CN117143559A - Mini LED polysiloxane packaging glue with uniform formability and high adhesion, and preparation method and application thereof - Google Patents
Mini LED polysiloxane packaging glue with uniform formability and high adhesion, and preparation method and application thereof Download PDFInfo
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- CN117143559A CN117143559A CN202311048902.8A CN202311048902A CN117143559A CN 117143559 A CN117143559 A CN 117143559A CN 202311048902 A CN202311048902 A CN 202311048902A CN 117143559 A CN117143559 A CN 117143559A
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- polysiloxane
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- -1 polysiloxane Polymers 0.000 title claims abstract description 137
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 135
- 239000003292 glue Substances 0.000 title claims abstract description 95
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 57
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 49
- 229920000570 polyether Polymers 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 54
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 10
- 101150065749 Churc1 gene Proteins 0.000 claims description 10
- 102100038239 Protein Churchill Human genes 0.000 claims description 10
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 3
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims description 3
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- GBFVZTUQONJGSL-UHFFFAOYSA-N ethenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C=C GBFVZTUQONJGSL-UHFFFAOYSA-N 0.000 claims description 3
- YWZHEUFCDPRCAD-OWOJBTEDSA-N (e)-pent-2-ene-1,5-diol Chemical compound OCC\C=C\CO YWZHEUFCDPRCAD-OWOJBTEDSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 9
- 229920000297 Rayon Polymers 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 23
- 229910052697 platinum Inorganic materials 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 15
- 239000010439 graphite Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 230000009974 thixotropic effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YWZHEUFCDPRCAD-UHFFFAOYSA-N pent-2-ene-1,5-diol Chemical compound OCCC=CCO YWZHEUFCDPRCAD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Abstract
The application relates to the field of viscose, and particularly discloses uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue, and a preparation method and application thereof, wherein the packaging glue comprises a component A and a component B, and specifically comprises the following raw materials in percentage by mass: a component: 60-80% of branched chain alkenyl polysiloxane, 2-10% of linear chain alkenyl polysiloxane and 0.1-0.5% of catalyst; and the component B comprises the following components: 10-20% of hydrogen-containing polysiloxane, 0.1-1% of inhibitor, 1-10% of filler and 1-5% of functional auxiliary agent. According to the application, the functional auxiliary agent containing the polyether chain segment and the polar group is introduced, so that the prepared Mini LED polysiloxane packaging glue has excellent bonding strength to a Mini LED substrate coated with ink, high reliability, uniform formability after curing, high light emitting efficiency, light transmittance maintained at more than 99%, hardness at more than 45D and excellent comprehensive performance.
Description
Technical Field
The application relates to the field of adhesives, in particular to a Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness, and a preparation method and application thereof.
Background
With the development of the LED industry, mini LEDs are the key development of the next stage of the LED industry. The Mini LED has the advantages of OLED, well solves the defects of high cost and short service life of the OLED, and has the advantages of zonal light control, high contrast and high color rendering compared with the traditional LED display.
The Mini LED polysiloxane packaging glue is covered on the chip in a lens mode, so that good optical refraction and chip protection effects can be achieved, and the light-emitting angle of the Mini LED chip is larger. On the one hand, the packaging glue used by the traditional LED at present cannot meet the packaging requirement of the Mini LED, on the other hand, because the traditional LED chip is provided with a dam to prevent the packaging glue from flowing so as to enable the packaging glue to be stably solidified and molded, and the Mini LED chip is smaller in size, and the periphery of the chip is not provided with the dam structure to prevent the glue from flowing, the Mini LED polysiloxane packaging glue is required to have the characteristic of dispensing and molding, and the light-emitting requirement of the chip can be met only by the convex lens shape; on the other hand, the Mini LED substrate is different from the traditional LED substrate, most of the Mini LED substrate can be covered with a layer of ink, and has higher requirements on the adhesion of packaging glue, and the Mini LED substrate needs to have stable adhesion performance with an ink interface. The Mini LED polysiloxane packaging glue on the market generally has the conditions of non-uniform shape or deformation after solidification, so that the uniform light-emitting requirement of the chip cannot be met after the packaging glue is covered on the chip, the problem of low adhesion combined with the ink interface of the base material also exists, the reliability of the Mini LED chip is lower, the yield of a finished product is low, and the use requirement of a customer cannot be met.
Disclosure of Invention
In order to solve the problems of uneven shape and lower adhesiveness on the surface of a chip substrate of the current Mini LED packaging glue after solidification, the application provides the Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness, and the preparation and application thereof.
In a first aspect, the application provides a Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness, which adopts the following technical scheme:
the Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness comprises a component A and a component B, and specifically comprises the following raw materials in percentage by mass:
in the component B, the functional auxiliary agent is obtained by hydrosilylation reaction of hydrogen-containing polysiloxane, unsaturated polyether and polar group-containing unsaturated compound, and the total molar quantity of carbon-carbon double bonds of the unsaturated polyether and carbon-carbon double bonds of the polar group-containing unsaturated compound is smaller than the molar quantity of hydrogen atoms in the hydrogen-containing polysiloxane;
the functional auxiliary agent comprises at least one of cyclic hydrogen polysiloxane and hydrogen branched polysiloxane;
the molecular structural formula of the unsaturated polyether is as follows: r is R 5 O(R 6 O) P H, wherein R 5 Unsaturated hydrocarbons selected from C2-C10; r is R 6 An alkylene group selected from C2-C10, more preferably C2-C6; p satisfies: p is more preferably more than or equal to 1 and less than or equal to 20, and is more preferably more than or equal to 2 and less than or equal to 8; the unsaturated compound containing polar group comprises vinylmethyldiethoxy silane, vinyltri (2-methoxyethoxy) silane, vinyltriisopropoxy silane, vinyltriisopropenoxy silane, gamma-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyAt least one of phenylsilane, 3-methacryloxypropyl methyldimethoxysilane, 1, 4-butenediol, 5-hexen-1, 2-ol, and 2-penten-1, 5-diol.
By adopting the technical scheme, the functional auxiliary agent which is obtained by the addition reaction of the hydrogen-containing polysiloxane, the unsaturated polyether and the polar group-containing unsaturated compound and contains the polyether chain segment and the polar group is introduced, and the compatibility of other raw materials such as branched chain alkenyl-containing polysiloxane, straight chain alkenyl-containing polysiloxane and hydrogen-containing polysiloxane is combined, so that the prepared Mini LED polysiloxane packaging glue has excellent bonding strength to the Mini LED substrate coated with the printing ink, the bonding strength is higher than 3MPa, the bonding force is good, the reliability is higher, the forming property after curing is uniform, compared with the non-curing deformation, the standard deviation of the height and width is less than or equal to 0.2, the height-width ratio is more than 0.3, the light extraction efficiency is high, the light transmittance is still maintained above 99%, the hardness is above 45D, and the comprehensive performance is excellent.
Specifically, the functional auxiliary agent is prepared by performing hydrosilylation reaction between double bonds in unsaturated polyether and polar group-containing unsaturated compound and hydrogen atoms in hydrogen-containing polysiloxane, and introducing a polyether chain segment and a large amount of polar groups into the polysiloxane; the functional auxiliary agent is applied to Mini LED packaging glue, the polyether chain segment of the functional auxiliary agent can improve the thixotropic property of the packaging glue, the formability is good, and the polar groups (such as alkoxy and hydroxyl) of the functional auxiliary agent can effectively improve the bonding strength of the packaging glue to the base material of the ink-containing layer, and the reliability and the yield are improved.
Preferably, the mass percentages of the component A and the component B are as follows:
preferably, the mass percentages of the component A and the component B are as follows:
preferably, the viscosity of the component A at 25 ℃ is 100-10000 mPas, preferably 500-3000 mPas, including but not limited to 500 mPas, 600 mPas, 700 mPas, 800 mPas, 900 mPas, 1000 mPas, 1200 mPas, 1500 mPas, 1800 mPas, 2000 mPas, 2200 mPas, 2500 mPas, 2800 mPas, 3000 mPas, etc.
Preferably, the viscosity of the component B at 25 ℃ is 100-20000 mPas, preferably 1000-15000 mPas, including but not limited to 1000 mPas, 1200 mPas, 1500 mPas, 2000 mPas, 3000 mPas, 4000 mPas, 5000 mPas, 6000 mPas, 7000 mPas, 8000 mPas, 9000 mPas, 10000 mPas, 12000Pa s, 13000 mPas, 14000 mPas, 15000 mPas, etc.
By adopting the technical scheme, the viscosity can be adjusted, the leveling property of the component A and the component B is improved, the compatibility of the component A and the component B is improved, and uniform mixing is facilitated, so that the stable Mini LED polysiloxane packaging glue is prepared.
Preferably, in the component A, the branched alkenyl-containing polysiloxane has the following molecular structural formula: (R) 1 3 SiO 0.5 ) a (R 1 2 SiO) b (R 1 SiO 1.5 ) c (SiO 2 ) d (OH) e ；
Wherein a, b, c, d, e is a molar ratio satisfying: a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 2, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0 and less than or equal to 1; more preferably, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 1.5, d=0 and less than or equal to 0 and less than or equal to e is more than or equal to 0 and less than or equal to 0.5, and even more preferably, a is more than or equal to 0.1 and less than or equal to 0.3, b is more than or equal to 0.1 and less than or equal to 0.2, c is more than or equal to 0.1 and less than or equal to 1.0, d=0 and e is more than or equal to 0.1 and less than or equal to 0.3;
wherein R is 1 Independently selected from one of C2-C12 unsaturated olefin, C1-C12 alkane, and C6-C12 aromatic unsaturated hydrocarbon group; preferred R 1 Independently selected from one of vinyl, methyl and phenyl.
Preferably, the branched alkenyl-containing polysiloxane has a viscosity of 100 to 30000 mPa-s, preferably 500 to 30000 mPa-s, more preferably 500 to 25000 mPa-s, at 25 ℃, including, but not limited to, 500 mPa-s, 1000 mPa-s, 1500 mPa-s, 2000 mPa-s, 2500 mPa-s, 3000 mPa-s, 4000 mPa-s, 5000 mPa-s, 8000 mPa-s, 10000 mPa-s, 15000 mPa-s, 20000 mPa-s, 25000 mPa-s, 30000 mPa-s, and the like;
preferably, the branched alkenyl-containing polysiloxane has a refractive index of 1.41 to 1.54, preferably 1.43 to 1.54, more preferably 1.45 to 1.50;
preferably, the branched alkenyl-containing polysiloxane has an alkenyl mass content of 1% to 6%, where the alkenyl mass content is the mass percent of alkenyl groups in 100g of branched alkenyl-containing polysiloxane.
By adopting the technical scheme, the adhesive can be uniformly mixed with materials such as straight-chain alkenyl-containing polysiloxane and the like, reacts with hydrogen-containing polysiloxane to generate stable polysiloxane packaging adhesive, has high bonding strength with a substrate, and has excellent refractive index of the prepared adhesive applied to a MiniLED and high light emitting efficiency.
Preferably, in the component A, the linear alkenyl-containing polysiloxane has the following molecular structural formula: (R) 2 3 SiO 0.5 ) f (R 2 2 SiO) g ；
Wherein f and g satisfy: f is more than or equal to 0 and less than or equal to 5, g is more preferably more than or equal to 0 and less than or equal to 50, f is more preferably more than or equal to 0 and less than or equal to 5, g is more preferably more than or equal to 10 and less than or equal to 20, f is more preferably more than or equal to 2 and less than or equal to 3, and g is more preferably more than or equal to 10 and less than or equal to 15;
wherein R is 2 Independently selected from one of C2-C12 unsaturated olefin, C1-C12 alkane, C6-C12 aromatic unsaturated hydrocarbon group, more preferably R 2 Independently selected from one of vinyl, methyl and phenyl;
preferably, the linear alkenyl-containing polysiloxane has a viscosity of 50 to 10000 mPas, preferably 100 to 5000 mPas, more preferably 100 to 2500 mPas, including but not limited to 100 mPas, 200 mPas, 500 mPas, 800 mPas, 1000 mPas, 1500 mPas, 2000 mPas, 2500 mPas, etc. at 25 ℃;
preferably, the linear alkenyl-containing polysiloxane has a refractive index of 1.41 to 1.54, preferably 1.43 to 1.54, more preferably 1.45 to 1.50;
preferably, the linear alkenyl-containing polysiloxane has an alkenyl mass content of 1% to 6%.
By adopting the technical scheme, the preparation method can react with hydrogen-containing polysiloxane to generate stable polysiloxane packaging glue, has high bonding strength, and the prepared Mini LED packaging material has high refractive index and light emitting efficiency.
Preferably, in the functional auxiliary agent, the molecular structural formula of the cyclic hydrogen-containing polysiloxane is as follows: (R) 3 HSiO) n The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 3 At least one selected from hydrogen group, phenyl group and methyl group, and at least contains one hydrogen group and phenyl group; n satisfies the following: n is more preferably more than or equal to 3 and less than or equal to 10, and is more preferably more than or equal to 4 and less than or equal to 8; further preferably, the cyclic hydrogen-containing polysiloxane is selected from (PhHSiO) 4 (Me 2 SiO) 2 。
The molecular structural formula of the branched polysiloxane containing hydrogen is as follows:
(R 4 3 SiO 0.5 ) n1 (R 4 2 SiO) n2 (R 4 SiO 1.5 ) n3 (SiO 2 ) n4 (OH) n5 ；
wherein R is 4 Independently selected from one of hydrogen group, C1-C12 alkane, C6-C12 aromatic unsaturated hydrocarbon group, and at least contains one hydrogen group; preferably R 4 Independently selected from one of hydrogen group, phenyl group and methyl group, and at least contains one hydrogen group; n1-n5 satisfy: n1 is more than or equal to 2 and less than or equal to 10, n2 is more than or equal to 0 and less than or equal to 20, n3 is more than or equal to 0 and less than or equal to 20, n4 is more than or equal to 0 and less than or equal to 20, and n5 is more than or equal to 0 and less than or equal to 20; more preferably, n1 is more than or equal to 2 and less than or equal to 6, n2 is more than or equal to 4 and less than or equal to 8, n3 is more than or equal to 2 and less than or equal to 3, n4=0 and n5=0;
more preferably, the branched polysiloxane containing hydrogen is selected from (Me 3 SiO 0.5 ) 2 (HMe 2 SiO 0.5 ) 4 (PhMeSiO) 6 (MeSiO 1.5 ) 2 。
By adopting the technical scheme, the excessive hydrogen-containing polysiloxane in the functional auxiliary agent and the hydrogen-containing polysiloxane in the component B can be compatible similarly, so that the compatible dispersion of the component A and the component B is promoted, and the stability of the glue is improved; and the addition reaction is carried out with branched chain polysiloxane containing alkenyl and straight chain polysiloxane containing alkenyl groups, so that the adhesive cement has adhesiveness and excellent formability.
Preferably, in the functional auxiliary agent, the unsaturated polyether is selected from CH 2 ＝CHCH 2 O(CH 2 CH 2 O) 2 H、CH 2 ＝CHCH 2 O(CH 2 CH 2 O) 6 At least one of H.
By adopting the technical scheme, unsaturated bonds in unsaturated polyether can be subjected to addition reaction with hydroxyl groups in hydrogen-containing polysiloxane in the functional additive preparation raw material, and the polyether can endow the glue with certain thixotropic property.
Preferably, in the functional auxiliary agent, the unsaturated compound containing polar groups comprises at least one of vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, vinyltriisopropenyloxysilane, gamma-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 1, 4-butenediol, 5-hexen-1, 2-ol and 2-pentene-1, 5-diol.
By adopting the technical scheme, the adhesive strength of the packaging glue to the base material containing the ink layer can be effectively improved by introducing polar groups such as alkoxy, hydroxyl and the like, and the reliability and the yield of the Mini LED are improved.
Preferably, in the functional auxiliary agent, the total molar amount of the carbon-carbon double bond of the unsaturated polyether and the carbon-carbon double bond of the polar group-containing unsaturated compound is smaller than the molar amount of the hydrogen atoms in the hydrogen-containing polysiloxane;
preferably, the ratio of the total molar amount of carbon-carbon double bonds of the unsaturated polyether and carbon-carbon double bonds of the polar group-containing unsaturated compound to the molar amount of hydrogen atoms in the hydrogen-containing polysiloxane is 1:1-4, more preferably 1:2-4, still more preferably 1:2-3, including but not limited to 1:2.25, 1:2.35, 1:2.45, 1:2.5, 1:2.8, 1:3.0, etc.;
the hydrogen atoms in the hydrogen-containing polysiloxane and the unsaturated polyether and the double bonds in the polar group-containing unsaturated compound are subjected to hydrosilylation reaction, wherein the molar quantity of the hydrogen atoms of the hydrogen-containing polysiloxane in the functional auxiliary agent is controlled to be larger than that of the carbon-carbon double bonds, so that the hydrogen atoms are excessive, the prepared functional auxiliary agent contains unreacted hydrogen atoms, has chemical activity, can participate in the curing reaction of the packaging glue and become a part of a chemical crosslinking network, and can effectively avoid the phenomenon that the surface of the packaging glue after curing is sticky and dust-stained due to precipitation of the micromolecular auxiliary agent in the subsequent use process, so that the light-emitting efficiency is affected.
Preferably, the molar ratio of unsaturated bonds of the unsaturated polyether to unsaturated bonds of the polar group-containing unsaturated compound is 1:0.5-3, more preferably 1:0.8-2, including but not limited to 1:0.8, 1:1.0, 1:1.2, 1:1.4, 1:1.6, 1:1.8, etc.
By adopting the technical scheme, the polyether chain segment of unsaturated polyether and the polar group of unsaturated compound can be introduced into polysiloxane, and the prepared packaging glue has excellent thixotropic stability and bonding strength, and improves the reliability and yield of processing application.
Preferably, the functional auxiliary agent is prepared by a preparation method comprising the following preparation steps,
mixing hydrogen-containing polysiloxane, unsaturated polyether and polar group-containing unsaturated compound, and carrying out catalytic reaction to obtain the functional auxiliary agent.
Preferably, the temperature of the reaction is 70-90 ℃, more preferably 80-90 ℃; the reaction time is 4 to 6 hours, more preferably about 5 hours.
Preferably, the functional auxiliary catalytic reaction is carried out in a solvent; the solvent includes toluene, cyclohexanone, etc.
Preferably, the catalyst used in the catalytic reaction comprises a platinum catalyst, more preferably a graphite oxide supported platinum catalyst; the catalyst is used in an amount (Pt concentration) of 20 to 40ppm, more preferably about 30 ppm.
Preferably, the catalytic reaction further comprises post-treatment, specifically removing the catalyst, and distilling under reduced pressure to remove the solvent, thereby finally obtaining the functional auxiliary agent.
Preferably, in the component B, the molecular structural formula of the hydrogen-containing polysiloxane is as follows: (R) 7 3 SiO 0.5 ) h (R 7 2 SiO) l (R 7 SiO 1.5 ) m ；
Wherein h, l, m satisfy: h is more than or equal to 0 and less than or equal to 5, l is more than or equal to 0 and less than or equal to 20, m is more than or equal to 0 and less than or equal to 55, and preferably, h, l and m are all 1; r is R 7 Independently selected from at least one of hydrogen, C1-C12 alkane, C6-C12 aromatic unsaturated hydrocarbon group, preferably R 7 Independently selected from at least one of hydrogen group, methyl group and phenyl group;
preferably, the hydrogen-containing polysiloxane has a viscosity of 50-20000 mPas, preferably 100-10000 mPas, more preferably 500-5000 mPas at 25 ℃, including but not limited to 500 mPas, 600 mPas, 700 mPas, 1000 mPas, 1500 mPas, 2000 mPas, 2500 mPas, 3000 mPas, 3500 mPas, 4000 mPas, 4500 mPas, 5000 mPas, etc.;
preferably, the hydrogen-containing polysiloxane has a refractive index of 1.41 to 1.54, preferably 1.43 to 1.54, more preferably 1.45 to 1.50;
preferably, the hydrogen-containing polysiloxane comprises 0.1% -1% of hydrogen matrix.
By adopting the technical scheme, the packaging glue with good bonding strength and good light transmittance is prepared by fully reacting with branched chain alkenyl-containing polysiloxane and linear chain alkenyl-containing polysiloxane under the action of the catalyst, and is applied to Mini LED packaging, and has good formability, small change of aspect ratio before and after solidification and high light-emitting efficiency.
Preferably, in the component A, the catalyst comprises a platinum catalyst, and the platinum catalyst comprises one or a combination of a plurality of chloroplatinic acid, karstedt platinum catalyst and Willing platinum catalyst.
By adopting the technical scheme, the catalytic efficiency is high, the reaction of the component A and the component B can be promoted to generate stable polysiloxane packaging glue, the curing formability is good, the aspect ratio is almost unchanged before and after curing, and the light emitting efficiency of the Mini LED is ensured.
Preferably, in the component B, the inhibitor comprises one or a combination of more of alkynol substances, vinyl ring bodies, polyvinyl silicone oil and maleate substances.
By adopting the technical scheme, the hydrogen-containing polysiloxane in the component B can be inhibited from reacting in the storage process, so that the component A and the component B can fully react after being mixed, and the thixotropic and stable packaging glue can be prepared.
Preferably, in the component B, the filler comprises one or more of titanium dioxide, zirconium dioxide, magnesium sulfate, calcium carbonate, fumed silica, precipitated silica, zinc oxide, kaolin, diatomite and ferric oxide. Further preferably, fumed silica having a surface subjected to a hydrophobic treatment is used; the particle size of the fumed silica subjected to the surface hydrophobic treatment is 1 to 100nm, more preferably 1 to 50nm; the specific surface area is 50-200mm 2 Preferably 100-150mm 2 /g。
By adopting the technical scheme, the adhesiveness and the bonding property of the packaging glue can be improved, so that the bonding strength of the packaging glue and the substrate ink layer is improved, and the thixotropic stability is good. In a second aspect, the application provides a preparation method of Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness, which adopts the following technical scheme:
a preparation method of Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness comprises the following steps:
uniformly mixing the materials of the component A to obtain the component A;
uniformly mixing the materials of the component B to obtain the component B;
the component A and the component B are independently packaged.
By adopting the technical scheme, the component A and the component B are respectively prepared, and the component A and the component B are mixed when in use, so that materials can be uniformly mixed and fully reacted, sizing is performed, the sizing fluidity is good, the aspect ratio is hardly changed before and after curing, the thixotropic stability is good, and the formability is good.
In a third aspect, the application provides an application of a Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness to Mini LEDs, which adopts the following technical scheme:
the application of the uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue on the Mini LED comprises the following steps: dispensing on the surface of the substrate chip, and then curing for 0.5-2 hours at the temperature of 110-130 ℃ to obtain the Mini LED packaging product.
By adopting the technical scheme, the surface of the substrate on which the packaging glue is stably cured and formed, the curing is sufficient, the aspect ratio of the point-shaped packaging glue before and after the curing is not greatly changed, the forming is stable, and the light emitting efficiency is good. Preferably, the dispensing pattern is in the shape of a convex lens.
Preferably, before dispensing and sizing, the base material is baked, preferably at 140-160 ℃ for 0.5-1.5 hours, so as to volatilize and remove volatile substances on the surface of the base material, improve the adhesion stability of the packaging glue on the surface of the base material, and have good formability.
In summary, the application has the following beneficial effects:
1. the application adopts the addition reaction of hydrogen-containing polysiloxane, unsaturated polyether and polar group-containing unsaturated compound to prepare the functional auxiliary agent containing polyether chain segments and polar groups, and combines the compatibility of other raw materials such as branched chain alkenyl-containing polysiloxane, straight chain alkenyl-containing polysiloxane, hydrogen-containing polysiloxane and the like, so that the prepared Mini LED polysiloxane packaging glue has excellent bonding strength to the Mini LED base material coated with ink, uniform formability after solidification, light transmittance still kept above 99%, hardness above 45D and excellent comprehensive performance.
2. According to the functional auxiliary agent, double bonds in unsaturated polyether and unsaturated compounds containing polar groups are subjected to hydrosilylation reaction with hydrogen atoms in hydrogen-containing polysiloxane, polyether chain segments and a large number of polar groups are introduced into the polysiloxane, the polyether chain segments of the functional auxiliary agent are utilized to improve the thixotropic property of the packaging glue, the formability is good, the polar groups (such as alkoxy and hydroxyl) of the functional auxiliary agent can effectively improve the bonding strength of the packaging glue to a substrate containing an ink layer, and the functional auxiliary agent is applied to the Mini LED packaging glue to improve the bonding strength, the forming stability, the reliability and the yield of the Mini LED packaging glue.
3. The molar weight of hydrogen atoms in the functional auxiliary agent is controlled to be larger than the molar weight of carbon-carbon double bonds, so that the hydrogen atoms are excessive, the prepared functional auxiliary agent contains unreacted hydrogen atoms, has chemical activity, can participate in the subsequent packaging glue curing reaction, improves the material compatibility of the packaging glue, does not have the conditions of precipitation and the like in the use process, and avoids the phenomenon of reduced light-emitting efficiency caused by sticky and dust-sticking on the surface of the cured packaging glue.
Drawings
Fig. 1 is a schematic diagram of a Mini LED structure encapsulated with the polysiloxane encapsulating glue according to the present application.
Reference numerals: 1. the cured packaging glue; 2. a light emitting chip; 3. printing ink; 4. a substrate.
Detailed Description
The application is described in further detail below with reference to fig. 1 and the examples.
The sources of the raw materials in the following examples and comparative examples of the present application are shown in the following table 1, and the sources of the raw materials in the following examples and comparative examples are specifically selected for the experiment, and the sources of the raw materials are not limited to the following manufacturer types in the actual production process of the Mini LED polysiloxane packaging glue.
TABLE 1 sources of raw materials and information comparison Table
Preparation example of functional auxiliary agent
Preparation example 1
The functional auxiliary agent for polysiloxane packaging glue is prepared by the following steps:
after 500mL of toluene was added to the reaction vessel, the following were added in order: 345g of branched polysiloxane containing phenyl groups and hydrogen atoms (the molar amount of the hydrogen atoms is 1 mol), 36.5g of unsaturated polyether (the molar amount of the carbon-carbon double bonds is 0.25 mol), 62g of gamma-methacryloxypropyl trimethoxysilane (the molar amount of the carbon-carbon double bonds is 0.25 mol), 3.33g of graphite oxide supported platinum catalyst (the Pt concentration is 30 ppm), heating the mixture in an oil bath at 80 ℃ for 5 hours after uniform mixing, filtering the graphite oxide supported platinum catalyst, distilling toluene under reduced pressure, and obtaining the functional auxiliary agent containing polyether segments and polar groups.
In this preparation example, the branched polysiloxane containing phenyl groups and hydrogen atoms has the molecular structural formula: (Me) 3 SiO 0.5 ) 2 (HMe 2 SiO 0.5 ) 4 (PhMeSiO) 6 (MeSiO 1.5 ) 2 ；
The molecular structural formula of the unsaturated polyether is as follows: CH (CH) 2 ＝CHCH 2 O(CH 2 CH 2 O) 2 H。
Preparation example 2
The functional auxiliary agent for polysiloxane packaging glue is prepared by the following steps:
after 500mL of toluene was added to the reaction vessel, the following were added in order: 345g of branched polysiloxane containing phenyl groups and hydrogen atoms (the molar amount of the hydrogen atoms is 1 mol), 36.5g of unsaturated polyether (the molar amount of the carbon-carbon double bonds is 0.25 mol), 40g of vinylmethyldiethoxysilane (the molar amount of the carbon-carbon double bonds is 0.25 mol), 1.87g of graphite oxide supported platinum catalyst (the concentration of Pt is 30 ppm), heating for 5h in an oil bath pot at 80 ℃ after uniform mixing, filtering to remove the graphite oxide supported platinum catalyst, and distilling toluene under reduced pressure to obtain the functional auxiliary agent containing polyether segments and polar groups.
In this preparation example, the branched polysiloxane containing phenyl groups and hydrogen atoms has the molecular structural formula: (Me) 3 SiO 0.5 ) 2 (HMe 2 SiO 0.5 ) 4 (PhMeSiO) 6 (MeSiO 1.5 ) 2 ；
The molecular structural formula of the unsaturated polyether is as follows: CH (CH) 2 ＝CHCH 2 O(CH 2 CH 2 O) 2 H。
Preparation example 3
The functional auxiliary agent for polysiloxane packaging glue is prepared by the following steps:
after 500mL of toluene was added to the reaction vessel, the following were added in order: 159g of cyclic polysiloxane containing phenyl groups and hydrogen atoms (the molar amount of the hydrogen atoms is 1 mol), 80.5g of unsaturated polyether (the molar amount of the carbon-carbon double bonds is 0.25 mol), 22g of 1, 4-butylene glycol (the molar amount of the carbon-carbon double bonds is 0.25 mol), 1.87g of graphite oxide supported platinum catalyst (the Pt concentration is 30 ppm), heating for 5h in an oil bath pot at 80 ℃ after uniform mixing, filtering to remove the graphite oxide supported platinum catalyst, and distilling off toluene under reduced pressure to obtain the functional auxiliary agent containing polyether segments and polar groups.
In this preparation, the cyclic polysiloxane containing phenyl groups and hydrogen atoms has the molecular structural formula: (PhHSiO) 4 (Me 2 SiO) 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular structural formula of the unsaturated polyether is as follows: CH (CH) 2 ＝CHCH 2 O(CH 2 CH 2 O) 6 H。
Preparation of comparative example 1
A functional auxiliary agent is prepared by the following steps:
after 500mL of toluene was added to the reaction vessel, the following were added in order: 159g of cyclic polysiloxane containing phenyl and hydrogen atoms (the molar quantity of the hydrogen atoms is 1 mol), 205g of unsaturated polyether (the molar quantity of carbon-carbon double bonds is 0.50 mol) and 2.96g of graphite oxide supported platinum catalyst (the Pt concentration is 30 ppm), heating the mixture for 5h in an oil bath pot at 80 ℃ after uniform mixing, filtering the mixture to remove the graphite oxide supported platinum catalyst, and distilling toluene under reduced pressure to obtain the functional auxiliary agent without polar groups.
In this comparative preparation, the cyclic polysiloxane containing phenyl groups and hydrogen atoms has the molecular structural formula: (PhHSiO) 4 (Me 2 SiO) 2 ；
The molecular structural formula of the unsaturated polyether is as follows: CH (CH) 2 ＝CHCH 2 O(CH 2 CH 2 O) 8 H。
Preparation of comparative example 2
A functional auxiliary agent is prepared by the following steps:
after 500mL of toluene was added to the reaction vessel, the following were added in order: 345g of branched polysiloxane containing phenyl and hydrogen atoms (the molar amount of the hydrogen atoms is 1 mol), 73g of unsaturated polyether (the molar amount of carbon-carbon double bonds is 0.50 mol), 1.84g of graphite oxide supported platinum catalyst (Pt concentration is 30 ppm), uniformly mixing, heating in an oil bath pot at 80 ℃ for 5 hours, filtering to remove the graphite oxide supported platinum catalyst, and distilling toluene under reduced pressure to obtain the functional auxiliary agent without polar groups.
In this comparative preparation, the branched polysiloxane containing phenyl groups and hydrogen atoms has the molecular structural formula: (Me) 3 SiO 0.5 ) 2 (HMe 2 SiO 0.5 ) 4 (PhMeSiO) 6 (MeSiO 1.5 ) 2 ；
The molecular structural formula of the unsaturated polyether is as follows: CH (CH) 2 ＝CHCH 2 O(CH 2 CH 2 O) 2 H。
Preparation of comparative example 3
A functional auxiliary agent is prepared by the following steps:
after 500mL of toluene was added to the reaction vessel, the following were added in order: 172.5g of branched polysiloxane containing phenyl groups and hydrogen atoms (the molar amount of the hydrogen atoms is 0.5 mol), 62g of gamma-methacryloxypropyl trimethoxysilane (the molar amount of carbon-carbon double bonds is 0.25 mol) and 3.10g of graphite oxide supported platinum catalyst (the Pt concentration is 30 ppm), are uniformly mixed, heated in an oil bath at 80 ℃ for 5 hours, filtered to remove the graphite oxide supported platinum catalyst, and toluene is distilled off under reduced pressure to obtain the functional auxiliary agent without polyether segments.
In this comparative preparation, the branched polysiloxane containing phenyl groups and hydrogen atoms has the molecular structural formula: (Me) 3 SiO 0.5 ) 2 (HMe 2 SiO 0.5 ) 4 (PhMeSiO) 6 (MeSiO 1.5 ) 2 。
Preparation of comparative example 4
The functional auxiliary agent without active hydrogen atoms is different from the preparation example 1 in that the total molar amount of hydrogen atoms in the raw materials is smaller than the total molar amount of vinyl, and the specific process comprises the following steps:
after 500mL of toluene was added to the reaction vessel, the following were added in order: 345g of branched polysiloxane containing phenyl groups and hydrogen atoms (the molar amount of the hydrogen atoms is 1 mol), 146g of unsaturated polyether (the molar amount of the carbon-carbon double bonds is 1 mol), 62g of gamma-methacryloxypropyl trimethoxysilane (the molar amount of the carbon-carbon double bonds is 0.25 mol), 3.33g of graphite oxide supported platinum catalyst (the Pt concentration is 30 ppm), heating for 5h in an oil bath pot at 80 ℃ after uniform mixing, filtering to remove the graphite oxide supported platinum catalyst, and distilling toluene under reduced pressure to obtain the functional auxiliary agent without active hydrogen atoms.
In this preparation example, the branched polysiloxane containing phenyl groups and hydrogen atoms has the molecular structural formula: (Me) 3 SiO 0.5 ) 2 (HMe 2 SiO 0.5 ) 4 (PhMeSiO) 6 (MeSiO 1.5 ) 2 ；
The molecular structural formula of the unsaturated polyether is as follows: CH (CH) 2 ＝CHCH 2 O(CH 2 CH 2 O) 2 H。
Examples
Examples 1 to 3
The Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness is prepared by the following steps:
mixing branched chain alkenyl polysiloxane, linear chain alkenyl polysiloxane and a catalyst, uniformly stirring at a rotating speed of 1500rpm, filtering and defoaming to obtain a component A;
mixing hydrogen-containing polysiloxane, an inhibitor, a filler and a functional additive, uniformly stirring at a rotating speed of 2000rpm, filtering and defoaming to obtain a component B;
and mixing the component A and the component B according to the weight ratio of 1:1 to prepare the Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness.
The sources and amounts of the raw materials for examples 1-3 are shown in Table 2 below.
Comparative example
Comparative examples 1 to 4
Comparative examples 1 to 4 differ from example 1 in that: the sources of the functional auxiliaries are different, see in particular table 2 below.
Comparative example 5
This comparative example 5 differs from example 1 in that: the functional auxiliary agent of the example 1 is replaced by branched polysiloxane containing phenyl and hydrogen atoms, and the molecular structural formula of the branched polysiloxane containing phenyl and hydrogen atoms is as follows:
(Me 3 SiO 0.5 ) 2 (HMe 2 SiO 0.5 ) 4 (PhMeSiO) 6 (MeSiO 1.5 ) 2 。
TABLE 2 comparison of raw material sources and amounts for examples 1-3 and comparative examples 1-5
Performance test the polysiloxane potting glues prepared in examples 1 to 3 and comparative examples 1 to 5 were tested for viscosity, refractive index, aspect ratio before curing, appearance after curing, light transmittance, hardness, adhesive strength, aspect ratio, and specific test methods and test results are shown below.
Method for detecting
(1) Viscosity test of glue before curing: the viscosity of the glue at the rotating speed of 10rpm is tested by referring to a single cylinder rotational viscosimeter method in the national standard GB/T2794-2013 adhesive viscosity measurement;
(2) Refractive index test of glue before curing: testing by referring to the method in national standard GB/T614-2006 chemical reagent refractive index determination;
(3) Appearance detection after curing: visual observation of appearance after curing;
the evaluation criteria were referenced as follows: o: transparent, x: slightly cloudy;
(4) Light transmittance after curing test: the method in the national standard GB/T24102008 transparent plastic transmittance measurement is referred to for testing;
(5) Hardness test after curing: pouring mixed glue into a cylinder mould with the length and the width of 30mm and the thickness of 10mm, curing for 1h at the temperature of 120 ℃, taking out a solid glue block, putting the solid glue block into a water bath kettle with the temperature of 30 ℃, after the temperature is stable, referring to national standard GB/T2411-2008, and testing the hardness of the glue block by using a Shore D hardness tester;
(6) And (3) testing the bonding strength after curing: coating Mini LED ink on a PCB board as a base material, and testing the glue to be tested by referring to the national standard GB/T315412015 method for tensile and shear bonding strength of a fine ceramic interface;
(7) Aspect ratio testing: the substrate was baked at 150 c for 1H to volatilize volatile materials from the substrate surface. Using a piezoelectric spray valve to glue, dispensing glue on the surface of a substrate chip, wherein the glue-applying quantity is 50, and the glue-dispensing pattern is a convex lens; and measuring the width and the height of the packaging glue before and after curing by using laser, calculating the standard deviation of the width and the height, and calculating the average aspect ratio before and after curing. The cured Mini LED is shown in figure 1, and the cured packaging glue is still convex lens.
(II) detection results
Table 3 table of polysiloxane encapsulating glue performance data for examples 1-3 and comparative examples 1-5
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From the data, the bonding strength of the Mini LED packaging glue in the embodiment 1-3 is 3.1-3.8MPa, and the reliability is high; the standard deviation of the height and the width is less than or equal to 0.2, the uniformity of the formed shape is good, the average value of the height-width ratio is more than or equal to 0.35, and the light emitting efficiency is high; the light transmittance is still maintained above 99%, and the hardness is above 45D.
In contrast, in both comparative examples 1 and 2, the functional auxiliary agent containing no polar group and only polyether segment was used, in comparative example 3, the functional auxiliary agent containing no polyether segment and only polar group was used, and in comparative example 5, the branched polysiloxane containing phenyl group and hydrogen atom was used as the functional auxiliary agent, the adhesive strength of the glue prepared in the above comparative examples was significantly reduced, the thixotropic property was reduced, and the average value of the aspect ratio after curing was reduced compared with that before curing, and in particular, the aspect ratio of comparative example 5 was significantly different before and after curing, and the molding uniformity was poor. The application shows that the functional auxiliary agent simultaneously containing polyether chain segments and polar groups is added into the packaging glue, and the dosage ratio of the functional auxiliary agent to other materials in the component A and the component B is controlled, so that the prepared packaging glue has better bonding strength to the Mini LED base material coated with the ink, and has the advantages of high reliability, good formability, high light emitting efficiency and excellent comprehensive performance.
The excessive hydrogen atoms in the functional auxiliary agents prepared in preparation examples 1-4 can participate in subsequent curing reaction, so that the bonding strength between the packaging glue and the PCB coated with the ink layer is further improved, the problem of reduced luminous efficiency caused by precipitation and stickiness of the functional auxiliary agent in the later use process is effectively avoided, and the functional auxiliary agent adopted in comparative example 4 does not contain excessive hydrogen atoms, so that the bonding strength, hardness and light transmittance are obviously reduced.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The Mini LED polysiloxane packaging glue with uniform formability and high adhesiveness is characterized in that: comprises a component A and a component B, and specifically comprises the following raw materials in percentage by mass:
a component: 60-80% of branched chain alkenyl polysiloxane;
2-10% of straight chain alkenyl polysiloxane;
0.1 to 0.5 percent of catalyst;
and the component B comprises the following components: 10-20% of hydrogen-containing polysiloxane;
0.1-1% of inhibitor;
1-10% of filler;
1-5% of functional auxiliary agent;
in the component B, the functional auxiliary agent is obtained by hydrosilylation reaction of hydrogen-containing polysiloxane and unsaturated polyether and polar group-containing unsaturated compound; the total molar amount of carbon-carbon double bonds of the unsaturated polyether and carbon-carbon double bonds of the polar group-containing unsaturated compound is less than the molar amount of hydrogen atoms in the hydrogen-containing polysiloxane;
the functional auxiliary agent comprises at least one of cyclic hydrogen polysiloxane and hydrogen branched polysiloxane;
the molecular structural formula of the unsaturated polyether is as follows: r is R 5 O(R 6 O) P H is formed; wherein R is 5 Unsaturated hydrocarbons selected from C2-C10; r is R 6 An alkylene group selected from C2-C10, more preferably C2-C6; p satisfies: p is more preferably more than or equal to 1 and less than or equal to 20, and is more preferably more than or equal to 2 and less than or equal to 8;
the polar group-containing unsaturated compound comprises at least one of vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, vinyltriisopropenyloxysilane, gamma-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 1, 4-butenediol, 5-hexene-1, 2-ol, 2-pentene-1, 5-diol.
2. The uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to claim 1, wherein the glue is characterized in that: in the component A, the molecular structural formula of the branched chain alkenyl-containing polysiloxane is as follows: (R) 1 3 SiO 0.5 ) a (R 1 2 SiO) b (R 1 SiO 1.5 ) c (SiO 2 ) d (OH) e ；
Wherein a, b, c, d, e is a molar ratio satisfying: a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 2, d is more than or equal to 0 and less than or equal to 0.5, and e is more than or equal to 0 and less than or equal to 1; more preferably, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 1.5, d is more than or equal to 0 and less than or equal to e is more than or equal to 0 and less than or equal to 0.5;
wherein R is 1 Independently selected from one of C2-C12 unsaturated olefin, C1-C12 alkane, and C6-C12 aromatic unsaturated hydrocarbon group;
preferably, the branched alkenyl-containing polysiloxane has a viscosity of 100 to 30000 mPa-s, preferably 500 to 30000 mPa-s, more preferably 500 to 25000 mPa-s at 25 ℃;
preferably, the branched alkenyl-containing polysiloxane has a refractive index of 1.41 to 1.54, preferably 1.43 to 1.54, more preferably 1.45 to 1.50;
preferably, the branched alkenyl-containing polysiloxane has an alkenyl mass content of 1% to 6%.
3. The uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to claim 1, wherein the glue is characterized in that: in the component A, the linear chain alkenyl-containing polysiloxane has the following molecular structural formula: (R) 2 3 SiO 0.5 ) f (R 2 2 SiO) g ；
Wherein f and g satisfy: f is more than or equal to 0 and less than or equal to 5, g is more preferably more than or equal to 0 and less than or equal to 50, f is more preferably more than or equal to 0 and less than or equal to 5, and g is more preferably more than or equal to 10 and less than or equal to 20;
wherein R is 2 Independently selected from one of C2-C12 unsaturated olefin, C1-C12 alkane, and C6-C12 aromatic unsaturated hydrocarbon group;
preferably, the linear alkenyl-containing polysiloxane has a viscosity of 50 to 10000 mPas, preferably 100 to 5000 mPas, more preferably 100 to 2500 mPas at 25 ℃;
preferably, the linear alkenyl-containing polysiloxane has a refractive index of 1.41 to 1.54, preferably 1.43 to 1.54, more preferably 1.45 to 1.50;
preferably, the linear alkenyl-containing polysiloxane has an alkenyl mass content of 1% to 6%.
4. The uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to claim 1, wherein the glue is characterized in that: in the functional auxiliary agent, the molecular structural formula of the cyclic hydrogen-containing polysiloxane is as follows: (R) 3 HSiO) n The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 3 At least one selected from hydrogen group, phenyl group and methyl group, and at least contains one hydrogen group and phenyl group; n satisfies the following: n is more preferably more than or equal to 3 and less than or equal to 10, and is more preferably more than or equal to 4 and less than or equal to 8;
the molecular structural formula of the branched polysiloxane containing hydrogen is as follows:
(R 4 3 SiO 0.5 ) n1 (R 4 2 SiO) n2 (R 4 SiO 1.5 ) n3 (SiO 2 ) n4 (OH) n5 ；
wherein R is 4 Independently selected from one of hydrogen group, C1-C12 alkane, C6-C12 aromatic unsaturated hydrocarbon group, and at least contains one hydrogen group; n1-n5 satisfy: n1 is more than or equal to 2 and less than or equal to 10, n2 is more than or equal to 0 and less than or equal to 20, n3 is more than or equal to 0 and less than or equal to 20, n4 is more than or equal to 0 and less than or equal to 20, and n5 is more than or equal to 0 and less than or equal to 20; more preferably, n1 is 2.ltoreq.6, n2 is 4.ltoreq.8, n3 is 2.ltoreq.3, n4=0, n5=0.
5. The uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to claim 1, wherein the glue is characterized in that: in the functional auxiliary agent, unsaturated polyether is selected from CH 2 =CHCH 2 O(CH 2 CH 2 O) 2 H、CH 2 =CHCH 2 O(CH 2 CH 2 O) 6 At least one of H.
6. The uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to claim 1, wherein the glue is characterized in that: in the functional auxiliary agent, the ratio of the total molar quantity of the carbon-carbon double bond of the unsaturated polyether and the carbon-carbon double bond of the unsaturated compound containing polar groups to the molar quantity of hydrogen atoms in the hydrogen-containing polysiloxane is 1:1-4, more preferably 1:2-4, and still more preferably 1:2-3;
preferably, the molar ratio of unsaturated bonds of the unsaturated polyether to unsaturated bonds of the polar group-containing unsaturated compound is 1:0.5 to 3, more preferably 1:0.8 to 2.
7. The uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to claim 1, wherein the glue is characterized in that: in the component B, the molecular structural formula of the hydrogen-containing polysiloxane is as follows: (R) 7 3 SiO 0.5 ) h (R 7 2 SiO) l (R 7 SiO 1.5 ) m ；
Wherein h, l, m satisfy: h is more than or equal to 0 and less than or equal to 5, l is more than or equal to 0 and less than or equal to 20, and m is more than or equal to 0 and less than or equal to 5; r is R 7 At least one independently selected from the group consisting of hydrogen radicals, C1-C12 alkanes, C6-C12 aromatic unsaturated hydrocarbon radicals;
preferably, the hydrogen-containing polysiloxane has a viscosity of 50-20000 mPas, preferably 100-10000 mPas, more preferably 500-5000 mPas at 25 ℃;
preferably, the hydrogen-containing polysiloxane has a refractive index of 1.41 to 1.54, preferably 1.43 to 1.54, more preferably 1.45 to 1.50;
preferably, the hydrogen-containing polysiloxane comprises 0.1% -1% of hydrogen matrix.
8. The uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to claim 1, wherein the glue is characterized in that: the inhibitor in the component B comprises one or a combination of more of alkynol substances, vinyl ring bodies, polyvinyl silicone oil and maleate substances.
9. A method for preparing the uniform-formability and high-adhesiveness Mini LED polysiloxane packaging glue according to any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
uniformly mixing the materials of the component A to obtain the component A;
uniformly mixing the materials of the component B to obtain the component B;
the component A and the component B are independently packaged.
10. Use of the uniform-formability, high-adhesion Mini LED polysiloxane encapsulating glue according to any one of claims 1-9 on Mini LEDs, characterized in that: the method comprises the following steps: dispensing on the surface of the substrate chip, and then curing for 0.5-2 hours at the temperature of 110-130 ℃ to obtain the Mini LED packaging product.
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| CN202311048902.8A CN117143559A (en) | 2023-08-18 | 2023-08-18 | Mini LED polysiloxane packaging glue with uniform formability and high adhesion, and preparation method and application thereof |
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| CN202311048902.8A CN117143559A (en) | 2023-08-18 | 2023-08-18 | Mini LED polysiloxane packaging glue with uniform formability and high adhesion, and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090294796A1 (en) * | 2006-05-11 | 2009-12-03 | Yoshitsugu Morita | Adhesive-Promoting Agent, Curable Organopolysiloxane Composition, and Semiconductor Device |
| CN103897404A (en) * | 2014-03-24 | 2014-07-02 | 惠州市安品新材料有限公司 | Application of modified polysiloxane in preparation of thixotropic addition type liquid silicone rubber |
| CN105802532A (en) * | 2016-05-26 | 2016-07-27 | 清远市美乐仕油墨有限公司 | Silicon boron tackifier, preparation method thereof and application thereof in double-component LED packaging gel |
| CN112979963A (en) * | 2020-12-30 | 2021-06-18 | 北京康美特科技股份有限公司 | Reactive silicone thixotropic agent, silicone packaging adhesive and LED element |
-
2023
- 2023-08-18 CN CN202311048902.8A patent/CN117143559A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090294796A1 (en) * | 2006-05-11 | 2009-12-03 | Yoshitsugu Morita | Adhesive-Promoting Agent, Curable Organopolysiloxane Composition, and Semiconductor Device |
| CN103897404A (en) * | 2014-03-24 | 2014-07-02 | 惠州市安品新材料有限公司 | Application of modified polysiloxane in preparation of thixotropic addition type liquid silicone rubber |
| CN105802532A (en) * | 2016-05-26 | 2016-07-27 | 清远市美乐仕油墨有限公司 | Silicon boron tackifier, preparation method thereof and application thereof in double-component LED packaging gel |
| CN112979963A (en) * | 2020-12-30 | 2021-06-18 | 北京康美特科技股份有限公司 | Reactive silicone thixotropic agent, silicone packaging adhesive and LED element |
| US20220204827A1 (en) * | 2020-12-30 | 2022-06-30 | Beijing Kmt Technology Co., Ltd. | Reactive organosilicon thixotropic agent, organosilicon encapsulation adhesive and led element |
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