CN108250925B - Primer and preparation method thereof, polyester film and preparation method thereof - Google Patents
Primer and preparation method thereof, polyester film and preparation method thereof Download PDFInfo
- Publication number
- CN108250925B CN108250925B CN201711380874.4A CN201711380874A CN108250925B CN 108250925 B CN108250925 B CN 108250925B CN 201711380874 A CN201711380874 A CN 201711380874A CN 108250925 B CN108250925 B CN 108250925B
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- CN
- China
- Prior art keywords
- primer
- polyester film
- epoxy resin
- acrylonitrile copolymer
- amine
- 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.)
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002987 primer (paints) Substances 0.000 claims abstract description 119
- 229920001577 copolymer Polymers 0.000 claims abstract description 101
- -1 polycyclic heteroatom compound Chemical class 0.000 claims abstract description 67
- 239000003822 epoxy resin Substances 0.000 claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 63
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 34
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000001723 curing Methods 0.000 claims description 21
- 229920002799 BoPET Polymers 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 7
- 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 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000005041 Mylar™ Substances 0.000 claims 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- 239000010410 layer Substances 0.000 description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- 239000000976 ink Substances 0.000 description 34
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 30
- 239000002585 base Substances 0.000 description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 238000011056 performance test Methods 0.000 description 22
- 238000009472 formulation Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 19
- 239000012975 dibutyltin dilaurate Substances 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 15
- 229920002554 vinyl polymer Polymers 0.000 description 13
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 11
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 10
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 10
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 10
- RQVWTMCUTHKGCM-UHFFFAOYSA-N S-Methyl benzenecarbothioate Chemical class CSC(=O)C1=CC=CC=C1 RQVWTMCUTHKGCM-UHFFFAOYSA-N 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 10
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical class [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 239000004632 polycaprolactone Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 229960001701 chloroform Drugs 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 239000004359 castor oil Substances 0.000 description 6
- 235000019438 castor oil Nutrition 0.000 description 6
- FTAORUVBXKFVDA-UHFFFAOYSA-N cyclohexylsulfanylcyclohexane Chemical compound C1CCCCC1SC1CCCCC1 FTAORUVBXKFVDA-UHFFFAOYSA-N 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- VGIYPVFBQRUBDD-UHFFFAOYSA-N ethenoxycyclohexane Chemical compound C=COC1CCCCC1 VGIYPVFBQRUBDD-UHFFFAOYSA-N 0.000 description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- VDHWOHDSOHPGPC-UHFFFAOYSA-N 3,3-dihydroxyoxepan-2-one Chemical compound OC1(O)CCCCOC1=O VDHWOHDSOHPGPC-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- HBBBDGWCSBWWKP-UHFFFAOYSA-J tetrachloroantimony Chemical compound Cl[Sb](Cl)(Cl)Cl HBBBDGWCSBWWKP-UHFFFAOYSA-J 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- DIYFBIOUBFTQJU-UHFFFAOYSA-N 1-phenyl-2-sulfanylethanone Chemical class SCC(=O)C1=CC=CC=C1 DIYFBIOUBFTQJU-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GGBJHURWWWLEQH-UHFFFAOYSA-N Butyl-cyclohexane Natural products CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical group 0.000 description 2
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 2
- NNGAQKAUYDTUQR-UHFFFAOYSA-N cyclohexanimine Chemical compound N=C1CCCCC1 NNGAQKAUYDTUQR-UHFFFAOYSA-N 0.000 description 2
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 description 2
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940106012 diethylene glycol adipate Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000008096 xylene Substances 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/06—Polyurethanes from polyesters
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Abstract
The invention relates to a primer, in particular to a primer and a preparation method thereof, and a polyester film and a preparation method thereof. The invention provides a primer and a preparation method thereof, a polyester film and a preparation method thereof, and aims to solve the problem that the adhesion between a polyester film coated with a primer and a later-coated ink layer is low after the polyester film is placed at normal temperature and humidity. The primer comprises an amine functional acrylic copolymer, an olefin-acrylonitrile copolymer, epoxy resin, polyester polyol, a polycyclic heteroatom compound, an auxiliary agent, a catalyst and a solvent. The primer coating formed by coating the polyester film with the primer provided by the invention does not need standing and curing, and the adhesive force between the primer coating and the polyester film layer can reach 0 grade, so that the subsequent continuous production is met; meanwhile, the polyester film coated with the base coat can be stored and placed at normal temperature and normal humidity, and when the UV ink is coated again, the ink layer and the base coat still keep good adhesion.
Description
Technical Field
The invention relates to a primer, in particular to a primer and a preparation method thereof, and a polyester film and a preparation method thereof.
Background
The polyester film is a transparent polyester film with different thicknesses obtained by melting and extruding polyethylene terephthalate high-molecular granules and various additives and then performing transverse and longitudinal stretching processing, because the polyester film has excellent transparency, flexibility and ductility and a series of characteristics of certain high and low temperature resistance and the like, the polyester film is widely applied to the fields of silk-screen packaging, medical treatment, ink spraying and the like, particularly in recent years, along with the vigorous improvement of national consumption capacity and the continuous development of logistics industry, the demand for polyester films for packaging articles has increased, the outer surface of the polyester film needs printing ink, however, because the surface energy of the polyester film is low, the ink is difficult to be well adhered after being coated on the surface of the polyester film, and in the general processing process, it is necessary to treat the surface of the polyester film to improve the adhesion of various inks to the surface.
Polyester film surface treatments can be generally classified into two types: corona treatment and base coating treatment. The corona treatment has certain use limitation and timeliness, the adhesion performance of the polyester film surface after corona treatment to the thermosetting coating is improved generally, the adhesion to the UV type ink is not ideal, the active center on the film surface after corona treatment gradually disappears along with the lapse of the standing time of the polyester film, and the adhesion of the polyester film to the thermosetting coating is also gradually reduced; the primer treatment is a commonly used method for treating the surface of a PET (polyethylene terephthalate) film at present, a primer is mainly a polyurethane coating, and the polyurethane coating obtained by the primer generally has the following problems in the market along with the selection of reaction monomers and reaction systems:
(1) the adhesiveness of the base coat and the polyester layer is difficult to reach the standard in a short time, and the concrete expression is as follows: the polyester film coated with the base coat is required to be kept stand and cured, if the polyester film is not cured, after the UV ink layer is coated, the ink layer can corrode the base coat due to the corrosion of the ink layer to the base coat, so that the base coat and the polyester film layer fall off, and the continuous production can not be met in a short time.
(2) The longest subsequent construction time of the UV printing ink is short, and the concrete expression is as follows: the polyester film coated with the base coat needs to be temporarily placed for several days for production scheduling reasons before the ink layer is produced, and when the UV ink layer is coated again, the adhesion between the ink layer and the base coat cannot reach the standard.
(3) The polyester film of coating under coat need carry out comparatively strict management and control to storing the humiture in the storage process, and the concrete expression is: the polyester film coated with the primer layer is stored under normal temperature and normal humidity conditions, the primer layer can accelerate crosslinking and curing due to the influence of environmental temperature and humidity, and when the UV ink is coated again, the phenomenon that the adhesive force between the ink and the primer layer does not reach the standard and falls off can occur.
Many manufacturers have been conducting research, but often after solving one of the above problems, new problems are introduced and mature primer products that meet the above performance requirements are not obtained.
Disclosure of Invention
The invention provides a primer and a preparation method thereof, a polyester film and a preparation method thereof, and aims to solve the problem that the adhesion between a polyester film coated with a primer and a later-coated ink layer is low after the polyester film is placed at normal temperature and humidity. The primer coating formed by coating the polyester film with the primer provided by the invention does not need standing and curing, and the adhesive force between the primer coating and the polyester film layer can reach 0 grade, so that the subsequent continuous production is met; meanwhile, the polyester film coated with the base coat can be stored and placed at normal temperature and normal humidity, when the UV printing ink is coated again, the condition that the adhesive force of the printing ink layer and the base coat is smaller than 2 grades can not be generated, and the printing ink layer and the base coat still can keep good adhesive property.
The invention provides a primer, which comprises the following components: amine-functionalized acrylic copolymer: 1% -15%; olefin-acrylonitrile copolymer: 1% -10%; epoxy resin: 1% -10%; polyester polyol: 1% -15%; polycyclic heteroatom compounds: 1% -5%; auxiliary agent: 0.5 to 5 percent; catalyst: 0.01 to 0.1 percent; solvent: 40% -93%; the percentages are weight percentages.
Further, the solid content of the primer is 4.6-36.9%, and the percentage is weight percentage.
Further, the solid content of the primer is preferably 13.4-21.3%.
Further, the solid content of the primer is most preferably 17.5-19.5%.
Further, the amine functional acrylic copolymer is obtained by the functionalization reaction of a compound containing amine functional group and the side chain of an acrylic monomer.
Further, the amine functional group-containing compound is selected from one or a combination of at least two of primary amine, secondary amine, tertiary amine, amide, imide, alcohol amine, amine polyheterocyclic compound, or aromatic amine compound.
Further, the amine functional group-containing compound is preferably one or a combination of at least two of primary amine, secondary amine, tertiary amine, amide, or amine polyheterocyclic compounds.
Further, the amine functional group-containing compound is most preferably one or a combination of at least two of a primary amine, a secondary amine, or an amine polyheterocyclic compound.
Further, the acrylic monomer is selected from two or a combination of at least three of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, or 2-hydroxyethyl acrylate.
Further, the acrylic monomer is preferably a combination of two or at least three of acrylic acid, methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, or hydroxyethyl methacrylate.
Further, the acrylic monomer is most preferably a combination of two or at least three of acrylic acid, methacrylic acid, or hydroxyethyl methacrylate.
Further, the amine-functionalized acrylic copolymer is selected from one or a combination of at least two of a primary amine-functionalized polyacrylic acid-methacrylic acid copolymer, an amine multiheterocyclic compound-functionalized polyacrylic acid-hydroxyethyl methacrylate copolymer, a primary amine-functionalized methyl acrylate-ethyl acrylate copolymer, a secondary amine-functionalized methyl methacrylate copolymer, a tertiary amine-functionalized methyl acrylate copolymer, an amide-functionalized methyl acrylate-hydroxyethyl methacrylate copolymer, or an amine multiheterocyclic compound-functionalized methyl acrylate-ethyl acrylate copolymer.
Further, the amine-functionalized acrylic copolymer is selected from one or a combination of at least two of a primary amine-functionalized polyacrylic acid-methacrylic acid copolymer, or an amine-polyheterocyclic compound-functionalized polyacrylic acid-hydroxyethyl methacrylate copolymer.
Further, the number average molecular weight of the olefin-acrylonitrile copolymer is 3500-20000.
Further, the number average molecular weight of the olefin-acrylonitrile copolymer is preferably 6000 to 12000.
Further, the number average molecular weight of the olefin-acrylonitrile copolymer is most preferably 10000 to 12000.
Further, the olefin-acrylonitrile copolymer is selected from one or a combination of at least two of aromatic or aliphatic olefin-acrylonitrile copolymers, and the olefin-acrylonitrile copolymer is selected from one or a combination of at least two of polyethylene-acrylonitrile copolymer, polyvinyl chloride-acrylonitrile copolymer, polypropylene-acrylonitrile copolymer, polybutadiene-acrylonitrile copolymer, polystyrene-acrylonitrile copolymer, polyvinyl acetate-acrylonitrile copolymer or polypropylene acetate-acrylonitrile copolymer.
Further, the olefin-acrylonitrile copolymer is preferably one or a combination of at least two of polyethylene-acrylonitrile copolymer, polyvinyl chloride-acrylonitrile copolymer, polypropylene-acrylonitrile copolymer, polybutadiene-acrylonitrile copolymer, or polyvinyl acetate-acrylonitrile copolymer.
Further, the olefin-acrylonitrile copolymer is most preferably one of a polyethylene-acrylonitrile copolymer, or a polybutadiene-acrylonitrile copolymer, or a combination of both.
Further, the epoxy resin is selected from one or a combination of at least two of bisphenol A-epoxy polycondensate, alicyclic epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic epoxy resin or glycidyl type epoxy resin.
Further, the epoxy resin is selected from one or a combination of at least two of bisphenol A-epoxy polycondensate, alicyclic epoxy resin, bisphenol F type epoxy resin, aliphatic glycidyl ether epoxy resin or aliphatic epoxy resin.
Further, the epoxy resin is selected from one of alicyclic epoxy resin or aliphatic epoxy resin or the combination of the two.
Further, the polyester polyol is selected from one or a combination of at least two of 1, 6-hexanediol polycarbonate diol, poly-caprolactone diol, poly castor oil adipate polyol, 1, 4-butanediol adipate diol, polyethylene glycol adipate-diethylene glycol diol, or polyethylene glycol adipate-propylene glycol diol.
Further, the polyester polyol is preferably one or a combination of at least two of poly castor oil adipate polyol, poly 1, 4-butylene adipate glycol, poly ethylene glycol-diethylene glycol adipate glycol, poly ethylene glycol-propylene glycol adipate glycol, or poly caprolactone glycol.
Further, the polyester polyol is most preferably one or a combination of polyethylene adipate glycol-diethylene glycol or poly-caprolactone glycol.
Further, the polycyclic heteroatom compound is selected from one or a combination of at least two of ethylene oxide, propylene oxide, aziridine, cyclohexylimine, ethylenimine, tetrahydrofuran, tetrahydropyrrole, pyrrole, thiophene, pyrimidine, quinoline, purine, caprolactam, cyclohexyl sulfide, ethylene sulfide, vinyl pyrrolidone, N-vinyl carbazole, or vinyl cyclohexyl ether.
Further, the polycyclic hetero atom compound is preferably one or a combination of at least two of ethylene oxide, propylene oxide, aziridine, cyclohexylimine, caprolactam, cyclohexyl thioether, ethylene sulfide, vinyl pyrrolidone, N-vinyl carbazole, or vinyl cyclohexyl ether.
Further, the polycyclic hetero atom compound is most preferably one or a combination of at least two of ethylene oxide, aziridine, or vinyl pyrrolidone.
Further, the auxiliary agent comprises 0.05-0.5% of initiator and 99.5-99.95% of curing agent, and the percentage is that the initiator or the curing agent accounts for the weight percentage of the auxiliary agent; the initiator is selected from one or the combination of at least two of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethyl benzoyl ethyl phosphonate, ferric chloride-antimony tetrachloride, stannic chloride-chloroalkane, dialkyl benzoyl methyl sulfonium salt or ferrocenium salt; the curing agent is diphenylmethane diisocyanate.
Further, the initiator is selected from one or a combination of at least two of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethyl benzoyl phosphonic acid ethyl ester, dialkyl benzoyl methyl sulfonium salt or ferrocene salt.
Further, the initiator is selected from one or a combination of at least two of 2,4, 6-trimethyl benzoyl phosphonic acid ethyl ester, dialkyl benzoyl methyl sulfonium salt or ferrocene salt.
Further, the catalyst is selected from one or a combination of at least two of dibutyl tin dilaurate, triethylene diamine, triethylamine, triisopropanolamine or N-alkyl-1, 4-oxazel.
Further, the catalyst is selected from one or a combination of at least two of dibutyl tin dilaurate, triethylamine and N-alkyl-1, 4-oxazahexane.
Further, the catalyst is selected from one or the combination of dibutyl tin dilaurate and triethylamine.
Further, the solvent is selected from one or a combination of at least two of acetone, toluene, methyl ethyl ketone, methanol, xylene, ethyl acetate, butyl acetate, cyclohexane, N-hexane, N-heptane, trichloromethane, carbon tetrachloride, tetrahydrofuran or N, N-dimethylacetamide.
Further, the solvent is selected from one or a combination of at least two of acetone, ethyl acetate, butyl acetate, cyclohexane and chloroform.
Further, the solvent is selected from one or a combination of at least two of ethyl acetate, cyclohexane and chloroform.
The invention also provides a preparation method of the primer, which comprises the following steps:
(1) adding amine functional acrylic copolymer and epoxy resin into a glass beaker with a certain mass of solvent according to a ratio, and stirring for 1 hour under an electric condition to form a uniformly mixed solution;
(2) adding the olefin-acrylonitrile copolymer, polyester polyol and polycyclic heteroatom compound into the solution obtained in the step (1) according to the proportion, and adding a solvent for dilution to obtain a uniformly mixed solution;
(3) and (3) adding an auxiliary agent and a catalyst into the solution obtained in the step (2) according to a ratio to prepare a primer.
Further, the steps (1) - (3) are carried out in an environment with yellow light lamp as the light environment.
The invention also provides a polyester film, which sequentially comprises a polyester layer, a bottom coating layer and an ink layer, wherein the bottom coating layer is formed by curing the bottom coating agent.
Further, the primer comprises the following components: amine-functionalized acrylic copolymer: 1% -15%; olefin-acrylonitrile copolymer: 1% -10%; epoxy resin: 1% -10%; polyester polyol: 1% -15%; polycyclic heteroatom compounds: 1% -5%; auxiliary agent: 0.5 to 5 percent; catalyst: 0.01 to 0.1 percent; solvent: 40% -93%; the percentages are weight percentages.
Further, the material of the substrate layer is selected from polyethylene terephthalate (PET).
The invention also provides a preparation method of the polyester film, which comprises the following steps:
(1) uniformly coating the uniformly mixed primer on the surface of the PET film by using a specific wire bar coater;
(2) placing the PET film coated with the primer on a transparent glass plate, and placing the transparent glass plate into a vacuum oven for drying;
(3) and (3) taking out the PET film and the glass plate in the step (2), and carrying out curing reaction on epoxy and olefin components in the base coat again under ultraviolet light.
(4) And (4) carrying out ink coating and curing on the PET film obtained in the step (3).
Further, the specification of the wire rod of the specific wire rod coating machine in the step (1) is 0.001-0.010 mm.
Further, in the step (2), the temperature of the vacuum oven is 50 ℃, the drying time is 1 min-5 h, and in the drying process, hydroxyl generated by the reaction in the primer and the hydroxyl of the self system are further crosslinked with the isocyanate curing agent.
Further, the energy of ultraviolet curing in the step (3) is 100-1200 mJ/cm2。
Furthermore, the total thickness of the polyester film is 6.5-511 micrometers, the thickness of the substrate layer is 5-500 micrometers, the thickness of the base coating layer is 0.5-10 micrometers, and the thickness of the ink layer is 1-10 micrometers.
Further, the primer comprises the following components: amine-functionalized acrylic copolymer: 2% -10%; olefin-acrylonitrile copolymer: 2% -10%; epoxy resin: 1.5% -8%; polyester polyol: 2% -14%; polycyclic heteroatom compounds: 2% -4%; auxiliary agent: 0.5 to 3.8 percent; catalyst: 0.01 to 0.07 percent; solvent: 66.49% -80.45%; the percentages are weight percentages. The total thickness of the polyester film is 27.2-29 μm, the thickness of the substrate layer is 20-25 μm, the thickness of the primer layer is 0.5-5 μm, and the thickness of the ink layer is 0.7 ∞
7.2 μm. The above technical solutions include examples 9 to 15.
Further, the primer comprises the following components: amine-functionalized acrylic copolymer: 6 percent; olefin-acrylonitrile copolymer: 5% -6%; epoxy resin: 1.5 to 6 percent; polyester polyol: 5% -10%; polycyclic heteroatom compounds: 3.5% -4%; auxiliary agent: 2.93% -3%; catalyst: 0.05 percent to 0.07 percent; solvent: 70% -70.95%; the percentages are weight percentages. The total thickness of the polyester film is 28.1-28.2 mu m, the thickness of the base material layer is 20 mu m, the thickness of the bottom coating layer is 1-2 mu m, and the thickness of the ink layer is 6.1-7.2 mu m. The above technical solutions include examples 9 to 10.
Compared with the prior art, the primer and the polyester film provided by the invention have the following advantages:
(1) the primer provided by the invention is prepared by stirring an amine functional acrylic copolymer and an epoxy resin into a uniform solution according to a certain proportion of solvents. During the stirring process, the amine functional group of the amine functional acrylic copolymer can promote part of the epoxy resin to carry out ring-opening reaction, so that a part of active hydroxyl groups are generated, and the crosslinking product of the amine functional acrylate and the epoxy resin can provide good adhesion performance for the polyester film while providing active hydrogen for a subsequent thermal crosslinking reaction system.
(2) On the basis of the point (1), adding aromatic or aliphatic olefin-acrylonitrile copolymer, polyester polyol, polycyclic heteroatom compound, auxiliary agent and catalyst into the point (1) to mix into a uniform solution with a certain solid content. After the primer is coated on the surface of the polyester film, vacuum baking is carried out, in the step, a-NCO functional group in a primer system can rapidly generate a thermal crosslinking reaction with an-OH functional group generated by the ring-opening reaction of the amine functional acrylate copolymer and the epoxy resin in the (1) th point and an-OH functional group in polyester polyol added in a subsequent system under the catalysis of a catalyst, the adhesion between the primer layer and the polyester film layer is further improved, and the addition of the aromatic or aliphatic olefin-acrylonitrile copolymer plays a certain role in reducing the glass transition temperature of the primer so as to prevent the primer from excessively curing and crosslinking in the subsequent curing process and weakening the physical acting force between the ink and the primer in the UV ink coating process.
(3) In point (2), the polyester film coated with the undercoat layer is taken out of the oven, and the undercoat layer is subjected to a UV light curing operation. In the step, a cationic initiator in the base coat system can generate active species under the radiation of UV light, and then the active species can carry out rapid crosslinking curing reaction on epoxy parts and polycyclic heteroatom compounds which are not subjected to ring opening thermosetting of epoxy resin in the system at an extremely high speed, so that the base coat is rapidly dried. The high molecular weight polymer is rapidly formed in a short time, so that a large amount of residual polar groups and partial light-cured unreacted components of the base coating layer are reserved, and the physical and chemical acting force support is provided for realizing good adhesion of the subsequent UV ink on the base coating layer, and in this step, the base coating layer and the polyester film layer form good adhesion performance.
(4) In summary, the primer provided by the invention combines the thermosetting crosslinking system with the UV light-initiated cationic polymerization process, and the polymerization reaction system is mixed to obtain the primer with excellent adhesion with the polyester film, so that the primer can meet the requirement of continuous production due to good adhesion between the ink layers coated after long-time, normal-temperature and normal-humidity storage.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The preparation method of the primer provided by the invention comprises the following steps:
(1) adding amine functional acrylic copolymer and epoxy resin into a glass beaker with a certain mass of solvent according to a ratio, and stirring for 1 hour under an electric condition to form a uniformly mixed solution;
(2) adding the olefin-acrylonitrile copolymer, polyester polyol and polycyclic heteroatom compound into the solution obtained in the step (1) according to the proportion, and adding a solvent for dilution to obtain a uniformly mixed solution;
(3) and (3) adding an auxiliary agent and a catalyst into the solution obtained in the step (2) according to a ratio to prepare a primer.
The preparation method of the polyester film provided by the invention comprises the following steps:
(1) uniformly coating the uniformly mixed primer on the surface of the PET film by using a specific wire bar coater;
(2) placing the PET film coated with the primer on a transparent glass plate, and placing the transparent glass plate into a vacuum oven for drying;
(3) and (3) taking out the PET film and the glass plate in the step (2), and carrying out curing reaction on epoxy and olefin components in the base coat again under ultraviolet light.
(4) And (4) carrying out ink coating and curing on the PET film obtained in the step (3).
Further, the specification of the wire rod of the specific wire rod coating machine in the step (1) is 0.001-0.010 mm.
Further, in the step (2), the temperature of the vacuum oven is 50 ℃, the drying time is 1 min-5 h, and in the drying process, hydroxyl generated by the reaction in the primer and the hydroxyl of the self system are further crosslinked with the isocyanate curing agent.
Further, the energy of ultraviolet curing in the step (3) is 100-1200 mJ/cm2。
The performance test method of the primer and the polyester film provided by the invention comprises the following steps:
1. solid content: the solid content of the primer was tested using the test method specified in 4.3 of GB/T2793-1995.
2. Adhesion of primer layer to substrate layer: and testing the adhesion between the base coat and the substrate layer by adopting a testing method specified in GB/T9286-98. The result level of the adhesion force is more than 0, more than 1, more than 2, more than 3, more than 4, more than 5.
3. Adhesion of ink layer to primer layer: the adhesion between the ink layer and the primer layer was tested using the test method specified in GB/T9286-98. After the base layer is coated with the base coat, the base layer is placed on the base layer at normal temperature (23 degrees) and normal humidity (70 RH%) for 0h, 24h, 48h, 4 days, 7 days and 8 days, and then the base layer is coated with the ink, and the adhesion force is respectively tested. The result level of the adhesion force is more than 0, more than 1, more than 2, more than 3, more than 4, more than 5.
4. Thickness: the thickness of the polyester film was measured using a Mitutoyo digital display micrometer.
Example 1
The primer formulation in example 1 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is a primary amine-functionalized polyacrylic acid-methyl acrylate copolymer; the olefin-acrylonitrile copolymer is polyethylene-acrylonitrile copolymer and has the number average molecular weight of 12000; the epoxy resin is bisphenol A-epoxy polycondensate; the polyester polyol is polycarbonate-1, 6-hexanediol diol; the polycyclic heteroatom compound is ethylene oxide; the auxiliary agent is 2-hydroxy-2-methyl-1-phenyl-1-acetone and diphenylmethane diisocyanate, and the weight ratio of the two is 0.05: 99.95; the catalyst is dibutyltin dilaurate; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 2
The primer formulation in example 2 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is a tertiary amine-functionalized methyl acrylate-ethyl acrylate copolymer; the olefin-acrylonitrile copolymer is polyvinyl chloride-acrylonitrile copolymer and has the number average molecular weight of 7000; the epoxy resin is alicyclic epoxy resin; the polyester polyol is poly-caprolactone diol; the polycyclic heteroatom compound is propylene oxide; the auxiliary agent is 2,4, 6-trimethyl benzoyl ethyl phosphonate and diphenylmethane diisocyanate, and the weight ratio of the two is 0.05: 99.95; the catalyst is triethylamine; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 3
The primer formulation in example 3 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is an amide-functionalized butyl acrylate-hexyl acrylate copolymer; the olefin-acrylonitrile copolymer is polypropylene-acrylonitrile copolymer and has a number average molecular weight of 5000; the epoxy resin is bisphenol F type epoxy resin; the polyester polyol is poly castor oil adipate polyol; the polycyclic heteroatom compound is aziridine; the auxiliary agent is ferric trichloride-antimony tetrachloride and diphenylmethane diisocyanate, and the weight ratio of the ferric trichloride to the antimony tetrachloride to the diphenylmethane diisocyanate is 0.05: 99.95,; the catalyst is dibutyltin dilaurate; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 4
The primer formulation in example 4 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is an imide-functionalized methacrylic acid-hexyl acrylate copolymer; the olefin-acrylonitrile copolymer is polybutadiene-acrylonitrile copolymer, and the number average molecular weight is 10000; the epoxy resin is polyphenol type glycidyl ether epoxy resin; the polyester polyol is poly adipic acid-1, 4-butanediol glycol ester diol; the polycyclic heteroatom compound is cycloheximide; the auxiliary agent is stannic chloride-chloralkane and diphenylmethane diisocyanate, and the weight ratio of the stannic chloride-chloralkane to the diphenylmethane diisocyanate is 0.05: 99.95,; the catalyst is triethylene diamine; the solvent was butyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 5
The primer formulation in example 5 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is an alkanolamine-functionalized methacrylic acid-methyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polystyrene-acrylonitrile copolymer, and the number average molecular weight is 20000; the epoxy resin is aliphatic glycidyl ether epoxy resin; the polyester polyol is polyethylene adipate-diglycol ester glycol; the polycyclic heteroatom compound is cycloheximide and vinyl cyclohexyl ether, and the weight ratio of the cycloheximide to the vinyl cyclohexyl ether is 1: 1; the auxiliary agent is dialkyl phenacyl sulfonium salt and diphenylmethane diisocyanate, and the weight ratio of the dialkyl phenacyl sulfonium salt to the diphenylmethane diisocyanate is 0.05: 99.95; the catalyst is triisopropanolamine; the solvent was butyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 6
The primer formulation in example 6 is shown in table 1, wherein:
the amine functionalized acrylic copolymer is an amine multi-heterocyclic compound functionalized polymethyl methacrylate-ethyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polyvinyl acetate-acrylonitrile copolymer with molecular weight of 6000; the epoxy resin is alicyclic epoxy resin; the polyester polyol is polyethylene glycol adipate-propylene glycol ester glycol; the polycyclic heteroatom compound is aziridine; the auxiliary agent is ferrocenyl salt and diphenylmethane diisocyanate, and the weight ratio of the ferrocenyl salt to the diphenylmethane diisocyanate is 1: 0.5: 8.5, and the weight ratio of the two is 0.05: 99.95; the catalyst is dibutyltin dilaurate; the solvent is ethyl acetate and chloroform, and the weight ratio of the ethyl acetate to the chloroform is 1: 1.
the results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 7
The primer formulation in example 7 is shown in table 1, wherein:
the amine functionalized acrylic copolymer is an aromatic amine functionalized polyethyl methacrylate-butyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polypropylene acetate-acrylonitrile copolymer, and the number average molecular weight is 3500; the epoxy resin is glycidyl epoxy resin; the polyester polyol is polycarbonate-1, 6-hexanediol diol; the polycyclic heteroatom compound is tetrahydrofuran; the auxiliary agent is 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2,4, 6-trimethyl benzoyl ethyl phosphonate and diphenylmethane diisocyanate, and the weight ratio of the three is 0.025: 0.025: 99.95; the catalyst is dibutyltin dilaurate and triethylenediamine, and the weight ratio of dibutyltin dilaurate to triethylenediamine is 1: 1; the solvent was butyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 8
The primer formulation in example 8 is shown in table 1, wherein:
the amine functionalized acrylic copolymer is a primary amine functionalized butyl methacrylate-hexyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polyethylene-acrylonitrile copolymer and has the number average molecular weight of 12000; the epoxy resin is bisphenol A-epoxy polycondensate; the polyester polyol is poly adipic acid-1, 4-butanediol glycol ester diol; the polycyclic heteroatom compound is tetrahydropyrrole; the auxiliary agent is ferric trichloride-antimony tetrachloride, stannic chloride-chloralkane and diphenylmethane diisocyanate, and the weight ratio of the ferric trichloride to the antimony tetrachloride to the stannic chloride to the diphenylmethane diisocyanate is 0.025: 0.025: 99.95; the catalyst is dibutyltin dilaurate; the solvent was butyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 9
The primer formulation in example 9 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is a primary amine-functionalized acrylic-methacrylic copolymer; the olefin-acrylonitrile copolymer is polyethylene-acrylonitrile copolymer and has the number average molecular weight of 12000; the epoxy resin is alicyclic epoxy resin; the polyester polyol is polyethylene adipate-diglycol ester glycol; the polycyclic heteroatom compound is ethylene oxide and vinyl pyrrolidone, and the weight ratio of the ethylene oxide to the vinyl pyrrolidone is 1: 1; the auxiliary agent is 2,4, 6-trimethyl benzoyl ethyl phosphonate ferrocenium salt, dialkyl benzoyl methyl sulfonium salt and diphenylmethane diisocyanate, and the weight ratio of the three is 0.25: 0.25: 99.5; the catalyst is dibutyltin dilaurate and triethylamine, and the weight ratio of dibutyltin dilaurate to triethylamine is 1: 1; the solvent is butyl acetate and trichloromethane, and the weight ratio of the butyl acetate to the trichloromethane is 1: 1.
the results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 10
The primer formulation in example 10 is shown in table 1, wherein:
the amine functionalized acrylic copolymer is an amine polyheterocyclic compound functionalized acrylic acid-hydroxyethyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polybutadiene-acrylonitrile copolymer, and the number average molecular weight is 10000; the epoxy resin is aliphatic epoxy resin; the polyester polyol is poly-caprolactone diol; the polycyclic heteroatom compound is aziridine and vinyl pyrrolidone, and the weight ratio of the aziridine to the vinyl pyrrolidone is 1: 1; the auxiliary agent is 2,4, 6-trimethyl benzoyl ethyl phosphonate, ferrocenium salts and diphenylmethane diisocyanate, and the weight ratio of the auxiliary agent to the auxiliary agent is 0.05: 0.05: 99.9; the catalyst is dibutyltin dilaurate and triethylamine, and the weight ratio of dibutyltin dilaurate to triethylamine is 1: 1; the solvent is butyl acetate and cyclohexane, and the weight ratio of the butyl acetate to the cyclohexane is 1: 1.
the results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 11
The primer formulation in example 11 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is a primary amine-functionalized poly (methyl acrylate-co-ethyl acrylate); the olefin-acrylonitrile copolymer is polyethylene-acrylonitrile copolymer and has the number average molecular weight of 12000; the epoxy resin is bisphenol A-epoxy polycondensate; the polyester polyol is poly castor oil adipate polyol; the polycyclic heteroatom compound is ethylene oxide and propylene oxide, and the weight ratio of the ethylene oxide to the propylene oxide is 1: 1; the auxiliary agent is 2-hydroxy-2-methyl-1-phenyl-1-acetone, ferrocenium salt and diphenylmethane diisocyanate, and the weight ratio of the auxiliary agent to the ferrocene salt to the diphenylmethane diisocyanate is 0.05: 0.05: 99.9; the catalyst is dibutyltin dilaurate; the solvent is acetone and cyclohexane, and the weight ratio of the acetone to the cyclohexane is 1: 1.
the results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 12
The primer formulation in example 12 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is a secondary amine-functionalized methacrylic acid-methyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polyvinyl chloride-acrylonitrile copolymer and has the number average molecular weight of 7000; the epoxy resin is alicyclic epoxy resin; the polyester polyol is poly adipic acid-1, 4-butanediol glycol ester diol; the polycyclic heteroatom compound is aziridine or cycloheximide, and the weight ratio of the aziridine to the cycloheximide is 1: 1; the auxiliary agent is 2-hydroxy-2-methyl-1-phenyl-1-acetone, dialkyl benzoyl methyl sulfonium salt and diphenylmethane diisocyanate, the weight ratio of the three is 0.05: 0.05: 99.9; the catalyst is triethylamine; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 13
The primer formulation in example 13 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is a tertiary amine-functionalized acrylic acid-methyl acrylate copolymer; the olefin-acrylonitrile copolymer is polypropylene-acrylonitrile copolymer and has a number average molecular weight of 5000; the epoxy resin is bisphenol F type epoxy resin; the polyester polyol is polyethylene adipate-diglycol ester glycol; the polycyclic heteroatom compound is caprolactam and cyclohexyl thioether, and the weight ratio of the caprolactam to the cyclohexyl thioether is 1: 1; the auxiliary agent is 2,4, 6-trimethyl benzoyl ethyl phosphonate, dialkyl benzoyl methyl sulfonium salt and diphenylmethane diisocyanate, and the weight ratio of the three is 0.05: 0.05: 99.9; the catalyst is N-alkyl-1, 4-oxazahexane; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 14
The primer formulation in example 14 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is an amide-functionalized methyl acrylate-hydroxyethyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polybutadiene-acrylonitrile copolymer, and the number average molecular weight is 10000; the epoxy resin is aliphatic glycidyl ether epoxy resin; the polyester polyol is polyethylene glycol adipate-propylene glycol ester glycol; the polycyclic heteroatom compound is ethylene sulfide and vinyl pyrrolidone, and the weight ratio of the ethylene sulfide to the vinyl pyrrolidone is 1: 1; the auxiliary agent is 2,4, 6-trimethyl benzoyl ethyl phosphonate, ferrocenium salt and diphenylmethane diisocyanate, and the weight ratio of the auxiliary agent to the auxiliary agent is 0.05: 0.05: 99.9; the catalyst is dibutyltin dilaurate and triethylamine, and the weight ratio of the dibutyltin dilaurate to the triethylamine is 1: 1; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 15
The primer formulation in example 15 is shown in table 1, wherein:
the amine functionalized acrylic copolymer is an amine multi-heterocyclic compound functionalized methyl acrylate-ethyl acrylate copolymer; the olefin-acrylonitrile copolymer is polyvinyl acetate-acrylonitrile copolymer, and the number average molecular weight is 6000; the epoxy resin is aliphatic epoxy resin; the polyester polyol is poly-caprolactone diol; the polycyclic heteroatom compound is N-vinyl carbazole and vinyl cyclohexyl ether, and the weight ratio of the N-vinyl carbazole to the vinyl cyclohexyl ether is 1: 1; the auxiliary agent is 2-hydroxy-2-methyl-1-phenyl-1-acetone, ferrocenium salts, 2,4, 6-trimethyl benzoyl ethyl phosphonate and diphenylmethane diisocyanate, and the weight ratio of the four is 0.03: 0.03: 0.04: 99.9; the catalyst is triethylamine and N-alkyl-1, 4-oxazahexane, and the weight ratio of the triethylamine to the N-alkyl-1, 4-oxazahexane is 1: 1; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 16
The primer formulation in example 16 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is a secondary amine-functionalized hexyl methacrylate-cyclohexyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polystyrene-acrylonitrile copolymer and polyvinyl acetate-acrylonitrile copolymer, and the weight ratio and the number average molecular weight of the two are 20000 and 6000 respectively; the epoxy resin is glycidyl epoxy resin; the polyester polyol is polycarbonate-1, 6-hexanediol diol and poly-caprolactone diol, and the weight ratio of the polycarbonate-1, 6-hexanediol diol to the poly-caprolactone diol is 1: 1; the polycyclic heteroatom compound is pyrrole and caprolactam, and the weight ratio of the pyrrole to the caprolactam is 1: 1; the auxiliary agent is alkane, dialkyl benzoyl methyl sulfonium salt and diphenylmethane diisocyanate, and the weight ratio of the alkane, the dialkyl benzoyl methyl sulfonium salt and the diphenylmethane diisocyanate is 0.025: 0.025: 99.95; the catalyst is N-alkyl-1, 4-oxazahexane; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 17
The primer formulation in example 17 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is an amide-functionalized cyclohexyl methacrylate-hydroxyethyl acrylate copolymer; the olefin-acrylonitrile copolymer is polybutadiene-acrylonitrile copolymer and polystyrene-acrylonitrile copolymer, and the weight ratio and the number average molecular weight of the polybutadiene-acrylonitrile copolymer and the polystyrene-acrylonitrile copolymer are 10000 and 20000 respectively; the epoxy resin is aliphatic epoxy resin; the polyester polyol is poly (castor oil adipate) polyol and poly (1, 4-butanediol adipate) glycol, and the weight ratio of the poly (castor oil adipate) polyol to the poly (1, 4-butanediol adipate) glycol is 1: 1; the polycyclic heteroatom compound is thiophene and cyclohexyl thioether, and the weight ratio of the thiophene to the cyclohexyl thioether is 1: 1; the auxiliary agents are ferric trichloride-antimony tetrachloride, dialkyl benzoyl methyl sulfonium salt and diphenylmethane diisocyanate, and the weight ratio of the ferric trichloride to the antimony tetrachloride to the dialkyl benzoyl methyl sulfonium salt to the diphenylmethane diisocyanate is 0.025: 0.025: 99.95; the catalyst is triisopropanolamine; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 18
The primer formulation in example 18 is shown in table 1, wherein:
the amine functionalized acrylic copolymer is an aromatic amine functionalized polyhydroxyethyl acrylate-hydroxyethyl methacrylate copolymer; the olefin-acrylonitrile copolymer is polypropylene-acrylonitrile copolymer and polybutadiene-acrylonitrile copolymer, and the weight ratio of the polypropylene-acrylonitrile copolymer to the polybutadiene-acrylonitrile copolymer is 1: 1. the number average molecular weights are 5000 and 10000 respectively; the epoxy resin is aliphatic glycidyl ether epoxy resin; the polyester polyol is polyethylene adipate-diethylene glycol and polyethylene adipate-propylene glycol, and the weight ratio of the two is 1: 1; the polycyclic heteroatom compound is pyrimidine and thiirane, and the weight ratio of the pyrimidine to the thiirane is 1: 1; the auxiliary agents are ferric trichloride-antimony tetrachloride, ferrocenyl salts and diphenylmethane diisocyanate, and the weight ratio of the ferric trichloride to the antimony tetrachloride is 0.025: 0.025: 99.95; the catalyst is dibutyltin dilaurate; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 19
The primer formulation in example 19 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is an alcohol amine-functionalized hydroxyethyl methacrylate-2-hydroxyethyl acrylate copolymer; the olefin-acrylonitrile copolymer is polyvinyl chloride-acrylonitrile copolymer and polypropylene-acrylonitrile copolymer, and the weight ratio of the polyvinyl chloride-acrylonitrile copolymer to the polypropylene-acrylonitrile copolymer is 1: 1. the number average molecular weights are 7000 and 5000, respectively; the epoxy resin is bisphenol F type epoxy resin; the polyester polyol is polycarbonate-1, 6-hexanediol diol and polyethylene adipate-propylene glycol, and the weight ratio of the polycarbonate-1, 6-hexanediol diol to the polyethylene adipate-propylene glycol is 1: 1; the polycyclic heteroatom compound is quinoline and vinyl pyrrolidone, and the weight ratio of the quinoline to the vinyl pyrrolidone is 1: 1; the auxiliary agent is tin tetrachloride-chloralkane, ferrocenium salt and diphenylmethane diisocyanate, and the weight ratio of the tin tetrachloride to the chloralkane to the ferrocenium salt to the diphenylmethane diisocyanate is 0.025: 0.025: 99.95; the catalyst is dibutyltin dilaurate; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
Example 20
The primer formulation in example 20 is shown in table 1, wherein:
the amine-functionalized acrylic copolymer is an imide-functionalized cyclohexyl methacrylate-hydroxyethyl acrylate copolymer; the olefin-acrylonitrile copolymer is polyethylene-acrylonitrile copolymer and polyvinyl chloride-acrylonitrile copolymer, and the weight ratio of the polyethylene-acrylonitrile copolymer to the polyvinyl chloride-acrylonitrile copolymer is 1: 1. the number average molecular weights were 12000 and 7000, respectively; the epoxy resin is bisphenol A-epoxy polycondensate; the polyester polyol is polycarbonate-1, 6-hexanediol diol and polyethylene adipate-diethylene glycol diol, and the weight ratio of the polycarbonate-1, 6-hexanediol diol to the polyethylene adipate-diethylene glycol diol is 1: 1; the polycyclic heteroatom compound is purine and N-vinyl carbazole, and the weight ratio of the purine to the N-vinyl carbazole is 1: 1; the auxiliary agent is 2-hydroxy-2-methyl-1-phenyl-1-acetone, ferrocenium salt and diphenylmethane diisocyanate, and the weight ratio of the auxiliary agent to the auxiliary agent is 0.025: 0.025: 99.95; the catalyst is dibutyltin dilaurate; the solvent was ethyl acetate.
The results of the performance tests on the primer and the polyester film are shown in Table 2, and the thickness of the polyester film is shown in Table 3.
TABLE 1 formulation ratios of primers provided in examples 1-20
TABLE 2 Performance test results for the primers and polyester films provided in examples 1-20
Table 3 thickness of polyester films provided in examples 1-20
As can be seen from Table 2, the primer layer and the substrate layer formed by curing the primer provided by the invention have good adhesion, and the ink layer and the primer layer have good adhesion. Among them, the polyester films provided in examples 9 to 15 have good comprehensive properties: the adhesive force of the base coat and the substrate layer is 0 grade, and the adhesive force of the ink layer and the base coat (0h, 24h, 48h, 4 days, 7 days and 8 days) is at least 0 grade, 1 grade, 2 grade and 2 grade respectively. In particular, examples 9-10 provide polyester films having a better combination of properties: the adhesion between the base coat and the substrate layer is 0 grade, and the adhesion between the ink layer and the base coat (0h, 24h, 48h, 4 days, 7 days and 8 days) is 0 grade.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the disclosure of the present invention are covered by the scope of the claims of the present invention.
Claims (12)
1. A primer, characterized in that the primer comprises the following components: amine-functionalized acrylic copolymer: 1% -15%; olefin-acrylonitrile copolymer: 1% -10%; epoxy resin: 1% -10%; polyester polyol: 1% -15%; polycyclic heteroatom compounds: 1% -5%; auxiliary agent: 0.5 to 5 percent; catalyst: 0.01 to 0.1 percent; solvent: 40% -93%; the percentages are weight percentages.
2. A primer coating according to claim 1, wherein the primer coating has a solid content of 4.6-36.9%, said percentage being by weight.
3. The primer coating according to claim 1, wherein the amine-functional acrylic copolymer is obtained by functionalizing a side chain of a compound having an amine functional group and an acrylic monomer.
4. The primer according to claim 1, wherein the number average molecular weight of the olefin-acrylonitrile copolymer is 3500 to 20000.
5. The primer according to claim 1, wherein the epoxy resin is one or a combination of two of bisphenol A-epoxy polycondensate and bisphenol F epoxy resin.
6. The primer according to claim 1, wherein the epoxy resin is an aliphatic epoxy resin.
7. The primer according to claim 1, wherein the epoxy resin is a glycidyl epoxy resin.
8. A process for preparing the primer according to any one of claims 1 to 7, wherein the preparation process comprises the steps of:
(1) adding amine functional acrylic copolymer and epoxy resin into a glass beaker with a certain mass of solvent according to a ratio, and stirring for 1 hour under an electric condition to form a uniformly mixed solution;
(2) adding the olefin-acrylonitrile copolymer, polyester polyol and polycyclic heteroatom compound into the solution obtained in the step (1) according to the proportion, and adding a solvent for dilution to obtain a uniformly mixed solution;
(3) and (3) adding an auxiliary agent and a catalyst into the solution obtained in the step (2) according to a ratio to prepare a primer.
9. The process for producing a primer according to claim 8, wherein the steps (1) to (3) are carried out in an environment where the light environment is a yellow lamp.
10. A polyester film comprising a polyester layer, a primer layer and an ink layer in this order, wherein the primer layer is formed by curing the primer according to any one of claims 1 to 5.
11. A mylar as recited in claim 10, wherein the polyester layer is selected from the group consisting of polyethylene terephthalate.
12. A method of making the polyester film of claim 10, comprising the steps of:
(1) uniformly coating the uniformly mixed primer on the surface of the PET film by using a specific wire bar coater;
(2) placing the PET film coated with the primer on a transparent glass plate, and placing the transparent glass plate into a vacuum oven for drying;
(3) taking out the PET film and the glass plate in the step (2), and carrying out re-curing reaction on epoxy resin and olefin-acrylonitrile copolymer components in the base coat under ultraviolet light;
(4) and (4) carrying out ink coating and curing on the PET film obtained in the step (3).
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Application publication date: 20180706 Assignee: NINGBO JIANGBEI EXCITON NEW MATERIAL TECHNOLOGY Co.,Ltd. Assignor: Ningbo Exciton Technology Co.,Ltd. Contract record no.: X2024330000049 Denomination of invention: A primer and its preparation method, a polyester film and its preparation method Granted publication date: 20200828 License type: Common License Record date: 20240429 |