CN117801742A - Photo-thermal dual-curing epoxy adhesive for display device packaging, and preparation method and application thereof - Google Patents
Photo-thermal dual-curing epoxy adhesive for display device packaging, and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 36
- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 25
- 238000001723 curing Methods 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 239000004593 Epoxy Substances 0.000 claims abstract description 50
- 125000002091 cationic group Chemical group 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000005538 encapsulation Methods 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 34
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 34
- 238000007641 inkjet printing Methods 0.000 claims description 18
- 244000028419 Styrax benzoin Species 0.000 claims description 17
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 17
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 17
- 229960002130 benzoin Drugs 0.000 claims description 17
- 235000019382 gum benzoic Nutrition 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- -1 hexafluorophosphate Chemical compound 0.000 claims description 15
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 12
- 229920006335 epoxy glue Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000003003 spiro group Chemical group 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- HZEOUPCNUWSUFL-UHFFFAOYSA-N 4,5,5-trimethyl-4-pentan-3-yl-1H-imidazole Chemical compound C(C)C(C1(N=CNC1(C)C)C)CC HZEOUPCNUWSUFL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001029 thermal curing Methods 0.000 claims description 4
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 3
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 2
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 claims description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- CSHJJWDAZSZQBT-UHFFFAOYSA-N 7a-methyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21C CSHJJWDAZSZQBT-UHFFFAOYSA-N 0.000 claims description 2
- KSMGAOMUPSQGTB-UHFFFAOYSA-N 9,10-dibutoxyanthracene Chemical compound C1=CC=C2C(OCCCC)=C(C=CC=C3)C3=C(OCCCC)C2=C1 KSMGAOMUPSQGTB-UHFFFAOYSA-N 0.000 claims description 2
- RAWPGIYPSZIIIU-UHFFFAOYSA-N [benzoyl(phenyl)phosphoryl]-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 RAWPGIYPSZIIIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 2
- XVKKIGYVKWTOKG-UHFFFAOYSA-N diphenylphosphoryl(phenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 XVKKIGYVKWTOKG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 239000012298 atmosphere Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 description 27
- 230000001070 adhesive effect Effects 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- JFFYKITVXPZLQS-UHFFFAOYSA-N 2-methylidenepropane-1,3-diol Chemical compound OCC(=C)CO JFFYKITVXPZLQS-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- IGHHPVIMEQGKNE-OJOKCITNSA-N [(1s,2s,3r,4r)-3-(hydroxymethyl)-2-bicyclo[2.2.1]hept-5-enyl]methanol Chemical compound C1[C@@H]2C=C[C@H]1[C@H](CO)[C@@H]2CO IGHHPVIMEQGKNE-OJOKCITNSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- RGXKKPWZFFCHNE-UHFFFAOYSA-N [3-(hydroxymethyl)-3-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)(CO)CC1C2 RGXKKPWZFFCHNE-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000003678 scratch resistant effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- CWLNAJYDRSIKJS-UHFFFAOYSA-N triethoxymethoxyethane Chemical compound CCOC(OCC)(OCC)OCC CWLNAJYDRSIKJS-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of organic films, and relates to photo-thermal dual-curing epoxy adhesive for packaging display devices, and a preparation method and application thereof, wherein the photo-thermal dual-curing epoxy adhesive comprises the following raw materials in parts by weight: 5 to 35 parts of spiro-type curable cationic monomer, 25 to 85 parts of epoxy monomer, 10 to 25 parts of reactive diluent, 0.1 to 10 parts of photo-crosslinking initiator and 0.1 to 10 parts of photosensitizer. The epoxy adhesive can be directly cured in the atmosphere by selecting an epoxy solvent-free system, has no oxygen polymerization inhibition problem, has small curing volume shrinkage, and can reduce the stress applied to the packaged device in the curing shrinkage process. The volume expansion caused in the ring opening process of the polymer is reduced by selecting a plurality of spiro-type curable cationic monomers and adding the formula, the volume shrinkage effect of other epoxy monomers is further counteracted, and the film after photo-curing by using the epoxy adhesive has higher hardness and excellent scratch resistance, thereby being beneficial to realizing high-performance encapsulation of mu LED devices.
Description
Technical Field
The invention belongs to the technical field of organic films, and relates to photo-thermal dual-curing epoxy adhesive for packaging a display device, and a preparation method and application thereof.
Background
The existing display technology realizes ultrathin, flexible and foldable design of the display screen, and has the advantages of high luminous brightness, high contrast, vivid color, high response speed, low energy consumption and the like, and the display technology has gradually logged in the display field.
Display device integration and packaging technology has become one of the key factors in determining device performance. For example, TFE technology applied to OLEDs in encapsulation technology is currently mainly based on solvent-free systems of (meth) acrylic polymers, and film encapsulation (TFE) technology based on inkjet printing is commonly used, which faces serious oxygen inhibition problems during the photo-curing process in the atmosphere, and therefore can only polymerize in an inert gas environment, increasing the process cost. Meanwhile, in order to be compatible with flexible electronic devices, the hardness of the traditional ink-jet printing TFE ink is focused on the flexibility of a film, and the hardness and scratch resistance are generally poor, so that the traditional ink-jet printing TFE ink cannot be directly used for the outermost layer of the device. More seriously, the volume shrinkage of the existing (meth) acrylate TFE packages before and after curing is large (typically > 7%), which is very disadvantageous for packaging of display devices, such as OLED devices and Micro LED (Micro Light Emitting Diode Display, abbreviated as μled) devices based on group III-IV element compound semiconductors, for luminescent materials and wires. And the larger volume shrinkage during curing is usually accompanied by larger mechanical stress, which may apply larger stress to the LED pixel unit with a specific microstructure, and even damage the device structure and failure of the package.
For this reason, developing and designing new TFE inkjet printing inks is of great importance for future display device design and mass production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides photo-thermal dual-curing epoxy adhesive for packaging a display device, and a preparation method and application thereof, so as to solve the problems of low hardness, low adhesive force, high curing shrinkage and high residual stress of a curing packaging film formed by the current ink-jet printing ink.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the invention provides a photo-thermal dual-curing epoxy adhesive for display device packaging, which comprises the following raw materials in parts by weight: 5 to 35 parts of spiro-type curable cationic monomer, 25 to 85 parts of epoxy monomer, 10 to 25 parts of reactive diluent, 0.1 to 10 parts of photo-crosslinking initiator and 0.1 to 10 parts of photosensitizer.
Further, the photo-thermal dual-curing epoxy adhesive also comprises 0-10 parts of thermosetting agent.
Further, the epoxy adhesive has a surface tension of 27.2-45.2 dyne/cm and a viscosity of 10.1-30.8 cps at 25+ -5deg.C.
Specifically, the spiro-based curable cationic monomer comprises at least one of the following general formulas:
wherein R in the general formula I and the general formula II 1 、R 2 、R 3 、R 4 Is a polysubstituted five-membered or six-membered saturated alicyclic ring; y in the general formula III 1 Refers to a C1-C20 substituted or unsubstituted alkyl group, Y 2 、Y 3 And Y 4 Is a polysubstituted five-membered or six-membered saturated alicyclic ring or spiro ring.
Furthermore, the spiro-type curable cationic monomer is at least one of the formulas 1-12, namely the spiro-type curable cationic monomer can be independently involved in the composition of photo-thermal dual-cured epoxy glue, and can also be simultaneously involved in the composition of glue by a plurality of monomers.
Further, the epoxy monomer is used as a main structure and comprises one or more of epoxy cyclohexane ultraviolet light curable cationic monomers, 3, 4-epoxy cyclohexyl methyl formate, 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane, 2- (3, 4-epoxy cyclohexyl) ethyl triethoxy silane, tetrahydroxy diepoxide and glycidyl ether or epoxy cyclohexane structure formed by C2-C30 tetrahydric alcohol or pentahydric alcohol and glycerin.
Further, the reactive diluent comprises a monofunctional glycidyl ether or a polyfunctional glycidyl ether; specifically, it may be triethylene glycol divinyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycidoxy triglycidyl ether, C2 to C30 tetrahydric alcohol or glycidyl ether formed by pentahydric alcohol and glycerin.
Further, the photo-crosslinking initiator includes one or more of diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, 4-isobutylphenyl-4 '-tolylidine hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, mixed sulfonium hexafluorophosphate, benzoyldiphenyl phosphine oxide, dibenzoylphenyl phosphine oxide, 3' -dimethyl-2-methoxybenzophenone, camphorquinone, and diethyltetramethylimidazole.
Further, the photosensitizer comprises one or more of ethyl p-N, N-dimethylaminobenzoate, 2-isopropylthioxanthone, 9, 10-dibutoxyanthracene and benzoin dimethyl ether.
Further, the thermosetting agent comprises one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, modified methyl tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride and diethyl tetramethyl imidazole.
In a second aspect, the invention also provides a preparation method of the photo-thermal dual-curing epoxy adhesive for packaging the display device, which comprises the steps of adding the raw materials into a reaction container according to the corresponding parts by weight, and mixing and stirring by using a stirrer to obtain the epoxy packaging adhesive.
Specifically, the optical properties and mechanical properties of the organic film are as follows:
optical properties: the light transmittance of the organic film to the wavelength of 400-780 nm can reach 94.2-99.8%; the yellowing index is less than 0.5; haze less than 0.2; the refractive index of the film is between 1.5 and 1.6.
Mechanical properties: the hardness of the organic film after photo-curing is more than 4H; scratch 50 times with 2000 mesh steel wool without scratches. After photo-curing, the organic film is heat-resistant,Excellent resistance to chemical changes, light resistance and high temperature and high humidity test, and Water Vapor Transmittance (WVTR) of an organic film having a thickness of 30 μm<100g/m 2 24h (60 ℃,90% RH), meeting or exceeding the packaging requirements of the outermost or middle layer of the mu LED.
The application of the photo-thermal dual-curing epoxy adhesive for packaging the display device can be used as an organic barrier film for waterproof and oxygen-blocking of electronic components, and comprises the following specific steps:
1) The epoxy glue is adhered to the surface of the electronic component in a spin coating, blade coating or ink-jet printing mode;
2) And irradiating the epoxy glue with ultraviolet light with the wavelength of 250-400 nm for 30-600 s to cure the epoxy glue to form an organic film with the wavelength of 5-55 mu m so as to protect electronic devices. Wherein, the organic film obtained by photo-curing has excellent adhesion on different kinds of back layers, and the ASTM grade is 4B-5B.
Specifically, the electronic components include other electronic components such as a μled, an organic light emitting diode, a photosensor, or a photovoltaic device.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1. the epoxy solvent-free system is selected, so that the epoxy solvent-free system can be directly cured in the atmosphere, and the oxygen polymerization inhibition problem encountered when the (methyl) acrylic acid system is photo-cured in the atmosphere can be avoided. Meanwhile, the volume shrinkage effect of the epoxy system in the curing process is generally smaller than that of the (methyl) acrylic system, so that the stress applied to the packaged device by the TFE primary slurry in the curing shrinkage process can be effectively reduced.
2. The invention selects various spiro-type curable cationic monomers, and can cause certain volume expansion in the ring-opening process of the polymer after the formula is added, so that the volume shrinkage effect of other epoxy monomers is further counteracted. In addition, the film after photo-curing has higher hardness and excellent scratch resistance, and is excellent in heat resistance, chemical resistance, light resistance and high-temperature and high-humidity test, thereby being beneficial to realizing high-performance packaging of the mu LED device.
3. The invention realizes an alternative ultraviolet light independent curing mode by selecting a proper photo-crosslinking initiator and a photosensitizer; or selecting proper photo-crosslinking initiator, photosensitizer and thermosetting agent to realize alternative photo-thermal dual curing mode. Under the condition of curing by only using a photocrosslinking initiator and a photosensitizer, the cured epoxy adhesive can realize primary curing (the curing rate is more than 80 percent) under the irradiation of ultraviolet light with the wavelength of 250-400 nm. For the subsequent process, the initially cured sample can be placed at room temperature continuously, so that the curing rate of the sample is gradually increased to more than 90% under the action of dark reaction; or adding a thermosetting agent such as anhydride thermosetting agent into the system, and accelerating the curing of the initially photo-cured sample in an environment of 80 ℃ for 40min, so that the final film curing rate can reach about 95%. These two alternative curing modes will provide flexible curing conditions for the user, which can meet the use requirements of various manufacturing processes.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are not intended to represent all embodiments consistent with the invention. Rather, they are merely examples of certain aspects of the invention that are consistent with the details of the claims below.
The invention discloses a high-hardness scratch-resistant epoxy adhesive with low curing shrinkage, which comprises the following raw materials in parts by weight: 5 to 35 parts of spiro curable cationic monomer, 25 to 85 parts of epoxy monomer, 10 to 25 parts of reactive diluent, 0.1 to 10 parts of photo-crosslinking initiator and 0.1 to 10 parts of photosensitizer.
Further, the photo-thermal dual-curing epoxy adhesive also comprises 0-10 parts of thermosetting agent.
Preferably, the spiro-type curable cationic monomer is 15-25 parts, the epoxy monomer is 50-75 parts, the reactive diluent is 15-25 parts, the photo-crosslinking initiator is 0.1-10 parts, the photosensitizer is 0.1-10 parts, and the thermosetting agent is 0-10 parts.
The preparation method of the epoxy adhesive comprises the following steps: the epoxy packaging adhesive is prepared by adding raw materials into a reaction container according to corresponding weight parts, and mixing and stirring by using a stirrer.
The present invention will be described in further detail with reference to examples for better understanding of the technical aspects of the present invention by those skilled in the art.
The preparation method of the spiro-type curable cationic monomer comprises the following steps:
preparation example 1
A1L three-necked flask with a stirrer was attached to a water separator equipped with a cooling back device, 500mL of a mixture of toluene and 3.80g (98%, 50 mmol) of 1, 3-propanediol (CAS number: 504-63-2) was added, the mixture was heated and refluxed for 2 hours, azeotropic dehydration was performed, the mixture was cooled to 70℃and then 0.08g of anhydrous p-toluenesulfonic acid was added, further cooled to room temperature, then 5.39mL of tetraethyl orthocarbonate (25 mmol) was slowly added, the reaction intermediate ethanol was removed by heating and refluxing the mixture, and then cooled to room temperature after refluxing for 1 hour. 2mL of triethylamine was added thereto, and the mixture was stirred at room temperature for 2.0 hours and then concentrated under reduced pressure to obtain a pale yellow liquid. The product is purified by flash column chromatography (silica gel, 10-20% diethyl ether/ethane) to obtain the product with the structure shown in the formula 1.
Preparation example 2
Based on preparation example 1, the difference from preparation example 1 is: 500mL of toluene was added to react with 4.41g (98%, 50 mmol) of 2-methylene-1, 3-propanediol (CAS number: 3513-81-3) to obtain a product having the structure shown in formula 2.
Preparation example 3
Based on preparation example 1, the difference from preparation example 1 is: a mixture of 500mL of toluene and 7.21g (98%, 50 mmol) of 1, 1-cyclohexanedimethanol (CAS number 2658-60-8) was added to conduct a reaction to give a product having the structure shown in formula 3.
Preparation example 4
Based on preparation example 1, the difference from preparation example 1 is: 500mL of toluene was added to react with 7.81g (98%, 50 mmol) of 2-methylene-1, 3-propanediol (CAS number: 15449-66-8) to obtain the product having the structure shown in formula 4.
Preparation example 5
Based on preparation example 1, the difference from preparation example 1 is: 500mL of toluene was added to a mixture of 7.71g (98%, 50 mmol) of bicyclo (2.2.1) heptane-2, 2-dimethanol (CAS number: 6707-12-6) to conduct a reaction, to obtain a product having the structure shown in formula 5.
Preparation example 6
Based on preparation example 1, the difference from preparation example 1 is: 500mL of toluene was added to a mixture of 5.51g (98%, 50 mmol) of catechol (CAS number: 04-427-5) to react, to obtain a product having the structure shown in formula 6.
Preparation example 7
Based on preparation example 1, the difference from preparation example 1 is: 500mL of toluene was added to react with 7.71g (98%, 50 mmol) of 5-norbornene-2-exo, 3-exo-dimethanol (CAS number: 699-95-6) to give the product having the structure shown in formula 7.
Preparation example 8
Based on preparation example 1, the difference from preparation example 1 is: 500mL of toluene was added to a mixture of 6.70g (98% and 50 mmol) of trimethylolpropane (CAS number: 201-074-9) to react to give a product of the formula 9, 3, 9-diethyl-3 ',9' -dimethylol-1,5,7,11-tetraoxaspiro [5,5] undecane, as a white solid at room temperature.
Example 1
The embodiment discloses a high-hardness scratch-resistant epoxy packaging adhesive with low curing shrinkage, wherein a spiro-type curable cationic monomer in raw materials adopts a structure shown in a formula 1, an epoxy monomer adopts 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, an active diluent adopts triethylene glycol divinyl ether, a photocrosslinking initiator adopts 4-isobutylphenyl-4 ' -tolyl iodine hexafluorophosphate, a photosensitizer adopts benzoin dimethyl ether, and a thermosetting agent adopts methylnadic anhydride.
The specific preparation process of the epoxy packaging adhesive comprises the following steps: 1.0g of spiro-curable cationic monomer with a structure shown in a formula 1, 3.0g of 3',4' -epoxycyclohexyl methyl 3, 4-epoxycyclohexyl carboxylate, 1.0g of triethylene glycol divinyl ether, 0.04g of 4-isobutylphenyl-4 ' -tolyl-iodohexafluorophosphate, 0.02g of benzoin dimethyl ether and 0.1g of methylnadic anhydride are added into a stainless steel container bottle, and stirred in a dark place for 30 minutes until an initiator is completely dissolved, and the ultraviolet light curing epoxy packaging adhesive (A1) is obtained after standing for 60 minutes,a1 was applied to the substrate surface by means of ink-jet printing and was applied in an amount of 30mW/cm 2 The film (B1) was obtained by curing by irradiation with an ultraviolet lamp for 600 seconds, and the initially photo-cured sample was transferred to an oven at 80℃for heat curing for 40 minutes, to obtain a film (C1).
Example 2
On the basis of embodiment 1, this embodiment is different from embodiment 1 in that: the spiro-type curable cationic monomer in the raw material adopts a structure shown in a formula 2, the epoxy monomer adopts 3, 4-epoxycyclohexyl formic acid-3 ',4' -epoxycyclohexyl methyl ester, the active diluent adopts triethylene glycol divinyl ether, the photocrosslinking initiator adopts 4-isobutylphenyl-4 ' -tolyl iodohexafluorophosphate, the photosensitizer adopts benzoin dimethyl ether, and the thermosetting agent adopts methylnadic anhydride.
The specific preparation process of the epoxy packaging adhesive comprises the following steps: adding 1.0g of spiro-curable cationic monomer with a structure shown in a formula 2, 2.5g of 3, 4-epoxycyclohexyl methyl 3',4' -epoxycyclohexyl methyl formate, 1.0g of triethylene glycol divinyl ether, 0.1g of 4-isobutylphenyl-4 ' -tolyl-iodohexafluorophosphate, 0.03g of benzoin dimethyl ether and 0.1g of methylnadic anhydride into a stainless steel container bottle, stirring in a dark place for 30min until an initiator is completely dissolved, standing for 60min to obtain ultraviolet light-cured epoxy encapsulation adhesive (A2), coating the A2 on the surface of a substrate in an ink-jet printing mode, and using 30mW/cm 2 The film (B2) was obtained by curing by irradiation with an ultraviolet lamp for 600 seconds, and the initially photo-cured sample was transferred to an oven at 80℃for 40 minutes to obtain a film (C2).
Example 3
On the basis of embodiment 1, this embodiment is different from embodiment 1 in that: the spiro-curable cationic monomer in the raw materials adopts a structure shown in a formula 3, the epoxy monomer adopts 2- (3, 4-epoxycyclohexane) ethyl trimethoxysilane, the active diluent adopts triethylene glycol divinyl ether, the photocrosslinking initiator adopts 4-isobutylphenyl-4' -tolyl iodohexafluorophosphate, the photosensitizer adopts benzoin dimethyl ether, and the thermal curing agent adopts methyl nadic anhydride.
The epoxy packaging adhesive hasThe preparation process of the body comprises the following steps: 1.5g of spiro-curable cationic monomer with a structure shown in a formula 3, 3.0g of 3',4' -epoxycyclohexyl methyl 3, 4-epoxycyclohexyl methyl formate, 1.0g of triethylene glycol divinyl ether, 0.2g of 4-isobutylphenyl-4 ' -tolyl-iodohexafluorophosphate, 0.03g of benzoin dimethyl ether and 0.1g of methylnadic anhydride are added into a stainless steel container bottle, the mixture is stirred in a dark place for 30 minutes until an initiator is completely dissolved, and an ultraviolet light curing epoxy encapsulating adhesive (A3) is obtained after standing for 60 minutes, the A3 is coated on the surface of a substrate in an ink-jet printing mode, and 30mW/cm of ultraviolet light curing epoxy encapsulating adhesive (A3) is obtained 2 The film (B3) was obtained by curing by irradiation with an ultraviolet lamp for 600 seconds, and the initially photo-cured sample was transferred to an oven at 80℃for 40 minutes to obtain a film (C3).
Example 4
On the basis of embodiment 3, this embodiment is different from embodiment 3 in that: the spiro-type curable cationic monomer in the raw material adopts a structure shown in a formula 5, the epoxy monomer adopts 3, 4-epoxycyclohexyl formic acid-3 ',4' -epoxycyclohexyl methyl ester, the active diluent adopts triethylene glycol divinyl ether, the photocrosslinking initiator adopts 4-isobutylphenyl-4 ' -tolyl iodohexafluorophosphate, the photosensitizer adopts benzoin dimethyl ether, and the thermosetting agent adopts methylnadic anhydride.
The specific preparation process of the epoxy packaging adhesive comprises the following steps: adding 1.5g of spiro-type curable cationic monomer with a structure shown in a formula 5, 3.5g of tetrahydrochysene diepoxide, 1.2g of triethylene glycol divinyl ether, 0.4g of 4-isobutylphenyl-4' -tolylidine hexafluorophosphate, 0.04g of benzoin dimethyl ether and 0.1g of methyl nadic anhydride into a stainless steel container bottle, stirring for 30min in a dark place until an initiator is completely dissolved, standing for 60min to obtain ultraviolet curable epoxy encapsulating adhesive (A4), coating the A4 on the surface of a substrate in an ink-jet printing mode, and using 30mW/cm 2 The film (B4) was obtained by curing by irradiation with an ultraviolet lamp for 600 seconds, and the initially photo-cured sample was transferred to an oven at 80℃for 40 minutes to obtain a film (C4).
Example 5
On the basis of embodiment 1, this embodiment is different from embodiment 1 in that: the spiro-type curable cationic monomer in the raw material adopts a structure shown in a formula 9, the epoxy monomer adopts 3, 4-epoxycyclohexyl formic acid-3 ',4' -epoxycyclohexyl methyl ester, the active diluent adopts triethylene glycol divinyl ether, the photocrosslinking initiator adopts 4-isobutylphenyl-4 ' -tolyl iodohexafluorophosphate, the photosensitizer adopts benzoin dimethyl ether, and the thermal curing agent is not used.
The specific preparation process of the epoxy packaging adhesive comprises the following steps: adding 2g of spiro-curable cationic monomer with a structure shown in a formula 9, 2.5g of 3, 4-epoxycyclohexyl methyl 3',4' -epoxycyclohexyl methyl formate, 1.2g of triethylene glycol divinyl ether, 0.3g of 4-isobutylphenyl-4 ' -tolyl iodohexafluorophosphate and 0.08g of ethyl p-N, N-dimethylaminobenzoate into a stainless steel container bottle, stirring for 30min in a dark place until an initiator is completely dissolved, standing for 60min to obtain ultraviolet light curable epoxy encapsulation adhesive (A5), coating the A5 on the surface of a substrate in an ink-jet printing mode, and using 30mW/cm 2 And (3) irradiating for 600s by an ultraviolet lamp to cure, so as to obtain a film (B5) with the thickness of 23 mu m, and standing a sample subjected to primary photo-curing for 12 hours at room temperature to obtain the film (C5).
Example 6
On the basis of embodiment 1, this embodiment is different from embodiment 1 in that: the spiro-curable cationic monomer in the raw materials is prepared by mixing structures shown in the formula 6 and the formula 7 according to a mass ratio of 1:1, the epoxy monomer is prepared by using tetrahydrochysene diepoxide, the reactive diluent is prepared by using triethylene glycol divinyl ether, the photocrosslinking initiator is prepared by using 4-isobutylphenyl-4' -tolyl iodohexafluorophosphate, the photosensitizer is prepared by using benzoin dimethyl ether, and the thermosetting agent is not used.
The specific preparation process of the epoxy packaging adhesive comprises the following steps: adding 2.6g of spiro-ring type curable cationic monomer with structures shown in formula 6 and formula 7 (the formula 6 and the formula 7 are mixed according to the mass ratio of 1:1), 3.0g of tetrahydrochysene diepoxide, 1.3g of triethylene glycol divinyl ether, 0.08g of 4-isobutylphenyl-4' -tolyl-iodohexafluorophosphate and 0.05g of benzoin dimethyl ether into a stainless steel container bottle, stirring for 30min in a dark place until the initiator is completely dissolved, standing for 60min to obtain ultraviolet light curable epoxy encapsulation adhesive (A6), coating the A6 on the surface of a substrate in an ink-jet printing mode, and using 30mW/cm 2 Ultraviolet of (2)And (3) irradiating for 600s by a lamp to cure to obtain a film (B6) with the thickness of 23 mu m, and standing a sample subjected to primary photo-curing for 12 hours at room temperature to obtain the film (C6).
Example 7
On the basis of embodiment 1, this embodiment is different from embodiment 1 in that: the spiro-curable cationic monomer in the raw materials adopts a structure shown in a formula 4, the epoxy monomer adopts 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane, the active diluent adopts triethylene glycol divinyl ether, the photocrosslinking initiator adopts 4-isobutylphenyl-4' -tolyl iodohexafluorophosphate, the photosensitizer adopts benzoin dimethyl ether, and the thermal curing agent is not used.
The specific preparation process of the epoxy packaging adhesive comprises the following steps: adding 0.5g of spiro-curable cationic monomer with a structure shown in formula 4, 3.5g of tetrahydroxy diepoxide, 0.5g of triethylene glycol divinyl ether, 0.04g of 4-isobutylphenyl-4' -tolyl iodohexafluorophosphate and 0.1g of benzoin dimethyl ether into a stainless steel container bottle, stirring for 30min in a dark place until the initiator is completely dissolved, standing for 60min to obtain ultraviolet light cured epoxy packaging adhesive (A7), coating A6 on the surface of a substrate in an ink-jet printing mode, and using 30mW/cm 2 And (3) irradiating for 600s by an ultraviolet lamp to cure, so as to obtain a film (B7) with the thickness of 23 mu m, and standing a sample subjected to primary photo-curing for 12 hours at room temperature to obtain a film (C7).
Comparative example 1
3.5g of 3, 4-epoxycyclohexylmethyl 3',4' -epoxycyclohexylmethyl 3, 5g of triethylene glycol divinyl ether, 0.04g of 4-isobutylphenyl-4 ' -tolylidine hexafluorophosphate, 0.02g of benzoin dimethyl ether and 0.1g of methylnadic anhydride are added into a stainless steel container bottle, the mixture is stirred for 30 minutes in a dark place until an initiator is completely dissolved, the mixture is left for 60 minutes to obtain ultraviolet light curing epoxy encapsulation adhesive (A8), the A8 is coated on the surface of a substrate in an ink-jet printing mode, and 30mW/cm of the ultraviolet light curing epoxy encapsulation adhesive is used 2 And (3) irradiating for 600s by an ultraviolet lamp to cure, so as to obtain a film (B8) with a thickness of 39 mu m, and standing the initially photo-cured sample at room temperature for 12h to obtain the film (C8).
Comparative example 2
Into a stainless steel container bottle, 3.5g of tetrahydrodiepoxide and 1.4g of triethylene glycol were chargedDivinyl ether, 0.04g of 4-isobutylphenyl-4' -tolyl iodohexafluorophosphate, 0.02g of benzoin dimethyl ether and 0.1g of methyl nadic anhydride, stirring in a dark place for 30min until the initiator is completely dissolved, standing for 60min to obtain ultraviolet light cured epoxy encapsulation adhesive (A9), coating the A9 on the surface of a substrate by using an ink jet printing mode, and using 30mW/cm 2 And (3) irradiating for 600s by an ultraviolet lamp to cure, so as to obtain a film (B9) with the thickness of 28 mu m, and standing a sample subjected to primary photo-curing for 12 hours at room temperature to obtain the film (C9).
Comparative example 3
Comparative example 1 differs from example 1 only in that the spiro-based curable cationic monomer in the raw material of comparative example 1 was replaced with cyclohexyl-1, 4-dimethanol monovinyl ether, and the remaining components and addition amounts were the same as in example 1.
Comparative example 4
The embodiment of comparative example 4 differs from example 1 in that 3.0g of the spiro-based curable cationic monomer was added.
The epoxy packaging adhesives prepared in examples 1 to 7 and comparative examples 1 to 4 were subjected to performance test, and specifically include the following aspects:
(1) Surface tension: the surface tension was measured using a surface tensiometer (QBZY-2 type surface tensiometer) and the test was performed at 25 ℃ and a defoaming centrifugation treatment was performed before the test, and the test was repeated 5 times for each sample, and the final data was averaged.
(2) Viscosity: adopting a rotary rheometer (EVO type rotary viscometer) to carry out viscosity test on the high-refraction precursor liquid, wherein the test is carried out at 25 ℃, a 20mm diameter conical rotor is selected for testing, and the shearing rate is set to be 0.01-500 s -1 And selecting 10s -1 The viscosity of the samples at shear rate was compared and each sample was tested 5 times in duplicate and the final data averaged.
(3) Photo-curing rate: ink jet printing of the ink composition for encapsulation on glass substrates and at 30mW/cm 2 It was subjected to UV curing by UV irradiation for 120s to produce a sample having dimensions of 3 cm. Times.7.5 cm. Times.18 μm (width. Times.length. Times.thickness), and then the sealant before curing was measured using FT-IR (Nicolet iS50, thermo-Fisher) toFilm at 1635cm after curing -1 (C=C) and 1720cm -1 Absorption peak intensity near (c=o).
Photo-curing rate (%) = |1- (F/S) |×100;
wherein F is 1635cm of cured film -1 The intensity of the nearby absorption peak and the absorption peak at 1720cm -1 A ratio of nearby absorption peak intensities; s is 1635cm of uncured ink -1 The intensity of the nearby absorption peak and the absorption peak at 1720cm -1 The ratio of the intensities of the absorption peaks in the vicinity.
(4) Pencil hardness: pencil hardness measurements were made using an electric pencil hardness tester (CT-PC 2) and a 6B-9H pencil from Mitsubishi (Mitsubishi). The pencil load on the sample was 500g, the pencil stretch angle was 45 °, and the pencil stretch speed was 48mm/min. When scratches were generated after five evaluations, one or more times, the measurement was performed using a pencil having the next lower pencil hardness, and the maximum pencil hardness value was obtained when there was no scratch in all five evaluations.
(5) Transmittance: the cured film was sampled according to the method of forming a cured pattern except that no reticle was used, and the transmittance of the cured film in the visible light range of 400nm to 800nm was measured by an ultraviolet-visible spectrophotometer (U-3900 Hitachi).
(6) Haze: the haze of the cured film at a wavelength of 400 to 780nm was measured by a BYK haze meter.
(7) Cure shrinkage: inkjet printing of uv curable epoxy encapsulation glue on glass substrate and at 30mW/cm 2 Is irradiated by an ultraviolet lamp for 600 seconds to be cured.
Cure shrinkage η= (Vb-Va)/vb×100%;
where Vb is the volume before curing and Va is the volume after curing.
The results of the properties of the compositions tested in each of the examples and comparative examples are shown in Table 1 below:
TABLE 1
As can be seen from table 1: the epoxy packaging adhesives corresponding to examples 1-7 have low curing shrinkage, the lowest curing shrinkage can be reduced to 2.86%, the high hardness, the scratch resistance are strong, and the surface tension and the viscosity are moderate; meanwhile, the epoxy packaging glue has high light transmittance (up to 98.9%), the prepared epoxy packaging glue can be singly photo-cured or photo-thermal dual-cured, and the spiro-type curable cationic monomer is easy to synthesize; meanwhile, the configuration method of the epoxy packaging adhesive is simple and easy to operate, and the obtained product has excellent performance. The epoxy packaging adhesive has the advantages of being beneficial to packaging and protecting novel electronic devices represented by mu LEDs.
In contrast, in comparative examples 1 and 2, the effect of very low curing shrinkage rate of the present invention could not be achieved when the addition amount of the spiro-type curable cationic monomer in comparative example 4 was too large, but the curing shrinkage rate of the epoxy encapsulating adhesive obtained was increased to 7.84% instead, instead of adding the spiro-type curable cationic monomer in comparative example 3 to the conventional curable cationic monomer; meanwhile, in comparative example 4, the curing rate is reduced when the addition amount of the spiro-type curable cationic monomer is too much, the film formation is difficult, the gel is difficult, the encapsulation requirements of the OLED device on hardness, adhesion, curing shrinkage, high light transmittance, surface tension and the like cannot be satisfied, and the adhesion ASTM grade is lower than 3B.
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
It will be understood that the invention is not limited to what has been described above and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. The photo-thermal dual-curing epoxy adhesive for packaging the display device is characterized by comprising the following raw materials in parts by weight: 5 to 35 parts of spiro-type curable cationic monomer, 25 to 85 parts of epoxy monomer, 10 to 25 parts of reactive diluent, 0.1 to 10 parts of photo-crosslinking initiator and 0.1 to 10 parts of photosensitizer.
2. The photo-thermal dual curing epoxy paste for display device package according to claim 1, further comprising 0 to 10 parts of a thermosetting agent.
3. The photo-thermal dual curing epoxy adhesive for display device packaging according to claim 2, wherein the thermal curing agent comprises one or more of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, modified methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and diethyl tetramethyl imidazole.
4. A photo-thermal dual cure epoxy glue for display device encapsulation according to claim 1, wherein the epoxy monomer comprises one or more of 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane, tetrahydrodiepoxide, and glycidyl ether or epoxycyclohexane structure formed by C2 to C30 tetrahydric or pentahydric alcohol and glycerol.
5. The photo-thermal dual cure epoxy glue for display device packaging of claim 1, wherein the spiro-type curable cationic monomer comprises at least one of the following formulas:
wherein R in the general formula I and the general formula II 1 、R 2 、R 3 And R is 4 Is a polysubstituted five-membered or six-membered saturated alicyclic ring; y in the general formula III 1 Is a C1-C20 substituted or unsubstituted alkyl group, Y 2 、Y 3 And Y 4 Is polysubstitutedFive-membered or six-membered saturated alicyclic or spiro ring.
6. The photo-thermal dual curing epoxy adhesive for display device packaging according to claim 5, wherein the spiro-type curable cationic monomer is at least one of formulas 1 to 12:
7. the photo-thermal dual curing epoxy adhesive for display device encapsulation of claim 1, wherein the photo-crosslinking initiator comprises one or more of diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, 4-isobutylphenyl-4 '-tolylidine hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, mixed sulfonium hexafluorophosphate, benzoyldiphenyl phosphine oxide, dibenzoylphenyl phosphine oxide, 3' -dimethyl-2-methoxybenzophenone, camphorquinone, and diethyltetramethylimidazole.
8. The photo-thermal dual curing epoxy glue for display device encapsulation of claim 1, wherein the photosensitizer comprises one or more of ethyl p-N, N-dimethylaminobenzoate, 2-isopropylthioxanthone, 9, 10-dibutoxyanthracene, benzoin dimethyl ether.
9. The preparation method of the photo-thermal dual-curing epoxy adhesive for packaging the display device according to any one of claims 1 to 8, which is characterized in that the epoxy adhesive is prepared by adding the raw materials into a reaction container according to the corresponding parts by weight and mixing and stirring the raw materials by using a stirrer.
10. The application of the photo-thermal dual-curing epoxy adhesive for packaging display devices according to any one of claims 1 to 8, wherein the photo-thermal dual-curing epoxy adhesive is used as an organic barrier film for water resistance and oxygen resistance of electronic components, and specifically comprises the following steps:
1) The epoxy glue is adhered to the surface of the electronic component in a spin coating, blade coating or ink-jet printing mode;
2) And irradiating the epoxy glue with ultraviolet light with the wavelength of 250-400 nm for 30-600 s to cure the epoxy glue to form an organic film with the wavelength of 5-55 mu m so as to protect electronic devices.
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