CN117603649A - High-low temperature impact resistant adhesive polymer, composition, pressure-sensitive adhesive tape and application - Google Patents
High-low temperature impact resistant adhesive polymer, composition, pressure-sensitive adhesive tape and application Download PDFInfo
- Publication number
- CN117603649A CN117603649A CN202311584512.2A CN202311584512A CN117603649A CN 117603649 A CN117603649 A CN 117603649A CN 202311584512 A CN202311584512 A CN 202311584512A CN 117603649 A CN117603649 A CN 117603649A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- acrylate
- adhesive
- hydroxyl
- curing agent
- 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
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000002998 adhesive polymer Substances 0.000 title claims abstract description 19
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 72
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 230000001070 adhesive effect Effects 0.000 claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 claims abstract description 55
- 239000004814 polyurethane Substances 0.000 claims abstract description 55
- 239000000853 adhesive Substances 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 229920005862 polyol Polymers 0.000 claims abstract description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 37
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- LDUOHXCVIFQGBK-UHFFFAOYSA-N carbonisocyanatidic acid Chemical group OC(=O)N=C=O LDUOHXCVIFQGBK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- -1 glycol ether polyol Chemical class 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 claims description 4
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 2
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 14
- 239000004593 Epoxy Substances 0.000 abstract description 6
- 239000004014 plasticizer Substances 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000003756 stirring Methods 0.000 description 24
- 239000002390 adhesive tape Substances 0.000 description 22
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000003292 glue Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 230000008602 contraction Effects 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- KKBYLNUMPXZUGE-UHFFFAOYSA-K di(decanoyloxy)bismuthanyl decanoate Chemical compound [Bi+3].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O KKBYLNUMPXZUGE-UHFFFAOYSA-K 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229920001875 Ebonite Polymers 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000447394 Desmos Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000001204 arachidyl 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])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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding 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
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
-
- 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
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Abstract
The invention discloses an adhesive polymer, a composition, a pressure-sensitive adhesive tape and application of the adhesive polymer and the composition. The polymer comprises a polyacrylate backbone and polyurethane branches; the branched chain is grafted to the main chain through a curing agent group, a precursor of the polyurethane branched chain is provided with a terminal hydroxyl group, a precursor of the curing agent group is provided with a plurality of isocyanate groups or epoxy groups, and a precursor of the polyacrylate main chain is provided with hydroxyl groups or carboxyl groups distributed in a molecular chain; the chemical bond linkage is formed by the reaction of a hydroxyl or carboxyl-epoxy group and/or a hydroxyl or carboxyl-isocyanate group. The hydroxyl-terminated polyurethane is synthesized by using low-Tg oligomer polyol, and covalent bond connection is formed between the hydroxyl-terminated polyurethane and the acrylate polymer with high soft monomer content through isocyanate or epoxy curing agent, so that the low-Tg acrylate adhesive is synthesized, and the low-Tg acrylate adhesive still has good toughness and bonding strength at a low temperature of minus 30 ℃, and effectively solves the problems of cold brittleness and precipitation of a small molecular plasticizer of the traditional acrylate adhesive.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives and pressure-sensitive adhesive tapes, in particular to a high-low temperature impact resistant adhesive polymer, a composition, a pressure-sensitive adhesive tape and application.
Background
The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.
With the continuous improvement of the liquid crystal display technology, the liquid crystal display panel with the advantages of light weight, convenience, low power consumption and the like is favored by the majority of users. Since the liquid crystal itself does not emit light, the LCD (Liquid Crystal Displa y ) is a passive light emitting device, and a BLU (Backlight unit) is required to provide a light source for the liquid crystal display to display images. The backlight modules of the display device can be classified into a direct type and a side-in type according to the arrangement mode of the backlight source. With the development of miniaturization and thinning of display devices, particularly small display devices applied to smart phones, tablet computers and the like, a side-entry backlight module is generally used for providing backlight.
The side-in backlight module comprises a back plate, a light guide plate ((Light Guide Plate, LGP) arranged on the back plate and light emitting diodes (Light Emitting Diode, LEDs) arranged on the side surface of the light guide plate, wherein the LEDs are used as luminous bodies and arranged on a flexible circuit board (Flexible Printed Circuit, FPC) to form a lamp strip, one end of the flexible circuit board FPC is stuck to the bottom of the LGP through a lamp front adhesive, and then the circuit board and a frame of the LED lamp strip are stuck and fixed through a fixing adhesive tape, so that the fixation between the LED lamp strip and the light guide plate and the frame in the backlight module is realized, as described in Chinese patent No. CN 115933242A, the LGP of the light guide plate is generally prepared from Polycarbonate (PC) or polymethyl methacrylate (Poly methylmethacrylate, PMMA) materials, both materials have a certain expansion and contraction coefficient at high and low temperatures, particularly PMMA has larger expansion and contraction coefficient in a high-low temperature state, and the expansion or contraction coefficient of the LGP actually measured in some applications reaches 1mm, when the backlight module with the structure is subjected to high-low temperature impact, the acting force generated when the LGP of the light guide plate is expanded at high temperature or contracted at low temperature is transmitted to the FPC of the flexible circuit board through the lamp front adhesive, so that the lamp front adhesive is required to have better cohesive strength and adhesive force at high temperature (about 60 ℃), the adhesive can still keep better toughness and adhesive force at low temperature (about-30 ℃), the continuous stress of the lamp front adhesive is prevented from being separated from the FPC or the LGP, or the FPC is deformed, the relative dislocation of a luminous body and the light guide plate is caused, the poor phenomenon of uneven brightness of the lamp front at the FP C position is required to have better cohesive strength and adhesive force at high temperature and low temperature, especially pressure-sensitive adhesive tapes which still have a good toughness at low temperatures.
Polyacrylate pressure-sensitive adhesives have many unique properties compared to pressure-sensitive adhesives of other materials (e.g., rubber, silicone, polyurethane, etc.), such as: excellent anti-aging characteristics (particularly, ultraviolet aging resistance), excellent optical transparency, and moderate price, and is widely used in transportation, electronic power, home appliances, and building markets. However, the traditional polyacrylate pressure-sensitive adhesive generally adopts a 'Fox' formula, the glass transition temperature of the polymer is designed by adjusting the proportion of soft and hard monomers and functional monomers so as to endow excellent pressure sensitivity at normal temperature, along with the diversification of the current market demands, increasingly severe requirements are put on the pressure-sensitive technology, especially in colder areas, such as northeast China, the winter temperature reaches minus 30 ℃, under such conditions, the 'hot-sticking and cold-embrittling' characteristics of the common polyacrylate pressure-sensitive adhesive obviously cannot meet the requirements, the cohesive force is reduced, and the adhesive remains on the surface of an adherend, is difficult to clean and is in adhesion failure.
To improve the adhesion strength of pressure-sensitive adhesives in low temperature environments, formulators often use monomers with lower glass transition temperatures, such as octyl acrylate, decyl acrylate, and the like (e.g., chinese patent No. CN 115612434A, CN 108587527A). However, long-chain acrylic esters have certain crystallinity, and crystallization of polymer branches can significantly affect the tackiness of the polymer. Other formulators add plasticizers to the pressure sensitive adhesive to lower the overall glass transition temperature. Since plasticizers are mostly small molecules, migration occurs in the pressure sensitive adhesive. Over time, the migration of small molecule pressure sensitive adhesives to the interface can significantly reduce the adhesive bond (e.g., chinese patent No. CN 112143417A). The Chinese patent No. CN 116285768A obtains the low-temperature-resistant pressure-sensitive adhesive by copolymerization of a (methyl) acrylic ester monomer with the carbon number of 1-12 of low Tg alkyl and an acrylic ester monomer containing isocyanate groups, and a plasticizer component containing modified hydroxyl groups, and by the affinity addition reaction of isocyanate and hydroxyl groups, the low-temperature-resistant pressure-sensitive adhesive has better low-temperature adhesive property and ageing-resistant property, but only provides the low-temperature stripping force property at-5 ℃ and is not clear.
In the aspect of low temperature resistance, organic silicon or polyurethane has unique advantages, the organic silicon modified acrylic ester has the problem of chemical compatibility between organic silicon and acrylic ester, in the aspect of improving the low temperature resistance of polyurethane modified polyacrylate pressure-sensitive adhesive, polyurethane prepolymer with double bonds at two ends is firstly synthesized in Chinese patent No. CN 109054701A, is subjected to free radical copolymerization with acrylic ester, and then a flexible polyisobutene chain segment is introduced into a molecular chain, so that the application of labels with low requirements on bonding strength at low temperature is satisfied, and low-temperature actual bonding strength data are not mentioned in the patent. The polyurethane modified polyacrylate pressure-sensitive adhesive is prepared by respectively synthesizing polyacrylate containing active hydrogen functional groups and polyurethane prepolymer blocked by isocyanate functional groups in Chinese patent No. 114437641A, then adding the polyurethane prepolymer blocked by isocyanate functional groups into the polyacrylate for reaction, wherein the polyurethane modified polyacrylate pressure-sensitive adhesive has 6N-9N/25mm at minus 30 ℃, is easy to generate bonding failure under the condition of larger internal stress at certain low temperature, and the polyurethane prepolymer blocked by isocyanate functional groups is dripped into the polyacrylate containing active hydrogen functional groups to have poor reaction controllability and possibly gel or poor product structure repeatability. Therefore, in the application of bonding the FPC and the LGP in the backlight module, a pressure-sensitive adhesive tape with good cohesive strength at high temperature, low-temperature toughness and bonding strength needs to be developed.
It should be noted that the foregoing description of the background art is only for the purpose of providing a clear and complete description of the technical solution of the present invention and is presented for the convenience of understanding by those skilled in the art. The above-described solutions are not considered to be known to the person skilled in the art simply because they are set forth in the background of the invention section.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-low temperature impact resistant adhesive polymer, a composition, a pressure-sensitive adhesive tape and application thereof, and mainly solves the problem of poor high-low temperature impact resistance of the existing polyacrylate adhesive composition; the flexible circuit board FPC and the light guide plate LGP can be adhered and assembled in a backlight module of display equipment, and the adhesive tape has good cohesive strength at high temperature and good toughness and adhesive strength at low temperature, and absorbs and releases strong internal stress generated by high-temperature expansion and low-temperature contraction of the LGP, so that the problem of uneven brightness of a display device is solved.
In order to solve the technical problems, in a first aspect, the present invention provides an adhesive polymer resistant to high and low temperature impact, which comprises a polyacrylate main chain and a polyurethane branched chain; the polyurethane branched chain is grafted to the polyacrylate main chain through a curing agent group, and when the polyurethane branched chain, the curing agent group and the polyacrylate main chain do not form chemical bond connection, a precursor of the polyurethane branched chain has a terminal hydroxyl group, a precursor of the curing agent group has a plurality of isocyanate groups or epoxy groups, and a precursor of the polyacrylate main chain has hydroxyl groups or carboxyl groups distributed in a molecular chain; chemical bond connection is formed between the polyurethane branched chain and the curing agent group and between the curing agent group and the polyacrylate main chain through hydroxyl or carboxyl-epoxy group and/or hydroxyl or carboxyl-isocyanate group reaction.
The method prepares the polyurethane modified acrylic ester adhesive polymer, and the system simultaneously comprises (a) the cross-linking connection of a polyacrylate main chain and a curing agent, (b) the chain extension or cross-linking connection of a polyurethane branched chain and the curing agent, and (c) the grafting connection of the polyacrylate main chain, the curing agent and the polyurethane branched chain; the crosslinking structure is formed to give the adhesive polymer good high temperature resistance, (b) the interpenetrating network structure of polyurethane and acrylic ester is possibly formed, and (c) the polyurethane grafting modified acrylic ester structure is formed, so that the compatibility between a polyurethane chain and a polyacrylate chain is effectively solved, and the final adhesive polymer has good toughness and bonding strength at low temperature; in addition, by the method, the risk of bursting existing in the prior art that the polyacrylate containing active hydrogen functional groups and the polyurethane prepolymer blocked by isocyanate functional groups are synthesized respectively firstly, and then the polyurethane prepolymer containing the terminal NCO is dripped into the polyacrylate for reaction is avoided, and the random randomness and the performance repeatability of a free radical copolymerization method for synthesizing the polyurethane prepolymer containing double bonds at both ends and the acrylate are adopted.
Further, the polyacrylate backbone includes polymerized soft monomers, hard monomers, and functional monomers having the hydroxyl or carboxyl groups. The number average molecular weight of the polyacrylate main chain is 20 ten thousand-80 ten thousand;
Further, the polyurethane branched chain comprises a molecular chain fragment formed by a combination of two or more of polybutadiene polyol, polytetramethylene ether glycol, polypropylene glycol ether, polyethylene oxide/propane polyol; the number average molecular weight of the polyurethane branched chain is 4000-20000.
And still further, the polyurethane branches comprise at least polybutadiene polyol.
The polyol molecular chain segment in the polyurethane has the function of reducing Tg, and can further improve the low temperature resistance of the adhesive polymer.
In a second aspect, the present invention also provides an adhesive composition resistant to high and low temperature impact, which includes the adhesive polymer and a first solvent. The composition can be in the form of a glue application, can also be used as a precursor of an adhesive tape, and can be coated and dried to form a pressure-sensitive adhesive tape and the like.
Further, the adhesive composition specifically comprises, in parts by mass:
further, the adhesive is characterized in that the acrylic polymer in the adhesive specifically comprises, in parts by mass:
wherein the functional monomer has a carboxyl group or a hydroxyl group.
The latter parts by mass are not equal to the former parts by mass, and represent only the parts by mass of each component in the adhesive composition and the parts by mass of the acrylate polymer alone; the acrylic polymer is also a composition, not a mere polymer, but a polymer is included in the name of the composition, but only for convenience of distinction from the former composition.
Further regarding the specific selection of the individual monomers, the soft monomers include any one or a combination of two or more of butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isononyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate;
further the hard monomer comprises any one or more than two of methyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate;
further, the functional monomer comprises any one or more than two of acrylic acid, methacrylic acid, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, 3- (3, 4-dihydroxyphenyl) -2-eicosanyl acrylate and 4-hydroxybutyl acrylate.
Further with respect to suitable solids content, the acrylate polymer has a solids content of 20-45%.
Further, the polyurethane prepolymer is at least prepared from oligomer polyol, isocyanate monomer and catalyst through nucleophilic addition polymerization; hydroxyl groups in the oligomer polyol prior to polymerization: the molar ratio of isocyanate groups in the isocyanate monomer is 3-6:1; the mass of the catalyst is 0.05-0.20% of the total mass of the oligomer polyol and the isocyanate monomer.
The third aspect of the present invention also provides a method for preparing the adhesive composition, corresponding to the composition and structural characteristics of the composition, comprising the steps of:
providing an acrylic polymer, a polyurethane prepolymer and a curing agent;
and mixing the acrylic polymer, the polyurethane prepolymer, the curing agent and the optional tackifying resin in a first solvent to form a grafting reaction system, and carrying out grafting reaction to obtain the adhesive composition.
The acrylic polymer and the polyurethane prepolymer can be prepared by self synthesis, and can be purchased commercially or entrusted to other enterprises for synthetic preparation, which belongs to the embodiment of the invention.
As a fourth aspect of the present invention, there is also provided a pressure-sensitive adhesive tape resistant to high and low temperature impact, comprising an adherend formed by at least coating and drying the above-mentioned adhesive composition.
More specifically, the adhesive tape is prepared by coating a release paper or a release film, and winding and cutting the release paper or the release film to form a continuous adhesive tape.
Finally, the invention also provides application of the pressure-sensitive adhesive tape in bonding of backlight modules.
By the technical scheme, the beneficial effects of the invention at least comprise:
1. the invention synthesizes hydroxyl-terminated polyurethane by using low glass transition temperature (Tg) oligomer polyol, and forms covalent bond connection with acrylate polymer with high soft monomer content through isocyanate or epoxy curing agent to synthesize low Tg acrylate adhesive, which can still have better toughness and bonding strength at low temperature of-30 ℃, thus effectively solving the problems of cold brittleness and precipitation of micromolecular plasticizer of the traditional acrylate adhesive;
2. the method for modifying the acrylic ester by using the polyurethane avoids the problems that in the prior art, a free radical copolymerization method is adopted to synthesize the polyurethane prepolymer with double bonds at two ends and acrylic ester, or the polyacrylate with active hydrogen functional groups and the polyurethane prepolymer blocked by isocyanate functional groups are respectively synthesized first, and then the NCO-terminated polyurethane prepolymer is dripped into the polyacrylate to react, so that the reaction is uncontrollable and the repeatability is poor;
3. according to the invention, through the formula design, the low-temperature toughness of the adhesive is endowed by utilizing the low-Tg polyol polymer, the high-temperature resistant crosslinking point and the colloid cohesive strength of the material are endowed by the curing agent, and the bonding strength is effectively improved by a small amount of tackifying resin, so that the adhesive has better high-temperature and low-temperature impact resistance; particularly, when the adhesive is applied to bonding of backlight modules, the adhesive can effectively absorb and release strong internal stress generated by high-temperature expansion and low-temperature contraction of the LGP, and solve the problem of uneven brightness in display.
The foregoing description is only an overview of the present invention and is intended to enable those skilled in the art to make more clear the scope of the present invention and to be practiced in accordance with the present invention as described below with reference to the preferred embodiments thereof.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, in the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and to distinguish between similar objects, and there is no order of preference between them, nor should they be construed as indicating or implying relative importance. Furthermore, in the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
The embodiment of the invention firstly provides an adhesive polymer resistant to high and low temperature impact, which comprises a polyacrylate main chain and a polyurethane branched chain; the polyurethane branched chain is grafted to the polyacrylate main chain through a curing agent group, and when the polyurethane branched chain, the curing agent group and the polyacrylate main chain do not form chemical bond connection, a precursor of the polyurethane branched chain is provided with a terminal hydroxyl group, a precursor of the curing agent group is provided with a plurality of isocyanate groups or a plurality of epoxy groups, and the precursor of the polyacrylate main chain is provided with hydroxyl groups or carboxyl groups distributed in a molecular chain; chemical bond connection is formed between the polyurethane branched chain and the curing agent group and between the curing agent group and the polyacrylate main chain through hydroxyl or carboxyl-epoxy group and/or hydroxyl or carboxyl-isocyanate group reaction.
Of course, the polymer may be used as an adhesive by directly synthesizing a composition comprising the polymer and a solvent through its corresponding synthesis steps, and not only this, but also by separating the polymer in various ways to obtain individual polymer components, for example, by drying to remove the solvent and then forming a tape or the like mainly comprising the polymer; the molecular structure of the polymer provided by the invention is within the practical scope of the invention no matter what way is used; in short, no matter the polymer molecular structure provided by the invention is used for preparing glue, adhesive tape or any other adhesive, the application mode of utilizing the excellent high and low temperature impact resistance brought by the molecular structure belongs to the protection scope of the invention.
In the above technical solution, the most critical technical means is also the most remarkable difference between the present invention and the prior art solution, in the present invention, the polyurethane branched chain is connected to the acrylate main chain through the curing agent having a plurality of isocyanate groups and/or epoxy groups, and the connecting group is the side carboxyl group or side hydroxyl group distributed on the acrylate main chain and the hydroxyl group at the end of the polyurethane branched chain; unlike the present invention, the co-addition polymerization mode employed in the prior art allows the polyurethane to polymerize directly in the backbone by addition polymerization, or other prior art allows the branches to be attached directly to the backbone by reactive functionalities, and not by bridging of the curing agent groups; this results in the invention having very outstanding low temperature performance compared to the prior art described above, due to: the method prepares the polyurethane modified acrylic ester adhesive polymer, and the system simultaneously comprises (a) the cross-linking connection of a polyacrylate main chain and a curing agent, (b) the chain extension or cross-linking connection of a polyurethane branched chain and the curing agent, and (c) the grafting connection of the polyacrylate main chain, the curing agent and the polyurethane branched chain; the crosslinking structure is formed to give the adhesive polymer good high temperature resistance, (b) the interpenetrating network structure of polyurethane and acrylic ester is possibly formed, and (c) the polyurethane grafting modified acrylic ester structure is formed, so that the compatibility between a polyurethane chain and a polyacrylate chain is effectively solved, and the final adhesive polymer has good toughness and bonding strength at low temperature; in addition, by the method, the risk of bursting existing in the prior art that the polyacrylate containing active hydrogen functional groups and the polyurethane prepolymer blocked by isocyanate functional groups are synthesized respectively firstly, and then the polyurethane prepolymer containing the terminal NCO is dripped into the polyacrylate for reaction is avoided, and the random randomness and the performance repeatability of a free radical copolymerization method for synthesizing the polyurethane prepolymer containing double bonds at both ends and the acrylate are adopted.
As some typical application examples of the above technical solutions, the embodiments of the present invention provide a pressure-sensitive adhesive resistant to high and low temperature impact, which includes, by weight:
in addition, a certain amount of crosslinking auxiliary agent which plays a role in crosslinking and curing can be selectively added into the pressure-sensitive adhesive, so that the crosslinking degree is improved during curing, and certainly whether or not to add, what kind of crosslinking auxiliary agent is added and the adding amount can be completely determined based on the actual application requirements, and the key core technical means and effects of the pressure-sensitive adhesive are not affected by the invention.
Further, the acrylic polymer comprises the following components in parts by weight:
in some embodiments, the soft monomer may be selected from any one or more of butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isononyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate, and not limited thereto, and soft monomers that can be used in the acrylic polymer may be used;
in some embodiments, the hard monomer is one or more of methyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and the like, and substitution of similar hard monomers is also possible;
In some embodiments, the functional monomer may be two or more of (meth) acrylic acid, propyl 2, 3-dihydroxyl (meth) acrylate, eicosyl 3- (3, 4-dihydroxyphenyl) -2-acrylate, 4-hydroxybutyl acrylate; the functional monomer belongs to an important monomer connected with a branched chain, and has a carboxyl or hydroxyl at the end, so that the functional monomer can be connected with a curing agent, and further the functional monomer can be connected with a side chain.
In some embodiments, the initiator is one of Benzoyl Peroxide (BPO), azobisisobutyronitrile (AIBN); the solvent can be any one or combination of toluene and ethyl acetate. Of course, the scope of choice of initiator and solvent is naturally not limited thereto, and alternatives to other initiators and solvents that can be used in the art are equally capable of synthesizing polymers having consistent molecular structural characteristics.
In some embodiments, the method for preparing the acrylic polymer comprises the following steps: (1) Accurately weighing soft monomer, hard monomer, toluene and ethyl acetate, adding into a reaction bottle, charging nitrogen to remove oxygen for 1h, heating to 50deg.C under stirring, and mixing well; (2) Heating to 80 ℃, adding 1/3 initiator and part of functional monomer, and stirring to react for 5h under nitrogen; (3) Continuously adding the residual 2/3 initiator and the residual functional monomer, and continuously reacting for 3 hours; (4) cooling, and adding ethyl acetate to a preset solid content;
More specifically, the solids content of the acrylic polymer is preferably 20% to 45%, which has a high correlation with the viscosity of the final composition.
Of course, not limited to this, acrylic polymers having the same structural characteristics can be directly commercially available.
On the other hand, the polyurethane prepolymer is prepared from oligomer polyol, isocyanate monomer and catalyst through affinity addition polymerization;
in some embodiments, the oligomer polyol is two or more of a polybutadiene polyol, a polytetramethylene ether glycol, a polypropylene glycol ether (and/or an oxyvinyl ether) polyol; polybutadiene polyol and polytetramethylene ether glycol, or polybutadiene polyol and polypropylene glycol ether (and/or oxyvinyl ether) polyol are preferred; more preferably, the polybutadiene polyol comprises 70% to 90% of the total weight of the oligomer polyol to ensure sufficient Tg reduction capability.
As a specific material choice for the above technical solutions, the polybutadiene polyol is preferably, for example, windfex-De-Save GermanyHT, or Mitsubishi chemical->H. Or NISSO from Nissan Kabushiki KaishaGI-2000、NISSO/>GI-3000, or POLY +.A. of ARCO in the United states>R-15M、POLY/>One or more of R-45 HT; the polytetramethylene ether glycol is preferably PTMG-1000, PTMG-2000, PTMG of three-dimensional chemical industry of Shanxi China -one of 3000; the polypropylene glycol ether (and/or oxyvinyl ether) polyol is preferably one or more of DP-2000, DP-2000E, DP-2500E, DP-3000, DP-3050E, DP-4000E, DP-6000E of Kunskian chemical industry (Kunskian), or DDL-2000D, DDL-2000E, DDL-3000D of Deshi Federation chemical industry (Chemie) of China, or C2020, C2020E, C2030, D, C, 2040D, C2120, C2140, F3330, H, F, 3135, F3128; it should be noted, however, that the sources of the above-described raw materials are merely exemplary and are not meant to be limiting to the practical scope of the above examples.
In some embodiments, the isocyanate monomer is preferably an aliphatic isocyanate monomer, preferably may be, for example, one or more of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI), xylylene Diisocyanate (XDI); and is also not limited thereto.
In some embodiments, to ensure that sufficient terminal hydroxyl groups are formed, the hydroxyl groups in the oligomer polyol in the reaction system are synthesized: the molar ratio of isocyanate groups in the isocyanate monomer is 3-6:1;
in some embodiments, the catalyst may be, for example, an organobismuth decanoate catalyst; the weight of the catalyst is 0.05-0.20% of the total weight of the oligomer polyol and the isocyanate monomer; of course, it is possible to select different catalysts to achieve the above reaction, and the optimum addition amounts of the different catalysts may be different, and may be adaptively adjusted, not limited to the scope of the present invention and the embodiments.
As a specific example of the above technical solution, the preparation method of the polyurethane prepolymer may include, for example: firstly, adding oligomer polyol subjected to vacuum heating dehydration into a three-neck flask provided with mechanical stirring and condensation reflux, heating to 80-100 ℃ while stirring, dropwise adding 2/4 of total metered isocyanate monomer, and reacting for 2 hours; then dropwise adding 1/3 of the total metered catalyst, adding toluene and MEK, dropwise adding 1/4 of the total metered isocyanate monomer, and continuing to react for 2 hours; then, 1/3 of the total metered amount of catalyst is added dropwise, toluene and MEK are added, and the remaining 1/4 of the total metered amount of isocyanate monomer is added dropwise; then toluene and MEK are added, the rest 1/3 of the catalyst is added dropwise, the reaction is continued until di-n-butylamine is used for titration to confirm that no residual NCO groups exist, and the catalyst is obtained after cooling. Further, the solids content of the polyurethane prepolymer is 20% to 50%.
With respect to the selection and the proportion of other materials, in some embodiments, the tackifying resin is one of rosin ester tackifying resins and terpene phenolic tackifying resins; wherein, the rosin tackifying resin is preferably one of GA-85, GA-90, GA-100 of the chemical of Sichuan of Japan or RE-100L of the company of Korea of the United states; among them, terpene phenol tackifying resins are preferably TP-96, TP-2040, TP-7042 of Uscotch company, or DRT company of America T105, or +.>803L.
Of course, the tackifying resin may be used as an auxiliary component, and may not be added.
In some embodiments, the curing agent is a mixture of both epoxy and isocyanate curing agents; wherein, the epoxy curing agent is preferably 0.01-0.04 part, and the isocyanate curing agent is preferably 0.99-3.96 parts; further, the epoxy-based curing agent is preferably 11029-X, 11021-C, or Hunstman, mitsubishi chemical corporation of JapanOne of GA-240; among them, the isocyanate-based curing agent is preferably one available from Covestro, germanyN 3800、/>N 3300、Desmo/>N 3900、/>XP 2763、XP 2838、/>XP 2489、/>XP 2847、/>L 75、One of XP 2617.
In some embodiments, the second solvent employed may be two of toluene, ethyl acetate, methyl ethyl ketone.
As a typical example of the above technical solution, the method for preparing the pressure-sensitive adhesive resistant to high and low temperature impact may generally include: firstly adding a solvent and tackifying resin, stirring for 10min, then adding an acrylic polymer and a polyurethane prepolymer, stirring for 30min, then adding a curing agent, stirring and mixing for 30min, and standing and defoaming to obtain a polyurethane-acrylic pressure-sensitive adhesive solution;
the above procedure gives a liquid composition which can be applied as glue, and further applications such as the above adhesive preparation of pressure sensitive double sided tape with a thickness of 30-80 um: coating the adhesive solution on a first release film, drying at 120 ℃ to form a glue film with the thickness of 12-37um, and then transferring the glue film to one surface of a 6-25um PET substrate to obtain a semi-finished product of the first release film/glue film/PET; and then the adhesive solution is coated on a second release film, dried at 120 ℃ to form a glue film with the thickness of 12-37um, transferred to the other surface of the semi-finished PET substrate in the last step to obtain the adhesive tape (the first release film/the glue film with the thickness of 12-37 um/the glue film with the thickness of 6-25 um/the glue film with the thickness of 12-37 um/the second release film) with the final structure, and the obtained adhesive tape is put into a baking oven with the temperature of 40-70 ℃ to be cured for 12-72 hours to obtain the final adhesive tape product.
Of course, the specific curing process and conditions may be adjusted as desired without regard to the critical steps of the present invention.
Further, as an extension application, the adhesive tape may be applied to an adhesive assembly of a flexible circuit board FPC and a light guide plate LGP in a backlight unit of a display device.
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, in the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and to distinguish between similar objects, and there is no order of preference between them, nor should they be construed as indicating or implying relative importance. Furthermore, in the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In addition, as shown in Table I, for the preparation of the acrylic Polymer (PA), the following examples were prepared according to the polymer synthesis and composition shown in Table 1.
Other soft monomers such as isodecyl acrylate or isononyl acrylate monomer formulations are referred to as isooctyl acrylate monomers and will not be described in detail.
TABLE one formulation for preparing acrylic Polymer (PA) (mass unit: g)
Example 1
The preparation of acrylic polymers PA-1 to PA-7 in this example comprises the following steps:
(1) Accurately weighing soft monomer, hard monomer, toluene and ethyl acetate, adding into a reaction bottle, charging nitrogen to remove oxygen for 1h, heating to 50deg.C under stirring, and mixing well;
(2) Heating to 80 ℃, adding 1/3 initiator and functional monomer (methyl) acrylic acid, and stirring and reacting for 5h under nitrogen;
(3) Continuously adding the residual 2/3 initiator and the residual functional monomer hydroxyl-containing acrylate monomer, and continuously reacting for 3 hours;
(4) Cooling, adding ethyl acetate, and the solid content is 35%.
Example 2
The process for preparing the adhesive composition of this example comprises the following specific components:
wherein the polyurethane prepolymer: from oligomeric polyolsHT and PTMG-1000, whereinHT is 70% of the total oligomeric polyol mass, and the isocyanate monomer is HMDI,>hydroxyl mole numbers of HT and PTMG-1000: HMDI has an isocyanate group molar number of 6:1 and a bismuth organic caproate catalyst mass of +. >HT, PTMG-1000 and HMDI were 0.05% by mass.
The preparation process comprises the following steps: first, vacuum heating and dehydratingHT and PTMG-1000, adding into a three-neck flask equipped with mechanical stirring and condensation reflux, and heating to 80deg.C under stirringDropwise adding 2/4 of HMDI in total metering amount, and reacting for 2 hours; then dropwise adding 1/3 of the total metered organic bismuth caproate catalyst, adding toluene and MEK, dropwise adding 1/4 of the total metered HMDI, and continuing to react for 2 hours; then, 1/3 of the total metered amount of the bismuth organic decanoate catalyst was added dropwise, toluene and MEK were added, and the remaining 1/4 of the total metered amount of HMDI was added dropwise; then toluene and MEK are added, the rest 1/3 of the total metered organic bismuth caproate catalyst is added dropwise, the reaction is continued until di-n-butylamine is used for titration to confirm that no residual NCO groups exist, and the polyurethane prepolymer is obtained after cooling, wherein the solid content is 35%.
Firstly adding 37.5 parts of toluene, 12.5 parts of ethyl acetate and 85 parts of tackifying resin GA-85 parts, stirring for 10min, then adding 30 parts of PA-1 part and the polyurethane prepolymer, stirring for 30min, then adding 0.025 part of curing agent 11029-X and 2.475 parts of L-75, stirring and mixing for 30min, and standing and defoaming to obtain the polyurethane-acrylic pressure-sensitive adhesive solution.
Examples 3 to 8
This embodiment is substantially the same as embodiment 2, with the main difference that:
other components, proportions and conditions are unchanged, and only PA-1 is replaced by PA-2 to PA-7 respectively.
Example 9
Wherein the polyurethane prepolymer adopted is: the oligomeric polyols include NISSOGI-2000, PTMG-2000 and DP-3000, wherein NISSO +.>GI-2000 represents 80% of the total oligomeric polyol mass, the isocyanate monomer is IPDI, NISSO->Hydroxyl mole number of GI-2000, PTMG-2000 and DP-3000: isocyanate group mole number of IPDI is 5:1, organic bismuth decanoate catalyst materialThe amount is NISSO->GI-2000, PTMG-2000 and DP-3000 and IPDI in an amount of 0.125% by weight.
The preparation procedure is the same as in examples 2-8.
When the composition is prepared, 27 parts of toluene and 8 parts of ethyl acetate are added, stirring is carried out for 10min, then 40 parts of PA-1 and 40 parts of the polyurethane prepolymer are added, stirring is carried out for 30min, and then 11029-C0.04 parts of curing agent and3.96 parts of N3300, stirring and mixing for 30min, and standing and defoaming to obtain polyurethane-acrylic pressure-sensitive adhesive solution.
Example 10
Polyurethane prepolymer: the oligomeric polyols include POLYR-45HT and F3330H, wherein POLY +.>R-45HT accounts for 90% of the total oligomer polyol mass, and the isocyanate monomer is HDI, POLY- >Hydroxyl mole number of R-45HT, and F3330H: the mol number of isocyanate groups of HDI is 3:1, and the mass of the organic bismuth decanoate catalyst is POLY +.>R-45HT, F3330H and HDI were 0.2% by mass. The preparation procedure was as in examples 2-9, except that the reaction temperature was adjusted to 100 ℃.
Adding 19 parts of toluene, 6 parts of ethyl acetate and 4 parts of tackifying resin TP-2040, stirring for 10min, adding 80 parts of PA-1 and 20 parts of polyurethane prepolymer, stirring for 30min, and adding a curing agentGA-240.01 parts and +.>XP 2489, 0.99 part, stirring and mixing for 30min, and standing and defoaming to obtain polyurethane-acrylic pressure-sensitive adhesive solution.
Application example 1
For examples 2-10, the unified tape structure was first release film/24 um adhesive film/12 um PET/24um adhesive film/second release film, with a total thickness of 60um, for convenience of subsequent tape physical property comparison. Coating the adhesive solutions of examples 2-10 on a first release film respectively, drying at 120 ℃ to form a glue film with the thickness of 24um, and then transferring the glue film to one surface of a 12-um PET substrate to obtain a semi-finished product of the first release film/glue film/PET; and then the adhesive solution is coated on a second release film, and is dried at 120 ℃ to form an adhesive film with the thickness of 24um, the adhesive film is transferred to the other surface of the semi-finished PET substrate in the last step, and the obtained adhesive tape is put into a 50 ℃ oven for curing for 48 hours, so that a final adhesive tape product is obtained.
Comparative example 1
A commercially available double sided tape 3806BWH-D2 of the ponding chemical industry Co., ltd. Of 60um was used as a comparison.
Comparative example 2
This comparative example is substantially the same as example 2, with the main difference that: the terminal groups of the polyurethane prepolymer become isocyanate groups instead of hydroxyl groups.
Isocyanate-terminated polyurethane prepolymer: from oligomeric polyolsHT and PTMG-1000, wherein>HT represents 70% of the total oligomeric polyol mass, the isocyanate monomer is HMDI,hydroxyl mole numbers of HT and PTMG-1000: HMDI has an isocyanate group molar number of 1:1.5 and a bismuth organic decanoate catalyst mass of +.>HT, PTMG-1000 and HMDI were 0.05% by mass.
The preparation process comprises the following steps: first, vacuum heating and dehydratingHT and PTMG-1000 are added into a three-neck flask with mechanical stirring and condensation reflux, the temperature is raised to 80 ℃ while stirring, all metered HMDI is added dropwise, and the reaction is carried out for 4 hours; adding toluene and MEK, dropwise adding all metered organic bismuth caproate catalyst, continuing to react until the NCO groups reach the set content by titration with di-n-butylamine, cooling to obtain the polyurethane prepolymer, and adding toluene and MEK to adjust the solid content to 35%.
The preparation method of the polyurethane-acrylic pressure-sensitive adhesive solution is the same as that of example 2.
Adhesive tape preparation method and application example 1
Comparative example 3
This comparative example provides an embodiment of a co-polymerization process for preparing a pressure sensitive adhesive tape, comprising the steps of:
(1) Synthesizing a polyurethane prepolymer with vinyl ends: from oligomeric polyolsHT and PTMG-1000, wherein>HT represents 70% of the total oligomeric polyol mass, the isocyanate monomer is HMDI,hydroxyl groups of HT, PTMG-1000 and 2-hydroxyethyl acrylate (2-HEA) and isocyanate groups of HMDI are equimolar, wherein vinyl groups are introduced for polyurethane chains after the polyurethane is blocked by the 2-HEA; the organic bismuth decanoate catalyst has the mass ofHT, PTMG-1000, 2-HEA, HMDI 0.05% of total mass.
The preparation process comprises the following steps: first, vacuum heating and dehydratingHT and PTMG-1000 are added into a three-neck flask with mechanical stirring and condensation reflux, the temperature is raised to 80 ℃ while stirring, all metered HMDI is added dropwise, and the reaction is carried out for 4 hours; toluene and MEK are added, then all metered organic bismuth decanoate catalyst is added dropwise, and the reaction is continued for 1h; cooling to 50 ℃, dropwise adding 2-HEA, and continuing to react until di-n-butylamine is used for titration to confirm that no residual NCO groups exist; cooling, adding toluene and MEK to obtain the polyurethane prepolymer with the solid content of 15%.
(2) Synthesis of polyurethane modified acrylate polymers: the composition and the proportion of the acrylic polymer are the same as those of PA-1, but the proportion of the acrylic polymer solid to the synthetic polyurethane prepolymer (1) is 70:30 (same as in example 2).
Accurately weighing the synthetic polyurethane prepolymer, soft monomer, hard monomer, solvent toluene and ethyl acetate, adding into a reaction bottle, charging nitrogen to remove oxygen for 1h, heating to 50 ℃ while stirring, and uniformly mixing; heating to 80 ℃, adding 1/3 initiator and functional monomer (methyl) acrylic acid, and stirring and reacting for 5h under nitrogen; continuously adding the residual 2/3 initiator and the residual functional monomer hydroxyl-containing acrylate monomer, and continuously reacting for 3 hours; cooling, adding ethyl acetate, and the solid content is 35%.
(3) Firstly adding 37.5 parts of toluene, 12.5 parts of ethyl acetate and 85 parts of tackifying resin GA-85 parts, stirring for 10min, then adding 100 parts of polyurethane modified acrylate polymer synthesized in the step (2), stirring for 30min, then adding 11029-X0.025 parts of curing agent and 2.475 parts of L-75, stirring and mixing for 30min, and standing and defoaming to obtain polyurethane-acrylate pressure-sensitive adhesive solution.
Adhesive tape preparation method and application example 1
The evaluation method of the adhesive tape is as follows:
1.180 degree peel strength (Room temperature)
The 180-degree peel strength test method is carried out according to the national standard (GB 2792-81) method.
The tape was cut into 1 inch (2.54 cm) wide, length greater than 200mm strips, gently attached to a standard stainless steel test plate (conforming to GB/T3280-1992), and rolled onto the test specimen using a 2.04kg heavy hard rubber roll at a speed of about 300 mm/min. Note that the rolling was performed only three times by reciprocating the sample with a force generated by the mass of the press roller. The test pieces were placed under a constant humidity of 50% RH.+ -. 5% RH controlled atmosphere at a constant temperature of 23.+ -. 2 ℃ for 72 hours, and the peel force was measured at a speed of 12 inches/min (303 mm/min) using a standard tensile machine (meeting the requirements of JB 706-77 for an identification tester), and each sample was averaged three times in N/25mm.
2.180 degree peel strength (-30 ℃ C.)
The test method is the same as 1, the tensile machine equipment is additionally provided with a temperature-increasing and temperature-decreasing closed box body, and the peel strength is directly tested by using the tensile machine after the manufactured peel sample strip is placed in the closed box body at the temperature of minus 30 ℃ for 2 hours.
3. Dynamic shear Strength (Room temperature)
The dynamic shear strength test method is carried out according to the national standard (GB/T33332-2016) method.
Cutting an adhesive tape into 12.5 mm-12.5 mm, adopting a lap joint mode of two test steel plates to prepare a sample, firstly pasting one surface of the adhesive tape to the center position of one steel plate, tearing off a release film on the other surface, putting the other steel plate, rolling the bonding area back and forth for 2 times along the length direction of the steel plate by using a compression roller at the speed of 10mm/min, placing the adhesive tape for 20min under the environment controlled by constant humidity 50%RH + -5%RH at the constant temperature of 23 DEG + -2 ℃, testing shearing strength at the speed of 5mm/min by using a standard tensile machine, and taking the average value in MPa for each sample three times.
4. Dynamic shear Strength (-30 ℃ C.)
And 3, the testing method is the same as 3, the tensile machine equipment is additionally provided with a closed box body with heating and cooling, and the dynamic shear strength is directly tested by using a tensile machine after the manufactured dynamic shear sample strip is placed in the closed box body at the temperature of minus 30 ℃ for 2 hours.
5. High temperature static shear Strength (Hold viscosity)
The test method of high-temperature static shear strength (holding viscosity) is tested according to the national standard (GB/T4851) method.
The tape was cut into 1 inch (2.54 cm) wide, approximately 100mm long strips. The bars were glued in parallel to the longitudinal direction of the plate in the middle of a standard stainless steel test plate (according to GB/T3280-1992) next to it, ensuring a 1 square inch bonding area. A hard rubber roll weighing 2.04kg was used to roll the test specimen at a speed of about 300 mm/min. Note that the rolling was performed only three times by reciprocating the sample with a force generated by the mass of the press roller. The test plate is placed for 72 hours under the constant humidity 50% RH + -5% RH controlled environment at the constant temperature of 23 ℃ + -2 ℃, then the test plate is vertically fixed on a test frame, and the loading plate and the 1kg weight are connected by a light pin. The whole test stand was placed in a test chamber adjusted to 70 ℃. The time for the sample to fall off the test plate was recorded,
each sample was tested three times and averaged in minutes.
According to the above evaluation method, the test results of the tape samples are shown in the following table two:
table II comparative example and test results of the properties of the adhesive tape samples prepared in this example
As can be seen from the second table, the double-sided adhesive tape prepared from the polyurethane modified acrylic adhesive has better adhesive strength at normal temperature, better cohesive strength at normal temperature and high temperature, and better toughness and adhesive strength at low temperature compared with the comparative example.
And compared with the comparative examples 2 and 3 in which the branched chains are directly connected with the main chain and the co-polymerization, the adhesive tape provided by the embodiment of the invention has better low-temperature bonding strength and other properties, which indicates that the embodiment of bridging the main chain and the branched chains through the curing agent group adopted by the invention has obvious improvement on the high-temperature and low-temperature impact resistance of the adhesive tape.
It is clear from this that, in the embodiment of the invention, hydroxyl-terminated polyurethane is synthesized by using low glass transition temperature (Tg) oligomer polyol, and through isocyanate or epoxy curing agent, covalent bond connection is formed between the hydroxyl-terminated polyurethane and acrylate polymer with high soft monomer content, so as to synthesize low Tg acrylate adhesive, which can still have good toughness and bonding strength at low temperature of-30 ℃, and effectively solve the problems of cold embrittlement and precipitation of small molecular plasticizers of the traditional acrylate adhesive; the method for modifying the acrylic ester by using the polyurethane avoids the problems of uncontrollable reaction and poor repeatability of the reaction of the prior art by adopting a method for synthesizing the polyurethane prepolymer with double bonds at both ends and acrylic ester to carry out free radical copolymerization, or respectively synthesizing the polyacrylate with active hydrogen functional groups and the polyurethane prepolymer blocked by isocyanate functional groups, and then dropwise adding the NCO-terminated polyurethane prepolymer into the polyacrylate; the adhesive is endowed with low-temperature toughness by using the low-Tg polyol polymer, the curing agent is endowed with high-temperature resistant crosslinking points and colloid cohesive strength, and a small amount of tackifying resin is used for effectively improving the bonding strength, so that the adhesive has better high-temperature and low-temperature impact resistance; particularly, when the adhesive is applied to bonding of backlight modules, the adhesive can effectively absorb and release strong internal stress generated by high-temperature expansion and low-temperature contraction of the LGP, and solve the problem of uneven brightness in display.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The high-low temperature impact resistant adhesive polymer is characterized by comprising a polyacrylate main chain and a polyurethane branched chain;
the polyurethane branched chain is grafted to the polyacrylate main chain through a curing agent group, and when the polyurethane branched chain, the curing agent group and the polyacrylate main chain do not form chemical bond connection, a precursor of the polyurethane branched chain is provided with a terminal hydroxyl group, a precursor of the curing agent group is provided with a plurality of isocyanate groups or a plurality of epoxy groups, and the precursor of the polyacrylate main chain is provided with hydroxyl groups or carboxyl groups distributed in a molecular chain;
chemical bond connection is formed between the polyurethane branched chain and the curing agent group and between the curing agent group and the polyacrylate main chain through hydroxyl or carboxyl-epoxy group and/or hydroxyl or carboxyl-isocyanate group reaction.
2. The adhesive polymer of claim 1, wherein the polyacrylate backbone comprises polymerized soft monomers, hard monomers, and functional monomers, the functional monomers having the hydroxyl or carboxyl groups; the number average molecular weight of the polyacrylate main chain is 20 ten thousand-80 ten thousand;
And/or the polyurethane branched chain comprises a molecular chain fragment formed by a combination of two or more of polybutadiene polyol, polytetramethylene ether glycol, polypropylene glycol ether polyol, polyethylene oxide/propane polyol; the number average molecular weight of the polyurethane branched chain is 4000-20000.
3. An adhesive composition resistant to high and low temperature impact, comprising the adhesive polymer of any one of claims 1-2 and a first solvent.
4. The adhesive composition according to claim 3, which comprises the following components in parts by mass:
5. the adhesive composition according to claim 4, wherein the acrylic polymer specifically comprises, in parts by mass:
wherein the functional monomer has a carboxyl group or a hydroxyl group.
6. The adhesive composition of claim 5, wherein the soft monomer comprises any one or a combination of two or more of butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, isononyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate;
and/or the hard monomer comprises any one or more than two of methyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate;
And/or the functional monomer comprises any one or more than two of acrylic acid, methacrylic acid, 2, 3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, 3- (3, 4-dihydroxyphenyl) -2-eicosanyl acrylate and 4-hydroxybutyl acrylate;
and/or the solid content of the acrylic polymer is 20-45%.
7. The adhesive composition of claim 4, wherein the polyurethane prepolymer is obtained by nucleophilic addition polymerization of at least an oligomeric polyol, an isocyanate monomer, and a catalyst;
hydroxyl groups in the oligomer polyol prior to polymerization: the molar ratio of isocyanate groups in the isocyanate monomer is 3-6:1;
the mass of the catalyst is 0.05-0.20% of the total mass of the oligomer polyol and the isocyanate monomer.
8. A method of preparing the adhesive composition of any one of claims 4-7, comprising:
providing an acrylic polymer, a polyurethane prepolymer and a curing agent;
and mixing the acrylic polymer, the polyurethane prepolymer, the curing agent and the optional tackifying resin in a first solvent to form a grafting reaction system, and carrying out grafting reaction to obtain the adhesive composition.
9. A pressure-sensitive adhesive tape resistant to high and low temperature impact, characterized in that it comprises an adherend formed at least from the adhesive composition according to any one of claims 4 to 7 after being coated and dried.
10. The use of the pressure-sensitive adhesive tape of claim 9 in the field of backlight module bonding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311584512.2A CN117603649A (en) | 2023-11-26 | 2023-11-26 | High-low temperature impact resistant adhesive polymer, composition, pressure-sensitive adhesive tape and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311584512.2A CN117603649A (en) | 2023-11-26 | 2023-11-26 | High-low temperature impact resistant adhesive polymer, composition, pressure-sensitive adhesive tape and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117603649A true CN117603649A (en) | 2024-02-27 |
Family
ID=89952852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311584512.2A Pending CN117603649A (en) | 2023-11-26 | 2023-11-26 | High-low temperature impact resistant adhesive polymer, composition, pressure-sensitive adhesive tape and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117603649A (en) |
-
2023
- 2023-11-26 CN CN202311584512.2A patent/CN117603649A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101490195B (en) | Adhesive composition for PDP front filter and use | |
| CN106634632B (en) | Preparation method of UV (ultraviolet) moisture dual-curing pressure-sensitive adhesive | |
| JP4036272B2 (en) | Adhesive composition and adhesive sheet | |
| CN107216792B (en) | Acrylic polyurethane coating and preparation method and application thereof | |
| KR102280540B1 (en) | Ultraviolet ray-curable adhesive agent, cured product and adhesive sheet | |
| KR102633504B1 (en) | Pressure sensitive adhesive, curable pressure sensitive adhesive composition, pressure sensitive adhesive sheet and method for producing the same | |
| TWI786263B (en) | Adhesive sheet, manufacturing method thereof, and image display device | |
| KR20120023908A (en) | Acrylic adhesive composition | |
| KR102559842B1 (en) | Pressure sensitive adhesive sheet and manufacturing method thereof, and pressure sensitive adhesive film | |
| TW201936819A (en) | Adhesive sheet, manufacturing method thereof, and method for manufacturing image display device made of an adhesive composition including a base polymer and a photocurable compound | |
| CN103031092A (en) | Pressure-sensitive adhesive composition and pressure sensitive adhesive tape | |
| KR20130031033A (en) | Adhesive composition for optical use, adhesive layer and adhesive sheet using the same | |
| CN109476977B (en) | Pressure-sensitive adhesive, pressure-sensitive adhesive film, pressure-sensitive adhesive tape, and film substrate | |
| CN103045155A (en) | Production method for pressure-sensitive adhesive composition | |
| JPH08120248A (en) | Pressure-sensitive acrylic adhesive composition | |
| CN117603649A (en) | High-low temperature impact resistant adhesive polymer, composition, pressure-sensitive adhesive tape and application | |
| CN113518808B (en) | Pressure-sensitive adhesive sheet, method for producing the same, and image display device | |
| TW202138514A (en) | Adhesive sheet and image display device having a first adhesive layer on one main surface of the transparent film substrate and a second adhesive layer on the other main surface | |
| JP4673943B2 (en) | Water-dispersed pressure-sensitive adhesive composition, process for producing the same, and pressure-sensitive adhesive sheets | |
| KR100405310B1 (en) | Acrylic pressure sensitive adhesive for the polarizing film | |
| KR102519549B1 (en) | Aqueous acrylic emulsion composition using urethane modified acrylic monomer | |
| CN114854337B (en) | Adhesive and preparation method thereof | |
| KR101915282B1 (en) | Adhesive composition for optical use | |
| CN117384572A (en) | Low-temperature-resistant acrylate pressure-sensitive adhesive, pressure-sensitive adhesive tape and preparation method thereof | |
| CN116874658A (en) | High deformation amount acrylic polymer, OCA optical adhesive and adhesive film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |