JP2021109957A - Method for preparing light resistant aqueous polyurethane coating agent and adhesive for carbon nanotube modification - Google Patents
Method for preparing light resistant aqueous polyurethane coating agent and adhesive for carbon nanotube modification Download PDFInfo
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- JP2021109957A JP2021109957A JP2020186827A JP2020186827A JP2021109957A JP 2021109957 A JP2021109957 A JP 2021109957A JP 2020186827 A JP2020186827 A JP 2020186827A JP 2020186827 A JP2020186827 A JP 2020186827A JP 2021109957 A JP2021109957 A JP 2021109957A
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- carbon nanotubes
- adhesive
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- preparing
- polyurethane coating
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 41
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 40
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 230000004048 modification Effects 0.000 title claims abstract description 27
- 238000012986 modification Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000945 filler Substances 0.000 claims abstract description 31
- SJSOFNCYXJUNBT-UHFFFAOYSA-N 3,4,5-trimethoxybenzoic acid Chemical compound COC1=CC(C(O)=O)=CC(OC)=C1OC SJSOFNCYXJUNBT-UHFFFAOYSA-N 0.000 claims abstract description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 26
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 21
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- LJHFIVQEAFAURQ-ZPUQHVIOSA-N (NE)-N-[(2E)-2-hydroxyiminoethylidene]hydroxylamine Chemical compound O\N=C\C=N\O LJHFIVQEAFAURQ-ZPUQHVIOSA-N 0.000 claims abstract description 16
- IWPZKOJSYQZABD-UHFFFAOYSA-N 3,4,5-trimethoxybenzoic acid Natural products COC1=CC(OC)=CC(C(O)=O)=C1 IWPZKOJSYQZABD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 8
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000011231 conductive filler Substances 0.000 claims description 34
- 239000005543 nano-size silicon particle Substances 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 28
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 11
- 235000005487 catechin Nutrition 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 11
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 10
- 229950001002 cianidanol Drugs 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 8
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001263 FEMA 3042 Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 239000012982 microporous membrane Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- 239000002071 nanotube Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 7
- 229940033123 tannic acid Drugs 0.000 claims description 7
- 235000015523 tannic acid Nutrition 0.000 claims description 7
- 229920002258 tannic acid Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HZNQSWJZTWOTKM-UHFFFAOYSA-N 2,3,4-trimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C(OC)=C1OC HZNQSWJZTWOTKM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- VZQPIJPXUKVLGD-UHFFFAOYSA-N dihydroxymethyl butanoate Chemical compound CCCC(=O)OC(O)O VZQPIJPXUKVLGD-UHFFFAOYSA-N 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 description 33
- 229920002635 polyurethane Polymers 0.000 description 26
- 238000012360 testing method Methods 0.000 description 22
- 230000006866 deterioration Effects 0.000 description 13
- 230000008859 change Effects 0.000 description 11
- 229920006264 polyurethane film Polymers 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- -1 acrylic ester Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- INJAHHABQHQOMY-UHFFFAOYSA-N 2-(dihydroxymethyl)butanoic acid Chemical compound CCC(C(O)O)C(O)=O INJAHHABQHQOMY-UHFFFAOYSA-N 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
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- 230000002265 prevention Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001765 catechin Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000556 factor analysis Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
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- 238000002407 reforming Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000013077 scoring method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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Abstract
Description
本発明は、機能性高分子材料の分野に関し、特に、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製方法に関する。 The present invention relates to the field of functional polymeric materials, and in particular to methods of preparing light-resistant aqueous polyurethane coatings and adhesives for modifying carbon nanotubes.
ＭＤＩタイプのポリウレタン（ＭＤＩ−ＰＵ）は、広く使用されている高分子材料であり、フォーム、エラストマー、ファイバー、接着剤およびコーティング剤等の分野で多くの用途がある。他のタイプのＰＵと比較して、その性能は優れており、価格が比較的低く、かつＭＤＩの毒性が低く、ＰＵを調製する過程で人体や環境に対する害が少ないで。ただし、分子構造にベンゼン環が存在するため、ＭＤＩ−ＰＵは日光の紫外線（ＵＶ）の作用下で劣化や分解を起こしやすくなり、材料の物理的および機械的特性が低下し、黄色く変色することがあり、屋外分野での用途に大きな影響を与える。また、ＭＤＩは世界の化学産業における中国の支配的な分野であり、ＭＤＩの黄変の問題はポリウレタンコーティング剤や接着剤をＭＤＩに応用する場合に困難であったため、ＭＤＩ−ＰＵの耐紫外線性を向上させることは、ＭＤＩ産業とＰＵ産業の継続的な発展を促進するために解決すべき課題となっている。 MDI type polyurethane (MDI-PU) is a widely used polymeric material and has many uses in the fields of foams, elastomers, fibers, adhesives and coatings. Compared to other types of PU, its performance is excellent, its price is relatively low, its toxicity of MDI is low, and it is less harmful to human body and environment in the process of preparing PU. However, due to the presence of a benzene ring in the molecular structure, MDI-PU is prone to deterioration and decomposition under the action of ultraviolet rays (UV) from sunlight, which deteriorates the physical and mechanical properties of the material and causes it to turn yellow. Has a great impact on applications in the outdoor field. In addition, MDI is China's dominant field in the world chemical industry, and the problem of yellowing of MDI was difficult when applying polyurethane coating agents and adhesives to MDI, so the UV resistance of MDI-PU. Is an issue to be solved in order to promote the continuous development of the MDI industry and the PU industry.
非特許文献１では、多種の有機劣化防止用助剤と無機ナノ亜鉛酸化物を使用してＭＤＩ−ＰＵをブレンド改質し、色差、機械的特性試験、光減量試験、減衰全反射フーリエ変換赤外分光法（ＡＴＲ−ＦＴ−ＩＲ）、熱分析（ＤＳＣ）などの試験、特性評価方法を用い、人工加速劣化試験によりその紫外線劣化防止能力を評価した後、最良の改質スキームを得ている。３つのカテゴリ（紫外線吸収剤、光安定剤、抗酸化剤）の５種の劣化防止助剤（ＵＶ−５３１、ＵＶ−Ｐ、ＨＳ−７７０、ＨＳ−９４４、Ｉｒｇａｎｏｘ１０１０）を使用して、ＭＤＩ−ＰＵを複合化・改質した。結果は、劣化防止剤ＨＳ−７７０＋ＵＶ−Ｐを組み合わせて使用すると、ＭＤＩ−ＰＵの光分解反応と架橋反応を効果的に抑制でき、材料の色安定性と機械的特性の保持率を向上させ、光分解生成物を減少させ、ガラス転移温度（Ｔｇ）の変化レベルを低下できることを示している。使用量が１．５％の場合、ＰＵフィルムに強い劣化防止効果があるだけでなく、材料に高い機械的特性と機械的特性の保持率を維持させることができる。該調製法では、ナノ材料で紫外線を分散・吸収するため、ポリウレタン中でナノ材料が凝集し安定性が低下し、同時にナノ材料を添加するとポリウレタンフィルムの機械的特性が低下してしまう。 In Non-Patent Document 1, MDI-PU is blended and modified using various organic deterioration prevention aids and inorganic nanozinc oxide, and color difference, mechanical property test, photoweight loss test, and attenuated total reflection Fourier transform red. After evaluating its UV deterioration prevention ability by artificial accelerated deterioration test using tests such as external spectroscopy (ATR-FT-IR) and thermal analysis (DSC) and characteristic evaluation methods, the best modification scheme is obtained. .. MDI- using 5 types of anti-deterioration aids (UV-531, UV-P, HS-770, HS-944, Irganox1010) in 3 categories (UV absorbers, light stabilizers, antioxidants) PU was compounded and modified. As a result, when the deterioration inhibitor HS-770 + UV-P is used in combination, the photodecomposition reaction and the cross-linking reaction of MDI-PU can be effectively suppressed, and the color stability of the material and the retention rate of mechanical properties are improved. It is shown that the photolysis products can be reduced and the change level of the glass transition temperature (Tg) can be lowered. When the amount used is 1.5%, not only the PU film has a strong anti-deterioration effect, but also the material can maintain high mechanical properties and retention rate of mechanical properties. In this preparation method, since the nanomaterial disperses and absorbs ultraviolet rays, the nanomaterial aggregates in the polyurethane and the stability is lowered, and at the same time, when the nanomaterial is added, the mechanical properties of the polyurethane film are deteriorated.
非特許文献２では、まずポリテトラメチレンエーテルグリコール（ＰＴＭＧ、分子量１０００）、イソホロンジイソシアネート（ＩＰＤＩ）、ジメチロールプロピオン酸（ＤＭＰＡ）を主原料として、２−［（２−アミノエチル）アミノ］エタンスルホン酸ナトリウム（Ａ９５）およびヒドラジン一水和物を後期鎖延長剤として使用して、水性ポリウレタン防眩性樹脂を調製し、ＷＰＵ防眩性樹脂のプレポリマーの合成工程に対するＷＰＵ調製の反応温度と時間の影響を検討し、プレ重合反応は、まず６０℃で１時間、次に８０℃で２時間反応させた後、５０℃で１５分中和し、最後に３５℃以下で３０分乳化することを決定した。ＦＴＩＲはＷＰＵプレポリマーとフィルムの構造を分析し、ＴＧは一連のフィルムの耐熱性を特性評価し、ＳＥＭ特性評価はコーティングの表面にナノスケールのミクロスフェアが形成されていることを証明した。このミクロスフェア構造により、コーティングは低い光沢度と高い光透過性能の特徴を兼ね備え、またＷＰＵの防眩性と耐水性に対するＤＭＰＡとＡ９５の使用量の影響も研究した。その結果、ＤＭＰＡの使用量が２．６〜３．０％、Ａ９５の使用量が４８〜５８％の範囲の場合、コーティングは防眩の要件を満たしているが、吸水率は６０％に達し、耐水性が劣っていることを示している。次に、「コアシェル型」アクリル酸エステル改質の水性ポリウレタン防眩性樹脂を研究した。ＦＴＩＲ分析は、ＷＰＵＡエマルションの調製に首尾よく成功したことを示し、ＴＥＭは、コアポリウレタンのシェルとしてアクリル酸エステルを使用した「コアシェル型」ミクロスフェア構造が形成されたことを証明した。単一因子分析法を用いて、フィルムの表面形態および防眩性に対するＲ値、ＤＭＰＡ使用量、ＨＥＡ／ＮＣＯおよびＭＭＡ使用量の影響を検討した。ＩＰＤＩの使用は、優れた耐黄変性を有し、コアシェル型アクリル酸エステル樹脂による改質工程が複雑で、イソシアナートの中で最も黄変するＭＤＩはこの方法では研究されていなかった。また、アクリル酸エステル樹脂の調製は複雑で製造コストも高いため、この技術を最適化する必要がある。 In Non-Patent Document 2, first, polytetramethylene ether glycol (PTMG, molecular weight 1000), isophorone diisocyanate (IPDI), and dimethylol propionic acid (DMPA) are used as main raw materials, and 2-[(2-aminoethyl) amino] ethanesulfone is used. Using sodium acid (A95) and hydrazine monohydrate as late chain extenders to prepare an aqueous polyurethane antiglare resin, the reaction temperature and time of WPU preparation to the prepolymer synthesis step of the WPU antiglare resin. The prepolymerization reaction is carried out by first reacting at 60 ° C. for 1 hour, then at 80 ° C. for 2 hours, then neutralizing at 50 ° C. for 15 minutes, and finally emulsifying at 35 ° C. or lower for 30 minutes. It was determined. FTIR analyzed the structure of WPU prepolymers and films, TG characterized the heat resistance of a series of films, and SEM characterization proved that nanoscale microspheres were formed on the surface of the coating. Due to this microsphere structure, the coating combines the characteristics of low gloss and high light transmission performance, and the effect of the amount of DMPA and A95 used on the antiglare and water resistance of WPU was also studied. As a result, when the amount of DMPA used is in the range of 2.6 to 3.0% and the amount of A95 used is in the range of 48 to 58%, the coating meets the antiglare requirement, but the water absorption rate reaches 60%. , Indicates that the water resistance is inferior. Next, we studied "core-shell type" acrylic acid ester-modified water-based polyurethane antiglare resins. FTIR analysis showed successful preparation of the WPUA emulsion, and TEM demonstrated that a "core-shell" microsphere structure was formed using acrylic ester as the shell of the core polyurethane. The effects of R-value, DMPA usage, HEA / NCO and MMA usage on the surface morphology and antiglare of the film were investigated using a single factor analysis method. The use of IPDI has excellent yellowing resistance, the modification process with core-shell acrylic ester resin is complicated, and the most yellowing MDI among isocyanates has not been studied by this method. In addition, the preparation of acrylic ester resin is complicated and the manufacturing cost is high, so it is necessary to optimize this technique.
したがって、本発明は、調製された水性ポリウレタンコーティング剤および接着剤が、より良好な安定性、耐光性、機械的特性および難燃性を有するカーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製方法を提供することを、技術的課題とするものである。 Therefore, in the present invention, the prepared water-based polyurethane coating agent and adhesive have better stability, light resistance, mechanical properties and flame retardancy, and the carbon nanotube-modified light-resistant water-resistant polyurethane coating agent and adhesive. It is a technical subject to provide a method for preparing the above.
本発明では、上記の目的を達成するために、次の技術的手段を採用する。
カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製方法であって、以下の工程（１）〜（３）を含むことを特徴とする。
（１）室温で質量比が１：（２〜５）：（１〜３）：（１．０〜１．３）のカップリング剤、脱イオン水、タンニン酸、窒化ホウ素ナノシートを混合し、３０〜４０分間加水分解して、加水分解物Ａを得る。得られた加水分解物Ａを８０〜９０℃の高速ミキサーに加え、３０〜４０分間混合を継続し、冷却して取り出し、真空乾燥して、改質用熱伝導性フィラーを得る改質用熱伝導性フィラーの調製工程。
（２）ポリマーポリオールと改質用熱伝導性フィラーを質量比（２〜３）：１で最初に超音波により１〜２．５時間分散させ、次に１００〜１１０℃で１〜２時間、減圧下で脱水して、成分Ａを得る成分Ａの調製工程。
（３）５０〜７０℃で成分Ａ、イソシアナート、ジブチルスズジラウレートを質量比（２．５〜３．０）：１：０．０２で６０〜８０ｒ／ｍｉｎの回転数で６０〜９０分間反応させ、次に７５〜８５℃に昇温し１〜３時間反応を継続し、０．１〜０．４倍の改質剤、０．２５〜０．３４倍のポリオール系鎖延長剤、０．０２〜０．０５倍のフィラーポリマー鎖および１．２倍の水を加え、８０〜９０℃で１〜２時間反応を継続し、さらに０．０１倍のメタクリル酸メチル、０．００５倍の過硫酸アンモニウムおよび０．１倍の水を加え、７０〜８０℃で１〜２時間反応させ、さらに０．０１倍のグリオキシムおよび０．００５倍の３，４，５−トリメトキシ安息香酸を加え、７０〜８０℃で１〜２時間反応させ、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤を得るカーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製工程。
加えられた改質剤、ポリオール系鎖延長剤、水、メタクリル酸メチル、過硫酸アンモニウム、フィラーポリマー鎖の倍数は、いずれもイソシアナートの質量を基準とし、加えられたグリオキシムおよび３，４，５−トリメトキシ安息香酸の倍数はいずれもメタクリル酸メチルの質量を基準とする。
In the present invention, the following technical means are adopted in order to achieve the above object.
A method for preparing a light-resistant aqueous polyurethane coating agent and an adhesive for modifying carbon nanotubes, which comprises the following steps (1) to (3).
(1) A coupling agent having a mass ratio of 1: (2 to 5): (1 to 3): (1.0 to 1.3) at room temperature, deionized water, tannic acid, and a boron nitride nanosheet are mixed. Hydrolyze for 30-40 minutes to give hydrolyzed product A. The obtained hydrolyzate A is added to a high-speed mixer at 80 to 90 ° C., mixing is continued for 30 to 40 minutes, cooled and taken out, and vacuum dried to obtain a heat conductive filler for reforming. The process of preparing the conductive filler.
(2) The polymer polyol and the thermally conductive filler for modification were first dispersed by ultrasonic waves at a mass ratio (2 to 3): 1 for 1 to 2.5 hours, and then at 100 to 110 ° C. for 1 to 2 hours. A step of preparing component A, which is dehydrated under reduced pressure to obtain component A.
(3) Ingredient A, isocyanate, and dibutyltin dilaurate are reacted at 50 to 70 ° C. at a mass ratio (2.5 to 3.0): 1: 0.02 at a rotation speed of 60 to 80 r / min for 60 to 90 minutes. Then, the temperature was raised to 75 to 85 ° C., and the reaction was continued for 1 to 3 hours. 02 to 0.05 times the filler polymer chain and 1.2 times the water were added, the reaction was continued at 80 to 90 ° C. for 1 to 2 hours, and 0.01 times the methyl methacrylate and 0.005 times the excess. Add ammonium sulfate and 0.1 times water and react at 70-80 ° C. for 1-2 hours, then add 0.01 times glyoxime and 0.005 times 3,4,5-trimethoxybenzoic acid, 70- A step of preparing a carbon nanotube-modified light-resistant aqueous polyurethane coating and an adhesive by reacting at 80 ° C. for 1 to 2 hours to obtain a carbon nanotube-modified light-resistant aqueous polyurethane coating and an adhesive.
The added modifier, polyol chain extender, water, methyl methacrylate, ammonium persulfate, and multiples of the filler polymer chain are all based on the mass of isocyanate, and the added glyoxime and 3,4,5- All multiples of trimethoxybenzoic acid are based on the mass of methyl methacrylate.
前記改質剤の調製方法として、０．１ｇのヒドロキシ化したカーボンナノチューブ、２５〜３５ｇのポリビニルアルコール、４ｇ〜２２ｇのカテキンを７０〜８０ｇの水に加え、６０〜７０℃で１〜２時間撹拌して反応させ、次に５ｇのアセトンを加え、４０〜５０℃で１〜２時間撹拌して反応させ、噴霧乾燥させることで、改質剤を得る。 As a method for preparing the modifier, 0.1 g of hydroxylated carbon nanotubes, 25 to 35 g of polyvinyl alcohol, 4 g to 22 g of catechin are added to 70 to 80 g of water, and the mixture is stirred at 60 to 70 ° C. for 1 to 2 hours. Then, 5 g of acetone is added, and the mixture is stirred and reacted at 40 to 50 ° C. for 1 to 2 hours, and spray-dried to obtain a modifier.
前記ヒドロキシ化したカーボンナノチューブの調製方法は、以下のとおりである。
１．１〜１．５ｇのカーボンナノチューブと３２０〜３５０ｍＬの混酸（濃硫酸と濃硝酸の体積比は３：１）を５００ｍＬフラスコに取り、反応温度は７５〜９５℃で、超音波出力２００Ｗ、超音波周波数４０ＫＨｚの超音波洗浄器内で２〜５時間凝縮・還流する。その後、ビーカーに移し、２５０ｇの脱イオン水で希釈し、直径０．２μｍの微孔性膜で吸引ろ過し、中性になるまで脱イオン水で繰り返し洗浄する。吸引ろ過後のカーボンナノチューブを１０５℃で乾燥させ、粉末状に粉砕してヒドロキシ化したカーボンナノチューブを得る。前記カーボンナノチューブは、化学蒸着法によって生成された直径２ｎｍ、チューブの長さ１００μｍ、純度９９．５ｗｔ％、アモルファスカーボン不純物＜５％、アッシュ不純物＜３ｗｔ％、比表面積７００ｍ２／ｇの単層カーボンナノチューブである。
The method for preparing the hydroxylated carbon nanotubes is as follows.
1.1 to 1.5 g of carbon nanotubes and 320 to 350 mL of mixed acid (volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3: 1) are placed in a 500 mL flask, the reaction temperature is 75 to 95 ° C., and the ultrasonic output is 200 W. Condensate and reflux for 2 to 5 hours in an ultrasonic cleaner with an ultrasonic frequency of 40 KHz. Then, the mixture is transferred to a beaker, diluted with 250 g of deionized water, suction-filtered with a microporous membrane having a diameter of 0.2 μm, and repeatedly washed with deionized water until neutral. The carbon nanotubes after suction filtration are dried at 105 ° C. and pulverized into powder to obtain hydroxylated carbon nanotubes. The carbon nanotubes are single-walled carbon produced by a chemical vapor deposition method, having a diameter of 2 nm, a tube length of 100 μm, a purity of 99.5 wt%, an amorphous carbon impurity <5%, an ash impurity <3 wt%, and a specific surface area of 700 m 2 / g. It is an nanotube.
前記フィラーポリマー鎖の調製は、以下の工程（１）〜（４）を含む：
（１）９〜１２ｇのナノシリコンカーバイドを１０５℃で真空乾燥させ、ナノシリコンカーバイドを３０ｇのＮ、Ｎ−ジメチルホルムアミドに分散させ、３０〜５０℃で１０〜３０分間超音波分散させて溶液Ａを得る工程、
（２）１２〜２２ｇのジフェニルメタンジイソシアネートと１２〜２２ｇのポリ乳酸を４２ｇのＮ、Ｎ−ジメチルホルムアミドに溶解して、溶液Ｂを得る工程、
（３）ナノシルバーと１，５−ナフタレンジスルホン酸を１：２０：５０−６０の比率で５０〜６０℃で１〜２時間撹拌して溶液Ｃを得る工程（前記ナノシルバーの重量はナノシリコンカーバイド重量の１／１００）、
（４）溶液Ｂを溶液Ａに滴下し、次に溶液Ｃを溶液Ａに加え、５０〜７０℃で２〜３時間撹拌して反応させ、フィラーポリマー鎖を得る工程。
The preparation of the filler polymer chain includes the following steps (1) to (4):
(1) 9 to 12 g of nanosilicon carbide is vacuum dried at 105 ° C., nanosilicon carbide is dispersed in 30 g of N, N-dimethylformamide, and ultrasonically dispersed at 30 to 50 ° C. for 10 to 30 minutes to solve solution A. The process of getting
(2) A step of dissolving 12 to 22 g of diphenylmethane diisocyanate and 12 to 22 g of polylactic acid in 42 g of N, N-dimethylformamide to obtain a solution B.
(3) A step of stirring nanosilver and 1,5-naphthalenedisulfonic acid at a ratio of 1:20:50-60 at 50-60 ° C. for 1 to 2 hours to obtain a solution C (the weight of the nanosilver is nanosilicon). 1/100 of the carbide weight),
(4) A step of dropping solution B into solution A, then adding solution C to solution A, and stirring and reacting at 50 to 70 ° C. for 2 to 3 hours to obtain a filler polymer chain.
前記カップリング剤は、３−アミノプロピルトリエトキシシランとモノアルコキシチタネートカップリング剤の１種または２種である。 The coupling agent is one or two of 3-aminopropyltriethoxysilane and a monoalkoxy titanate coupling agent.
前記ポリマーポリオールは、ポリテトラメチレンエーテルグリコール、ポリカーボネートジオールのいずれかである。 The polymer polyol is either polytetramethylene ether glycol or polycarbonate diol.
前記ポリオール系鎖延長剤は、ジヒドロキシメチル酪酸、ジメチロールプロピオン酸のいずれかである。 The polyol chain extender is either dihydroxymethylbutyric acid or dimethylolpropionic acid.
前記イソシアナートは、ＭＤＩ型イソシアナートである。 The isocyanate is an MDI type isocyanate.
従来技術と比較して、本発明は以下の有利な効果を有する。
（１）本発明は、ポリマーポリオールおよびイソシアナートを使用して重合反応を起こしてポリウレタンを生成し、その後、ポリビニルアルコールおよびカテキンによってポリウレタンを改質する。カテキンの表面のフェノール性ヒドロキシ基とポリビニルアルコール主鎖中のヒドロキシ基が水素結合を形成することで、最初の物理的架橋ネットワークを形成し、ポリビニルアルコールセグメントのヒドロキシ基は水素結合の作用により微結晶領域を形成し、２番目の物理的架橋ネットワークを形成する。カテキンとポリビニルアルコールとの間の架橋ネットワークとポリウレタンは同時に互いに絡み合って３番目の物理的架橋ネットワークを形成する。これに基づいて調製されたポリウレタンコーティング剤と感圧接着剤は、より優れた安定性およびより高い引張強度、靭性、耐引裂性を有し、同時にヒドロキシ化したカーボンナノ、ポリビニルアルコール、カテキンが水素結合を形成し、ポリウレタンの機械的特性と難燃性を向上させる。
Compared with the prior art, the present invention has the following advantageous effects.
(1) In the present invention, a polymerization reaction is carried out using a polymer polyol and an isocyanate to produce a polyurethane, and then the polyurethane is modified with polyvinyl alcohol and catechin. The phenolic hydroxy group on the surface of the catechin and the hydroxy group in the polyvinyl alcohol main chain form a hydrogen bond to form the first physical cross-linking network, and the hydroxy group of the polyvinyl alcohol segment is microcrystallized by the action of the hydrogen bond. It forms a region and forms a second physical bridging network. The cross-linked network between catechin and polyvinyl alcohol and polyurethane are simultaneously intertwined with each other to form a third physical cross-linked network. Polyurethane coatings and pressure-sensitive adhesives prepared on this basis have better stability and higher tensile strength, toughness and tear resistance, while at the same time hydroxyated carbon nano, polyvinyl alcohol and catechins are hydrogen. It forms a bond and improves the mechanical properties and flame retardancy of polyurethane.
（２）本発明のフィラーポリマー鎖は、ジフェニルメタンジイソシアネートおよびナノシリコン窒化物で調製される。ジフェニルメタンジイソシアネートを高い熱伝導性を有するナノシリコン窒化物で充填することにより、すなわち、可撓性構造を有するジフェニルメタンジイソシアネートでナノシリコンカーバイドを直列に接続することにより、ジフェニルメタンジイソシアネートの熱伝導性が向上するだけでなく、含有量が少ないシリコンカーバイドをジフェニルメタンジイソシアネート中に充填し、連続的な熱伝導経路を形成する。フィラーポリマー鎖の導入は、熱伝導性を効果的に改善し、熱伝導性フィラーの添加量を減らすだけでなく、その機械的特性をよりよく保持することもできる。ポリ乳酸はフィラーの通気性を高めることで、ポリウレタン表面の通気性を高め、ポリウレタン表面の細孔からの熱放散を容易にし、ポリウレタンが光を吸収した後の色の変化を減らす。ナノシルバーは1,5-ナフタレンジスルホン酸の改質下でガスを放出して完全燃焼させることができ、煙の濃度を低下できる。 (2) The filler polymer chain of the present invention is prepared with diphenylmethane diisocyanate and nanosilicon nitride. By filling diphenylmethane diisocyanate with nanosilicon nitride having high thermal conductivity, that is, by connecting nanosilicon carbides in series with diphenylmethane diisocyanate having a flexible structure, the thermal conductivity of diphenylmethane diisocyanate is improved. Not only that, silicon carbide with a low content is filled in diphenylmethane diisocyanate to form a continuous heat conduction path. The introduction of the filler polymer chain can not only effectively improve the thermal conductivity and reduce the amount of the thermally conductive filler added, but also better retain its mechanical properties. Polylactic acid increases the breathability of the filler, increasing the breathability of the polyurethane surface, facilitating heat dissipation from the pores of the polyurethane surface, and reducing the color change after the polyurethane absorbs light. Nanosilver can release gas and burn completely under the modification of 1,5-naphthalenedisulfonic acid, and can reduce the concentration of smoke.
（３）本発明は、機械的特性および熱伝導性に優れた炭素ベースの材料を充填することにより、接着剤の熱伝導性を効果的に高める。充填型熱伝導性ポリベース接着剤の熱伝導メカニズムは、以下のとおりである。接着剤内部の熱が熱伝導性フィラー間、熱伝導性フィラーとポリウレタンとの間の相互接触、および熱伝導性フィラーとポリウレタンとの間の相互作用によって実現される。熱伝導性が悪いポリウレタンマトリックスに熱伝導性フィラーを充填した後、互いに接触する熱伝導性フィラーおよび熱伝導性フィラーとポリウレタンマトリックスとの間の相互作用により、接着剤の内部に熱伝導ネットワーク構造が形成される。これは熱伝導ネットワークチェーンと呼ばれる。熱は熱伝導ネットワークチェーンから効果的に伝達される。 (3) The present invention effectively enhances the thermal conductivity of an adhesive by filling it with a carbon-based material having excellent mechanical properties and thermal conductivity. The heat conduction mechanism of the filled heat conductive polybase adhesive is as follows. The heat inside the adhesive is achieved by the interaction between the thermally conductive fillers, between the thermally conductive fillers and the polyurethane, and between the thermally conductive fillers and the polyurethane. After filling a polyurethane matrix with poor thermal conductivity with a thermally conductive filler, the thermally conductive filler that comes into contact with each other and the interaction between the thermally conductive filler and the polyurethane matrix create a thermally conductive network structure inside the adhesive. It is formed. This is called a heat conductive network chain. Heat is effectively transferred from the heat transfer network chain.
（４）熱伝導性フィラー自体は、粒子が小さく、比表面積が大きいため、ポリウレタン充填工程で凝集しやすい。そこで本発明では、カップリング剤を用いて熱伝導性フィラーを処理し、凝集した熱伝導性フィラーにより接着剤の使用特性に影響を与えるのを回避する。同時に、本発明のポリウレタンとカテチンおよびポリビニルアルコールとの間は、複数の物理的架橋ネットワークおよびフィラーポリマー鎖を形成するため、熱伝導性フィラーがネットワーク構造に充填され、熱伝導性フィラーを均一に分布できるだけではなく、ポリウレタンの機械的特性を十分に維持できる。 (4) Since the thermally conductive filler itself has small particles and a large specific surface area, it easily aggregates in the polyurethane filling step. Therefore, in the present invention, the heat conductive filler is treated with a coupling agent to prevent the aggregated heat conductive filler from affecting the usage characteristics of the adhesive. At the same time, in order to form a plurality of physically crosslinked networks and filler polymer chains between the polyurethane of the present invention and catetin and polyvinyl alcohol, the thermally conductive filler is filled in the network structure and the thermally conductive filler is uniformly distributed. Not only is it possible, but the mechanical properties of polyurethane can be sufficiently maintained.
（５）本発明により調製されたポリウレタンコーティング剤および接着剤は、熱伝導性フィラーを用いて太陽の直射日光による熱を分散させ、ポリウレタンの表面粗さを増加させてグレアを低減するが、光散乱効果の増加は常に光透過性を伴い、表面粗さを増加するとポリウレタンフィルムの表面平滑性を低下させるため、メタクリル酸メチルのポリマーを用いてポリウレタンの粗い空隙を埋める。同時に、メタクリル酸ポリメチルフィルムの光透過性はポリウレタンの乱反射に影響を与えず、グリオキシムと３，４，５−トリメトキシ安息香酸を用いてポリウレタンの粗い空隙へのポリメチルメタクリレートの充填を促進する。 (5) The polyurethane coating agent and adhesive prepared according to the present invention use a heat conductive filler to disperse heat from the direct sunlight of the sun, increase the surface roughness of polyurethane and reduce glare, but light. Since an increase in the scattering effect is always accompanied by light transmission and an increase in surface roughness reduces the surface smoothness of the polyurethane film, a polymer of methyl methacrylate is used to fill the coarse voids of the polyurethane. At the same time, the light transmittance of the polymethyl methacrylate film does not affect the diffuse reflection of the polyurethane, and glycim and 3,4,5-trimethoxybenzoic acid are used to promote the filling of the coarse voids of the polyurethane with polymethyl methacrylate.
以下、実施例を挙げて、本発明をより具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
（１）改質用熱伝導性フィラーの調製：室温で質量比が１：２：１：１の３−アミノプロピルトリエトキシシラン、脱イオン水、タンニン酸、窒化ホウ素ナノシートを混合し、３０分間加水分解して、加水分解物Ａを得た。得られた加水分解物Ａを８０℃の高速ミキサーに加え、３０分間混合を継続し、冷却して取り出し、真空乾燥して、改質用熱伝導性フィラーを得た。
（２）成分Ａの調製：ポリテトラメチレンエーテルグリコールと改質用熱伝導性フィラーを質量比２：１で最初に超音波により１時間分散させ、次に１００℃で１時間、減圧下で脱水して、成分Ａを得た。
（３）カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製：５０℃で成分Ａ、ＭＤＩ型イソシアナート、ジブチルスズジラウレートを質量比２．５：１：０．０２で６０ｒ／ｍｉｎの回転数で６０分間反応させ、次に７５℃に昇温し１時間反応を継続し、０．１倍の改質剤、０．２５倍のジヒドロキシメチル酪酸、０．０２倍のフィラーポリマー鎖および１．２倍の水を加え、８０℃で１時間反応を継続し、さらに０．０１倍のメタクリル酸メチル、０．００５倍の過硫酸アンモニウムおよび０．１倍の水を加え、７０℃で１時間反応させ、さらに０．０１倍のグリオキシムおよび０．００５倍の３，４，５−トリメトキシ安息香酸を加え、７０℃で１時間反応させ、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤を得た。前記メタクリル酸メチル、改質剤、ジメチル酪酸剤ポリオール系鎖延長剤（以下同じ）、過硫酸アンモニウム、フィラーポリマー鎖、水の倍数は、イソシアナートの質量を基準とし、グリオキシムおよび３，４，５−トリメトキシ安息香酸の倍数はいずれもメタクリル酸メチルの質量を基準とした。
(1) Preparation of thermally conductive filler for modification: Mix 3-aminopropyltriethoxysilane, deionized water, tannic acid, and boron nitride nanosheet having a mass ratio of 1: 2: 1: 1 at room temperature for 30 minutes. Hydrolysis was performed to obtain hydrolyzate A. The obtained hydrolyzate A was added to a high-speed mixer at 80 ° C., mixing was continued for 30 minutes, cooled and taken out, and vacuum dried to obtain a thermally conductive filler for modification.
(2) Preparation of component A: Polytetramethylene ether glycol and a heat conductive filler for modification are first dispersed by ultrasonic waves at a mass ratio of 2: 1 for 1 hour, and then dehydrated at 100 ° C. for 1 hour under reduced pressure. Then, the component A was obtained.
(3) Preparation of light-resistant aqueous polyurethane coating agent and adhesive for modifying carbon nanotubes: Component A, MDI-type isocyanate, and dibutyltin dilaurate at 50 ° C. at a mass ratio of 2.5: 1: 0.02 at 60 r / min. The reaction was carried out at rotation speed for 60 minutes, then the temperature was raised to 75 ° C. and the reaction was continued for 1 hour, with 0.1 times the modifier, 0.25 times the dihydroxymethylbutyric acid, 0.02 times the filler polymer chain and Add 1.2 times water and continue the reaction at 80 ° C. for 1 hour, then add 0.01 times methyl methacrylate, 0.005 times ammonium persulfate and 0.1 times water and 1 at 70 ° C. After time reaction, 0.01 times more glyoxime and 0.005 times 3,4,5-trimethoxybenzoic acid were added, and the mixture was reacted at 70 ° C. for 1 hour to modify a carbon nanotube-modified light-resistant aqueous polyurethane coating agent and adhere. I got the agent. The methyl methacrylate, modifier, dimethylbutyric acid polyol-based chain extender (same below), ammonium persulfate, filler polymer chain, and multiples of water are based on the mass of isocyanate, and glyoxime and 3,4,5- All multiples of trimethoxybenzoic acid were based on the mass of methyl methacrylate.
前記改質剤の調製方法として、０．１ｇのヒドロキシ化したカーボンナノチューブ、２５ｇのポリビニルアルコール、４ｇのカテキンを７０ｇの水に加え、６０℃で１時間撹拌して反応させ、次に５ｇのアセトンを加え、４０℃で１時間撹拌して反応させ、噴霧乾燥させることで、改質剤を得た。 As a method for preparing the modifier, 0.1 g of hydroxylated carbon nanotubes, 25 g of polyvinyl alcohol, and 4 g of catechin are added to 70 g of water, and the mixture is stirred and reacted at 60 ° C. for 1 hour, and then 5 g of acetone. Was added, and the mixture was stirred at 40 ° C. for 1 hour to react and spray-dried to obtain a modifier.
前記ヒドロキシ化したカーボンナノチューブの調製方法は、以下のとおりである。
１．１ｇのカーボンナノチューブと３２０ｍＬの混酸（濃硫酸と濃硝酸の体積比は３：１）を５００ｍＬフラスコに取り、反応温度は７５℃で、超音波出力２００Ｗ、超音波周波数４０ＫＨｚの超音波洗浄器内で２時間凝縮・還流した。その後、ビーカーに移し、２５０ｇの脱イオン水で希釈し、直径０．２μｍの微孔性膜で吸引ろ過し、中性になるまで脱イオン水で繰り返し洗浄した。吸引ろ過後のカーボンナノチューブを１０５℃で乾燥させ、粉末状に粉砕してヒドロキシ化したカーボンナノチューブを得た。前記カーボンナノチューブは、化学蒸着法によって生成された直径２ｎｍ、チューブの長さ１００μｍ、純度９９．５ｗｔ％、アモルファスカーボン不純物＜５％、アッシュ不純物＜３ｗｔ％、比表面積７００ｍ２／ｇの単層カーボンナノチューブであった。
The method for preparing the hydroxylated carbon nanotubes is as follows.
Take 1.1 g of carbon nanotubes and 320 mL of mixed acid (volume ratio of concentrated sulfuric acid and concentrated nitric acid is 3: 1) in a 500 mL flask, and ultrasonically clean at a reaction temperature of 75 ° C., ultrasonic output of 200 W, and ultrasonic frequency of 40 KHz. Condensed and refluxed in the vessel for 2 hours. Then, it was transferred to a beaker, diluted with 250 g of deionized water, suction-filtered with a microporous membrane having a diameter of 0.2 μm, and repeatedly washed with deionized water until neutral. The carbon nanotubes after suction filtration were dried at 105 ° C. and pulverized into powder to obtain hydroxylated carbon nanotubes. The carbon nanotubes are single-walled carbon produced by a chemical vapor deposition method, having a diameter of 2 nm, a tube length of 100 μm, a purity of 99.5 wt%, an amorphous carbon impurity <5%, an ash impurity <3 wt%, and a specific surface area of 700 m 2 / g. It was an nanotube.
前記フィラーポリマー鎖の調製は、以下の工程（１）〜（４）を含む：
（１）９ｇのナノシリコンカーバイドを１０５℃で真空乾燥させ、ナノシリコンカーバイドを３０ｇのＮ、Ｎ−ジメチルホルムアミドに分散させ、３０℃で１０分間超音波分散させて溶液Ａを得る工程、
（２）１２ｇのジフェニルメタンジイソシアネートと１２ｇのポリ乳酸を４２ｇのＮ、Ｎ−ジメチルホルムアミドに溶解して、溶液Ｂを得る工程、
（３）ナノシルバーと１，５−ナフタレンジスルホン酸を１：２０：５０の比率で５０℃で１時間撹拌して溶液Ｃを得る工程（前記ナノシルバーの重量はナノシリコンカーバイド重量の１／１００）、
（４）溶液Ｂを溶液Ａに滴下し、次に溶液Ｃを溶液Ａに加え、５０℃で２時間撹拌して反応させ、フィラーポリマー鎖を得る工程。
The preparation of the filler polymer chain includes the following steps (1) to (4):
(1) A step of vacuum-drying 9 g of nanosilicon carbide at 105 ° C., dispersing the nanosilicon carbide in 30 g of N, N-dimethylformamide, and ultrasonically dispersing the nanosilicon carbide at 30 ° C. for 10 minutes to obtain a solution A.
(2) A step of dissolving 12 g of diphenylmethane diisocyanate and 12 g of polylactic acid in 42 g of N, N-dimethylformamide to obtain a solution B.
(3) A step of stirring nanosilver and 1,5-naphthalenedisulfonic acid at a ratio of 1:20:50 at 50 ° C. for 1 hour to obtain a solution C (the weight of the nanosilver is 1/100 of the weight of the nanosilicon carbide. ),
(4) A step of dropping solution B into solution A, then adding solution C to solution A, and stirring and reacting at 50 ° C. for 2 hours to obtain a filler polymer chain.
（１）改質用熱伝導性フィラーの調製：室温で質量比が１：５：３：１．３のモノアルコキシチタネートカップリング剤（モノアルコキシ脂肪酸チタン酸エステルカップリング剤、南京全希化工有限会社製）、脱イオン水、タンニン酸、窒化ホウ素ナノシートを混合し、４０分間加水分解して、加水分解物Ａを得た。得られた加水分解物Ａを９０℃の高速ミキサーに加え、４０分間混合を継続し、冷却して取り出し、真空乾燥して、改質用熱伝導性フィラーを得た。
（２）成分Ａの調製：ポリカーボネートジオールと改質用熱伝導性フィラーを質量比３：１で最初に超音波により２．５時間分散させ、次に１１０℃で２時間、減圧下で脱水して、成分Ａを得た。
（３）カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製：７０℃で成分Ａ、ＭＤＩ型イソシアナート、ジブチルスズジラウレートを質量比３．０：１：０．０２で８０ｒ／ｍｉｎの回転数で９０分間反応させ、次に８５℃に昇温し３時間反応を継続し、０．４倍の改質剤、０．３４倍のジメチロールプロピオン酸、０．０５倍のフィラーポリマー鎖および１．２倍の水を加え、９０℃で２時間反応を継続し、さらに０．０１倍のメタクリル酸メチル、０．００５倍の過硫酸アンモニウムおよび０．１倍の水を加え、８０℃で２時間反応させ、さらに０．０１倍のグリオキシムおよび０．００５倍の３，４，５−トリメトキシ安息香酸を加え、８０℃で２時間反応させ、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤を得た。前記メタクリル酸メチル、改質剤、ポリオール系鎖延長剤、過硫酸アンモニウム、フィラーポリマー鎖、水の倍数は、イソシアナートの質量を基準とし、グリオキシムおよび３，４，５−トリメトキシ安息香酸の倍数はいずれもメタクリル酸メチルの質量を基準とした。
(1) Preparation of thermally conductive filler for modification: Monoalkoxy titanate coupling agent having a mass ratio of 1: 5: 3: 1.3 at room temperature (monoalkoxy fatty acid titanate ester coupling agent, Nanjing Zenkaku Kogyo Co., Ltd.) (Manufactured by the company), deionized water, tannic acid, and boron nitride nanosheet were mixed and hydrolyzed for 40 minutes to obtain a hydrolyzate A. The obtained hydrolyzate A was added to a high-speed mixer at 90 ° C., mixing was continued for 40 minutes, cooled and taken out, and vacuum dried to obtain a thermally conductive filler for modification.
(2) Preparation of component A: Polycarbonate diol and thermally conductive filler for modification were first dispersed by ultrasonic waves at a mass ratio of 3: 1 for 2.5 hours, and then dehydrated at 110 ° C. for 2 hours under reduced pressure. To obtain component A.
(3) Preparation of light-resistant aqueous polyurethane coating agent and adhesive for modifying carbon nanotubes: Component A, MDI-type isocyanate, and dibutyltin dilaurate at 70 ° C. at a mass ratio of 3.0: 1: 0.02 at 80 r / min. The reaction was carried out at a rotation speed of 90 minutes, then the temperature was raised to 85 ° C. and the reaction was continued for 3 hours. And 1.2 times water was added and the reaction was continued at 90 ° C. for 2 hours, and 0.01 times methyl methacrylate, 0.005 times ammonium persulfate and 0.1 times water were further added and at 80 ° C. After reacting for 2 hours, 0.01 times more glyoxime and 0.005 times 3,4,5-trimethoxybenzoic acid were added, and the mixture was reacted at 80 ° C. for 2 hours to modify a carbon nanotube-modified light-resistant aqueous polyurethane coating agent. I got the adhesive. The multiples of methyl methacrylate, modifier, polyol chain extender, ammonium persulfate, filler polymer chain, and water are based on the mass of isocyanate, and any multiple of glyoxime and 3,4,5-trimethoxybenzoic acid. Was also based on the mass of methyl methacrylate.
前記改質剤の調製方法として、０．１ｇのヒドロキシ化したカーボンナノチューブ、３５ｇのポリビニルアルコール、２２ｇのカテキンを８０ｇの水に加え、７０℃で2時間撹拌して反応させ、次に５ｇのアセトンを加え、５０℃で２時間撹拌して反応させ、噴霧乾燥させることで、改質剤を得た。 As a method for preparing the modifier, 0.1 g of hydroxylated carbon nanotubes, 35 g of polyvinyl alcohol, and 22 g of catechin are added to 80 g of water, and the mixture is stirred at 70 ° C. for 2 hours to react, and then 5 g of acetone. Was added, and the mixture was stirred at 50 ° C. for 2 hours to react and spray-dried to obtain a modifier.
前記ヒドロキシ化したカーボンナノチューブの調製方法は、以下のとおりである。
１．５ｇのカーボンナノチューブと３５０ｍＬの混酸（濃硫酸と濃硝酸の体積比は３：１）を５００ｍＬフラスコに取り、反応温度は９５℃で、超音波出力２００Ｗ、超音波周波数４０ＫＨｚの超音波洗浄器内で５時間凝縮・還流した。その後、ビーカーに移し、２５０ｇの脱イオン水で希釈し、直径０．２μｍの微孔性膜で吸引ろ過し、中性になるまで脱イオン水で繰り返し洗浄した。吸引ろ過後のカーボンナノチューブを１０５℃で乾燥させ、粉末状に粉砕してヒドロキシ化したカーボンナノチューブを得た。前記カーボンナノチューブは、化学蒸着法によって生成された直径２ｎｍ、チューブの長さ１００μｍ、純度９９．５ｗｔ％、アモルファスカーボン不純物＜５％、アッシュ不純物＜３ｗｔ％、比表面積７００ｍ２／ｇの単層カーボンナノチューブであった。
The method for preparing the hydroxylated carbon nanotubes is as follows.
Take 1.5 g of carbon nanotubes and 350 mL of mixed acid (volume ratio of concentrated sulfuric acid and concentrated nitric acid is 3: 1) in a 500 mL flask, and ultrasonically clean at a reaction temperature of 95 ° C., ultrasonic output of 200 W, and ultrasonic frequency of 40 KHz. Condensed and refluxed in the vessel for 5 hours. Then, it was transferred to a beaker, diluted with 250 g of deionized water, suction-filtered with a microporous membrane having a diameter of 0.2 μm, and repeatedly washed with deionized water until neutral. The carbon nanotubes after suction filtration were dried at 105 ° C. and pulverized into powder to obtain hydroxylated carbon nanotubes. The carbon nanotubes are single-walled carbon produced by a chemical vapor deposition method, having a diameter of 2 nm, a tube length of 100 μm, a purity of 99.5 wt%, an amorphous carbon impurity <5%, an ash impurity <3 wt%, and a specific surface area of 700 m 2 / g. It was an nanotube.
前記フィラーポリマー鎖の調製は、以下の工程（１）〜（４）を含む：
（１）１２ｇのナノシリコンカーバイドを１０５℃で真空乾燥させ、ナノシリコンカーバイドを３０ｇのＮ、Ｎ−ジメチルホルムアミドに分散させ、５０℃で３０分間超音波分散させて溶液Ａを得る工程、
（２）２２ｇのジフェニルメタンジイソシアネートと２２ｇのポリ乳酸を４２ｇのＮ、Ｎ−ジメチルホルムアミドに溶解して、溶液Ｂを得る工程、
（３）ナノシルバーと１，５−ナフタレンジスルホン酸を１：２０：６０の比率で６０℃で２時間撹拌して溶液Ｃを得る工程（前記ナノシルバーの重量はナノシリコンカーバイド重量の１／１００）、
（４）溶液Ｂを溶液Ａに滴下し、次に溶液Ｃを溶液Ａに加え、７０℃で３時間撹拌して反応させ、フィラーポリマー鎖を得る工程。
The preparation of the filler polymer chain includes the following steps (1) to (4):
(1) A step of vacuum-drying 12 g of nanosilicon carbide at 105 ° C., dispersing the nanosilicon carbide in 30 g of N, N-dimethylformamide, and ultrasonically dispersing the nanosilicon carbide at 50 ° C. for 30 minutes to obtain a solution A.
(2) A step of dissolving 22 g of diphenylmethane diisocyanate and 22 g of polylactic acid in 42 g of N, N-dimethylformamide to obtain a solution B.
(3) A step of stirring nanosilver and 1,5-naphthalenedisulfonic acid at a ratio of 1:20:60 at 60 ° C. for 2 hours to obtain a solution C (the weight of the nanosilver is 1/100 of the weight of the nanosilicon carbide. ),
(4) A step of dropping solution B into solution A, then adding solution C to solution A, and stirring and reacting at 70 ° C. for 3 hours to obtain a filler polymer chain.
（１）改質用熱伝導性フィラーの調製：室温で質量比が１：３．５：２：１．１５の３−アミノプロピルトリエトキシシラン、脱イオン水、タンニン酸、窒化ホウ素ナノシートを混合し、３５分間加水分解して、加水分解物Ａを得た。得られた加水分解物Ａを８５℃の高速ミキサーに加え、３５分間混合を継続し、冷却して取り出し、真空乾燥して、改質用熱伝導性フィラーを得た。
（２）成分Ａの調製：ポリテトラメチレンエーテルグリコールと改質用熱伝導性フィラーを質量比２．５：１で最初に超音波により１．５時間分散させ、次に１０５℃で１．５時間、減圧下で脱水して、成分Ａを得た。
（３）カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製：６０℃で成分Ａ、ＭＤＩ型イソシアナート、ジブチルスズジラウレートを質量比２．７５：１：０．０２で７０ｒ／ｍｉｎの回転数で７５分間反応させ、次に８０℃に昇温し２時間反応を継続し、０．２５倍の改質剤、０．３倍のジヒドロキシメチル酪酸、０．０３５倍のフィラーポリマー鎖および１．２倍の水を加え、８５℃で１．５時間反応を継続し、さらに０．０１倍のメタクリル酸メチル、０．００５倍の過硫酸アンモニウムおよび０．１倍の水を加え、７５℃で１．５時間反応させ、さらに０．０１倍のグリオキシムおよび０．００５倍の３，４，５−トリメトキシ安息香酸を加え、７５℃で１．５時間反応させ、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤を得た。前記メタクリル酸メチル、改質剤、ポリオール系鎖延長剤、フィラーポリマー鎖、過硫酸アンモニウム、水の倍数は、イソシアナートの質量を基準とし、グリオキシムおよび３，４，５−トリメトキシ安息香酸の倍数はいずれもメタクリル酸メチルの質量を基準とした。
(1) Preparation of thermally conductive filler for modification: 3-aminopropyltriethoxysilane having a mass ratio of 1: 3.5: 2: 1.15 at room temperature, deionized water, tannic acid, and boron nitride nanosheets are mixed. Then, it was hydrolyzed for 35 minutes to obtain hydrolyzate A. The obtained hydrolyzate A was added to a high-speed mixer at 85 ° C., mixing was continued for 35 minutes, cooled and taken out, and vacuum dried to obtain a thermally conductive filler for modification.
(2) Preparation of component A: Polytetramethylene ether glycol and a heat conductive filler for modification are first dispersed by ultrasonic waves at a mass ratio of 2.5: 1 for 1.5 hours, and then 1.5 at 105 ° C. Dehydration under reduced pressure for hours gave component A.
(3) Preparation of light-resistant aqueous polyurethane coating agent and adhesive for modifying carbon nanotubes: Component A, MDI-type isocyanate, and dibutyltin dilaurate at 60 ° C. at a mass ratio of 2.75: 1: 0.02 at 70 r / min. The reaction was carried out at rotation speed for 75 minutes, then the temperature was raised to 80 ° C. and the reaction was continued for 2 hours, with 0.25 times the modifier, 0.3 times the dihydroxymethylbutyric acid, 0.035 times the filler polymer chain and Add 1.2 times water and continue the reaction at 85 ° C. for 1.5 hours, then add 0.01 times methyl methacrylate, 0.005 times ammonium persulfate and 0.1 times water to 75 ° C. For 1.5 hours, 0.01 times more glyoxime and 0.005 times 3,4,5-trimethoxybenzoic acid were added, and the mixture was reacted at 75 ° C. for 1.5 hours to modify the light resistance of carbon nanotubes. Aqueous polyurethane coatings and adhesives were obtained. The multiples of methyl methacrylate, modifier, polyol chain extender, filler polymer chain, ammonium persulfate, and water are based on the mass of isocyanate, and the multiples of glyoxime and 3,4,5-trimethoxybenzoic acid are any. Was also based on the mass of methyl methacrylate.
前記改質剤の調製方法として、０．１ｇのヒドロキシ化したカーボンナノチューブ、３０ｇのポリビニルアルコール、１３ｇのカテキンを７５ｇの水に加え、６５℃で１．５時間撹拌して反応させ、次に５ｇのアセトンを加え、４５℃で１．５時間撹拌して反応させ、噴霧乾燥させることで、改質剤を得た。 As a method for preparing the modifier, 0.1 g of hydroxylated carbon nanotubes, 30 g of polyvinyl alcohol, and 13 g of catechin are added to 75 g of water, and the mixture is stirred at 65 ° C. for 1.5 hours to react, and then 5 g. Acetone was added, and the mixture was stirred at 45 ° C. for 1.5 hours to react and spray-dried to obtain a modifier.
前記ヒドロキシ化したカーボンナノチューブの調製方法は、以下のとおりである。
１．３ｇのカーボンナノチューブと３３５ｍＬの混酸（濃硫酸と濃硝酸の体積比は３：１）を５００ｍＬフラスコに取り、反応温度は８５℃で、超音波出力２００Ｗ、超音波周波数４０ＫＨｚの超音波洗浄器内で３．５時間凝縮・還流した。その後、ビーカーに移し、２５０ｇの脱イオン水で希釈し、直径０．２μｍの微孔性膜で吸引ろ過し、中性になるまで脱イオン水で繰り返し洗浄した。吸引ろ過後のカーボンナノチューブを１０５℃で乾燥させ、粉末状に粉砕してヒドロキシ化したカーボンナノチューブを得た。前記カーボンナノチューブは、化学蒸着法によって生成された直径２ｎｍ、チューブの長さ１００μｍ、純度９９．５ｗｔ％、アモルファスカーボン不純物＜５％、アッシュ不純物＜３ｗｔ％、比表面積７００ｍ２／ｇの単層カーボンナノチューブであった。
The method for preparing the hydroxylated carbon nanotubes is as follows.
Take 1.3 g of carbon nanotubes and 335 mL of mixed acid (volume ratio of concentrated sulfuric acid and concentrated nitric acid is 3: 1) in a 500 mL flask, and ultrasonically clean at a reaction temperature of 85 ° C., ultrasonic output of 200 W, and ultrasonic frequency of 40 KHz. Condensed and refluxed in the vessel for 3.5 hours. Then, it was transferred to a beaker, diluted with 250 g of deionized water, suction-filtered with a microporous membrane having a diameter of 0.2 μm, and repeatedly washed with deionized water until neutral. The carbon nanotubes after suction filtration were dried at 105 ° C. and pulverized into powder to obtain hydroxylated carbon nanotubes. The carbon nanotubes are single-walled carbon produced by a chemical vapor deposition method, having a diameter of 2 nm, a tube length of 100 μm, a purity of 99.5 wt%, an amorphous carbon impurity <5%, an ash impurity <3 wt%, and a specific surface area of 700 m 2 / g. It was an nanotube.
前記フィラーポリマー鎖の調製は、以下の工程（１）〜（４）を含む：
（１）１０．５ｇのナノシリコンカーバイドを１０５℃で真空乾燥させ、ナノシリコンカーバイドを３０ｇのＮ、Ｎ−ジメチルホルムアミドに分散させ、４０℃で２０分間超音波分散させて溶液Ａを得る工程、
（２）１７ｇのジフェニルメタンジイソシアネートと１７ｇのポリ乳酸を４２ｇのＮ、Ｎ−ジメチルホルムアミドに溶解して、溶液Ｂを得る工程、
（３）ナノシルバーと１，５−ナフタレンジスルホン酸を１：２０：５５の比率で５５℃で１．５時間撹拌して溶液Ｃを得る工程（前記ナノシルバーの重量はナノシリコンカーバイド重量の１／１００）、
（４）溶液Ｂを溶液Ａに滴下し、次に溶液Ｃを溶液Ａに加え、６０℃で２．５時間撹拌して反応させ、フィラーポリマー鎖を得る工程。
The preparation of the filler polymer chain includes the following steps (1) to (4):
(1) A step of vacuum-drying 10.5 g of nanosilicon carbide at 105 ° C., dispersing the nanosilicon carbide in 30 g of N, N-dimethylformamide, and ultrasonically dispersing the nanosilicon carbide at 40 ° C. for 20 minutes to obtain a solution A.
(2) A step of dissolving 17 g of diphenylmethane diisocyanate and 17 g of polylactic acid in 42 g of N, N-dimethylformamide to obtain a solution B.
(3) A step of stirring nanosilver and 1,5-naphthalenedisulfonic acid at a ratio of 1:20:55 at 55 ° C. for 1.5 hours to obtain a solution C (the weight of the nanosilver is 1 of the weight of the nanosilicon carbide. / 100),
(4) A step of dropping solution B into solution A, then adding solution C to solution A, and stirring and reacting at 60 ° C. for 2.5 hours to obtain a filler polymer chain.
（１）改質用熱伝導性フィラーの調製：室温で質量比が１：３．５：２：１．１５のモノアルコキシチタネートカップリング剤（モノアルコキシ脂肪酸チタン酸エステルカップリング剤、南京全希化工有限会社製）、脱イオン水、タンニン酸、窒化ホウ素ナノシートを混合し、3０分間加水分解して、加水分解物Ａを得た。得られた加水分解物Ａを９０℃の高速ミキサーに加え、４０分間混合を継続し、冷却して取り出し、真空乾燥して、改質用熱伝導性フィラーを得た。
（２）成分Ａの調製：ポリカーボネートジオールと改質用熱伝導性フィラーを質量比２．２：１で最初に超音波により１時間分散させ、次に１１０℃で２時間、減圧下で脱水して、成分Ａを得た。
（３）カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製：５５℃で成分Ａ、ＭＤＩ型イソシアナート、ジブチルスズジラウレートを質量比２．８：１：０．０２で８０ｒ／ｍｉｎの回転数で９０分間反応させ、次に８５℃に昇温し１．５時間反応を継続し、０．３倍の改質剤、０．２５倍のジメチロールプロピオン酸、０．０２倍のフィラーポリマー鎖および１．２倍の水を加え、９０℃で２時間反応を継続し、さらに０．０１倍のメタクリル酸メチル、０．００５倍の過硫酸アンモニウムおよび０．１倍の水を加え、８０℃で２時間反応させ、さらに０．０１倍のグリオキシムおよび０．００５倍の３，４，５−トリメトキシ安息香酸を加え、８０℃で２時間反応させ、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤を得た。前記メタクリル酸メチル、改質剤、ポリオール系鎖延長剤、フィラーポリマー鎖、過硫酸アンモニウム、水の倍数は、イソシアナートの質量を基準とし、グリオキシムおよび３，４，５−トリメトキシ安息香酸の倍数はいずれもメタクリル酸メチルの質量を基準とした。
(1) Preparation of thermally conductive filler for modification: Monoalkoxy titanate coupling agent having a mass ratio of 1: 3.5: 2: 1.15 at room temperature (monoalkoxy fatty acid titanate ester coupling agent, Nanjing Zenki (Manufactured by Kako Co., Ltd.), deionized water, tannic acid, and boron nitride nanosheet were mixed and hydrolyzed for 30 minutes to obtain a hydrolyzate A. The obtained hydrolyzate A was added to a high-speed mixer at 90 ° C., mixing was continued for 40 minutes, cooled and taken out, and vacuum dried to obtain a thermally conductive filler for modification.
(2) Preparation of component A: Polycarbonate diol and thermally conductive filler for modification were first dispersed by ultrasonic waves at a mass ratio of 2.2: 1 for 1 hour, and then dehydrated at 110 ° C. for 2 hours under reduced pressure. To obtain component A.
(3) Preparation of light-resistant aqueous polyurethane coating agent and adhesive for modifying carbon nanotubes: Ingredient A, MDI-type isocyanate, and dibutyltin dilaurate at 55 ° C. at a mass ratio of 2.8: 1: 0.02 at 80 r / min. The reaction was carried out at a rotation speed of 90 minutes, then the temperature was raised to 85 ° C. and the reaction was continued for 1.5 hours. Add the polymer chain and 1.2 times water, continue the reaction at 90 ° C. for 2 hours, then add 0.01 times methyl methacrylate, 0.005 times ammonium persulfate and 0.1 times water, 80. After reacting at ° C for 2 hours, 0.01 times more glyoxime and 0.005 times 3,4,5-trimethoxybenzoic acid were added, and the reaction was carried out at 80 ° C. for 2 hours to modify a carbon nanotube-modified light-resistant aqueous polyurethane coating. Agents and adhesives were obtained. The multiples of methyl methacrylate, modifier, polyol chain extender, filler polymer chain, ammonium persulfate, and water are based on the mass of isocyanate, and the multiples of glyoxime and 3,4,5-trimethoxybenzoic acid are any. Was also based on the mass of methyl methacrylate.
前記改質剤の調製方法として、０．１ｇのヒドロキシ化したカーボンナノチューブ、３０ｇのポリビニルアルコール、１０ｇのカテキンを７０ｇの水に加え、７０℃で２時間撹拌して反応させ、次に５ｇのアセトンを加え、５０℃で２時間撹拌して反応させ、噴霧乾燥させることで、改質剤を得た。 As a method for preparing the modifier, 0.1 g of hydroxylated carbon nanotubes, 30 g of polyvinyl alcohol, and 10 g of catechin are added to 70 g of water, and the mixture is stirred and reacted at 70 ° C. for 2 hours, and then 5 g of acetone. Was added, and the mixture was stirred at 50 ° C. for 2 hours to react and spray-dried to obtain a modifier.
前記ヒドロキシ化したカーボンナノチューブの調製方法は、以下のとおりである。
１．２ｇのカーボンナノチューブと３２０ｍＬの混酸（濃硫酸と濃硝酸の体積比は３：１）を５００ｍＬフラスコに取り、反応温度は８０℃で、超音波出力２００Ｗ、超音波周波数４０ＫＨｚの超音波洗浄器内で３時間凝縮・還流した。その後、ビーカーに移し、２５０ｇの脱イオン水で希釈し、直径０．２μｍの微孔性膜で吸引ろ過し、中性になるまで脱イオン水で繰り返し洗浄した。吸引ろ過後のカーボンナノチューブを１０５℃で乾燥させ、粉末状に粉砕してヒドロキシ化したカーボンナノチューブを得た。前記カーボンナノチューブは、化学蒸着法によって生成された直径２ｎｍ、チューブの長さ１００μｍ、純度９９．５ｗｔ％、アモルファスカーボン不純物＜５％、アッシュ不純物＜３ｗｔ％、比表面積７００ｍ２／ｇの単層カーボンナノチューブであった。
The method for preparing the hydroxylated carbon nanotubes is as follows.
Take 1.2 g of carbon nanotubes and 320 mL of mixed acid (volume ratio of concentrated sulfuric acid and concentrated nitric acid is 3: 1) in a 500 mL flask, and ultrasonically clean at a reaction temperature of 80 ° C., ultrasonic output of 200 W, and ultrasonic frequency of 40 KHz. Condensed and refluxed in the vessel for 3 hours. Then, it was transferred to a beaker, diluted with 250 g of deionized water, suction-filtered with a microporous membrane having a diameter of 0.2 μm, and repeatedly washed with deionized water until neutral. The carbon nanotubes after suction filtration were dried at 105 ° C. and pulverized into powder to obtain hydroxylated carbon nanotubes. The carbon nanotubes are single-walled carbon produced by a chemical vapor deposition method, having a diameter of 2 nm, a tube length of 100 μm, a purity of 99.5 wt%, an amorphous carbon impurity <5%, an ash impurity <3 wt%, and a specific surface area of 700 m 2 / g. It was an nanotube.
前記フィラーポリマー鎖の調製は、以下の工程（１）〜（４）を含む：
（１）１０ｇのナノシリコンカーバイドを１０５℃で真空乾燥させ、ナノシリコンカーバイドを３０ｇのＮ、Ｎ−ジメチルホルムアミドに分散させ、３５℃で２０分間超音波分散させて溶液Ａを得る工程、
（２）１４ｇのジフェニルメタンジイソシアネートと１０ｇのポリ乳酸を４２ｇのＮ、Ｎ−ジメチルホルムアミドに溶解して、溶液Ｂを得る工程、
（３）ナノシルバーと１，５−ナフタレンジスルホン酸を１：２０：５５の比率で５５℃で２時間撹拌して溶液Ｃを得る工程（前記ナノシルバーの重量はナノシリコンカーバイド重量の１／１００）、
（４）溶液Ｂを溶液Ａに滴下し、次に溶液Ｃを溶液Ａに加え、７０℃で３時間撹拌して反応させ、フィラーポリマー鎖を得る工程。
The preparation of the filler polymer chain includes the following steps (1) to (4):
(1) A step of vacuum-drying 10 g of nanosilicon carbide at 105 ° C., dispersing the nanosilicon carbide in 30 g of N, N-dimethylformamide, and ultrasonically dispersing the nanosilicon carbide at 35 ° C. for 20 minutes to obtain a solution A.
(2) A step of dissolving 14 g of diphenylmethane diisocyanate and 10 g of polylactic acid in 42 g of N, N-dimethylformamide to obtain a solution B.
(3) A step of stirring nanosilver and 1,5-naphthalenedisulfonic acid at a ratio of 1:20:55 at 55 ° C. for 2 hours to obtain a solution C (the weight of the nanosilver is 1/100 of the weight of the nanosilicon carbide. ),
(4) A step of dropping solution B into solution A, then adding solution C to solution A, and stirring and reacting at 70 ° C. for 3 hours to obtain a filler polymer chain.
（１）改質用熱伝導性フィラーの調製：室温で質量比が１：３：３：１．３の３−アミノプロピルトリエトキシシラン、脱イオン水、タンニン酸、窒化ホウ素ナノシートを混合し、４０分間加水分解して、加水分解物Ａを得た。得られた加水分解物Ａを９０℃の高速ミキサーに加え、４０分間混合を継続し、冷却して取り出し、真空乾燥して、改質用熱伝導性フィラーを得た。
（２）成分Ａの調製：ポリカーボネートジオールと改質用熱伝導性フィラーを質量比２．５：１で最初に超音波により１時間分散させ、次に１０0℃で１時間、減圧下で脱水して、成分Ａを得た。
（３）カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製：６０℃で成分Ａ、ＭＤＩ型イソシアナート、ジブチルスズジラウレートを質量比２．８：１：０．０２で７０ｒ／ｍｉｎの回転数で７０分間反応させ、次に８０℃に昇温し２時間反応を継続し、０．２倍の改質剤、０．２５倍のジヒドロキシメチル酪酸、０．０２倍のフィラーポリマー鎖および１．２倍の水を加え、８０℃で１時間反応を継続し、さらにメ０．０１倍のタクリル酸メチル、０．００５倍の過硫酸アンモニウムおよび０．１倍の水を加え、７０℃で１時間反応させ、さらに０．０１倍のグリオキシムおよび０．００５倍の３，４，５−トリメトキシ安息香酸を加え、８０℃で２時間反応させ、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤を得た。前記メタクリル酸メチル、改質剤、ポリオール系鎖延長剤、フィラーポリマー鎖、過硫酸アンモニウム、水の倍数は、イソシアナートの質量を基準とし、グリオキシムおよび３，４，５−トリメトキシ安息香酸の倍数はいずれもメタクリル酸メチルの質量を基準とした。
(1) Preparation of thermally conductive filler for modification: At room temperature, 3-aminopropyltriethoxysilane having a mass ratio of 1: 3: 3: 1.3, deionized water, tannic acid, and boron nitride nanosheets are mixed. Hydrolysis was performed for 40 minutes to obtain hydrolyzate A. The obtained hydrolyzate A was added to a high-speed mixer at 90 ° C., mixing was continued for 40 minutes, cooled and taken out, and vacuum dried to obtain a thermally conductive filler for modification.
(2) Preparation of component A: Polycarbonate diol and thermally conductive filler for modification were first dispersed by ultrasonic waves at a mass ratio of 2.5: 1 for 1 hour, and then dehydrated at 100 ° C. for 1 hour under reduced pressure. To obtain component A.
(3) Preparation of light-resistant aqueous polyurethane coating agent and adhesive for modifying carbon nanotubes: Component A, MDI-type isocyanate, and dibutyltin dilaurate at 60 ° C. at a mass ratio of 2.8: 1: 0.02 at 70 r / min. The reaction was carried out at rotation speed for 70 minutes, then the temperature was raised to 80 ° C. and the reaction was continued for 2 hours, with 0.2 times the modifier, 0.25 times the dihydroxymethylbutyric acid, 0.02 times the filler polymer chain and Add 1.2 times water and continue the reaction at 80 ° C. for 1 hour, then add 0.01 times methyl tacrylate, 0.005 times ammonium persulfate and 0.1 times water at 70 ° C. After reacting for 1 hour, 0.01 times more glyoxime and 0.005 times 3,4,5-trimethoxybenzoic acid were added, and the mixture was reacted at 80 ° C. for 2 hours to modify a carbon nanotube-modified light-resistant aqueous polyurethane coating agent. Obtained adhesive. The multiples of methyl methacrylate, modifier, polyol chain extender, filler polymer chain, ammonium persulfate, and water are based on the mass of isocyanate, and the multiples of glyoxime and 3,4,5-trimethoxybenzoic acid are any. Was also based on the mass of methyl methacrylate.
前記改質剤の調製方法として、０．１ｇのヒドロキシ化したカーボンナノチューブ、２５ｇのポリビニルアルコール、２２ｇのカテキンを８０ｇの水に加え、６０℃で１時間撹拌して反応させ、次に５ｇのアセトンを加え、４０℃で１時間撹拌して反応させ、噴霧乾燥させることで、改質剤を得た。 As a method for preparing the modifier, 0.1 g of hydroxylated carbon nanotubes, 25 g of polyvinyl alcohol, and 22 g of catechin are added to 80 g of water, and the mixture is stirred at 60 ° C. for 1 hour to react, and then 5 g of acetone. Was added, and the mixture was stirred at 40 ° C. for 1 hour to react and spray-dried to obtain a modifier.
前記ヒドロキシ化したカーボンナノチューブの調製方法は、以下のとおりである。
１．２ｇのカーボンナノチューブと３２０ｍＬの混酸（濃硫酸と濃硝酸の体積比は３：１）を５００ｍＬフラスコに取り、反応温度は７５℃で、超音波出力２００Ｗ、超音波周波数４０ＫＨｚの超音波洗浄器内で５時間凝縮・還流した。その後、ビーカーに移し、２５０ｇの脱イオン水で希釈し、直径０．２μｍの微孔性膜で吸引ろ過し、中性になるまで脱イオン水で繰り返し洗浄した。吸引ろ過後のカーボンナノチューブを１０５℃で乾燥させ、粉末状に粉砕してヒドロキシ化したカーボンナノチューブを得た。前記カーボンナノチューブは、化学蒸着法によって生成された直径２ｎｍ、チューブの長さ１００μｍ、純度９９．５ｗｔ％、アモルファスカーボン不純物＜５％、アッシュ不純物＜３ｗｔ％、比表面積７００ｍ２／ｇの単層カーボンナノチューブであった。
The method for preparing the hydroxylated carbon nanotubes is as follows.
Take 1.2 g of carbon nanotubes and 320 mL of mixed acid (volume ratio of concentrated sulfuric acid and concentrated nitric acid is 3: 1) in a 500 mL flask, and ultrasonically clean at a reaction temperature of 75 ° C., ultrasonic output of 200 W, and ultrasonic frequency of 40 KHz. Condensed and refluxed in the vessel for 5 hours. Then, it was transferred to a beaker, diluted with 250 g of deionized water, suction-filtered with a microporous membrane having a diameter of 0.2 μm, and repeatedly washed with deionized water until neutral. The carbon nanotubes after suction filtration were dried at 105 ° C. and pulverized into powder to obtain hydroxylated carbon nanotubes. The carbon nanotubes are single-walled carbon produced by a chemical vapor deposition method, having a diameter of 2 nm, a tube length of 100 μm, a purity of 99.5 wt%, an amorphous carbon impurity <5%, an ash impurity <3 wt%, and a specific surface area of 700 m 2 / g. It was an nanotube.
前記フィラーポリマー鎖の調製は、以下の工程（１）〜（４）を含む：
（１）１０ｇのナノシリコンカーバイドを１０５℃で真空乾燥させ、ナノシリコンカーバイドを３０ｇのＮ、Ｎ−ジメチルホルムアミドに分散させ、５０℃で３０分間超音波分散させて溶液Ａを得る工程、
（２）２２ｇのジフェニルメタンジイソシアネートと１２ｇのポリ乳酸を４２ｇのＮ、Ｎ−ジメチルホルムアミドに溶解して、溶液Ｂを得る工程、
（３）ナノシルバーと１，５−ナフタレンジスルホン酸を１：２０：６０の比率で６０℃で２時間撹拌して溶液Ｃを得る工程（前記ナノシルバーの重量はナノシリコンカーバイド重量の１／１００）、
（４）溶液Ｂを溶液Ａに滴下し、次に溶液Ｃを溶液Ａに加え、５0℃で２時間撹拌して反応させ、フィラーポリマー鎖を得る工程。
The preparation of the filler polymer chain includes the following steps (1) to (4):
(1) A step of vacuum-drying 10 g of nanosilicon carbide at 105 ° C., dispersing the nanosilicon carbide in 30 g of N, N-dimethylformamide, and ultrasonically dispersing the nanosilicon carbide at 50 ° C. for 30 minutes to obtain a solution A.
(2) A step of dissolving 22 g of diphenylmethane diisocyanate and 12 g of polylactic acid in 42 g of N, N-dimethylformamide to obtain a solution B.
(3) A step of stirring nanosilver and 1,5-naphthalenedisulfonic acid at a ratio of 1:20:60 at 60 ° C. for 2 hours to obtain a solution C (the weight of the nanosilver is 1/100 of the weight of the nanosilicon carbide. ),
(4) A step of dropping solution B into solution A, then adding solution C to solution A, and stirring and reacting at 50 ° C. for 2 hours to obtain a filler polymer chain.
以下は、性能テストおよび結果の分析である。
一、熱伝導率とポリウレタンフィルムの平滑性：ＡＳＴＭ Ｅ１５３０−２００６に従って、ポリウレタン接着剤の熱伝導率を定常熱伝導率計でテストした。テスト結果を表１に示す。ここで、特許文献１の実施例１で調製した製品を比較例１とし、特許文献２の実施例２で調製された製品を比較例２として使用した。３人の高分子教師（副教授の称号以上）により表面平滑性をスコア１〜１０でスコア付けし、スコア１０が最高、スコア１が最低である。
The following is a performance test and analysis of the results.
1. Thermal conductivity and smoothness of polyurethane film: According to ASTM E1530-2006, the thermal conductivity of the polyurethane adhesive was tested with a stationary thermal conductivity meter. The test results are shown in Table 1. Here, the product prepared in Example 1 of Patent Document 1 was used as Comparative Example 1, and the product prepared in Example 2 of Patent Document 2 was used as Comparative Example 2. The surface smoothness was scored by three polymer teachers (associate professor title or higher) with a score of 1 to 10, with a score of 10 being the highest and a score of 1 being the lowest.
表１から、本発明は良好な熱伝導性を有することが分かる。また、表１から、改質剤およびヒドロキシ化したカーボンナノチューブが熱伝導率に大きな影響を与えることが分かる。スコア付け結果は、本発明のポリウレタンフィルムの平滑性が優れていることを示している。 From Table 1, it can be seen that the present invention has good thermal conductivity. Further, from Table 1, it can be seen that the modifier and the hydroxylated carbon nanotubes have a great influence on the thermal conductivity. The scoring results show that the polyurethane film of the present invention has excellent smoothness.
二、ポリウレタンコーティング剤の難燃性：ＡＳＴＭ Ｅ ６６２およびＧＢ８３２３−８７に定められている煙密度測定方法で、大きさ１０ｃｍ×１０ｃｍ、厚さ１０ｍｍのフィルムの試験片を作製し、非特許文献４でポリウレタンコーティング剤によって形成されたフィルムの有炎燃焼時間（燃焼継続時間）を測定した。 2. Flame retardancy of polyurethane coating agent: A test piece of a film having a size of 10 cm × 10 cm and a thickness of 10 mm was prepared by the smoke density measuring method specified in ASTM E 662 and GB8323-87, and Non-Patent Document 4 The flame burning time (burning duration) of the film formed by the polyurethane coating agent was measured in.
ナノシルバーは、１，５−ナフタレンジスルホン酸の改質下でガスを放出し、それを完全燃焼させ、煙の濃度を下げることができる。ＡＳＴＭ Ｅ１３５４−１９９０（２００４規格）を用いて、英国ＦＴＴ社のコーンカロリーメータ２０００で分析・測定した。試験片の大きさは１０ｃｍｘ１０ｃｍ、厚さは１０ｍｍ、熱放射電力は１２ｋｗ／ｍ２であった。試験結果を表２および表３に示す。ここで比較例３は、特許文献３の実施例２で調製した製品を採用した。 Nanosilver can release gas under modification of 1,5-naphthalenedisulfonic acid and burn it completely to reduce the concentration of smoke. Analysis and measurement were performed using an ASTM E1354-1990 (2004 standard) with a cone calorie meter 2000 manufactured by FTT of the United Kingdom. The size of the test piece was 10 cm x 10 cm, the thickness was 10 mm, and the thermal radiant power was 12 kW / m 2 . The test results are shown in Tables 2 and 3. Here, as Comparative Example 3, the product prepared in Example 2 of Patent Document 3 was adopted.
表２と表３から、１，５−ナフタレンジスルホン酸を加えずに得られた材料のＣＯの濃度は比較的高いことが分かり、煙中の有毒ガスとしてのCOを制御する必要がある。 From Tables 2 and 3, it can be seen that the CO concentration of the material obtained without adding 1,5-naphthalenedisulfonic acid is relatively high, and it is necessary to control CO as a toxic gas in smoke.
三、ポリウレタンコーティングおよび接着剤の耐光性：調製されたＰＵフィルムを人工加速劣化試験用のランプ式黄変試験器に入れた。光源は赤色ランプであり、放射波長は３２０ｎｍ〜４００ｎｍであり、最大強度波長は３６０ｎｍであった。試験片とＵＶＡランプの間の距離は１５ｃｍであり、テスト温度は６０℃であり、照射時間は９６時間であった。 3. Light resistance of polyurethane coating and adhesive: The prepared PU film was placed in a lamp-type yellowing tester for an artificial accelerated deterioration test. The light source was a red lamp, the emission wavelength was 320 nm to 400 nm, and the maximum intensity wavelength was 360 nm. The distance between the test piece and the UVA lamp was 15 cm, the test temperature was 60 ° C., and the irradiation time was 96 hours.
全てのＰＵフィルムがＵＶ光で異なる時間に劣化した後、比色計で色の変化を測定した。テスト条件は、プローブの直径が８ｍｍ、主光源がＤ６５、観測角度が１０°であった。 After all PU films were degraded by UV light at different times, the color change was measured with a colorimeter. The test conditions were a probe diameter of 8 mm, a main light source of D65, and an observation angle of 10 °.
ＣＩＥの Ｌ＊ａ＊ｂ＊色空間の原理に従って、試験片劣化前後の色差変化を測定した。ＣＩＥ（Ｌ＊ａ＊ｂ＊）１９７６の計算式を（１）〜（４）に示す［６３］。
＜数１＞
ΔＬ＊＝ Ｌ＊劣化後 − Ｌ＊劣化前 （１）
＜数２＞
Δａ＊＝ ａ＊劣化後− ａ＊劣化前 （２）
＜数３＞
Δｂ＊＝ ｂ＊劣化後− ｂ＊劣化前 （３）
＜数４＞
ΔＥ＊＝［（ΔＬ＊）２ ＋（Δａ＊）２＋（Δｂ＊）２ ］１／２ （４）
According to the CIE L * a * b * color space principle, the color difference change before and after the deterioration of the test piece was measured. The calculation formula of CIE (L * a * b *) 1976 is shown in (1) to (4) [63] .
<Number 1>
ΔL * = L * After deterioration -L * Before deterioration (1)
<Number 2>
Δa * = a * After deterioration -a * Before deterioration (2)
<Number 3>
Δb * = b * after deterioration − b * before deterioration (3)
<Number 4>
ΔE * = [(ΔL *) 2 + (Δa *) 2 + (Δb *) 2 ] 1/2 (4)
式中、Ｌは試験片の明るさの変化を表し、＋Ｌは明るくなること、−Ｌは暗くなることを意味する。ａは試験片の赤緑の変化を表し、＋ａは赤くなること、−ａは緑になることを意味する。ｂは試験片の黄青の変化を表し、＋ｂは黄色に変わることを意味し、−ｂは青に変わることを意味する。コーティング剤の耐光性を定量的に表し、分光光度計で測定して逆色差値△Ｅを求め、コーティング剤と上塗りの耐光性を表す。△Ｅは色の変化の度合いを表し、△Ｅが大きいほど色の変化がはっきりする。一般的に、△Ｅ値０〜１．５はわずかな変化、△Ｅ値１．５〜３．０は知覚可能な変化、△Ｅ値３．０〜６．０は大きな変化となる（非特許文献３を参照）。大きさ１０ｃｍ×１０ｃｍ、厚さ１０ｍｍのポリウレタンフィルムの試験片を作製してテストした。テスト結果を表４に示す。特許文献１の実施例１で調製された製品を比較例１とし、特許文献２の実施例２で調製された製品を比較例２として使用した。 In the formula, L represents a change in the brightness of the test piece, + L means brightening, and -L means darkening. a represents a change in reddish green of the test piece, + a means that it becomes red, and -a means that it becomes green. b represents the change in yellow-blue of the test piece, + b means that it turns yellow, and -b means that it turns blue. The light resistance of the coating agent is quantitatively expressed, and the reverse color difference value ΔE is obtained by measuring with a spectrophotometer, and the light resistance of the coating agent and the top coat is expressed. ΔE represents the degree of color change, and the larger ΔE, the clearer the color change. In general, ΔE values 0 to 1.5 are slight changes, ΔE values 1.5 to 3.0 are perceptible changes, and ΔE values 3.0 to 6.0 are large changes (non-). See Patent Document 3). A test piece of a polyurethane film having a size of 10 cm × 10 cm and a thickness of 10 mm was prepared and tested. The test results are shown in Table 4. The product prepared in Example 1 of Patent Document 1 was used as Comparative Example 1, and the product prepared in Example 2 of Patent Document 2 was used as Comparative Example 2.
表４から、本発明は耐光性を向上する上で明らかな利点を有することが分かる。 From Table 4, it can be seen that the present invention has a clear advantage in improving the light resistance.
コーティング剤の耐光性を定量的に表し、分光光度計で測定して逆色差値△Ｅを求め、コーティング剤と上塗りの耐光性を表す。△Ｅは色の変化の度合いを表し、△Ｅが大きいほど色の変化がはっきりする。一般的に、△Ｅ値０〜１．５はわずかな変化、△Ｅ値１．５〜３．０は知覚可能な変化、△Ｅ値３．０〜６．０は大きな変化となる（非特許文献３を参照）。大きさ１０ｃｍ×１０ｃｍ、厚さ１０ｍｍのポリウレタンフィルムの試験片を作製してテストした。テスト結果を表５に示す。 The light resistance of the coating agent is quantitatively expressed, and the reverse color difference value ΔE is obtained by measuring with a spectrophotometer, and the light resistance of the coating agent and the top coat is expressed. ΔE represents the degree of color change, and the larger ΔE, the clearer the color change. In general, ΔE values 0 to 1.5 are slight changes, ΔE values 1.5 to 3.0 are perceptible changes, and ΔE values 3.0 to 6.0 are large changes (non-). See Patent Document 3). A test piece of a polyurethane film having a size of 10 cm × 10 cm and a thickness of 10 mm was prepared and tested. The test results are shown in Table 5.
表５からグリオキシムを加えていないスキームは、製品の耐光性が低下することが分かる。 From Table 5, it can be seen that the scheme without glycimme reduces the light resistance of the product.
四、ポリウレタンコーティング剤および接着剤のフィルム平滑性：厚さ１０ｍｍのポリウレタンフィルムを作製してテストした。テストのスコア付け方法は、上記と同じであり、結果を表６に示す。 4. Film smoothness of polyurethane coating agent and adhesive: A polyurethane film having a thickness of 10 mm was prepared and tested. The test scoring method is the same as above and the results are shown in Table 6.
表６からグリオキシムまたは３，４，５−トリメトキシ安息香酸を添加しない場合のポリウレタンフィルムの平滑性が低下することが分かる。 It can be seen from Table 6 that the smoothness of the polyurethane film is reduced when glyoxime or 3,4,5-trimethoxybenzoic acid is not added.
上記の実施例は、本発明の技術的手段を説明するためにのみ使用され、本発明はそのような実施形態に限定されるものではない。前述の実施形例を参照して、本発明を詳細に説明してきたが、当業者は前述の各実施例に記載されている技術的手段について変更するか、または技術的特徴の一部を同等に置換することができ、これらの変更または置換は、対応する技術的手段の本質が本発明の各実施例の技術的手段の精神および範囲から逸脱することはないことは、当業者は理解すべきである。 The above examples are used only to illustrate the technical means of the invention, and the invention is not limited to such embodiments. Although the present invention has been described in detail with reference to the above-described embodiments, those skilled in the art will modify the technical means described in each of the above-described embodiments or equip them with some of the technical features. It will be appreciated by those skilled in the art that these modifications or substitutions will not deviate from the spirit and scope of the technical means of each embodiment of the invention. Should be.
Claims (8)
（１）室温で質量比が１：（２〜５）：（１〜３）：（１．０〜１．３）のカップリング剤、脱イオン水、タンニン酸、窒化ホウ素ナノシートを混合し、３０〜４０分間加水分解して、加水分解物Ａを得、得られた加水分解物Ａを８０〜９０℃の高速ミキサーに加え、３０〜４０分間混合を継続し、冷却して取り出し、真空乾燥して、改質用熱伝導性フィラーを得る改質用熱伝導性フィラーの調製工程。
（２）ポリマーポリオールと改質用熱伝導性フィラーを質量比（２〜３）：１で最初に超音波により１〜２．５時間分散させ、次に１００〜１１０℃で１〜２時間、減圧下で脱水して、成分Ａを得る成分Ａの調製工程。
（３）５０〜７０℃で成分Ａ、イソシアナート、ジブチルスズジラウレートを質量比（２．５〜３．０）：１：０．０２で６０〜８０ｒ／ｍｉｎの回転数で６０〜９０分間反応させ、次に７５〜８５℃に昇温し１〜３時間反応を継続し、０．１〜０．４倍の改質剤、０．２５〜０．３４倍のポリオール系鎖延長剤、０．０２〜０．０５倍のフィラーポリマー鎖および１．２倍の水を加え、８０〜９０℃で１〜２時間反応を継続し、さらに０．０１倍のメタクリル酸メチル、０．００５倍の過硫酸アンモニウムおよび０．１倍の水を加え、７０〜８０℃で１〜２時間反応させ、さらに０．０１倍のグリオキシムおよび０．００５倍の３，４，５−トリメトキシ安息香酸を加え、７０〜８０℃で１〜２時間反応させ、カーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤を得るカーボンナノチューブ改質の耐光性水性ポリウレタンコーティング剤および接着剤の調製工程。
加えられた改質剤、ポリオール系鎖延長剤、水、メタクリル酸メチル、過硫酸アンモニウム、フィラーポリマー鎖の倍数は、いずれもイソシアナートの質量を基準とし、加えられたグリオキシムおよび３，４，５−トリメトキシ安息香酸の倍数はいずれもメタクリル酸メチルの質量を基準とする。 A method for preparing a light-resistant water-resistant polyurethane coating agent and an adhesive for modifying carbon nanotubes, which comprises the following steps (1) to (3). Adhesive preparation method.
(1) A coupling agent having a mass ratio of 1: (2 to 5): (1 to 3): (1.0 to 1.3) at room temperature, deionized water, tannic acid, and a boron nitride nanosheet are mixed. Hydrolyze for 30-40 minutes to obtain hydrolyzate A, add the resulting hydrolyzate A to a high speed mixer at 80-90 ° C., continue mixing for 30-40 minutes, cool and remove, vacuum dry. The process of preparing the thermally conductive filler for modification to obtain the thermally conductive filler for modification.
(2) The polymer polyol and the thermally conductive filler for modification were first dispersed by ultrasonic waves at a mass ratio (2 to 3): 1 for 1 to 2.5 hours, and then at 100 to 110 ° C. for 1 to 2 hours. A step of preparing component A, which is dehydrated under reduced pressure to obtain component A.
(3) Ingredient A, isocyanate, and dibutyltin dilaurate are reacted at 50 to 70 ° C. at a mass ratio (2.5 to 3.0): 1: 0.02 at a rotation speed of 60 to 80 r / min for 60 to 90 minutes. Then, the temperature was raised to 75 to 85 ° C., and the reaction was continued for 1 to 3 hours. 02 to 0.05 times the filler polymer chain and 1.2 times the water were added, the reaction was continued at 80 to 90 ° C. for 1 to 2 hours, and 0.01 times the methyl methacrylate and 0.005 times the excess. Add ammonium sulfate and 0.1 times water and react at 70-80 ° C. for 1-2 hours, then add 0.01 times glyoxime and 0.005 times 3,4,5-trimethoxybenzoic acid, 70- A step of preparing a carbon nanotube-modified light-resistant aqueous polyurethane coating and an adhesive by reacting at 80 ° C. for 1 to 2 hours to obtain a carbon nanotube-modified light-resistant aqueous polyurethane coating and an adhesive.
The added modifier, polyol chain extender, water, methyl methacrylate, ammonium persulfate, and multiples of the filler polymer chain are all based on the mass of isocyanate, and the added glyoxime and 3,4,5- All multiples of trimethoxybenzoic acid are based on the mass of methyl methacrylate.
１．１〜１．５ｇのカーボンナノチューブと３２０〜３５０ｍＬの混酸（濃硫酸と濃硝酸の体積比は３：１）を５００ｍＬフラスコに取り、反応温度は７５〜９５℃で、超音波出力２００Ｗ、超音波周波数４０ＫＨｚの超音波洗浄器内で２〜５時間凝縮・還流する。その後、ビーカーに移し、２５０ｇの脱イオン水で希釈し、直径０．２μｍの微孔性膜で吸引ろ過し、中性になるまで脱イオン水で繰り返し洗浄する。吸引ろ過後のカーボンナノチューブを１０５℃で乾燥させ、粉末状に粉砕してヒドロキシ化したカーボンナノチューブを得る。前記カーボンナノチューブは、化学蒸着法によって生成された直径２ｎｍ、チューブの長さ１００μｍ、純度９９．５ｗｔ％、アモルファスカーボン不純物＜５％、アッシュ不純物＜３ｗｔ％、比表面積７００ｍ２／ｇの単層カーボンナノチューブである。 The method for preparing a light-resistant aqueous polyurethane coating agent and an adhesive for modifying carbon nanotubes according to claim 2, wherein the method for preparing the hydroxylated carbon nanotubes is as follows.
1.1 to 1.5 g of carbon nanotubes and 320 to 350 mL of mixed acid (volume ratio of concentrated sulfuric acid to concentrated nitric acid is 3: 1) are placed in a 500 mL flask, the reaction temperature is 75 to 95 ° C., and the ultrasonic output is 200 W. Condensate and reflux for 2 to 5 hours in an ultrasonic cleaner with an ultrasonic frequency of 40 KHz. Then, the mixture is transferred to a beaker, diluted with 250 g of deionized water, suction-filtered with a microporous membrane having a diameter of 0.2 μm, and repeatedly washed with deionized water until neutral. The carbon nanotubes after suction filtration are dried at 105 ° C. and pulverized into powder to obtain hydroxylated carbon nanotubes. The carbon nanotubes are single-walled carbon produced by a chemical vapor deposition method, having a diameter of 2 nm, a tube length of 100 μm, a purity of 99.5 wt%, an amorphous carbon impurity <5%, an ash impurity <3 wt%, and a specific surface area of 700 m 2 / g. It is an nanotube.
（１）９〜１２ｇのナノシリコンカーバイドを１０５℃で真空乾燥させ、ナノシリコンカーバイドを３０ｇのＮ、Ｎ−ジメチルホルムアミドに分散させ、３０〜５０℃で１０〜３０分間超音波分散させて溶液Ａを得る工程、
（２）１２〜２２ｇのジフェニルメタンジイソシアネートと１２〜２２ｇのポリ乳酸を４２ｇのＮ、Ｎ−ジメチルホルムアミドに溶解して、溶液Ｂを得る工程、
（３）ナノシルバーと１，５−ナフタレンジスルホン酸を１：２０：５０−６０の比率で５０〜６０℃で１〜２時間撹拌して溶液Ｃを得る工程（前記ナノシルバーの重量はナノシリコンカーバイド重量の１／１００）、
（４）溶液Ｂを溶液Ａに滴下し、次に溶液Ｃを溶液Ａに加え、５０〜７０℃で２〜３時間撹拌して反応させ、フィラーポリマー鎖を得る工程。 The method for preparing a light-resistant aqueous polyurethane coating agent and an adhesive for modifying carbon nanotubes according to claim 1, wherein the preparation of the filler polymer chain includes the following steps (1) to (4).
(1) 9 to 12 g of nanosilicon carbide is vacuum dried at 105 ° C., nanosilicon carbide is dispersed in 30 g of N, N-dimethylformamide, and ultrasonically dispersed at 30 to 50 ° C. for 10 to 30 minutes to solve solution A. The process of getting
(2) A step of dissolving 12 to 22 g of diphenylmethane diisocyanate and 12 to 22 g of polylactic acid in 42 g of N, N-dimethylformamide to obtain a solution B.
(3) A step of stirring nanosilver and 1,5-naphthalenedisulfonic acid at a ratio of 1:20:50-60 at 50-60 ° C. for 1 to 2 hours to obtain a solution C (the weight of the nanosilver is nanosilicon). 1/100 of the carbide weight),
(4) A step of dropping solution B into solution A, then adding solution C to solution A, and stirring and reacting at 50 to 70 ° C. for 2 to 3 hours to obtain a filler polymer chain.
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