WO2022244650A1 - Isocyanate-containing composition and two-part reaction type polyurethane resin composition - Google Patents
Isocyanate-containing composition and two-part reaction type polyurethane resin composition Download PDFInfo
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- WO2022244650A1 WO2022244650A1 PCT/JP2022/019775 JP2022019775W WO2022244650A1 WO 2022244650 A1 WO2022244650 A1 WO 2022244650A1 JP 2022019775 W JP2022019775 W JP 2022019775W WO 2022244650 A1 WO2022244650 A1 WO 2022244650A1
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- WIPO (PCT)
- Prior art keywords
- group
- isocyanate
- containing composition
- general formula
- polyol
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 105
- 239000012948 isocyanate Substances 0.000 title claims abstract description 73
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 73
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 33
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- 238000006757 chemical reactions by type Methods 0.000 title abstract 2
- 150000003077 polyols Chemical class 0.000 claims abstract description 84
- 229920005862 polyol Polymers 0.000 claims abstract description 81
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 38
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 38
- 239000011256 inorganic filler Substances 0.000 claims abstract description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 30
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000000524 functional group Chemical group 0.000 claims abstract description 19
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 phthalate diester Chemical class 0.000 claims description 72
- 239000004014 plasticizer Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 11
- 125000006353 oxyethylene group Chemical group 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 230000017525 heat dissipation Effects 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 15
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 14
- 239000005062 Polybutadiene Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 229920002857 polybutadiene Polymers 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 13
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 150000005690 diesters Chemical group 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229940087291 tridecyl alcohol Drugs 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 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
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 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
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 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 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical class CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 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
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 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 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002818 heptacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RMIBXGXWMDCYEK-UHFFFAOYSA-N oxonane-2,9-dione Chemical compound O=C1CCCCCCC(=O)O1 RMIBXGXWMDCYEK-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 230000000865 phosphorylative effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 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
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-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
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000003981 vehicle Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C08G18/08—Processes
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/202—Casings or frames around the primary casing of a single cell or a single battery
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a two-component reactive polyurethane resin composition and an isocyanate-containing composition used as a polyisocyanate component thereof.
- Patent Document 1 discloses blending an inorganic filler, a plasticizer, and a phosphate ester into a polyurethane resin obtained by reacting a polyisocyanate and a polybutadiene polyol. Heat dissipation can be improved by containing it in a high compounding ratio.
- the inorganic filler When blending an inorganic filler into a polyurethane resin composition, generally, the inorganic filler is blended with the polyol component, and the polyisocyanate component containing no inorganic filler is added and mixed to react the two components.
- the polyol component containing an inorganic filler is difficult to mix with a polyisocyanate component containing no inorganic filler. If an inorganic filler is blended with the polyisocyanate component in order to improve the mixability of the two, the storage stability of the polyisocyanate component is lowered.
- an embodiment of the present invention is a polyurethane resin composition containing an inorganic filler, while suppressing deterioration in storage stability of an isocyanate-containing composition used as a polyisocyanate component, polyol used as a polyol component
- An object of the present invention is to provide an isocyanate-containing composition capable of improving miscibility with the containing composition.
- R 1 represents OH or a group represented by the following general formula (2)
- a compound in which R 1 is OH and R 1 is represented by general formula (2) It may be a mixture with a compound, and in general formula (3), k represents the number of 1 or 0, and X represents a linking group of —CH 2 —, —CO(CH 2 ) p — or —COCH ⁇ CH—.
- R 2 and R 3 each independently represents a hydrocarbon group having 6 to 30 carbon atoms
- a 1 O and A 3 O each independently represent an oxyalkylene group having 2 to 4 carbon atoms
- m and n are the average addition of alkylene oxide.
- the embodiment of the present invention it is possible to improve the miscibility with the polyol-containing composition while suppressing deterioration of the storage stability of the isocyanate-containing composition.
- the two-liquid reactive polyurethane resin composition according to the present embodiment comprises a polyol-containing composition as a polyol component and an isocyanate-containing composition as a polyisocyanate component.
- the isocyanate-containing composition contains a urethane prepolymer (a).
- a urethane prepolymer
- the average number of functional groups (average number of hydroxyl groups) of the polyol is 2.5 or less, the hardness of the polyurethane resin after curing can be kept low. When used as a gap filler to fill the gap, the reaction force generated against the external force can be reduced.
- the average number of functional groups of the polyol is preferably 2.4 or less, more preferably 2.3 or less.
- the lower limit of the average functional group number of the polyol is not particularly limited, and for example, the average functional group number may be 1.7 or more.
- the above polyol preferably has hydroxyl groups at both ends, and therefore preferably has an average functional group number of 2.0 or more.
- the storage stability of the isocyanate-containing composition can be improved.
- the weight average molecular weight of the polyol is preferably 800 or more.
- the upper limit of the weight average molecular weight of the polyol is not particularly limited. As used herein, the weight average molecular weight is a value calculated using a calibration curve based on standard polystyrene by GPC (gel permeation chromatography) measurement.
- polyether polyols examples include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, etc., and these can be used singly or in combination of two or more.
- polyether polyols include polyoxyalkylene polyols obtained by adding ethylene oxide or propylene oxide to polyhydric alcohols or polyamines.
- Polyester polyols include those obtained by dehydration condensation of carboxylic acids such as adipic acid and phthalic acid and polyhydric alcohols such as ethylene glycol and 1,4-butanediol.
- polybutadiene polyol those having hydroxyl groups at both ends of the polybutadiene structure are more preferable, and hydrogenated polybutadiene polyols may also be used. Among these, it is preferable to use polypropylene glycol and/or polybutadiene polyol.
- the polyisocyanate is not particularly limited, and examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates.
- aliphatic diisocyanates and alicyclic diisocyanates are used. They may be used together.
- aliphatic diisocyanate examples include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 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. Moreover, you may use these in combination of 2 or more types.
- HDI hexamethylene diisocyanate
- 2,2,4-trimethylhexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate
- lysine diisocyanate 2 -methylpentane-1,5-diisocyanate
- 3-methylpentane-1,5-diisocyanate 3-methylpentane-1,5-diisocyanate and the
- alicyclic diisocyanates examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and the like. is mentioned. Moreover, you may use these in combination of 2 or more types.
- the urethane prepolymer (a) is obtained by reacting the above-mentioned polyol and polyisocyanate under the condition of excessive isocyanate groups.
- the urethane prepolymer (a) is preferably a terminal isocyanate prepolymer having isocyanate groups at both ends.
- the amount of the urethane prepolymer (a) is not particularly limited, but it is preferably 1.0 to 15% by mass, more preferably 1.5 to 10% by mass in 100% by mass of the isocyanate-containing composition. .
- the isocyanate-containing composition contains an inorganic filler (b). By blending the inorganic filler (b), heat dissipation can be imparted to the cured polyurethane resin.
- the inorganic filler (b) is not particularly limited, and examples thereof include metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. etc. These can be used either singly or in combination of two or more.
- the content of the inorganic filler (b) is preferably 50 to 95% by mass in 100% by mass of the isocyanate-containing composition.
- the compounding amount is 50% by mass or more, the heat dissipation property of the polyurethane resin can be improved.
- the amount is 95% by mass or less, the storage stability of the isocyanate-containing composition can be improved.
- the blending amount is more preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 90% by mass or less.
- the isocyanate-containing composition contains a plasticizer (c).
- a plasticizer c
- the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
- the plasticizer (c) is not particularly limited, and conventionally known ones blended in polyurethane resins can be used.
- Adipic acid diesters such as diisononyl adipate, trimellitic acid esters such as trioctyl trimellitate and triisononyl trimellitate, pyromellitic acid esters such as tetraoctyl pyromellitate and tetraisononyl pyromellitate, tricresyl phosphate , trixylenyl phosphate, cresyl diphenyl phosphate, and the like, and phosphoric acid triesters and the like, and these can be used either singly or in combination of two or more.
- phthalate diesters and/or adipate diesters are preferred as the plasticizer (c).
- the amount of the plasticizer (c) is not particularly limited, and may be, for example, 1 to 40% by mass, 3 to 35% by mass, or 5 to 30% by mass in 100% by mass of the isocyanate-containing composition. It may be 10 to 20% by mass.
- the isocyanate-containing composition contains at least one compound (hereinafter sometimes referred to as compound (d)) selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (3). include.
- compound (d) selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (3).
- the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
- compounds represented by the following general formula (1) are phosphate esters.
- R 1 represents OH or a group represented by general formula (2) below.
- the phosphate ester represented by formula (1) may be a compound (monoester) in which R 1 is OH, a compound (diester) in which R 1 is represented by general formula (2), or a mixture of both. good.
- R 2 represents a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 8 to 20 carbon atoms.
- the hydrocarbon group includes a linear or branched alkyl group, alkenyl group, aryl group, or aralkyl group, and these groups may have a substituent.
- alkyl groups include hexyl, isohexyl, heptyl, isoheptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, and dodecyl.
- alkenyl groups include hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, and oleyl groups.
- aryl groups include phenyl, tolyl, xylyl, cumenyl, mesityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, and octylphenyl groups.
- nonylphenyl group decylphenyl group, undecylphenyl group, dodecylphenyl group, styrenated phenyl group, p-cumylphenyl group, phenylphenyl group, benzylphenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group and the like.
- aralkyl groups include benzyl, phenethyl, styryl, cinnamyl, benzhydryl, and trityl groups.
- a 1 O represents an oxyalkylene group having 2 to 4 carbon atoms.
- m represents the average number of added moles of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, more preferably a number of 7 to 20 is.
- the oxyalkylene chain represented by (A 1 O) m has an oxyethylene group content of 20 mol % or more. That is, when the oxyethylene group is EO and the oxyalkylene group other than the oxyethylene group is AO, EO/AO (molar ratio) is 100/0 to 20/80.
- the content of oxyethylene groups is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and may be 100 mol %.
- the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene groups may be added randomly or by block addition.
- the phosphate ester represented by formula (1) can be obtained, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then adding the alkylene oxide terminal of the resulting polyether monool. It can be produced by reacting a hydroxyl group with a phosphorylating agent such as phosphoric anhydride, orthophosphoric acid, polyphosphoric acid, and phosphoric acid chloride. Depending on the manufacturing method, a monoester type compound and a diester type compound may be obtained as a mixture, and these may be separated or used as a mixture as they are. Moreover, it can also be used by reacting in the presence of water to increase the content of the monoester type compound.
- a phosphorylating agent such as phosphoric anhydride, orthophosphoric acid, polyphosphoric acid, and phosphoric acid chloride.
- a monoester type compound and a diester type compound may be obtained as a mixture, and these may be separated or used
- the compound represented by the following general formula (3) is a sulfate ester, a sulfonic acid or a carboxylic acid, and these may be used alone or in combination of two or more.
- k represents the number of 1 or 0.
- Z in formula (3) represents a carboxy group (--COOH), a sulfo group (--SO 3 H), or a salt thereof, and may be in a mixture of acid and salt forms.
- Salts include, for example, alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts.
- alkali metal salts include sodium salts, potassium salts, lithium salts and the like.
- alkaline earth metal salts include calcium salts and magnesium salts.
- alkanolamine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, triisopropanolamine salts, and the like.
- R 3 in formula (3) represents a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 8 to 20 carbon atoms.
- the hydrocarbon group includes a linear or branched alkyl group, alkenyl group, aryl group, or aralkyl group, and these groups may have a substituent. Specific examples of the alkyl group, alkenyl group, aryl group, and aralkyl group are the same as those for R 2 .
- a 3 O represents an oxyalkylene group having 2 to 4 carbon atoms.
- n represents the average number of added moles of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, more preferably a number of 7 to 20 is.
- the oxyalkylene chain represented by (A 3 O) m has an oxyethylene group content of 20 mol % or more. That is, when the oxyethylene group is EO and the oxyalkylene group other than the oxyethylene group is AO, EO/AO (molar ratio) is 100/0 to 20/80.
- the content of oxyethylene groups is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and may be 100 mol %.
- the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene groups may be added randomly or by block addition.
- the compound represented by formula (3) is a carboxylic acid.
- the carboxylic acid of formula (3) can be obtained, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then using a monohalogenated acetic acid or a salt thereof, in the presence of a base.
- it can be produced by a ring-opening reaction with an alkylene oxide terminal hydroxyl group using an acid anhydride.
- a sulfate ester can be produced by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then reacting sulfamic acid with a hydroxyl group at the end of the alkylene oxide.
- a sulfonic acid can be produced by adding the above alkylene oxide and then reacting it with a hydroxyl group at the end of the alkylene oxide using a monohalogenated sulfonic acid or a salt thereof.
- the amount of the compound (d) is not particularly limited, and may be, for example, 0.01 to 5% by mass, 0.03 to 2% by mass, or 0.05 to 1% in 100% by mass of the isocyanate-containing composition. % by mass may be used.
- the urethane prepolymer (a) may be used alone as the polyisocyanate compound, or the urethane prepolymer (a) may be used in combination with another polyisocyanate compound.
- polyisocyanate compounds are not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, and Aromatic polyisocyanates, and modified and polynuclear compounds thereof may be mentioned, and any one of them may be used alone or two or more of them may be used in combination.
- Specific examples of aliphatic polyisocyanates and alicyclic polyisocyanates include the above-mentioned aliphatic diisocyanates and alicyclic diisocyanates.
- aromatic polyisocyanates examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3- phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like.
- Modified products of these polyisocyanate compounds include, for example, isocyanurate modified products, allophanate modified products, buret modified products, adduct modified products, and carbodiimide modified products.
- polyisocyanate compounds it is preferable to use isocyanurate-modified polyisocyanate compounds, more preferably isocyanurate-modified aliphatic polyisocyanates.
- the amount of the modified isocyanurate compounded is not particularly limited. % by mass.
- the polyisocyanate compound preferably contains the urethane prepolymer (a) as a main component, and even when used in combination with other polyisocyanate compounds, the total polyisocyanate compound exceeds 50% by mass, more preferably 60% by mass.
- the above is preferably the urethane prepolymer (a).
- the isocyanate-containing composition contains various additives such as moisture absorbers, antioxidants, foam stabilizers, diluents, flame retardants, ultraviolet absorbers, and colorants. It can be added as long as it does not damage it.
- the isocyanate value (NCOV) of the isocyanate-containing composition is not particularly limited, and may be 1.0 to 10 mgKOH/g, 1.5 to 8.0 mgKOH/g, or 2.0 to 7.5 mgKOH/g. .
- the polyol-containing composition contains polyol (e).
- the polyol (e) is not particularly limited, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, etc., and these can be used singly or in combination of two or more. .
- polybutadiene polyol is preferably used.
- the polybutadiene polyol those having hydroxyl groups at both ends of the polybutadiene structure are more preferable, and hydrogenated polybutadiene polyols may also be used.
- the average functionality of polybutadiene polyol is preferably 2.0 to 2.5, more preferably 2.1 to 2.4.
- the amount of the polyol (e) is not particularly limited, but it is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 30% by mass in 100% by mass of the polyol-containing composition. 20% by mass.
- the polyol-containing composition contains an inorganic filler (f).
- an inorganic filler (f) By blending the inorganic filler (f), heat dissipation can be imparted to the cured polyurethane resin.
- the inorganic filler (f) is not particularly limited, and examples thereof include metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. etc. These can be used either singly or in combination of two or more.
- the content of the inorganic filler (f) is preferably 50 to 95% by mass, more preferably 60% by mass or more, and more preferably 70% by mass or more in 100% by mass of the polyol-containing composition. , more preferably 80% by mass or more, and preferably 90% by mass or less.
- the polyol-containing composition may contain a plasticizer (g). By containing the plasticizer (g), the hardness of the cured polyurethane resin can be lowered.
- the plasticizer (g) is not particularly limited, and includes the above-mentioned phthalate diesters, adipate diesters, trimellitate esters, pyromellitic acid esters, and phosphate triesters. The above can be used in combination. Among these, phthalate diesters and/or adipate diesters are preferred as the plasticizer (g).
- the amount of the plasticizer (g) is not particularly limited, and may be, for example, 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass in 100% by mass of the polyol-containing composition. It may be 5 to 15% by mass.
- the polyol-containing composition may contain a phosphate ester (h). By containing the phosphate ester (h), the viscosity of the polyol-containing composition (h) can be reduced. A compound represented by the above formula (1) is used as the phosphate ester (h).
- the amount of the phosphate ester (h) is not particularly limited, and may be, for example, 0.01 to 5% by mass, 0.03 to 2% by mass, or 0.05% by mass in 100% by mass of the polyol-containing composition. It may be up to 1% by mass.
- additives such as a moisture absorbent, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, and a colorant may be added according to the present embodiment. It can be added as long as it does not impair the purpose.
- metal catalysts such as organic tin catalysts, organic lead catalysts, and organic bismuth catalysts, and various urethane polymerization catalysts such as amine catalysts can be used.
- the hydroxyl value (OHV) of the polyol-containing composition is not particularly limited, and may be 1.0-15 mgKOH/g or 2.0-10 mgKOH/g.
- the two-component reactive polyurethane resin composition according to the present embodiment is usually composed of a first component that is a polyol-containing composition and a second component that is an isocyanate-containing composition.
- the third liquid may contain any of the above-mentioned other components as optional components.
- the two-component reactive polyurethane resin composition can be produced by preparing a polyol-containing composition and an isocyanate-containing composition, respectively. Anything is fine.
- the polyol-containing composition and the isocyanate-containing composition, which are filled in separate containers, may be mixed at the time of use so that the polyol and the polyisocyanate react to form a polyurethane resin and cure. At that time, it may be cured by heating.
- the two-liquid reactive polyurethane resin composition according to the embodiment may be obtained by mixing a polyol-containing composition and an isocyanate-containing composition, may be in a liquid state before curing, or may be in a cured state. .
- the mixing ratio of the polyol-containing composition and the isocyanate-containing composition is not particularly limited.
- the molar ratio NCO/OH (index) of may be from 0.5 to 1.2, or from 0.6 to 0.9.
- NCO/OH is calculated as NCOV/OHV from the above isocyanate value (NCOV) and hydroxyl value (OHV).
- the hardness of the two-liquid reactive polyurethane resin composition after curing is not particularly limited, but the shore C hardness is preferably 60 or less, and may be 30-60.
- the thermal conductivity (JIS R2618) of the two-liquid reactive polyurethane resin composition after curing is not particularly limited, and may be, for example, 1.0 W/m ⁇ K or more, or 2.0 W/m ⁇ K or more. 0 to 3.0 W/m ⁇ K.
- Two-liquid reactive polyurethane resin composition is not particularly limited, and can be used for various applications such as electrical and electronic parts and vehicles. It is suitable for use as a heat-dissipating material because it has heat-dissipating properties when an inorganic filler is added. As one embodiment, it is preferably used as a heat dissipation gap filler for a heat source such as a battery.
- the two-liquid reactive polyurethane resin composition will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited thereto.
- Polyol ⁇ Polybutadiene polyol: "POLYVEST HT" manufactured by Evonik, average functionality 2.3
- Polybutadiene polyol "POLYVEST HT” manufactured by Evonik, average functionality 2.3
- Plasticizer ⁇ DUP: diundecyl phthalate
- DOA di-2-ethylhexyl adipate
- Prepolymer 1 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 700, hydroxyl value 160) (“EXENOL 720” manufactured by AGC Co., Ltd.) and 67 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 1) by reacting at 90°C for 2 hours. Obtained.
- HDI hexamethylene diisocyanate
- EXENOL 720 manufactured by AGC Co., Ltd.
- Prepolymer 2 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 26 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M” manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 1000, hydroxyl value 112) ("EXENOL 1020" manufactured by AGC Co., Ltd.) and 74 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 2) by reacting at 90°C for 2 hours. Obtained.
- HDI hexamethylene diisocyanate
- EXENOL 1020 manufactured by AGC Co., Ltd.
- Prepolymer 3 10 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M” manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 3000, hydroxyl value 35) (“EXENOL 3020” manufactured by AGC Co., Ltd.) and 90 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 3) by reacting it at 120°C for 6 hours. Obtained.
- HDI hexamethylene diisocyanate
- EXENOL 3020 manufactured by AGC Co., Ltd.
- Prepolymer 4 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 31 parts by mass of isophorone diisocyanate (IPDI) ("IPDI” manufactured by EVONIK) and polypropylene glycol (average functionality: 2.0 , weight average molecular weight: 1000, hydroxyl value: 112) ("EXENOL 1020" manufactured by AGC) was reacted with 69 parts by mass at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 4).
- IPDI isophorone diisocyanate
- EVONIK polypropylene glycol
- EXENOL 1020 manufactured by AGC
- Prepolymer 5 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 46 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 400, hydroxyl value 281) ("EXENOL 420" manufactured by AGC Co., Ltd.) and 54 parts by mass of the isocyanate group-terminated urethane prepolymer (Prepolymer 5) by reacting it at 90°C for 2 hours. Obtained.
- HDI hexamethylene diisocyanate
- Duranate 50M polypropylene glycol
- Prepolymer 6 12 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M” manufactured by Asahi Kasei Corporation) and polybutadiene polyol (average functional group number 2.3, weight average molecular weight 3000, hydroxyl value 46) ("POLYVEST HT” manufactured by EVONIK) and 88 parts by mass of the mixture were reacted at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 6). rice field.
- HDI hexamethylene diisocyanate
- POLYVEST HT polybutadiene polyol
- Prepolymer 7 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (“Duranate 50M” manufactured by Asahi Kasei Corporation) and castor oil (average functional group number of 2 .7, weight average molecular weight 941, hydroxyl value 161) ("URIC H30" manufactured by Ito Seiyu Co., Ltd.) and 68 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 7) were reacted at 90°C for 2 hours. Obtained.
- HDI hexamethylene diisocyanate
- Carboxylic acid 1 200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid.
- Carboxylic acid 2 200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Then, 156 g (1 mol) of suberic anhydride is reacted at 120° C.
- carboxylic acid 2 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10, k : 1, X: -CO-(CH 2 ) 6 -, Z: -COOH).
- [Weight average molecular weight and number average molecular weight] It is a value calculated from the elution time of a measurement sample using a calibration curve prepared from the molecular weight of standard polystyrene and the elution time measured by the GPC method (gel permeation chromatography method).
- TSKgel Hxl Tosoh Corporation
- the mobile phase was THF (tetrahydrofuran)
- the mobile phase flow rate was 1.0 mL/min
- the column temperature was 40°C
- the sample injection volume was 50 ⁇ L
- the sample concentration was Measurement was performed under the condition of 0.2% by mass.
- the isocyanate content is measured according to A method of JIS K1603-1:2007, and the isocyanate value is calculated by the following formula from the obtained isocyanate content.
- 56.11 Molecular weight of potassium hydroxide 1000: Conversion factor from g to mg 42.02: Molecular weight of NCO 100: Conversion factor from percentage to /g
- Polyol-containing compositions A1-7 were prepared according to the formulations (% by mass) shown in Table 1 below, and isocyanate-containing compositions B1-21 were prepared according to the formulations (% by mass) shown in Table 2 below.
- the isocyanate-containing compositions B1-21 were evaluated for storage stability.
- polyol-containing compositions A1 to 7 and isocyanate-containing compositions B1 to 21 were mixed in the combinations and volume mixing ratios shown in Table 3 below, and the miscibility of the two was evaluated.
- the hardness of the cured product was measured.
- the storage stability, mixability, and hardness measurement/evaluation methods are as follows.
- Comparative Example 1 the hardness of the cured product was high because the polyol constituting the isocyanate group-containing urethane prepolymer had a large average number of functional groups.
- Comparative Example 2 since the weight-average molecular weight of the polyol constituting the isocyanate group-containing urethane prepolymer was small, the isocyanate-containing composition solidified after being stored at 60°C for one month, resulting in low storage stability.
- Comparative Example 3 since the isocyanate-containing composition did not contain a compound (d) such as a phosphate ester or an ammonium sulfate salt, the storage stability was lowered.
- Comparative Example 4 since the isocyanate-containing composition did not contain an inorganic filler, the isocyanate-containing composition and the polyol-containing composition were poorly mixed. In Comparative Example 5, since the isocyanate-containing composition did not contain a plasticizer, the storage stability was poor, and the miscibility with the polyol-containing composition was also poor.
- the isocyanate-containing composition has excellent storage stability, has good miscibility with the polyol-containing composition, and has a hardness of 60 or less after curing, which is good. good results were obtained.
Abstract
The present invention improves, in a polyurethane resin composition containing an inorganic filler, the miscibility of an isocyanate-containing composition with respect to a polyol-containing composition while suppressing the reduction in storage stability of the isocyanate-containing composition. An isocyanate-containing composition according to an embodiment of the present invention is to be used as a polyisocyanate component for a two-part reaction type polyurethane resin composition, and contains: an isocyanate group-containing urethane prepolymer obtained by causing a reaction between a polyisocyanate and a polyol having an average functional group number of 2.5 or less and a weight average molecular weight of 700 or more; an inorganic filler; a plasticizing agent; and at least one selected from the group consisting of compounds represented by general formula (1) and/or compounds represented by general formula (3).
Description
本発明は、２液反応型ポリウレタン樹脂組成物、およびそのポリイソシアネート成分として用いられるイソシアネート含有組成物に関する。
The present invention relates to a two-component reactive polyurethane resin composition and an isocyanate-containing composition used as a polyisocyanate component thereof.
ポリウレタン樹脂組成物に無機充填剤を配合することにより放熱性を付与することが知られている。例えば、特許文献１には、ポリイソシアネートとポリブタジエンポリオールとの反応により得られるポリウレタン樹脂中に、無機充填剤と、可塑剤と、リン酸エステルを配合することが開示されており、無機充填剤を高い配合比率で含有させることにより放熱性を高めることができる。
It is known to add heat dissipation to a polyurethane resin composition by adding an inorganic filler. For example, Patent Document 1 discloses blending an inorganic filler, a plasticizer, and a phosphate ester into a polyurethane resin obtained by reacting a polyisocyanate and a polybutadiene polyol. Heat dissipation can be improved by containing it in a high compounding ratio.
ポリウレタン樹脂組成物に無機充填剤を配合する場合、一般に、ポリオール成分に無機充填剤を配合しておき、これに無機充填剤を含まないポリイソシアネート成分を加えて混合し、両成分を反応させている。しかしながら、無機充填剤を含むポリオール成分は、無機充填剤を含まないポリイソシアネート成分と混合しにくいという問題がある。両者の混合性を向上するために、ポリイソシアネート成分に無機充填剤を配合すると、ポリイソシアネート成分の貯蔵安定性が低下する。
When blending an inorganic filler into a polyurethane resin composition, generally, the inorganic filler is blended with the polyol component, and the polyisocyanate component containing no inorganic filler is added and mixed to react the two components. there is However, there is a problem that a polyol component containing an inorganic filler is difficult to mix with a polyisocyanate component containing no inorganic filler. If an inorganic filler is blended with the polyisocyanate component in order to improve the mixability of the two, the storage stability of the polyisocyanate component is lowered.
本発明の実施形態は、以上の点に鑑み、無機充填剤を含むポリウレタン樹脂組成物において、ポリイソシアネート成分として用いられるイソシアネート含有組成物の貯蔵安定性の低下を抑えながら、ポリオール成分として用いられるポリオール含有組成物との混合性を向上することができる、イソシアネート含有組成物を提供することを目的とする。
In view of the above points, an embodiment of the present invention is a polyurethane resin composition containing an inorganic filler, while suppressing deterioration in storage stability of an isocyanate-containing composition used as a polyisocyanate component, polyol used as a polyol component An object of the present invention is to provide an isocyanate-containing composition capable of improving miscibility with the containing composition.
本発明は以下に示される実施形態を含む。
［１］ ２液反応型ポリウレタン樹脂組成物のポリイソシアネート成分として用いられるイソシアネート含有組成物であって、平均官能基数が２．５以下かつ重量平均分子量が７００以上のポリオールとポリイソシアネートとを反応させて得られるイソシアネート基含有ウレタンプレポリマー、無機充填剤、可塑剤、および、下記一般式（１）で表される化合物および下記一般式（３）で表される化合物からなる群から選択される少なくとも一種を含み、一般式（１）において、Ｒ１はＯＨまたは下記一般式（２）に示す基を表し、Ｒ１がＯＨで表される化合物とＲ１が一般式（２）で表される化合物との混合物でもよく、一般式（３）において、ｋは１または０の数を表し、Ｘは－ＣＨ２－、－ＣＯ（ＣＨ２）ｐ－または－ＣＯＣＨ＝ＣＨ－である連結基を表し、ここでｐは２～６の整数を表し、Ｚはカルボキシ基、スルホ基またはこれらの塩を表し、一般式（１）、一般式（２）および一般式（３）において、Ｒ２およびＲ３はそれぞれ独立に炭素数６～３０の炭化水素基を表し、Ａ１ＯおよびＡ３Ｏはそれぞれ独立に炭素数２～４のオキシアルキレン基を表し、ｍおよびｎはアルキレンオキシドの平均付加モル数であってそれぞれ独立に１～１００の数を表し、（Ａ１Ｏ）ｍおよび（Ａ３Ｏ）ｎはそれぞれ独立にオキシエチレン基の含有量が２０モル％以上である、イソシアネート含有組成物。
The present invention includes embodiments shown below.
[1] An isocyanate-containing composition used as a polyisocyanate component of a two-liquid reactive polyurethane resin composition, wherein a polyol having an average functional group number of 2.5 or less and a weight average molecular weight of 700 or more is reacted with a polyisocyanate. At least selected from the group consisting of an isocyanate group-containing urethane prepolymer, an inorganic filler, a plasticizer, and a compound represented by the following general formula (1) and a compound represented by the following general formula (3) In general formula (1), R 1 represents OH or a group represented by the following general formula (2), and a compound in which R 1 is OH and R 1 is represented by general formula (2) It may be a mixture with a compound, and in general formula (3), k represents the number of 1 or 0, and X represents a linking group of —CH 2 —, —CO(CH 2 ) p — or —COCH═CH—. where p represents an integer of 2 to 6, Z represents a carboxy group, a sulfo group or a salt thereof, and in general formula (1), general formula (2) and general formula (3), R 2 and R 3 each independently represents a hydrocarbon group having 6 to 30 carbon atoms, A 1 O and A 3 O each independently represent an oxyalkylene group having 2 to 4 carbon atoms, and m and n are the average addition of alkylene oxide. an isocyanate-containing composition, wherein the number of moles each independently represents a number from 1 to 100, and (A 1 O) m and (A 3 O) n each independently have an oxyethylene group content of 20 mol % or more; thing.
［１］ ２液反応型ポリウレタン樹脂組成物のポリイソシアネート成分として用いられるイソシアネート含有組成物であって、平均官能基数が２．５以下かつ重量平均分子量が７００以上のポリオールとポリイソシアネートとを反応させて得られるイソシアネート基含有ウレタンプレポリマー、無機充填剤、可塑剤、および、下記一般式（１）で表される化合物および下記一般式（３）で表される化合物からなる群から選択される少なくとも一種を含み、一般式（１）において、Ｒ１はＯＨまたは下記一般式（２）に示す基を表し、Ｒ１がＯＨで表される化合物とＲ１が一般式（２）で表される化合物との混合物でもよく、一般式（３）において、ｋは１または０の数を表し、Ｘは－ＣＨ２－、－ＣＯ（ＣＨ２）ｐ－または－ＣＯＣＨ＝ＣＨ－である連結基を表し、ここでｐは２～６の整数を表し、Ｚはカルボキシ基、スルホ基またはこれらの塩を表し、一般式（１）、一般式（２）および一般式（３）において、Ｒ２およびＲ３はそれぞれ独立に炭素数６～３０の炭化水素基を表し、Ａ１ＯおよびＡ３Ｏはそれぞれ独立に炭素数２～４のオキシアルキレン基を表し、ｍおよびｎはアルキレンオキシドの平均付加モル数であってそれぞれ独立に１～１００の数を表し、（Ａ１Ｏ）ｍおよび（Ａ３Ｏ）ｎはそれぞれ独立にオキシエチレン基の含有量が２０モル％以上である、イソシアネート含有組成物。
[1] An isocyanate-containing composition used as a polyisocyanate component of a two-liquid reactive polyurethane resin composition, wherein a polyol having an average functional group number of 2.5 or less and a weight average molecular weight of 700 or more is reacted with a polyisocyanate. At least selected from the group consisting of an isocyanate group-containing urethane prepolymer, an inorganic filler, a plasticizer, and a compound represented by the following general formula (1) and a compound represented by the following general formula (3) In general formula (1), R 1 represents OH or a group represented by the following general formula (2), and a compound in which R 1 is OH and R 1 is represented by general formula (2) It may be a mixture with a compound, and in general formula (3), k represents the number of 1 or 0, and X represents a linking group of —CH 2 —, —CO(CH 2 ) p — or —COCH═CH—. where p represents an integer of 2 to 6, Z represents a carboxy group, a sulfo group or a salt thereof, and in general formula (1), general formula (2) and general formula (3), R 2 and R 3 each independently represents a hydrocarbon group having 6 to 30 carbon atoms, A 1 O and A 3 O each independently represent an oxyalkylene group having 2 to 4 carbon atoms, and m and n are the average addition of alkylene oxide. an isocyanate-containing composition, wherein the number of moles each independently represents a number from 1 to 100, and (A 1 O) m and (A 3 O) n each independently have an oxyethylene group content of 20 mol % or more; thing.
［２］ 前記ポリイソシアネートが、脂肪族ジイソシアネートおよび／または脂環式ジイソシアネートである、［１］に記載のイソシアネート含有組成物。
［３］ 前記イソシアネート含有組成物１００質量％中に前記無機充填剤を５０～９５質量％含有する、［１］または［２］に記載のイソシアネート含有組成物。
［４］ 前記可塑剤がフタル酸ジエステルおよび／またはアジピン酸ジエステルである、［１］～［３］のいずれか１項に記載のイソシアネート含有組成物。
［５］ ［１］～［４］のいずれか１項に記載のイソシアネート含有組成物と、ポリオールおよび無機充填剤を含むポリオール含有組成物と、を備える、２液反応型ポリウレタン樹脂組成物。
［６］ 放熱材料として用いられる［５］に記載の２液反応型ポリウレタン樹脂組成物。 [2] The isocyanate-containing composition according to [1], wherein the polyisocyanate is an aliphatic diisocyanate and/or an alicyclic diisocyanate.
[3] The isocyanate-containing composition according to [1] or [2], which contains 50 to 95% by mass of the inorganic filler in 100% by mass of the isocyanate-containing composition.
[4] The isocyanate-containing composition according to any one of [1] to [3], wherein the plasticizer is a diester phthalate and/or diester adipic acid.
[5] A two-component reactive polyurethane resin composition comprising the isocyanate-containing composition according to any one of [1] to [4], and a polyol-containing composition containing a polyol and an inorganic filler.
[6] The two-component reactive polyurethane resin composition according to [5], which is used as a heat dissipation material.
［３］ 前記イソシアネート含有組成物１００質量％中に前記無機充填剤を５０～９５質量％含有する、［１］または［２］に記載のイソシアネート含有組成物。
［４］ 前記可塑剤がフタル酸ジエステルおよび／またはアジピン酸ジエステルである、［１］～［３］のいずれか１項に記載のイソシアネート含有組成物。
［５］ ［１］～［４］のいずれか１項に記載のイソシアネート含有組成物と、ポリオールおよび無機充填剤を含むポリオール含有組成物と、を備える、２液反応型ポリウレタン樹脂組成物。
［６］ 放熱材料として用いられる［５］に記載の２液反応型ポリウレタン樹脂組成物。 [2] The isocyanate-containing composition according to [1], wherein the polyisocyanate is an aliphatic diisocyanate and/or an alicyclic diisocyanate.
[3] The isocyanate-containing composition according to [1] or [2], which contains 50 to 95% by mass of the inorganic filler in 100% by mass of the isocyanate-containing composition.
[4] The isocyanate-containing composition according to any one of [1] to [3], wherein the plasticizer is a diester phthalate and/or diester adipic acid.
[5] A two-component reactive polyurethane resin composition comprising the isocyanate-containing composition according to any one of [1] to [4], and a polyol-containing composition containing a polyol and an inorganic filler.
[6] The two-component reactive polyurethane resin composition according to [5], which is used as a heat dissipation material.
本発明の実施形態によれば、イソシアネート含有組成物の貯蔵安定性の低下を抑えながら、ポリオール含有組成物との混合性を向上することができる。
According to the embodiment of the present invention, it is possible to improve the miscibility with the polyol-containing composition while suppressing deterioration of the storage stability of the isocyanate-containing composition.
本実施形態に係る２液反応型ポリウレタン樹脂組成物は、ポリオール成分としてのポリオール含有組成物と、ポリイソシアネート成分としてのイソシアネート含有組成物と、を備える。
The two-liquid reactive polyurethane resin composition according to the present embodiment comprises a polyol-containing composition as a polyol component and an isocyanate-containing composition as a polyisocyanate component.
＜イソシアネート含有組成物＞
［ウレタンプレポリマー（ａ）］
イソシアネート含有組成物は、ウレタンプレポリマー（ａ）を含む。ウレタンプレポリマー（ａ）として、本実施形態では、平均官能基数が２．５以下かつ重量平均分子量が７００以上のポリオールと、ポリイソシアネートと、を構成成分とするイソシアネート基含有ウレタンプレポリマーが用いられる。 <Isocyanate-containing composition>
[Urethane prepolymer (a)]
The isocyanate-containing composition contains a urethane prepolymer (a). As the urethane prepolymer (a), in the present embodiment, an isocyanate group-containing urethane prepolymer containing a polyol having an average functional group number of 2.5 or less and a weight average molecular weight of 700 or more and a polyisocyanate as constituent components is used. .
［ウレタンプレポリマー（ａ）］
イソシアネート含有組成物は、ウレタンプレポリマー（ａ）を含む。ウレタンプレポリマー（ａ）として、本実施形態では、平均官能基数が２．５以下かつ重量平均分子量が７００以上のポリオールと、ポリイソシアネートと、を構成成分とするイソシアネート基含有ウレタンプレポリマーが用いられる。 <Isocyanate-containing composition>
[Urethane prepolymer (a)]
The isocyanate-containing composition contains a urethane prepolymer (a). As the urethane prepolymer (a), in the present embodiment, an isocyanate group-containing urethane prepolymer containing a polyol having an average functional group number of 2.5 or less and a weight average molecular weight of 700 or more and a polyisocyanate as constituent components is used. .
上記ポリオールの平均官能基数（平均水酸基数）が２．５以下であることにより、硬化後のポリウレタン樹脂の硬度を低く抑えることができ、例えば、２液反応型ポリウレタン樹脂組成物をバッテリー周りの隙間を埋めるギャップフィラーとして用いたときに、外力に対して発生する反力を低減することができる。上記ポリオールの平均官能基数は、２．４以下であることが好ましく、より好ましくは２．３以下である。上記ポリオールの平均官能基数の下限は特に限定されず、例えば平均官能基数は１．７以上でもよい。上記ポリオールは両末端に水酸基を持つことが好ましく、従って平均官能基数は２．０以上であることが好ましい。
When the average number of functional groups (average number of hydroxyl groups) of the polyol is 2.5 or less, the hardness of the polyurethane resin after curing can be kept low. When used as a gap filler to fill the gap, the reaction force generated against the external force can be reduced. The average number of functional groups of the polyol is preferably 2.4 or less, more preferably 2.3 or less. The lower limit of the average functional group number of the polyol is not particularly limited, and for example, the average functional group number may be 1.7 or more. The above polyol preferably has hydroxyl groups at both ends, and therefore preferably has an average functional group number of 2.0 or more.
上記ポリオールの重量平均分子量（Ｍｗ）が７００以上であることにより、イソシアネート含有組成物の貯蔵安定性を向上することができる。ポリオールの重量平均分子量は、８００以上であることが好ましい。ポリオールの重量平均分子量の上限は、特に限定されず、例えば重量平均分子量は１００００以下でもよく、５０００以下でもよい。本明細書において重量平均分子量は、ＧＰＣ法（ゲルパーミエーションクロマトグラフィー法）の測定により、標準ポリスチレンによる検量線を用いて算出される値である。
When the weight average molecular weight (Mw) of the polyol is 700 or more, the storage stability of the isocyanate-containing composition can be improved. The weight average molecular weight of the polyol is preferably 800 or more. The upper limit of the weight average molecular weight of the polyol is not particularly limited. As used herein, the weight average molecular weight is a value calculated using a calibration curve based on standard polystyrene by GPC (gel permeation chromatography) measurement.
上記ポリオールとしては、特に限定されず、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどが挙げられ、これらはいずれか一種または二種以上組み合わせて用いることができる。ポリエーテルポリオールとしては、例えば、多価アルコールやポリアミンにエチレンオキシドやプロピレンオキシドを付加させて得られたポリオキシアルキレンポリオールが挙げられる。ポリエステルポリオールとしては、アジピン酸やフタル酸などのカルボン酸と、エチレングリコール、１，４－ブタンジオールなどの多価アルコールを脱水縮合して得られるものが挙げられる。ポリブタジエンポリオールとしては、ポリブタジエン構造の両末端にそれぞれ水酸基を有するものがより好ましく、水素添加したものでもよい。これらの中でも、ポリプロピレングリコールおよび／またはポリブタジエンポリオールを用いることが好ましい。
The above polyols are not particularly limited, and examples include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, etc., and these can be used singly or in combination of two or more. Examples of polyether polyols include polyoxyalkylene polyols obtained by adding ethylene oxide or propylene oxide to polyhydric alcohols or polyamines. Polyester polyols include those obtained by dehydration condensation of carboxylic acids such as adipic acid and phthalic acid and polyhydric alcohols such as ethylene glycol and 1,4-butanediol. As the polybutadiene polyol, those having hydroxyl groups at both ends of the polybutadiene structure are more preferable, and hydrogenated polybutadiene polyols may also be used. Among these, it is preferable to use polypropylene glycol and/or polybutadiene polyol.
上記ポリイソシアネートとしては、特に限定されず、例えば、脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネートなどが挙げられるが、好ましくは、脂肪族ジイソシアネート、脂環式ジイソシアネートを用いることであり、両者を併用してもよい。
The polyisocyanate is not particularly limited, and examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Preferably, aliphatic diisocyanates and alicyclic diisocyanates are used. They may be used together.
上記脂肪族ジイソシアネートとしては、例えば、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（ＨＤＩ）、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－ジイソシアネートなどが挙げられる。また、これらを２種以上組み合わせて使用してもよい。
Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 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. Moreover, you may use these in combination of 2 or more types.
脂環式ジイソシアネートとしては、例えば、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）シクロヘキサンなどが挙げられる。また、これらを２種以上組み合わせて使用してもよい。
Examples of alicyclic diisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and the like. is mentioned. Moreover, you may use these in combination of 2 or more types.
ウレタンプレポリマー（ａ）は、上記ポリオールとポリイソシアネートとを、イソシアネート基過剰条件で反応させることにより得られる。ウレタンプレポリマー（ａ）を得るために用いるイソシアネート基と水酸基の割合（モル比）は、特に限定されないが、イソシアネート基：水酸基＝１．５～２．５：１であることが好ましく、より好ましくは１．７～２．３：１である。ウレタンプレポリマー（ａ）は、好ましくは両末端にイソシアネート基を有する末端イソシアネートプレポリマーである。
The urethane prepolymer (a) is obtained by reacting the above-mentioned polyol and polyisocyanate under the condition of excessive isocyanate groups. The ratio (molar ratio) between the isocyanate group and the hydroxyl group used to obtain the urethane prepolymer (a) is not particularly limited, but the isocyanate group:hydroxyl group=1.5 to 2.5:1 is preferred, and more preferred. is 1.7-2.3:1. The urethane prepolymer (a) is preferably a terminal isocyanate prepolymer having isocyanate groups at both ends.
ウレタンプレポリマー（ａ）の配合量は、特に限定されないが、イソシアネート含有組成物１００質量％中に１．０～１５質量％であることが好ましく、より好ましくは１．５～１０質量％である。
The amount of the urethane prepolymer (a) is not particularly limited, but it is preferably 1.0 to 15% by mass, more preferably 1.5 to 10% by mass in 100% by mass of the isocyanate-containing composition. .
［無機充填剤（ｂ）］
イソシアネート含有組成物は、無機充填剤（ｂ）を含む。無機充填剤（ｂ）を配合することにより、硬化後のポリウレタン樹脂に放熱性を付与することができる。 [Inorganic filler (b)]
The isocyanate-containing composition contains an inorganic filler (b). By blending the inorganic filler (b), heat dissipation can be imparted to the cured polyurethane resin.
イソシアネート含有組成物は、無機充填剤（ｂ）を含む。無機充填剤（ｂ）を配合することにより、硬化後のポリウレタン樹脂に放熱性を付与することができる。 [Inorganic filler (b)]
The isocyanate-containing composition contains an inorganic filler (b). By blending the inorganic filler (b), heat dissipation can be imparted to the cured polyurethane resin.
無機充填剤（ｂ）としては、特に限定されず、例えば、アルミナ、酸化マグネシウムなどの金属酸化物、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、窒化アルミニウム、窒化ホウ素などの金属窒化物などが挙げられる。これらはいずれか一種または二種以上組み合わせて用いることができる。
The inorganic filler (b) is not particularly limited, and examples thereof include metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. etc. These can be used either singly or in combination of two or more.
無機充填剤（ｂ）の配合量は、イソシアネート含有組成物１００質量％中に５０～９５質量％であることが好ましい。該配合量が５０質量％以上であることにより、ポリウレタン樹脂の放熱性を向上することができる。該配合量が９５質量％以下であることにより、イソシアネート含有組成物の貯蔵安定性を向上することができる。該配合量は、より好ましくは６０質量％以上であり、より好ましくは７０質量％以上であり、更に好ましくは８０質量％以上であり、また９０質量％以下であることが好ましい。
The content of the inorganic filler (b) is preferably 50 to 95% by mass in 100% by mass of the isocyanate-containing composition. When the compounding amount is 50% by mass or more, the heat dissipation property of the polyurethane resin can be improved. When the amount is 95% by mass or less, the storage stability of the isocyanate-containing composition can be improved. The blending amount is more preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and preferably 90% by mass or less.
［可塑剤（ｃ）］
イソシアネート含有組成物は、可塑剤（ｃ）を含む。後述する（ｄ）成分とともに可塑剤（ｃ）を配合することで、イソシアネート含有組成物の貯蔵安定性が向上し、またポリオール含有組成物との混合性を向上することができる。 [Plasticizer (c)]
The isocyanate-containing composition contains a plasticizer (c). By blending the plasticizer (c) together with the component (d) described below, the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
イソシアネート含有組成物は、可塑剤（ｃ）を含む。後述する（ｄ）成分とともに可塑剤（ｃ）を配合することで、イソシアネート含有組成物の貯蔵安定性が向上し、またポリオール含有組成物との混合性を向上することができる。 [Plasticizer (c)]
The isocyanate-containing composition contains a plasticizer (c). By blending the plasticizer (c) together with the component (d) described below, the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
可塑剤（ｃ）としては、特に限定されず、ポリウレタン樹脂に配合される従来公知のものを使用することができ、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、テトライソノニルピロメリテートなどのピロメリット酸エステル、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、クレジルジフェニルホスフェートなどリン酸トリエステルなどが挙げられ、これらはいずれか一種または二種以上組み合わせて用いることができる。これらの中でも、可塑剤（ｃ）としては、フタル酸ジエステルおよび／またはアジピン酸ジエステルが好ましい。
The plasticizer (c) is not particularly limited, and conventionally known ones blended in polyurethane resins can be used. Adipic acid diesters such as diisononyl adipate, trimellitic acid esters such as trioctyl trimellitate and triisononyl trimellitate, pyromellitic acid esters such as tetraoctyl pyromellitate and tetraisononyl pyromellitate, tricresyl phosphate , trixylenyl phosphate, cresyl diphenyl phosphate, and the like, and phosphoric acid triesters and the like, and these can be used either singly or in combination of two or more. Among these, phthalate diesters and/or adipate diesters are preferred as the plasticizer (c).
可塑剤（ｃ）の配合量は、特に限定されず、例えば、イソシアネート含有組成物１００質量％中に１～４０質量％でもよく、３～３５質量％でもよく、５～３０質量％でもよく、１０～２０質量％でもよい。
The amount of the plasticizer (c) is not particularly limited, and may be, for example, 1 to 40% by mass, 3 to 35% by mass, or 5 to 30% by mass in 100% by mass of the isocyanate-containing composition. It may be 10 to 20% by mass.
［化合物（ｄ）］
イソシアネート含有組成物は、一般式（１）で表される化合物および一般式（３）で表される化合物からなる群から選択される少なくとも一種（以下、化合物（ｄ）ということがある。）を含む。化合物（ｄ）を可塑剤（ｃ）とともに配合することにより、イソシアネート含有組成物の貯蔵安定性が向上し、またポリオール含有組成物との混合性を向上することができる。 [Compound (d)]
The isocyanate-containing composition contains at least one compound (hereinafter sometimes referred to as compound (d)) selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (3). include. By blending the compound (d) together with the plasticizer (c), the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
イソシアネート含有組成物は、一般式（１）で表される化合物および一般式（３）で表される化合物からなる群から選択される少なくとも一種（以下、化合物（ｄ）ということがある。）を含む。化合物（ｄ）を可塑剤（ｃ）とともに配合することにより、イソシアネート含有組成物の貯蔵安定性が向上し、またポリオール含有組成物との混合性を向上することができる。 [Compound (d)]
The isocyanate-containing composition contains at least one compound (hereinafter sometimes referred to as compound (d)) selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (3). include. By blending the compound (d) together with the plasticizer (c), the storage stability of the isocyanate-containing composition can be improved, and the miscibility with the polyol-containing composition can be improved.
化合物（ｄ）のうち下記一般式（１）で表される化合物は、リン酸エステルである。
Among compounds (d), compounds represented by the following general formula (1) are phosphate esters.
式（１）中、Ｒ１はＯＨまたは下記一般式（２）に示す基を表す。式（１）で表されるリン酸エステルは、Ｒ１がＯＨで表される化合物（モノエステル）でも、Ｒ１が一般式（２）で表される化合物（ジエステル）でも、両者の混合物でもよい。
In formula (1), R 1 represents OH or a group represented by general formula (2) below. The phosphate ester represented by formula (1) may be a compound (monoester) in which R 1 is OH, a compound (diester) in which R 1 is represented by general formula (2), or a mixture of both. good.
式（１）および式（２）において、Ｒ２は、炭素数６～３０の炭化水素基を表し、より好ましくは炭素数８～２０の炭化水素基を表す。炭化水素基としては、直鎖又は分岐のアルキル基、又はアルケニル基、又はアリール基、又はアラルキル基が挙げられ、これらの基は置換基を有していてもよい。
In formulas (1) and (2), R 2 represents a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 8 to 20 carbon atoms. The hydrocarbon group includes a linear or branched alkyl group, alkenyl group, aryl group, or aralkyl group, and these groups may have a substituent.
アルキル基の具体例としては、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、２－エチルヘキシル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、イソウンデシル基、ドデシル基、イソドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、イソテトラデシル基、ペンタデシル基、イソペンタデシル基、ヘキサデシル基、イソヘキサデシル基、２－ヘキシルデシル基、ヘプタデシル基、イソヘプタデシル基、オクタデシル基、イソオクタデシル基、２－オクチルデシル基、２－ヘキシルドデシル基、ノナデシル基、イソノナデシル基、エイコシル基、イソエイコシル基、ヘンエイコシル基、イソヘンエイコシル基、ドコシル基、イソドコシル基、トリコシル基、イソトリコシル基、テトラコシル基、イソテトラコシル基、ペンタコシル基、イソペンタコシル基、ヘキサコシル基、イソヘキサコシル基、ヘプタコシル基、イソヘプタコシル基等が挙げられる。
Specific examples of alkyl groups include hexyl, isohexyl, heptyl, isoheptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, and dodecyl. group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, pentadecyl group, isopentadecyl group, hexadecyl group, isohexadecyl group, 2-hexyldecyl group, heptadecyl group, isoheptadecyl group, octadecyl group, Isooctacyl group, 2-octyldecyl group, 2-hexyldodecyl group, nonadecyl group, isononadecyl group, eicosyl group, isoeicosyl group, heneicosyl group, isoheneicosyl group, docosyl group, isodocosyl group, tricosyl group, isotricosyl group, tetracosyl group group, isotetracosyl group, pentacosyl group, isopentacosyl group, hexacosyl group, isohexacosyl group, heptacosyl group, isoheptacosyl group and the like.
アルケニル基の具体例としては、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、オレイル基等が挙げられる。
Specific examples of alkenyl groups include hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, and oleyl groups.
アリール基の具体例としては、フェニル基、トリル基、キシリル基、クメニル基、メシチル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、ヘプチルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基、スチレン化フェニル基、ｐ－クミルフェニル基、フェニルフェニル基、ベンジルフェニル基、α－ナフチル基、β－ナフチル基等が挙げられる。
Specific examples of aryl groups include phenyl, tolyl, xylyl, cumenyl, mesityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, and octylphenyl groups. , nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, styrenated phenyl group, p-cumylphenyl group, phenylphenyl group, benzylphenyl group, α-naphthyl group, β-naphthyl group and the like.
アラルキル基の具体例としては、ベンジル基、フェネチル基、スチリル基、シンナミル基、ベンズヒドリル基、トリチル基等が挙げられる。
Specific examples of aralkyl groups include benzyl, phenethyl, styryl, cinnamyl, benzhydryl, and trityl groups.
式（１）および式（２）において、Ａ１Ｏは炭素数２～４のオキシアルキレン基を表す。ｍは、アルキレンオキシドの平均付加モル数を表し、１～１００の数であり、好ましくは３～５０の数であり、より好ましくは５～３０の数であり、更に好ましくは７～２０の数である。（Ａ１Ｏ）ｍで表されるオキシアルキレン鎖は、オキシエチレン基の含有量が２０モル％以上である。すなわち、オキシエチレン基をＥＯとし、オキシエチレン基以外のオキシアルキレン基をＡＯとしたとき、ＥＯ／ＡＯ（モル比）＝１００／０～２０／８０である。オキシエチレン基の含有量は５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、８０モル％以上であることが更に好ましく、１００モル％でもよい。オキシアルキレン鎖が複数種のオキシアルキレン基からなる場合、オキシアルキレン基はランダム付加でもよく、ブロック付加でもよい。
In formulas (1) and (2), A 1 O represents an oxyalkylene group having 2 to 4 carbon atoms. m represents the average number of added moles of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, more preferably a number of 7 to 20 is. The oxyalkylene chain represented by (A 1 O) m has an oxyethylene group content of 20 mol % or more. That is, when the oxyethylene group is EO and the oxyalkylene group other than the oxyethylene group is AO, EO/AO (molar ratio) is 100/0 to 20/80. The content of oxyethylene groups is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and may be 100 mol %. When the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene groups may be added randomly or by block addition.
式（１）で表されるリン酸エステルは、例えば、炭素数６～３０のモノアルコールやフェノール類に公知の方法によりアルキレンオキシドを付加した後、得られたポリエーテルモノオールのアルキレンオキシド末端の水酸基に、無水リン酸、オルトリン酸、ポリリン酸、オキシ塩化リン酸等のリン酸化剤を反応させることにより製造することができる。製造方法によってはモノエステル型の化合物とジエステル型の化合物が混合体として得られるが、これらは分離してもよいし、そのまま混合物として使用してもよい。また、水の存在下で反応させ、モノエステル型の化合物の含有割合を高めて使用することもできる。
The phosphate ester represented by formula (1) can be obtained, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then adding the alkylene oxide terminal of the resulting polyether monool. It can be produced by reacting a hydroxyl group with a phosphorylating agent such as phosphoric anhydride, orthophosphoric acid, polyphosphoric acid, and phosphoric acid chloride. Depending on the manufacturing method, a monoester type compound and a diester type compound may be obtained as a mixture, and these may be separated or used as a mixture as they are. Moreover, it can also be used by reacting in the presence of water to increase the content of the monoester type compound.
化合物（ｄ）のうち下記一般式（３）で表される化合物は、硫酸エステル、スルホン酸またはカルボン酸であり、これらはいずれか一種でも二種以上併用してもよい。
Among the compounds (d), the compound represented by the following general formula (3) is a sulfate ester, a sulfonic acid or a carboxylic acid, and these may be used alone or in combination of two or more.
式（３）中、ｋは、１または０の数を表す。Ｘは、－ＣＨ２－、－ＣＯ（ＣＨ２）ｐ－または－ＣＯＣＨ＝ＣＨ－である連結基を表し、ここでｐは２～６の整数を表す。
In formula (3), k represents the number of 1 or 0. X represents a linking group of -CH 2 -, -CO(CH 2 ) p - or -COCH=CH-, where p represents an integer of 2-6.
式（３）中のＺは、カルボキシ基（－ＣＯＯＨ）、スルホ基（－ＳＯ３Ｈ）、またはこれらの塩を表し、酸型と塩型が混在してもよい。塩としては、例えば、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アルカノールアミン塩が挙げられる。アルカリ金属塩の例としては、ナトリウム塩、カリウム塩、リチウム塩等が挙げられる。アルカリ土類金属塩の例としては、カルシウム塩及びマグネシウム塩等が挙げられる。アルカノールアミン塩の例としては、モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩、トリイソプロパノールアミン塩等が挙げられる。
Z in formula (3) represents a carboxy group (--COOH), a sulfo group (--SO 3 H), or a salt thereof, and may be in a mixture of acid and salt forms. Salts include, for example, alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts. Examples of alkali metal salts include sodium salts, potassium salts, lithium salts and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of alkanolamine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, triisopropanolamine salts, and the like.
式（３）中のＲ３は、炭素数６～３０の炭化水素基を表し、より好ましくは炭素数８～２０の炭化水素基を表す。炭化水素基としては、直鎖又は分岐のアルキル基、又はアルケニル基、又はアリール基、又はアラルキル基が挙げられ、これらの基は置換基を有していてもよい。アルキル基、アルケニル基、アリール基、アラルキル基の具体例については、Ｒ２と同様である。
R 3 in formula (3) represents a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 8 to 20 carbon atoms. The hydrocarbon group includes a linear or branched alkyl group, alkenyl group, aryl group, or aralkyl group, and these groups may have a substituent. Specific examples of the alkyl group, alkenyl group, aryl group, and aralkyl group are the same as those for R 2 .
式（３）において、Ａ３Ｏは炭素数２～４のオキシアルキレン基を表す。ｎは、アルキレンオキシドの平均付加モル数を表し、１～１００の数であり、好ましくは３～５０の数であり、より好ましくは５～３０の数であり、更に好ましくは７～２０の数である。（Ａ３Ｏ）ｍで表されるオキシアルキレン鎖は、オキシエチレン基の含有量が２０モル％以上である。すなわち、オキシエチレン基をＥＯとし、オキシエチレン基以外のオキシアルキレン基をＡＯとしたとき、ＥＯ／ＡＯ（モル比）＝１００／０～２０／８０である。オキシエチレン基の含有量は５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、８０モル％以上であることが更に好ましく、１００モル％でもよい。オキシアルキレン鎖が複数種のオキシアルキレン基からなる場合、オキシアルキレン基はランダム付加でもよく、ブロック付加でもよい。
In formula (3), A 3 O represents an oxyalkylene group having 2 to 4 carbon atoms. n represents the average number of added moles of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, more preferably a number of 7 to 20 is. The oxyalkylene chain represented by (A 3 O) m has an oxyethylene group content of 20 mol % or more. That is, when the oxyethylene group is EO and the oxyalkylene group other than the oxyethylene group is AO, EO/AO (molar ratio) is 100/0 to 20/80. The content of oxyethylene groups is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 80 mol % or more, and may be 100 mol %. When the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene groups may be added randomly or by block addition.
上記Ｚがカルボキシ基の場合、式（３）で表される化合物はカルボン酸である。その場合、式（３）のカルボン酸は、例えば、炭素数６～３０のモノアルコールやフェノール類に公知の方法によりアルキレンオキシドを付加した後、モノハロゲン化酢酸またはその塩を用い、塩基存在下でアルキレンオキシド末端の水酸基と反応させることにより製造することができる。あるいはまた、酸無水物を用いてアルキレンオキシド末端の水酸基との開環反応による方法により製造することができる。モノハロゲン化酢酸またはその塩を用いる場合、式（３）において、ｋ＝１、Ｘが－ＣＨ２－、ＺがＣＯＯＨまたはその塩であるカルボン酸が得られる。また、酸無水物を用いた場合、ｋ＝１、Ｘが－ＣＯ（ＣＨ２）ｐ
－または－ＣＯＣＨ＝ＣＨ－、ＺがＣＯＯＨであるカルボン酸が得られる。 When Z is a carboxy group, the compound represented by formula (3) is a carboxylic acid. In that case, the carboxylic acid of formula (3) can be obtained, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then using a monohalogenated acetic acid or a salt thereof, in the presence of a base. can be produced by reacting with a hydroxyl group at the end of an alkylene oxide. Alternatively, it can be produced by a ring-opening reaction with an alkylene oxide terminal hydroxyl group using an acid anhydride. When a monohalogenated acetic acid or a salt thereof is used, a carboxylic acid of formula (3) is obtained in which k=1, X is —CH 2 —, and Z is COOH or a salt thereof. Also, when using an acid anhydride, k = 1, X is —CO(CH 2 ) p
- or -COCH=CH-, carboxylic acids where Z is COOH are obtained.
－または－ＣＯＣＨ＝ＣＨ－、ＺがＣＯＯＨであるカルボン酸が得られる。 When Z is a carboxy group, the compound represented by formula (3) is a carboxylic acid. In that case, the carboxylic acid of formula (3) can be obtained, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then using a monohalogenated acetic acid or a salt thereof, in the presence of a base. can be produced by reacting with a hydroxyl group at the end of an alkylene oxide. Alternatively, it can be produced by a ring-opening reaction with an alkylene oxide terminal hydroxyl group using an acid anhydride. When a monohalogenated acetic acid or a salt thereof is used, a carboxylic acid of formula (3) is obtained in which k=1, X is —CH 2 —, and Z is COOH or a salt thereof. Also, when using an acid anhydride, k = 1, X is —CO(CH 2 ) p
- or -COCH=CH-, carboxylic acids where Z is COOH are obtained.
上記Ｚがスルホ基の場合、式（３）で表される化合物は、ｋ＝０であれば硫酸エステルであり、ｋ＝１であればスルホン酸である。例えば、硫酸エステルについては、炭素数６～３０のモノアルコールやフェノール類に公知の方法によりアルキレンオキシドを付加した後、スルファミン酸をアルキレンオキシド末端の水酸基と反応させることにより製造することができる。また、例えば、スルホン酸については、上記のアルキレンオキシドを付加した後、モノハロゲン化スルホン酸またはその塩を用いてアルキレンオキシド末端の水酸基と反応させることにより製造することができる。
When Z is a sulfo group, the compound represented by formula (3) is a sulfate ester if k=0, and a sulfonic acid if k=1. For example, a sulfate ester can be produced by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then reacting sulfamic acid with a hydroxyl group at the end of the alkylene oxide. Further, for example, a sulfonic acid can be produced by adding the above alkylene oxide and then reacting it with a hydroxyl group at the end of the alkylene oxide using a monohalogenated sulfonic acid or a salt thereof.
化合物（ｄ）の配合量は、特に限定されず、例えば、イソシアネート含有組成物１００質量％中に０．０１～５質量％でもよく、０．０３～２質量％でもよく、０．０５～１質量％でもよい。
The amount of the compound (d) is not particularly limited, and may be, for example, 0.01 to 5% by mass, 0.03 to 2% by mass, or 0.05 to 1% in 100% by mass of the isocyanate-containing composition. % by mass may be used.
［その他の成分］
イソシアネート含有組成物において、ポリイソシアネート化合物としては、上記ウレタンプレポリマー（ａ）単独でもよいが、ウレタンプレポリマー（ａ）とともに他のポリイソシアネート化合物を併用してもよい。 [Other ingredients]
In the isocyanate-containing composition, the urethane prepolymer (a) may be used alone as the polyisocyanate compound, or the urethane prepolymer (a) may be used in combination with another polyisocyanate compound.
イソシアネート含有組成物において、ポリイソシアネート化合物としては、上記ウレタンプレポリマー（ａ）単独でもよいが、ウレタンプレポリマー（ａ）とともに他のポリイソシアネート化合物を併用してもよい。 [Other ingredients]
In the isocyanate-containing composition, the urethane prepolymer (a) may be used alone as the polyisocyanate compound, or the urethane prepolymer (a) may be used in combination with another polyisocyanate compound.
他のポリイソシアネート化合物としては、特に限定されず、１分子中に２つ以上のイソシアネート基を有する種々のポリイソシアネート化合物を用いることができ、例えば、脂肪族ポリイソシアネート、脂環式ポリイソシアネート、および芳香族ポリイソシアネート、ならびにこれらの変性体および多核体が挙げられ、いずれか１種用いても２種以上併用してもよい。脂肪族ポリイソシアネートおよび脂環式ポリイソシアネートの具体例としては、上述した脂肪族ジイソシアネートおよび脂環式ジイソシアネートが挙げられる。芳香族ポリイソシアネートとしては、例えば、トリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、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（ＸＤＩ）、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などが挙げられる。これらのポリイソシアネート化合物の変性体としては、例えば、イソシアヌレート変性体、アロファネート変性体、ビュレット変性体、アダクト変性体、カルボジイミド変性体などが挙げられる。
Other polyisocyanate compounds are not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, and Aromatic polyisocyanates, and modified and polynuclear compounds thereof may be mentioned, and any one of them may be used alone or two or more of them may be used in combination. Specific examples of aliphatic polyisocyanates and alicyclic polyisocyanates include the above-mentioned aliphatic diisocyanates and alicyclic diisocyanates. Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3- phenylene diisocyanate, 1,4-phenylene diisocyanate, and the like. Modified products of these polyisocyanate compounds include, for example, isocyanurate modified products, allophanate modified products, buret modified products, adduct modified products, and carbodiimide modified products.
これらの中でも、他のポリイソシアネート化合物としては、上記ポリイソシアネート化合物のイソシアヌレート変性体を用いることが好ましく、より好ましくは脂肪族ポリイソシアネートのイソシアヌレート変性体である。その場合、該イソシアヌレート変性体の配合量は、特に限定されないが、例えば、イソシアネート含有組成物１００質量％中に０．０５～５質量％であることが好ましく、より好ましくは０．１～２質量％である。なお、ポリイソシアネート化合物は、上記ウレタンプレポリマー（ａ）を主成分とすることが好ましく、他のポリイソシアネート化合物を併用する場合でも、ポリイソシアネート化合物全体の５０質量％超、より好ましくは６０質量％以上が上記ウレタンプレポリマー（ａ）であることが好ましい。
Among these, as other polyisocyanate compounds, it is preferable to use isocyanurate-modified polyisocyanate compounds, more preferably isocyanurate-modified aliphatic polyisocyanates. In that case, the amount of the modified isocyanurate compounded is not particularly limited. % by mass. The polyisocyanate compound preferably contains the urethane prepolymer (a) as a main component, and even when used in combination with other polyisocyanate compounds, the total polyisocyanate compound exceeds 50% by mass, more preferably 60% by mass. The above is preferably the urethane prepolymer (a).
イソシアネート含有組成物には、上記成分の他、例えば、吸湿剤、酸化防止剤、整泡剤、希釈剤、難燃剤、紫外線吸収剤、着色剤などの各種添加剤を、本実施形態の目的を損なわない範囲で加えることができる。
In addition to the above components, the isocyanate-containing composition contains various additives such as moisture absorbers, antioxidants, foam stabilizers, diluents, flame retardants, ultraviolet absorbers, and colorants. It can be added as long as it does not damage it.
イソシアネート含有組成物のイソシアネート価（ＮＣＯＶ）は、特に限定されず、１．０～１０ｍｇＫＯＨ／ｇでもよく、１．５～８．０ｍｇＫＯＨ／ｇでもよく、２．０～７．５ｍｇＫＯＨ／ｇでもよい。
The isocyanate value (NCOV) of the isocyanate-containing composition is not particularly limited, and may be 1.0 to 10 mgKOH/g, 1.5 to 8.0 mgKOH/g, or 2.0 to 7.5 mgKOH/g. .
＜ポリオール含有組成物＞
［ポリオール（ｅ）］
ポリオール含有組成物は、ポリオール（ｅ）を含む。ポリオール（ｅ）としては、特に限定されず、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどが挙げられ、これらはいずれか一種または二種以上組み合わせて用いることができる。これらの中でも、ポリブタジエンポリオールを用いることが好ましい。ポリブタジエンポリオールとしては、ポリブタジエン構造の両末端にそれぞれ水酸基を有するものがより好ましく、水素添加したものでもよい。ポリブタジエンポリオールの平均官能基数は２．０～２．５であることが好ましく、より好ましくは２．１～２．４である。 <Polyol-containing composition>
[Polyol (e)]
The polyol-containing composition contains polyol (e). The polyol (e) is not particularly limited, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, etc., and these can be used singly or in combination of two or more. . Among these, polybutadiene polyol is preferably used. As the polybutadiene polyol, those having hydroxyl groups at both ends of the polybutadiene structure are more preferable, and hydrogenated polybutadiene polyols may also be used. The average functionality of polybutadiene polyol is preferably 2.0 to 2.5, more preferably 2.1 to 2.4.
［ポリオール（ｅ）］
ポリオール含有組成物は、ポリオール（ｅ）を含む。ポリオール（ｅ）としては、特に限定されず、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどが挙げられ、これらはいずれか一種または二種以上組み合わせて用いることができる。これらの中でも、ポリブタジエンポリオールを用いることが好ましい。ポリブタジエンポリオールとしては、ポリブタジエン構造の両末端にそれぞれ水酸基を有するものがより好ましく、水素添加したものでもよい。ポリブタジエンポリオールの平均官能基数は２．０～２．５であることが好ましく、より好ましくは２．１～２．４である。 <Polyol-containing composition>
[Polyol (e)]
The polyol-containing composition contains polyol (e). The polyol (e) is not particularly limited, and examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, etc., and these can be used singly or in combination of two or more. . Among these, polybutadiene polyol is preferably used. As the polybutadiene polyol, those having hydroxyl groups at both ends of the polybutadiene structure are more preferable, and hydrogenated polybutadiene polyols may also be used. The average functionality of polybutadiene polyol is preferably 2.0 to 2.5, more preferably 2.1 to 2.4.
ポリオール（ｅ）の配合量は、特に限定されないが、ポリオール含有組成物１００質量％中に２～３０質量％であることが好ましく、より好ましくは３～２５質量％であり、更に好ましくは５～２０質量％である。
The amount of the polyol (e) is not particularly limited, but it is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 5 to 30% by mass in 100% by mass of the polyol-containing composition. 20% by mass.
［無機充填剤（ｆ）］
ポリオール含有組成物は、無機充填剤（ｆ）を含む。無機充填剤（ｆ）を配合することにより、硬化後のポリウレタン樹脂に放熱性を付与することができる。無機充填剤（ｆ）としては、特に限定されず、例えば、アルミナ、酸化マグネシウムなどの金属酸化物、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、窒化アルミニウム、窒化ホウ素などの金属窒化物などが挙げられる。これらはいずれか一種または二種以上組み合わせて用いることができる。 [Inorganic filler (f)]
The polyol-containing composition contains an inorganic filler (f). By blending the inorganic filler (f), heat dissipation can be imparted to the cured polyurethane resin. The inorganic filler (f) is not particularly limited, and examples thereof include metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. etc. These can be used either singly or in combination of two or more.
ポリオール含有組成物は、無機充填剤（ｆ）を含む。無機充填剤（ｆ）を配合することにより、硬化後のポリウレタン樹脂に放熱性を付与することができる。無機充填剤（ｆ）としては、特に限定されず、例えば、アルミナ、酸化マグネシウムなどの金属酸化物、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、窒化アルミニウム、窒化ホウ素などの金属窒化物などが挙げられる。これらはいずれか一種または二種以上組み合わせて用いることができる。 [Inorganic filler (f)]
The polyol-containing composition contains an inorganic filler (f). By blending the inorganic filler (f), heat dissipation can be imparted to the cured polyurethane resin. The inorganic filler (f) is not particularly limited, and examples thereof include metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. etc. These can be used either singly or in combination of two or more.
無機充填剤（ｆ）の配合量は、ポリオール含有組成物１００質量％中に５０～９５質量％であることが好ましく、より好ましくは６０質量％以上であり、より好ましくは７０質量％以上であり、更に好ましくは８０質量％以上であり、また９０質量％以下であることが好ましい。
［可塑剤（ｇ）］
ポリオール含有組成物は、可塑剤（ｇ）を含んでもよい。可塑剤（ｇ）を含むことにより、硬化後のポリウレタン樹脂の硬度を下げることができる。可塑剤（ｇ）としては、特に限定されず、上述のフタル酸ジエステル、アジピン酸ジエステル、トリメリット酸エステル、ピロメリット酸エステル、リン酸トリエステルなどが挙げられ、これらはいずれか一種または二種以上組み合わせて用いることができる。これらの中でも、可塑剤（ｇ）としては、フタル酸ジエステルおよび／またはアジピン酸ジエステルが好ましい。 The content of the inorganic filler (f) is preferably 50 to 95% by mass, more preferably 60% by mass or more, and more preferably 70% by mass or more in 100% by mass of the polyol-containing composition. , more preferably 80% by mass or more, and preferably 90% by mass or less.
[Plasticizer (g)]
The polyol-containing composition may contain a plasticizer (g). By containing the plasticizer (g), the hardness of the cured polyurethane resin can be lowered. The plasticizer (g) is not particularly limited, and includes the above-mentioned phthalate diesters, adipate diesters, trimellitate esters, pyromellitic acid esters, and phosphate triesters. The above can be used in combination. Among these, phthalate diesters and/or adipate diesters are preferred as the plasticizer (g).
［可塑剤（ｇ）］
ポリオール含有組成物は、可塑剤（ｇ）を含んでもよい。可塑剤（ｇ）を含むことにより、硬化後のポリウレタン樹脂の硬度を下げることができる。可塑剤（ｇ）としては、特に限定されず、上述のフタル酸ジエステル、アジピン酸ジエステル、トリメリット酸エステル、ピロメリット酸エステル、リン酸トリエステルなどが挙げられ、これらはいずれか一種または二種以上組み合わせて用いることができる。これらの中でも、可塑剤（ｇ）としては、フタル酸ジエステルおよび／またはアジピン酸ジエステルが好ましい。 The content of the inorganic filler (f) is preferably 50 to 95% by mass, more preferably 60% by mass or more, and more preferably 70% by mass or more in 100% by mass of the polyol-containing composition. , more preferably 80% by mass or more, and preferably 90% by mass or less.
[Plasticizer (g)]
The polyol-containing composition may contain a plasticizer (g). By containing the plasticizer (g), the hardness of the cured polyurethane resin can be lowered. The plasticizer (g) is not particularly limited, and includes the above-mentioned phthalate diesters, adipate diesters, trimellitate esters, pyromellitic acid esters, and phosphate triesters. The above can be used in combination. Among these, phthalate diesters and/or adipate diesters are preferred as the plasticizer (g).
可塑剤（ｇ）の配合量は、特に限定されず、例えば、ポリオール含有組成物１００質量％中に１～３０質量％でもよく、３～２５質量％でもよく、５～２０質量％でもよく、５～１５質量％でもよい。
［リン酸エステル（ｈ）］
ポリオール含有組成物は、リン酸エステル（ｈ）を含んでもよい。リン酸エステル（ｈ）を含むことにより、ポリオール含有組成物（ｈ）の粘度を低減することができる。リン酸エステル（ｈ）としては上記式（１）で表される化合物が用いられる。 The amount of the plasticizer (g) is not particularly limited, and may be, for example, 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass in 100% by mass of the polyol-containing composition. It may be 5 to 15% by mass.
[Phosphate ester (h)]
The polyol-containing composition may contain a phosphate ester (h). By containing the phosphate ester (h), the viscosity of the polyol-containing composition (h) can be reduced. A compound represented by the above formula (1) is used as the phosphate ester (h).
［リン酸エステル（ｈ）］
ポリオール含有組成物は、リン酸エステル（ｈ）を含んでもよい。リン酸エステル（ｈ）を含むことにより、ポリオール含有組成物（ｈ）の粘度を低減することができる。リン酸エステル（ｈ）としては上記式（１）で表される化合物が用いられる。 The amount of the plasticizer (g) is not particularly limited, and may be, for example, 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass in 100% by mass of the polyol-containing composition. It may be 5 to 15% by mass.
[Phosphate ester (h)]
The polyol-containing composition may contain a phosphate ester (h). By containing the phosphate ester (h), the viscosity of the polyol-containing composition (h) can be reduced. A compound represented by the above formula (1) is used as the phosphate ester (h).
リン酸エステル（ｈ）の配合量は、特に限定されず、例えば、ポリオール含有組成物１００質量％中に０．０１～５質量％でもよく、０．０３～２質量％でもよく、０．０５～１質量％でもよい。
The amount of the phosphate ester (h) is not particularly limited, and may be, for example, 0.01 to 5% by mass, 0.03 to 2% by mass, or 0.05% by mass in 100% by mass of the polyol-containing composition. It may be up to 1% by mass.
［その他の成分］
ポリオール含有組成物には、上記成分の他、例えば、吸湿剤、触媒、酸化防止剤、整泡剤、希釈剤、難燃剤、紫外線吸収剤、着色剤などの各種添加剤を、本実施形態の目的を損なわない範囲で加えることができる。 [Other ingredients]
In the polyol-containing composition, in addition to the above components, various additives such as a moisture absorbent, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, and a colorant may be added according to the present embodiment. It can be added as long as it does not impair the purpose.
ポリオール含有組成物には、上記成分の他、例えば、吸湿剤、触媒、酸化防止剤、整泡剤、希釈剤、難燃剤、紫外線吸収剤、着色剤などの各種添加剤を、本実施形態の目的を損なわない範囲で加えることができる。 [Other ingredients]
In the polyol-containing composition, in addition to the above components, various additives such as a moisture absorbent, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, an ultraviolet absorber, and a colorant may be added according to the present embodiment. It can be added as long as it does not impair the purpose.
触媒としては、例えば、有機スズ触媒、有機鉛触媒、有機ビスマス触媒などの金属触媒、アミン触媒などの各種ウレタン重合触媒を用いることができる。
As the catalyst, for example, metal catalysts such as organic tin catalysts, organic lead catalysts, and organic bismuth catalysts, and various urethane polymerization catalysts such as amine catalysts can be used.
ポリオール含有組成物の水酸基価（ＯＨＶ）は、特に限定されず、１．０～１５ｍｇＫＯＨ／ｇでもよく、２．０～１０ｍｇＫＯＨ／ｇでもよい。
The hydroxyl value (OHV) of the polyol-containing composition is not particularly limited, and may be 1.0-15 mgKOH/g or 2.0-10 mgKOH/g.
＜２液反応型ポリウレタン樹脂組成物＞
本実施形態に係る２液反応型ポリウレタン樹脂組成物は、通常は、ポリオール含有組成物である第１液とイソシアネート含有組成物である第２液とで構成されるが、ポリオール含有組成物およびイソシアネート含有組成物の他に、任意成分としての上記その他の成分を含むものを第３液として備えてもよい。 <Two-liquid reactive polyurethane resin composition>
The two-component reactive polyurethane resin composition according to the present embodiment is usually composed of a first component that is a polyol-containing composition and a second component that is an isocyanate-containing composition. In addition to the contained composition, the third liquid may contain any of the above-mentioned other components as optional components.
本実施形態に係る２液反応型ポリウレタン樹脂組成物は、通常は、ポリオール含有組成物である第１液とイソシアネート含有組成物である第２液とで構成されるが、ポリオール含有組成物およびイソシアネート含有組成物の他に、任意成分としての上記その他の成分を含むものを第３液として備えてもよい。 <Two-liquid reactive polyurethane resin composition>
The two-component reactive polyurethane resin composition according to the present embodiment is usually composed of a first component that is a polyol-containing composition and a second component that is an isocyanate-containing composition. In addition to the contained composition, the third liquid may contain any of the above-mentioned other components as optional components.
２液反応型ポリウレタン樹脂組成物は、ポリオール含有組成物とイソシアネート含有組成物をそれぞれ調製することにより製造することができ、すなわち、ポリオール含有組成物とイソシアネート含有組成物はそれぞれ別の容器に充填されたものでもよい。別々の容器に充填されたポリオール含有組成物とイソシアネート含有組成物は、使用時に混合されることによりポリオールとポリイソシアネートが反応してポリウレタン樹脂が形成され、硬化してもよい。その際、加熱により硬化させてもよい。実施形態に係る２液反応型ポリウレタン樹脂組成物は、ポリオール含有組成物とイソシアネート含有組成物を混合して得られたものであってもよく、硬化前の液状でもよく、硬化していてもよい。
The two-component reactive polyurethane resin composition can be produced by preparing a polyol-containing composition and an isocyanate-containing composition, respectively. Anything is fine. The polyol-containing composition and the isocyanate-containing composition, which are filled in separate containers, may be mixed at the time of use so that the polyol and the polyisocyanate react to form a polyurethane resin and cure. At that time, it may be cured by heating. The two-liquid reactive polyurethane resin composition according to the embodiment may be obtained by mixing a polyol-containing composition and an isocyanate-containing composition, may be in a liquid state before curing, or may be in a cured state. .
２液反応型ポリウレタン樹脂組成物において、ポリオール含有組成物とイソシアネート含有組成物との混合比は、特に限定されず、例えば、ポリオール含有組成物に含まれる水酸基に対するイソシアネート含有組成物に含まれるイソシアネート基のモル比ＮＣＯ／ＯＨ（インデックス）が０．５～１．２でもよく、０．６～０．９でもよい。ここで、ＮＣＯ／ＯＨは、上記のイソシアネート価（ＮＣＯＶ）と水酸基価（ＯＨＶ）から、ＮＣＯＶ／ＯＨＶとして算出される。
In the two-component reactive polyurethane resin composition, the mixing ratio of the polyol-containing composition and the isocyanate-containing composition is not particularly limited. The molar ratio NCO/OH (index) of may be from 0.5 to 1.2, or from 0.6 to 0.9. Here, NCO/OH is calculated as NCOV/OHV from the above isocyanate value (NCOV) and hydroxyl value (OHV).
２液反応型ポリウレタン樹脂組成物において、ポリオール含有組成物とイソシアネート含有組成物との容量配合比は、特に限定されないが、ポリオール含有組成物／イソシアネート含有組成物＝３０／７０～７０／３０であることが好ましく、より好ましくは４０／６０～６０／４０であり、更に好ましくは４５／５５～５５／４５である。
In the two-liquid reactive polyurethane resin composition, the mixing ratio by volume of the polyol-containing composition and the isocyanate-containing composition is not particularly limited, but is polyol-containing composition/isocyanate-containing composition=30/70 to 70/30. is preferred, more preferably 40/60 to 60/40, still more preferably 45/55 to 55/45.
２液反応型ポリウレタン樹脂組成物の硬化後の硬度は、特に限定されないが、ショア（shore）Ｃの硬度が６０以下であることが好ましく、３０～６０でもよい。
The hardness of the two-liquid reactive polyurethane resin composition after curing is not particularly limited, but the shore C hardness is preferably 60 or less, and may be 30-60.
２液反応型ポリウレタン樹脂組成物の硬化後の熱伝導率（ＪＩＳ Ｒ２６１８）は、特に限定されず、例えば１．０Ｗ／ｍ・Ｋ以上でもよく、２．０Ｗ／ｍ・Ｋ以上でもよく、２．０～３．０Ｗ／ｍ・Ｋでもよい。
The thermal conductivity (JIS R2618) of the two-liquid reactive polyurethane resin composition after curing is not particularly limited, and may be, for example, 1.0 W/m·K or more, or 2.0 W/m·K or more. 0 to 3.0 W/m·K.
＜２液反応型ポリウレタン樹脂組成物の用途＞
本実施形態に係る２液反応型ポリウレタン樹脂組成物の用途は、特に限定されず、電気電子部品や車載向けなどの様々な用途に用いることができる。無機充填剤を配合することで放熱性を持つことから放熱材料として好適に用いられる。一実施形態として、バッテリー等の熱源に対する放熱性のギャップフィラーとして好適に用いられる。 <Application of two-liquid reactive polyurethane resin composition>
Applications of the two-liquid reactive polyurethane resin composition according to the present embodiment are not particularly limited, and can be used for various applications such as electrical and electronic parts and vehicles. It is suitable for use as a heat-dissipating material because it has heat-dissipating properties when an inorganic filler is added. As one embodiment, it is preferably used as a heat dissipation gap filler for a heat source such as a battery.
本実施形態に係る２液反応型ポリウレタン樹脂組成物の用途は、特に限定されず、電気電子部品や車載向けなどの様々な用途に用いることができる。無機充填剤を配合することで放熱性を持つことから放熱材料として好適に用いられる。一実施形態として、バッテリー等の熱源に対する放熱性のギャップフィラーとして好適に用いられる。 <Application of two-liquid reactive polyurethane resin composition>
Applications of the two-liquid reactive polyurethane resin composition according to the present embodiment are not particularly limited, and can be used for various applications such as electrical and electronic parts and vehicles. It is suitable for use as a heat-dissipating material because it has heat-dissipating properties when an inorganic filler is added. As one embodiment, it is preferably used as a heat dissipation gap filler for a heat source such as a battery.
以下、実施例及び比較例に基づいて、２液反応型ポリウレタン樹脂組成物について詳細に説明するが、本発明はこれにより限定されない。
The two-liquid reactive polyurethane resin composition will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited thereto.
実施例及び比較例において使用した原料を以下に示す。
［無機充填剤］
・水酸化アルミニウム：住友化学株式会社製「ＣＷ－３５０」（密度２．４ｇ／ｃｍ３）
・アルミナ１：デンカ株式会社製「ＤＡＷ－４５」（密度４．０ｇ／ｃｍ３）
・アルミナ２：デンカ株式会社製「ＤＡＷ－０３」（密度４．０ｇ／ｃｍ３） Raw materials used in Examples and Comparative Examples are shown below.
[Inorganic filler]
・ Aluminum hydroxide: "CW-350" manufactured by Sumitomo Chemical Co., Ltd. (density 2.4 g / cm 3 )
・Alumina 1: “DAW-45” manufactured by Denka Co., Ltd. (density 4.0 g/cm 3 )
・Alumina 2: “DAW-03” manufactured by Denka Co., Ltd. (density 4.0 g/cm 3 )
［無機充填剤］
・水酸化アルミニウム：住友化学株式会社製「ＣＷ－３５０」（密度２．４ｇ／ｃｍ３）
・アルミナ１：デンカ株式会社製「ＤＡＷ－４５」（密度４．０ｇ／ｃｍ３）
・アルミナ２：デンカ株式会社製「ＤＡＷ－０３」（密度４．０ｇ／ｃｍ３） Raw materials used in Examples and Comparative Examples are shown below.
[Inorganic filler]
・ Aluminum hydroxide: "CW-350" manufactured by Sumitomo Chemical Co., Ltd. (density 2.4 g / cm 3 )
・Alumina 1: “DAW-45” manufactured by Denka Co., Ltd. (density 4.0 g/cm 3 )
・Alumina 2: “DAW-03” manufactured by Denka Co., Ltd. (density 4.0 g/cm 3 )
［ポリオール］
・ポリブタジエンポリオール：エボニック社製「ＰＯＬＹＶＥＳＴ ＨＴ」、平均官能基数２．３
［可塑剤］
・ＤＵＰ：フタル酸ジウンデシル
・ＤＯＡ：アジピン酸ジ２－エチルヘキシル [Polyol]
· Polybutadiene polyol: "POLYVEST HT" manufactured by Evonik, average functionality 2.3
[Plasticizer]
・DUP: diundecyl phthalate ・DOA: di-2-ethylhexyl adipate
・ポリブタジエンポリオール：エボニック社製「ＰＯＬＹＶＥＳＴ ＨＴ」、平均官能基数２．３
［可塑剤］
・ＤＵＰ：フタル酸ジウンデシル
・ＤＯＡ：アジピン酸ジ２－エチルヘキシル [Polyol]
· Polybutadiene polyol: "POLYVEST HT" manufactured by Evonik, average functionality 2.3
[Plasticizer]
・DUP: diundecyl phthalate ・DOA: di-2-ethylhexyl adipate
［ポリイソシアネート化合物］
・イソシアヌレート：イソシアヌレート変性ＨＤＩ、万華化学製「ＨＴ６００」
［吸湿剤］
・吸湿剤：ユニオン昭和株式会社製「モレキュラーシーブ３ＡＢ」 [Polyisocyanate compound]
・Isocyanurate: Isocyanurate-modified HDI, Wanhua Chemical "HT600"
[Moisture absorbent]
・Moisture absorbent: "Molecular sieve 3AB" manufactured by Union Showa Co., Ltd.
・イソシアヌレート：イソシアヌレート変性ＨＤＩ、万華化学製「ＨＴ６００」
［吸湿剤］
・吸湿剤：ユニオン昭和株式会社製「モレキュラーシーブ３ＡＢ」 [Polyisocyanate compound]
・Isocyanurate: Isocyanurate-modified HDI, Wanhua Chemical "HT600"
[Moisture absorbent]
・Moisture absorbent: "Molecular sieve 3AB" manufactured by Union Showa Co., Ltd.
実施例および比較例で使用したイソシアネート基含有ウレタンプレポリマーであるプレポリマー１～７の合成例を以下に示す。
Synthesis examples of prepolymers 1 to 7, which are isocyanate group-containing urethane prepolymers used in Examples and Comparative Examples, are shown below.
［プレポリマー１］
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）３３質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量７００、水酸基価１６０）（ＡＧＣ株式会社製「エクセノール７２０」）６７質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー１）を得た。 [Prepolymer 1]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 700, hydroxyl value 160) (“EXENOL 720” manufactured by AGC Co., Ltd.) and 67 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 1) by reacting at 90°C for 2 hours. Obtained.
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）３３質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量７００、水酸基価１６０）（ＡＧＣ株式会社製「エクセノール７２０」）６７質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー１）を得た。 [Prepolymer 1]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 700, hydroxyl value 160) (“EXENOL 720” manufactured by AGC Co., Ltd.) and 67 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 1) by reacting at 90°C for 2 hours. Obtained.
［プレポリマー２］
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）２６質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量１０００、水酸基価１１２）（ＡＧＣ株式会社製「エクセノール１０２０」）７４質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー２）を得た。 [Prepolymer 2]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 26 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 1000, hydroxyl value 112) ("EXENOL 1020" manufactured by AGC Co., Ltd.) and 74 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 2) by reacting at 90°C for 2 hours. Obtained.
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）２６質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量１０００、水酸基価１１２）（ＡＧＣ株式会社製「エクセノール１０２０」）７４質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー２）を得た。 [Prepolymer 2]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 26 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 1000, hydroxyl value 112) ("EXENOL 1020" manufactured by AGC Co., Ltd.) and 74 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 2) by reacting at 90°C for 2 hours. Obtained.
［プレポリマー３］
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）１０質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量３０００、水酸基価３５）（ＡＧＣ株式会社製「エクセノール３０２０」）９０質量部とを１２０℃で６時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー３）を得た。 [Prepolymer 3]
10 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 3000, hydroxyl value 35) (“EXENOL 3020” manufactured by AGC Co., Ltd.) and 90 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 3) by reacting it at 120°C for 6 hours. Obtained.
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）１０質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量３０００、水酸基価３５）（ＡＧＣ株式会社製「エクセノール３０２０」）９０質量部とを１２０℃で６時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー３）を得た。 [Prepolymer 3]
10 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Corporation) and polypropylene glycol (average functional group number 2.0, weight average molecular weight 3000, hydroxyl value 35) (“EXENOL 3020” manufactured by AGC Co., Ltd.) and 90 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 3) by reacting it at 120°C for 6 hours. Obtained.
［プレポリマー４］
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、イソホロンジイソシアネート（ＩＰＤＩ）（ＥＶＯＮＩＫ社製「ＩＰＤＩ」）３１質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量１０００、水酸基価１１２）（ＡＧＣ株式会社製「エクセノール１０２０」）６９質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー４）を得た。 [Prepolymer 4]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 31 parts by mass of isophorone diisocyanate (IPDI) ("IPDI" manufactured by EVONIK) and polypropylene glycol (average functionality: 2.0 , weight average molecular weight: 1000, hydroxyl value: 112) ("EXENOL 1020" manufactured by AGC) was reacted with 69 parts by mass at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 4).
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、イソホロンジイソシアネート（ＩＰＤＩ）（ＥＶＯＮＩＫ社製「ＩＰＤＩ」）３１質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量１０００、水酸基価１１２）（ＡＧＣ株式会社製「エクセノール１０２０」）６９質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー４）を得た。 [Prepolymer 4]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 31 parts by mass of isophorone diisocyanate (IPDI) ("IPDI" manufactured by EVONIK) and polypropylene glycol (average functionality: 2.0 , weight average molecular weight: 1000, hydroxyl value: 112) ("EXENOL 1020" manufactured by AGC) was reacted with 69 parts by mass at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 4).
［プレポリマー５］
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）４６質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量４００、水酸基価２８１）（ＡＧＣ株式会社製「エクセノール４２０」）５４質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー５）を得た。 [Prepolymer 5]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 46 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 400, hydroxyl value 281) ("EXENOL 420" manufactured by AGC Co., Ltd.) and 54 parts by mass of the isocyanate group-terminated urethane prepolymer (Prepolymer 5) by reacting it at 90°C for 2 hours. Obtained.
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）４６質量部と、ポリプロピレングリコール（平均官能基数２．０、重量平均分子量４００、水酸基価２８１）（ＡＧＣ株式会社製「エクセノール４２０」）５４質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー５）を得た。 [Prepolymer 5]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 46 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Corporation "Duranate 50M") and polypropylene glycol (average functional group number 2.0, weight average molecular weight 400, hydroxyl value 281) ("EXENOL 420" manufactured by AGC Co., Ltd.) and 54 parts by mass of the isocyanate group-terminated urethane prepolymer (Prepolymer 5) by reacting it at 90°C for 2 hours. Obtained.
［プレポリマー６］
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）１２質量部と、ポリブタジエンポリオール（平均官能基数２．３、重量平均分子量３０００、水酸基価４６）（ＥＶＯＮＩＫ社製「ＰＯＬＹＶＥＳＴ ＨＴ」）８８質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー６）を得た。 [Prepolymer 6]
12 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Corporation) and polybutadiene polyol (average functional group number 2.3, weight average molecular weight 3000, hydroxyl value 46) ("POLYVEST HT" manufactured by EVONIK) and 88 parts by mass of the mixture were reacted at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 6). rice field.
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）１２質量部と、ポリブタジエンポリオール（平均官能基数２．３、重量平均分子量３０００、水酸基価４６）（ＥＶＯＮＩＫ社製「ＰＯＬＹＶＥＳＴ ＨＴ」）８８質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー６）を得た。 [Prepolymer 6]
12 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Corporation) and polybutadiene polyol (average functional group number 2.3, weight average molecular weight 3000, hydroxyl value 46) ("POLYVEST HT" manufactured by EVONIK) and 88 parts by mass of the mixture were reacted at 90°C for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 6). rice field.
［プレポリマー７］
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）３３質量部と、ひまし油（平均官能基数２．７、重量平均分子量９４１、水酸基価１６１）（伊藤製油株式会社製「ＵＲＩＣ Ｈ３０」）６８質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー７）を得た。 [Prepolymer 7]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (“Duranate 50M” manufactured by Asahi Kasei Corporation) and castor oil (average functional group number of 2 .7, weight average molecular weight 941, hydroxyl value 161) ("URIC H30" manufactured by Ito Seiyu Co., Ltd.) and 68 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 7) were reacted at 90°C for 2 hours. Obtained.
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた４つ口フラスコ内で、ヘキサメチレンジイソシアネート（ＨＤＩ）（旭化成株式会社製「デュラネート５０Ｍ」）３３質量部と、ひまし油（平均官能基数２．７、重量平均分子量９４１、水酸基価１６１）（伊藤製油株式会社製「ＵＲＩＣ Ｈ３０」）６８質量部とを９０℃で２時間反応させることにより、イソシアネート基末端ウレタンプレポリマー（プレポリマー７）を得た。 [Prepolymer 7]
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) (“Duranate 50M” manufactured by Asahi Kasei Corporation) and castor oil (average functional group number of 2 .7, weight average molecular weight 941, hydroxyl value 161) ("URIC H30" manufactured by Ito Seiyu Co., Ltd.) and 68 parts by mass of the isocyanate group-terminated urethane prepolymer (prepolymer 7) were reacted at 90°C for 2 hours. Obtained.
実施例および比較例で使用した化合物（ｄ）であるリン酸エステル１～３、硫酸アンモニウム塩、カルボン酸１～３の合成例を以下に示す。
Synthesis examples of phosphate esters 1 to 3, ammonium sulfate salts, and carboxylic acids 1 to 3, which are compounds (d) used in Examples and Comparative Examples, are shown below.
［リン酸エステル１］
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、得られたエチレンオキシド１０モル付加体に無水リン酸４７ｇ（０．３３モル）を８０℃で５時間反応させることで一般式（１）のリン酸エステル１（式中、Ｒ２：トリデシル、Ａ１Ｏ：ＥＯ、ｍ：１０、モノエステルとジエステルのモル比１：１の混合物）を得た。 [Phosphate ester 1]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Next, 47 g (0.33 mol) of phosphoric anhydride was reacted with the resulting 10 mol adduct of ethylene oxide at 80° C. for 5 hours to obtain a phosphoric acid ester 1 of general formula (1) (wherein R 2 : tridecyl, A 1 O:EO, m:10, a mixture of mono- and diesters in a molar ratio of 1:1).
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、得られたエチレンオキシド１０モル付加体に無水リン酸４７ｇ（０．３３モル）を８０℃で５時間反応させることで一般式（１）のリン酸エステル１（式中、Ｒ２：トリデシル、Ａ１Ｏ：ＥＯ、ｍ：１０、モノエステルとジエステルのモル比１：１の混合物）を得た。 [Phosphate ester 1]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Next, 47 g (0.33 mol) of phosphoric anhydride was reacted with the resulting 10 mol adduct of ethylene oxide at 80° C. for 5 hours to obtain a phosphoric acid ester 1 of general formula (1) (wherein R 2 : tridecyl, A 1 O:EO, m:10, a mixture of mono- and diesters in a molar ratio of 1:1).
［リン酸エステル２］
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、ラウリル１８６ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド８１５ｇ（１８．５モル）を逐次導入して反応させた後、酢酸で中和した。次いで、得られたエチレンオキシド１８．５モル付加体に無水リン酸４７ｇ（０．３３モル）を８０℃で５時間反応させることで一般式（１）のリン酸エステル２（式中、Ｒ２：ラウリル、Ａ１Ｏ：ＥＯ、ｍ：１８．５、モノエステルとジエステルのモル比１：１の混合物）を得た。 [Phosphate ester 2]
186 g (1.0 mol) of lauryl and 5 g of potassium hydroxide as a catalyst are charged into an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube, The atmosphere in the autoclave was replaced with nitrogen, and 815 g (18.5 mol) of ethylene oxide was successively introduced under conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Next, 47 g (0.33 mol) of phosphoric anhydride was reacted with the obtained 18.5 mol adduct of ethylene oxide at 80° C. for 5 hours to give the phosphoric acid ester 2 of general formula (1) (wherein R 2 : Lauryl, A 1 O:EO, m: 18.5, a mixture of mono- and diesters in a molar ratio of 1:1).
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、ラウリル１８６ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド８１５ｇ（１８．５モル）を逐次導入して反応させた後、酢酸で中和した。次いで、得られたエチレンオキシド１８．５モル付加体に無水リン酸４７ｇ（０．３３モル）を８０℃で５時間反応させることで一般式（１）のリン酸エステル２（式中、Ｒ２：ラウリル、Ａ１Ｏ：ＥＯ、ｍ：１８．５、モノエステルとジエステルのモル比１：１の混合物）を得た。 [Phosphate ester 2]
186 g (1.0 mol) of lauryl and 5 g of potassium hydroxide as a catalyst are charged into an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube, The atmosphere in the autoclave was replaced with nitrogen, and 815 g (18.5 mol) of ethylene oxide was successively introduced under conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Next, 47 g (0.33 mol) of phosphoric anhydride was reacted with the obtained 18.5 mol adduct of ethylene oxide at 80° C. for 5 hours to give the phosphoric acid ester 2 of general formula (1) (wherein R 2 : Lauryl, A 1 O:EO, m: 18.5, a mixture of mono- and diesters in a molar ratio of 1:1).
［リン酸エステル３］
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド２６４ｇ（６モル）とプロピレンオキシド２９０ｇ（５モル）を同時に反応させた後、酢酸で中和した。次いで、得られたエチレンオキシドおよびプロピレンオキシド付加体に無水リン酸４７ｇ（０．３３モル）を８０℃で５時間反応させることで一般式（１）のリン酸エステル３（式中、Ｒ２：トリデシル、（Ａ１Ｏ）ｍ：ＥＯ／ＰＯ（オキシプロピレン基）＝６／５（モル比）のランダム付加体、ｍ：１１、モノエステルとジエステルのモル比１：１の混合物）を得た。 [Phosphate ester 3]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 264 g (6 mol) of ethylene oxide and 290 g (5 mol) of propylene oxide were simultaneously reacted under conditions of a pressure of 0.15 MPa and a temperature of 130°C, and then neutralized with acetic acid. did. Then, the resulting ethylene oxide and propylene oxide adduct was reacted with 47 g (0.33 mol) of phosphoric anhydride at 80° C. for 5 hours to obtain a phosphoric acid ester 3 of general formula (1) (wherein R 2 : tridecyl). , (A 1 O) m : EO/PO (oxypropylene group) = 6/5 (molar ratio) random adduct, m: 11, mixture of monoester and diester molar ratio 1:1).
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド２６４ｇ（６モル）とプロピレンオキシド２９０ｇ（５モル）を同時に反応させた後、酢酸で中和した。次いで、得られたエチレンオキシドおよびプロピレンオキシド付加体に無水リン酸４７ｇ（０．３３モル）を８０℃で５時間反応させることで一般式（１）のリン酸エステル３（式中、Ｒ２：トリデシル、（Ａ１Ｏ）ｍ：ＥＯ／ＰＯ（オキシプロピレン基）＝６／５（モル比）のランダム付加体、ｍ：１１、モノエステルとジエステルのモル比１：１の混合物）を得た。 [Phosphate ester 3]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 264 g (6 mol) of ethylene oxide and 290 g (5 mol) of propylene oxide were simultaneously reacted under conditions of a pressure of 0.15 MPa and a temperature of 130°C, and then neutralized with acetic acid. did. Then, the resulting ethylene oxide and propylene oxide adduct was reacted with 47 g (0.33 mol) of phosphoric anhydride at 80° C. for 5 hours to obtain a phosphoric acid ester 3 of general formula (1) (wherein R 2 : tridecyl). , (A 1 O) m : EO/PO (oxypropylene group) = 6/5 (molar ratio) random adduct, m: 11, mixture of monoester and diester molar ratio 1:1).
［硫酸アンモニウム塩］
撹拌機、温度計、還流管を備えた反応容器に、スチレン化フェノール（モノスチレン化フェノール：ジスチレン化フェノール：トリスチレン化フェノール＝８０：１９：１（質量比）の混合物）２２０ｇ（１．０モル）をオートクレーブに移し、触媒として水酸化カリウムを用いて、圧力０．１５ＭＰａ、温度１３０℃の条件にて、エチレンオキサイド７９２ｇ（１８モル）を付加反応させることにより、ポリオキシエチレンスチレン化フェニルエーテルを得た。続いて、得られたポリオキシエチレンスチレン化フェニルエーテルを、撹拌器、温度計及び窒素導入管を備えた反応容器に移し、窒素雰囲気下、温度１２０℃の条件にてスルファミン酸９７ｇ（１モル）を反応させた。その後、モノエタノールアミンを添加して１質量％水溶液におけるｐＨが７．５となるように調整し、一般式（３）の硫酸アンモニウム塩（式中、Ｒ３：スチレン化フェニル、Ａ３Ｏ：ＥＯ、ｎ：１８、ｋ：０、Ｚ：－ＳＯ３ＮＨ４）を得た。 [Ammonium sulfate]
220 g (1.0 mol) is transferred to an autoclave, and using potassium hydroxide as a catalyst, 792 g (18 mol) of ethylene oxide is subjected to an addition reaction at a pressure of 0.15 MPa and a temperature of 130 ° C. to give polyoxyethylene styrenated phenyl ether. got Subsequently, the obtained polyoxyethylene styrenated phenyl ether was transferred to a reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, and 97 g (1 mol) of sulfamic acid was added under a nitrogen atmosphere at a temperature of 120°C. reacted. Thereafter, monoethanolamine is added to adjust the pH in a 1% by mass aqueous solution to 7.5, and the ammonium sulfate salt of general formula (3) (wherein R 3 : styrenated phenyl, A 3 O: EO , n: 18, k: 0, Z: —SO 3 NH 4 ).
撹拌機、温度計、還流管を備えた反応容器に、スチレン化フェノール（モノスチレン化フェノール：ジスチレン化フェノール：トリスチレン化フェノール＝８０：１９：１（質量比）の混合物）２２０ｇ（１．０モル）をオートクレーブに移し、触媒として水酸化カリウムを用いて、圧力０．１５ＭＰａ、温度１３０℃の条件にて、エチレンオキサイド７９２ｇ（１８モル）を付加反応させることにより、ポリオキシエチレンスチレン化フェニルエーテルを得た。続いて、得られたポリオキシエチレンスチレン化フェニルエーテルを、撹拌器、温度計及び窒素導入管を備えた反応容器に移し、窒素雰囲気下、温度１２０℃の条件にてスルファミン酸９７ｇ（１モル）を反応させた。その後、モノエタノールアミンを添加して１質量％水溶液におけるｐＨが７．５となるように調整し、一般式（３）の硫酸アンモニウム塩（式中、Ｒ３：スチレン化フェニル、Ａ３Ｏ：ＥＯ、ｎ：１８、ｋ：０、Ｚ：－ＳＯ３ＮＨ４）を得た。 [Ammonium sulfate]
220 g (1.0 mol) is transferred to an autoclave, and using potassium hydroxide as a catalyst, 792 g (18 mol) of ethylene oxide is subjected to an addition reaction at a pressure of 0.15 MPa and a temperature of 130 ° C. to give polyoxyethylene styrenated phenyl ether. got Subsequently, the obtained polyoxyethylene styrenated phenyl ether was transferred to a reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, and 97 g (1 mol) of sulfamic acid was added under a nitrogen atmosphere at a temperature of 120°C. reacted. Thereafter, monoethanolamine is added to adjust the pH in a 1% by mass aqueous solution to 7.5, and the ammonium sulfate salt of general formula (3) (wherein R 3 : styrenated phenyl, A 3 O: EO , n: 18, k: 0, Z: —SO 3 NH 4 ).
［カルボン酸１］
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、トルエン溶媒中に、上記エチレンオキシド付加物及びモノクロロ酢酸ナトリウム１５１ｇ（１．３モル）を反応器にとり、均一になるよう撹拌した。その後、反応系の温度が６０℃の条件で、水酸化ナトリウム５２ｇ（１．３モル）を添加した後、反応系の温度を８０℃に昇温させ、３時間反応させた。反応後、９８質量％硫酸１２０ｇ（１．２モル）を滴下することにより、白色懸濁溶液を得た。次いで、この白色懸濁溶液を蒸留水で洗浄し、溶媒を減圧留去することにより、一般式（３）のカルボン酸１を得た（式中、Ｒ３：トリデシル、Ａ３Ｏ：ＥＯ、ｎ：１０、ｋ：１、Ｘ：－ＣＨ２－、Ｚ：－ＣＯＯＨ）。 [Carboxylic acid 1]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Next, the above ethylene oxide adduct and 151 g (1.3 mol) of sodium monochloroacetate were placed in a reactor in a toluene solvent and stirred until uniform. After that, 52 g (1.3 mol) of sodium hydroxide was added under the condition that the temperature of the reaction system was 60° C., and then the temperature of the reaction system was raised to 80° C., and the reaction was carried out for 3 hours. After the reaction, 120 g (1.2 mol) of 98% by mass sulfuric acid was added dropwise to obtain a white suspension solution. Subsequently, this white suspension was washed with distilled water, and the solvent was distilled off under reduced pressure to obtain carboxylic acid 1 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10, k: 1, X: —CH 2 —, Z: —COOH).
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、トルエン溶媒中に、上記エチレンオキシド付加物及びモノクロロ酢酸ナトリウム１５１ｇ（１．３モル）を反応器にとり、均一になるよう撹拌した。その後、反応系の温度が６０℃の条件で、水酸化ナトリウム５２ｇ（１．３モル）を添加した後、反応系の温度を８０℃に昇温させ、３時間反応させた。反応後、９８質量％硫酸１２０ｇ（１．２モル）を滴下することにより、白色懸濁溶液を得た。次いで、この白色懸濁溶液を蒸留水で洗浄し、溶媒を減圧留去することにより、一般式（３）のカルボン酸１を得た（式中、Ｒ３：トリデシル、Ａ３Ｏ：ＥＯ、ｎ：１０、ｋ：１、Ｘ：－ＣＨ２－、Ｚ：－ＣＯＯＨ）。 [Carboxylic acid 1]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Next, the above ethylene oxide adduct and 151 g (1.3 mol) of sodium monochloroacetate were placed in a reactor in a toluene solvent and stirred until uniform. After that, 52 g (1.3 mol) of sodium hydroxide was added under the condition that the temperature of the reaction system was 60° C., and then the temperature of the reaction system was raised to 80° C., and the reaction was carried out for 3 hours. After the reaction, 120 g (1.2 mol) of 98% by mass sulfuric acid was added dropwise to obtain a white suspension solution. Subsequently, this white suspension was washed with distilled water, and the solvent was distilled off under reduced pressure to obtain carboxylic acid 1 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10, k: 1, X: —CH 2 —, Z: —COOH).
［カルボン酸２］
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、スベリン酸無水物１５６ｇ（１モル）を１２０℃で２時間反応させることで一般式（３）のカルボン酸２（式中、Ｒ３：トリデシル、Ａ３Ｏ：ＥＯ、ｎ：１０、ｋ：１、Ｘ：－ＣＯ-（ＣＨ２）６－、Ｚ：－ＣＯＯＨ）。 [Carboxylic acid 2]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Then, 156 g (1 mol) of suberic anhydride is reacted at 120° C. for 2 hours to give carboxylic acid 2 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10, k : 1, X: -CO-(CH 2 ) 6 -, Z: -COOH).
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、スベリン酸無水物１５６ｇ（１モル）を１２０℃で２時間反応させることで一般式（３）のカルボン酸２（式中、Ｒ３：トリデシル、Ａ３Ｏ：ＥＯ、ｎ：１０、ｋ：１、Ｘ：－ＣＯ-（ＣＨ２）６－、Ｚ：－ＣＯＯＨ）。 [Carboxylic acid 2]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Then, 156 g (1 mol) of suberic anhydride is reacted at 120° C. for 2 hours to give carboxylic acid 2 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10, k : 1, X: -CO-(CH 2 ) 6 -, Z: -COOH).
［カルボン酸３］
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、無水マレイン酸１９８ｇ（１モル）を１２０℃で２時間反応させることで一般式（３）のカルボン酸３を得た（式中、Ｒ３：トリデシル、Ａ３Ｏ：ＥＯ、ｎ：１０、ｋ：１、Ｘ：－ＣＯ－ＣＨ２＝ＣＨ２－、Ｚ：－ＣＯＯＨ）。 [Carboxylic acid 3]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Subsequently, 198 g (1 mol) of maleic anhydride was reacted at 120° C. for 2 hours to obtain carboxylic acid 3 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10 , k: 1, X: —CO—CH 2 =CH 2 —, Z: —COOH).
撹拌機、温度計、窒素導入管、原料仕込用導入管、及び減圧用排気管を備えた温度調節機付きのオートクレーブに、トリデシルアルコール２００ｇ（１．０モル）、触媒として水酸化カリウム５ｇを仕込み、オートクレーブ内の雰囲気を窒素で置換し、圧力０．１５ＭＰａ、温度１３０℃の条件下でエチレンオキサイド４４０ｇ（１０モル）を逐次導入して反応させた後、酢酸で中和した。次いで、無水マレイン酸１９８ｇ（１モル）を１２０℃で２時間反応させることで一般式（３）のカルボン酸３を得た（式中、Ｒ３：トリデシル、Ａ３Ｏ：ＥＯ、ｎ：１０、ｋ：１、Ｘ：－ＣＯ－ＣＨ２＝ＣＨ２－、Ｚ：－ＣＯＯＨ）。 [Carboxylic acid 3]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst were placed in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen inlet tube, a raw material inlet tube, and a decompression exhaust tube. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was successively introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130° C., followed by neutralization with acetic acid. Subsequently, 198 g (1 mol) of maleic anhydride was reacted at 120° C. for 2 hours to obtain carboxylic acid 3 of general formula (3) (wherein R 3 : tridecyl, A 3 O: EO, n: 10 , k: 1, X: —CO—CH 2 =CH 2 —, Z: —COOH).
平均官能基数、重量平均分子量、水酸基価、およびイソシアネート価の測定方法は以下のとおりである。
［平均官能基数］
平均官能基数は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により数平均分子量（Ｍｎ）を測定し、ＪＩＳ Ｋ１５５７－１：２００７のＡ法に準じて水酸基価（ｍｇＫＯＨ／ｇ）を測定して下記式より算出される値である。
平均官能基数＝｛（水酸基価）×（Ｍｎ）｝／（５６．１１×１０００） Methods for measuring the average functional group number, weight average molecular weight, hydroxyl value, and isocyanate value are as follows.
[Average number of functional groups]
The average number of functional groups, GPC (gel permeation chromatography) to measure the number average molecular weight (Mn), according to the A method of JIS K1557-1: 2007 to measure the hydroxyl value (mgKOH / g) from the following formula It is a calculated value.
Average functionality = {(hydroxyl value) x (Mn)}/(56.11 x 1000)
［平均官能基数］
平均官能基数は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により数平均分子量（Ｍｎ）を測定し、ＪＩＳ Ｋ１５５７－１：２００７のＡ法に準じて水酸基価（ｍｇＫＯＨ／ｇ）を測定して下記式より算出される値である。
平均官能基数＝｛（水酸基価）×（Ｍｎ）｝／（５６．１１×１０００） Methods for measuring the average functional group number, weight average molecular weight, hydroxyl value, and isocyanate value are as follows.
[Average number of functional groups]
The average number of functional groups, GPC (gel permeation chromatography) to measure the number average molecular weight (Mn), according to the A method of JIS K1557-1: 2007 to measure the hydroxyl value (mgKOH / g) from the following formula It is a calculated value.
Average functionality = {(hydroxyl value) x (Mn)}/(56.11 x 1000)
［重量平均分子量および数平均分子量］
ＧＰＣ法（ゲルパーミエーションクロマトグラフィー法）で測定し、標準ポリスチレンの分子量と溶出時間から作成した検量線を用いて、測定試料の溶出時間から算出した値である。測定条件に関し、カラムにＴＳＫｇｅｌ Ｈｘｌ（東ソー株式会社）を用いて、移動相はＴＨＦ（テトラヒドロフラン）、移動相流量は１．０ｍＬ／ｍｉｎ、カラム温度は４０℃、試料注入量は５０μＬ、試料濃度は０．２質量％の条件で測定を行った。 [Weight average molecular weight and number average molecular weight]
It is a value calculated from the elution time of a measurement sample using a calibration curve prepared from the molecular weight of standard polystyrene and the elution time measured by the GPC method (gel permeation chromatography method). Regarding the measurement conditions, TSKgel Hxl (Tosoh Corporation) was used for the column, the mobile phase was THF (tetrahydrofuran), the mobile phase flow rate was 1.0 mL/min, the column temperature was 40°C, the sample injection volume was 50 µL, and the sample concentration was Measurement was performed under the condition of 0.2% by mass.
ＧＰＣ法（ゲルパーミエーションクロマトグラフィー法）で測定し、標準ポリスチレンの分子量と溶出時間から作成した検量線を用いて、測定試料の溶出時間から算出した値である。測定条件に関し、カラムにＴＳＫｇｅｌ Ｈｘｌ（東ソー株式会社）を用いて、移動相はＴＨＦ（テトラヒドロフラン）、移動相流量は１．０ｍＬ／ｍｉｎ、カラム温度は４０℃、試料注入量は５０μＬ、試料濃度は０．２質量％の条件で測定を行った。 [Weight average molecular weight and number average molecular weight]
It is a value calculated from the elution time of a measurement sample using a calibration curve prepared from the molecular weight of standard polystyrene and the elution time measured by the GPC method (gel permeation chromatography method). Regarding the measurement conditions, TSKgel Hxl (Tosoh Corporation) was used for the column, the mobile phase was THF (tetrahydrofuran), the mobile phase flow rate was 1.0 mL/min, the column temperature was 40°C, the sample injection volume was 50 µL, and the sample concentration was Measurement was performed under the condition of 0.2% by mass.
［水酸基価］
ＪＩＳ Ｋ１５５７－１：２００７のＡ法に準じて測定。 [Hydroxyl value]
Measured according to A method of JIS K1557-1:2007.
ＪＩＳ Ｋ１５５７－１：２００７のＡ法に準じて測定。 [Hydroxyl value]
Measured according to A method of JIS K1557-1:2007.
［イソシアネート価］
イソシアネート含有率をＪＩＳ Ｋ１６０３－１：２００７のＡ法に準拠して測定し、求めたイソシアネート含有率から下記式によりイソシアネート価を算出される値である。
５６．１１：水酸化カリウムの分子量
１０００：ｇからｍｇへの変換係数
４２．０２：ＮＣＯの分子量
１００：百分率から／ｇへの変換係数 [Isocyanate value]
The isocyanate content is measured according to A method of JIS K1603-1:2007, and the isocyanate value is calculated by the following formula from the obtained isocyanate content.
56.11: Molecular weight of potassium hydroxide 1000: Conversion factor from g to mg 42.02: Molecular weight of NCO 100: Conversion factor from percentage to /g
イソシアネート含有率をＪＩＳ Ｋ１６０３－１：２００７のＡ法に準拠して測定し、求めたイソシアネート含有率から下記式によりイソシアネート価を算出される値である。
１０００：ｇからｍｇへの変換係数
４２．０２：ＮＣＯの分子量
１００：百分率から／ｇへの変換係数 [Isocyanate value]
The isocyanate content is measured according to A method of JIS K1603-1:2007, and the isocyanate value is calculated by the following formula from the obtained isocyanate content.
［実施例１～１６および比較例１～５］
下記表１に示す配合（質量％）に従い、ポリオール含有組成物Ａ１～７を調製するとともに、下記表２に示す配合（質量％）に従い、イソシアネート含有組成物Ｂ１～２１を調製した。イソシアネート含有組成物Ｂ１～２１については、貯蔵安定性を評価した。また、下記表３に示す組合せおよび容量配合比にてポリオール含有組成物Ａ１～７とイソシアネート含有組成物Ｂ１～２１を混合し、両者の混合性を評価した。また、混合し硬化させた後に硬化物の硬度を測定した。貯蔵安定性、混合性、および硬度の測定・評価方法は以下のとおりである。 [Examples 1 to 16 and Comparative Examples 1 to 5]
Polyol-containing compositions A1-7 were prepared according to the formulations (% by mass) shown in Table 1 below, and isocyanate-containing compositions B1-21 were prepared according to the formulations (% by mass) shown in Table 2 below. The isocyanate-containing compositions B1-21 were evaluated for storage stability. In addition, polyol-containing compositions A1 to 7 and isocyanate-containing compositions B1 to 21 were mixed in the combinations and volume mixing ratios shown in Table 3 below, and the miscibility of the two was evaluated. Moreover, after mixing and curing, the hardness of the cured product was measured. The storage stability, mixability, and hardness measurement/evaluation methods are as follows.
下記表１に示す配合（質量％）に従い、ポリオール含有組成物Ａ１～７を調製するとともに、下記表２に示す配合（質量％）に従い、イソシアネート含有組成物Ｂ１～２１を調製した。イソシアネート含有組成物Ｂ１～２１については、貯蔵安定性を評価した。また、下記表３に示す組合せおよび容量配合比にてポリオール含有組成物Ａ１～７とイソシアネート含有組成物Ｂ１～２１を混合し、両者の混合性を評価した。また、混合し硬化させた後に硬化物の硬度を測定した。貯蔵安定性、混合性、および硬度の測定・評価方法は以下のとおりである。 [Examples 1 to 16 and Comparative Examples 1 to 5]
Polyol-containing compositions A1-7 were prepared according to the formulations (% by mass) shown in Table 1 below, and isocyanate-containing compositions B1-21 were prepared according to the formulations (% by mass) shown in Table 2 below. The isocyanate-containing compositions B1-21 were evaluated for storage stability. In addition, polyol-containing compositions A1 to 7 and isocyanate-containing compositions B1 to 21 were mixed in the combinations and volume mixing ratios shown in Table 3 below, and the miscibility of the two was evaluated. Moreover, after mixing and curing, the hardness of the cured product was measured. The storage stability, mixability, and hardness measurement/evaluation methods are as follows.
［貯蔵安定性］
調製したイソシアネート含有組成物を６０℃で１か月貯蔵した後の性状を評価し、液体のままの場合を「液体」、液体から固化した場合を「固化」と表３に示した。 [Storage stability]
The properties of the prepared isocyanate-containing composition after being stored at 60° C. for one month were evaluated.
調製したイソシアネート含有組成物を６０℃で１か月貯蔵した後の性状を評価し、液体のままの場合を「液体」、液体から固化した場合を「固化」と表３に示した。 [Storage stability]
The properties of the prepared isocyanate-containing composition after being stored at 60° C. for one month were evaluated.
［混合性］
自転公転ミキサーを用いて、ポリオール含有組成物とイソシアネート含有組成物を、常温下、２０００ｒｐｍで３０分間攪拌し、それにより混合が可能であった場合を「〇」、混合できなかった場合「×」と表３に示した。 [Mixability]
Using a rotation/revolution mixer, the polyol-containing composition and the isocyanate-containing composition were stirred at room temperature and 2000 rpm for 30 minutes, and "O" was obtained when mixing was possible, and "X" was obtained when mixing was not possible. and shown in Table 3.
自転公転ミキサーを用いて、ポリオール含有組成物とイソシアネート含有組成物を、常温下、２０００ｒｐｍで３０分間攪拌し、それにより混合が可能であった場合を「〇」、混合できなかった場合「×」と表３に示した。 [Mixability]
Using a rotation/revolution mixer, the polyol-containing composition and the isocyanate-containing composition were stirred at room temperature and 2000 rpm for 30 minutes, and "O" was obtained when mixing was possible, and "X" was obtained when mixing was not possible. and shown in Table 3.
［硬度］
ポリオール含有組成物とイソシアネート含有組成物を常温下で混合して硬化させ、常温にて７日間経過後の硬度（ショアＣ）をＪＩＳ Ｋ７３１２：１９９６（スプリング硬さ試験タイプＣ）により測定した。 [hardness]
The polyol-containing composition and the isocyanate-containing composition were mixed and cured at room temperature, and the hardness (Shore C) after 7 days at room temperature was measured according to JIS K7312:1996 (spring hardness test type C).
ポリオール含有組成物とイソシアネート含有組成物を常温下で混合して硬化させ、常温にて７日間経過後の硬度（ショアＣ）をＪＩＳ Ｋ７３１２：１９９６（スプリング硬さ試験タイプＣ）により測定した。 [hardness]
The polyol-containing composition and the isocyanate-containing composition were mixed and cured at room temperature, and the hardness (Shore C) after 7 days at room temperature was measured according to JIS K7312:1996 (spring hardness test type C).
結果は表３に示すとおりである。比較例１では、イソシアネート基含有ウレタンプレポリマーを構成するポリオールの平均官能基数が大きいため、硬化物の硬度が高かった。比較例２では、イソシアネート基含有ウレタンプレポリマーを構成するポリオールの重量平均分子量が小さいため、イソシアネート含有組成物は６０℃×１か月の貯蔵で固まってしまい、貯蔵安定性が低かった。比較例３では、イソシアネート含有組成物にリン酸エステルや硫酸アンモニウム塩等の化合物（ｄ）を配合していないため、貯蔵安定性が低下した。比較例４では、イソシアネート含有組成物に無機充填剤を配合していないため、イソシアネート含有組成物とポリオール含有組成物との混合性が悪かった。比較例５では、イソシアネート含有組成物に可塑剤を配合していないため、貯蔵安定性に劣っており、また、ポリオール含有組成物との混合性にも劣っていた。
The results are shown in Table 3. In Comparative Example 1, the hardness of the cured product was high because the polyol constituting the isocyanate group-containing urethane prepolymer had a large average number of functional groups. In Comparative Example 2, since the weight-average molecular weight of the polyol constituting the isocyanate group-containing urethane prepolymer was small, the isocyanate-containing composition solidified after being stored at 60°C for one month, resulting in low storage stability. In Comparative Example 3, since the isocyanate-containing composition did not contain a compound (d) such as a phosphate ester or an ammonium sulfate salt, the storage stability was lowered. In Comparative Example 4, since the isocyanate-containing composition did not contain an inorganic filler, the isocyanate-containing composition and the polyol-containing composition were poorly mixed. In Comparative Example 5, since the isocyanate-containing composition did not contain a plasticizer, the storage stability was poor, and the miscibility with the polyol-containing composition was also poor.
これに対し、実施例１～１６であると、イソシアネート含有組成物の貯蔵安定性に優れるとともに、ポリオール含有組成物との混合性も良好であり、また硬化後の硬度も６０以下であり、良好な結果が得られた。
On the other hand, in Examples 1 to 16, the isocyanate-containing composition has excellent storage stability, has good miscibility with the polyol-containing composition, and has a hardness of 60 or less after curing, which is good. good results were obtained.
以上、本発明のいくつかの実施形態を説明したが、これら実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその省略、置き換え、変更などは、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。
Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and modifications can be made without departing from the scope of the invention. These embodiments, their omissions, replacements, modifications, etc., are included in the invention described in the scope of claims and equivalents thereof, as well as being included in the scope and gist of the invention.
Claims (6)
- ２液反応型ポリウレタン樹脂組成物のポリイソシアネート成分として用いられるイソシアネート含有組成物であって、
平均官能基数が２．５以下かつ重量平均分子量が７００以上のポリオールとポリイソシアネートとを反応させて得られるイソシアネート基含有ウレタンプレポリマー、
無機充填剤、
可塑剤、および、
下記一般式（１）で表される化合物および下記一般式（３）で表される化合物からなる群から選択される少なくとも一種を含み、
一般式（１）において、Ｒ１はＯＨまたは下記一般式（２）に示す基を表し、Ｒ１がＯＨで表される化合物とＲ１が一般式（２）で表される化合物との混合物でもよく、
一般式（３）において、ｋは１または０の数を表し、Ｘは－ＣＨ２－、－ＣＯ（ＣＨ２）ｐ－または－ＣＯＣＨ＝ＣＨ－である連結基を表し、ここでｐは２～６の整数を表し、Ｚはカルボキシ基、スルホ基またはこれらの塩を表し、
一般式（１）、一般式（２）および一般式（３）において、Ｒ２およびＲ３はそれぞれ独立に炭素数６～３０の炭化水素基を表し、Ａ１ＯおよびＡ３Ｏはそれぞれ独立に炭素数２～４のオキシアルキレン基を表し、ｍおよびｎはアルキレンオキシドの平均付加モル数であってそれぞれ独立に１～１００の数を表し、（Ａ１Ｏ）ｍおよび（Ａ３Ｏ）ｎはそれぞれ独立にオキシエチレン基の含有量が２０モル％以上である、
イソシアネート含有組成物。
An isocyanate group-containing urethane prepolymer obtained by reacting a polyol having an average functional group number of 2.5 or less and a weight average molecular weight of 700 or more with a polyisocyanate,
inorganic fillers,
a plasticizer, and
At least one selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (3),
In general formula (1), R 1 represents OH or a group represented by the following general formula (2), and a mixture of a compound in which R 1 is OH and a compound in which R 1 is represented by general formula (2) But it's okay,
In general formula (3), k represents the number of 1 or 0, X represents a linking group of -CH 2 -, -CO(CH 2 ) p - or -COCH=CH-, where p is 2 represents an integer of ~6, Z represents a carboxy group, a sulfo group or a salt thereof,
In general formula (1), general formula (2) and general formula (3), R 2 and R 3 each independently represent a hydrocarbon group having 6 to 30 carbon atoms, and A 1 O and A 3 O each independently represents an oxyalkylene group having 2 to 4 carbon atoms, m and n are the average number of moles of alkylene oxide added and each independently represents a number of 1 to 100, (A 1 O) m and (A 3 O) n each independently has an oxyethylene group content of 20 mol% or more;
An isocyanate-containing composition.
- 前記ポリイソシアネートが、脂肪族ジイソシアネートおよび／または脂環式ジイソシアネートである、請求項１に記載のイソシアネート含有組成物。 The isocyanate-containing composition according to claim 1, wherein the polyisocyanate is an aliphatic diisocyanate and/or an alicyclic diisocyanate.
- 前記イソシアネート含有組成物１００質量％中に前記無機充填剤を５０～９５質量％含有する、請求項１または２に記載のイソシアネート含有組成物。 The isocyanate-containing composition according to claim 1 or 2, which contains 50 to 95% by mass of the inorganic filler in 100% by mass of the isocyanate-containing composition.
- 前記可塑剤がフタル酸ジエステルおよび／またはアジピン酸ジエステルである、請求項１～３のいずれか１項に記載のイソシアネート含有組成物。 The isocyanate-containing composition according to any one of claims 1 to 3, wherein the plasticizer is a phthalate diester and/or an adipate diester.
- 請求項１～４のいずれか１項に記載のイソシアネート含有組成物と、 ポリオールおよび無機充填剤を含むポリオール含有組成物と、を備える、２液反応型ポリウレタン樹脂組成物。 A two-liquid reactive polyurethane resin composition comprising the isocyanate-containing composition according to any one of claims 1 to 4, and a polyol-containing composition containing a polyol and an inorganic filler.
- 放熱材料として用いられる請求項５に記載の２液反応型ポリウレタン樹脂組成物。
6. The two-liquid reactive polyurethane resin composition according to claim 5, which is used as a heat dissipation material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202280034602.1A CN117295776A (en) | 2021-05-17 | 2022-05-10 | Isocyanate-containing composition and two-part reaction type polyurethane resin composition |
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| JP2021083460 | 2021-05-17 | ||
| JP2021-083460 | 2021-05-17 | ||
| JP2021-159946 | 2021-09-29 | ||
| JP2021159946A JP7053936B1 (en) | 2021-05-17 | 2021-09-29 | Isocyanate-containing composition and two-component reaction type polyurethane resin composition |
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| WO2022244650A1 true WO2022244650A1 (en) | 2022-11-24 |
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| Country | Link |
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| JP (1) | JP7053936B1 (en) |
| CN (1) | CN117295776A (en) |
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| WO (1) | WO2022244650A1 (en) |
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| JP6932872B1 (en) * | 2020-01-06 | 2021-09-08 | 富士高分子工業株式会社 | Thermally conductive silicone gel composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008222773A (en) * | 2007-03-09 | 2008-09-25 | Auto Kagaku Kogyo Kk | Polyurethane-based curable resin composition and coating material comprising the same |
| JP2016008301A (en) * | 2014-06-26 | 2016-01-18 | 東ソー株式会社 | Polyurethane elastomer-formable composition to be used in industrial mechanical component member, and industrial mechanical component obtained by using the composition |
-
2021
- 2021-09-29 JP JP2021159946A patent/JP7053936B1/en active Active
-
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- 2022-05-03 TW TW111116641A patent/TW202246371A/en unknown
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008222773A (en) * | 2007-03-09 | 2008-09-25 | Auto Kagaku Kogyo Kk | Polyurethane-based curable resin composition and coating material comprising the same |
| JP2016008301A (en) * | 2014-06-26 | 2016-01-18 | 東ソー株式会社 | Polyurethane elastomer-formable composition to be used in industrial mechanical component member, and industrial mechanical component obtained by using the composition |
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| JP2022176868A (en) | 2022-11-30 |
| TW202246371A (en) | 2022-12-01 |
| JP7053936B1 (en) | 2022-04-12 |
| CN117295776A (en) | 2023-12-26 |
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