CN114958209B - Ultraviolet light curing adhesive with delayed curing function and preparation method thereof - Google Patents
Ultraviolet light curing adhesive with delayed curing function and preparation method thereof Download PDFInfo
- Publication number
- CN114958209B CN114958209B CN202210572953.XA CN202210572953A CN114958209B CN 114958209 B CN114958209 B CN 114958209B CN 202210572953 A CN202210572953 A CN 202210572953A CN 114958209 B CN114958209 B CN 114958209B
- Authority
- CN
- China
- Prior art keywords
- curing
- rosin modified
- ultraviolet light
- aziridine
- curing adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 33
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 33
- 230000003111 delayed effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 35
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 34
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 150000001541 aziridines Chemical class 0.000 claims abstract description 17
- -1 acrylic ester Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- ZEJWZIZFOBFKOC-UHFFFAOYSA-N 1-(aziridin-1-yl)ethanol Chemical compound CC(O)N1CC1 ZEJWZIZFOBFKOC-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 239000012949 free radical photoinitiator Substances 0.000 abstract description 3
- 238000002834 transmittance Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 34
- 238000004806 packaging method and process Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- DTEAMMSJXLXUOQ-UHFFFAOYSA-N 1-hydroxyaziridine Chemical compound ON1CC1 DTEAMMSJXLXUOQ-UHFFFAOYSA-N 0.000 description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 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 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 2
- OQILSTRGJVCFAG-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound CCCC(O)OCC1CO1 OQILSTRGJVCFAG-UHFFFAOYSA-N 0.000 description 1
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical compound CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound 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 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- HWJYGSDXNANCJM-UHFFFAOYSA-N tridodecyl borate Chemical compound CCCCCCCCCCCCOB(OCCCCCCCCCCCC)OCCCCCCCCCCCC HWJYGSDXNANCJM-UHFFFAOYSA-N 0.000 description 1
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 1
- 229960001082 trimethoprim Drugs 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- GZKLCETYSGSMRA-UHFFFAOYSA-N trioctadecyl borate Chemical compound CCCCCCCCCCCCCCCCCCOB(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC GZKLCETYSGSMRA-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- RTMBXAOPKJNOGZ-UHFFFAOYSA-N tris(2-methylphenyl) borate Chemical compound CC1=CC=CC=C1OB(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C RTMBXAOPKJNOGZ-UHFFFAOYSA-N 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
- 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
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The ultraviolet curing adhesive with the delayed curing function is prepared from the following raw materials in percentage by weight: 40-70% of rosin modified aziridine resin, 15-35% of acrylic ester monomer, 10-30% of rosin modified acrylic ester resin, 0.3-6% of free radical photoinitiator, 0.1-5% of photoacid generator and 0.01-1% of stabilizer. The ultraviolet light curing adhesive has the function of delaying curing, can be used in opaque application scenes, solves the problem that the conventional ultraviolet light curing adhesive is limited by material light transmittance, and has the advantages of excellent curing property, high bonding reliability and wide application range.
Description
Technical Field
The invention belongs to the field of photo-curing materials, and relates to an ultraviolet curing adhesive with a delayed curing function and a preparation method thereof.
Background
The photo-curing material is widely researched due to the outstanding advantages of high curing speed, environmental friendliness, low energy consumption, no solvent volatilization and the like, and is rapidly popularized in various industries. However, the ultraviolet light curing adhesive has the own limitation, the conventional ultraviolet light curing adhesive can only be used in the bonding application of light-transmitting materials, and in the bonding occasion of light-impermeable materials, the ultraviolet light curing adhesive can not be cured because of light-impermeable materials, and has obvious limitation in practical application; the ultraviolet light curing adhesive has the function of delaying curing, can be used in opaque application scenes, and solves the problem that the conventional ultraviolet light curing adhesive is limited by material light transmittance.
Disclosure of Invention
In order to solve the problem that ultraviolet light curing glue cannot be cured in opaque materials in the prior art, the invention provides ultraviolet light curing glue with a delay function and a preparation method thereof, so that the ultraviolet light curing glue cured product has the delay curing function and can be applied to opaque material bonding.
The technical scheme for solving the technical problems is as follows:
An ultraviolet curing adhesive with a delayed curing function comprises the following raw materials in percentage by weight: 40-70% of rosin modified aziridine resin, 15-35% of acrylic ester monomer, 10-30% of rosin modified acrylic ester resin, 0.3-6% of free radical photoinitiator, 0.1-5% of photoacid generator and 0.01-1% of stabilizer.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the rosin modified aziridine resin is a rosin modified aziridine resin containing an aziridine reaction group and synthesized by using rosin glycol, diisocyanate and hydroxy aziridine, wherein the rosin glycol is dihydric alcohol containing two hydroxy groups and having a basic structure of abietic acid, and the diisocyanate comprises: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI), or the like, and mixtures of any of them. By hydroxyaziridine is meant a compound containing both hydroxyl and aziridine groups, such as 1-hydroxyethyl aziridine (cas: 1072-52-2). Rosin-modified aziridine resin having a structural formula represented by the following general formula (I):
The synthesis method comprises the following steps: 200g of rosin glycol, 11.6g of toluene diisocyanate and 0.01g of catalyst dibutyl tin dilaurate are added into a three-neck flask with a thermometer, the temperature is raised to 65 ℃, the temperature is controlled to be 70-75 ℃, and the reaction is carried out for 2-3 hours; 3.2g of 1-hydroxyethyl aziridine (1072-52-2) is added, the temperature is controlled at 70-75 ℃, and the reaction is carried out for 2-3 hours; and (3) analyzing NCO groups by using an infrared spectrometer, and stopping heating reaction when NCO peaks completely disappear to obtain rosin modified aziridine resin, wherein the reaction formula is as follows:
Further, the acrylate monomer is a monofunctional or difunctional or higher functional acrylate monomer, and comprises one or a mixture of any of tetrahydrofuran acrylate (THFA), isooctyl methacrylate (ISOA), lauryl methacrylate (LA), isobornyl methacrylate (IBOA), N-Dimethylacrylamide (DMAA) and 1, 6-hexanediol diacrylate (HDDA).
Further, the rosin modified acrylic ester resin has a molecular structural formula as follows:
Further, the radical photoinitiator is one or a mixture of any of the trade marks 1173 (2-hydroxy-2-methyl-1-phenylpropion), 184 (1-hydroxycyclohexyl benzophenone), 907 (2-methyl-1- (4-methylsulfanyl-phenyl) -2-morpholin-1-one), 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone), 819 (bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide), 651 (alpha, alpha' -dimethylbenzoyl ketal), ITX (isopropylthioxanthone), BP (benzophenone), OMBB (methyl o-benzoyl benzoate), TPO (2, 4, 6-trimethylbenzoyl diphenyl phosphorus oxide).
Further, the photoacid generator includes sulfonium salts and iodonium salt type cationic photoinitiators that generate super-strong protonic acids upon UV illumination. For example: IRGACURE 250 from BASF corporation, WPI-113, WPI-116 and WPI-124 from Fujifillm corporation, japan.
Further, the stabilizer in the synthesis method is one or a mixture of a plurality of boric acid esters, aluminum chelates and organic acids, and comprises trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, dodecyl borate, tricetyl borate, trioctadecyl borate, triortholyl borate, tricresyl borate, triethanolamine borate, barbituric acid and the like.
The preparation method of the ultraviolet light curing adhesive with the delayed curing function comprises the following steps: weighing 40-70% of rosin modified aziridine resin, 15-35% of acrylic ester monomer, 10-30% of rosin modified acrylic ester resin, 0.3-6% of free radical photoinitiator, 0.1-5% of photoacid generator and 0.01-1% of stabilizer, sequentially adding into a stirrer, vacuumizing to a vacuum degree of minus 0.08-minus 0.05MPa, stirring for 0.5-2 hours at 500-1000 rpm, stirring uniformly, naturally airing to room temperature, and sealing and packaging.
The beneficial effects of the invention are as follows: the ultraviolet light curing adhesive prepared by the invention utilizes the mechanism that the aziridine reacts under the catalysis of acid, when the photo-acid generator in the formula is irradiated by UV, super strong protonic acid is generated, the super strong protonic acid catalyzes the aziridine to carry out polymerization reaction, and the polymerization reaction of the acid catalyzed aziridine is not instantaneous unlike the instantaneous reaction of the free radical polymerization of acrylic ester, so the formula has the reaction characteristic of UV delay curing; according to the invention, through molecular structure design, an aziridine group is introduced into a macromolecular chain of rosin ester to synthesize rosin modified aziridine resin, and the resin containing a rosin structure has better adhesive force to a substrate; the ultraviolet curing adhesive has the functions of delaying curing, meeting the situation of bonding opaque materials, and has the advantages of high adhesion to base materials, excellent curing properties and high bonding reliability, and can be widely applied to the high-end electronic packaging industry.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
Synthetic examples
The synthetic method of the rosin modified aziridine resin comprises the following steps: 200g of rosin glycol, 11.6g of toluene diisocyanate and 0.01g of catalyst dibutyl tin dilaurate are added into a three-neck flask with a thermometer, the temperature is raised to 65 ℃, the temperature is controlled to be 70-75 ℃, and the reaction is carried out for 2-3 hours; adding 3.2g of hydroxy aziridine (1072-52-2), controlling the temperature at 70-75 ℃ and reacting for 2-3h; and (3) analyzing the NCO groups by using an infrared spectrometer, and stopping the heating reaction when the NCO peak completely disappears, so as to obtain the rosin modified aziridine resin.
Example 1
Accurately weighing 55g of rosin modified aziridine resin, 20g of THFA, 21g of rosin modified acrylic resin, 184 g of photoinitiator, 0.5g of photoinitiator TPO, 250 g of photoacid generator IRGACURE and 0.6g of triethyl borate; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.08 MPa, stirring for 2 hours at 500 rpm, naturally airing to room temperature to obtain ultraviolet light curing adhesive, and sealing and packaging.
Example 2
Accurately weighing 45g of rosin modified aziridine resin, 30g of IBOA, 26g of rosin modified acrylic resin, 184 g of photoinitiator, 1.1g of photoinitiator TPO, 250.5 g of photoacid generator IRGACURE and 0.3g of barbituric acid; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.05 MPa, stirring for 1 hr at 750 rpm, naturally airing to room temperature to obtain ultraviolet light cured adhesive, and sealing and packaging.
Example 3
Accurately weighing 67g of rosin modified aziridine resin, 15g of IBOA, 14g of rosin modified acrylic resin, 651 3g of photoinitiator, 1.1g of photoinitiator TPO, 5g of photoacid generator WPI-116 and 0.06g of barbituric acid; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.06 MPa, stirring at 700 rpm for 1.5 hr, stirring uniformly, naturally airing to room temperature to obtain ultraviolet light cured adhesive, and sealing and packaging.
Example 4
Accurately weighing 58g of rosin modified aziridine resin, 29g of LA, 11g of rosin modified acrylic resin, 184 g of photoinitiator, 1.5g of photoinitiator TPO, 250.9 g of photoacid generator IRGACURE and 0.16g of barbituric acid; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.07 MPa, stirring for 1 hr at 800rpm, naturally airing to room temperature to obtain ultraviolet light cured adhesive, and sealing and packaging.
Example 5
Accurately weighing 65g of rosin modified aziridine resin, 10g of THFA, 13g of IBOA, 21g of rosin modified acrylic resin, 651 2g of photoinitiator, 0.5g of photoinitiator TPO, 2.3g of photoacid generator WPI-124 and 0.29g of trimethoprim borate; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.08 MPa, stirring at 1000 rpm for 0.5 hr, stirring uniformly, naturally airing to room temperature to obtain ultraviolet light cured adhesive, and sealing and packaging.
Comparative example 1
Accurately weighing the following raw materials, CN966J75 of the company sartomer, 55g; LA,48g; 1173,2g of photoinitiator; 1g of a photoinitiator TPO; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.08 MPa, stirring for 2 hours at 500 rpm, naturally airing to room temperature to obtain ultraviolet light curing adhesive, and sealing and packaging.
Comparative example 2
Accurately weighing 6127 g and 42g of Changxing chemical; IBOA,51g; 651,3g of photoinitiator; 1g of a photoinitiator TPO; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.05 MPa, stirring for 1 hr at 750 rpm, naturally airing to room temperature to obtain ultraviolet light cured adhesive, and sealing and packaging.
Comparative example 3
Accurately weighing 60g of bisphenol A type epoxy resin, 5g of polycaprolactone polyol, 1g of cationic curing agent, 1g of 1173 photoinitiator, 2g of butanediol glycidyl ether, 0.01 g of isopropyl thioxanthone, 0.1 g of polyethyleneimine modified graphene oxide and 1g of gas phase silicon thixotropic agent; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.05 MPa, stirring for 1 hr at 750 rpm, naturally airing to room temperature to obtain ultraviolet light cured adhesive, and sealing and packaging.
Comparative example 4
Accurately weighing the following raw materials, mixing 0.2g of photo-alkaline agent and 7.73g of bisphenol A epoxy resin (E51), stirring at 110 ℃ until the raw materials are clear and transparent, and cooling to room temperature; then adding 4.23g of bisphenol A Epoxy Acrylate (EA), 1, 6-hexanediol diacrylate (HDDA) 1.94g, pentaerythritol tetra-3-mercaptopropionate (SH 4) 8.2g, photosensitizer 2-Isopropyl Thioxanthone (ITX) 0.1g, free radical inhibitor 2, 2, 6, 6-tetramethyl piperidine-1-oxyl free radical (TEMPO) 0.1g into the system; sequentially adding the above components into a double planetary power mixing stirrer, vacuumizing to vacuum degree of-0.05 MPa, stirring for 1 hr at 750 rpm, naturally airing to room temperature to obtain ultraviolet light cured adhesive, and sealing and packaging.
The performance of the ultraviolet curing adhesive with the delayed curing function of the present invention was tested by the following test.
Test examples Performance test
Laminating time test: and dispensing on a black substrate, activating by UV light, standing for different times, and then attaching an aluminum sheet, wherein if the cohesive strength of the adhesive is too high, the adhesive cannot be attached, and the longest time which can be attached is the attachable time.
UV activated curing conditions: the light intensity is 50mW/cm 2, and the illumination time is 10s;
Shear strength: black pc+aluminum substrate.
Drop performance test: the height is 1.8m, the falling is carried out for 50 times, and whether cracking occurs or not is judged.
The test results are shown in table 1:
table 1 results of test of comparing the Performance of the samples prepared in examples 1 to 5 with that of the ordinary UV-curable adhesive
| Sample preparation | UV activated, conformable time | Shear Strength for 30min | Shear Strength for 60min | Shear Strength for 24h | Elongation% | Drop performance |
| Sample of example 1 | 6min | 1.3MPa | 2.4MPa | 9.2MPa | 346 | No cracking |
| Sample of example 2 | 11min | 0.6MPa | 1.3MPa | 11.5MPa | 325 | No cracking |
| Sample of example 3 | 4min | 2.3MPa | 3.7MPa | 12.3MPa | 343 | No cracking |
| Sample of example 4 | 7min | 1.1MPa | 2.3MPa | 7.3MPa | 329 | No cracking |
| Sample of example 5 | 9min | 0.9MPa | 1.8MPa | 11.8MPa | 311 | No cracking |
| Sample of comparative example 1 | Failure to bond after UV activation | - | - | - | - | - |
| Sample of comparative example 2 | Failure to bond after UV activation | - | - | - | - | - |
| Sample of comparative example 3 | 8min | 0.9MPa | 1.9MPa | 23MPa | 208 | Cracking of |
| Sample of comparative example 4 | 23min | 0.1MPa | 0.4MPa | 1.2MPa | 89 | Cracking of |
From the above results, it can be seen that the ultraviolet light curing adhesive with delayed curing function of the invention has delayed curing function, good adhesion to a substrate, larger elongation and better dropping performance compared with the existing common light curing adhesive.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (1)
1. An ultraviolet light curing adhesive with a delayed curing function comprises 67g of rosin modified aziridine resin, 15g of IBOA, 14g of rosin modified acrylic ester, 651 3g of photoinitiator, 1.1g of photoinitiator TPO, 5g of photoacid generator WPI-116 and 0.06g of barbituric acid; sequentially adding the components into a double planetary power mixing stirrer, vacuumizing to the vacuum degree of-0.06 MPa, stirring for 1.5 hours at 700 revolutions per minute, uniformly stirring, and naturally airing to room temperature to obtain ultraviolet curing adhesive; the synthetic method of the rosin modified aziridine resin comprises the following steps: 200g of rosin glycol, 11.6g of toluene diisocyanate and 0.01g of catalyst dibutyl tin dilaurate are added into a three-neck flask with a thermometer, the temperature is raised to 65 ℃, the temperature is controlled to be 70-75 ℃, and the reaction is carried out for 2-3 hours; adding 3.2g of 1-hydroxyethyl aziridine, controlling the temperature at 70-75 ℃ and reacting for 2-3h; analyzing NCO groups by using an infrared spectrometer, and stopping heating reaction when NCO peaks completely disappear; the rosin modified acrylic ester has the following molecular structural formula:
。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210572953.XA CN114958209B (en) | 2022-05-25 | 2022-05-25 | Ultraviolet light curing adhesive with delayed curing function and preparation method thereof |
| PCT/CN2023/083241 WO2023226568A1 (en) | 2022-05-25 | 2023-03-23 | Ultraviolet-curing adhesive having curing delaying function, and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210572953.XA CN114958209B (en) | 2022-05-25 | 2022-05-25 | Ultraviolet light curing adhesive with delayed curing function and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114958209A CN114958209A (en) | 2022-08-30 |
| CN114958209B true CN114958209B (en) | 2024-06-14 |
Family
ID=82956737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210572953.XA Active CN114958209B (en) | 2022-05-25 | 2022-05-25 | Ultraviolet light curing adhesive with delayed curing function and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114958209B (en) |
| WO (1) | WO2023226568A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958209B (en) * | 2022-05-25 | 2024-06-14 | 烟台德邦科技股份有限公司 | Ultraviolet light curing adhesive with delayed curing function and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277669A (en) * | 2002-03-25 | 2003-10-02 | Toyo Ink Mfg Co Ltd | Binder composition for printing ink |
| CN105829468A (en) * | 2013-12-18 | 2016-08-03 | 3M创新有限公司 | Post-curable pressure-sensitive adhesive |
| CN108003802A (en) * | 2017-12-07 | 2018-05-08 | 烟台德邦科技有限公司 | Thermal self-healing ultraviolet curing adhesive based on gradual polymerization mechanism |
| CN109072037A (en) * | 2016-06-09 | 2018-12-21 | 横滨橡胶株式会社 | Two-solution curing type carbamate adhesive composite |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3922762B2 (en) * | 1997-06-05 | 2007-05-30 | 積水化学工業株式会社 | Acrylic adhesive composition |
| TW200636032A (en) * | 2005-04-13 | 2006-10-16 | Lg Chemical Ltd | Acrylic adhesive composition having excellent impact resistance, optical film using the adhesive composition, and liquid crystal display comprising the optical film |
| US7652103B2 (en) * | 2008-02-14 | 2010-01-26 | 3M Innovative Properties Company | Acrylic pressure-sensitive adhesives with aziridine crosslinking agents |
| CN102127183B (en) * | 2010-01-20 | 2014-08-20 | 3M创新有限公司 | Crosslinkable acrylate adhesive polymer composite |
| KR101649760B1 (en) * | 2015-04-29 | 2016-08-19 | 한국신발피혁연구원 | Manufacturing method of one-component water based adhesive composition having excellent water resistant and heat resistant and one-component water based adhesive composition using the same |
| CN105153407B (en) * | 2015-10-20 | 2017-01-04 | 山东科技大学 | A kind of thermosetting rosin resin compositions and preparation method thereof |
| EP3170876A1 (en) * | 2015-11-17 | 2017-05-24 | 3M Innovative Properties Company | Post-curable precursor of an acrylic-based pressure-sensitive adhesive |
| CN105733493B (en) * | 2016-05-11 | 2018-06-08 | 烟台德邦科技有限公司 | A kind of ultraviolet cured adhesive with low volatile content |
| CN113528065B (en) * | 2020-04-16 | 2023-02-17 | 3M创新有限公司 | Acrylic pressure-sensitive adhesive composition, product thereof and related preparation method |
| CN112225878B (en) * | 2020-09-01 | 2021-11-23 | 华南理工大学 | High-alkali-resistance aqueous bi-component isocyanate curing agent and preparation method thereof |
| CN114958209B (en) * | 2022-05-25 | 2024-06-14 | 烟台德邦科技股份有限公司 | Ultraviolet light curing adhesive with delayed curing function and preparation method thereof |
-
2022
- 2022-05-25 CN CN202210572953.XA patent/CN114958209B/en active Active
-
2023
- 2023-03-23 WO PCT/CN2023/083241 patent/WO2023226568A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003277669A (en) * | 2002-03-25 | 2003-10-02 | Toyo Ink Mfg Co Ltd | Binder composition for printing ink |
| CN105829468A (en) * | 2013-12-18 | 2016-08-03 | 3M创新有限公司 | Post-curable pressure-sensitive adhesive |
| CN109072037A (en) * | 2016-06-09 | 2018-12-21 | 横滨橡胶株式会社 | Two-solution curing type carbamate adhesive composite |
| CN108003802A (en) * | 2017-12-07 | 2018-05-08 | 烟台德邦科技有限公司 | Thermal self-healing ultraviolet curing adhesive based on gradual polymerization mechanism |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114958209A (en) | 2022-08-30 |
| WO2023226568A1 (en) | 2023-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109370507B (en) | Low-viscosity environment-friendly UV/moisture dual-curing three-proofing adhesive and preparation method thereof | |
| CN102337099B (en) | Single-component photo-curable and thermal-curable adhesive and preparation method thereof | |
| US8048979B2 (en) | Process for synthesis of telechelic urethane acrylate UV curable pre-polymeric materials | |
| CN112552866B (en) | UV-LED and moisture dual-curing environment-friendly three-proofing adhesive and preparation method thereof | |
| CN111205810B (en) | Photo-thermal dual-curing adhesive and preparation method thereof | |
| CN101143979A (en) | Anti-flaming ultraviolet radiation solidifying coating for metal | |
| CN114958209B (en) | Ultraviolet light curing adhesive with delayed curing function and preparation method thereof | |
| CN107129788B (en) | UV (ultraviolet) curing pressure-sensitive adhesive | |
| AU2020101245A4 (en) | A Benzophenone Derivative Containing Aromatic Ester Group and Preparation Method and Application Thereof | |
| CN111138290A (en) | Aromatic ring-containing benzophenone derivative and preparation method and application thereof | |
| CN114933849B (en) | Ultraviolet light aging resistant photocureable coating based on carboxylated graphite phase carbon nitride and preparation method thereof | |
| CN111139020A (en) | Thermosetting and UV curing composite adhesive and preparation method thereof | |
| CN113493654B (en) | Photo-thermal dual-curing adhesive and preparation method thereof | |
| CN106753183A (en) | One kind can the quick-setting ultraviolet cured adhesive of low energy and preparation method thereof | |
| CN110922603B (en) | Photocuring resin modified by different chain segments and preparation method and application thereof | |
| CN101787241A (en) | Water-based UV-light curing coating | |
| KR20190027064A (en) | Flame retardant uv curable adhesive composition and method for preparation using the same | |
| CN113980582B (en) | Light, heat and moisture curable adhesive and preparation method thereof | |
| CN111909075B (en) | Rigid acrylate UV (ultraviolet) photocuring modified tung oil resin and preparation method and application thereof | |
| CN115873510B (en) | High-temperature-resistant high-humidity high-bonding-strength UV adhesive for battery shell film and preparation method thereof | |
| CA1064190A (en) | U.v.-curable resinous compounds and compositions | |
| CN113817086B (en) | Bio-based light-cured resin composition and preparation method and application thereof | |
| CN114561174B (en) | UV (ultraviolet) curing pressure-sensitive adhesive and preparation method thereof | |
| CN117866468B (en) | Dual-curable high-wettability UV three-proofing paint and preparation method thereof | |
| CN114874743B (en) | High-adhesion UV (ultraviolet) photocuring polyurethane adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |