JP2020519712A - 反応性紫外線吸収剤およびその適用 - Google Patents
反応性紫外線吸収剤およびその適用 Download PDFInfo
- Publication number
- JP2020519712A JP2020519712A JP2019560212A JP2019560212A JP2020519712A JP 2020519712 A JP2020519712 A JP 2020519712A JP 2019560212 A JP2019560212 A JP 2019560212A JP 2019560212 A JP2019560212 A JP 2019560212A JP 2020519712 A JP2020519712 A JP 2020519712A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane
- reactive
- absorber
- component
- 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.)
- Granted
Links
- 239000006096 absorbing agent Substances 0.000 title claims abstract description 78
- 239000004814 polyurethane Substances 0.000 claims abstract description 107
- 229920002635 polyurethane Polymers 0.000 claims abstract description 106
- 239000000203 mixture Substances 0.000 claims description 30
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 25
- 229920005862 polyol Polymers 0.000 claims description 22
- 150000003077 polyols Chemical class 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 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 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- -1 compatibilizer Substances 0.000 claims description 8
- 230000009931 harmful effect Effects 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000006261 foam material Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 239000000565 sealant Substances 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000006078 metal deactivator Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- 230000000655 anti-hydrolysis Effects 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 230000001627 detrimental effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000010586 diagram Methods 0.000 abstract 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 38
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 38
- 239000000463 material Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000032683 aging Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000006750 UV protection Effects 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OYGYNUPKLMDVHM-UHFFFAOYSA-N 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(N2N=C3C=CC=CC3=N2)=C1O OYGYNUPKLMDVHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- SQUPNRHBFGTRBB-UHFFFAOYSA-N CCC(CC)(CN=O)COC(CCc(cc1C(C)(C)C)cc(-[n]2nc(C=CC(C3)[AlH2])c3n2)c1N=O)=O Chemical compound CCC(CC)(CN=O)COC(CCc(cc1C(C)(C)C)cc(-[n]2nc(C=CC(C3)[AlH2])c3n2)c1N=O)=O SQUPNRHBFGTRBB-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 229920000562 Poly(ethylene adipate) Polymers 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/329—Hydroxyamines containing aromatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7692—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing at least one isocyanate or isothiocyanate group linked to an aromatic ring by means of an aliphatic group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
(a)ポリオール;
(b)ポリイソシアネート;および
(c)前述の反応性紫外線吸収剤、
を含み、成分(a)、成分(b)および成分(c)の総重量に基づいて、反応性紫外線吸収剤の量が約0.1重量%〜約50重量%、例えば約0.5重量%〜約10重量%である。
ベンゾトリアゾール化合物は、簡単な方法で合成できることが研究から見出されている。ベンゾトリアゾール化合物は少なくとも以下の利点を有する: 化合物が良好な耐加水分解性を有し、耐加水分解性反応性紫外線吸収剤として使用することができるようなポリオールの形態である; 化合物はアルカリ性であり、ポリウレタンの主成分であるアルコールおよびポリオールに優れた溶解性を有する。これらの特性のために、ポリウレタン用途における紫外線吸収剤であるのに特に適しており; 最後に、化合物は良好な熱安定性を有し、優れた紫外線耐性効果を提供することができる。
上述のように、本発明の反応性紫外線吸収剤は、ポリウレタン材料における使用に特に適している。したがって、(a)ポリオール、(b)ポリイソシアネート、(c)本発明の反応性紫外線吸収剤を含み、成分(a)と成分(b)がポリウレタンを形成するための主要成分であり、成分(c)が紫外線の有害な影響に抗する能力をポリウレタンに与える成分である、ポリウレタン前駆体組成物をも本発明は提供する。
本発明のポリウレタン前駆体組成物は例えば、溶融重合または溶液重合によってポリウレタン材料を形成するために使用することができる。以下の実施例で確認されるように、本発明のポリウレタン材料は成分(c)が関与する反応によって形成される部分を含むという事実により、優れた安定性を有する。本発明のポリウレタン材料は、常温常圧で長期間保存しても、紫外線吸収剤の沈殿やブルーミングの問題がない。また、本発明のポリウレタン材料は、紫外線耐性に優れる。重合を用いて本発明のポリウレタンを調製するために、当業者は重合を完了するために、それらの一般的な技術知識および本明細書の説明に頼ることができる。重合の関連する例は、以下の実施例において提供され、ここでは記載されない。
調製例1: 反応性紫外線吸収剤Iの合成
1Lの三つ口フラスコを準備し、3―(2H―ベンゾトリアゾール―2―イル)―5―(1,1―ジメチルエチル)―4―ヒドロキシ―ベンゼンプロパン酸(CAS#84268―36―0)を106g、トリメチロールプロパン(CAS#77―99―6)を162g、p―トルエンスルホン酸(PTSA,CAS#104―15―4)を1.0g、およびトルエン500gを室温で順次添加し、均一に撹拌した。混合物を110度に加熱し、3時間還流して水を除去し、反応させた。高速液体クロマトグラフィー(HPLC)によって反応が完了したことを確認した後、反応生成物を300gおよび200gの純水でそれぞれ1回抽出した。有機層を集め、冷却し、濾過して固体生成物を集めた。固体生成物を90℃〜100℃で乾燥させて、式I(式中、R1はH)の構造を有する反応性紫外線吸収剤Iを得た。収率は80%と計算された。反応性紫外線吸収剤Iを核磁気共鳴分析に供したところ、次の結果が得られた:
1H NMR (CDCl3, 500MHz)δ= 11.80(s, 1H), 8.13(d, J = 2.5Hz, 1H), 7.92〜7.94(m, 2H), 7.48〜7.50(m, 2H), 7.21(d, J = 2.5Hz, 1H), 4.22(s, 2H), 3.48〜3.53(m, 4H), 3.01(t, J = 7.5Hz, 2H), 2.77(t, J = 7.5Hz, 2H), 2.72(t, J = 6.0Hz, 2H), 1.64(s, 9H), 1.20〜1.23(m, 2H), 0.81(t, J = 8.0Hz, 3H)13C NMR(d6−DMSO, 75.5MHz)δ= 7.3, 21.6, 29.3, 29.7, 35.0, 35.1, 42.4, 60.9, 64.2, 117.6, 119.4, 125.6, 128.0, 131.4, 138.6, 142.5, 146.6, 172.2
3―(2H―ベンゾトリアゾール―2―イル)―5―(1,1―ジメチルエチル)―4―ヒドロキシ―ベンゼンプロパン酸が3―(5―クロロ―2H―ベンゾトリアゾール―2―イル)―5―(1,1―ジメチルエチル) ―4―ヒドロキシ―ベンゼンプロパン酸(CAS#83573―67―5)128gに置換されたことを除いて、式1(R1がCl)の構造を持つ反応性紫外線吸収剤IIを調製するために、反応性紫外線吸収剤Iの合成工程が繰り返された。反応性紫外線吸収剤IIの収率は82%であった。反応性紫外線吸収剤IIを核磁気共鳴分析に供したところ、次の結果が得られた:
1H NMR (CDCl3, 300MHz)δ= 11.56(s, 1H), 8.09(d, J = 2.1Hz, 1H), 7.86〜7.93(m, 2H), 7.44(dd, J = 1.8, 9.0Hz, 1H), 7.22(d, J = 2.1Hz, 1H), 4.22(s, 2H), 3.44〜3.56(m, 4H), 3.01(t, J = 7.5Hz, 2H), 2.76(t, J = 7.5Hz, 2H), 2.65(t, J = 6.0Hz, 2H), 1.49(s, 9H), 1.18〜1.25(m, 2H), 0.84(t, J = 8.1Hz, 3H)
反応性紫外線吸収剤Iおよび下記式Aで表される比較反応性紫外線吸収剤A(特許文献3に開示されている式(IIIa)を有する反応性紫外線吸収剤の実施形態)を、100mlの溶媒にグラム単位でそれぞれ別々に添加し、次いで十分に撹拌し、振動させた。添加した反応性紫外線吸収剤が溶解しなくなるまで、目視検査下で反応性紫外線吸収剤の溶解を観察した。本発明の反応性紫外線吸収剤Iの溶解度と比較反応性紫外線吸収剤Aの溶解度とを異なる溶媒について比較し、その結果を以下の表1に示す。
本発明の反応性紫外線吸収剤I、比較反応性紫外線吸収剤A、および下記式Bで表される比較反応性紫外線吸収剤B(特許文献3に開示されている式(IIIb)を有する反応性紫外線吸収剤の一実施形態)を各2gずつ10mlのジメチルホルムアミド(DMF)に溶解し、得られたジメチルホルムアミド溶液を150℃で3時間熱処理した。溶液のガードナー色スケールを比色計(Lovibond PFXi―195)によって測定した。熱処理前後の色(デルタ色)の変化を計算し、その結果を下記表2に示す。
[熱可塑性ポリウレタンA:紫外線吸収剤を添加しない]
PEBA2000(Headway Groupから入手可能; OH値56.1)を133.5g、1,4―ブチレングリコールを16.5g、およびジブチルスズジラウレート200ppmを反応ポットに添加し、110℃に加熱した。さらに、メチレンジフェニルジイソシアネート(MDI) 66.8gを110℃に予熱し、反応ポットに添加し、反応のために3分間撹拌した。反応が完了した後、熱可塑性ポリウレタン(TPU)プラスチックブロックが得られた。このプラスチックブロックを反応ポットから注ぎ出し、熱いうちに平板にプレスし、オーブンに入れて70℃で24時間焼成し、対照群の熱可塑性ポリウレタンAを得た。
熱可塑性ポリウレタンAの調製方法を繰り返して熱可塑性ポリウレタンB1を調製し、約1重量%の反応性紫外線吸収剤Iを含む熱可塑性ポリウレタンB1を得たが、ただし、MDIの量を63.8gに調整し、反応性紫外線吸収剤Iを2.2g添加して反応させた。
熱可塑性ポリウレタンAの調製方法を繰り返し、熱可塑性ポリウレタンB2を調製し、約5重量%の反応性紫外線吸収剤Iを含有する熱可塑性ポリウレタンB2を得たが、ただし、MDIの量を68.5gに調整し、反応性紫外線吸収剤Iの量を11.0gに調整した。
熱可塑性ポリウレタンAを80℃で1時間保持した後、熱可塑性ポリウレタンAと非反応性紫外線吸収剤Chiguard 234とを重量比99:1で混合した。混合物をブラベンダープラストグラフに入れ、175℃、回転速度100rpmで2分間混合した後、放出して熱可塑性ポリウレタンC1配合物を得た。20gの混合熱可塑性ポリウレタンC1配合物を、ホットプレス成形機(Long Chang Mechanical Industrial Co., LTD.から入手可能)に載せ、80kg/cm2の圧力および185℃の温度で1.5分間ホットプレスした。その後、ホットプレス成形された熱可塑性ポリウレタンC1をコールドプレス機に載せ、50kg/cm2の圧力で5〜10分間冷却し、金型(14cm×14cm×0.07cmの大きさ)にプレスして、1重量%の非反応性紫外線吸収剤を含有する熱可塑性ポリウレタンC1のサンプルを得た。
熱可塑性ポリウレタンC1のサンプルを調製するための方法を繰り返して、熱可塑性ポリウレタンC2のサンプルを調製したが、ただし、非反応性紫外線吸収剤を2重量%含有する熱可塑性ポリウレタンC2のサンプルを得るために、熱可塑性ポリウレタンAと非反応性紫外線吸収剤Chiguard 234の重量比を98:2に調整した。
[水性ポリウレタンA:紫外線吸収剤を添加しない]
イソホロンジイソシアネート(IPDI) 66g、ポリテトラヒドロフラングリコール(Mw=2000) 98g、ポリ(エチレンアジペート)グリコール(Mw=2000) 98g、2,2―ジメチロールプロピオン酸(DMPA) 18g、アセトン100g、およびジブチルスズジラウレート触媒200ppmを反応フラスコに入れた。55℃で5時間反応させた後、トリエチルアミン13gと水507gを加え、激しく撹拌した。その後、エチレンジアミン3.5gを連鎖延長剤として添加した。最後に、減圧蒸留を行ってアセトンを除去し、水性ポリウレタンAを得た。
水性ポリウレタンAの調製方法を繰り返し、水性ポリウレタンB1を得たが、ただし、紫外線吸収剤Iを1.4gさらに添加して反応させ、ポリウレタン成分に対して約0.5重量%の反応性紫外線吸収剤Iを含有する水性ポリウレタンB1を得た。
水性ポリウレタンAの調製方法を繰り返して水性ポリウレタンB2を調製したが、ただし、DMPAの量を16.6gに調整し、反応性紫外線吸収剤Iを2.8g添加して反応させ、ポリウレタン成分に対して約1重量%の反応性紫外線吸収剤Iを含有する水性ポリウレタンB2を得た。
水性ポリウレタンAを280.4gおよび1gの非反応性紫外線吸収剤Chiguard 5530を混合し、均一に撹拌して、ポリウレタン成分に基づいて約1重量%の非反応性紫外線吸収剤を含有する水性ポリウレタンCを調製した。
Claims (10)
- (a)ポリオール;
(b)ポリイソシアネート;および
(c)請求項1に記載の反応性紫外線吸収剤、
を含み、前記反応性紫外線吸収剤の量が、成分(a)、成分(b)および成分(c)の総重量に基づいて約0.1重量%〜約50重量%であるポリウレタン前駆体組成物。 - 前記反応性紫外線吸収剤の量が、成分(a)、成分(b)および成分(c)の総重量に基づいて約0.5重量%〜約10重量%である請求項2に記載のポリウレタン前駆体組成物。
- ポリオールが、エチレングリコール、1,2―プロピレングリコール、1,3―プロピレングリコール、1,2―ブチレングリコール、1,3―ブチレングリコール、1,4―ブチレングリコール、グリセロール、トリメチロールプロパン、ペンタエリトリトール、ポリカーボネートポリオール、ポリアクリレートポリオール、ポリエーテルポリオール、ポリエステルポリオール、およびこれらの組み合わせからなる群から選択される請求項2に記載のポリウレタン前駆体組成物。
- 前記ポリイソシアネートが、トルエンジイソシアネート(TDI)、メチレンジフェニルジイソシアネート(MDI)、ヘキサメチレンジイソシアネート(HDI)、シクロヘキシルジイソシアネート(CHDI)、テトラメチルキシレンジイソシアネート(TMXDI)、水素化m―キシリレンジイソシアネート(H6XDI)、イソホロンジイソシアネート(IPDI)、ジシクロヘキシルメタン4,4' ―ジイソシアネート(HMDI)、ビウレット、ダイマーおよびトリマー、ならびにこれらのプレポリマーからなる群より選択される請求項2に記載のポリウレタン前駆体組成物。
- 溶媒、触媒、酸化防止剤、充填剤、相溶化剤、難燃剤、熱安定剤、光安定剤、金属不活性化剤、可塑剤、潤滑剤、乳化剤、染料、顔料、光沢剤、帯電防止剤、発泡剤、連鎖延長剤、加水分解防止剤、界面活性剤、架橋剤、光開始剤、pH調節剤、接着促進剤、殺菌剤、およびこれらの組み合わせからなる群から選択される成分をさらに含む請求項2〜5のいずれか1項に記載のポリウレタン前駆体組成物。
- 連鎖延長剤が、ジメチロールプロピオン酸(DMPA)、ジメチロールブタン酸(DMBA)、およびこれらの組み合わせからなる群から選択される親水性型連鎖延長剤である請求項6に記載のポリウレタン前駆体組成物。
- 請求項2〜7のいずれか1項に記載のポリウレン前駆体組成物を重合反応にかけることによって調製される紫外線の有害な影響に抗するポリウレタン。
- 請求項8に記載のポリウレタンを含み、繊維、塗料、エラストマー、発泡材料、接着剤またはシール剤の形成で提供されるポリウレタン製品。
- 請求項8に記載のポリウレタンを使用することを含む紫外線の有害な影響に抗する方法。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2017/092254 WO2019006750A1 (zh) | 2017-07-07 | 2017-07-07 | 反应型紫外光吸收剂及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2020519712A true JP2020519712A (ja) | 2020-07-02 |
JP6843269B2 JP6843269B2 (ja) | 2021-03-17 |
Family
ID=64950483
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019560212A Active JP6843269B2 (ja) | 2017-07-07 | 2017-07-07 | 反応性紫外線吸収剤およびその適用 |
Country Status (8)
Country | Link |
---|---|
US (1) | US10717714B2 (ja) |
EP (1) | EP3650445B1 (ja) |
JP (1) | JP6843269B2 (ja) |
KR (1) | KR102291750B1 (ja) |
CN (1) | CN110799502B (ja) |
CA (1) | CA3062853C (ja) |
ES (1) | ES2945327T3 (ja) |
WO (1) | WO2019006750A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109912771B (zh) * | 2019-03-20 | 2021-10-12 | 浙江华峰热塑性聚氨酯有限公司 | 低析出长效耐黄变热塑性聚氨酯弹性体及其制备方法 |
CN112552250B (zh) * | 2020-12-14 | 2022-04-29 | 天津利安隆新材料股份有限公司 | 反应型苯并三氮唑类化合物、其应用及包括其的高分子聚合物材料 |
CN113897121B (zh) * | 2021-10-18 | 2022-08-09 | 上海昶瀚科技有限公司 | 一种耐黄变自修复涂层组合物、汽车漆面保护膜及其制备方法 |
WO2023213785A1 (en) * | 2022-05-06 | 2023-11-09 | Basf Se | Uv light stabilizers |
CN115141555B (zh) * | 2022-08-05 | 2023-11-03 | 常州百佳年代薄膜科技股份有限公司 | 可回收可剥离的光伏胶膜 |
WO2024103246A1 (zh) * | 2022-11-15 | 2024-05-23 | 奇钛科技股份有限公司 | 聚合物结构体及其应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63222885A (ja) * | 1987-02-18 | 1988-09-16 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | インキ−ジェット印刷用記録材料のための光安定剤としての特定のベンゾトリアゾール誘導体の使用方法 |
CN104610179A (zh) * | 2015-02-05 | 2015-05-13 | 天津大学 | 一种苯并三唑类紫外线吸收剂的连续合成方法 |
WO2016021664A1 (ja) * | 2014-08-05 | 2016-02-11 | ミヨシ油脂株式会社 | マトリックスに紫外線吸収能及び/又は高屈折率を付与するための添加剤とそれを用いた樹脂部材 |
CN106083749A (zh) * | 2016-05-31 | 2016-11-09 | 启东金美化学有限公司 | 一种苯并三唑类紫外线吸收剂的制备方法 |
CN109912771A (zh) * | 2019-03-20 | 2019-06-21 | 浙江华峰热塑性聚氨酯有限公司 | 低析出长效耐黄变热塑性聚氨酯弹性体及其制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3264154D1 (en) * | 1981-01-23 | 1985-07-25 | Ciba Geigy Ag | 2-(2-hydroxyphenyl)-benzotriazoles, their use as ultraviolet stabilizers and their preparation |
US4853471A (en) | 1981-01-23 | 1989-08-01 | Ciba-Geigy Corporation | 2-(2-Hydroxyphenyl)-benztriazoles, their use as UV-absorbers and their preparation |
US5459222A (en) * | 1993-06-04 | 1995-10-17 | Ciba-Geigy Corporation | UV-absorbing polyurethanes and polyesters |
KR970010024B1 (ko) * | 1994-08-22 | 1997-06-20 | 한국과학기술연구원 | 기능 블럭도를 이용한 연속 공정 제어 알고리즘 생성 방법 및 장치 |
IN1997CH00157A (ja) * | 1996-10-01 | 2006-06-09 | Recticel | |
US7381762B2 (en) | 2004-08-20 | 2008-06-03 | Milliken & Company | Ultraviolet light (UV) absorbing compounds and compositions containing UV absorbing compounds |
-
2017
- 2017-07-07 US US16/609,901 patent/US10717714B2/en active Active
- 2017-07-07 ES ES17916744T patent/ES2945327T3/es active Active
- 2017-07-07 EP EP17916744.0A patent/EP3650445B1/en active Active
- 2017-07-07 CN CN201780089426.0A patent/CN110799502B/zh active Active
- 2017-07-07 KR KR1020197032356A patent/KR102291750B1/ko active IP Right Grant
- 2017-07-07 WO PCT/CN2017/092254 patent/WO2019006750A1/zh unknown
- 2017-07-07 JP JP2019560212A patent/JP6843269B2/ja active Active
- 2017-07-07 CA CA3062853A patent/CA3062853C/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63222885A (ja) * | 1987-02-18 | 1988-09-16 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | インキ−ジェット印刷用記録材料のための光安定剤としての特定のベンゾトリアゾール誘導体の使用方法 |
WO2016021664A1 (ja) * | 2014-08-05 | 2016-02-11 | ミヨシ油脂株式会社 | マトリックスに紫外線吸収能及び/又は高屈折率を付与するための添加剤とそれを用いた樹脂部材 |
CN104610179A (zh) * | 2015-02-05 | 2015-05-13 | 天津大学 | 一种苯并三唑类紫外线吸收剂的连续合成方法 |
CN106083749A (zh) * | 2016-05-31 | 2016-11-09 | 启东金美化学有限公司 | 一种苯并三唑类紫外线吸收剂的制备方法 |
CN109912771A (zh) * | 2019-03-20 | 2019-06-21 | 浙江华峰热塑性聚氨酯有限公司 | 低析出长效耐黄变热塑性聚氨酯弹性体及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR102291750B1 (ko) | 2021-08-23 |
WO2019006750A1 (zh) | 2019-01-10 |
CN110799502B (zh) | 2022-12-30 |
US20200199084A1 (en) | 2020-06-25 |
EP3650445A4 (en) | 2021-01-13 |
CN110799502A (zh) | 2020-02-14 |
JP6843269B2 (ja) | 2021-03-17 |
CA3062853C (en) | 2021-06-08 |
ES2945327T3 (es) | 2023-06-30 |
US10717714B2 (en) | 2020-07-21 |
EP3650445A1 (en) | 2020-05-13 |
KR20200008999A (ko) | 2020-01-29 |
CA3062853A1 (en) | 2019-11-29 |
EP3650445B1 (en) | 2023-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102291750B1 (ko) | 반응성 자외선 흡수제 및 이의 적용 | |
RU2440376C9 (ru) | Полиуретанмочевина и способ ее получения | |
JP6533577B2 (ja) | ポリウレタンゲルおよびその製造方法 | |
CN109134802B (zh) | 一种含磷无卤阻燃热塑性聚氨酯弹性体组合物及其制备方法和用途 | |
CN111065666B (zh) | 聚氨酯树脂、成型品、及聚氨酯树脂的制造方法 | |
KR20130092383A (ko) | 폴리카보네이트디올 및 그 제조법, 그리고 그것을 사용한 폴리우레탄 및 활성 에너지선 경화성 중합체 조성물 | |
EP3022244B2 (en) | Isocyanate prepolymer composition and crosslinked polyurethane prepared therefrom | |
TW202112890A (zh) | 聚醚聚碳酸酯二醇及其製造方法 | |
KR20080112272A (ko) | 성형 폴리우레탄 부재와 이것의 제조 방법 및 용도 | |
JP6341062B2 (ja) | ポリカーボネートジオールおよびそれを用いたポリウレタン並びにウレタン(メタ)アクリレート | |
BR112020017350A2 (pt) | Composição de poliuretano termoplástico, artigo com conjunto de compressão reduzido, e, método para reduzir o conjunto de compressão de um poliuretano termoplástico | |
JPH047327A (ja) | 脂肪族コポリカーボネート及び該単位を含有するポリウレタン | |
JP5071958B2 (ja) | 水性ポリウレタン組成物 | |
JP6329457B2 (ja) | コポリカーボネートジオール、熱可塑性ポリウレタン、コーティング組成物及び塗膜 | |
TWI638039B (zh) | 反應型紫外光吸收劑及其應用 | |
HU226701B1 (en) | Reactive binding agent with an extended pot life | |
JP5386142B2 (ja) | ポリウレタンエラストマーおよび成形品 | |
JP5997665B2 (ja) | 熱硬化性ポリウレタンウレア樹脂組成物および成形品 | |
KR20200088371A (ko) | 내화학성 및 내오염성 열가소성 폴리우레탄 조성물 | |
TW202204463A (zh) | 活性能量射線硬化性聚胺基甲酸酯樹脂、硬化性樹脂組成物及活性能量射線硬化性聚胺基甲酸酯樹脂之製造方法 | |
JPH10130357A (ja) | 熱可塑性ポリウレタン組成物およびその製造方法 | |
JP2019044003A (ja) | 二液硬化型ウレタン樹脂組成物及びフィルム成形品 | |
JP7057858B1 (ja) | ポリウレタン樹脂の製造方法、および、ポリウレタン樹脂 | |
WO2023153397A1 (ja) | プレポリマー組成物、ポリウレタン樹脂、弾性成形品およびプレポリマー組成物の製造方法 | |
WO2023153398A1 (ja) | プレポリマー組成物、ポリウレタン樹脂、弾性成形品およびプレポリマー組成物の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191031 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191031 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200828 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200911 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210203 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210222 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6843269 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |