CN115074061B - 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
- CN115074061B CN115074061B CN202210793491.4A CN202210793491A CN115074061B CN 115074061 B CN115074061 B CN 115074061B CN 202210793491 A CN202210793491 A CN 202210793491A CN 115074061 B CN115074061 B CN 115074061B
- Authority
- CN
- China
- Prior art keywords
- monomer
- impregnated paper
- surface coating
- sodium
- diisocyanate
- 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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- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims abstract description 32
- 239000000853 adhesive Substances 0.000 title claims abstract description 30
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- -1 acrylic ester Chemical class 0.000 claims abstract description 37
- 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 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 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
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 56
- 239000003999 initiator Substances 0.000 claims description 28
- 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 24
- 125000005442 diisocyanate group Chemical group 0.000 claims description 19
- 239000004970 Chain extender Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000004026 adhesive bonding Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- 230000002209 hydrophobic effect Effects 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 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
- 230000000844 anti-bacterial effect Effects 0.000 claims description 10
- 239000003899 bactericide agent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 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 8
- 230000003472 neutralizing effect Effects 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
- 239000002518 antifoaming agent Substances 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
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 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
- 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-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
- 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
- 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
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical group CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-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
- 239000013530 defoamer Substances 0.000 claims 1
- 150000005846 sugar alcohols Polymers 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 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920000877 Melamine resin Polymers 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 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
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- 239000003292 glue Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QYYMDNHUJFIDDQ-UHFFFAOYSA-N 5-chloro-2-methyl-1,2-thiazol-3-one;2-methyl-1,2-thiazol-3-one Chemical compound CN1SC=CC1=O.CN1SC(Cl)=CC1=O QYYMDNHUJFIDDQ-UHFFFAOYSA-N 0.000 description 5
- 230000002070 germicidal effect Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 238000002474 experimental method Methods 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
- 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
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 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
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration 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
- 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
- 239000002987 primer (paints) Substances 0.000 description 1
- 238000007639 printing Methods 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
- 159000000000 sodium salts Chemical class 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
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
-
- 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
-
- 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
-
- 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, raw materials adopted by the prepared formaldehyde-free surface coating adhesive and formaldehyde-free production, film-forming, crosslinking and curing processes are free of formaldehyde, and the problem of formaldehyde release caused by melamine-formaldehyde adhesive for traditional impregnated paper is solved. The invention solves the problems of insufficient hardness and scratch resistance of the surface coating adhesive existing in the prior aldehyde-free new technology by introducing the polyol with the self-lubricating function and the organosilicon modified polyurethane/acrylic ester cross network structure formed by polysiloxane. The surface coating adhesive for the impregnated paper does not contain any organic solvent, and realizes true zero VOC. The invention utilizes carbodiimide, organosilicon cross-linking agent, isocyanate, aziridine and carboxyl and hydroxyl to carry out multiple cross-linking, thus not only solving the problems of alcohol resistance and water resistance of the surface coating adhesive existing in the prior aldehyde-free new technology, but also solving the problems of long curing time, no demoulding and easy moisture absorption of the surface coating adhesive.
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, formaldehyde is contained in the raw materials, and harmful substances such as formaldehyde, phenol and the like are released in the glue solution preparation, paper impregnation, board pressing and pasting and the use process of finished furniture, so that the health of people is endangered. Therefore, in order to solve the pollution of formaldehyde to air and protect the life and health of people, many researchers are devoted to research and development work of formaldehyde-free impregnated paper adhesives.
Patent CN109385229A discloses a modified composite formaldehyde-free wear-resistant adhesive and a manufacturing method thereof, wherein the transparency of the adhesive is only 61-66%, and the display of printing lines is seriously affected, so that the decorative and aesthetic effects are affected. In addition, polyvinyl acetate and polyvinyl alcohol components are liable 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 adopted as a surface coating, the VOC emission is high, the pencil hardness is only HB, after a plate is attached, nail pressing and marking are carried out, and the requirements of end consumers are difficult to meet.
Patent CN112159502a discloses a preparation method of formaldehyde-free glue for impregnated paper, which adopts a post-crosslinking acrylic emulsion system, and the acrylic emulsion has the problems of poor solvent resistance, especially poor alcohol resistance.
Patent CN104140777a discloses a formaldehyde-free impregnated paper laminated decorative board and a preparation method thereof, which adopts xylenol, melamine, furfural, methanol and other components to prepare formaldehyde-free glue, has the problem of easy yellowing during baking, and contains a large amount of low-flash-point toxic methanol solvent.
Patent CN113024756a discloses an formaldehyde-free environment-friendly resin colloid for impregnated paper and a preparation method thereof, formaldehyde is still adopted as a raw material, and the problem of formaldehyde release caused by glue solution preparation or a small amount of free phenol is contained. Patent CN110450239a discloses a preparation method of novel formaldehyde-free gummed paper, which adopts heat-sensitive blocked isocyanate as a curing agent, the curing time is long, the production efficiency is affected, and the dried gummed paper needs to be sealed and stored immediately so as not to affect the pressing and pasting of the plate.
Disclosure of Invention
The invention aims to solve the technical problems that: (1) The melamine-formaldehyde surface coating glue for the traditional impregnated paper has the problem of formaldehyde; (2) The existing aldehyde-free new technology has the problems of insufficient hardness of the surface coating adhesive and scratch resistance; (3) The existing formaldehyde-free new technology has the problems that the surface coating is not alcohol-resistant and water-resistant; (4) The existing formaldehyde-free new technology has the problems of long curing time of the surface coating, no demolding and easy moisture absorption.
In order to solve the problems, the inventor provides a preparation method of novel formaldehyde-free gum dipping film paper through numerous experiments, which comprises the following steps:
s1, soaking base paper in a bottom gluing, and taking out and drying the soaked base paper to obtain base paper with front and back surfaces coated with the bottom gluing;
s2, coating back glue on one side of the base paper coated with the back glue obtained in the step S1, coating face glue on the other side of the base paper, and drying to obtain the novel formaldehyde-free gum dipping film paper;
s3, carrying out veneering hot pressing on the back glue coated side of the novel formaldehyde-free impregnated paper obtained in the step S2 and the base material, and completing curing and bonding of the impregnated paper and the base material.
The invention provides a face 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 end-capped polysiloxane and monovinyl polysiloxane;
the hydrophobic monomer is one or more selected from 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-styrenesulfonate;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and 2,2' -azo (2-methylpropionamidine) dihydrochloride;
the neutralizer is one or more selected from ammonia water, N-dimethylethanolamine, triethylamine and 2-amino-2-methyl-1-propanol;
the external crosslinking agent is one or more selected from water-based carbodiimide, water-based organosilicon crosslinking 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 hydroxy acrylic ester monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate;
the catalyst is dibutyl tin 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 vacuum conditions 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 50-90 ℃ for reaction for 2-5 hours;
3) Cooling to 60-70 ℃, adding hydroxy acrylic ester monomer, and reacting for 2-3 hours;
4) Cooling to 30-50 ℃, adding water for emulsification, and obtaining the polyurethane resin containing double bonds.
Preferably, in the surface-coating for impregnated paper, the antifoaming agent is basf NXZ.
Preferably, in the surface gluing for the impregnated paper, the mildew-proof bactericide is KATHON CG bactericide.
Preferably, deionized water is used as a solvent in the surface gluing for the impregnated paper.
The invention also provides a preparation method of the face gluing 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 into pre-emulsion at high speed, and adding into a monomer high-position dropwise adding groove;
s2, uniformly mixing an initiator and part of deionized water, and adding the mixture into an initiator high-level dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base solution, and heating to 70-97 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10-40 min, synchronously dripping the rest initiator solution and the pre-emulsion, dripping for 1.5-5 h, preserving heat for 0.5-2.5 h, and then cooling;
s5, sequentially adding a neutralizing agent, an external crosslinking 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 prepared by the invention does not contain formaldehyde in raw materials, production, manufacture and film-forming crosslinking curing processes, solves the problem of formaldehyde release caused by melamine-formaldehyde adhesive for traditional impregnated paper, and realizes real formaldehyde-free effect for home decoration.
(2) The invention solves the problems of insufficient hardness and scratch resistance of the surface coating adhesive existing in the prior aldehyde-free new technology by introducing the polyol with the self-lubricating function and the organosilicon modified polyurethane/acrylic ester cross network structure formed by polysiloxane.
(3) The surface coating adhesive for the impregnated paper does not contain any organic solvent, and realizes true zero VOC.
(4) The invention utilizes carbodiimide, organosilicon cross-linking agent, isocyanate, aziridine and carboxyl and hydroxyl to carry out multiple cross-linking, thus not only solving the problems of alcohol resistance and water resistance of the surface coating adhesive existing in the prior aldehyde-free new technology, but also solving the problems of long curing time, no demoulding and easy moisture absorption of the surface coating adhesive.
Drawings
Fig. 1 is a flow chart of a preparation process of the face gluing for impregnated paper.
Detailed Description
The reagents used in this example are all common commercial products or prepared by conventional means, and the equipment used is conventional in the art, and the following are some examples of the inventors in experiments:
example 1
The preparation method of the face gluing for the 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 into pre-emulsion at high speed, and adding into a monomer high-position dropwise adding groove;
s2, uniformly mixing an initiator and part of deionized water, and adding the mixture into an initiator high-level dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base solution, and heating to 85 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 20min, synchronously dripping the rest initiator solution and the pre-emulsion, dripping for 3h, preserving heat for 2h, and then cooling;
s5, sequentially adding a neutralizing agent, an external crosslinking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
The surface gluing 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 monomer: 5% butyl acrylate, 10% methyl methacrylate, 5% isobornyl methacrylate;
hydrophilic monomer: 2% methacrylic acid;
emulsifying agent: 1% allyloxy nonylphenol polyoxyethylene ether sulfate;
and (3) an 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 germicide;
27.3% deionized water;
the consumption of the components is calculated according to the total formula;
wherein the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
a diisocyanate: 7% isophorone diisocyanate;
polyol: 15% polypropylene glycol, 5% polycaprolactone polyol);
hydrophilic chain extender: 1% dimethylolpropionic acid;
hydroxy acrylate monomer: 2% hydroxyethyl acrylate;
0.1% dibutyltin dilaurate;
69.9% deionized water;
the preparation process of the polyurethane resin containing double bonds comprises the following steps:
1) Respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under vacuum conditions 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 hydroxy acrylic ester monomer, and reacting for 2 hours;
4) Cooling to 40 ℃, adding water for emulsification, and obtaining the polyurethane resin containing double bonds.
Example 2
The preparation method of the face gluing for the 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 into pre-emulsion at high speed, and adding into a monomer high-position dropwise adding groove;
s2, uniformly mixing an initiator and part of deionized water, and adding the mixture into an initiator high-level dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base solution, and heating to 87 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10min, synchronously dripping the rest initiator solution and the pre-emulsion, dripping for 3h, preserving heat for 2h, and then cooling;
s5, sequentially adding a neutralizing agent, an external crosslinking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
The surface gluing for the impregnated paper comprises the following components in percentage by mass:
35% of polyurethane resin containing double bonds;
double bond-containing polysiloxane monomer: 3% monoacrylate-terminated polysiloxane;
hydrophobic monomer: 15% of isooctyl acrylate, 5% of styrene and 10% of isobornyl methacrylate;
hydrophilic monomer: 1.5% methacrylic acid, 0.5% acrylamide;
emulsifying agent: 1% of allyloxy nonylphenol polyoxyethylene ether sulfate and 1% of sodium allyloxy hydroxypropyl sulfonate;
and (3) an 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 germicide;
24.3% deionized water;
the consumption of the components is calculated according to the total formula;
wherein the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
a 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 polyurethane resin containing double bonds comprises the following steps:
1) Respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under vacuum conditions 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 hydroxy acrylic ester monomer, and reacting for 3 hours;
4) Cooling to 40 ℃, adding water for emulsification, and obtaining the polyurethane resin containing double bonds.
Example 3
The preparation method of the face gluing for the 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 into pre-emulsion at high speed, and adding into a monomer high-position dropwise adding groove;
s2, uniformly mixing an initiator and part of deionized water, and adding the mixture into an initiator high-level dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base solution, and heating to 90 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10min, synchronously dripping the rest initiator solution and the pre-emulsion, dripping for 2.5h, preserving heat for 1.5h, and then cooling;
s5, sequentially adding a neutralizing agent, an external crosslinking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the surface coating adhesive for the impregnated paper.
The surface gluing for the impregnated paper comprises the following components in percentage by mass:
35% of polyurethane resin containing double bonds;
double bond-containing polysiloxane monomer: 4% monovinyl polysiloxane;
hydrophobic monomer: 15% of isooctyl acrylate and 10% of methyl styrene;
hydrophilic monomer: 2% of dimethylaminoethyl acrylate and 3% of acrylamide;
emulsifying agent: 1% of sodium 2-acrylamide-2-methylpropanesulfonate and 2% of sodium p-styrenesulfonate;
and (3) an initiator: 2% potassium persulfate;
neutralizing agent: 1% N, N-dimethylethanolamine;
external crosslinking agent: 2% aqueous carbodiimide, 2% aqueous silicone crosslinker;
0.5% basf NXZ;
0.5% kathon CG germicide;
20% deionized water;
the consumption of the components is calculated according to the total formula;
wherein the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
a diisocyanate: 10% dimer acid diisocyanate;
polyol: 15% polypropylene glycol, 5% polycarbonate polyol;
hydrophilic chain extender: 2% sodium 1, 4-butanediol-2-sulfonate;
hydroxy acrylate monomer: 3% hydroxypropyl acrylate;
0.1% dibutyltin dilaurate;
64.9% deionized water;
the preparation process of the polyurethane resin containing double bonds comprises the following steps:
1) Respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under vacuum conditions 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 hydroxy acrylic ester monomer, and reacting for 2 hours;
4) Cooling to 40 ℃, adding water for emulsification, and obtaining the polyurethane resin containing double bonds.
Example 4
The preparation method of the novel formaldehyde-free gum dipping film paper comprises the following steps:
(1) Soaking the base paper in the base glue, and then taking out and drying the soaked base paper to obtain the base paper with the front and back surfaces coated with the base glue;
(2) Coating back glue on one side of the base paper coated with the back glue obtained in the step (1) close to a base material, coating the top glue prepared in the embodiment 1 on the other side of the base paper, and drying to obtain novel aldehyde-free gum dipping film paper;
(3) Carrying out veneering hot pressing on the coated back adhesive side of the novel formaldehyde-free impregnated paper obtained in the step (2) and a base material to finish the solidification and adhesion of the impregnated paper and the base material;
the formula of the primer coating:
hydrophilic crosslinking monomer: 25% methacrylic acid, 15% acrylic acid;
permeable monomer: sodium salt of allyl alkyl sulfosuccinate (model M-12S, purchased from Shanghai loyalty fine chemical Co., ltd.) 10% sodium 2-acrylamido-2-methylpropanesulfonate;
hydrophobic monomer: 20% of ethyl acrylate, 5% of methyl methacrylate and 5% of styrene;
internal crosslinking monomer: 0.5% of trimethylolpropane triacrylate;
external crosslinking agent: 6% isocyanate;
and (3) an initiator: 5% potassium persulfate;
0.5% basf NXZ;
0.5% kathon CG germicide;
233% deionized water.
The formula of the back adhesive coating comprises the following components:
hydrophilic crosslinking monomer: 10% methacrylic acid, 8% acrylic acid
Adhesion monomer is improved: 5% ethylene glycol methacrylate phosphate, 5% epoxy E51;
hydrophobic monomer: 30% of isooctyl acrylate, 10% of methyl methacrylate and 20% of styrene;
emulsifying agent: 3% of allyloxy nonylphenol polyoxyethylene ether sulfate and 2% of sodium 2-acrylamide-2-methylpropanesulfonate;
external crosslinking agent: 3% Wan jun chemical industryC5, 3% Wanjun chemical industry->C32；
And (3) an initiator: 0.6% potassium persulfate;
0.2% basf NXZ;
0.2% kathon CG germicide;
150% deionized water.
The surface properties of the impregnated paper after hot pressing were subjected to the relevant tests, and the results are shown below:
although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. The surface coating adhesive for the impregnated paper is characterized by comprising the following components in percentage by mass:
30% -50% of polyurethane resin containing double bonds;
1% -5% of double bond-containing polysiloxane monomer;
10% -30% of hydrophobic monomer;
1% -5% of hydrophilic monomer;
0.5% -3% of emulsifying agent;
initiator 0.1% -1%;
1% -5% of a neutralizer;
1% -5% of an external cross-linking agent;
0.05% -1% of defoaming agent;
0.1% -1% of mildew-proof bactericide;
20% -50% of water;
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 end-capped polysiloxane and monovinyl polysiloxane;
the hydrophobic monomer is one or more selected from 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-styrenesulfonate;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and 2,2' -azo (2-methylpropionamidine) dihydrochloride;
the neutralizer is one or more selected from ammonia water, N-dimethylethanolamine, triethylamine and 2-amino-2-methyl-1-propanol;
the external crosslinking agent is one or more selected from water-based carbodiimide, water-based organosilicon crosslinking agent, water-based blocked isocyanate and water-based blocked aziridine;
the double bond-containing polyurethane resin is prepared from the following raw materials in percentage by weight:
5% -15% of diisocyanate;
5% -20% of polyalcohol;
1% -3% of hydrophilic chain extender;
0.5% -5% of hydroxy acrylic ester monomer;
0.05% -0.3% of catalyst;
60% -80% of water;
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 hydroxy acrylic ester monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate;
the catalyst is dibutyl tin dilaurate.
2. The topcoat for impregnated paper according to claim 1, wherein the double bond-containing polyurethane resin is prepared by the steps of:
1) Respectively dehydrating and drying the polyol, the hydrophilic chain extender, the catalyst and the diisocyanate under vacuum conditions to obtain a dehydrated product;
2) Adding dehydrated polyol, a hydrophilic chain extender and a catalyst into a reaction kettle, introducing nitrogen, then dropwise adding dehydrated diisocyanate, and heating to 50-90 ℃ for reaction for 2-5 hours;
3) Cooling to 60-70 ℃, adding a hydroxy acrylic ester monomer, and reacting for 2-3 hours;
4) And cooling to 30-50 ℃, and adding water for emulsification to obtain the polyurethane resin containing double bonds.
3. The topcoat for impregnated paper according to claim 1, wherein the defoamer is basf NXZ.
4. The topcoat adhesive for impregnated paper according to claim 1, wherein the mildewproof bactericide is KATHON CG bactericide.
5. The method for preparing the face gluing for impregnated paper according to any one of claims 1 to 4, comprising the steps of:
s1, dispersing double bond-containing polyurethane resin, double bond-containing polysiloxane monomer, hydrophobic monomer, hydrophilic monomer, emulsifier and deionized water into pre-emulsion at high speed, and adding into a monomer high-position dropwise adding groove;
s2, uniformly mixing an initiator and part of deionized water, and adding the mixture into an initiator high-level dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as a reaction base solution, and heating to 70-97 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10-40 min, synchronously dripping the rest initiator solution and the pre-emulsion, dripping for 1.5-5 h, preserving heat for 0.5-2.5 h, and then cooling;
s5, sequentially adding a neutralizing agent, an external crosslinking 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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| 交联型有机硅改性聚氨酯丙烯酸酯乳液的合成及其性能;狄剑锋;刘裕文;纪凤龙;;纺织学报(第01期);第75-80页 * |
| 有机硅改性水性聚氨酯丙烯酸酯的制备及性能;毛祖秋;石红翠;张博;姚卫琴;宋利青;马国章;;聚氨酯工业(第03期);第13-16页 * |
| 有机硅改性聚氨酯-丙烯酸酯共聚乳液的研究;赵秀丽;陈向荣;丁小斌;郑朝辉;彭宇行;龙新平;;涂料工业(第12期);第7-11页 * |
| 聚硅氧烷-聚丙烯酸酯-聚氨酯三元复合乳液的制备与表征及其胶膜性能;姜绪宝;朱晓丽;张召;孔祥正;;化学学报(第09期);第1115-1125页 * |
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| CN115074061A (en) | 2022-09-20 |
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