CN114316811A - Adhesive and preparation method and application thereof - Google Patents
Adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN114316811A CN114316811A CN202111641660.4A CN202111641660A CN114316811A CN 114316811 A CN114316811 A CN 114316811A CN 202111641660 A CN202111641660 A CN 202111641660A CN 114316811 A CN114316811 A CN 114316811A
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- parts
- acrylate
- component
- adhesive
- epoxy resin
- Prior art date
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- 239000000853 adhesive Substances 0.000 title claims abstract description 61
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 32
- 238000001723 curing Methods 0.000 claims abstract description 30
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000013007 heat curing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 25
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 19
- 239000003607 modifier Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 12
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 12
- RFOWDPMCXHVGET-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl) prop-2-enoate Chemical compound FC1=C(F)C(F)=C(OC(=O)C=C)C(F)=C1F RFOWDPMCXHVGET-UHFFFAOYSA-N 0.000 claims description 11
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- -1 2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluorooctane-1, 8-diyl Chemical group 0.000 claims description 5
- 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 5
- 239000000654 additive Substances 0.000 claims description 5
- 150000001412 amines Chemical group 0.000 claims description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 5
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 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 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- HMXSIEIEXLGIET-UHFFFAOYSA-N 2-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl)oxirane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC1CO1 HMXSIEIEXLGIET-UHFFFAOYSA-N 0.000 claims description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- GOEJXYYVIPTRLO-UHFFFAOYSA-N C(CC)OC(C=C)=O.N=C=O Chemical compound C(CC)OC(C=C)=O.N=C=O GOEJXYYVIPTRLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical group C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 2
- UXAHWNVIDMAVTK-UHFFFAOYSA-N butyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCCCOC(=O)C=C UXAHWNVIDMAVTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 claims description 2
- KYBYPDUGGWLXNO-GRVYQHKQSA-N ethane-1,2-diamine;(9z,12z)-octadeca-9,12-dienoic acid Chemical compound NCCN.CCCCC\C=C/C\C=C/CCCCCCCC(O)=O.CCCCC\C=C/C\C=C/CCCCCCCC(O)=O KYBYPDUGGWLXNO-GRVYQHKQSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000013008 thixotropic agent Substances 0.000 claims description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims 2
- 229940095102 methyl benzoate Drugs 0.000 claims 2
- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 claims 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- 239000003755 preservative agent Substances 0.000 claims 1
- 230000002335 preservative effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 39
- 239000000463 material Substances 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 11
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 8
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 5
- 238000001029 thermal curing Methods 0.000 description 5
- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CLISWDZSTWQFNX-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)F CLISWDZSTWQFNX-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 101000859864 Rattus norvegicus Gamma-crystallin E Proteins 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- HNVAGBIANFAIIL-UHFFFAOYSA-N 2-hydroxy-2-methylpropanal Chemical compound CC(C)(O)C=O HNVAGBIANFAIIL-UHFFFAOYSA-N 0.000 description 1
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008365 aromatic ketones Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The embodiment of the invention discloses an adhesive and a preparation method and application thereof, and relates to the technical field of chemical materials. The adhesive disclosed by the invention comprises the following raw materials in parts by weight: 40-60 parts of epoxy resin, 1-8.5 parts of light pre-curing component, 84-116.5 parts of heat curing component, 1-2 parts of photoinitiator, 30-50 parts of diluent and 5-20 parts of moisture-resistant component; the initiator is used for initiating the light pre-curing component to perform a crosslinking reaction with the epoxy resin to realize pre-curing. The adhesive disclosed by the invention generates free radicals under ultraviolet irradiation by adding the initiator, and the free radicals are subjected to crosslinking reaction with the moisture-resistant component, the light precuring component and the active groups in the epoxy resin to realize precuring, so that the subsequent processes can be rapidly carried out, and the yield of products is further improved.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to an adhesive and a preparation method and application thereof.
Background
With the rapid development of the electronic industry, the electronic devices are developed toward miniaturization, high capacity and high performance, and the high integration and ultra-thin type of electronic components have become trends, so that it is imperative to adopt an adhesion process instead of the conventional process. Meanwhile, water vapor in the atmosphere can corrode precision elements, and fire is caused by partial discharge and ignition in high-voltage occasions of electronic and electric appliances; therefore, the requirement on the waterproof vapor permeability of the adhesive for the electronic and electric appliances is higher and higher.
Among materials currently used for sealing to isolate water vapor, acrylic ester materials are used by most people, such as CN107151540A, CN108329870A, CN108329870A, CN108329870A and CN107011810A, but because high temperature and high humidity have strong destructive effect on ester groups, such adhesives are generally difficult to withstand high temperature and high humidity tests for a long time, and thus the sealing property is reduced; the epoxy resin adhesive can withstand high temperature and high humidity tests for a long time, but cannot be cured quickly, and pollution or poor adhesion caused by non-uniform flowing of the adhesive is easy to occur in the subsequent process or in the transportation process, so that the yield of products is influenced.
Disclosure of Invention
In view of the above, the invention provides an adhesive, a preparation method and an application thereof, which are used for solving the problems of long curing time and easy flowing of epoxy resin adhesives in the prior art.
The first aspect of the invention provides an adhesive, which comprises the following raw materials in parts by weight: 40-60 parts of epoxy resin, 1-8.5 parts of light pre-curing component, 84-116.5 parts of heat curing component, 1-2 parts of photoinitiator, 30-50 parts of diluent and 5-20 parts of moisture-resistant component; the initiator is used for initiating the light pre-curing component to perform a crosslinking reaction with the epoxy resin to realize pre-curing;
the light precuring component is selected from compounds containing one or more than two of acrylate-based structures, methacrylate-based structures and vinyl structures on each molecule;
the moisture-resistant component is selected from compounds containing fluorine atoms and active groups on each molecule, and the active groups comprise one or more than two of epoxy groups, acrylate groups and methacrylate groups;
the diluent is selected from compounds containing one or more than two of epoxy group, acrylate group, methacrylate group and vinyl ether group on each molecule.
The second aspect of the present invention provides a preparation method of the above adhesive, including the following steps: and mixing the epoxy resin, the light precuring component, the thermosetting component, the photoinitiator, the diluent and the moisture-resistant component to prepare the adhesive.
The third aspect of the invention protects the application of the adhesive in the sealing of the display device.
The embodiment of the invention has the following beneficial effects:
the adhesive comprises a light precuring component, a moisture resistant component, a diluent, epoxy resin, a photoinitiator and a thermal curing agent, wherein the light precuring component is selected from compounds containing one or more than two of an acrylate-based structure, a methacrylate-based structure and a vinyl structure on each molecule; the moisture-resistant component is selected from compounds containing fluorine atoms and active groups on each molecule, the active groups comprise one or more than two of epoxy groups, acrylate groups and methacrylate groups, and the moisture-resistant component is bonded to a polymer crosslinking network through chemical bonds and is difficult to slowly migrate to a surface (interface) due to the action of surface tension, so that the adhesive can keep the characteristic of low moisture permeation for a long time.
The initiator generates free radicals under the irradiation of ultraviolet light, and the free radicals and active groups in the moisture-resistant component, the light precuring component, the diluent and the epoxy resin are subjected to cross-linking reaction to realize rapid precuring within 3 seconds.
The diluent is selected from one or more compounds containing epoxy groups, acrylate groups, methacrylate groups and vinyl ether groups on each molecule, and the groups are the same as the components, so that the dispersibility of each component is improved, and the pre-curing effect is improved. In practical application, the adhesive subjected to ultraviolet rapid pre-curing is not easy to flow, so that subsequent processes can be performed as soon as possible, and the yield of products is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses an adhesive which comprises the following raw materials in parts by weight: 40-60 parts of epoxy resin, 1-8.5 parts of light pre-curing component, 84-116.5 parts of heat curing component, 1-2 parts of photoinitiator, 30-50 parts of diluent and 5-20 parts of moisture-resistant component; the initiator is used for inducing the light-emitting pre-curing component to perform a crosslinking reaction with the epoxy resin to realize pre-curing; the term "precure" used in the present invention refers to the adhesive flowing state alone, i.e. the precured adhesive loses fluidity, and does not mean that all the crosslinking reaction is completed, and the subsequent conventional thermosetting treatment is still required.
The light precuring component is selected from compounds containing one or more than two of acrylate-based structures, methacrylate-based structures and vinyl structures on each molecule; the light precuring component is selected from compounds containing one or more than two of acrylate-based structure, methacrylate-based structure and vinyl structure on each molecule. The viscosity of the adhesive is between 100 and 2000mPa.s, preferably between 200 and 1000mPa.s, and more preferably between 300 and 800 mPa.s. The adhesive has ultraviolet light with the wavelength of 300nm-395nm and the concentration of 300mJ/cm2-30000mJ/cm2The precuring can be realized under the condition of energy radiation.
The moisture-resistant component is selected from compounds containing fluorine atoms and active groups on each molecule, and the active groups comprise one or more than two of epoxy groups, acrylate groups and methacrylate groups; the moisture resistant component is bonded to the polymer crosslinked network through chemical bonds and is difficult to slowly migrate to the surface (interface) due to the action of surface tension, so that the adhesive can keep the characteristic of low moisture permeation for a long time.
The diluent is selected from compounds containing one or more of epoxy groups, acrylate groups, methacrylate groups and vinyl ether groups per molecule.
In a particular embodiment, the photo-precuring component is selected from compounds containing more than two acrylate structures per molecule and/or compounds containing one acrylate structure and one isocyanate structure per molecule.
Preferably, the compound containing two or more acrylate structures per molecule is selected from the group consisting of S-ethoxylated bisphenol a dimethacrylate (octomer SR150) and/or tetrafunctional epoxy acrylate (Sartomer 2204 NS);
preferably, the compound containing one acrylate structure and one isocyanate structure per molecule is selected from the group consisting of isocyanate ethyl acrylate (C)6H7NO3Chemical structural formula is) One or more than two of isocyanate ethyl methacrylate, isocyanate propyl acrylate and isocyanate butyl acrylate. The light precuring component contains both acrylate and isocyanate, the acrylate part can realize UV rapid curing, the isocyanate part can react with a thermal curing agent, the thermal curing agent is further cured with the epoxy component, and finally the acrylate part and the epoxy part are crosslinked together to form a stable and compact network structure, so that the sealing and waterproof performance of the adhesive is further improved.
In one embodiment, the diluent has a viscosity of 1.0 to 3000 mpa.s. The molecular weight of the diluent may be less than 1500. Advantageously, its molecular weight is less than 750, more suitably less than 500. The viscosity of the diluent is preferably less than 2000cps, more preferably 10 to 500cps at 25 ℃.
Further, the diluent is selected from compounds containing an acrylate group and/or a methacrylate group and a vinyl ether group per molecule, and the compounds containing an acrylate group and/or a methacrylate group and a vinyl ether group per molecule have a structural formula shown in formula 1:
wherein R is1One or more selected from hydrogen, aliphatic C1-C6 alkyl and C1-C6 cycloalkyl; r2One or more selected from C2-C20 alkylene, C2-C20 hydrocarbon diyl and polyoxyalkylene; r3Selected from hydrogen and/or methyl.
In a particular embodiment, the photoinitiator is selected from a cleavage type radical initiator and/or a hydrogen abstraction type radical initiator. The cracking type free radical initiator is characterized in that initiator molecules are transited to an excited singlet state after absorbing light energy and are transited to an excited triplet state through intersystem transition, a molecular structure is in an unstable state when the initiator molecules are in the excited singlet state or the excited triplet state, weak bonds in the initiator molecules are subjected to homolytic cracking to generate primary active free radicals, and thus the vinyl monomers are subjected to initiation polymerization; the hydrogen abstraction type radical initiator generally has an aromatic ketone structure as the main component, and also comprises some polycyclic aromatic hydrocarbons. They have a certain light-absorbing property, and the co-initiator, i.e. the hydrogen donor, which is matched with them, has no absorption in the range of long-wavelength ultraviolet light. The hydrogen abstraction photoinitiator absorbs ultraviolet energy and generates bimolecular action with the initiator aid in an excited state to generate active free radicals.
The thermosetting component is selected from amine epoxy resin curing agent and/or thiol epoxy resin curing agent.
Further, the amine epoxy resin curing agent comprises polyamide with the number average molecular weight of 100-1000 and/or polyether amine with the number average molecular weight of 200-5000.
The epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin and hydrogenated bisphenol F epoxy resin.
In one embodiment of the present invention, the substrate is,
the moisture resistant component is selected from the group consisting of 3- (1H,1H,5H octafluoropentoxy) -1, 2-propylene oxide (CAS registry No.: 19932-27-5), 3- (perfluoro-n-octyl) -1, 2-propylene oxide (CAS registry No.: 38565-53-6),2,2' - (2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluorooctane-1, 8-diyl) bis (ethylene oxide) (CAS registry No.: 74328-56-6), 2,2,3,3, 3-pentafluoropropyl methacrylate (CAS registry No.: 45115-53-5), 3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl methacrylate (CAS No.: 144-53-8), and pentafluorophenol acrylate (CAS No.: 71195-85-2) One or more than two of them.
The diluent is one or more selected from the group consisting of HELOXY Modifier 65, HELOXY Modifier 71, HELOXY Modifier 84, epoxy diluent 207(Dow Chemical Company), epoxy diluent AGE (Dow Chemical Company), epoxy diluent 691(Dow Chemical Company), trimethylolpropane triacrylate (TMPTA for short), 1, 6-hexanediol diacrylate (HDDA), and pentaerythritol tetraacrylate (PET 4A for short).
The photoinitiator is selected from phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (CAS accession number 162881-26-7), 1-hydroxycyclohexyl phenyl ketone (CAS accession number 947-19-3, New Tianjin Jieshi Co., Ltd.), 2-hydroxy-2-methyl-1-phenyl-1-propanone (CAS accession number 7473-98-5), benzoin dimethyl ether (CAS accession number 24650-42-8), benzophenone (CAS accession number 119-61-9), 2-isopropyl thioxanthone (CAS accession number 495-84-1), 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-propanone (CAS accession number 71868-10-5), 2-benzyl-2-dimethylamino-1- (4-morpholinobenzylphenyl) butanone (CAS registry No. 119313-12-1), phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (CAS registry No. 162881-26-7), 1'- (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-propanone (CAS registry No. 474510-57-1), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (CAS registry No. 119313-12-1), 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (CAS registry No. 106797-53-9), One or more of methyl benzoylformate (CAS registry number: 15206-55-0), 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide (CAS registry number: 75980-60-8) and 2-isopropylthioxanthone (IGM RESINS ITX, 2,4 isomer mixture, CAS registry number: 5495-84-1).
The thermosetting component includes:
the polyamide with the number average molecular weight of 100-1000 is selected from one or more of German Kenin polyamide Versamid 115, German Kenin polyamide Versamid 125 and German Kenin polyamide Versamid 140;
the polyether amine with the number average molecular weight of 200-;
the thiol epoxy resin curing agent is selected from QE-340M (Dongli Polythiol) and/or pentaerythritol tetrakis (3-mercaptobutanoate) (Showa Karenz MT PE 1).
The epoxy resin includes: :
the bisphenol A type epoxy resin is selected from one or more of EPlKOTE 828EL (Vast. Special Chemical Co., Hexion Specialty Chemicals), EPlKOTE 827 (Vast. Special Chemical Co., Hexion Specialty Chemicals), DER331 (Dow Chemical Company), E51 epoxy resin (Baling petrochemical Co., Ltd.) and E44 epoxy resin (Baling petrochemical Co., Ltd.);
the bisphenol F epoxy resin is selected from novolac epoxy resin F51 (the holy petrochemical company, Inc.) and/or EPlKOTE 862 bisphenol F type epoxy resin (the Hansen Specialty Chemicals, Hexion Specialty Chemicals);
the hydrogenated bisphenol A epoxy resin is selected from EP-4080E (Adeka Co., LTD., Edeka Co., Ltd., China) and/or SF-3000 hydrogenated bisphenol A type epoxy resins (Senffida chemical Co., Ltd., Suzhou).
In a specific embodiment, the adhesive further comprises the following raw materials in parts by weight: 0.1 to 61 portions of additive, wherein the additive is one or more than two of performance modifier, filler, thixotropic agent, silane coupling agent, colorant, surfactant, preservative-stabilizer, plasticizer, lubricant, defoaming agent and leveling agent. They may be incorporated in a small amount or a large amount in the adhesive formulation, either alone or in combination, depending on the purpose. In particular, the composition is preferably selected from additives of property-modifying resins, organic or inorganic fillers and silane coupling agents.
The invention also discloses a preparation method of the adhesive, which comprises the following steps: the adhesive is prepared by mixing 40-60 parts of epoxy resin, 1-8.5 parts of light pre-curing component, 84-116.5 parts of heat curing component, 1-2 parts of photoinitiator, 30-50 parts of diluent and 5-20 parts of moisture-resistant component. The components are mixed in no order, preferably in an environment isolated from ultraviolet light, and other components except for the light precuring component can be mixed first, and if the components exist, the resin and the non-soluble solid (powder) are mixed for no less than 10 minutes in a three-roll grinder.
The invention also discloses an application of the adhesive in display device sealing. The method is mainly applied to a drop injection (ODF) process for manufacturing the seal of the display device, after the ODF process is finished, the adhesive can be pre-fixed through ultraviolet light, so that the flowability of the adhesive is lost, the pollution or poor seal caused by non-uniform flowing of the adhesive in other subsequent processes and/or a transfer process is not worried about, the subsequent thermal curing is not influenced, and the thermal curing time can be shortened to a certain extent.
Example 1
50G 828EL (Hexion Specialty Chemicals, Vast. Specialty Chemicals), 30G HELOXY Modifier 65, 20G 3- (1H,1H, 5H-octafluoropentyloxy) -1, 2-propylene oxide (Aladdin, CAS Reg.No.: 19932-27-5), 111.09G polyamide 650 (Mitsui chemical G-725), 1.11g of tetrafunctional epoxy acrylate (Sartomer 2204NS), 1g of 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiyun New materials Co., Ltd., CAS accession number: 947-19-3), 0.6g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS accession number: 162881-26-7) and 1g of gamma- (2, 3-glycidoxy) propyl trimethoxy silane (KH 560 for short, Aladdin) were mixed under the condition of isolating ultraviolet light to prepare the adhesive.
Example 2
50g 828EL (Hexion Specialty Chemicals, Vast. Specialty Chemicals), 40g HELOXY Modifier 65, 10g 3- (1H,1H,5H octafluoropentyloxy) -1, 2-propylene oxide (Aladdin, CAS Reg.No.: 19932-27-5), 95.83g tetrafunctional mercapto curing agent (Showa Denz MT PE1), 2.87g of tetrafunctional epoxy acrylate (Sartomer 2204NS), 1g of 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiyun New materials Co., Ltd., CAS accession number: 947-19-3), 0.6g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS accession number: 162881-26-7) and 1g of gamma- (2, 3-glycidoxy) propyl trimethoxy silane (KH 560 for short, Aladdin) were mixed under the condition of isolating ultraviolet light to prepare the adhesive.
Example 3
40G 828EL (Hexion Specialty Chemicals, Vast. Specialty Chemicals), 45G HELOXY Modifier 65, 10G 3- (1H,1H, 5H-octafluoropentyloxy) -1, 2-propylene oxide (Aladdin, CAS Reg.No.: 19932-27-5), 104.37G polyamide 650 (Mitsui chemical G-725), 3.13g of tetrafunctional epoxy acrylate (Sartomer 2204NS), 1g of 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiyun New materials Co., Ltd., CAS accession number: 947-19-3), 0.6g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS accession number: 162881-26-7) and 1g of gamma- (2, 3-glycidoxy) propyl trimethoxy silane (KH 560 for short, Aladdin) were mixed under the condition of isolating ultraviolet light to prepare the adhesive.
Example 4
40g 828EL (Hansen Specialty Chemicals), 10g EP-4080E (Adeka Co., LTD., Edideae, Inc.), 40g HELOXY Modifier 65, 10g 3- (1H,1H,5H octafluoropentoxy) -1, 2-propylene oxide (Aladdin, CAS registry: 19932-27-5), 116.10g polyetheramine T5000 (U.S. Hunemann HUNTSMAN), 5.80g isocyanate ethyl acrylate (Aladdin), 1g 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiu material Co., CAS registry: 947-19-3), 0.6g phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS registry: 162881-26-7) and 1g gamma- (2, 3-glycidoxy) propyltrimethoxysilane (560), aladdin) under the condition of isolating ultraviolet light to prepare the adhesive.
Example 5
40g 828EL (Hexion Specialty Chemicals, Vast. Specialty Chemicals), 40g HELOXY Modifier 65, 10g trimethylolpropane triacrylate (Aladdin), 10g 3- (1H,1H,5H octafluoropentoxy) -1, 2-propylene oxide (Aladdin, CAS Reg.No. 19932-27-5), 84.37g tetrafunctional mercapto curing agent (Showa Denz MT PE1), 8.47g ethyl isocyanate acrylate (Aladdin), 1g 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiu-Nissan-Shui-Nissan-GmbH, CAS Reg.No. 947-19-3), 0.6g phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS Reg.No. 162881-26-7) and 1g gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane (KH 560), aladdin) under the condition of isolating ultraviolet light to prepare the adhesive.
Example 6
40G 828EL (Vast. Special Chemicals), 20G EP-4080E (Adeka Co., LTD., Edisco, Inc.), 30G HELOXY Modifier 65, 10G pentafluorophenol acrylate (Aladdin, CAS Reg. No.: 71195-85-2), 66.73G polyamide 650 (Mitsui Chemicals G-725), 0.67G tetrafunctional epoxy acrylate (Sartomer 2204NS), 37.81G polyetheramine T5000 (Henschelmann SMAN, USA), 1.89G ethyl isocyanate acrylate (Aladdin) were added.
Example 7
30G 828EL (Vast. Special Chemicals, Hexion Specialty Chemicals), 20G EP-4080E (AdDicke, China investment Co., Ltd., ADEKA Co., LTD.), 40G trimethylolpropane triacrylate (Aladdin), 10G pentafluorophenol acrylate (Aladdin, CAS registry No.: 71195-85-2), 48.74G tetrafunctional mercapto curing agent (Sho and electrician Karenz MT PE1), 1.46G tetrafunctional epoxy acrylate (Sartomer 2204NS), 45.44G polyamide 650 (Mitsui chemical G-725), 1.36G isocyanate ethyl acrylate (Aladdin), 1G 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiu Co., Ltd., CAS registry No.: 947-19-3), 0.6G phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS: 162881-3626-gamma. and 2G new materials (gamma.), 3-glycidoxy) propyl trimethoxy silane (KH 560 for short, Aladdin) is mixed under the condition of isolating ultraviolet light to prepare the adhesive.
Example 8
30g 828EL (Hansen Special Chemicals, Hexion Specialty Chemicals), 20g EP-4080E (Adeka Co., LTD., Edideae, Inc.), 30g HELOXY Modifier 65, 15g trimethylolpropane triacrylate (Aladdin), 5g pentafluorophenol acrylate (Aladdin, CAS registry: 71195-85-2), 53.81g polyetheramine T5000 (Hungman HUNTSMAN), 2.69g ethyl isocyanate acrylate (Aladdin), 44g tetrafunctional mercapto curing agent (Showa and electrician Karenz PE MT 1), 4.4g ethyl isocyanate acrylate (Aladdin), 1g 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiutai Co., Ltd., CAS registry: 947-19-3), 0.6g phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (57: 162881 g γ -3626) and new material (367-3626), 3-glycidoxy) propyl trimethoxy silane (KH 560 for short, Aladdin) is mixed under the condition of isolating ultraviolet light to prepare the adhesive.
Comparative example 1
An adhesive was prepared by mixing 50G 828EL (Hexion Specialty Chemicals, Vast. Specialty Chemicals), 30G HELOXY Modifier 65, 20G 3- (1H,1H,5H octafluoropentyloxy) -1, 2-propylene oxide (Aladdin, CAS Reg.No.: 19932-27-5), 108.3G polyamide 650 (G-725 from Mitsui chemical), 1G 1-hydroxycyclohexylphenylketone (Tianjin Jiu Co., Ltd., CAS Reg. No.: 947-19-3), 0.6G phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS Reg.: 162881-26-7) and 1G γ -2, 3-glycidoxy) propyltrimethoxysilane (KH 560, Aladdin) under the exclusion of ultraviolet light.
Comparative example 2
50g 828EL (Vast. Special Chemicals, Hexion Specialty Chemicals), 40g HELOXY Modifier 65, 10g pentafluorophenol acrylate (Aladdin, CAS Reg. No.: 71195-85-2), 96.3g tetrafunctional mercapto curing agent (Karenz MT PE1), 1g 1-hydroxycyclohexyl phenyl ketone (Tianjin Jiu New materials Co., Ltd., CAS Reg. No.: 947-19-3), 0.6g phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS Reg. No.: 162881-26-7) and 1g gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane (KH 560, Aladdin) were mixed under UV-blocking conditions to make an adhesive.
Comparative example 3
40G 828EL (Hexion Specialty Chemicals, Vast. Specialty Chemicals), 45G HELOXY Modifier 65, 10G 3- (1H,1H,5H octafluoropentyloxy) -1, 2-propylene oxide (Aladdin, CAS registry: 19932-27-5), 104.37G polyamide 650 (Mitsui chemical G-725), 1G 1-hydroxycyclohexylphenylketone (Tianjin Nissan New materials Co., Ltd., CAS registry: 947-19-3), 0.6G phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (IGM RESINS, CAS registry: 162881-26-7) and 1G γ -2, 3-glycidoxy) propyltrimethoxysilane (KH 560, Aladdin) were mixed under ultraviolet light blocking conditions to prepare an adhesive.
Comparative example 4
The commercially available UV-curable product DS7400 UV (Henkel hysol) was selected as comparative example 4.
Test example 1
And (3) performance testing: the adhesives prepared in examples 1 to 8 and comparative examples 1 to 4 were subjected to a viscosity test, a shear test, a water vapor transmission test, and a comparison, respectively. The performance test method comprises the following steps:
viscosity measurement
The viscosity of the adhesive components and the freshly mixed epoxy adhesive were tested at 10RPM using a Brookfield viscometer with a # 14 spindle. The adhesives and components were tested at room temperature.
Shear force assessment
On a plain silicate glass plate, 4X 4mm PET blocks were UV (395nm, 800 mW/cm)2) The samples were evaluated as Shear (Die Shear) force with light for 3s, Shear test speed 10 mm/min.
Evaluation of Water vapor Transmission
The water vapor permeability is evaluated by referring to GB 1037-88 'test method for water vapor permeability of plastic film and sheet-cup method', the test environment is 65 ℃, 90 RH% and 240 hours.
The test results are detailed in table 1:
table 1 adhesive performance test results
And (4) analyzing results: from the above data it is clear that the results for the pre-fixing case are:
the difference between example 1 and comparative example 1 is that example 1 was supplemented with 1.11g of a tetrafunctional epoxy acrylate, i.e., a photo-precuring component, and the test results show that example 1 had essentially no flow and comparative example 1 had flow.
The difference between example 2 and comparative example 2 is that example 2 was supplemented with 2.87g of a tetrafunctional epoxy acrylate, i.e., a photo-precuring component, and the results of the test were that example 2 was substantially non-flowing and comparative example 2 was flowing.
Example 3 differs from comparative example 3 in that example 3 was supplemented with 3.13g of a tetrafunctional epoxy acrylate, i.e., a light precured component, and the test results showed no flow for example 3 and flow for comparative example 3. Example 3 the pre-cure effect was improved by increasing the amount of photo pre-cure component added relative to example 2.
The pre-cure component of example 5 was added in the largest amount and the pre-cure effect was not the best. It is clear that the more the amount of the pre-curing component, the better.
Examples 6 to 8 all showed better effects than example 5, and examples 6 to 8 differed from example 5 in that the amount of the precured component added was different, and examples 6 to 8 showed two precured components added and the total amount was smaller than that of the precured component in example 5, and it was found that the effect of using two precured components in combination was better than that of using one precured component alone.
The best precuring effect is obtained in example 7 in examples 6-8, and the amount of the precuring component in example 7 is between that in example 6 and example 8, and it is understood that the content of the precuring component is not more and is better to be adapted to the amount of the initiator and the epoxy resin.
In summary, under the condition that the amounts of the epoxy resin and the photoinitiator are basically constant, the precuring effect of adding one precuring component and the precuring effect of adding two precuring components are related to the total amount of the precuring components, and the addition amount of the precuring components has an optimal value. The precuring effect of adding two precuring components is better than that of adding one precuring component alone.
The results regarding the resistance to moisture are:
the water vapor permeability of the examples 1-8 is close to that of the comparative examples 1-4, and the values of some examples are slightly higher than that of the comparative example 4, namely, the water vapor resistance of the invention meets the water vapor resistance requirement in the existing market.
After the adhesive dispensing process is completed, the adhesive is pre-fixed and loses fluidity through ultraviolet illumination, so that the subsequent processes can be conveniently performed, and the process flexibility and the product yield are improved.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. The adhesive is characterized by comprising the following raw materials in parts by weight: 40-60 parts of epoxy resin, 1-8.5 parts of light pre-curing component, 84-116.5 parts of heat curing component, 1-2 parts of photoinitiator, 30-50 parts of diluent and 5-20 parts of moisture-resistant component; the initiator is used for initiating the light pre-curing component to perform a crosslinking reaction with the epoxy resin to realize pre-curing;
the light precuring component is selected from compounds containing one or more than two of acrylate-based structures, methacrylate-based structures and vinyl structures on each molecule;
the moisture-resistant component is selected from compounds containing fluorine atoms and active groups on each molecule, and the active groups comprise one or more than two of epoxy groups, acrylate groups and methacrylate groups;
the diluent is selected from compounds containing one or more than two of epoxy group, acrylate group, methacrylate group and vinyl ether group on each molecule.
2. The adhesive of claim 1, wherein the photo-precuring component is selected from compounds containing two or more acrylate structures per molecule and/or compounds containing both acrylate and isocyanate structures per molecule.
3. The adhesive of claim 2, wherein the compound having two or more acrylate structures per molecule is selected from ethoxylated bisphenol a dimethacrylate and/or tetrafunctional epoxy acrylate;
the compound containing an acrylate structure and an isocyanate structure on each molecule is selected from one or more of isocyanate ethyl acrylate, isocyanate propyl acrylate and isocyanate butyl acrylate.
4. The adhesive according to any one of claims 1 to 3, wherein the diluent has a viscosity of 1.0 to 3000 mPa.s.
5. The adhesive of claim 4,
the diluent is selected from compounds containing an acrylate group and/or a methacrylate group and a vinyl ether group per molecule, and the compounds containing an acrylate group and/or a methacrylate group and a vinyl ether group per molecule have a structural formula shown in formula 1:
wherein R is1One or more selected from hydrogen, aliphatic C1-C6 alkyl and C1-C6 cycloalkyl; r2One or more selected from C2-C20 alkylene, C2-C20 hydrocarbon diyl and polyoxyalkylene; r3Selected from hydrogen and/or methyl.
6. The adhesive of claim 5 wherein the photoinitiator is selected from the group consisting of a cleavage type radical initiator and/or a hydrogen abstraction type radical initiator;
the thermosetting component is selected from amine epoxy resin curing agent and/or thiol epoxy resin curing agent;
the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin and hydrogenated bisphenol F epoxy resin.
7. The adhesive of claim 6,
the moisture-resistant component is one or more than two selected from 3- (1H,1H,5H octafluoropentyloxy) -1, 2-propylene oxide, 3- (perfluoro-n-octyl) -1, 2-propylene oxide, 2' - (2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluorooctane-1, 8-diyl) bis (ethylene oxide), 2,3, 3-pentafluoropropyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl methacrylate and pentafluorophenol acrylate;
the diluent is selected from one or more than two of HELOXY Modifier 65, HELOXY Modifier 71, HELOXY Modifier 84, epoxy diluent 207, epoxy diluent AGE, epoxy diluent 691, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate and pentaerythritol tetraacrylate;
the photoinitiator is selected from phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzoin dimethyl ether, benzophenone, 2-isopropyl thioxanthone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinebenzylphenyl) butanone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1' - (methylenebis-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone, methyl benzoate, ethyl benzoate, and methyl benzoate, One or more than two of 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, methyl benzoylformate, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 2-isopropyl thioxanthone;
the thermosetting component is selected from Versamid 115, Versamid 125, Versamid 140, polyetheramine D230, polyetheramine D2000, polyetheramine T5000, QE-340M, and pentaerythritol tetrakis (3-mercaptobutanoate).
8. The adhesive according to claim 6, characterized by further comprising the following raw materials in parts by weight: 0.1-61 parts of additive, wherein the additive comprises one or more of performance modifier, filler, thixotropic agent, silane coupling agent, colorant, surfactant, preservative, stabilizer, plasticizer, lubricant, defoaming agent and leveling agent.
9. A process for the preparation of the adhesive according to any one of claims 1 to 8, comprising the steps of: the adhesive is prepared by mixing 40-60 parts of epoxy resin, 1-8.5 parts of light pre-curing component, 84-116.5 parts of heat curing component, 1-2 parts of photoinitiator, 30-50 parts of diluent and 5-20 parts of moisture-resistant component.
10. Use of the adhesive according to any one of claims 1 to 8 in the sealing of a display device.
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030192638A1 (en) * | 2001-11-02 | 2003-10-16 | Jie Yang | Hybrid adhesives, articles, and methods |
CN101389725A (en) * | 2006-02-27 | 2009-03-18 | 住友电木株式会社 | Adhesive film |
US20140238580A1 (en) * | 2011-11-06 | 2014-08-28 | Henkel (China) Company Limited | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
CN106928893A (en) * | 2015-10-26 | 2017-07-07 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of cation type ultraviolet photo and hot dual deep cure adhesive |
CN107384282A (en) * | 2017-08-02 | 2017-11-24 | 浙江大学 | A kind of flexible electronic substrate adhesive and its preparation method and application |
CN110055021A (en) * | 2019-05-18 | 2019-07-26 | 福建省昌德胶业科技有限公司 | A kind of high water vapor rejection composition epoxy resin and its application in lithium-ion-power cell |
CN110184021A (en) * | 2019-05-29 | 2019-08-30 | 上海昀通电子科技有限公司 | Adhesive compound and application thereof |
CN111234713A (en) * | 2019-05-29 | 2020-06-05 | 深圳市鑫东邦科技有限公司 | Underfill adhesive and preparation method thereof |
CN111826109A (en) * | 2020-06-22 | 2020-10-27 | 上海回天新材料有限公司 | UV-curable two-component epoxy adhesive |
CN112063347A (en) * | 2020-08-25 | 2020-12-11 | 深圳市优宝新材料科技有限公司 | Moisture resistant compositions and methods of making the same |
CN112778913A (en) * | 2020-12-30 | 2021-05-11 | 东莞市派乐玛新材料技术开发有限公司 | UV curing adhesive and preparation method and application thereof |
CN113493654A (en) * | 2021-06-16 | 2021-10-12 | 烟台德邦科技股份有限公司 | Photo-thermal dual-curing adhesive and preparation method thereof |
-
2021
- 2021-12-29 CN CN202111641660.4A patent/CN114316811A/en active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030192638A1 (en) * | 2001-11-02 | 2003-10-16 | Jie Yang | Hybrid adhesives, articles, and methods |
CN101389725A (en) * | 2006-02-27 | 2009-03-18 | 住友电木株式会社 | Adhesive film |
US20140238580A1 (en) * | 2011-11-06 | 2014-08-28 | Henkel (China) Company Limited | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
CN106928893A (en) * | 2015-10-26 | 2017-07-07 | 黑龙江省科学院石油化学研究院 | A kind of preparation method of cation type ultraviolet photo and hot dual deep cure adhesive |
CN107384282A (en) * | 2017-08-02 | 2017-11-24 | 浙江大学 | A kind of flexible electronic substrate adhesive and its preparation method and application |
CN110055021A (en) * | 2019-05-18 | 2019-07-26 | 福建省昌德胶业科技有限公司 | A kind of high water vapor rejection composition epoxy resin and its application in lithium-ion-power cell |
CN110184021A (en) * | 2019-05-29 | 2019-08-30 | 上海昀通电子科技有限公司 | Adhesive compound and application thereof |
CN111234713A (en) * | 2019-05-29 | 2020-06-05 | 深圳市鑫东邦科技有限公司 | Underfill adhesive and preparation method thereof |
CN111826109A (en) * | 2020-06-22 | 2020-10-27 | 上海回天新材料有限公司 | UV-curable two-component epoxy adhesive |
CN112063347A (en) * | 2020-08-25 | 2020-12-11 | 深圳市优宝新材料科技有限公司 | Moisture resistant compositions and methods of making the same |
CN112778913A (en) * | 2020-12-30 | 2021-05-11 | 东莞市派乐玛新材料技术开发有限公司 | UV curing adhesive and preparation method and application thereof |
CN113493654A (en) * | 2021-06-16 | 2021-10-12 | 烟台德邦科技股份有限公司 | Photo-thermal dual-curing adhesive and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
Y.H.HUI: "贝雷:油脂化学与工艺学", vol. 5, 中国轻工业出版社, pages: 265 - 266 * |
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