXNG-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical compound COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a silicon-containing epoxy compound and a composition containing the silicon-containing epoxy compound. The main components of the resin composition provided by the invention, besides the silicon-containing epoxy compound, also comprise phenolic epoxy resin, aliphatic epoxy resin, a cationic initiator, a coupling agent and a solid filler, and the resin composition is in a semitransparent state at normal temperature and has better stability. By UV light-heat dual curing, the resin composition has no oxygen inhibition phenomenon in the curing process, and the obtained cured product has the characteristics of high thermal stability and high adhesive strength, and has low water vapor transmittance, thereby being particularly suitable for packaging electronic display elements.
Description
Technical Field
The invention belongs to the technical field of display element packaging materials, and particularly relates to a silicon-containing epoxy compound and a composition thereof.
Background
In recent years, research on organic thin film devices such as organic electroluminescent display devices and solar cells has been greatly advanced. The organic light-emitting display element commonly used at present is a thin film structure body in which an organic photoelectric material layer is clamped between a pair of electrodes which are opposite to each other, and the material does not need a backlight source, so that the material has the characteristics of low energy consumption, good visual identification, convenience for thinning and flexibility and the like, and has a very good application prospect. For such a display element structure, when the organic light emitting material layer or the electrode thereof is exposed to air, stability and service life are greatly affected. Therefore, the display element and the electrode must be isolated from air by using an encapsulating material, which has high requirements on the adhesive strength, shrinkage rate, thermal stability and moisture permeability of the encapsulating material.
A wide variety of resin compositions for sealing display elements are currently on the market. CN109285969B discloses an encapsulation method of an OLED display element and an OLED display element, which includes a first organic protection layer and a second inorganic protection layer, and increases the thermal conductivity, sealing property and structural strength of the device. CN109950419B discloses an OLED device packaging structure, a display device and a packaging method, wherein the packaging structure can effectively prevent or remove water and oxygen, ensure the drying of electrodes or organic functional layers, and prolong the service life of the OLED device. The above patents all provide resin-based packaging materials, but with the demands of panel production on cost reduction, energy consumption reduction and the like, the performance requirements of the packaging materials, especially the film thickness, water vapor transmittance and shrinkage rate of the packaging materials, are high, and the packaging requirements of high-performance display elements cannot be met.
Based on the requirement of high-performance display element packaging, the display element packaging material which has the characteristics of uniform filler particle size and good stability, can form a thin protective film when used as the display element packaging material, has adhesive strength and low water vapor permeability and has a good market prospect is developed.
Disclosure of Invention
The invention aims to provide a display element packaging material which has the characteristics of uniform filler particle size and good stability, can form a thin protective film when used as a display element packaging material, and has adhesive strength and low water vapor permeability.
In view of the above, the present invention fills this need in the art by providing silicon-containing epoxy compounds and compositions thereof.
In one aspect, the present invention relates to a silicon-containing epoxy compound having a structure represented by formula 1-1, formula 1-2, or formula 1-3:
wherein m is a positive integer selected from 1-5, and n is a positive integer selected from 1-5; r 1 Or R 2 A group selected from:
further, the present invention provides a silicon-containing epoxy compound, which comprises:
in another aspect, the present invention relates to a composition comprising any of the silicon-containing epoxy compounds of the structures shown in formulas 1-1, 1-2, or 1-3.
The composition provided by the invention further comprises phenolic epoxy resin, aliphatic epoxy resin, cationic initiator, coupling agent and solid filler.
Further, in the composition provided by the invention, by mass fraction, the proportion of the silicon-containing epoxy compound in the composition is 10-40%, the proportion of the novolac epoxy resin is 10-40%, the proportion of the aliphatic epoxy resin is 3-20%, and the total proportion of the silicon-containing epoxy compound, the novolac epoxy resin and the aliphatic epoxy resin is 30-80%; in the composition, the cationic initiator accounts for 0.01-5 wt%, the coupling agent accounts for 0.1-10 wt%, and the solid filler accounts for 20-40 wt%.
In the composition provided by the invention, the novolac epoxy resin is one of phenol novolac epoxy resin, bisphenol A novolac epoxy resin and bisphenol F novolac epoxy resin, and the aliphatic epoxy resin is one of a compound shown in a formula 2-1 and a compound shown in a formula 2-2
The cationic initiator comprisesOne of sulfonium salt, phosphonium salt, quaternary ammonium salt, diazonium salt and iodonium salt, wherein the anion part of the sulfonium salt, the phosphonium salt, the quaternary ammonium salt, the diazonium salt and the iodonium salt is BF 4 - 、PF 6 - 、SbF 6 - One of (1); the coupling agent comprises a silane coupling agent, and the silane coupling agent comprises 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-aminopropyl trimethoxy silane and 3-isocyanate propyl trimethoxy silane; the solid filler comprises one of alumina, magnesium silicate, diatomite, silicon dioxide and titanium dioxide, and the particle size of the solid filler is 0.1-15 mu m.
In some possible embodiments, methods for improving the application performance of the composition in an electronic display element by adding auxiliary materials, which are commonly used in the industries of adding an antioxidant to the composition to improve the stability of the composition, adding a toughening agent to improve the toughness of a cured product, adding a thixotropic agent (such as fumed silica, organic bentonite, polyamide wax and the like) to change the processability and stability of the composition, and the like, are all considered to be included in the scope of the invention.
On the other hand, the present invention does not specifically limit the curing mode of the composition. Illustratively, the curing mode of the composition provided by the invention is UV light-heat dual curing, the added cationic initiator is selected from one of sulfonium salt, phosphonium salt, quaternary ammonium salt, diazonium salt and iodonium salt, and the anion part of the sulfonium salt, the phosphonium salt, the quaternary ammonium salt, the diazonium salt and the iodonium salt is BF 4 - 、PF 6 - 、SbF 6 - One of (1); preferably, the cationic initiator is a sulfonium salt, and the mass fraction of the cationic initiator in the composition is 0.01-5%; illustratively, the cationic initiator is selected from UVI1176, UVI1190, UVI6974, UVI6976, UVI6990, UVI6992, SP-150, SP-170, FC-508, FC-512, IRGACURE290, and the like; in some possible embodiments, a thermal initiator can be added without affecting the performance of the composition, and the thermal initiator is 0.01-5% by mass of the composition.
Specifically, the present invention provides a method for curing a composition comprising: photocuring was carried out under a 365nm UV mercury lamp and then thermal curing was continued in an oven at 80 ℃.
The present invention has been accomplished by a highly reactive cationic resin composition which can form a thin protective film when used as a display element encapsulating material, while having adhesive strength and low water vapor permeability. The invention further claims the use of the composition according to the invention in the encapsulation of electronic display elements and an electronic display element in which the cover layer material comprises the compound according to the invention or the composition according to the invention.
Compared with the prior art, the invention has the following beneficial effects or advantages:
the present invention provides a silicon-containing epoxy resin, and provides a photocurable resin composition comprising the silicon-containing epoxy compound. The silicon-containing epoxy resin has high reaction activity, the resin composition can be quickly cured under the ultraviolet irradiation-heating condition, the phenomenon of oxygen inhibition does not exist in the curing process, and the obtained cured product has the characteristics of high thermal stability and high adhesive strength, has low water vapor transmittance, and is particularly suitable for packaging electronic display elements.
Drawings
FIG. 1 is a TGA chart of a cured product of the resin composition shown in test group 2 of example 5.
FIG. 2 is a TGA chart of a cured product of the resin composition shown in the comparative example 5.
FIG. 3 is a photomicrograph of a film of the resin composition shown in test group 2 of example 5.
Detailed Description
The following examples are given to illustrate the technical aspects of the present invention, but the present invention is not limited to the following examples.
Example 1
This example provides a method for synthesizing a compound of formula 1-1-3, which is similar to the example, and the structure of the compound is shown in formula 1-1-1, formula 1-1-2, formula 1-1-4, formula 1-1-5, formula 1-1-6, formula 1-1-7, or formula 1-1-8.
200mL of tetrahydrofuran and 20.0g of the compound of formula 1-1-3-1 were added to a reaction flask, and after nitrogen was introduced to remove the air, 110mL of sodium bis (trimethylsilyl) amide tetrahydrofuran solution (2.0M in THF) and 20.0g of the compound of formula 1-1-3-2 were continuously added, and the reaction was stirred at room temperature for 3 hours. TLC monitoring raw materials complete reaction, reaction liquid is washed to neutral, organic phase filtration and decompression after removing solvent and low boiling point compounds, 29.0g compounds formula 1-1-3-3, yield 73.2%.
200mL of tetrahydrofuran, 20.0g of the compound of formula 1-1-3-3, 13.2g of an aqueous solution of sodium hydroxide dissolved in 30mL of water, and 0.92g of tetrabutylammonium chloride were added to a reaction flask, stirred for 30min, added with 24.3g of the compound of formula 1-1-3-4, and heated to 50 ℃ to continue the reaction for 4 h. After the raw materials are completely reacted, cooling to room temperature, washing the reaction solution to be neutral, filtering an organic phase, and removing the solvent and the low-boiling-point compound under reduced pressure to obtain 26.8g of a compound shown as a formula 1-1-3, wherein the yield is 82.9 percent, and the nuclear magnetic characterization data of the compound is as follows: 1 H NMR(400MHz,CDCl3)δ7.35-7.49(m,10H),4.03(d,J＝6.4Hz,2H),3.55-3.72(m,10H),3.27-3.38(m,6H),2.44-2.67(m,12H)。
example 2
This example provides a method for synthesizing a compound of formula 1-2-1, which is similar to the example, and the structure of the compound is shown in formula 1-2-2, formula 1-2-3, formula 1-2-4, formula 1-2-5, formula 1-2-6, formula 1-2-7, or formula 1-2-8.
200mL of tetrahydrofuran and 20.0g of the compound of formula 1-2-1-1 were added to a reaction flask, and after nitrogen was introduced to remove air, 68.5mL of sodium bis (trimethylsilyl) amide tetrahydrofuran solution (2.0M in THF) and 19.6g of the compound of formula 1-2-1-2 were further added, and the reaction was stirred at room temperature for 3 hours. TLC monitors that the raw materials are completely reacted, the reaction solution is washed to be neutral, the organic phase is filtered, and the solvent and the low boiling point compound are removed under reduced pressure, so that 25.9g of the compound shown as the formula 1-2-1-3 is obtained, and the yield is 65.9%.
200mL of tetrahydrofuran, 20.0g of the compound of formula 1-2-1-3, 4.2g of an aqueous solution of sodium hydroxide dissolved in 30mL of water, and 0.28g of tetrabutylammonium chloride were added to a reaction flask, stirred for 30min, then 7.7g of the compound of formula 1-1-3-4 was added, and the reaction was continued for 4h by heating to 50 ℃. Cooling to room temperature after the raw materials completely react, washing the reaction solution to be neutral, filtering an organic phase, and removing the solvent and the low-boiling-point compound under reduced pressure to obtain 20.9g of the compound shown as the formula 1-2-1, wherein the yield is 87.5 percent, and the nuclear magnetism characterization data is as follows: 1 H NMR(400MHz,CDCl3)δ7.14(d,J＝6.0Hz,4H),7.00(d,J＝6.0Hz,4H),6.67(m,2H),6.35(d,J＝8.8Hz,2H),6.39(d,J＝12.4Hz,2H),4.63(m,2H),4.05(m,2H),3.75(m,2H),3.59(m,2H),3.35-3.52(m,6H),2.47-2.63(m,6H),0.65(s,12H)；
example 3
This example provides a method for synthesizing a compound of formula 1-3-1, which is similar to the example, and the structure of the compound is shown in formula 1-3-2, formula 1-3-3, formula 1-3-4, formula 1-3-5, formula 1-3-6, formula 1-3-7, or formula 1-3-8.
Adding 300mL of dichloromethane, 20.0g of compound formula 1-3-1-1 and 12.2g of triethylamine into a reaction bottle, cooling the reaction system to 0 ℃, dropwise adding 18.2g of oxalyl chloride, naturally heating to room temperature after dropwise adding, and continuously stirring for 2 h. And (3) after the raw materials completely react, removing the solvent and unreacted micromolecules in the reaction liquid under reduced pressure, then dropwise adding the reaction liquid into a dichloromethane solution of 12.2g of the compound formula 1-3-3-1, stirring and reacting for 2 hours, washing the reaction liquid to be neutral after the reaction is completely finished, filtering an organic phase, and removing the solvent and the low-boiling-point compound under reduced pressure to obtain 22.0g of the compound formula 1-3-1-2 with the yield of 76.2%.
200mL of tetrahydrofuran, 20.0g of the compound of formula 1-3-1-2, 8.0g of an aqueous solution of sodium hydroxide dissolved in 20mL of water, 0.55g of tetrabutylammonium chloride were added to a reaction flask, stirred and reacted for 30min, 18.4g of the compound of formula 1-1-3-4 was added, and the reaction solution was heated to 50 ℃ and stirred for 2 h. Cooling to room temperature after the raw materials completely react, washing the reaction solution to be neutral, filtering an organic phase, and removing the solvent and the low-boiling-point compound under reduced pressure to obtain 16.8g of the compound shown as the formula 1-3-1 with the yield of 57.3%, wherein the nuclear magnetism characterization data is as follows: 1 HNMR(400MHz,CDCl3)δ7.82(d,J＝6.0Hz,4H),6.93(d,J＝6.0Hz,4H),4.13-4.37(m,6H),3.32-3.58(m,12H),2.37-2.63(m,12H),0.16(s,6H)。
example 4
This example provides a method for preparing a composition comprising any of the silicon-containing epoxy compounds having the structure shown in formulas 1-1, 1-2, or 1-3.
The component ratios in parts by mass are shown in table 1.
TABLE 1 compositions of different Components
The above components were uniformly and sufficiently mixed by a stirrer, and degassed in a homogenizer to obtain the composition for display element encapsulation.
Curing the composition: the resin composition prepared above was coated on a release film with a thickness of 100 μm using a coater, and the prepared film was irradiated with ultraviolet light having a wavelength of 365nm at 1500mJ/cm 2 And then baked in an oven at 80 ℃ for 30 min.
And (4) evaluating the performance of the composition. The following properties were evaluated for each composition in table 1:
1. viscosity of the oil
For each of the resin compositions obtained in examples and comparative examples, the viscosity of the composition at 25 ℃ was measured using a rotary viscometer.
2. Thermal stability
Testing the glass transition temperature of the cured resin composition shown in the table 1 by using a Differential Scanning Calorimeter (DSC), wherein the testing temperature range is from room temperature to 300 ℃, the heating rate is 10 ℃/min, the nitrogen flow is 30mL/min, and the glass transition temperature of the cured resin to be tested is recorded;
and testing the heat loss mass change of the cured material by using a thermogravimetric analyzer, wherein the testing temperature range is from room temperature to 600 ℃, the heating rate is 10 ℃/min, the nitrogen flow is 30mL/min, and the temperature of 5% weight loss of the cured material to be tested in the nitrogen atmosphere is recorded.
3.Outgas
Adding the prepared packaging adhesive into a sample bottle, sealing, and irradiating under 365nm ultraviolet light to 1500mJ/cm 2 And then baked in an oven at 80 ℃ for 30 min. And detecting the content of organic matters in the gas in the sample bottle by a VOC detector.
4. Water vapor transmission rate
A film of the composition was prepared in a thickness of 100 μm using a coater and irradiated under ultraviolet light having a wavelength of 365nm at 1500mJ/cm 2 And then baked in an oven at 80 ℃ for 30min, and the water vapor transmission rate of the product under the conditions of 60 ℃ and 90% of relative humidity is tested by a moisture-penetrability tester.
5. Adhesive strength
A10 μm thick film of the composition was prepared on a glass base plate using a coater, irradiated with ultraviolet light having a wavelength of 365nm at 1500mJ/cm2, and then baked in an oven at 80 ℃ for 30 min. And after the cured film is cooled to room temperature, cutting the film into hundreds of grids by using a hundreds of grids cutter, wherein the cutter point and the film form an angle of 45 degrees in the cutting process, and the cutter point needs to scratch the glass bottom plate. After cutting, using a soft brush to brush off scraps, adhering a 3M transparent adhesive tape on the scribed hundred grids, applying force to firmly adhere the adhesive tape, then holding one end of the adhesive tape, tearing the adhesive tape at an angle of 60 degrees with the film, and judging the adhesion strength of the cured composition according to the falling-off condition of the film on the glass bottom plate. The case where the film was hardly peeled off was "Δ", the case where the film was slightly peeled off but the peeled area was less than 5% was "o", and the case where the peeled area was more than 5% but less than 15% was "excellent". The results of the composition performance tests shown in Table 1 are shown in Table 2 below.
TABLE 2 results of resin composition Property test
The "viscosity" properties of the compositions in the table reflect the flowability of the compositions; "Tg, TGA" reflects the stability of the composition under heating conditions of the cured product after UV-thermal curing; "outgas" represents the amount of organic volatile gases released by the composition during curing; the water vapor permeability reflects the moisture isolation capability of a cured product film, and the adhesion strength reflects the adhesion condition of the cured composition to a glass substrate, and reflects the protection capability of the cured product to the internal environment of the display element.
As can be seen from Table 2, the viscosity of the composition obtained in the range of the adding proportion of each component of the composition provided by the invention is between 10W and 50W, and the cured product has higher thermal stability (the glass transition temperature Tg is more than 120 ℃, the 5% thermal weight loss temperature is more than 150 ℃) after UV irradiation-thermal curing, and less organic volatile gas is released in the curing process; the cured product film of the composition provided by the invention has stronger water vapor isolation capability and stronger adhesion to a glass substrate, and can provide stable protection for a packaged display element.
Example 5
This example provides a comparative test of the performance of a composition containing a silicon epoxy compound versus a composition not containing a silicon epoxy compound.
The component ratios in parts by mass are shown in table 3.
TABLE 3 compositions of different Components
Note: the aliphatic epoxy resin is 2021P, CellOxide, the cationic initiator is triaryl sulfonium hexafluorophosphate, the coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the solid filler is magnesium silicate.
The above components were uniformly and sufficiently mixed by a stirrer, and degassed in a homogenizer to obtain the composition for display element encapsulation.
Curing the composition: the resin composition prepared above was coated on a release film with a thickness of 100 μm using a coater, and the prepared film was irradiated with ultraviolet light having a wavelength of 365nm at 1500mJ/cm 2 And then baked in an oven at 80 ℃ for 30 min.
And (4) evaluating the performance of the composition. The resin compositions obtained in the test group and the comparative group were evaluated for their performances in the same manner as in example 4, and the respective performance test methods were the same as in example 4. The results of the composition performance tests shown in Table 3 are shown in Table 4 below.
TABLE 4 results of resin composition Property test
From Table 4, it can be seen that the compositions prepared using the resins of the present invention have higher Tg temperatures, which are increased by 15% to 40% over the comparative compositions; in addition, the 5% thermal weight loss temperature is improved by 2-8%, and the outgas test result shows that the amount of the organic volatile gas released by the composition in the curing process is reduced by 35-60%, which indicates that the cured product of the composition in the curing process and after curing has good thermal stability. The water vapor transmission rate detection result shows that the water vapor transmission rate of the 100 mu m film cured product of the composition prepared by the resin is 55-75 percent of that of a comparison sample; the adhesion test result shows that the composition provided by the invention has stronger adhesion to glass; therefore, the composition provided by the invention can provide better water and oxygen resisting conditions for the display element and ensure the stability of the environment where the element is located.
As can be seen from fig. 1 and 2, the composition prepared by the resin of the present invention has higher 1% thermal weight loss temperature and 5% thermal weight loss temperature, i.e. better thermal stability, compared with the comparative group. In addition, the film photomicrograph shown in fig. 3 also shows that the composition provided by the invention can provide better water and oxygen resisting conditions for the display element and ensure the stability of the environment where the element is located.
In view of the foregoing, the present invention provides an epoxy resin having good thermal stability and its use in a photocurable resin composition for electronic display applications. The resin composition provided by the invention adopts UV light-heat dual curing, the cured product has good thermal stability, high adhesion strength and low water vapor transmittance, and can provide better protection for a display element when being applied to the packaging of the display element, so that the resin composition has a stronger advantage in the aspect of packaging protection for the display element.
As described above, the present invention can be preferably implemented, and the above-mentioned embodiments only describe the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various changes and modifications of the technical solution of the present invention made by those skilled in the art without departing from the design spirit of the present invention shall fall within the protection scope defined by the present invention.
Claims (10)
1. A silicon-containing epoxy compound is characterized in that the structure is shown as formula 1-1, formula 1-2 or formula 1-3:
wherein m is a positive integer selected from 1-5, and n is a positive integer selected from 1-5;
R 1 or R 2 A group selected from:
2. the silicon-containing epoxy compound according to claim 1, comprising:
3. the silicon-containing epoxy compound according to claim 1, comprising:
4. the silicon-containing epoxy compound according to claim 1, comprising:
5. a composition comprising the silicon-containing epoxy compound according to any one of claims 1 to 4.
6. The composition of claim 5, further comprising a novolac epoxy resin, an aliphatic epoxy resin, a cationic initiator, a coupling agent, and a solid filler.
7. The composition according to claim 6, wherein the composition comprises, by mass, 10% to 40% of the silicon-containing epoxy compound, 10% to 40% of the novolac epoxy resin, 3% to 20% of the aliphatic epoxy resin, and 30% to 80% of the silicon-containing epoxy compound, the novolac epoxy resin, and the aliphatic epoxy resin; in the composition, the cationic initiator accounts for 0.01-5 wt%, the coupling agent accounts for 0.1-10 wt%, and the solid filler accounts for 20-40 wt%.
8. The composition of claim 6, wherein the novolac epoxy resin is one of phenol novolac epoxy resin, bisphenol a novolac epoxy resin, and bisphenol F novolac epoxy resin, and the aliphatic epoxy resin is one of a compound represented by formula 2-1 and a compound represented by formula 2-2
The cation initiator comprises one of sulfonium salt, phosphonium salt, quaternary ammonium salt, diazonium salt and iodonium salt, and the anion part of the sulfonium salt, the phosphonium salt, the quaternary ammonium salt, the diazonium salt and the iodonium salt is
One of (1); the coupling agent comprises a silane coupling agent, and the silane coupling agent comprises 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3-aminopropyl trimethoxy silane and 3-isocyanate propyl trimethoxy silane; the above-mentionedThe solid filler comprises one of alumina, magnesium silicate, diatomite, silicon dioxide and titanium dioxide, and the particle size of the solid filler is 0.1-15 mu m.
9. Use of the silicon-containing epoxy compound according to any one of claims 1 to 4 in an encapsulating material for electronic display elements.
10. Use of the composition of any one of claims 5 to 9 in the encapsulation of electronic display elements.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199276A (en) * | 2011-03-16 | 2011-09-28 | 大连理工大学 | Silicon-containing epoxy resin composition for light-emitting diode (LED) package and preparation method thereof |
| CN104914675A (en) * | 2015-04-08 | 2015-09-16 | 乐道战略材料有限公司 | Photosensitivity siloxane and hyperbranched polyether polyol-containing photosensitive resin composition used for used for three-dimensional rapid moulding |
| CN112979692A (en) * | 2021-03-01 | 2021-06-18 | 宁波公牛电器有限公司 | Modified silane compound, hand feeling coating, electrical product and preparation method |
| CN113816929A (en) * | 2021-09-29 | 2021-12-21 | 西安瑞联新材料股份有限公司 | Aliphatic epoxy compound and pouring sealant prepared from same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199276A (en) * | 2011-03-16 | 2011-09-28 | 大连理工大学 | Silicon-containing epoxy resin composition for light-emitting diode (LED) package and preparation method thereof |
| CN104914675A (en) * | 2015-04-08 | 2015-09-16 | 乐道战略材料有限公司 | Photosensitivity siloxane and hyperbranched polyether polyol-containing photosensitive resin composition used for used for three-dimensional rapid moulding |
| CN112979692A (en) * | 2021-03-01 | 2021-06-18 | 宁波公牛电器有限公司 | Modified silane compound, hand feeling coating, electrical product and preparation method |
| CN113816929A (en) * | 2021-09-29 | 2021-12-21 | 西安瑞联新材料股份有限公司 | Aliphatic epoxy compound and pouring sealant prepared from same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115404030A (en) * | 2021-05-27 | 2022-11-29 | 双叶电子工业株式会社 | Curable resin composition and organic EL element |
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