CN114874255B - Silicon-containing epoxy compound and composition thereof - Google Patents
Silicon-containing epoxy compound and composition thereof Download PDFInfo
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- CN114874255B CN114874255B CN202210399835.3A CN202210399835A CN114874255B CN 114874255 B CN114874255 B CN 114874255B CN 202210399835 A CN202210399835 A CN 202210399835A CN 114874255 B CN114874255 B CN 114874255B
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 239000004593 Epoxy Substances 0.000 title claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 10
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 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
- 239000005022 packaging material Substances 0.000 claims description 10
- 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
- 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
- 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 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
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical group 0.000 claims description 3
- 150000001768 cations Chemical class 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
- 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
- 239000004843 novolac epoxy resin Substances 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011342 resin composition Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 238000002834 transmittance Methods 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000010408 film Substances 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000001723 curing Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005538 encapsulation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 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
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- -1 organobentonite Substances 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement 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
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000010409 thin film Substances 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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
Landscapes
- 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
Disclosed are a silicon-containing epoxy compound, and a composition comprising the same. The resin composition provided by the invention mainly comprises phenolic epoxy resin, aliphatic epoxy resin, cationic initiator, coupling agent and solid filler in addition to the silicon-containing epoxy compound, and is semitransparent at normal temperature and has good stability. By UV light-heat dual curing of the resin composition, oxygen polymerization inhibition phenomenon does not exist in the curing process, and the obtained cured product has the characteristics of high heat stability and high adhesive strength, has low water vapor transmittance, and is 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, organic thin film devices such as organic electroluminescent display devices and solar cells have been studied and developed greatly. The organic light-emitting display element commonly used at present is a film structure body with an organic photoelectric material layer sandwiched between a pair of electrodes which are opposite to each other, and the material has the characteristics of low energy consumption, good visual recognition, convenience in thinning and flexibility and the like because a backlight source is not needed, so that the organic light-emitting display element has very good application prospect. For such display element structures, stability and lifetime are greatly affected when the organic light emitting material layer or electrode is exposed to air. Therefore, the display element and the electrode must be isolated from air by the encapsulation material, which has high requirements for the adhesion strength, shrinkage, thermal stability and moisture vapor transmission rate of the encapsulation material used.
There are various resin compositions for sealing display elements on the market. CN109285969B discloses a packaging method of an OLED display element and an OLED display element, which include a first organic protective layer and a second inorganic protective layer, which increase the thermal conductivity, sealability and structural strength of the device. CN109950419B discloses an OLED device packaging structure, a display device and a packaging method, where the packaging structure can effectively prevent or remove water and oxygen, ensure drying of electrodes or organic functional layers, and prolong the service life of the OLED device. The above patents all provide packaging materials based on resin, but with the demands of panel production on the aspects of cost reduction, energy consumption reduction and the like, the performance requirements of the packaging materials, especially the film thickness, the water vapor transmittance and the shrinkage rate of the packaging materials, are higher, and the packaging requirements of high-performance display elements cannot be met.
Based on the packaging requirement of the high-performance display element, the display element packaging material which has the characteristics of uniform particle size and good stability of the filler, can form a thinner protective film when used as the display element packaging material, has both adhesive strength and low water vapor transmittance, and has good market prospect.
Disclosure of Invention
The invention aims to provide a display element packaging material which has the characteristics of uniform particle size and good stability of filler, can form a thinner protective film when used as the display element packaging material, and has adhesive strength and low water vapor transmittance.
In view of the above, the present invention meets 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 to 5, and n is a positive integer selected from 1 to 5; r is R 1 Or R is 2 A group selected from:
further, the silicon-containing epoxy compound provided by the invention comprises:
in another aspect, the present invention is directed to a composition comprising a silicon-containing epoxy compound having a structure as shown in any one of formulas 1-1, 1-2, or 1-3.
Further, 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, the silicon-containing epoxy compound accounts for 10% -40% of the composition, the phenolic epoxy resin accounts for 10% -40%, the aliphatic epoxy resin accounts for 3% -20%, and the total of the silicon-containing epoxy compound, the phenolic epoxy resin and the aliphatic epoxy resin accounts for 30% -80%; the composition comprises, by mass, 0.01% -5% of the cationic initiator, 0.1% -10% of the coupling agent and 20% -40% of the solid filler.
Further, in the composition provided by the invention, the phenolic epoxy resin is one of phenol type phenolic epoxy resin, bisphenol A type phenolic epoxy resin and bisphenol F type phenolic 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 2-2The 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, phosphonium salt, quaternary ammonium salt, diazonium salt and iodonium salt is BF 4 - 、PF 6 - 、SbF 6 - One of the following; the coupling agent comprises a silane coupling agent, wherein the silane coupling agent comprises 3- (2, 3-glycidoxy) 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, the methods of adding antioxidants to the compositions of the present invention to improve the stability of the compositions, adding toughening agents to improve the toughness of the cured products, adding thixotropic agents (e.g., fumed silica, organobentonite, polyamide waxes, etc.) to alter the processability and stability of the compositions, and improving their performance in electronic display devices by adding adjuvants, which are common in the industry, are considered to be within the scope of the present invention.
On the other hand, the present invention is not particularly limited in the manner of curing the composition. The curing mode of the composition provided by the invention is UV photo-thermal dual curing, and the added cationic initiator is selected from one of sulfonium salt, phosphonium salt, quaternary ammonium salt, diazonium salt and iodonium salt, wherein the anion part of the sulfonium salt, phosphonium salt, quaternary ammonium salt, diazonium salt and iodonium salt is BF 4 - 、PF 6 - 、SbF 6 - One of the following; preferably, the cationic initiator is sulfonium salt, and the mass fraction of the cationic initiator in the composition is 0.01% -5%; illustratively, the cationic initiator is selected from the group consisting of 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 also be added to the composition without affecting the properties of the composition, the thermal initiator being present in the composition at a ratio of 0.01% to 5% by mass.
Specifically, the present invention provides a method for curing a composition comprising: the photo-curing was carried out under a 365nm ultraviolet mercury lamp and then continued in an oven at 80 ℃.
The present invention has been achieved by a cationic resin composition having a high reactivity, which can form a thin protective film when used as a packaging material for display elements, and at the same time has the object of having adhesive strength and low water vapor permeability. Thus, the invention further claims the use of the composition of the invention in the encapsulation of electronic display elements and an electronic display element in which the cover material comprises the compound provided by the invention or the composition provided by 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 reactivity, the resin composition can be rapidly cured under the ultraviolet irradiation-heating condition, the oxygen polymerization inhibition phenomenon 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 graph of a cured product of the resin composition shown in test group 2 in example 5.
FIG. 2 is a TGA graph of a cured product of the resin composition shown in the comparative group in example 5.
FIG. 3 is a film micrograph of the resin composition of test group 2 of example 5.
Detailed Description
The following describes the technical aspects of the present invention with reference to examples, but the present invention is not limited to the following examples.
Example 1
The embodiment provides a method for synthesizing a compound of formula 1-1-3, wherein the structure is shown as 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, and the method for synthesizing the compound is similar to the embodiment.
200mL of tetrahydrofuran, 20.0g of compound formula 1-1-3-1 was added to the reaction flask, nitrogen was introduced to remove the excess air in the reaction flask, and then 110mL of a solution of sodium bis (trimethylsilyl) amide in tetrahydrofuran (2.0M in THF) was continuously added thereto, and 20.0g of compound formula 1-1-3-2 was reacted under stirring at room temperature for 3 hours. After TLC monitoring the complete reaction of the starting materials, the reaction solution was washed with water to neutrality, the organic phase was filtered and the solvent and low boiling point compounds were removed under reduced pressure to give 29.0g of compound of formula 1-1-3-3 in 73.2% yield.
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, 0.92g of tetrabutylammonium chloride were added to the reaction flask, and after stirring for 30 minutes, 24.3g of the compound of formula 1-1-3-4 was added, and the mixture was heated to 50℃for further reaction for 4 hours. Waiting for raw materialsAfter complete reaction, the reaction solution is cooled to room temperature, the reaction solution is washed to be neutral, the organic phase is filtered and then the solvent and the low boiling point compound are removed under reduced pressure, 26.8g of compound formula 1-1-3 is obtained, the yield is 82.9%, and the nuclear magnetism characterization data are 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
The embodiment provides a method for synthesizing a compound of formula 1-2-1, wherein the structure is shown as 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, and the method for synthesizing the compound is similar to the embodiment.
200mL of tetrahydrofuran, 20.0g of Compound 1-2-1-1 were added to the reaction flask, nitrogen was introduced to remove the excess air from the flask, 68.5mL of a solution of sodium bis (trimethylsilyl) amide in tetrahydrofuran (2.0M in THF) was further added thereto, 19.6g of Compound 1-2-1-2 was stirred at room temperature to react for 3 hours. After TLC monitoring the complete reaction of the starting materials, the reaction solution was washed with water to neutrality, the organic phase was filtered and the solvent and low boiling point compounds were removed under reduced pressure to give 25.9g of compound of formula 1-2-1-3 in 65.9% yield.
200mL of tetrahydrofuran, 20.0g of an aqueous solution of sodium hydroxide of the compound formula 1-2-1-3,4.2g of tetrabutylammonium chloride dissolved in 30mL of water, and 7.7g of the compound formula 1-1-3-4 were added after stirring for 30min, and the reaction was continued by heating to 50℃for 4 hours. After the raw materials are completely reacted, the reaction solution is cooled to room temperature, the reaction solution is washed to be neutral, the organic phase is filtered and then the solvent and the low boiling point compound are removed under reduced pressure, 20.9g of compound formula 1-2-1 is obtained, the yield is 87.5%, and the nuclear magnetism characterization data are 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
The embodiment provides a method for synthesizing a compound of formula 1-3-1, wherein the structure is shown as 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, and the method for synthesizing the compound is similar to the embodiment.
300mL of dichloromethane, 20.0g of compound formula 1-3-1-1 and 12.2g of triethylamine are added into a reaction bottle, the reaction system is cooled to 0 ℃, 18.2g of oxalyl chloride is added dropwise after the reaction system is cooled to 0 ℃, and the reaction bottle is naturally warmed to room temperature after the dropwise addition, and stirring is continued for 2h. After the raw materials are completely reacted, the solvent and unreacted micromolecules in the reaction solution are removed under reduced pressure, then 12.2g of a dichloromethane solution of the compound formula 1-3-3-1 is added dropwise, the reaction solution is stirred for 2 hours, after the reaction is completed, the reaction solution is washed to be neutral, the organic phase is filtered, the solvent and the low-boiling point compounds are removed under reduced pressure, 22.0g of the compound formula 1-3-1-2 is obtained, and the yield is 76.2%.
200mL of tetrahydrofuran, 20.0g of a 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 the reaction flask, and after stirring for 30 minutes, 18.4g of a compound of formula 1-1-3-4 was added, and the reaction mixture was heated to 50℃and stirred for 2 hours. After the raw materials are completely reacted, cooling to room temperature, washing the reaction liquid to be neutral, filtering an organic phase, removing a solvent and low boiling point compounds under reduced pressure to obtain 16.8g of compound formula 1-3-1, wherein the yield is 57.3%, and the nuclear magnetism characterization data are 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 one of the silicon-containing epoxy compounds having the structures shown in formula 1-1, formula 1-2 or formula 1-3.
The respective groups were allocated in parts by mass as shown in table 1.
TABLE 1 compositions of different compositions
The above components were uniformly and sufficiently stirred and mixed using a stirrer, and deaerated in a homogenizer to obtain the composition for display element encapsulation.
Curing the composition: the prepared resin composition was applied to a release film in 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 30min.
And evaluating the performance of the composition. The following performance evaluations were performed for each composition in table 1:
1. viscosity of the mixture
For each of the resin compositions obtained in examples and comparative examples, the viscosity of the composition at 25℃was measured using a rotational viscometer.
2. Thermal stability
The glass transition temperature of the cured product of the resin composition shown in Table 1 is measured by using a Differential Scanning Calorimeter (DSC), the measurement temperature ranges 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 product to be measured is recorded;
and (3) testing the heat loss mass change of the solidified material by using a thermogravimetric analyzer, wherein the testing temperature ranges from room temperature to 600 ℃, the heating rate is 10 ℃/min, the nitrogen flow is 30mL/min, and the temperature of the solidified material to be tested, which is subjected to weight loss of 5% in the nitrogen atmosphere, is recorded.
3.Outgas
Adding the prepared packaging adhesive into a sample bottle, sealing, and placing in 365nm wavelength ultravioletIrradiating 1500mJ/cm under external light 2 And then baked in an oven at 80 ℃ for 30min. And taking the gas in the sample bottle, and detecting the organic matter content in the gas by using a VOC detector.
4. Water vapor transmission rate
A100 μm thick film of the composition was prepared using a coater, and was irradiated with ultraviolet light of 365nm wavelength at 1500mJ/cm 2 Then baked in an oven at 80 ℃ for 30min, and tested by a moisture permeability tester for moisture vapor permeability under the condition of 60 ℃ and relative humidity of 90%.
5. Adhesive strength
A10 μm thick film of the composition was prepared on a glass base plate using a coater, placed under ultraviolet light of 365nm wavelength and irradiated at 1500mJ/cm2, and then baked in an oven at 80℃for 30 minutes. And (3) cutting the film into a hundred lattices by using a hundred lattice knife after the film of the cured product is cooled to room temperature, wherein a knife point forms an angle of 45 degrees with the film in the cutting process, and the knife point is required to scratch the glass bottom plate. And brushing off scraps by using a soft brush after cutting, adhering the 3M transparent adhesive tape to the scratched hundred grids and 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 smoothly, and judging the adhesion strength of the cured composition according to the falling condition of the film on the glass bottom plate. The case where the film was hardly peeled was defined as "delta", the case where the film was peeled slightly but the peeled area was less than 5% was defined as "o", and the case where the peeled area was more than 5% but less than 15% was defined as "o". The results of the performance tests for the compositions shown in Table 1 are shown in Table 2 below.
TABLE 2 results of Performance test of resin compositions
The "viscosity" properties of the compositions in the tables represent the flowability of the compositions; "Tg, TGA" reflects the stability of a composition after UV-thermal curing under heating; "outgas" represents the amount of organic volatile gases released by the composition during curing; the water vapor transmittance reflects the capability of the cured film to isolate water, and the adhesion strength reflects the adhesion condition of the composition to the glass substrate after curing, so that the capability of the cured film for protecting the internal environment of the display element is reflected.
From Table 2, it is clear that the viscosity of the composition obtained in the range of the addition ratio of each component of the composition provided by the invention is between 10W and 50W, the cured product has relatively high thermal stability (glass transition temperature Tg >120 ℃ C., 5% thermal weight loss temperature >150 ℃ C.) after UV irradiation-thermal curing, and less organic volatile gas is released during curing; the cured film of the composition provided by the invention has strong capability of isolating water vapor, has strong 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 properties of a composition containing a silicon epoxy compound versus a composition containing no silicon epoxy compound.
The respective groups were allocated in parts by mass as shown in table 3.
TABLE 3 compositions of different compositions
Note that: the aliphatic epoxy resin is 2021P, celloxide, the cation initiator is triarylsulfonium 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 stirred and mixed using a stirrer, and deaerated in a homogenizer to obtain the composition for display element encapsulation.
Curing the composition: the prepared resin composition was applied to a release film in 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 30min.
And evaluating the performance of the composition. The respective resin compositions obtained in the test group and the comparative group were evaluated for the performances in the same manner as described in example 4, and the respective performance test methods were the same as in example 4. The results of the performance tests for the compositions shown in Table 3 are shown in Table 4 below.
TABLE 4 results of Performance test of resin compositions
From Table 4, it can be seen that the compositions formulated with the resins of the present invention have a higher Tg temperature, 15% to 40% higher than the comparative compositions; in addition, the 5% thermal weight loss temperature is improved by 2% -8%, and the outgas test result shows that the organic volatile gas amount released by the composition in the curing process is reduced by 35% -60%, which indicates that the composition has good thermal stability in the curing process and after curing. The water vapor transmittance detection result shows that the water vapor transmittance of a 100 mu m film of a composition cured product prepared by using the resin of the invention is 55% -75% 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 good water and oxygen isolation conditions for the display element, and ensure the stability of the environment where the element is positioned.
As can be seen from fig. 1 and 2, the compositions formulated with the resins of the present invention have a higher 1% weight loss temperature and 5% weight loss temperature, i.e., better thermal stability, than the comparative group. In addition, the film photomicrograph shown in FIG. 3 also shows that the composition provided by the invention can provide good water and oxygen isolation conditions for the display element, and ensure the stability of the environment where the element is located.
In summary, the present invention provides an epoxy resin with good thermal stability and its application in a photocurable resin composition for electronic display field. The resin composition provided by the invention adopts UV light-heat dual curing, and the cured product has good thermal stability, high adhesion strength and low water vapor transmittance, and can provide better protection for the display element when being applied to encapsulation of the display element, so that the resin composition has stronger advantages in the aspect of encapsulation protection for the display element.
The present invention may be better implemented as described above, and the above examples are merely illustrative of preferred embodiments of the present invention and not intended to limit the scope of the present invention, and various changes and modifications made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the present invention without departing from the spirit of the design of the present invention.
Claims (7)
1. A silicon-containing epoxy compound, characterized in that the structure of the silicon-containing epoxy compound comprises:
2. a composition comprising the silicon-containing epoxy compound according to claim 1.
3. The composition of claim 2, further comprising a phenolic epoxy resin, an aliphatic epoxy resin, a cationic initiator, a coupling agent, and a solid filler.
4. A composition according to claim 3, wherein the composition comprises, in mass fraction, 10% to 40% of the silicon-containing epoxy compound, 10% to 40% of the phenolic epoxy resin, 3% to 20% of the aliphatic epoxy resin, and 30% to 80% of the total of the silicon-containing epoxy compound, the phenolic epoxy resin and the aliphatic epoxy resin; the composition comprises, by mass, 0.01% -5% of the cationic initiator, 0.1% -10% of the coupling agent and 20% -40% of the solid filler.
5. The composition according to claim 3, wherein the novolac epoxy resin is one of phenol novolac epoxy resin, bisphenol A novolac epoxy resin, 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 2-2The 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, phosphonium salt, quaternary ammonium salt, diazonium salt and iodonium salt is BF 4 - 、PF 6 - 、SbF 6 - One of the following; the coupling agent comprises a silane coupling agent, wherein the silane coupling agent comprises 3- (2, 3-glycidoxy) 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.
6. Use of the silicon-containing epoxy compound according to claim 1 in an electronic display element packaging material.
7. Use of a composition according to any one of claims 2 to 5 in packaging of electronic display elements.
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| 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 |
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