CN117106389A - UV (ultraviolet) curing composition capable of being stored at normal temperature, adhesive film, preparation method and application thereof - Google Patents
UV (ultraviolet) curing composition capable of being stored at normal temperature, adhesive film, preparation method and application thereof Download PDFInfo
- Publication number
- CN117106389A CN117106389A CN202310691775.7A CN202310691775A CN117106389A CN 117106389 A CN117106389 A CN 117106389A CN 202310691775 A CN202310691775 A CN 202310691775A CN 117106389 A CN117106389 A CN 117106389A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- modified
- curing
- acrylic monomer
- thiol
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000002313 adhesive film Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000001723 curing Methods 0.000 claims abstract description 58
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 30
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 30
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 10
- WXUZQTFPERWSEC-UHFFFAOYSA-N [O].C(C1CO1)OCC1CO1 Chemical group [O].C(C1CO1)OCC1CO1 WXUZQTFPERWSEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003573 thiols Chemical class 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 24
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- -1 thiol compound Chemical class 0.000 claims description 17
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 16
- 229940106681 chloroacetic acid Drugs 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- YBRBMKDOPFTVDT-UHFFFAOYSA-O tert-butylammonium Chemical compound CC(C)(C)[NH3+] YBRBMKDOPFTVDT-UHFFFAOYSA-O 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000002390 adhesive tape Substances 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 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 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 claims description 3
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- RSJLWBUYLGJOBD-UHFFFAOYSA-M diphenyliodanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[I+]C1=CC=CC=C1 RSJLWBUYLGJOBD-UHFFFAOYSA-M 0.000 claims description 3
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- NTYQWXQLHWROSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2,2,2-tris(sulfanyl)acetic acid Chemical compound OC(=O)C(S)(S)S.CCC(CO)(CO)CO NTYQWXQLHWROSQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002985 plastic film Substances 0.000 claims 1
- 229920006255 plastic film Polymers 0.000 claims 1
- 230000002035 prolonged effect Effects 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 7
- 239000003292 glue Substances 0.000 abstract description 7
- 230000009257 reactivity Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- KOPMZTKUZCNGFY-UHFFFAOYSA-N 1,1,1-triethoxybutane Chemical compound CCCC(OCC)(OCC)OCC KOPMZTKUZCNGFY-UHFFFAOYSA-N 0.000 description 2
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 2
- FGWYWKIOMUZSQF-UHFFFAOYSA-N 1,1,1-triethoxypropane Chemical compound CCOC(CC)(OCC)OCC FGWYWKIOMUZSQF-UHFFFAOYSA-N 0.000 description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 239000004823 Reactive adhesive Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- DLDIDQIZPBIVNQ-UHFFFAOYSA-N hydron;2-methylpropan-2-amine;chloride Chemical compound Cl.CC(C)(C)N DLDIDQIZPBIVNQ-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application provides a UV (ultraviolet) curing composition capable of being stored at normal temperature, a glue film, a preparation method and application thereof, wherein the UV curing composition at least comprises epoxy modified acrylic resin, and is obtained by copolymerizing an acrylic monomer with unsaturated bonds and an acrylic monomer containing epoxy groups; an epoxy resin; the curing agent is a modified polyfunctional mercaptan curing agent; a photo-base initiator and/or a photosensitizer; wherein, the epoxy group in the epoxy group acrylic monomer comprises furan ring ether oxygen group and/or glycidyl ether oxygen group. Compared with trifunctional, tetrafunctional and hexafunctional mercaptan curing agents in the prior art, the modified mercaptan curing agent has little influence on the performance of the cured adhesive film product, but introduces alkyl groups on carbon atoms of thiol groups to inhibit the reactivity of the thiol groups through steric hindrance effect, so that the stability of the UV curing composition under the condition of no light is prolonged, the storage time of the UV curing composition before curing is greatly prolonged, and the UV curing composition can be stored for more than 30 days in a dark place at normal temperature.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to a UV (ultraviolet) curing composition capable of being stored at normal temperature, a glue film, a preparation method and application thereof.
Background
Electronic devices often bond substrates with adhesives, and with the development of industry, the types of optional substrates are also varied, such as polycarbonate, alumina, metal, glass, etc., and in order to improve good adhesion between substrates, the adhesion performance is often enhanced by heating the structural adhesive to a certain temperature. The reason is that low temperature cured, heat reactive adhesives generally exhibit low glass transition temperatures (Tg), whereas low glass transition temperature adhesives exhibit poor performance reliability when used in structural adhesives, while higher glass transition temperature adhesives tend to exhibit good performance reliability when used as structural adhesives. Thus, in order for a thermally reactive adhesive to achieve a high Tg of the cured composition, curing is typically initiated at high temperatures, which may exceed 100 ℃. However, most components in electronic devices are sensitive to heat and heating processes, and an increase in temperature above 100 ℃ can cause softening or melting of the components, compromising the functionality of the components, resulting in device destruction.
Thus, in the prior art, low temperature curing is typically achieved using UV curing. When the UV cured adhesive tape or film is uncured, the adhesive tape or film has the advantages of die-cuttability, capability of providing initial strength, no adhesive overflow, good appearance and the like, so that the UV curing method is widely focused in the technical field of adhesives. Generally, the adhesive film of the UV-curable adhesive tape is composed of three parts of a pressure-sensitive adhesive, a curable component and a photoinitiator. UV curable tapes can be classified into UV free radical curing systems, UV cationic curing systems and UV anionic curing systems according to the initiator. Among them, the UV radical curing adhesive tape is too fast to be cured, does not form a good adhesive strength, and cannot be used for adhesion of opaque surfaces. For example, as disclosed in chinese patent No. 103365084a, a photocurable resin composition, a dry film, a cured product, and a printed wiring board are disclosed, but such adhesives are usually pressure sensitive adhesives, and when used for bonding, the problems of low bonding strength, low modulus, incomplete curing, etc. are usually caused by too high a photocuring speed.
In addition, the adhesive film produced by the low-temperature UV curing method has the defect of poor initial adhesion, for example, chinese patent No. 110643286A discloses a UV curing composition, an adhesive film, an adhesive tape and an adhesive member containing the composition, and a photo-alkali initiator is adopted to catalyze the curing of mercaptan and epoxy resin, but the adopted mercaptan curing agent has the problem of storage stability, and the product is stored for about 7days at room temperature in a dark place, so that the service performance of the product is seriously affected. Chinese patent No. CN115449321 a discloses an epoxy acrylic structural adhesive capable of UV low-temperature curing and a preparation method thereof, wherein an acrylic monomer containing unsaturated bond and an acrylic monomer containing epoxy group are copolymerized to obtain epoxy acrylic acid and two or more thiol groups to improve the initial adhesion of the adhesive film, but the solution still cannot solve the technical problem of short light-proof storage time of the curing composition for preparing the adhesive film.
Clearly, the storage time of the film products produced by low-temperature curing has disadvantages that affect the performance of the products on the one hand and that too short a storage time results in a great limitation of the raw material arrangement and the areas of market circulation and transport on the other hand.
Disclosure of Invention
In view of the above, the present application provides a UV curable composition, a UV curable adhesive film capable of being stored at normal temperature, and a preparation method and application thereof, wherein a method of modifying a polyfunctional thiol is adopted to inhibit the reactivity of thiol groups, thereby prolonging the service life of the resin composition and prolonging the shelf life of the adhesive film product.
In order to achieve the above object, the present application provides a UV curable composition comprising at least an epoxy-modified acrylic resin obtained by copolymerizing an unsaturated bond-containing acrylic monomer and an epoxy group-containing acrylic monomer; an epoxy resin; the curing agent is a modified polyfunctional mercaptan curing agent; a photo-base initiator and/or a photosensitizer; wherein, the epoxy group in the epoxy group acrylic monomer comprises furan ring ether oxygen group and/or glycidyl ether oxygen group; the number average molecular weight Mn of the epoxy modified acrylic resin is 70000-110000, and the glass transition temperature is 0.109 ℃.
Preferably, in the modified multifunctional thiol curing agent, the multifunctional thiol is a thiol compound having at least 3 thiol groups.
Preferably, the thiol functional groups in the multifunctional thiol have the formulaWherein R is 1 Is any one of methyl, ethyl or propyl.
Preferably, the multifunctional thiol is any one of TMPMA (trimethylolpropane trimercaptan), PETMP (tetra (3-mercaptopropionic acid) ester), and hexa-functional thiol.
Preferably, the preparation method of the modified multifunctional mercaptan curing agent comprises the following steps:
(1) Mixing polyfunctional mercaptan and tertiary butyl ammonium chloride and then reacting to obtain a reaction mixture;
(2) Chloroacetic acid is added into the reaction mixture to unbalance ions in the mixture, so that the thiol on carbon and tertiary butyl ammonium chloride are subjected to catalytic reaction;
(3) Adding triethoxyalkyl compound, stirring, concentrating, precipitating and drying after the reaction is finished to obtain the modified multifunctional mercaptan curing agent.
Preferably, the unsaturated bond acrylic monomer is one or more of Methyl Acrylate (MA), butyl Acrylate (BA) and Acrylonitrile (AN).
Preferably, the epoxy-based acrylic monomer includes one or more of tetrahydrofuran methacrylate (THFMA), phenyl glycidyl ether (GPE), glycidyl Methacrylate (GMA).
Preferably, the epoxy resin is one or more of bisphenol A type, phenolic aldehyde modified type and aliphatic epoxy.
More preferably, the epoxy resin is a bisphenol a epoxy resin, including south asia 901 resin and/or 128 resin.
Preferably, the photoinitiator is mainly iodonium salt, and comprises one or more of diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and diphenyliodonium tetrafluoroborate.
Preferably, the photosensitizer is one or more of fluorene, fluorenone, anthraquinone, anthrone, fluoranthene and benzyl ketal.
Preferably, the preparation method of the epoxy modified acrylic resin comprises the following steps: mixing the unsaturated bond acrylic monomer and the epoxy acrylic monomer, adding the mixture into an initiator and a solvent, and carrying out reaction by adopting a staged addition method; the step of adding comprises the steps of adding 1/2 to 1/3 of the mixture into a reactor for reaction, stirring and reacting under nitrogen atmosphere, dripping the rest 1/2 to 2/3 into the reactor by adopting a dripping method, and reacting for 8 to 12 hours at 50 to 80 ℃ after the titration is completed to obtain the epoxy modified acrylic resin;
preferably, the initiator is azobisisobutyronitrile; the solvent is ethyl acetate; the mass ratio of the unsaturated bond-containing acrylic monomer to the epoxy group-containing acrylic monomer is 90-97:3-10.
By introducing an acrylic monomer containing epoxy groups, the epoxy groups are introduced into the acrylic resin, so that on one hand, the polarity of a molecular chain can be improved, the initial viscosity of a glue film product before UV activation and solidification is improved, and the glue film product is better positioned and bonded with a to-be-adhered object; on the other hand, according to the similar compatibility principle, the introduced epoxy group can improve the compatibility with the epoxy resin; finally, the addition amount of the acrylic monomer containing epoxy groups is too small, and the tackifying and compatibility improving effects are not obvious; and gel phenomenon is easy to occur when the addition amount is too large, and the modulus of collodion cotton is influenced.
Further, t-butyl ammonium chloride reacts with thiols to form thiolate anions, which are a strong affinity reagent, specifically, the reaction equation for thiol synthesis is:
taking PETMP (tetra (3-mercaptopropionic acid) ester) as an example, the structural formula of PETMP is as follows:
after modification, the structural formula of the modified tetrafunctional thiol is:
wherein R is 1 Is methyl, ethyl or propyl.
According to the application, the storage time of the UV curing composition is realized by modifying the polyfunctional mercaptan and reducing the reactivity of the mercaptan, and after the mercaptan is modified, alkyl is introduced into alpha carbon in the mercaptan molecule, on the one hand, the alkyl belongs to a hydrophobic group, so that the water-splitting property can be inhibited, the odor is reduced, and the water resistance is improved; on the other hand, the alkyl group on the alpha carbon in the thiol molecule is superior to the steric hindrance effect in that the reactivity of the thiol group can be effectively suppressed, thereby prolonging the life cycle of the resin mixture.
However, when the carbon chain length of the introduced alkyl group is too long, the influence of reactivity is large, and the reaction speed of the curing reaction is suppressed.
The curing composition prepared by adopting the technical scheme can be stored for a long time under normal temperature, and is uniformly coated on a release film, and the UV curing adhesive film is obtained after the curing composition is completely dried. The UV cured adhesive film provided by the scheme of the application can be stored for more than 30 days in a dark place under the normal temperature condition, and is far superior to the prior art that the UV cured adhesive film is stored for about 10 days in a dark place under the normal temperature condition, and the storage period is greatly improved.
In principle, the analysis: the use of conventional polyfunctional thiols such as PETMP suffers from poor storage stability, and is largely due to the fact that: the photo-alkali initiator used in the system slowly releases alkaline substances (Lewis base) under the condition of room temperature, and the polyfunctional mercaptan and the epoxy resin hardly undergo curing reaction at room temperature, but the curing reaction is geometrically multiplied under the action of base catalysis, so that the storage stability of the epoxy system is greatly influenced due to the characteristic that the photo-alkali initiator can slowly decompose to generate base at room temperature. The application prevents the reactivity of the polyfunctional mercaptan and the epoxy resin by introducing alkyl on alpha carbon through steric hindrance, thereby delaying the reaction rate of the epoxy resin and improving the storage period.
The beneficial technical effects obtained by the application are as follows:
1. compared with trifunctional, tetrafunctional and hexafunctional mercaptan curing agents in the prior art, the modified mercaptan curing agent has little influence on the performance of cured adhesive film products, but introduces alkyl on alpha carbon atoms of thiol groups, and inhibits the reactivity of the thiol groups through steric hindrance effect, so that the stability of the UV curing composition under the condition of no light is prolonged, the light-shielding storage of the UV curing composition under the normal temperature condition is prolonged to more than 30 Days, the oven storage at 80 ℃ is improved to 7Days from 0.8Day, and the storage time of the UV curing composition before curing is greatly prolonged.
2. According to the technical scheme, a plurality of hard resin monomers are adopted for mixing modification, and acrylic ester is modified by utilizing the reaction of an unsaturated bond acrylic monomer and an epoxy group-containing acrylic monomer to obtain epoxy modified acrylic resin, so that the mechanical modulus of the resin is improved; by introducing an acrylic monomer containing epoxy groups, the epoxy groups are introduced into the acrylic resin, so that on one hand, the polarity of a molecular chain can be improved, the initial viscosity of a glue film product before UV activation and solidification is improved, and the glue film product is better positioned and bonded with a to-be-adhered object; on the other hand, according to the similar compatibility principle, the introduced epoxy group can improve the compatibility with the epoxy resin; finally, too little of the GMA monomer is introduced to improve the effect less significantly, and too much is liable to gel.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments.
The application provides a UV curing composition capable of being stored at normal temperature, which at least comprises epoxy modified acrylic resin, wherein the epoxy modified acrylic resin is obtained by copolymerizing an acrylic monomer with unsaturated bonds and an acrylic monomer containing epoxy groups; an epoxy resin; the curing agent is a modified polyfunctional mercaptan curing agent; a photo-base initiator and/or a photosensitizer; wherein, the epoxy group in the epoxy group acrylic monomer comprises furan ring ether oxygen group and/or glycidyl ether oxygen group.
As one of the preferred embodiments, the unsaturated bond acrylic monomer is one or more of Methyl Acrylate (MA), butyl Acrylate (BA), acrylonitrile (AN);
as one of the preferred embodiments, the epoxy-based acrylic monomer includes one or more of tetrahydrofuran methacrylate (THFMA), phenyl glycidyl ether (GPE), glycidyl Methacrylate (GMA);
as one of the preferred embodiments, the epoxy resin is one or more of bisphenol a type, phenolic aldehyde modified type and aliphatic epoxy;
as one of preferred embodiments, the photoinitiator is mainly an iodonium salt, including one or more of diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and diphenyliodonium tetrafluoroborate;
as one of the preferred embodiments, the photosensitizer is one or more of fluorene, fluorenone, anthraquinone, anthrone, fluoranthene and benzyl ketal.
As one of the preferred embodiments, in the modified multifunctional thiol curing agent, the multifunctional thiol is a thiol compound having at least 3 mercapto groups; preferably, the thiol functional groups in the multifunctional thiol have the formulaWherein R is 1 Is any one of methyl, ethyl or propyl; preferably, the multifunctional thiol is TMPMA (trimethylolpropane trimercapto acetate), PETMP (tetra (3-mercaptopropionic acid) ester) Any of the six-functional thiols.
As one of the preferred embodiments, the method for preparing the modified multifunctional thiol curing agent includes:
(1) Mixing polyfunctional mercaptan and tertiary butyl ammonium chloride and then reacting to obtain a reaction mixture;
(2) Chloroacetic acid is added into the reaction mixture to lead ions in the mixture to form unbalance, so that the thiol on carbon and tertiary butyl ammonium chloride are subjected to catalytic reaction;
(3) Adding triethoxyalkyl compound, stirring, concentrating, precipitating and drying after the reaction is finished to obtain the modified multifunctional mercaptan curing agent.
As one of preferred embodiments, the method for preparing the epoxy-modified acrylic resin includes: mixing an unsaturated bond acrylic monomer and an epoxy acrylic monomer, adding the mixture into an initiator and a solvent, and reacting by adopting a staged addition method; the step of adding comprises the steps of adding 1/2 to 1/3 of the mixture into a reactor for reaction, stirring and reacting under nitrogen atmosphere, dripping the rest 1/2 to 2/3 into the reactor by adopting a dripping method, and reacting for 8 to 12 hours at 50 to 80 ℃ after the titration is completed to obtain the epoxy modified acrylic resin; wherein, the initiator can be azodiisobutyronitrile; the solvent is ethyl acetate; the mass ratio of the unsaturated bond-containing acrylic monomer to the epoxy group-containing acrylic monomer is: 90-97:3-10.
The UV curing composition prepared by adopting the technical scheme can be stored for a long time under normal temperature, and particularly, the storage temperature of an oven at 80 ℃ is increased from 0.8Day to 7Days. Compared with the prior art, the storage time is greatly prolonged.
The technical scheme of the application is further described in detail through specific examples.
The reagents used in the following examples include: epoxy resin: bisphenol a type epoxy resins (south asia 901, 128 resins); photo-base catalyst: sulfonium salts (Japanese Sanyo chemical U-CAT 5002); photosensitizer: 2-Isopropylthioxanthone (ITX); silane coupling agent: dadarl a-187; leveling wetting/defoaming agent: BYK 333; an antioxidant: antioxidant 1010 and antioxidant 168 (Shanghai Xuan Mo chemical); PETMP (Shanghai boquidambar); the other reagents were all derived from the microphone reagent net.
Example 1
The embodiment provides a glue film, which mainly comprises a UV curing composition capable of being stored at normal temperature, and comprises the following specific steps:
1. synthesis of epoxy modified acrylic resin:
and (3) fully and uniformly mixing methyl acrylate, acrylonitrile, glycidyl methacrylate, azodiisobutyronitrile and ethyl acetate according to the mass ratio of 80:15:5:0.5:150, adding one third of the mixed solution into a four-neck flask, carrying out oil bath at 65 ℃, stirring for reaction under the protection of nitrogen, adding the rest two thirds of the mixed solution into the four-neck flask in a titration manner, wherein the titration time is 4H, after all the titration is finished, carrying out constant-temperature reaction at 65 ℃ for 10 hours, taking out the reaction solution, adding butanone as a solvent, and adjusting the solid content to 40%, thus obtaining the epoxy modified acrylic resin.
Wherein, the mole ratio of PETMP to triethoxymethane theory is: 1:1.05.
The addition amount of chloroacetic acid is as follows: the molar ratio of PETMP to chloroacetic acid is 10:1.
The number average molecular weight Mn of the epoxy-modified acrylic resin was 91000 by GPC measurement using a gel permeation chromatograph, and the glass transition temperature was 0.109℃by calculation according to the FOX formula.
2. Synthesis of modified mercaptan curing agent:
mixing PETMP and tertiary butyl ammonium chloride in a molar ratio of 1:2, preparing a reaction mixture, adding chloroacetic acid to unbalance ions in the reaction mixture, carrying out catalytic reaction on thiol on carbon and tertiary butyl ammonium chloride, and stirring for 30min at room temperature; adding triethoxymethane as a carrier of methyl, and continuously stirring for 2 hours to obtain a product of more than 90%; quantitatively concentrating with ethanol/water mixed solution by rotary evaporator, adding precipitating agent Alumen (aluminum potassium sulfate dodecahydrate), and precipitating the reactant; refining and drying to obtain the modified mercaptan curing agent PETMP-1.
Wherein, the mole ratio of PETMP to triethoxymethane is: 1:1.05; the molar ratio of PETMP to chloroacetic acid is 10:1.
Preparation of UV-curable composition:
uniformly mixing epoxy modified acrylic resin, epoxy resin, modified mercaptan PETMP-1 curing agent, a photo-alkali initiator, a photosensitizer, a silane coupling agent, a leveling wetting agent, a defoaming agent, an antioxidant and the like according to a certain proportion to obtain a UV curing composition, standing for defoaming; specifically, the components are added in the mass parts of 17.5 parts of epoxy modified acrylic resin, 5 parts of 901 epoxy resin, 5 parts of 128 epoxy resin, 15.34 parts of modified mercaptan curing agent PETMP-15.44 parts of photo-alkali initiator CAT U5002, 0.22 part of photosensitizer ITX, 0.06 part of silane coupling agent A-187, 0.06 part of leveling wetting agent BYK333, 0.05 part of antioxidant 1010, 0.05 part of antioxidant 168, and 5 parts of solvent (butanone).
4. Preparation of adhesive film
And uniformly coating the UV curing composition on a release film, baking for 3 minutes in a 110 ℃ oven, and coating a lighter release film after the release film is completely dried to obtain the adhesive film with the thickness of 50 mu m.
Example 2
This example differs from example 1 in that in step 2, the synthesis of the modified thiol curing agent comprises:
mixing PETMP and tertiary butyl ammonium chloride in a molar ratio of 1:2, preparing a reaction mixture, adding chloroacetic acid to unbalance ions in the reaction mixture, carrying out catalytic reaction on thiol on carbon and tertiary butyl ammonium chloride, and stirring for 30min at room temperature; adding triethoxyethane as ethyl carrier, stirring for 2 hr to obtain product over 90%; quantitatively concentrating with ethanol/water mixed solution, and adding precipitant to precipitate reactant; refining and drying to obtain the modified mercaptan curing agent PETMP-2.
Wherein, the mole ratio of PETMP to triethoxyethane theory is: 1:1.05; the addition amount of chloroacetic acid is as follows: the molar ratio of PETMP to chloroacetic acid is 10:1.
In the preparation step of the adhesive film, PETMP-2 was used instead of PETMP-1 of example 1, and the addition amounts were the same. The other steps and the addition ratio of each raw material were the same as in example 1.
Example 3
This example differs from example 1 in that in step 2, the synthesis of the modified thiol curing agent comprises:
mixing PETMP and tertiary butyl ammonium chloride in a molar ratio of 1:2, preparing a reaction mixture, adding chloroacetic acid to unbalance ions in the reaction mixture, carrying out catalytic reaction on thiol on carbon and tertiary butyl ammonium chloride, and stirring for 30min at room temperature; adding triethoxypropane as a carrier of propyl, and continuously stirring for 2 hours to obtain a product of more than 90%; quantitatively concentrating with ethanol/water mixed solution, and adding precipitant to precipitate reactant; refining and drying to obtain the modified mercaptan curing agent PETMP-3.
Wherein, the mole ratio of PETMP to triethoxypropane is as follows: 1:1.05.
The addition amount of chloroacetic acid is as follows: the molar ratio of PETMP to chloroacetic acid is 10:1.
In the preparation step of the adhesive film, PETMP-3 was used instead of PETMP-1 of example 1, and the addition amounts were the same. The other steps and the addition ratio of each raw material were the same as in example 1.
Example 4
This example differs from example 1 in that in step 1, the mass ratio of each monomer for the synthesis of the epoxy-modified acrylic resin includes: methyl acrylate, acrylonitrile, glycidyl methacrylate, azodiisobutyronitrile and ethyl acetate in the mass ratio of 82 to 15 to 3 to 0.5 to 150.
The other steps and the addition ratio of each raw material were the same as in example 1.
Example 5
This example differs from example 1 in that in step 1, the mass ratio of each monomer for the synthesis of the epoxy-modified acrylic resin includes: methyl acrylate, acrylonitrile, glycidyl methacrylate, azodiisobutyronitrile and ethyl acetate in the mass ratio of 70:15:10:0.5:150.
The other steps and the addition ratio of each raw material were the same as in example 1.
Example 6
This example differs from example 1 in that in step 3, the amount of the addition of the photo-alkali initiator was 0.8 part. The other steps and the addition amount of the raw materials are the same.
Comparative example 1
This comparative example differs from example 1 in that the mass ratio of each monomer for the synthesis of the epoxy-modified acrylic resin in step 1 includes: methyl acrylate, acrylonitrile, glycidyl methacrylate, azodiisobutyronitrile and ethyl acetate in the mass ratio of 68 to 15 to 12 to 0.5 to 150. The other steps and the addition amount of the raw materials are the same.
Comparative example 2
This comparative example differs from example 1 in that the mass ratio of each monomer for the synthesis of the epoxy-modified acrylic resin in step 1 includes: methyl acrylate, acrylonitrile, glycidyl methacrylate, azodiisobutyronitrile and ethyl acetate in the mass ratio of 83:15:2:0.5:150. The other steps and the addition amount of the raw materials are the same.
The epoxy modified acrylic resin synthesized by the embodiment is used for preparing the adhesive film, so that the adhesive is difficult to disperse and cannot form a film.
Comparative example 3
This example differs from example 1 in that in step 2, the synthesis of the modified thiol curing agent comprises:
mixing PETMP and tertiary butyl ammonium chloride in a molar ratio of 1:2, preparing a reaction mixture, adding chloroacetic acid to unbalance ions in the reaction mixture, carrying out catalytic reaction on thiol on carbon and tertiary butyl ammonium chloride, and stirring for 30min at room temperature; adding triethoxy n-butane as a carrier of n-butyl, and continuously stirring for 2 hours to obtain a product of more than 90%; quantitatively concentrating with ethanol/water mixed solution, and adding precipitant to precipitate reactant; refining and drying to obtain the modified mercaptan curing agent PETMP-2.
Wherein, the mole ratio of PETMP to triethoxy n-butane theory is: 1:1.05; the addition amount of chloroacetic acid is as follows: the molar ratio of PETMP to chloroacetic acid is 10:1. The other steps and the addition amount of the raw materials are the same.
Comparative example 4
The comparative example differs from example 1 in that in step 3, the amount of the addition of the photo-alkali initiator was 0.2 part. The other steps and the addition amount of the raw materials are the same.
Comparative example 5
The difference between this comparative example and example 1 is that unmodified PETMP was used in step 3, and the amount added was unchanged. The other steps and the addition amount of the raw materials are the same.
Specifically, in examples and comparative examples, the addition ratio of the components of each raw material in the synthesis of the epoxy-modified acrylic resin and the modified thiol-curing agent PETMP-1 is shown in Table 1 (unit: parts).
TABLE 1 raw material ratio for the Synthesis of epoxy-modified acrylic resin and modified thiol-curing agent
The adhesive films prepared in the above examples and comparative examples were subjected to performance test, and the test standards or methods thereof include:
initial 180 ° peel force before cure: the object to be attached was a 50um thick PET film and 304SUS steel plate, tested according to astm d3330 standard method.
Thickness of the adhesive film: the gauge head diameter was 30mm and the test pressure was less than 2Kpa according to astm d3574 standard method.
Dynamic shear strength after curing: the adherend was 304SUS as tested according to ASTM D1002 standard method.
UV activated curing conditions: (1) 70mW 365nm LED@60 (UV activated);
(2) 70 ℃ C.@ 3hours (post cure).
Storage time: and observing whether the appearance of the adhesive film is solidified and hardened, and recording the time when the appearance is abnormal.
The test results are shown in Table 2.
TABLE 2 Performance test results of the adhesive films prepared in examples and comparative examples
As can be seen from the results of Table 2, the storage time of the adhesive film prepared by the technical scheme of the application is obviously prolonged, and the adhesive film can be stored for more than 60 days in normal-temperature light-shielding storage examples 1-5 and can be stored for 7days in 80 ℃ light-shielding storage, so that technical support is provided for the transportation and storage of the adhesive film.
Referring to comparative example 5, the preparation of the adhesive film using unmodified PETMP of the prior art, which can be stored at 80℃for only 0.8 days in the dark, was carried out. Obviously, through the modification of PETMP, the light-proof storage time of the adhesive film at 80 ℃ can be prolonged from 0.8day to 7days.
The above is only a preferred embodiment of the present application, which is not to be construed as limiting the scope of the present application, and various modifications and variations of the present application will be apparent to those skilled in the art. Variations, modifications, substitutions, integration and parameter changes may be made to these embodiments by conventional means or may be made to achieve the same functionality within the spirit and principles of the present application without departing from such principles and spirit of the application.
Claims (10)
1. A UV curable composition capable of being stored at normal temperature, comprising at least
An epoxy-modified acrylic resin obtained by copolymerizing an unsaturated bond-containing acrylic monomer and an epoxy group-containing acrylic monomer;
an epoxy resin;
the curing agent is a modified polyfunctional mercaptan curing agent;
a photo-base initiator and/or a photosensitizer;
wherein the epoxy group in the acrylic monomer containing epoxy group comprises furan ring ether oxygen group and/or glycidyl ether oxygen group.
2. The UV-curable composition according to claim 1, wherein the UV-curable composition is,
the number average molecular weight Mn of the epoxy modified acrylic resin is 70000 to 110000.
And/or, in the modified multifunctional thiol curing agent, the multifunctional thiol is a thiol compound having at least 3 thiol groups.
3. The UV adhesive film storable at room temperature as claimed in claim 2, wherein the thiol functional group in the modified multifunctional thiol has a structural formula ofWherein R is 1 Is any one of methyl, ethyl or propyl.
4. A UV curable composition according to claim 3, wherein the multifunctional thiol is any one of TMPMA (trimethylolpropane trimercapto acetate), PETMP (tetra (3-mercaptopropionate), hexa-functional thiol.
5. The UV curable composition according to any one of claims 1 to 4, wherein the modified multifunctional thiol curing agent is prepared by a process comprising:
(1) Mixing polyfunctional mercaptan and tertiary butyl ammonium chloride and then reacting to obtain a reaction mixture;
(2) Chloroacetic acid is added into the reaction mixture to unbalance ions in the mixture, so that the thiol on carbon and tertiary butyl ammonium chloride are subjected to catalytic reaction;
(3) Adding triethoxyalkyl compound, stirring, concentrating, precipitating and drying after the reaction is finished to obtain the modified multifunctional mercaptan curing agent.
6. The UV curable composition according to any one of claims 1 to 4, wherein the unsaturated bond-containing acrylic monomer is one or more of Methyl Acrylate (MA), butyl Acrylate (BA), acrylonitrile (AN);
the epoxy-based acrylic monomer comprises one or more of tetrahydrofuran methacrylate (THFMA), phenyl glycidyl ether (GPE) and Glycidyl Methacrylate (GMA);
the epoxy resin is one or more of bisphenol A type, phenolic aldehyde modified type and aliphatic epoxy;
the photoinitiator is mainly iodonium salt, and comprises one or more of diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate and diphenyliodonium tetrafluoroborate;
the photosensitizer is one or more of fluorene, fluorenone, anthraquinone, anthrone, fluoranthene and benzyl ketal.
7. The UV curable composition according to claim 6, wherein the method for preparing the epoxy-modified acrylic resin comprises: mixing the unsaturated bond acrylic monomer and the epoxy group-containing acrylic monomer, adding the mixture into an initiator and a solvent, and carrying out reaction by adopting a staged addition method; the step of adding comprises the steps of adding 1/2 to 1/3 of the mixture into a reactor for reaction, stirring and reacting under nitrogen atmosphere, dripping the rest 1/2 to 2/3 into the reactor by adopting a dripping method, and reacting for 8 to 12 hours at 50 to 80 ℃ after the titration is completed to obtain the epoxy modified acrylic resin;
the initiator is azodiisobutyronitrile; the solvent is ethyl acetate; the mass ratio of the unsaturated bond-containing acrylic monomer to the epoxy group-containing acrylic monomer is: 95:5.
8. A film of adhesive comprising the UV curable composition of any one of claims 1-7 stored at ambient temperature.
9. A method for preparing a plastic film according to claim 8,
s1, preparing epoxy modified acrylic resin;
s2, preparing a modified polyfunctional mercaptan curing agent;
s3, uniformly mixing the epoxy modified acrylic resin, the modified polyfunctional mercaptan curing agent, the epoxy resin, the photobase catalyst and the auxiliary agent, and standing for defoaming to obtain a curing composition;
s4, uniformly coating the curing composition on a release film, and obtaining the UV curing adhesive film after the release film is completely dried.
10. An adhesive tape comprising the adhesive film according to claim 8 or an adhesive film produced by the production method according to claim 9.
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