JP2010150477A - Polyurethane resin composition and polyurethane resin - Google Patents
Polyurethane resin composition and polyurethane resin Download PDFInfo
- Publication number
- JP2010150477A JP2010150477A JP2008332502A JP2008332502A JP2010150477A JP 2010150477 A JP2010150477 A JP 2010150477A JP 2008332502 A JP2008332502 A JP 2008332502A JP 2008332502 A JP2008332502 A JP 2008332502A JP 2010150477 A JP2010150477 A JP 2010150477A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- resin composition
- castor oil
- diisocyanate
- inorganic filler
- 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
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 75
- 239000011342 resin composition Substances 0.000 title claims abstract description 44
- 239000004359 castor oil Substances 0.000 claims abstract description 26
- 235000019438 castor oil Nutrition 0.000 claims abstract description 26
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 24
- 150000003077 polyols Chemical class 0.000 claims abstract description 24
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 23
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 23
- 239000011256 inorganic filler Substances 0.000 claims abstract description 18
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 13
- -1 phosphate ester Chemical class 0.000 description 19
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- 229940087291 tridecyl alcohol Drugs 0.000 description 6
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 230000017525 heat dissipation Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003230 hygroscopic agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 235000004443 Ricinus communis Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 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
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
- BEWFIPLBFJGWSR-UHFFFAOYSA-N butyl 12-acetyloxyoctadec-9-enoate Chemical compound CCCCCCC(OC(C)=O)CC=CCCCCCCCC(=O)OCCCC BEWFIPLBFJGWSR-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CTJJGIVJOBVMEO-UHFFFAOYSA-N tetraoctyl benzene-1,2,4,5-tetracarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC(C(=O)OCCCCCCCC)=C(C(=O)OCCCCCCCC)C=C1C(=O)OCCCCCCCC CTJJGIVJOBVMEO-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-VBJOUPRGSA-N triricinolein Chemical class CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC)COC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-VBJOUPRGSA-N 0.000 description 1
- YPDXSCXISVYHOB-UHFFFAOYSA-N tris(7-methyloctyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCC(C)C)C(C(=O)OCCCCCCC(C)C)=C1 YPDXSCXISVYHOB-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、ポリウレタン樹脂組成物及びポリウレタン樹脂に関し、より詳細には、粘度低化により十分な混合が可能で、硬化後において優れた放熱性を長期間にわたって維持し得るポリウレタン樹脂組成物、及びこれを硬化させたポリウレタン樹脂に関する。 The present invention relates to a polyurethane resin composition and a polyurethane resin, and more specifically, a polyurethane resin composition that can be sufficiently mixed by reducing viscosity and can maintain excellent heat dissipation after curing for a long period of time, and this Relates to a polyurethane resin obtained by curing
従来より、電子回路基板や電子部品は、外部からの汚染を防ぐためにポリウレタン樹脂等を用いて封止することが行われている（特許文献１）。また、近年、ＬＳＩ等に見られるように、電子回路の集積化、小型化及び高機能化によって電子回路基板上の発熱量が局所的に増大しているため、ポリウレタン樹脂は高温条件下に曝されている。このような高温条件下における硬度変化を低減するために、ポリオール成分としてポリブタジエンポリオールの水素添加物や、ポリイソプレンの水素添加物の使用が検討されている（例えば、特許文献２）。また、発生する熱をより効率的に外部に放出する必要性が高くなっていることから、これらのポリウレタン樹脂には、多量の無機充填材が配合されているのが通常である。 Conventionally, electronic circuit boards and electronic components have been sealed using polyurethane resin or the like in order to prevent external contamination (Patent Document 1). In recent years, as seen in LSIs and the like, the amount of heat generated on an electronic circuit board is locally increased due to the integration, miniaturization, and higher functionality of electronic circuits. Has been. In order to reduce the change in hardness under such high temperature conditions, the use of a hydrogenated polybutadiene polyol or a hydrogenated polyisoprene as a polyol component has been studied (for example, Patent Document 2). Moreover, since the necessity to discharge | release generated heat | fever more efficiently outside is high, it is normal that a large amount of inorganic fillers are mix | blended with these polyurethane resins.
しかしながら、多量の無機充填材を配合したポリウレタン樹脂を製造する場合、硬化前のポリウレタン樹脂組成物の段階で粘度が大きくなるため、十分に混合することができず、均一なポリウレタン樹脂を得ることができなくなるという問題がある。ポリウレタン樹脂組成物の混合が不十分な場合、均一なポリウレタン樹脂を得ることができなくなり、放熱性を長期間にわたって維持することができないという問題がある。
本発明は上記従来技術に鑑みて為されたものであり、本発明の目的は、粘度低下により十分な混合が可能で、硬化後において優れた放熱性と可撓性を長期間にわたって維持し得るポリウレタン樹脂組成物、及びこれを硬化させたポリウレタン樹脂を提供することである。 The present invention has been made in view of the above prior art, and an object of the present invention is that sufficient mixing is possible due to a decrease in viscosity, and excellent heat dissipation and flexibility after curing can be maintained over a long period of time. A polyurethane resin composition and a polyurethane resin obtained by curing the polyurethane resin composition are provided.
本発明のポリウレタン樹脂組成物は、（Ａ）ポリイソシアネートと、（Ｂ）ひまし油系ポリオールの水素添加物と、（Ｃ）無機充填材と、（Ｄ）可塑剤とを含有していることを特徴とする。 The polyurethane resin composition of the present invention contains (A) a polyisocyanate, (B) a hydrogenated castor oil-based polyol, (C) an inorganic filler, and (D) a plasticizer. And
本発明のポリウレタン樹脂組成物では、ポリオール成分として（Ｂ）ひまし油系ポリオールの水素添加物が配合されているため、無機充填材が多量に配合されていても混合時の粘度が増大せず、均一に混合することが可能となっている。 In the polyurethane resin composition of the present invention, since a hydrogenated product of (B) castor oil-based polyol is blended as a polyol component, even when a large amount of inorganic filler is blended, the viscosity at the time of mixing does not increase and is uniform. Can be mixed.
また、本発明のポリウレタン樹脂組成物では、一般式（１）で表される（Ｅ）リン酸エステルを配合してもよい。一般式（１）のリン酸エステルを配合すれば、（Ｃ）無機充填材を高い配合比率で使用した場合にも、比較的低粘度を保ったままポリウレタン組成物を均一に混合することができる。 Moreover, in the polyurethane resin composition of this invention, you may mix | blend (E) phosphate ester represented by General formula (1). If the phosphate ester of the general formula (1) is blended, the polyurethane composition can be uniformly mixed while maintaining a relatively low viscosity even when the inorganic filler (C) is used at a high blending ratio. .
本発明のポリウレタン樹脂は、上記ポリウレタン樹脂組成物を硬化させることにより得られる。 The polyurethane resin of the present invention is obtained by curing the polyurethane resin composition.
本発明のポリウレタン樹脂組成物は、ポリオール成分として（Ｂ）ひまし油系ポリオールの水素添加物を含有しているため、無機充填材が多量に配合されていても混合時の粘度が増大せず、均一に混合することが可能となっている。また、高温条件下における硬度変化が小さいことから長期間にわたって基材に十分密着し、発生する多量の熱を外部に放出することが可能となっている。 Since the polyurethane resin composition of the present invention contains a hydrogenated product of (B) castor oil-based polyol as a polyol component, the viscosity at the time of mixing does not increase even when a large amount of inorganic filler is blended. Can be mixed. In addition, since the change in hardness under high temperature conditions is small, it is possible to sufficiently adhere to the substrate over a long period of time and release a large amount of generated heat to the outside.
本発明のポリウレタン樹脂組成物は、（Ａ）ポリイソシアネートと、（Ｂ）ひまし油系ポリオールの水素添加物との反応によりポリウレタン樹脂を生成する。ここで使用し得る（Ａ）ポリイソシアネートとしては、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネートを挙げることができる。 The polyurethane resin composition of the present invention produces a polyurethane resin by a reaction between (A) polyisocyanate and (B) a hydrogenated product of castor oil-based polyol. Examples of (A) polyisocyanate that can be used here include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate.
脂肪族ポリイソシアネートとしては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２−メチルペンタン−１，５−ジイソシアネート、３−メチルペンタン−１，５−ジイソシアネート等を挙げることができる。 Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 , 5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like.
脂環族ポリイソシアネートとしては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン等を挙げることができる。 Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Can be mentioned.
芳香族ポリイソシアネートとしては、トリレンジイソシアネート、２，２’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、ポリメチレンポリフェニルポリイソシアネート、４，４’−ジベンジルジイソシアネート、１，５−ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート等を挙げることができる。 Aromatic polyisocyanates include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, 4,4′- Examples thereof include dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like.
芳香脂肪族ポリイソシアネートとしては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α，α−テトラメチルキシリレンジイソシアネート等を挙げることができる。 Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate, and the like.
また、これらの有機ポリイソシアネートのカルボジイミド体、アロハネート体、ビューレット体、イソシアヌレート体、アダクト体等の変性体を挙げることができる。尚、これらは、単独で又は２種以上を併用して用いることもできる。 Moreover, modified bodies, such as a carbodiimide body, an allophanate body, a burette body, an isocyanurate body, an adduct body, etc. of these organic polyisocyanates can be mentioned. In addition, these can also be used individually or in combination of 2 or more types.
これらのうち、特に、変色が起こりにくいという観点から、脂肪族ポリイソシアネート及び脂環族ポリイソシアネートが好ましく、ヘキサメチレンジイソシアネート変性イソシアヌレート体、ヘキサメチレンジイソシアネート変性ビューレット体、及びヘキサメチレンジイソシアネート変性アダクト体がより好ましい。 Of these, aliphatic polyisocyanates and alicyclic polyisocyanates are preferable from the viewpoint that discoloration hardly occurs. Hexamethylene diisocyanate-modified isocyanurate, hexamethylene diisocyanate-modified burette, and hexamethylene diisocyanate-modified adduct Is more preferable.
また、本発明においては、上記ポリイソシアネートと特定の構造を有する（Ｂ）ポリオールとをイソシアネート基過剰条件で反応させて得られるウレタンプレポリマーを（Ａ）ポリイソシアネートとして使用してもよい。 Moreover, in this invention, you may use the urethane prepolymer obtained by making the said polyisocyanate and (B) polyol which has a specific structure react on isocyanate group excess conditions as (A) polyisocyanate.
また、本発明のポリウレタン樹脂組成物において、ポリオール成分として使用されるのは、ひまし油系ポリオールの水素添加物である。ここで、ひまし油系ポリオールの水素添加物とは、ひまし油に水素付加した水添ひまし油のほか、ひまし油脂肪酸に水素を付加した水添ひまし油脂肪酸や水添ひまし油を用いて得られる水添ひまし油変性ポリオールが挙げられる。なお、以下、「水添」と記載するものは、「水素添加物」を意味している。 In the polyurethane resin composition of the present invention, a hydrogenated product of castor oil-based polyol is used as the polyol component. Here, the hydrogenated product of castor oil-based polyol includes hydrogenated castor oil hydrogenated to castor oil, hydrogenated castor oil fatty acid obtained by adding hydrogen to castor oil fatty acid, and hydrogenated castor oil-modified polyol obtained using hydrogenated castor oil. Can be mentioned. In the following description, “hydrogenation” means “hydrogenated product”.
水添ひまし油変性ポリオールとしては、例えば、水添ひまし油と水添ひまし油以外の油脂とのエステル交換反応物、水添ひまし油と水添ひまし油脂肪酸を含む水添油脂脂肪酸とのエステル化反応物、水添ひまし油と多価アルコールとのエステル化反応物、水添ひまし油脂肪酸と多価アルコールとのエステル化反応物、水添ひまし油に含まれる水酸基の一部を酢酸などのモノカルボン酸でエステル化した反応生成物などが挙げられる。 Examples of the hydrogenated castor oil-modified polyol include transesterification products of hydrogenated castor oil and fats other than hydrogenated castor oil, esterification products of hydrogenated castor oil and hydrogenated fat fatty acids including hydrogenated castor oil fatty acids, hydrogenated Esterification reaction product of castor oil and polyhydric alcohol, reaction product of hydrogenation castor oil fatty acid and polyhydric alcohol, esterification of a part of hydroxyl groups contained in hydrogenated castor oil with monocarboxylic acid such as acetic acid Such as things.
（Ｂ）ひまし油系ポリオールの水素添加物のヨウ素価は、２０ｇ／１００ｇ以下であることが好ましく、１０ｇ／１００ｇ以下がより好ましい。ヨウ素価が上記範囲より大きいと、高温条件下における硬度上昇が大きくなり、基材に十分密着することができなくなる場合があるからである。 (B) The iodine value of the hydrogenated product of castor oil-based polyol is preferably 20 g / 100 g or less, more preferably 10 g / 100 g or less. This is because if the iodine value is larger than the above range, the increase in hardness under high temperature conditions becomes large, and it may not be possible to sufficiently adhere to the substrate.
本発明のポリウレタン樹脂組成物においては、（Ａ）ポリイソシアネート成分に含まれるイソシアネート基と、（Ｂ）ひまし油系ポリオールの水素添加物に含まれる水酸基の和とのモル比（ＮＣＯ／ＯＨ）が、０．３〜１．１であることが好ましい。イソシアネート基と水酸基のモル比がこの範囲より小さいと、得られる樹脂の耐熱性が低くなり、この範囲より大きいと、樹脂が硬くなり、基材に十分密着できなくなる場合があるからである。 In the polyurethane resin composition of the present invention, the molar ratio (NCO / OH) of (A) the isocyanate group contained in the polyisocyanate component and (B) the sum of the hydroxyl groups contained in the hydrogenated product of castor oil-based polyol, It is preferable that it is 0.3-1.1. This is because if the molar ratio of the isocyanate group to the hydroxyl group is smaller than this range, the resulting resin has low heat resistance, and if it is larger than this range, the resin becomes hard and may not be sufficiently adhered to the substrate.
本発明のポリウレタン樹脂組成物に配合される（Ｃ）無機充填材としては、例えば、酸化アルミニウム、酸化マグネシウムなどの金属酸化物、窒化アルミニウム、窒化ホウ素んなどの金属窒化物、水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物が挙げられる。 Examples of the inorganic filler (C) blended in the polyurethane resin composition of the present invention include metal oxides such as aluminum oxide and magnesium oxide, metal nitrides such as aluminum nitride and boron nitride, aluminum hydroxide, and water. Examples thereof include metal hydroxides such as magnesium oxide.
（Ｃ）無機充填材は、平均粒子径の異なる少なくとも２種類の混合物であることが好ましい。具体的には、（Ｃ１）平均粒子径の最も大きい無機充填材と（Ｃ２）平均粒子径の最も小さい無機充填材との平均粒子径の比（Ｃ１）／（Ｃ２）が、１．５〜１００であることが好ましく、２〜５０であることがより好ましい。上記範囲内とすることにより、ポリオール成分をより低粘度化することができる。 (C) The inorganic filler is preferably at least two kinds of mixtures having different average particle diameters. Specifically, the ratio (C1) / (C2) of the average particle diameter of (C1) the inorganic filler having the largest average particle diameter and (C2) the inorganic filler having the smallest average particle diameter is 1.5 to 100 is preferable, and 2 to 50 is more preferable. By making it within the above range, the viscosity of the polyol component can be further reduced.
さらに、（Ｃ１）平均粒子径の最も大きい無機充填材と（Ｃ２）平均粒子径の最も小さい無機充填材の重量比は、（Ｃ１）／（Ｃ２）＝９９／１〜５０／５０であることが好ましい。 Furthermore, the weight ratio of (C1) the inorganic filler having the largest average particle diameter and (C2) the smallest inorganic filler having the smallest average particle diameter is (C1) / (C2) = 99/1 to 50/50. Is preferred.
（Ｃ）無機充填材の配合量は、ポリウレタン樹脂組成物を１００重量％とした場合に、３０〜９５重量％であることが好ましく、５０〜９５重量％であることがより好ましく、６０〜９５重量％であることが更に好ましく、７０〜９０重量％であることが最も好ましい。（Ｃ）無機充填材の配合量が上記範囲より多いと混合初期粘度が高くなりすぎる傾向にあり、上記範囲より少ないと十分な放熱性が得られにくくなる傾向にある。 (C) The amount of the inorganic filler is preferably 30 to 95% by weight, more preferably 50 to 95% by weight, more preferably 60 to 95, when the polyurethane resin composition is 100% by weight. More preferably, it is 70% by weight, most preferably 70% by weight. When the blending amount of the inorganic filler (C) is larger than the above range, the initial mixing viscosity tends to be too high, and when it is less than the above range, sufficient heat dissipation tends to be difficult to obtain.
本発明のポリウレタン樹脂組成物には、（Ｄ）可塑剤が配合される。可塑剤としては、例えば、ジオクチルフタレート、ジイソノニルフタレート、ジウンデシルフタレートなどのフタル酸ジエステル、ジオクチルアジペート、ジイソノニルアジペートなどのアジピン酸ジエステル、トリオクチルトリメリテート、トリイソノニルトリメリテート、などのトリメリット酸エステル、テトラオクチルピロメリテートなどのピロメリット酸エステル、メチルアセチルリシノレート、ブチルアセチルリシノレート、アセチル化リシノール酸トリグリセリド、アセチル化ポリリシノール酸トリグリセリドなどのひまし油系エステル、トリクレジルホスフェート、トリキシレニルホスフェートなどのリン酸トリエステルが挙げられる。 (D) A plasticizer is mix | blended with the polyurethane resin composition of this invention. As the plasticizer, for example, phthalic acid diesters such as dioctyl phthalate, diisononyl phthalate, diundecyl phthalate, adipic acid diesters such as dioctyl adipate and diisononyl adipate, trioctyl trimellitate, triisononyl trimellitate, etc. Acid esters, pyromellitic acid esters such as tetraoctyl pyromellitate, methylacetylricinoleate, butylacetylricinoleate, acetylated ricinoleic acid triglyceride, castor oil esters such as acetylated polyricinoleic acid triglyceride, tricresyl phosphate, trixylate And phosphoric acid triesters such as nyl phosphate.
上記（Ｄ）可塑剤の配合量は、ポリウレタン樹脂組成物を１００重量％とした場合に、１〜３０重量％であることが好ましく、３〜２０重量％であることがより好ましく、５〜１５重量％であることが更に好ましい。（Ｄ）可塑剤の配合量が上記範囲より少ないと、ポリオール成分の十分な減粘効果と、ポリウレタン樹脂の可撓性が得られ難くなる傾向にあり、上記範囲より多いと、ポリウレタン樹脂の強度などの各種物性が低下する傾向にある。 The blending amount of the plasticizer (D) is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, based on 100% by weight of the polyurethane resin composition, and 5 to 15%. More preferably, it is% by weight. (D) If the blending amount of the plasticizer is less than the above range, a sufficient viscosity reducing effect of the polyol component and the flexibility of the polyurethane resin tend to be difficult to obtain. Various physical properties such as
更に、本発明のポリウレタン樹脂組成物には、一般式（１）で表される（Ｅ）リン酸エステルを配合してもよい。 Furthermore, you may mix | blend (E) phosphate ester represented by General formula (1) with the polyurethane resin composition of this invention.
ここで、Ｒは炭素数１〜３０の炭化水素基、ｍは０〜２０の整数、ｎは１〜２０の整数、Ｒ’はＯＨ又は一般式（２）に示す基であり、一般式（１）及び一般式（２）においてＲ”はＣＨ3又はＣＨ2ＣＨ3であり、「／」はその左右に記載されているオキシアルキレン基がブロック付加でもランダム付加でもよいことを表している。 Here, R is a hydrocarbon group having 1 to 30 carbon atoms, m is an integer of 0 to 20, n is an integer of 1 to 20, and R ′ is OH or a group represented by the general formula (2). In 1) and general formula (2), R ″ is CH 3 or CH 2 CH 3 , and “/” represents that the oxyalkylene groups described on the left and right sides thereof may be block addition or random addition.
この（Ｅ）リン酸エステルは、例えば、炭素数１〜３０のモノアルコールに公知の方法によりアルキレンオキサイドを付加したポリエーテルモノオールと、無水リン酸とを反応させて得ることができる。なお、上記アルキレンオキサイドは、エチレンオキサイドを必須成分とするものであればよく、プロピレンオキサイドやブチレンオキサイドを併用することもできる。更に、アルキレンオキサイドの付加モル数や、ポリエーテルモノオールと無水リン酸との反応割合は、上記一般式（１）の条件を満たすように適宜選択されるものである。 This (E) phosphate ester can be obtained, for example, by reacting a polyether monool obtained by adding an alkylene oxide to a monoalcohol having 1 to 30 carbon atoms by a known method and anhydrous phosphoric acid. In addition, the said alkylene oxide should just have ethylene oxide as an essential component, and can also use propylene oxide and butylene oxide together. Furthermore, the number of added moles of alkylene oxide and the reaction ratio between the polyether monool and phosphoric anhydride are appropriately selected so as to satisfy the condition of the general formula (1).
本発明のポリウレタン樹脂組成物に使用される一般式（１）で表される（Ｅ）リン酸エステルの配合量は、ポリウレタン樹脂組成物を１００重量％とした場合に、０．０１〜２重量％の範囲が好ましく、０．０１〜１重量％の範囲がより好ましい。上記範囲を超えると、使用量の増加による更なる減粘効果は得られ難くなるとともに、ポリウレタン樹脂の物性も低下する傾向が現れ、また、上記範囲未満では、（Ｅ）リン酸エステルの添加による減粘効果が得られない。 The compounding quantity of (E) phosphate ester represented by General formula (1) used for the polyurethane resin composition of this invention is 0.01-2 weight when a polyurethane resin composition is 100 weight%. % Is preferable, and a range of 0.01 to 1% by weight is more preferable. When the above range is exceeded, it is difficult to obtain a further viscosity-reducing effect due to an increase in the amount used, and the physical properties of the polyurethane resin also tend to be reduced, and below the above range, the addition of (E) phosphate ester The effect of reducing viscosity cannot be obtained.
本発明のポリウレタン樹脂組成物には、酸化防止剤、吸湿剤、防黴剤、シランカップリング剤など、必要に応じて各種の添加剤を添加することができる。例えば、酸化防止剤としては、ジブチルヒドロキシトルエン（ＢＨＴ）、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタンなどのフェノール含有酸化防止剤、フェニルジイソデシルホスファイトなどのリン含有酸化防止剤、ジラウリル−３，３’−チオジプロピオン酸エステルなどのイオウ含有酸化防止剤、２，４−ビス（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３’，５’−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジンなどのフェノールとイオウとを一分子中に含有する酸化防止剤などを挙げることができる。酸化防止剤を用いる場合、ポリウレタン樹脂組成物を１００重量％とした場合に、０．０１〜５重量％の範囲で添加することが好ましい。また、吸湿剤としては、ゼオライト、水硬性アルミナ、塩化カルシウムなどを挙げることができる。吸湿剤を用いる場合、ポリウレタン樹脂を１００重量％とした場合に、０．１〜３重量％の範囲で添加することが好ましい。 Various additives such as an antioxidant, a hygroscopic agent, an antifungal agent, and a silane coupling agent can be added to the polyurethane resin composition of the present invention as necessary. For example, as an antioxidant, phenol-containing antioxidants such as dibutylhydroxytoluene (BHT), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, Phosphorus-containing antioxidants such as phenyl diisodecyl phosphite, sulfur-containing antioxidants such as dilauryl-3,3′-thiodipropionic acid ester, 2,4-bis (n-octylthio) -6- (4-hydroxy- An antioxidant containing phenol and sulfur in one molecule such as 3 ′, 5′-di-t-butylanilino) -1,3,5-triazine can be mentioned. When using antioxidant, when a polyurethane resin composition is 100 weight%, it is preferable to add in 0.01-5 weight%. Further, examples of the hygroscopic agent include zeolite, hydraulic alumina, calcium chloride and the like. When using a hygroscopic agent, it is preferable to add in the range of 0.1 to 3% by weight when the polyurethane resin is 100% by weight.
また、本発明のポリウレタン樹脂組成物の調製に際しては、ポリウレタン樹脂の硬化を早めるために触媒を添加してもよい。触媒としては、通常、ポリウレタン樹脂の製造に使用される、金属触媒やアミン系触媒を使用することができる。金属触媒としては、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクテートなどの錫触媒、オクチル酸鉛、オクテン酸鉛、ナフテン酸鉛などの鉛触媒、オクチル酸ビスマス、ネオデカン酸ビスマスなどのビスマス触媒などを挙げることができる。アミン系触媒としては、ジエチレントリアミンなどを挙げることができる。 In preparing the polyurethane resin composition of the present invention, a catalyst may be added in order to accelerate the curing of the polyurethane resin. As the catalyst, a metal catalyst or an amine-based catalyst usually used for producing a polyurethane resin can be used. Metal catalysts include tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin dioctate, lead catalysts such as lead octylate, lead octenoate and lead naphthenate, bismuth catalysts such as bismuth octylate and bismuth neodecanoate, etc. Can be mentioned. Examples of the amine catalyst include diethylenetriamine.
本発明のポリウレタン樹脂組成物は、硬化後のタイプＡによる硬度が８０以下となることが好ましい。更に、硬化後の熱伝導率が１Ｗ／ｍ・Ｋ以上であることが好ましい。 The polyurethane resin composition of the present invention preferably has a hardness of 80 or less according to type A after curing. Furthermore, it is preferable that the heat conductivity after hardening is 1 W / m · K or more.
以下、実施例及び比較例に基づいて、本発明のポリウレタン樹脂組成物及びポリウレタン樹脂について詳細に説明する。なお、本明細書中に於ける「部」、「％」は、特に明示した場合を除き、「重量部」、「重量％」をそれぞれ表している。 Hereinafter, based on an Example and a comparative example, the polyurethane resin composition and polyurethane resin of this invention are demonstrated in detail. In the present specification, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
以下の実施例及び比較例においては、以下の原料を使用した。
・ポリイソシアネート
デュラネートTKA-100（ヘキサメチレンジイソシアネート変性イソシアヌレート体、旭化成社製）
・ひまし油系ポリオールの水素添加物
URIC PH-5001（ヨウ素価：１０ｇ以下／１００ｇ、伊藤製油社製）
HS 2T-1208（ヨウ素価：１０ｇ以下／１００ｇ、豊国製油社製）
HS 2T-166H（ヨウ素価：１０ｇ以下／１００ｇ、豊国製油社製）
・無機充填材
水酸化アルミニウムＡ（平均粒子径：３．２μｍ）
水酸化アルミニウムＢ（平均粒子径：３５μｍ）
酸化アルミニウムＡ（平均粒子径：４５μｍ）
・酸化防止剤
ＢＨＴ（ジブチルヒドロキシトルエン）
・吸湿剤
ゼオラムＡ４（ゼオライト、東ソー社製）
・比較例用のポリオール
エポール（ヨウ素価：７．９ｇ／１００ｇ、ポリイソプレンポリオールの水素添加物、出光興産社製）
KRASOL HLBH P3000（ヨウ素価：１．１ｇ／１００ｇ、ポリブタジエンポリオールの水素添加物、サートマー社製）
ひまし油Ｄ（ひまし油、伊藤製油社製）
また、（Ｅ）リン酸エステル成分については、以下のようにして合成した。
In the following examples and comparative examples, the following raw materials were used.
・ Polyisocyanate Duranate TKA-100 (hexamethylene diisocyanate modified isocyanurate, manufactured by Asahi Kasei)
・ Hydrogenated castor oil polyol
URIC PH-5001 (Iodine value: 10 g or less / 100 g, manufactured by Ito Oil Co., Ltd.)
HS 2T-1208 (Iodine value: 10 g or less / 100 g, manufactured by Toyokuni Oil)
HS 2T-166H (Iodine value: 10 g or less / 100 g, manufactured by Toyokuni Oil)
・ Inorganic filler Aluminum hydroxide A (average particle size: 3.2 μm)
Aluminum hydroxide B (average particle size: 35 μm)
Aluminum oxide A (average particle size: 45 μm)
・ Antioxidant BHT (dibutylhydroxytoluene)
・ Hygroscopic agent Zeolum A4 (Zeolite, manufactured by Tosoh Corporation)
Polyol Epol for Comparative Example (Iodine value: 7.9 g / 100 g, hydrogenated polyisoprene polyol, manufactured by Idemitsu Kosan Co., Ltd.)
KRASOL HLBH P3000 (Iodine value: 1.1 g / 100 g, polybutadiene polyol hydrogenated product, manufactured by Sartomer)
Castor oil D (castor oil, manufactured by Ito Refinery)
The (E) phosphate ester component was synthesized as follows.
（Ｅ−１：リン酸エステル１の合成）
ラウリルアルコールを出発物質とし、プロピレンオキサイド２モルおよびエチレンオキサイド８モルを公知の方法でブロック付加して、ラウリルアルコールのアルキレンオキサイド付加物を得た。
(E-1: Synthesis of phosphate ester 1)
Using lauryl alcohol as a starting material, 2 mol of propylene oxide and 8 mol of ethylene oxide were block-added by a known method to obtain an alkylene oxide adduct of lauryl alcohol.
続いて、四つ口フラスコに、上記ラウリルアルコールのアルキレンオキサイド付加物３００ｇと、無水リン酸２７．１ｇとを、モル比２．４：１にて仕込み、撹拌しながら７０℃にて４時間反応を行い、リン酸エステル１（リン酸のＯＨ基の理論上の置換数１．２）を得た。 Subsequently, 300 g of the above alkylene oxide adduct of lauryl alcohol and 27.1 g of phosphoric anhydride were charged in a four-necked flask at a molar ratio of 2.4: 1 and reacted at 70 ° C. for 4 hours with stirring. To obtain phosphoric acid ester 1 (theoretical substitution number 1.2 of OH group of phosphoric acid).
（Ｅ−２：リン酸エステル２の合成）
トリデシルアルコールを出発物質とし、エチレンオキサイド１０モルを公知の方法を用いて付加して、トリデシルアルコールのアルキレンオキサイド付加物Ａを得た。
(E-2: Synthesis of phosphate ester 2)
Tridecyl alcohol was used as a starting material, and 10 mol of ethylene oxide was added using a known method to obtain an alkylene oxide adduct A of tridecyl alcohol.
続いて、四つ口フラスコに、上記トリデシルアルコールのアルキレンオキサイド付加物Ａの３００ｇと、無水リン酸２２．２ｇとを、モル比３：１にて仕込み、撹拌しながら７０℃にて４時間反応を行い、リン酸エステル２（リン酸のＯＨ基の理論上の置換数１．５）を得た。 Subsequently, 300 g of the above tridecyl alcohol alkylene oxide adduct A and 22.2 g of phosphoric anhydride were charged in a four-necked flask at a molar ratio of 3: 1 and stirred at 70 ° C. for 4 hours. Reaction was carried out to obtain phosphoric acid ester 2 (theoretical substitution number 1.5 of OH group of phosphoric acid).
（Ｅ−３：リン酸エステル３の合成）
トリデシルアルコールを出発物質とし、エチレンオキサイド７モルを公知の方法を用いて付加して、トリデシルアルコールのアルキレンオキサイド付加物Ｂを得た。
(E-3: Synthesis of phosphate ester 3)
Tridecyl alcohol was used as a starting material, and 7 mol of ethylene oxide was added using a known method to obtain an alkylene oxide adduct B of tridecyl alcohol.
続いて、四つ口フラスコに、上記トリデシルアルコールのアルキレンオキサイド付加物Ｂの３００ｇと、無水リン酸２３．３ｇとを、モル比３．６：１にて仕込み、撹拌しながら７０℃にて４時間反応を行い、リン酸エステル３（リン酸のＯＨ基の理論上の置換数１．８）を得た。 Subsequently, 300 g of the above-mentioned alkylene oxide adduct B of tridecyl alcohol and 23.3 g of phosphoric anhydride were charged in a four-necked flask at a molar ratio of 3.6: 1 at 70 ° C. with stirring. Reaction was performed for 4 hours to obtain phosphoric ester 3 (theoretical substitution number of phosphoric acid OH group 1.8).
（ポリウレタン樹脂組成物の製造）
表１に示す配合により、実施例１〜７及び比較例１〜３のポリウレタン樹脂組成物を調製した。調製に際しては、表１に示す成分のうち、（Ａ）ポリイソシアネート成分を除く成分を、混合機（商品名：あわとり練太郎、シンキー社製）を用いて２０００ｒｐｍで３分間混合した後、２５℃に調整した。続いて、この混合物に２５℃に調整したポリイソシアネート成分を加え、同上の混合機を用いて２０００ｒｐｍで１分間混合することにより、各実施例のポリウレタン樹脂組成物を得た。
(Production of polyurethane resin composition)
The polyurethane resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared according to the formulation shown in Table 1. In the preparation, among the components shown in Table 1, (A) the components other than the polyisocyanate component were mixed at 2000 rpm for 3 minutes using a mixer (trade name: Awatori Nertaro, manufactured by Shinky Corp.), then 25 Adjusted to ° C. Then, the polyisocyanate component adjusted to 25 degreeC was added to this mixture, and the polyurethane resin composition of each Example was obtained by mixing for 1 minute at 2000 rpm using the mixer same as the above.
（ポリウレタン樹脂の製造）
次に、上記で調製したポリウレタン樹脂組成物を用いてポリウレタン樹脂の試験片を作製した。まず、上記ポリウレタン樹脂組成物を１１０×１１０×１０ｍｍの金型に充填し、蓋をして２３℃で４８時間養生した後、これを脱型してポリウレタン樹脂の試験片を得た。但し、比較例１及び２のポリウレタン樹脂組成物の場合は、高粘度のため、均一なポリウレタン樹脂が得ることができなかった。
(Manufacture of polyurethane resin)
Next, a polyurethane resin test piece was prepared using the polyurethane resin composition prepared above. First, the polyurethane resin composition was filled in a 110 × 110 × 10 mm mold, capped and cured at 23 ° C. for 48 hours, and then demolded to obtain a polyurethane resin test piece. However, in the case of the polyurethane resin compositions of Comparative Examples 1 and 2, a uniform polyurethane resin could not be obtained due to high viscosity.
＜性能試験＞
上記で得られた実施例１〜７及び比較例１〜３について、組成物調製時の混合初期の重合粘度の測定を行い、実施例１〜７及び脱型が可能であった比較例３の樹脂については、更に熱伝導率、硬度（タイプＡ）、耐熱性試験後の硬度(タイプＡ)の評価を行った。各試験結果を表１に併せて示した。各試験方法は、以下に示すとおりである。
<Performance test>
For Examples 1 to 7 and Comparative Examples 1 to 3 obtained above, the polymerization viscosity at the beginning of mixing at the time of preparing the composition was measured, and Examples 1 to 7 and Comparative Example 3 in which demolding was possible. The resin was further evaluated for thermal conductivity, hardness (type A), and hardness after heat resistance test (type A). The test results are also shown in Table 1. Each test method is as follows.
（混合初期粘度）
得られたポリウレタン樹脂組成物を２５℃に調整し、混合開始から１０分後の粘度をＢＨ型粘度計を用いて測定した。
(Initial mixing viscosity)
The obtained polyurethane resin composition was adjusted to 25 ° C., and the viscosity 10 minutes after the start of mixing was measured using a BH viscometer.
（熱伝導率）
熱伝導率は、ＪＩＳ Ｒ２６１８に従い、熱伝導率計（京都電子工業（株）製、ＱＴＭ−Ｄ３）を用いて測定した。
(Thermal conductivity)
The thermal conductivity was measured according to JIS R2618 using a thermal conductivity meter (manufactured by Kyoto Electronics Industry Co., Ltd., QTM-D3).
（硬度（タイプＡ））
ＪＩＳ Ｋ６２５３に従って測定した。
(Hardness (Type A))
It measured according to JIS K6253.
（耐熱性試験後の硬度(タイプＡ)）
１５０℃の条件下に９０時間の耐熱性試験を行った後のポリウレタン樹脂について、ＪＩＳ Ｋ６２５３に従って硬度（タイプＡ）を測定した。
(Hardness after heat resistance test (Type A))
The hardness (type A) was measured according to JIS K6253 for the polyurethane resin after performing a heat resistance test for 90 hours under the condition of 150 ° C.
＜試験結果＞
実施例１〜７のポリウレタン樹脂組成物は、何れも混合可能な粘度であった。特に、リン酸エステルを配合した場合には、より低粘度となった。一方、比較例３のポリウレタン樹脂組成物は混合可能な粘度ではあったが、比較例１及び２の組成物は粘度が非常に高く、混合か不可能となり、均一なポリウレタン樹脂を得ることができなかった。
<Test results>
The polyurethane resin compositions of Examples 1 to 7 all had a mixable viscosity. In particular, when a phosphate ester was blended, the viscosity became lower. On the other hand, the polyurethane resin composition of Comparative Example 3 had a viscosity that could be mixed, but the compositions of Comparative Examples 1 and 2 had a very high viscosity, making mixing impossible, and a uniform polyurethane resin could be obtained. There wasn't.
また、実施例１〜７のポリウレタン樹脂は、何れも熱伝導率が高く、十分な放熱性を有していることが分かる。 In addition, it can be seen that the polyurethane resins of Examples 1 to 7 all have high heat conductivity and sufficient heat dissipation.
更に、実施例１〜７のポリウレタン樹脂は、耐熱性試験後においても硬度がほとんど変化しておらず、耐熱性に優れていることが分かる。一方、比較例３のポリウレタン樹脂は、耐熱性試験後において大幅な硬度上昇が見られることが分かる。 Furthermore, it can be seen that the polyurethane resins of Examples 1 to 7 have almost no change in hardness even after the heat resistance test and are excellent in heat resistance. On the other hand, it can be seen that the polyurethane resin of Comparative Example 3 shows a significant increase in hardness after the heat resistance test.
本発明のポリウレタン樹脂組成物は、低粘度で十分な混合が可能であり、高温条件下における硬度変化が小さいことから長期間にわたって基材に十分密着し、発生する多量の熱を外部に放出し得るポリウレタン樹脂が得られるので、電気製品、電子部品等の分野で利用が可能である。 The polyurethane resin composition of the present invention has a low viscosity and can be sufficiently mixed. Since the change in hardness under high temperature conditions is small, the polyurethane resin composition sufficiently adheres to the substrate over a long period of time and releases a large amount of generated heat to the outside. Since the obtained polyurethane resin is obtained, it can be used in the fields of electrical products, electronic parts and the like.
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| JP2016216566A (en) * | 2015-05-18 | 2016-12-22 | サンユレック株式会社 | Polyurethane resin composition |
| WO2019107199A1 (en) * | 2017-11-28 | 2019-06-06 | 株式会社デンソー | Curable resin composition and electrical component using this |
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| JPS57190013A (en) * | 1981-05-18 | 1982-11-22 | Sumitomo Chem Co Ltd | Thixotropic polyurethane composition |
| JPS57192459A (en) * | 1981-05-22 | 1982-11-26 | Sumitomo Chem Co Ltd | Inflammable and thixotropic polyurethane composition |
| JPS60245609A (en) * | 1984-05-18 | 1985-12-05 | Kyowa Gas Chem Ind Co Ltd | Curable composition of improved flow |
| JPS6315876A (en) * | 1986-07-05 | 1988-01-22 | Mitsui Toatsu Chem Inc | One-pack urethane sealant composition |
| JPH07101762A (en) * | 1993-10-01 | 1995-04-18 | Takemoto Oil & Fat Co Ltd | Fluidity imparting method to polymer mortar or polymer concrete |
| JP2002037835A (en) * | 2000-07-21 | 2002-02-06 | Asahi Kasei Corp | Polyisocyanate composition having excellent thixotropy |
| JP2003034710A (en) * | 2001-07-25 | 2003-02-07 | Asahi Kasei Corp | Acrylic polyisocyanate composition and sealing material containing the same |
| JP2011051093A (en) * | 2008-05-26 | 2011-03-17 | Sakura Color Products Corp | Eraser |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016216566A (en) * | 2015-05-18 | 2016-12-22 | サンユレック株式会社 | Polyurethane resin composition |
| WO2019107199A1 (en) * | 2017-11-28 | 2019-06-06 | 株式会社デンソー | Curable resin composition and electrical component using this |
| JP2019099595A (en) * | 2017-11-28 | 2019-06-24 | 株式会社デンソー | Curable resin composition and electrical component using the same |
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