CN114276279B - Hydrogen abstraction type photoinitiator, preparation method and application thereof - Google Patents
Hydrogen abstraction type photoinitiator, preparation method and application thereof Download PDFInfo
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- CN114276279B CN114276279B CN202111636130.0A CN202111636130A CN114276279B CN 114276279 B CN114276279 B CN 114276279B CN 202111636130 A CN202111636130 A CN 202111636130A CN 114276279 B CN114276279 B CN 114276279B
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- China
- Prior art keywords
- photoinitiator
- hydrogen abstraction
- reaction
- diisocyanate
- acrylate
- Prior art date
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 31
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 41
- 229920000768 polyamine Polymers 0.000 claims description 39
- 150000002148 esters Chemical class 0.000 claims description 38
- 239000002313 adhesive film Substances 0.000 claims description 34
- 238000001723 curing Methods 0.000 claims description 34
- 229940126062 Compound A Drugs 0.000 claims description 33
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 150000008366 benzophenones Chemical class 0.000 claims description 23
- -1 butenedioic acid diester Chemical class 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006845 Michael addition reaction Methods 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011976 maleic acid Substances 0.000 claims description 10
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 8
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
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- 239000000126 substance Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003848 UV Light-Curing Methods 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 4
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 claims description 4
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical group N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 4
- GTVVADNAPPKOSH-SNAWJCMRSA-N (e)-4-butan-2-yloxy-4-oxobut-2-enoic acid Chemical compound CCC(C)OC(=O)\C=C\C(O)=O GTVVADNAPPKOSH-SNAWJCMRSA-N 0.000 claims description 3
- GTVVADNAPPKOSH-PLNGDYQASA-N (z)-4-butan-2-yloxy-4-oxobut-2-enoic acid Chemical compound CCC(C)OC(=O)\C=C/C(O)=O GTVVADNAPPKOSH-PLNGDYQASA-N 0.000 claims description 3
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 claims description 3
- DSTWFRCNXMNXTR-AATRIKPKSA-N dipropyl (e)-but-2-enedioate Chemical compound CCCOC(=O)\C=C\C(=O)OCCC DSTWFRCNXMNXTR-AATRIKPKSA-N 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 3
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 claims description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 claims description 2
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 claims description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- VHMFUIWQKYCNMG-UHFFFAOYSA-N 3-hydroxyiminopentane-2,4-dione Chemical compound CC(=O)C(=NO)C(C)=O VHMFUIWQKYCNMG-UHFFFAOYSA-N 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 15
- 230000009977 dual effect Effects 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 9
- 230000005012 migration Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
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- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 125000004185 ester group Chemical group 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 14
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 13
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 12
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- 125000003545 alkoxy group Chemical group 0.000 description 11
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- 239000012965 benzophenone Substances 0.000 description 10
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 5
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- WELLGRANCAVMDP-UHFFFAOYSA-N isocyanatoethane;prop-2-enoic acid Chemical compound CCN=C=O.OC(=O)C=C WELLGRANCAVMDP-UHFFFAOYSA-N 0.000 description 5
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003828 free initiator Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/48—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/56—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
Abstract
The invention relates to the technical field of photoinitiator synthesis, in particular to a hydrogen abstraction type photoinitiator and a preparation method and application thereof. The hydrogen abstraction photoinitiator has a tertiary amine and polyaspartic acid ester structure, is a single-component initiator with photo-thermal dual curing, does not need to add a tertiary amine auxiliary initiator, has extremely low micromolecule migration and leaching rate and extremely low smell, and has good photoinitiation activity and solubility.
Description
Technical Field
The invention relates to the technical field of photoinitiator synthesis, in particular to a hydrogen abstraction type photoinitiator and a preparation method and application thereof.
Background
The photoinitiator is a key component of the ultraviolet curing system and is directly related to whether the oligomer and the thinner can be rapidly converted from a liquid state to a solid state when the formula system is irradiated by light. With the continuous development of technology and the increasing demands placed by the market, the migration and tendency of the photoinitiators to be extracted after the curing process has been completed should be minimized.
Benzophenone is widely used as a hydrogen abstraction photoinitiator, has low price, good surface curing, difficult yellowing and good solubility, and is one of the most widely used photoinitiators in an ultraviolet curing system. But the tendency of benzophenones to migrate or be abstracted from the cured product is severe. In order to improve the migration and odor problems of benzophenone, patent application publication CN101012180A discloses chemically combining benzophenone and amine in one molecule to make a single-component hydrogen abstraction photoinitiator.
The full-lamination technology of the display device is classified into OCA (Optical Clear additive) and LOCA (Liquid Optical Clear additive) full lamination. The LOCA adhesive in the existing market belongs to UV adhesive, needs to be cured through UV light irradiation, but due to the structural design of the touch screen TP, a screen frame and a functional sheet FPC are not transparent, UV light cannot penetrate through the LOCA adhesive to reach the LOCA adhesive, the LOCA adhesive slowly overflows in the subsequent storage or use process, appearance pollution and even the inside of a product are damaged, and finally the product is damaged. During curing, the screen frame and the opaque flexible circuit board on the sensor are difficult to be cured completely, re-curing is needed, glue overflow is difficult to control, glue overflowing to the edge is difficult to clean, especially, glue overflow during large-size gluing is difficult to control, production cost is high, and production efficiency is low.
In order to solve the problem of glue overflow of a light blocking part of a product during curing, a side surface UV curing process is added in the prior art so as to achieve curing and edge sealing of an outer edge and reduce the risk of glue overflow. However, side curing presents two problems: firstly, side curing can only seal edges, the problem that liquid is not dry still exists in a light blocking part with a large area, and when heating and pressurizing are needed (for example, heating, pressurizing and defoaming are needed during subsequent OCA attaching), uncured liquid optical cement overflows; secondly, the side curing requires higher energy to cure the edge, but the high energy side curing can cause the white cover plate to yellow, which affects the appearance. Therefore, in order to solve the problems of side curing, the liquid optical cement needs to be used together with an accelerator, the curing speed of the liquid optical cement is accelerated by the accelerator, and the problem that the light blocking part is not cured is solved. However, the promoting efficiency of the existing liquid optical cement promoter is low, the curing effect of the outer edge contacting with oxygen is poor, and meanwhile, the existing liquid optical cement has the problem of poor storage stability, so that the problem of side curing cannot be better solved.
In summary, the current commercialized benzophenone photoinitiator has pollution caused by migration and exudation problems, and in the field of ultraviolet-thermal dual curing of OCA, peroxide is mostly adopted as a thermal initiator, and a pre-coating accelerator is needed to be used in combination, so that the increase of process steps brings about the increase of operation difficulty and bonding cost. Therefore, if the two technical problems are solved simultaneously through the chemical structure design of the photoinitiator, the market competitiveness of the OCA product is greatly improved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a hydrogen abstraction type photoinitiator to solve the technical problems of migration and exudation of the photoinitiator in the prior art.
The second object of the present invention is to provide a method for producing a hydrogen abstraction type photoinitiator.
The third purpose of the invention is to provide the application of the hydrogen abstraction type photoinitiator in the OCA adhesive film.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a hydrogen abstraction photoinitiator having the formula:
wherein X 1 And X 2 At least one selected from
R 1 To comprise
Organic radical of a structural unit, R 2 Any one selected from alkylene and alkyleneoxy groups, R 3 Selected from alkyl and alkoxy groupsAny one of (a); r is 4 Any one selected from H and methyl;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 Each independently selected from any one of H, alkyl, alkoxy and aromatic groups.
The hydrogen abstraction photoinitiator has a tertiary amine and polyaspartic acid ester structure, is a single-component initiator with photo-thermal dual curing, does not need to add a tertiary amine auxiliary initiator, has extremely low micromolecule migration and leaching rate and extremely low smell, and has good photoinitiation activity and solubility.
In a specific embodiment of the present invention, X 1 And X 2 Are all made of
Or, X 1 And X 2 One of them is
The other is H.
In a particular embodiment of the invention, R 2 Selected from among branched alkylene groups having 2 to 12 carbon atoms, linear alkylene groups, branched alkyleneoxy groups, and linear alkyleneoxy groups.
In a particular embodiment of the invention, R 3 Selected from any one of branched alkyl, linear alkyl, branched alkoxy and linear alkoxy having 2 to 12 carbon atoms.
In a particular embodiment of the invention, R 1 Is composed of
R 5 Selected from alkylene groups having 1 to 5 carbon atoms, R 6 Selected from the group consisting of asymmetric cycloalkyl groups.
In a particular embodiment of the invention, R 6 Is composed of
In a particular embodiment of the invention, R 1 Is composed of
Any one of the above.
The invention also provides a preparation method of any one of the hydrogen abstraction type photoinitiators, which comprises the following steps:
(a) Compound A 1 Or compound A 2 With diisocyanates and hydroxyl-containing (meth) acrylates to give compounds containing
Benzophenone derivatives of structural units;
(b) Carrying out Michael addition reaction on polyaspartic acid ester polyamine and the benzophenone derivative to obtain the photoinitiator;
wherein, compound A 1 And compound A 2 Are respectively of the formula
The structural formula of the polyaspartic acid ester polyamine is shown as
In a specific embodiment of the invention, the polyaspartate polyamine is derived primarily from the reaction of a dialkyl triamine and a butene diacid diester; the structural formulas of the dialkyl triamine and the butenedioic acid diester are respectively shown in the specification
Further, the dialkyl triamine comprises any one or more of diethylene triamine, dipropylene triamine and bis-hexamethylene triamine; the butenedioic acid diester comprises a maleic acid diester and/or a fumaric acid diester, wherein the maleic acid diester is selected from any one or more of diethyl maleate, dipropyl maleate, dibutyl maleate and methylpropyl maleate, and the fumaric acid diester is selected from any one or more of diethyl fumarate, dipropyl fumarate, dibutyl fumarate and methylpropyl fumarate.
In a particular embodiment of the invention, the molar ratio between the dialkyltriamine and the diester of maleic acid is 1: 1.8 to 2.2.
In a particular embodiment of the invention, the diisocyanate comprises toluene diisocyanate and/or isophorone diisocyanate.
In a specific embodiment of the present invention, the hydroxyl group-containing (meth) acrylate includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
In a specific embodiment of the present invention, the polyaspartic acid ester polyamine and the benzophenone derivative are reacted at a molar ratio of 1: 1 (0.9 to 1.1), preferably 1: 1, in the step (b).
In a specific embodiment of the present invention, in step (b), the polyaspartate polyamine is added to the benzophenone derivative.
The invention also provides another preparation method of any one of the hydrogen abstraction photoinitiators, which comprises the following steps:
(a1) Compound A 1 Or compound A 2 With monomers containing isocyanate and (meth) acrylate to give compounds containing
Benzophenone derivatives of structural units;
(b1) Carrying out Michael addition reaction on polyaspartic acid ester polyamine and the benzophenone derivative to obtain the photoinitiator;
wherein, compound A 1 And compound A 2 Are respectively of the formula
The structural formula of the polyaspartic acid ester polyamine is shown as
In a specific embodiment of the present invention, the isocyanate and (meth) acrylate containing monomer comprises isocyanate ethyl acrylate and/or isocyanate ethyl methacrylate.
The invention also provides an application of any one of the hydrogen abstraction photoinitiators in the OCA adhesive film.
The invention also provides an OCA composition which comprises 1-10% of hydrogen abstraction type photoinitiator by mass percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) The hydrogen abstraction type photoinitiator is used as a single-component initiator capable of dual curing, a tertiary amine auxiliary initiator is not required to be added, the small molecule migration leaching rate is lower than 0.01% (even in a shading area), the odor is extremely low, and the photoinitiator has good photoinitiation activity and solubility;
(2) The OCA adhesive film system obtained by compounding the hydrogen abstraction photoinitiator has a storage period of more than 3 months, the viscosity is only slightly increased in the process, the side curing of the light blocking part can be well realized, and the problems of edge glue overflow and insufficient adhesion after attaching are avoided;
(3) The OCA adhesive film structure obtained by the hydrogen abstraction photoinitiator forms a polyurethane/polyurea and acrylate polymer interpenetrating network (IPN) structure, and strong hydrogen bond action between carbamate and carbamido in the polyurethane/polyurea structure is used as a physical crosslinking point, so that the cohesive force of the adhesive film can be enhanced, the cohesive force and the bonding reliability are improved, and the creep resistance is greatly improved on the basis of keeping good elasticity.
Detailed Description
While the technical solutions of the present invention will be described clearly and completely with reference to the specific embodiments, those skilled in the art will understand that the following described examples are some, but not all, examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. 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 examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
A hydrogen abstraction photoinitiator having the formula:
wherein, X 1 And X 2 At least one selected from
R 1 To comprise
Organic radical of a structural unit, R 2 Any one selected from alkylene and alkyleneoxy groups, R 3 Any one selected from alkyl and alkoxy groups; r is 4 Any one selected from H and methyl;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 Each independently selected from H, alkyl, alkaneAny one of an oxy group and an aromatic group.
As in various embodiments, the hydrogen abstraction photoinitiator may be of the formula
(X 1 Can be selected from any one of H, alkyl, alkoxy and aromatic groups) or
As in the different embodiments, Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 And Y 8 Each independently selected from any one of H, alkyl, alkoxy and aromatic groups; wherein, the alkyl can be alkyl with 1-4 carbon atoms, such as methyl, ethyl, propyl, butyl, etc.; the alkoxy group may be an alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, etc.; the aromatic group may be an aromatic ring such as benzene, an aromatic fused ring such as naphthalene, or the like.
The hydrogen abstraction photoinitiator has a tertiary amine and polyaspartic acid ester structure, is a single-component initiator with photo-thermal dual curing, does not need to add a tertiary amine auxiliary initiator, has extremely low micromolecule migration and leaching rate and extremely low smell, and has good photoinitiation activity and solubility.
In a specific embodiment of the present invention, X 1 And X 2 Are all made of
Or, X 1 And X 2 One of them is
The other is H.
In a particular embodiment of the invention, R 2 Selected from branched alkylene groups having 2 to 12 carbon atoms, linear alkylene groups, branched alkyleneoxy groups and linear alkyleneoxy groups.
As in various embodimentsIn, R 2 The number of carbons of (a) may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12; for example, the linear alkylene group may have the formula
n is an integer between 2 and 12; for example, the branched alkylene can have the formula
n 1 Is an integer between 1 and 11, or can have a plurality of branches; such as linear alkyleneoxy groups of the formula
n 2 Is an integer between 2 and 12; for example, the branched alkyleneoxy group can be of the formula
n 3 Is an integer of 1 to 11, or may have a plurality of branches.
In a particular embodiment of the invention, R 2 Selected from linear alkylene with 2-6 carbon atoms.
In a particular embodiment of the invention, R 3 Selected from any one of branched alkyl, linear alkyl, branched alkoxy and linear alkoxy having 1 to 12 carbon atoms.
As in the different embodiments, R 3 The number of carbons of (a) may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12; for example, the straight chain alkyl group can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the formula is shown in the specification
n 4 Is an integer between 0 and 11; for example, the branched alkyl group can be isopropyl, isobutyl, isoamyl, isohexyl, isoheptyl, isooctyl, and the like, and has a formula
n 5 Is between 1 and 10Or may have a plurality of branches.
In a particular embodiment of the invention, R 3 Selected from linear alkyl groups having 1 to 4 carbon atoms.
In a particular embodiment of the invention, R 1 Is composed of
R 5 Selected from alkylene groups having 1 to 5 carbon atoms, R 6 Selected from asymmetric cycloalkyl groups.
As in the different embodiments, R 5 Can be-CH 2 -、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -and so on.
In a particular embodiment of the invention, R 1 Wherein the site linked to the benzophenone group is the urethane structure side and the site linked to N is the (meth) acrylate side.
In a particular embodiment of the invention, R 6 Is composed of
In a particular embodiment of the invention, R 1 Is composed of
Any one of the above.
In a specific embodiment of the present invention, the hydrogen abstraction-type photoinitiator has any one of the following structural formulas:
the invention also provides a preparation method of any one of the hydrogen abstraction type photoinitiators, which comprises the following steps:
(a) Compound A 1 Or compound A 2 With diisocyanates and hydroxyl-containing (meth) acrylates to give compounds containing
A benzophenone derivative of a structural unit;
(b) Performing Michael addition reaction on polyaspartic acid ester polyamine and the benzophenone derivative to obtain the photoinitiator;
wherein, compound A 1 And compound A 2 Are respectively of the formula
The structural formula of the polyaspartic acid ester polyamine is shown as
As in the specific embodiments, compound A 1 And compound A 2 Can be respectively shown as
(4-hydroxybenzophenone) and
(4, 4' -dihydroxybenzophenone).
In a specific embodiment of the invention, the polyaspartate polyamine is derived primarily from the reaction of a dialkyl triamine and a butene diacid diester; the structural formulas of the dialkyl triamine and the butenedioic acid diester are respectively shown as
Further, the dialkyl triamine comprises any one or more of diethylene triamine, dipropylene triamine and bis-hexamethylene triamine; the butenedioic acid diester comprises a maleic acid diester and/or a fumaric acid diester, wherein the maleic acid diester is selected from any one or more of diethyl maleate, dipropyl maleate, dibutyl maleate and methylpropyl maleate, and the fumaric acid diester is selected from any one or more of diethyl fumarate, dipropyl fumarate, dibutyl fumarate and methylpropyl fumarate.
In a specific embodiment of the invention, the polyaspartic acid ester polyamine is mainly obtained by Michael addition reaction of dialkyl triamine and butene diacid diester.
In the preparation of polyaspartic ester polyamines, the primary amine groups of the dialkyltriamines react with the butenedioic acid diesters, while the secondary amine groups hardly participate in the addition reaction due to steric effects. Then, the steric hindrance effect of the hindered secondary amine generated by the primary amine in the Michael addition reaction and the (meth) acrylate unit in the benzophenone derivative is inhibited by the steric hindrance effect, and the activity is extremely low.
In the preparation of polyaspartic acid ester polyamine, the reaction process is as follows:
in practice, the preparation of polyaspartic ester polyamines comprises: slowly dripping the butenedioic acid diester into the dialkyl triamine, and heating to 40-60 ℃ to react for 3-6 h after finishing dripping. Further, N is introduced into the system 2 10-30 min; the dropping time of the butenedioic diester is 0.5 to 1 hour, and the temperature in the dropping process is controlled to be 25 to 30 ℃.
In a particular embodiment of the invention, the molar ratio between the dialkyltriamine and the diester of butenedioic acid is 1: 1.8 to 2.2, preferably 1: 2.
In a particular embodiment of the invention, in step (a), compound A 1 Or compound A 2 Firstly reacting with diisocyanate to obtain an intermediate, and then reacting with hydroxyl-containing (methyl) acrylate. In order to obtain benzophenone derivatives in high yields, the intermediate needs to be an NCO-terminated product, and the resulting monofunctional and difunctional NCO-containing intermediates are each of the following structural formulae:
in order to reduce the formation of benzophenone end-capping products or oligomers (with the compound A) 2 For example, 4' -dihydroxybenzophenone) as a raw material, tolylene diisocyanate TDI and isophorone diisocyanate IPDI having different NCO reactivity are preferably used as a raw material for synthesis, and the diisocyanate is more preferably IPDI in view of yellowing resistance.
In a particular embodiment of the invention, in step (a), the reaction is carried out under the action of a catalyst. To enhance the difference in NCO reactivity. Further, the catalyst is an organotin-based catalyst, such as dibutyltin dilaurate (DBTDL). Furthermore, the dosage of the catalyst is 0.02-0.2% of the total mass of the reactants.
In a particular embodiment of the invention, in step (a), compound A 1 Or compound A 2 The reaction temperature with diisocyanate is 30-60 ℃. In actual operation, the reaction time in the step is regulated and controlled by monitoring the NCO peak area of the reaction liquid through infrared spectroscopy, when the NCO peak area in the reaction liquid is constant, the reaction is stopped, and then the next step of reaction with the hydroxyl-containing (methyl) acrylate is carried out.
In a specific embodiment of the present invention, the hydroxyl group-containing (meth) acrylate includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
In a specific embodiment of the present invention, in the step (a), the reaction temperature of the intermediate with the hydroxyl group-containing (meth) acrylate is 20 to 50 ℃. In actual operation, the reaction time in the step is regulated and controlled by monitoring the NCO peak area of the reaction liquid through infrared spectroscopy, and the reaction is stopped when the NCO peak area in the reaction liquid disappears.
In a specific embodiment of the present invention, the polyaspartic acid ester polyamine and the benzophenone derivative are reacted at a molar ratio of 1: 1 (0.9 to 1.1), preferably 1: 1, in the step (b). Wherein, the reaction molar ratio refers to the molar ratio of non-hindered secondary amine of polyaspartic ester polyamine to terminal alkenyl in the benzophenone derivative.
In a specific embodiment of the present invention, the reaction temperature in the preparation of the polyaspartic acid ester polyamine is 25 to 60 ℃. In actual operation, the unsaturated value in the reaction system is measured by a mercaptan-iodine titration method, the reaction conversion rate is obtained, and the reaction time is regulated and controlled.
In a specific embodiment of the present invention, in step (b), the polyaspartate polyamine is added to the benzophenone derivative. In practical operation, the polyaspartic acid ester polyamine is slowly dripped into the reaction liquid of the benzophenone derivative obtained in the step (a).
In the specific implementation mode of the invention, in the step (b), the dripping time of the polyaspartic ester polyamine is 1-3 h, and the temperature of the reaction system is controlled within 40 ℃ in the dripping process; after the dropwise addition is finished, the reaction is carried out for 2 to 4 hours at the temperature of between 45 and 50 ℃.
The steric hindrance type secondary amine group in the polyaspartic acid ester polyamine has low reactivity due to steric hindrance effect, the reactivity with (methyl) acrylic ester unit in the benzophenone derivative is far less than that with other secondary amine in the polyaspartic acid ester polyamine, and the probability of reaction of the steric hindrance type secondary amine and the (methyl) acrylic ester unit can be further reduced by a dropwise adding mode. Taking the monofunctional benzophenone derivative as an example, the reaction process is as follows:
the invention also provides another preparation method of any one of the hydrogen abstraction photoinitiators, which comprises the following steps:
(a1) Compound A 1 Or compound A 2 With a monomer containing isocyanate and (meth) acrylate to give a polymer containing
A benzophenone derivative of a structural unit;
(b1) Carrying out Michael addition reaction on polyaspartic acid ester polyamine and the benzophenone derivative to obtain the photoinitiator;
wherein, compound A 1 And compound A 2 Are respectively of the formula
The structural formula of the polyaspartic acid ester polyamine is shown as
In a specific embodiment of the present invention, the isocyanate and (meth) acrylate-containing monomer comprises isocyanate ethyl acrylate and/or isocyanate ethyl methacrylate.
In a particular embodiment of the invention, in step (a 1), the reaction is carried out under the action of a catalyst. Further, the catalyst is an organotin-based catalyst, such as dibutyltin dilaurate (DBTDL). Furthermore, the dosage of the catalyst is 0.02-0.2% of the total mass of the reactants.
In a particular embodiment of the invention, in step (a 1), the reaction is carried out at a temperature of from 20 to 30 ℃, for example at room temperature. In actual operation, the reaction time of the step can be regulated and controlled by monitoring the NCO peak area of the reaction liquid through infrared spectroscopy, and the reaction is stopped when the NCO peak area in the reaction liquid disappears.
In the above process, the step (b 1) is operated under the same conditions as those in the step (b) of the above process.
In a particular embodiment of the invention, both step (a) and step (a 1) are reactions carried out in the presence of an organic solvent, which may be ethyl acetate, for example.
In a specific embodiment of the present invention, the organic solvent is added in an amount corresponding to the amount of the compound A 1 Or compound A 2 In a ratio of (0.9 to 1.1) L: 1mol, e.g. 1L: 1mol.
In a specific embodiment of the present invention, a polymerization inhibitor is added to the reaction liquid containing the benzophenone derivative obtained in step (a) or step (a 1). Wherein, the polymerization inhibitor can be p-methoxyphenol.
In a specific embodiment of the present invention, after the step (b) or step (b 1) reaction is completed, the solvent is removed to obtain the photoinitiator. The hydrogen abstraction type photoinitiator prepared by the invention can be used for downstream application of subsequent products without further separation and purification.
The invention also provides an application of any one of the hydrogen abstraction photoinitiators in an OCA adhesive film. In order to better remove bubbles in the lamination process of the fully laminated OCA adhesive film, the OCA adhesive film needs to have better fluidity. When the photoinitiator is attached, the photoinitiator can play a role of a plasticizer in the composition of an OCA adhesive film, so that the modulus of the adhesive film is reduced, and the fluidity is improved. After the lamination is finished, in order to improve the bonding reliability of the lamination, the adhesive film is required to have higher modulus, and when high-temperature and high-pressure defoaming is carried out, the photo-thermal dual hydrogen abstraction photoinitiator not only can play a role in photoinitiation, and steric type secondary amine reacts with closed NCO to generate carbamido, but also can react with tertiary C-H to generate photochemical reaction shown in the specification, so that the crosslinking density is further improved, the modulus of the OCA adhesive film is increased, and the mobility of the photoinitiator is greatly reduced. Because of the thermally induced reaction of the light-shielded region, low mobility is exhibited even in the light-shielded region.
The wavy line referred to in the present invention indicates the position of the attachment to the rest of the compound in the group.
The invention also provides an OCA composition which comprises 1-10% of hydrogen abstraction type photoinitiator by mass percent.
In a particular embodiment of the invention, the OCA composition comprises the following components in mass percent: 70-97% of acrylate monomer and prepolymer, 1-10% of hydrogen abstraction type photoinitiator and 2-20% of closed isocyanate.
In practical operation, the OCA composition further comprises a radiation curing photoinitiator or a thermal cracking free radical initiator, such as Irgacure 651, wherein the photoinitiator is cured by a low-pressure mercury lamp when an OCA adhesive film is prepared at the front end; after the hydrogen abstraction photoinitiator is bonded, a high-pressure mercury lamp is adopted for curing; the two curing methods have different wave bands and different processes. As in the various embodiments, the Irgacure 651 photoinitiator is used in an amount of 0.1 to 0.2wt%, such as 0.1 to 0.15wt%, based on the sum of the weight of the acrylate monomer, prepolymer, hydrogen abstraction photoinitiator, and blocked isocyanate.
The method for preparing the OCA adhesive film by adopting the OCA composition can comprise the following steps: mixing acrylate monomer, prepolymer, hydrogen abstraction type photoinitiator and Irgacure 651 photoinitiator, and reacting at 70-100 mJ/cm 2 Performing irradiation treatment for 3-6 min under the condition to obtain viscous liquid; then uniformly mixing the viscous liquid with the blocked isocyanate and Irgacure 651 photoinitiator, coating the mixture, and then coating the mixture at a concentration of 70-100 mJ/cm 2 And carrying out irradiation treatment for 3-6 min under the condition. The dosage of the Irgacure 651 photoinitiator added for the first time is 0.01 to 0.02 percent by weight, such as 0.02 percent by weight, of the sum of the mass of the acrylate monomer, the prepolymer, the hydrogen abstraction photoinitiator and the blocked isocyanate; the amount of the Irgacure 651 photoinitiator added for the second time is 0.09-0.18 wt%, such as 0.1wt%, of the sum of the mass of the acrylate monomer, the prepolymer, the hydrogen abstraction photoinitiator and the blocked isocyanate.
In a specific embodiment of the present invention, the blocked isocyanate includes any one or more of acetone oxime, cyclohexanone oxime, acetyl ketone oxime, methyl ethyl ketone oxime, diethyl malonate blocked hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, 1, 4-cyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, and isophorone diisocyanate.
In a specific embodiment of the present invention, the acrylate monomer includes a tertiary carbon-containing acrylate monomer. Further, the acrylate monomer comprises isooctyl acrylate and/or 2-ethylhexyl acrylate.
In a specific embodiment of the present invention, the light curing conditions of the OCA composition include: the UV curing energy is 1000-2500 mJ/cm 2 (ii) a The thermal curing conditions for the OCA composition include: the curing temperature is 70-90 ℃, and the curing time is 10-20 min.
In practice, the OCA composition may be cured thermally before being cured by light, or both cured by light and thermally.
Some of the material information used in the following embodiments may be as follows, but is not limited to:
diethylenetriamine, dipropylenetriamine and dihexamethylenetriamine, the purity of which is more than 98 percent, and TCI;
diethyl maleate with purity of more than 99 percent, annaiji;
dibutyl maleate with purity of more than 99.5 percent, and alatin;
diethyl fumarate with purity of more than 98.5 percent, and alatin;
isocyanate ethyl acrylate AOI and isocyanate ethyl methacrylate MOI, the purity of which is more than 97 percent, zhang Hour Topu chemical industry;
isophorone diisocyanate (IPDI), purity > 99%, vanhua chemistry;
4-hydroxybenzophenone and 4,4' -dihydroxybenzophenone, purity > 98%, TCI;
dibutyltin dilaurate DBTDL, the purity is more than 95 percent, TCI;
4- (2-hydroxyethoxy) benzophenone with purity of more than 98%, new materials Co., ltd for Tianjin;
acryloyl chloride, purity > 98%, TCI;
triethylamine, purity > 99%, TCI;
diethanolamine, purity > 99%, TCI.
And (3) testing and characterizing:
1. infrared: and (3) qualitatively characterizing the structure of the product by adopting a Fourier transform infrared spectrum. The instrument model is as follows: a Bruker Vector model 33 FT-IR spectrometer; the detection range is mainly 400-4000 cm -1 In between, the extent of reaction is detected by monitoring the change in the characteristic group absorption peak area.
2. Nuclear magnetism: the PAE product is subjected to nuclear magnetic resonance spectroscopy 1 And (5) qualitatively characterizing by H NMR. The instrument model is as follows: bruker 400MHz. And (3) testing conditions: and (3) preparing a sample by using deuterated DMSO as a solvent.
3. Ultraviolet absorption spectrum:
the main component of the initiator can be obtained by adopting an ultraviolet spectrophotometer U-3900 model, selecting acetonitrile as a solvent and testing the ultraviolet absorption spectrum of the photoinitiator in the range of 200-350 nmThe absorbance values at the absorption range and the maximum absorption wavelength were calculated by the following formula to find the maximum molar extinction coefficient. The concentration of the sample in the test process is 5 multiplied by 10 -5 mol/L。
A＝c·ε·l
Wherein A is absorbance; c is the substance concentration; epsilon is the molar extinction coefficient; l is the optical path length.
4. Relative mobility of the photoinitiator:
tripropylene glycol diacrylate (TPGDA) solutions containing the following mole fractions of photoinitiators were prepared, respectively:
(1) TPGDA solution of 1wt% Benzophenone (BP) and 1wt% triethanolamine;
(2) 1wt% TPGDA solution of the example photoinitiator;
(3) 1wt% TPGDA solution of the photoinitiator of the comparative example.
Injecting into silica gel pad mold with size of 40mm 6mm 1mm, and irradiating in high pressure mercury lamp UV curing box for 5min with light intensity of 40mW/cm 2 . And then mashing the cured sample strips, weighing 0.1g of the sample strips, soaking the sample strips in 10mL of dichloromethane at room temperature for 5 days, and measuring the absorbance of the photoinitiator in the soaking solution at the maximum absorption peak by using an ultraviolet-visible spectrophotometer. The relative concentrations of the various photoinitiators were calculated from the following formula, and the relative mobilities of the synthetic photoinitiators of examples and comparative examples were measured using the relative concentration value of the photoinitiator BP as a reference.
C＝A/(ε×L×V)×10 -2 ；
R＝C 1 /C 2 ×100％。
In the formula: c is the relative molar concentration of the photoinitiator in the extract (the soaking solution); a is the absorbance at the maximum absorption peak of the photoinitiator; l is the optical path length; epsilon is the molar absorption coefficient at the maximum absorption peak of the photoinitiator; c 1 The relative molar concentrations of the photoinitiators were synthesized for the inventive and comparative examples; c 2 Is the relative molar concentration of BP; the inventive and comparative examples, in which R is, synthesize the relative mobility of the photoinitiator.
Example 1
This example provides a hydrogen abstraction-type photoinitiator and a method of making the same, the hydrogen abstraction-type photoinitiator having the following structure:
the synthetic route is as follows:
specifically, the preparation method of the hydrogen abstraction type photoinitiator comprises the following steps:
(1) Carbamate synthesis: pre-drying ethyl acetate solvent by using a 4A molecular sieve to remove water; the reaction was dried with a forced air oven using glassware. 142g (1.0 mol) of ethyl isocyanate Acrylate (AOI) and 2g of di-n-butyltin dilaurate (DBTDL) were weighed into a 3L jacketed glass reaction kettle equipped with a mechanical stirrer and shielded from light, and stirred at room temperature to obtain a mixture. 107g (0.5 mol) of 4,4 '-dihydroxybenzophenone (4, 4' -DHBP) was dissolved in 1L of ethyl acetate, placed in a 1.5L isobaric dropping funnel, added dropwise to the above mixture, and dropped over 2.5 h. After the dripping is finished, the reaction is continued until the area of NCO peak is monitored by infrared ray (2268 cm) -1 ) Reducing the reaction solution until the solution disappears, adding 0.3g of p-methoxyphenol polymerization inhibitor, and stirring uniformly.
(2) Michael addition 1: 103.2g (1 mol) of diethylenetriamine are introduced into a 1L four-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer, a constant-pressure dropping funnel, N being connected thereto 2 An air path pipe and a bubbler, 344.4g (2 mol) of diethyl maleate is added into a constant pressure dropping funnel, and N is introduced into the system 2 Replacing air in the system for 10 min; slowly dripping diethyl maleate into a flask under the condition of stirring at 25 ℃, finishing dripping at a constant speed for 1h, controlling the reaction temperature to be 30 ℃, then heating to 60 ℃ for reaction for 3h, measuring the unsaturated value in the reaction system to be 0.33mg of maleic acid/g of resin by a mercaptan-iodine titration method, indicating that the reaction conversion rate of maleic ester is 99.9 percent, stopping the reaction, and obtaining polyaspartic ester polyamine.
(3) Michael addition 2: at 1L constantAdding polyaspartic ester polyamine obtained in the step (2) into a pressure dropping funnel, slowly dropwise adding the polyaspartic ester polyamine into the reaction liquid obtained in the step (1), finishing dropping for 2h, controlling the temperature of a reaction system within 30 ℃ during dropwise adding, keeping the temperature for reaction for 5h at 25 ℃ after completing dropwise adding, and monitoring the reaction liquid through infrared until the characteristic peak of the C = C double bond of the acrylic ester (1637 cm) -1 ) And stopping stirring until the reaction disappears, and removing the reaction solvent ethyl acetate by rotary evaporation to obtain the hydrogen abstraction type photoinitiator.
Structural characterization data of the prepared hydrogen abstraction photoinitiator:
infrared Spectrum (KBr pellet), v (cm) -1 ): 3319 (secondary amine N-H stretching vibration peak), 2980, 2920, 2850 (methyl, methylene, methine stretching vibration peak), 1725 (ester group, ketone, urethane carbonyl C = O stretching vibration peak), 1538 (amide N-H deformation vibration peak of urethane and C-N stretching vibration peak coupling).
NMR characterization structure: 1 h NMR (DMSO), δ:7.72 (d, 4H), 7.43 (d, 4H), 6.76 (s, 2H), 4.01-4.11 (m, 24H), 3.76 (m, 4H), 3.14 (m, 4H), 2.90 (m, 8H), 2.65 (m, 8H), 2.48 (m, 12H), 1.21 (m, 24H). The hydrogen abstraction photoinitiator produced was confirmed to be the target product structure.
Example 2
This example provides a hydrogen abstraction-type photoinitiator and a method of making the same, the hydrogen abstraction-type photoinitiator having the following structure:
the synthetic route is as follows:
specifically, the preparation method of the hydrogen abstraction type photoinitiator comprises the following steps:
(1) Carbamate synthesis: drying the solvent ethyl acetate by using a 4A molecular sieve in advance to remove water; the reaction was dried with a forced air oven using glassware. Weighing 222.3g (1.0 mol) of isophorone diisocyanate (IPDI), 2g of di-n-butyltin dilaurate (DBTDL) were added to a 3L jacketed glass reaction kettle equipped with mechanical stirring and light-shielded, and stirred at room temperature to obtain a mixture. 198g (1 mol) of 4-hydroxybenzophenone (4-HBP) was added to 1L of ethyl acetate to dissolve, and the solution was put into a 1.5L constant pressure dropping funnel, and added dropwise to the above mixture over 2.5 h. After the dripping is finished, the reaction is continued until the area of NCO peak is monitored by infrared ray (2268 cm) -1 ) No longer changing; then adding 116.2 (1 mol) hydroxyethyl acrylate (HEA) into the dropping funnel, dropping into the reaction solution at room temperature for 2.5h, gradually heating to 50 ℃, and continuing to react until the area of NCO peak (2268 cm) is monitored by infrared ray -1 ) Reducing the reaction solution until the solution disappears, adding 0.3g of p-methoxyphenol polymerization inhibitor, and stirring uniformly.
(2) Michael addition 1: 215.38g (1 mol) of bis-hexamethylene triamine are introduced into a 1L four-necked round-bottomed flask equipped with a mechanical stirrer, thermometer, isobaric dropping funnel, N-connection 2 An air path pipe and a bubbler, 344.36g (2 mol) of diethyl maleate is added into a constant pressure dropping funnel, and N is introduced into the system 2 Replacing air in the system for 10 min; slowly dripping diethyl maleate into a flask under the condition of stirring at 25 ℃, finishing dripping at a constant speed for 1h, controlling the reaction temperature to be 30 ℃, then heating to 60 ℃ for reaction for 3h, measuring the unsaturated value in the reaction system to be 0.33mg maleic acid/g resin by a mercaptan-iodine titration method, indicating that the conversion rate of the maleic acid ester reaction is 99.9%, and stopping the reaction to obtain polyaspartic acid ester polyamine.
(3) Michael addition 2: adding the polyaspartic ester polyamine obtained in the step (2) into a 1L constant-pressure dropping funnel, slowly dropwise adding the polyaspartic ester polyamine into the reaction liquid obtained in the step (1), finishing dropping for 2h, controlling the temperature of a reaction system within 30 ℃ during dropwise adding, keeping the temperature at 25 ℃ for reacting for 5h after completing dropwise adding, and monitoring the reaction liquid by infrared until the characteristic peak of the C = C double bond of the acrylic ester (1637 cm) -1 ) And stopping stirring until the reaction disappears, and removing the reaction solvent ethyl acetate by rotary evaporation to obtain the hydrogen abstraction type photoinitiator.
Structural characterization data of the prepared hydrogen abstraction photoinitiator:
infrared Spectrum (KBr pellet), v (cm) -1 ): 3319 (secondary amine N-H stretching vibration peak), 2980, 2920, 2850 (methyl, methylene, methine stretching vibration peak), 1725 (ester group, ketone, urethane carbonyl C = O stretching vibration peak), 1538 (amide N-H deformation vibration peak of urethane and C-N stretching vibration peak coupling).
The NMR characterization structure is: 1 h NMR (DMSO), δ:7.81 (d, 2H), 7.72 (d, 2H), 7.61 (m, 1H), 7.51 (m, 2H), 7.43 (m, 2H), 4.31 (m, 4H), 4.01 to 4.11 (m, 10H), 3.76 (m, 2H), 3.54 (m, 1H), 2.90 to 3.01 (m, 10H), 2.5 (m, 6H), 1.67 (m, 4H), 1.29 to 1.39 (m, 16H), 1.07 (m, 14H), 0.94 (s, 3H), 0.87 (s, 6H). The hydrogen abstraction photoinitiator thus obtained was confirmed to have the target product structure.
Example 3
This example provides a hydrogen abstraction-type photoinitiator and a method of making the same, the hydrogen abstraction-type photoinitiator having the structure:
the synthetic route is as follows:
specifically, the preparation method of the hydrogen abstraction type photoinitiator comprises the following steps:
(1) Carbamate synthesis: pre-drying ethyl acetate solvent by using a 4A molecular sieve to remove water; the reaction was dried with a forced air oven using glassware. 142g (1.0 mol) of ethyl isocyanate Acrylate (AOI) and 2g of di-n-butyltin dilaurate (DBTDL) were weighed into a 3L jacketed glass reactor equipped with a mechanical stirrer and shielded from light, and stirred at room temperature to obtain a mixture. 198.3g (1 mol) of 4-hydroxybenzophenone (4-HBP) was added to 1L of ethyl acetate to dissolve it, and the resulting solution was placed in a 1.5L isobaric dropping funnel and added dropwise toThe mixture was added dropwise over 2.5 h. After the dripping is finished, the reaction is continued until the area of NCO peak is monitored by infrared (2268 cm) -1 ) Reducing the reaction solution until the solution disappears, adding 0.3g of p-methoxyphenol polymerization inhibitor, and stirring uniformly.
(2) Michael addition 1: 131.2g (1 mol) of dipropylenetriamine are introduced into a 1L four-necked round-bottomed flask equipped with a mechanical stirrer, thermometer, isobaric dropping funnel, connected with N 2 An air path pipe and a bubbler, 456.6g (2 mol) of dibutyl maleate is added into a constant-pressure dropping funnel, and N is introduced into the system 2 Replacing air in the system for 10 min; slowly dripping dibutyl maleate into a flask under the condition of stirring at 25 ℃, finishing dripping at a constant speed for 1h, controlling the reaction temperature to be 30 ℃, then heating to 60 ℃ for reaction for 24h, measuring the unsaturated value in the reaction system to be 0.33mg of maleic acid/g of resin by a mercaptan-iodine titration method, indicating that the reaction conversion rate of maleic ester is 99.9 percent, and stopping the reaction to obtain polyaspartic acid ester polyamine.
(3) Michael addition 2: adding the polyaspartic ester polyamine obtained in the step (2) into a 1L constant-pressure dropping funnel, slowly dropwise adding the polyaspartic ester polyamine into the reaction liquid obtained in the step (1), finishing dropping for 2h, controlling the temperature of a reaction system within 30 ℃ during dropwise adding, keeping the temperature for reaction for 5h at 25 ℃ after completing dropwise adding, and monitoring the reaction liquid through infrared until the characteristic peak of C = C double bond of acrylate (1637 cm) -1 ) And stopping stirring until the reaction disappears, and removing the reaction solvent ethyl acetate by rotary evaporation to obtain the hydrogen abstraction type photoinitiator.
Structural characterization data of the prepared hydrogen abstraction type photoinitiator:
infrared Spectrum (KBr pellet), v (cm) -1 ): 3319 (secondary amine N-H stretching vibration peak), 2980, 2920, 2850 (stretching vibration peak of methyl, methylene, methine), 1725 (stretching vibration peak of carbonyl C = O of ester group, ketone, carbamate), 1538 (coupling of C-N stretching vibration peak and N-H deformation vibration peak of amide of carbamate).
NMR characterization structure: 1 H NMR(DMSO)，δ：7.81(d,2H)，7.72(d,2H)，7.61(m,1H)，7.51(m,2H)，7.43(m,2H),4.06～4.13(m,12H)，3.15(m,2H)，2.9(d,4H)，2.75(m,2H)，2.68(m,2H)，2.54(m,4H)，2.35(m,2H)，1.54(m,8H)，1.40(m, 8H), 1.11 (d, 6H), 0.90 (m, 12H). The hydrogen abstraction photoinitiator produced was confirmed to be the target product structure.
Example 4
The present example provides OCA compositions and their preparation, wherein the formulations of each group of OCA compositions are shown in table 1:
TABLE 1 formulation systems for different OCA compositions
Wherein EHA is 2-ethylhexyl acrylate (Happy chemical industry); HEA is 2-hydroxyethyl acrylate (Changxing chemical industry); THFA is tetrahydrofurfuryl acrylate (of the changxing chemical industry); ACMO is acryloylmorpholine (japan gigashi); methyl ethyl ketoxime blocks IPDI (wanhua chemistry). The photoinitiator was the hydrogen abstraction type photoinitiator prepared in examples 1 to 3, and nos. 1# (1-1 #, 2-1#, 3-1 #), 2# (1-2 #, 2-2#, 3-2 #), 3# (1-3 #, 2-3#, and 3-3 #) correspond to the photoinitiators in examples 1 to 3, respectively.
The preparation of the OCA composition comprises:
(1) All the components in Step1 of the above formulation system and 0.02% by mass (0.02% here means: 0.02% of the sum of all the components in Step1 and Step 2) of a photoinitiator (Irgacure 651) were mixed thoroughly in a reactor. With N 2 After replacing the dissolved oxygen, the solution is irradiated by a low-pressure mercury lamp (the irradiation dose is about 70-100 mJ/cm) 2 ) For several minutes (3-6 min) to prepare a viscous liquid with a viscosity of 2000-5000 cp at 25 ℃.
(2) The components in Step2 and 0.1% by mass percent (0.1% herein means that the sum of all the components in Step1 and Step2 is 0.1%) of photoinitiator Irgacure 651 are added into a reactor and mixed well, so as to prepare the OCA composition.
(3) And (3) coating the composition obtained in the step (2) between a light layer and a heavy layer of ethylene terephthalate (PET) release films to form an OCA coating film with the thickness of 175 mu m. Using a low-pressure UV mercury lamp at 1000mJ/cm 2 Is irradiated with a dose of fromThereby preparing an OCA adhesive film.
Comparative example 1
Comparative example 1 provides a photoinitiator and a method of making the same, the photoinitiator having the following structure:
the synthetic route is as follows:
specifically, the preparation method of the photoinitiator comprises the following steps:
484.6g (2 mol) of 4- (2-hydroxyethoxy) benzophenone, 222.6g (2.2 mol) of triethylamine and 1kg of dichloromethane were placed in a 3L jacketed glass reactor equipped with a mechanical stirring blade, a thermometer, a constant pressure dropping funnel, connected with N 2 Cooling to 0 deg.C with gas line pipe and bubbler, adding 199.2g (2.2 mol) of acryloyl chloride into constant pressure dropping funnel, and introducing N into the system 2 Replacing air in the system for 20 min; slowly dripping acryloyl chloride into a glass reaction kettle under the stirring condition of 0-5 ℃, finishing dripping at a constant speed for 2h, naturally heating to 10 ℃ for reacting overnight, filtering to remove triethylamine hydrochloride, and using NaHCO 3 Extracting the saturated solution, removing the solvent by rotary evaporation, and recrystallizing with a mixed solvent of n-hexane and dichloromethane to obtain white granular crystals, namely the photoinitiator.
Characterization data of the structure of the photoinitiators prepared:
infrared Spectrum (KBr pellet), v (cm) -1 ): 1725 (stretching vibration peak of ester carbonyl C = O), 1650 (stretching vibration peak of ketone carbonyl C = O), 808 (bending vibration peak of carbon-carbon double bond = C — H).
The NMR characterization structure is: 1 h NMR (DMSO), δ:7.84 (d, 2H), 7.77 (d, 2H), 7.59 (t, 1H), 7.49 (t, 2H), 7.00 (d, 2H), 6.48 (d, 1H), 6.19 (dd, 1H), 5.89 (d, 1H), 4.57 (m, 2H), 4.32 (m, 2H). The structure of the obtained photoinitiator was confirmed to be the target product.
Comparative example 2
Comparative example 2 provides a photoinitiator and a method of making the same, the photoinitiator having the following structure:
the synthetic route is as follows:
specifically, the preparation method of the photoinitiator comprises the following steps:
4296.5g (1 mol) of the photoinitiator obtained in comparative example 1 and 500g of ethanol are added into a 2L jacketed glass reaction kettle which is provided with a mechanical stirring paddle, a thermometer, a constant pressure dropping funnel and a bubbler, the temperature is reduced to 0 ℃, 105.2 (1 mol) of diethanolamine is added into the constant pressure dropping funnel, the diethanolamine is slowly dropped into the glass reaction kettle under the stirring condition of 0-5 ℃, the uniform dropping is completed within 2h, then the reaction is kept at 0 ℃ for overnight, the solvent is removed by rotary evaporation, and the ethyl acetate solvent is used for recrystallization to obtain light yellow solid, namely the single-component photoinitiator.
Structural characterization data of the prepared photoinitiators:
infrared Spectrum (KBr pellet), v (cm) -1 ): 3449 (hydroxyl group O — H stretching vibration peak), 1725 (ester group carbonyl C = O stretching vibration peak), 1650 (ketone carbonyl C = O stretching vibration peak), 1351 (tertiary amine C — N stretching vibration peak).
NMR characterization structure: 1 h NMR (DMSO), δ:7.81 (d, 2H), 7.73 (d, 2H), 7.60 (t, 1H), 7.50 (t, 2H), 7.01 (d, 2H), 4.43 (m, 4H), 3.76 (m, 2H), 3.42 (m, 4H), 2.57 (m, 4H), 2.49 (m, 2H). The structure of the obtained photoinitiator was confirmed to be the target product.
Comparative example 3
Comparative example 3 referring to example 4, an OCA composition is provided, and the formulations for each group of OCA compositions are shown in table 2, prepared in the same manner as in example 4.
TABLE 2 formulation systems for different OCA compositions
Wherein, 4# (1-4 #, 2-4#, 3-4 #), 5# (1-5 #, 2-5#, 3-5 #) correspond to the photoinitiators of comparative examples 1 and 2, respectively.
Experimental example 1
Preparation of samples for performance characterization:
uncured test specimen: the OCA adhesive films prepared by the methods of example 4 and comparative example 3 were cut into adhesive films of 100mm × 25mm × 175 μm (length × width × thickness), the light PET release film was peeled off and removed, and the films were attached to a glass sheet, and then, defoaming was performed at 60 ℃/0.5MPa under high temperature and high pressure conditions for 30min, and the films were naturally cooled to room temperature.
Sample after heat curing: the uncured sample was further cured at 85 ℃ for 10min under a light-shielding condition, and then cooled to room temperature.
Sample after photo-thermal dual cure: the uncured sample is further subjected to photo-thermal curing for 10min at 85 ℃ under a high-pressure mercury lamp, and the irradiation energy of the high-pressure UV mercury lamp is 2000mJ/cm 2 And naturally cooling to room temperature.
And (3) carrying out performance evaluation on the prepared OCA adhesive film, wherein the specific sample preparation and characterization method comprises the following steps:
1. ink wetting Properties:
the uncured OCA adhesive film was subjected to this test to evaluate the ability of the OCA adhesive film to fill and wet the ink step during lamination, and to prevent the formation of new bubbles after deformation at larger ink steps. Use a vacuum laminator (13N/cm) 2 Lamination under pressure 15s,30pa vacuum), an OCA sample was laminated between a plain rectangular (19 cm × 12 cm) glass panel and a rectangular (19 cm × 12 cm) glass panel with black ink (50 μm high × 0.6cm wide) along the four edges. The laminate was then degassed under high pressure (60 ℃ C. And 0.5MPa for 30 min) withThe OCA glue layer near the ink edge is then inspected for bubbles that may have formed in it that would obstruct the viewing area of the display. The wetting effect is represented by the following symbols: 0 means the fewest bubbles around the ink (< 5), Δ means some bubbles around the ink (> 5 but < 10), and X means a large number of bubbles around the ink (> 10).
2. And (3) inspecting the bonding reliability:
in order to compare and illustrate the bonding reliability of the OCA adhesive films prepared by the photoinitiators of the different examples and comparative examples of the present invention, after the OCA adhesive films prepared by the examples 4 and the comparative examples 3 are cured after being bonded, the high temperature, high humidity and aging resistance is tested.
And (4) testing standard: GBT2423.3-2006 environmental test for Electrical and electronic products.
And (3) placing the sample in a constant-temperature wet and hot box with the temperature of 85 ℃ and the relative humidity of 85%, and carrying out appearance observation, light transmittance and haze test and 180-degree peeling force test after 1000 h.
And (3) appearance inspection:
the detection method comprises the following steps: and (3) performing appearance inspection on the sample strip after the reliability experiment, and visually inspecting the sample strip by an inspector under a common light source (the background is black) at an angle of 0-90 degrees with the finished product.
And (4) judging the standard: the presence or absence of bubbles; whether the edge is whitish or not.
Light transmittance and haze test:
and (4) testing standard: GB/T2410-2008 determination of transparent plastic light transmittance and haze, and the test light wavelength range is 380-780 nm.
180 ℃ peel strength (unit N/25 mm):
and (4) testing standard: GB/T2792-1998 test method for 180 DEG peeling strength of pressure-sensitive adhesive tape.
Initiator migration characterization results are shown in table 3 below:
TABLE 3 initiator relative mobility of OCA cured films
The initiator mobility comparison results of the above examples and comparative examples show that the photo-thermal dual-curing initiator prepared by the present invention has much lower solvent extraction rate, i.e., significantly lower initiator mobility, than the polymerizable photoinitiator of comparative example 1 or the one-component photoinitiator of comparative example 2. This is mainly because the dual-cure initiator of the present invention not only has relatively larger molecular weight and better compatibility and dispersion in the system, but also gives the initiator more sufficient ways to integrate into the polymer chain, thereby resulting in a greatly reduced proportion of free initiator. Even after simple thermal curing, relatively low mobility.
In order to compare the effects of different initiators on the performance of the OCA adhesive films, the performance of the OCA adhesive films obtained according to the formulations in tables 1 and 2 was evaluated, and the results are shown in table 4.
TABLE 4 Performance test results of OCA adhesive films before and after photo-thermal dual post-curing
The performance test results of the OCA adhesive films obtained by the initiators of the above examples and comparative examples show that, compared with the polymerizable photoinitiator of comparative example 1 or the single-component photoinitiator of comparative example 2, the photo-thermal dual-curing initiator prepared by the invention has better plasticizing effect, and the wettability to the ink segment difference and the stripping force after bonding are obviously better than those of the polymerizable photoinitiator of comparative example 1 or the single-component photoinitiator of comparative example 2 under the same formula system. After photo-thermal dual curing, the generation of cross-linking causes the shrinkage of the adhesive film to generate stress, and the stripping force is slightly reduced. However, the occurrence of crosslinking simultaneously imparts more excellent adhesion reliability under the conditions of the double 85 test (85 ℃/85% RH humidity) to the adhesive film. The photo-thermal dual curing agents in the examples of the present invention are superior to the comparative examples in appearance, light transmittance, haze and peeling force after the reliability test.
In order to examine the effect of simple heat curing on the performance of the OCA adhesive film under the light-shielding condition, the performance data shown in table 5 were obtained by characterization.
TABLE 5 Performance test results of OCA adhesive film before and after thermosetting
The comparison result shows that under the same formula system, the initiator enables the adhesive film to form an interpenetrating network structure of acrylate polymer and polyurethane after thermosetting, so that the adhesive film in the shading area has better bonding and peeling strength, can better block the permeation of water vapor, has better bonding reliability after a double 85 test, particularly shows no visible deterioration of appearance, and keeps satisfactory bonding strength. The initiators in comparative examples 1 and 2 do not have thermosetting effect, and therefore, delamination and bubbles are easily generated under high temperature and high humidity, and the adhesive force is greatly reduced, which may cause flash and adhesive defect at the frame of the display.
In conclusion, compared with the existing photoinitiator, the photo-thermal dual-curing initiator disclosed by the invention can solve the problem of better curing effect of an opaque area, and endows the OCA adhesive film composition with more excellent ink step difference filling performance, adhesive force and adhesive reliability.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (17)
1. The hydrogen abstraction photoinitiator is characterized in that the structural formula is as follows:
wherein the content of the first and second substances,
X 1 and X 2 Are all made of
Or, X 1 And X 2 One of them is
The other is H;
R 1 is composed of
R 5 is-CH 2 -、-CH 2 CH 2 -or-CH 2 CH 2 CH 2 -；R 6 Is composed of
R 2 Selected from linear alkylene with 2 to 6 carbon atoms; r 3 Selected from linear alkyl with 1 to 4 carbon atoms; r 4 Is H;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 and Y 8 Is H.
2. The hydrogen abstraction-type photoinitiator of claim 1, wherein R is 1 Is composed of
Any one of the above.
3. The hydrogen abstraction-type photoinitiator of claim 2, wherein R is 5 is-CH 2 CH 2 -。
4. A method for producing a hydrogen abstraction-type photoinitiator according to any one of claims 1 to 3, comprising the steps of:
(a) Compound A 1 Or compound A 2 With diisocyanates and hydroxyl-containing acrylates to give compounds containing
A benzophenone derivative of a structural unit;
(b) Carrying out Michael addition reaction on polyaspartic acid ester polyamine and the benzophenone derivative to obtain the photoinitiator;
wherein, compound A 1 And compound A 2 Are respectively of the formula
The structural formula of the polyaspartic acid ester polyamine is shown as
R 2 Selected from linear alkylene groups having 2 to 6 carbon atoms, R 3 Any one selected from linear alkyl groups having 1 to 4 carbon atoms; r is 4 Is H; r 5 is-CH 2 -、-CH 2 CH 2 -or-CH 2 CH 2 CH 2 -；R 6 Is composed of
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 And Y 8 Is H.
5. The method of claim 4, wherein the polyaspartic acid ester polyamine is derived from the reaction of a dialkyl triamine and a butene diacid diester; the structural formulas of the dialkyl triamine and the butenedioic acid diester are respectively shown as
6. The method of claim 5, wherein the dialkyl triamine is selected from one or more of diethylenetriamine, dipropylenetriamine, and dihexamethylenetriamine.
7. The method according to claim 5, wherein the hydrogen abstraction-type photoinitiator is selected from the group consisting of a maleic acid diester selected from one or more of diethyl maleate, dipropyl maleate, dibutyl maleate and methylpropyl maleate, and/or a fumaric acid diester selected from one or more of diethyl fumarate, dipropyl fumarate, dibutyl fumarate and methylpropyl fumarate.
8. The method according to claim 5, wherein the molar ratio of the dialkyltriamine to the butenedioic acid diester is 1: 1 (1.8 to 2.2).
9. The method of claim 5, wherein the polyaspartate polyamine and the benzophenone derivative are reacted at a molar ratio of 1: 1 (0.9 to 1.1) in the step (b).
10. The method for producing a hydrogen abstraction-type photoinitiator according to claim 4, wherein the diisocyanate is isophorone diisocyanate.
11. The method for producing a hydrogen abstraction-type photoinitiator according to claim 4, wherein the hydroxyl group-containing acrylate is at least one selected from the group consisting of hydroxyethyl acrylate and hydroxypropyl acrylate.
12. A method for producing a hydrogen abstraction-type photoinitiator according to any one of claims 1 to 3, comprising the steps of:
(a1) Compound A 1 Or compound A 2 Reacting with a monomer containing isocyanate and acrylate to obtain a mixture containing
A benzophenone derivative of a structural unit;
(b1) Performing Michael addition reaction on polyaspartic acid ester polyamine and the benzophenone derivative to obtain the photoinitiator;
wherein, compound A 1 And compound A 2 Are respectively of the formula
The structural formula of the polyaspartic acid ester polyamine is shown as
R 2 Selected from linear alkylene groups having 2 to 6 carbon atoms, R 3 Any one selected from linear alkyl groups having 1 to 4 carbon atoms; r 4 Is H; r 5 is-CH 2 CH 2 -；
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 And Y 8 Is H;
the monomer containing isocyanate and acrylate is isocyanate ethyl acrylate.
13. Use of the hydrogen abstraction type photoinitiator according to any one of claims 1 to 3 in the preparation of OCA adhesive films.
An OCA composition comprising 1 to 10wt% of the hydrogen abstraction photoinitiator according to any one of claims 1 to 3.
15. The OCA composition of claim 14, wherein the OCA composition comprises the following components in percent by mass: 70-97% of acrylate monomers and prepolymers, 1-10% of hydrogen abstraction type photoinitiator and 2-20% of closed isocyanate.
16. The OCA composition of claim 15, wherein the blocked isocyanate is selected from any one of hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, 1, 4-cyclohexyl diisocyanate, 4' -dicyclohexylmethane diisocyanate, and isophorone diisocyanate blocked with any one of acetone oxime, cyclohexanone oxime, acetyl ketoxime, methyl ethyl ketoxime, and diethyl malonate.
17. The OCA composition of claim 14, wherein the OCA composition photocuring conditions comprise: the UV curing energy is 1000-2500 mJ/cm 2 (ii) a The heat curing conditions of the OCA composition include: the curing temperature is 70-90 ℃, and the curing time is 10-20 min.
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| CN106279470B (en) * | 2016-08-08 | 2018-02-13 | 上海交通大学 | Amphipathy macromolecule hydrogen-capture-type light initiator based on hyperbranched polyetheramine and preparation method thereof |
| CN110407719A (en) * | 2018-04-27 | 2019-11-05 | 北京化工大学常州先进材料研究院 | A kind of polymerizable mono-stripped hydrogen light initiating agent and preparation method thereof |
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| CN114276279B (en) * | 2021-12-29 | 2022-12-30 | 广州鹿山先进材料有限公司 | Hydrogen abstraction type photoinitiator, preparation method and application thereof |
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| CN101012180A (en) * | 2007-02-05 | 2007-08-08 | 武汉大学 | Single-component hydrogen-capture-type light initiator and its preparing method and use |
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