CN115074061A - Surface coating adhesive for impregnated paper and preparation method thereof - Google Patents
Surface coating adhesive for impregnated paper and preparation method thereof Download PDFInfo
- Publication number
- CN115074061A CN115074061A CN202210793491.4A CN202210793491A CN115074061A CN 115074061 A CN115074061 A CN 115074061A CN 202210793491 A CN202210793491 A CN 202210793491A CN 115074061 A CN115074061 A CN 115074061A
- Authority
- CN
- China
- Prior art keywords
- impregnated paper
- monomer
- surface coating
- sodium
- acrylate
- 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.)
- Granted
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- 238000000576 coating method Methods 0.000 title claims abstract description 49
- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 polysiloxane Polymers 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 52
- 239000003999 initiator Substances 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 229920005749 polyurethane resin Polymers 0.000 claims description 23
- 125000005442 diisocyanate group Chemical group 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 239000004970 Chain extender Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 7
- 230000000844 anti-bacterial effect Effects 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000003899 bactericide agent Substances 0.000 claims description 7
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical group CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 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 4
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000005336 allyloxy group Chemical group 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 2
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 2
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 229940086542 triethylamine Drugs 0.000 claims description 2
- 229940121375 antifungal agent Drugs 0.000 claims 1
- 239000003429 antifungal agent Substances 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 24
- 238000004132 cross linking Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 229920000877 Melamine resin Polymers 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 206010001598 Alcohol intolerance Diseases 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000003292 glue Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000855 fungicidal effect Effects 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VFTKIWJJPDJBKD-UHFFFAOYSA-N OCCC[Na] Chemical compound OCCC[Na] VFTKIWJJPDJBKD-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- VMJLKERPLGRIQJ-UHFFFAOYSA-N propane-1,1,1-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(O)(O)O VMJLKERPLGRIQJ-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/28—Presence of paper
- C09J2400/283—Presence of paper in the substrate
-
- 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
- C09J2451/00—Presence of graft polymer
Abstract
The invention discloses a surface coating adhesive for impregnated paper and a preparation method thereof, wherein the prepared aldehyde-free surface coating adhesive does not contain formaldehyde in the processes of production, preparation, film forming, crosslinking and curing, and solves the problem of formaldehyde release caused by the traditional melamine-formaldehyde adhesive for impregnated paper. The invention solves the problems of insufficient hardness and poor scratch resistance of the surface coating adhesive in the prior aldehyde-free new technology by introducing the cross network structure of the organosilicon modified polyurethane/acrylate formed by the polyol with the self-lubricating effect and the polysiloxane. The surface coating adhesive for the impregnated paper does not contain any organic solvent, and the real zero VOC is realized. According to the invention, carbodiimide, an organic silicon cross-linking agent, isocyanate and aziridine are subjected to multiple cross-linking with carboxyl and hydroxyl, so that the problems of alcohol intolerance and water intolerance of the surface coating in the existing aldehyde-free new technology are solved, and the problems of long curing time, no demolding and easiness in moisture absorption of the surface coating are solved.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a surface coating adhesive for impregnated paper and a preparation method thereof.
Background
In the existing impregnated paper production process, melamine glue and urea-formaldehyde glue are indispensable raw materials, the raw materials contain formaldehyde, and harmful substances such as formaldehyde, phenol and the like can be released in glue solution preparation, paper impregnation, plate pressing and finished furniture use processes, so that the health of people is harmed. Therefore, in order to solve the problem of formaldehyde pollution to air and protect the life health of people, a plurality of researchers are dedicated to the research and development work of the formaldehyde-free impregnated paper adhesive.
Patent CN109385229A discloses a modified composite formaldehyde-free wear-resistant adhesive and a manufacturing method thereof, wherein the transparency is only 61% -66%, and the display of printing lines is seriously influenced, so that the decorative aesthetic effect is influenced. In addition, polyvinyl acetate and polyvinyl alcohol are easy to yellow and affect water resistance.
Patent CN109851720A discloses an aldehyde-free impregnating adhesive and a synthesis process thereof, wherein thermoplastic polyurethane modified acrylic emulsion is used as a top coating, the VOC emission is high, the pencil hardness is only HB, and after a plate is attached, a nail is pressed and scratched with marks, so that the requirements of end consumers are difficult to meet.
Patent CN112159502A discloses a method for preparing formaldehyde-free glue for impregnated paper, which adopts a post-crosslinking acrylic emulsion system, and the acrylic emulsion has the problem of poor solvent resistance, especially poor alcohol resistance.
Patent CN104140777A discloses a formaldehyde-free impregnated paper laminated decorative board and a preparation method thereof, wherein formaldehyde-free glue is prepared from xylenol, melamine, furfural, methanol and other components, so that the problem of easy yellowing during baking exists, and a large amount of toxic methanol solvent with low flash point is contained.
Patent CN113024756A discloses an aldehyde-free environment-friendly resin colloid for impregnated paper and a preparation method thereof, wherein formaldehyde is still used as a raw material, and the problem of formaldehyde release in glue solution preparation or the problem of containing a small amount of free phenol exists. Patent CN110450239A discloses a method for preparing a novel formaldehyde-free impregnated film paper, which uses heat-sensitive blocked isocyanate as a curing agent, and has a long curing time, which affects the production efficiency, and the dried impregnated paper needs to be sealed and stored immediately, so as to avoid affecting the pressing and sticking with the sheet material.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: (1) the problem that the melamine-formaldehyde surface coating adhesive for the traditional impregnated paper contains formaldehyde; (2) the problems of insufficient hardness and poor scratch resistance of a top coating adhesive in the existing aldehyde-free new technology are solved; (3) the problems of alcohol intolerance and water intolerance of the surface coating glue in the existing aldehyde-free new technology exist; (4) the problems of long curing time, no demoulding and easy moisture absorption of the surface coating in the prior aldehyde-free new technology exist.
In order to solve the problems, the inventor provides a preparation method of novel formaldehyde-free gummed membrane paper through numerous tests, which comprises the following steps:
s1, soaking base paper in a base coating adhesive, taking out the soaked base paper, and drying to obtain base paper with the front surface coated with the base coating adhesive and the back surface coated with the base coating adhesive;
s2, coating back glue on one side, close to the base material, of the base paper coated with the base glue obtained in the step S1, coating surface glue on the other side of the base paper, and drying to obtain the novel aldehyde-free impregnated membrane paper;
and S3, carrying out veneering hot pressing on the coated back adhesive side of the novel formaldehyde-free impregnated membrane paper obtained in the step S2 and the base material to finish the curing and bonding of the impregnated paper and the base material.
The invention provides a surface coating adhesive for impregnated paper, which comprises the following components in percentage by mass:
the sum of the mass percentages of the components is 100 percent;
the double bond-containing polysiloxane monomer is selected from one or more of monoacrylate terminated polysiloxane and monovinyl polysiloxane;
the hydrophobic monomer is selected from one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, styrene, butyl methacrylate, isobornyl methacrylate and methyl styrene;
the hydrophilic monomer is selected from one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, beta-acryloxypropionic acid, methacrylic acid, acrylic acid and acrylamide;
the emulsifier is selected from one or more of allyloxy nonylphenol polyoxyethylene ether, allyloxy nonylphenol polyoxyethylene ether sulfate, sodium vinylsulfonate, sodium allylsulfonate, sodium methallyl sulfonate, sodium allyloxy hydroxypropyl sulfonate, sodium 2-acrylamide-2-methylpropanesulfonate and sodium p-styrene sulfonate;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and 2, 2' -azo (2-methylpropylamidine) dihydrochloride;
the neutralizing agent is selected from one or more of ammonia water, N-dimethylethanolamine, triethylamine and 2-amino-2-methyl-1-propanol;
the external cross-linking agent is selected from one or more of water-based carbodiimide, water-based organosilicon cross-linking agent, water-based blocked isocyanate and water-based blocked aziridine.
Preferably, the double-bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
the sum of the mass percentages of the components is 100 percent;
the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, dimer acid diisocyanate, 4' -diphenylmethane diisocyanate and hexamethylene diisocyanate;
the polyol is one or more of polyethylene glycol, polypropylene glycol, polycarbonate polyol and polycaprolactone polyol;
the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 2-propanediol-3-sodium sulfonate, 1, 2-dihydroxy-3-sodium propane sulfonate and 1, 4-butanediol-2-sodium sulfonate;
the hydroxyl acrylate monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate;
the catalyst is dibutyltin dilaurate.
More preferably, the preparation process of the double bond-containing polyurethane resin comprises the following steps:
1) respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under a vacuum condition to obtain a dehydrated product;
2) adding dehydrated polyol, hydrophilic chain extender and catalyst into a reaction kettle, introducing nitrogen, then dropwise adding dehydrated diisocyanate, heating to 50-90 ℃ and reacting for 2-5 hours;
3) cooling to 60-70 ℃, adding a hydroxyl acrylate monomer, and reacting for 2-3 hours;
4) and cooling to 30-50 ℃, and adding water for emulsification to obtain the double-bond-containing polyurethane resin.
Preferably, in the surface sizing agent for impregnated paper, the defoaming agent is basf NXZ.
Preferably, in the surface coating for the impregnated paper, the mildew-proof bactericide is KATHON CG bactericide.
Preferably, deionized water is used as a solvent in the surface sizing for the impregnated paper.
The invention also provides a preparation method of the surface coating for the impregnated paper, which comprises the following steps:
s1, dispersing double bond-containing polyurethane resin, double bond-containing polysiloxane monomer, hydrophobic monomer, hydrophilic monomer, emulsifier and deionized water at high speed to form pre-emulsion, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 70-97 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10-40 min, synchronously dropwise adding the rest initiator solution and the pre-emulsion for 1.5-5 h, preserving heat for 0.5-2.5 h, and then cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the formaldehyde-free surface coating adhesive prepared by the invention does not contain formaldehyde in the raw materials, production, preparation, film forming, crosslinking and curing processes, solves the problem of formaldehyde release caused by the melamine-formaldehyde adhesive for the traditional impregnated paper, and realizes real formaldehyde-free home decoration.
(2) The invention solves the problems of insufficient hardness and poor scratch resistance of the surface coating adhesive in the prior aldehyde-free new technology by introducing the cross network structure of the organosilicon modified polyurethane/acrylate formed by the polyol with the self-lubricating effect and the polysiloxane.
(3) The surface coating adhesive for the impregnated paper does not contain any organic solvent, and the real zero VOC is realized.
(4) The invention utilizes carbodiimide, organosilicon cross-linking agent, isocyanate, aziridine to multiply cross-link with carboxyl and hydroxyl, not only solves the problems of the prior aldehyde-free new technology that the surface coating is not alcohol-resistant and water-resistant, but also solves the problems of long curing time, demoulding resistance and easy moisture absorption of the surface coating.
Drawings
FIG. 1 is a flow chart of a preparation process of surface coating for impregnated paper according to the present invention.
Detailed Description
In this example, unless otherwise specified, the reagents used were all common commercial products or prepared by conventional means, the equipment used was conventional in the art, and the following are some examples in the experiments performed by the inventors:
example 1
A preparation method of surface coating for impregnated paper comprises the following steps:
s1, dispersing double-bond-containing polyurethane resin, double-bond-containing polysiloxane monomer, hydrophobic monomer, hydrophilic monomer, emulsifier and deionized water at high speed into pre-emulsion, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 85 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 20min, synchronously dropwise adding the rest initiator solution and the pre-emulsion, dropwise adding for 3h, preserving heat for 2h, and cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
The surface coating adhesive for the impregnated paper comprises the following components in percentage by mass:
40% of double bond-containing polyurethane resin;
double bond-containing polysiloxane monomer: 5% monoacrylate-terminated polysiloxane;
hydrophobic monomers: 5% butyl acrylate, 10% methyl methacrylate, 5% isobornyl methacrylate;
hydrophilic monomer: 2% methacrylic acid;
emulsifier: 1% allyloxy nonylphenol polyoxyethylene ether sulfate;
initiator: 0.5% ammonium persulfate;
neutralizing agent: 2% ammonia water;
external crosslinking agent: 2% aqueous blocked aziridine;
0.1% basf NXZ;
0.1% KATHON CG fungicide;
27.3% deionized water;
the dosage of each component is calculated according to the total formula amount;
wherein, the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
diisocyanate: 7% of isophorone diisocyanate;
polyol: 15% polypropylene glycol, 5% polycaprolactone polyol);
hydrophilic chain extender: 1% dimethylolpropionic acid;
hydroxyl acrylate monomer: 2% hydroxyethyl acrylate;
0.1% dibutyltin dilaurate;
69.9% deionized water;
the preparation process of the double-bond-containing polyurethane resin comprises the following steps:
1) respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under a vacuum condition to obtain a dehydrated product;
2) adding dehydrated polyol, hydrophilic chain extender and catalyst into a reaction kettle, introducing nitrogen, then dropwise adding dehydrated diisocyanate, and heating to 70 ℃ for reaction for 4 hours;
3) cooling to 60 ℃, adding a hydroxyl acrylate monomer, and reacting for 2 hours;
4) cooling to 40 ℃, adding water for emulsification to obtain the double bond-containing polyurethane resin.
Example 2
A preparation method of surface coating for impregnated paper comprises the following steps:
s1, dispersing double-bond-containing polyurethane resin, double-bond-containing polysiloxane monomer, hydrophobic monomer, hydrophilic monomer, emulsifier and deionized water at high speed into pre-emulsion, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 87 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10min, synchronously dropwise adding the rest initiator solution and the pre-emulsion, dropwise adding for 3h, preserving heat for 2h, and then cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
The surface coating adhesive for the impregnated paper comprises the following components in percentage by mass:
35% of double bond-containing polyurethane resin;
double bond-containing polysiloxane monomer: 3% monoacrylate-terminated polysiloxane;
hydrophobic monomers: 15% of isooctyl acrylate, 5% of styrene and 10% of isobornyl methacrylate;
hydrophilic monomer: 1.5% methacrylic acid, 0.5% acrylamide;
emulsifier: 1% of allyloxy nonyl phenol polyoxyethylene ether sulfate and 1% of allyloxy hydroxypropyl sodium sulfonate;
initiator: 0.5% potassium persulfate;
neutralizing agent: 1% N, N-dimethylethanolamine;
external crosslinking agent: 2% aqueous blocked aziridine;
0.1% basf NXZ;
0.1% KATHON CG fungicide;
24.3% deionized water;
the dosage of each component is calculated according to the total formula amount;
wherein, the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
diisocyanate: 10% hexamethylene diisocyanate;
polyol: 10% polyethylene glycol, 10% polycarbonate polyol;
hydrophilic chain extender: 2% sodium 1, 2-dihydroxy-3-propanesulfonate;
hydroxy acrylate monomer: 5% hydroxyethyl methacrylate;
0.1% dibutyltin dilaurate;
62.9% deionized water;
the preparation process of the double-bond-containing polyurethane resin comprises the following steps:
1) respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under a vacuum condition to obtain a dehydrated product;
2) adding dehydrated polyol, hydrophilic chain extender and catalyst into a reaction kettle, introducing nitrogen, then dropwise adding dehydrated diisocyanate, and heating to 80 ℃ for reaction for 3 hours;
3) cooling to 65 ℃, adding a hydroxyl acrylate monomer, and reacting for 3 hours;
4) cooling to 40 ℃, adding water for emulsification to obtain the double bond-containing polyurethane resin.
Example 3
A preparation method of surface coating for impregnated paper comprises the following steps:
s1, dispersing double-bond-containing polyurethane resin, double-bond-containing polysiloxane monomer, hydrophobic monomer, hydrophilic monomer, emulsifier and deionized water at high speed into pre-emulsion, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 90 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10min, synchronously dropwise adding the rest initiator solution and the pre-emulsion, dropwise adding for 2.5h, preserving heat for 1.5h, and then cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
The surface coating adhesive for the impregnated paper comprises the following components in percentage by mass:
35% of double bond-containing polyurethane resin;
double bond-containing polysiloxane monomer: 4% monovinyl polysiloxane;
hydrophobic monomer: 15% isooctyl acrylate, 10% methyl styrene;
hydrophilic monomer: 2% dimethylaminoethyl acrylate, 3% acrylamide;
emulsifier: 1% of 2-acrylamide-2-methyl sodium propane sulfonate and 2% of sodium p-styrene sulfonate;
initiator: 2% potassium persulfate;
neutralizing agent: 1% N, N-dimethylethanolamine;
external crosslinking agent: 2% of water-based carbodiimide and 2% of water-based organic silicon cross-linking agent;
0.5% basf NXZ;
0.5% KATHON CG fungicide;
20% deionized water;
the dosage of each component is calculated according to the total formula amount;
wherein, the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
diisocyanate: 10% dimer acid diisocyanate;
polyol: 15% polypropylene glycol, 5% polycarbonate polyol;
hydrophilic chain extender: 2% 1, 4-butanediol-2-sulfonic acid sodium salt;
hydroxyl acrylate monomer: 3% hydroxypropyl acrylate;
0.1% dibutyltin dilaurate;
64.9% deionized water;
the preparation process of the double-bond-containing polyurethane resin comprises the following steps:
1) respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under a vacuum condition to obtain a dehydrated product;
2) adding dehydrated polyol, hydrophilic chain extender and catalyst into a reaction kettle, introducing nitrogen, then dropwise adding dehydrated diisocyanate, and heating to 80 ℃ for reaction for 3 hours;
3) cooling to 70 ℃, adding a hydroxyl acrylate monomer, and reacting for 2 hours;
4) cooling to 40 ℃, adding water for emulsification to obtain the double bond-containing polyurethane resin.
Example 4
A preparation method of novel aldehyde-free impregnated membrane paper comprises the following steps:
(1) soaking base paper in the base coating adhesive, taking out the soaked base paper and drying to obtain the base paper with the base coating adhesive on the front surface and the back surface;
(2) coating back glue on one side, close to a base material, of the base paper coated with the bottom glue obtained in the step (1), coating the surface glue prepared in the embodiment 1 on the other side of the base paper, and drying to obtain novel formaldehyde-free gumming film paper;
(3) carrying out veneering hot pressing on one side of the novel formaldehyde-free impregnated film paper obtained in the step (2), which is coated with the back glue, and the base material to finish the curing and bonding of the impregnated paper and the base material;
the formula of the bottom coating adhesive is as follows:
hydrophilic crosslinking monomer: 25% methacrylic acid, 15% acrylic acid;
permeable monomer: 7.5% allyl alkyl sulfosuccinate sodium salt (model M-12S, purchased from Shanghai loyal Fine chemical Co., Ltd.), 10% sodium 2-acrylamido-2-methylpropanesulfonate;
hydrophobic monomers: 20% ethyl acrylate, 5% methyl methacrylate, 5% styrene;
internal crosslinking monomer: 0.5% trihydroxypropane triacrylate;
external crosslinking agent: 6% of isocyanate;
initiator: 5% potassium persulfate;
0.5% basf NXZ;
0.5% KATHON CG fungicide;
233% deionized water.
The back coating formula comprises:
hydrophilic crosslinking monomer: 10% methacrylic acid, 8% acrylic acid
Improving the adhesive force monomer: 5% of ethylene glycol methacrylate phosphate, 5% of epoxy resin E51;
hydrophobic monomers: 30% of isooctyl acrylate, 10% of methyl methacrylate and 20% of styrene;
emulsifier: 3% of allyloxy nonylphenol polyoxyethylene ether sulfate and 2% of 2-acrylamide-2-methylpropanesulfonic acid sodium salt;
external crosslinking agent: 3% Wanjun chemical industry
C5, 3% Wanjun chemical industry
C32；
Initiator: 0.6% potassium persulfate;
0.2% basf NXZ;
0.2% KATHON CG fungicide;
150% deionized water.
The surface properties of the impregnated paper after hot pressing were tested in relation to each other and the results are shown below:
although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The top coating adhesive for the impregnated paper is characterized by comprising the following components in percentage by mass:
the sum of the mass percentages of the components is 100 percent;
the double bond-containing polysiloxane monomer is selected from one or more of monoacrylate-terminated polysiloxane and monovinyl polysiloxane;
the hydrophobic monomer is selected from one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, styrene, butyl methacrylate, isobornyl methacrylate and methyl styrene;
the hydrophilic monomer is selected from one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, beta-acryloxypropionic acid, methacrylic acid, acrylic acid and acrylamide;
the emulsifier is selected from one or more of allyloxy nonyl phenol polyoxyethylene ether, allyloxy nonyl phenol polyoxyethylene ether sulfate, sodium vinylsulfonate, sodium allylsulfonate, sodium methallyl sulfonate, sodium allyloxy hydroxypropyl sulfonate, sodium 2-acrylamide-2-methylpropanesulfonate and sodium p-styrene sulfonate;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and 2, 2' -azo (2-methylpropylamidine) dihydrochloride;
the neutralizing agent is selected from one or more of ammonia water, N-dimethylethanolamine, triethylamine and 2-amino-2-methyl-1-propanol;
the external cross-linking agent is selected from one or more of waterborne carbodiimide, waterborne organosilicon cross-linking agent, waterborne blocked isocyanate and waterborne blocked aziridine.
2. The top coating for the impregnated paper according to claim 1, wherein the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
the sum of the mass percentages of the components is 100 percent;
the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, dimer acid diisocyanate, 4' -diphenylmethane diisocyanate and hexamethylene diisocyanate;
the polyol is one or more of polyethylene glycol, polypropylene glycol, polycarbonate polyol and polycaprolactone polyol;
the hydrophilic chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 2-propanediol-3-sodium sulfonate, 1, 2-dihydroxy-3-sodium propane sulfonate and 1, 4-butanediol-2-sodium sulfonate;
the hydroxyl acrylate monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate;
the catalyst is dibutyltin dilaurate.
3. The top coating for impregnated paper according to claim 2, wherein the double bond-containing polyurethane resin is prepared by the following steps:
1) respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under a vacuum condition to obtain a dehydrated product;
2) adding dehydrated polyol, hydrophilic chain extender and catalyst into a reaction kettle, introducing nitrogen, then dropwise adding dehydrated diisocyanate, heating to 50-90 ℃ and reacting for 2-5 hours;
3) cooling to 60-70 ℃, adding a hydroxyl acrylate monomer, and reacting for 2-3 hours;
4) and cooling to 30-50 ℃, and adding water for emulsification to obtain the double-bond-containing polyurethane resin.
4. The top coating for impregnated paper according to claim 1, wherein the defoaming agent is basf NXZ.
5. The top-coating adhesive for impregnated paper according to claim 1, wherein the antifungal agent is KATHON CG.
6. The preparation method of the surface sizing agent for the impregnated paper according to any one of claims 1 to 5, characterized by comprising the following steps:
s1, dispersing double-bond-containing polyurethane resin, double-bond-containing polysiloxane monomer, hydrophobic monomer, hydrophilic monomer, emulsifier and deionized water at high speed into pre-emulsion, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 70-97 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10-40 min, synchronously dropwise adding the rest initiator solution and the pre-emulsion for 1.5-5 h, preserving heat for 0.5-2.5 h, and then cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
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