JP4493980B2 - Urethane sealant composition for clean rooms - Google Patents
Urethane sealant composition for clean rooms Download PDFInfo
- Publication number
- JP4493980B2 JP4493980B2 JP2003367620A JP2003367620A JP4493980B2 JP 4493980 B2 JP4493980 B2 JP 4493980B2 JP 2003367620 A JP2003367620 A JP 2003367620A JP 2003367620 A JP2003367620 A JP 2003367620A JP 4493980 B2 JP4493980 B2 JP 4493980B2
- Authority
- JP
- Japan
- Prior art keywords
- urethane
- sealant composition
- organic
- clean room
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 50
- 239000004591 urethane sealant Substances 0.000 title claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 49
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 29
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 24
- 239000003566 sealing material Substances 0.000 claims description 24
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 16
- 229930006000 Sucrose Natural products 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000005720 sucrose Substances 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000007423 decrease Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 6
- 238000013008 moisture curing Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000000565 sealant Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 description 26
- 238000001723 curing Methods 0.000 description 23
- 150000003077 polyols Chemical class 0.000 description 23
- -1 polymethylene Polymers 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 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 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000001414 amino alcohols Chemical class 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 235000013312 flour Nutrition 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000013008 thixotropic agent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 230000009974 thixotropic effect Effects 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UVDDHYAAWVNATK-VGKOASNMSA-L (z)-4-[dibutyl-[(z)-4-oxopent-2-en-2-yl]oxystannyl]oxypent-3-en-2-one Chemical compound CC(=O)\C=C(C)/O[Sn](CCCC)(CCCC)O\C(C)=C/C(C)=O UVDDHYAAWVNATK-VGKOASNMSA-L 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- JUYONNFUNDDKBE-UHFFFAOYSA-J tri(oct-2-enoyloxy)stannyl oct-2-enoate Chemical compound [Sn+4].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O JUYONNFUNDDKBE-UHFFFAOYSA-J 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229950002083 octabenzone Drugs 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- YUIFFNHNYKNVNQ-UHFFFAOYSA-N phenyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(=O)OC=2C=CC=CC=2)=C1 YUIFFNHNYKNVNQ-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
Description
本願発明は、イソシアネート基含有ウレタンプレポリマーを含む新規なクリーンルーム用ウレタン系シーリング材組成物に関するものである。 The present invention relates to a novel urethane sealant composition for clean rooms containing an isocyanate group-containing urethane prepolymer.
従来より、半導体、食品、医薬品などの工場や研究所などで使用されているクリーンルームにおいては、室内空気中の浮遊粒子状物質を捕集、除去して清浄化した雰囲気中で作業が行われていたが、最近では、半導体のより高度な集積化や食品、医薬品のより高度な安全衛生の要求などにより、クリーンルーム内の空気中には浮遊粒子状物質だけでなく、クリーンルーム内で製造、試験あるいは使用される製品や機器類などに液状汚染物質やガス状有機物が微量であっても付着しないことが要求されている。
従来クリーンルームの壁材や間仕切り用のパーティションの目地や隙間に、密封あるいは防水を目的として１成分形や２成分系のシリコーン系シーリング材が使用されており、これらは低分子のシランやアルコールあるいはオキシムなどのガス状有機物を発生することが判明し、この改善のために湿式シール材としてポリウレタン系のものが提案されている。
例えば、少なくとも一方はガス状有機物を発生しない、硬化後にポリウレタン樹脂となる主成分および添加剤からなるポリウレタン系湿式シール材が提案されている（たとえば、特許文献１参照）。しかしながら、このシール材は、ガス状有機物は発生しないが、可塑剤成分が低分子量であり、ポリウレタン樹脂との相溶性が悪く、硬化後のシーリング材表面に移行し（ブリードし）表面に出てきてしまうため、その可塑剤成分が精密機械、シリコーンウェハー、食品等に付着し汚染させてしまうという欠点と揺変性付与剤を使用していないため垂直の目地等に充填施工した場合、湿式シール材がタレ（スランプ）を超こしてしまうという欠点がある。
また、硬化後にポリウレタン樹脂となる主成分と添加剤とを有してなり、有機溶剤が配合されないで用いられるポリウレタン系一液湿気硬化性組成物が開示されている（特許文献２参照）。しかしながら、この硬化性組成物は、ガス状有機物は発生しないものの特殊な揺変性付与剤を使用するためこの揺変性付与材の製造が困難であるという欠点があり、また、可塑剤成分が硬化物表面にブリードし前記と同様の付着汚染を引き起こすという欠点がある。
Traditionally, in clean rooms used in factories and research laboratories of semiconductors, foods, pharmaceuticals, etc., work has been performed in a clean atmosphere by collecting and removing suspended particulate matter in indoor air. However, recently, due to higher integration of semiconductors and higher safety and health requirements for foods and pharmaceuticals, not only suspended particulate matter in the air in clean rooms, but also manufacturing, testing or testing in clean rooms. It is required that liquid pollutants and gaseous organic substances do not adhere to products and equipment used even if they are in trace amounts.
Conventionally, one-component or two-component silicone sealants have been used in the joints and gaps of clean room walls and partition partitions for the purpose of sealing or waterproofing, and these are low-molecular silanes, alcohols, or oximes. In order to improve this, a polyurethane-based material has been proposed.
For example, there has been proposed a polyurethane-based wet sealing material that includes a main component and an additive that become a polyurethane resin after curing, at least one of which does not generate a gaseous organic substance (see, for example, Patent Document 1). However, this sealing material does not generate gaseous organic matter, but the plasticizer component has a low molecular weight and is poorly compatible with the polyurethane resin, and migrates (bleeds) to the surface of the sealing material after curing and emerges on the surface. As a result, the plasticizer component will adhere to and contaminate precision machinery, silicone wafers, foods, etc. However, there is a drawback that it will exceed the sauce (slump).
Further, a polyurethane one-part moisture curable composition that has a main component and an additive that become a polyurethane resin after curing and is used without blending an organic solvent is disclosed (see Patent Document 2). However, although this curable composition does not generate a gaseous organic substance, it has a drawback that it is difficult to produce the thixotropic agent because a special thixotropic agent is used, and the plasticizer component is a cured product. There is a drawback in that it bleeds on the surface and causes the same adhesion contamination as described above.
本発明は、このような従来の欠点を解決して、大気中などの水分（湿気など）により硬化して、適度なモジュラスおよび高い伸びと接着性を有する優れたゴム状弾性体となり、硬化途中ならびに硬化後においても、さらに周囲の雰囲気が常温においても、５０〜１００℃の高温においても揮発成分（ガス状有機物）が発生せず、かつ硬化物の表面に可塑剤等の液状物が移行（ブリード）することがないため、クリーンルーム内で製造あるいは使用される製品や精密機器類などを汚染することがない、さらには、硬化促進触媒を添加して硬化速度を高めても充填塗布時にタレない（スランプしない）優れたクリーンルーム用ウレタン系シーリング材組成物を提供することを目的とする。 The present invention solves such conventional drawbacks and cures by moisture (such as moisture) in the atmosphere to form an excellent rubber-like elastic body having an appropriate modulus and high elongation and adhesion. In addition, even after curing, no volatile components (gaseous organic substances) are generated even when the ambient atmosphere is at room temperature or at a high temperature of 50 to 100 ° C., and a liquid material such as a plasticizer migrates to the surface of the cured product ( The product and precision equipment manufactured or used in a clean room will not be contaminated, and even if a curing acceleration catalyst is added to increase the curing speed, there will be no sagging during filling and coating. An object of the present invention is to provide an excellent urethane sealant composition for clean rooms (does not slump).
上述した欠点を改善すべく研究を進めたところ、イソシアネート基含有ウレタンプレポリマーと実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂と有機表面処理炭酸カルシウムとを組み合わせることにより上記問題を改善できることができるという知見を得て、本願発明に至ったものである。
より詳細には、本願発明は、
（１）イソシアネート基含有ウレタンプレポリマーと、実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂と、有機表面処理炭酸カルシウムとを含有し、かつ揮発成分を実質的に含有しないことを特徴とするクリーンルーム用ウレタン系シーリング材組成物。
（２）前記実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂が、数平均分子量１，０００〜２０，０００のものであることを特徴とする（１）に記載のクリーンルーム用ウレタン系シーリング材組成物。
（３）耐候安定剤、充填剤、カップリング剤、保存安定性改良剤（脱水剤）および着色剤の群より選ばれる１種または２種以上の添加剤をさらに含有することを特徴とする、（１）または（２）に記載のクリーンルーム用ウレタン系シーリング材組成物。
（４）前記揮発成分が、前記クリーンルーム用ウレタン系シーリング材組成物を９０℃の高温雰囲気に３時間置いたときに質量の減少として測定される成分であって、該質量の減少が前記クリーンルーム用ウレタン系シーリング材組成物の０．１質量％未満である、（１）ないし（３）のいずれかの１項に記載のクリーンルーム用ウレタン系シーリング材組成物。
に関するものである。
As a result of research to improve the above-mentioned drawbacks, it was found that a combination of an isocyanate group-containing urethane prepolymer, a polyether resin of sucrose having substantially no reactive functional group, and an organic surface-treated calcium carbonate The inventors have obtained the knowledge that can be improved and have arrived at the present invention.
More specifically, the present invention is
(1) It contains an isocyanate group-containing urethane prepolymer, a polyether resin of sucrose having substantially no reactive functional group, and organic surface-treated calcium carbonate, and is substantially free of volatile components. A urethane-based sealing material composition for clean rooms.
(2) The sucrose polyetherized resin having substantially no reactive functional group has a number average molecular weight of 1,000 to 20,000. Urethane sealant composition.
(3) It further comprises one or more additives selected from the group consisting of a weathering stabilizer, a filler, a coupling agent, a storage stability improver (dehydrating agent) and a coloring agent, (1) or urethane sealant composition for clean room as described in (2).
(4) The volatile component is a component measured as a decrease in mass when the urethane-based sealing material composition for clean room is placed in a high temperature atmosphere at 90 ° C. for 3 hours, and the decrease in the mass is for the clean room. 4. The urethane sealant composition for clean rooms according to any one of (1) to (3), which is less than 0.1% by mass of the urethane sealant composition.
It is about.
本願発明で使用する各成分などについて説明する。 Each component used in the present invention will be described.
イソシアネート基含有ウレタンプレポリマーは、本願発明において硬化成分として使用するものであり、有機ポリイソシアネートと活性水素含有化合物とを活性水素（基）に対してイソシアネート基過剰条件で反応させて得られるものである。 The isocyanate group-containing urethane prepolymer is used as a curing component in the present invention, and is obtained by reacting an organic polyisocyanate and an active hydrogen-containing compound with active hydrogen (group) under an isocyanate group excess condition. is there.
有機ポリイソシアネートとしては、具体的には例えば、フェニレンジイソシアネート、ジフエニルジイソシアネート、ナフタレンジイソシアネート、４，４’−ジフエニルメタンジイソシアネート、２，４’−ジフエニルメタンジイソシアネート等のジフエニルメタンジイソシアネート（ＭＤＩ）類、２，４−トルエンジイソシアネート、２，６−トルエンジイソシアネート等のトルエンジイソシアネート（ＴＤＩ）類、ジフェニルエーテルジイソシアネート等の芳香族ジイソシアネート、キシリレンジイソシアネート等の芳香脂肪族ジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、プロピレンジイソシアネート、ブチレンジイソシアネート等の脂肪族ジイソシアネート、シクロヘキサンジイソシアネート、メチレンビス（シクロヘキシルイソシアネート）、イソホロンジイソシアネート等の脂環族ジイソシアネート、およびこれらジイソシアネートのカルボジイミド変性体、ビウレット変性体、アロファネート変性体、二量体、三量体、または、ポリメチレンポリフェニルポリイソシアネート（クルードＭＤＩ、ポリメリックＭＤＩ）などが挙げられ、これらは単独または２種以上を組合わせて用いることができる。これらのうち、硬化後の引張り接着性などが優れている点で、芳香族ジイソシアネート、芳香脂肪族ジイソシアネートが好ましく、さらにＴＤＩ類が好ましく、特に２，４−トルエンジイソシアネートが好ましい。 Specific examples of the organic polyisocyanate include diphenylmethane diisocyanate (MDI) such as phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4′-diphenylmethane diisocyanate. , Toluene diisocyanates (TDI) such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, aromatic diisocyanates such as diphenyl ether diisocyanate, araliphatic diisocyanates such as xylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, Aliphatic diisocyanates such as propylene diisocyanate and butylene diisocyanate, cyclohexane diisocyanate , Alicyclic diisocyanates such as methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and carbodiimide modified, biuret modified, allophanate modified, dimer, trimer or polymethylene polyphenyl polyisocyanate of these diisocyanates (Crude MDI, polymeric MDI) etc. are mentioned, These can be used individually or in combination of 2 or more types. Of these, aromatic diisocyanates and araliphatic diisocyanates are preferable, TDIs are more preferable, and 2,4-toluene diisocyanate is particularly preferable because of excellent tensile adhesiveness after curing.
前記活性水素含有化合物としては、高分子ポリオール、アミノアルコール、ポリアミンなどが挙げられる。これらの化合物のうち、高分子のポリオールが好適である。 Examples of the active hydrogen-containing compound include polymer polyols, amino alcohols, and polyamines. Of these compounds, polymeric polyols are preferred.
高分子ポリオールとしては、ポリエステルポリオール、ポリカーボネートポリオール、ポリエーテルポリオール、ポリオレフィンポリオール、動植物系ポリオール、これらのコポリオール等、またはこれらの２種以上の混合物が挙げられる。これらの高分子ポリオールのうち、作業性、接着性、耐候性などが優れている点から、ポリエーテルポリオールが好ましい。 Examples of the polymer polyol include polyester polyols, polycarbonate polyols, polyether polyols, polyolefin polyols, animal and plant polyols, copolyols thereof, and the like, or mixtures of two or more thereof. Of these polymer polyols, polyether polyols are preferred because of their excellent workability, adhesion, weather resistance, and the like.
ポリエステルポリオールとしては、例えば、コハク酸、アジピン酸、セバシン酸、アゼライン酸、テレフタル酸、イソフタル酸、オルソフタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、へキサヒドロオルソフタル酸、ナフタレンジカルボン酸、トリメリット酸等のポリカルボン酸、酸エステル、または酸無水物等の１種以上と、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、ネオペンチルグリコール、１，８−オクタンジオール、１，９−ノナンジオール、ジエチレングリコール、ジプロピレングリコール、１，４−シクロへキサンジメタノール、ビスフェノールＡのエチレンオキサイドあるいはプロピレンオキサイド付加物、トリメチロールプロパン、グリセリン、ペンタエリスリトール等の低分子アルコール類、ヘキサメチレンジアミン、キシリレンジアミン、イソホロンジアミン等の低分子アミン類、モノエタノールアミン、ジエタノールアミン等の低分子アミノアルコール類の1種以上との脱水縮合反応で得られる、ポリエステルポリオールまたはポリエステルアミドポリオールが挙げられる。
また、例えば、低分子アルコール類、低分子アミン類、低分子アミノアルコール類を開始剤として、ε-カプロラクトン、γ一バレロラクトン等の環状エステル（ラクトン）モノマーの開環重合で得られるラクトン系ポリエステルポリオールが挙げられる。
Examples of polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, triphthalic acid, and the like. One or more of polycarboxylic acids such as merit acid, acid esters, or acid anhydrides, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9- Nonanediol, diethylene glycol, dipropylene glycol, , 4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular alcohols such as trimethylolpropane, glycerin and pentaerythritol, low molecular amines such as hexamethylenediamine, xylylenediamine and isophoronediamine Polyester polyols or polyester amide polyols obtained by a dehydration condensation reaction with one or more low molecular amino alcohols such as monoethanolamine and diethanolamine.
Also, for example, lactone polyesters obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular alcohols, low molecular amines, and low molecular amino alcohols as initiators. A polyol is mentioned.
ポリカーボネートポリオールとしては、例えば、前述のポリエステルポリオールの合成に用いられる低分子アルコール類とホスゲンとの脱塩酸反応、あるいは前記低分子アルコール類とジエチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、ジフェニルカーボネート等とのエステル交換反応で得られるものが挙げられる。 Examples of the polycarbonate polyol include dehydrochlorination reaction of low molecular alcohols and phosgene used in the synthesis of the polyester polyol described above, or esters of the low molecular alcohols with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What is obtained by an exchange reaction is mentioned.
ポリエーテルポリオールとしては、例えば、前述のポリエステルポリオールの合成に用いられる低分子アルコール類、低分子アミン類、低分子アミノアルコール類を開始剤として、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等を開環重合させたポリオキシエチレンポリオール、ポリオキシプロピレンポリオール、ポリテトラメチレンエーテルポリオール、これらを共重合したポリエーテルポリオール、更に、前述のポリエステルポリオール、ポリカーボネートポリオールを開始剤としたポリエステルエーテルポリオールなどが挙げられる。また、イソシアネート基含有ウレタンプレポリマーの変性用として、メチルアルコール、エチルアルコール、プロピルアルコールなどのモノアルコール類を開始剤として、前記プロピレンオキサイドなどのエポキシドを開環重合させたポリオキシアルキレンモノオールなども使用できる。これらのうち、特にポリオキシプロピレンポリオールが好ましい。 Examples of polyether polyols include ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc. using low molecular alcohols, low molecular amines, and low molecular amino alcohols used in the synthesis of the above-described polyester polyol as initiators. Polyoxyethylene polyols, polyoxypropylene polyols, polytetramethylene ether polyols, polyether polyols obtained by copolymerizing these, and polyester ether polyols using the above-described polyester polyols and polycarbonate polyols as initiators. In addition, for modification of an isocyanate group-containing urethane prepolymer, polyoxyalkylene monool obtained by ring-opening polymerization of an epoxide such as propylene oxide using a monoalcohol such as methyl alcohol, ethyl alcohol, or propyl alcohol as an initiator Can be used. Of these, polyoxypropylene polyol is particularly preferable.
ポリオレフィンポリオールとしては、例えば、水酸基含有ポリブタジエン、水素添加した水酸基含有ポリブタジエン、水酸基含有ポリイソプレン、水素添加した水酸基含有ポリイソプレン、水酸基含有塩素化ポリプロピレン、水酸基含有塩素化ポリエチレンなどが挙げられる。 Examples of the polyolefin polyol include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene.
動植物系ポリオールとしては、例えば、ヒマシ油系ジオールなどが挙げられる。
これらの高分子ポリオールの数平均分子量は５００〜３０，０００、特に１，０００〜２０，０００が好ましい。
Examples of animal and plant-based polyols include castor oil-based diols.
These polymer polyols preferably have a number average molecular weight of 500 to 30,000, particularly 1,000 to 20,000.
鎖延長剤としては、前記のポリエステルポリオールの合成に用いられる低分子アルコール類、低分子アミン類、低分子アミノアルコール類等のうち分子量５００未満のもの、またはこれらの２種以上の混合物が好適に例示される。
前記の活性水素含有化合物として挙げた化合物は１種または２種以上を組合わせて使用することができる。
As the chain extender, those having a molecular weight of less than 500 among low molecular alcohols, low molecular amines, low molecular amino alcohols and the like used in the synthesis of the polyester polyol, or a mixture of two or more of these are preferably used. Illustrated.
The compounds mentioned as the active hydrogen-containing compound can be used alone or in combination of two or more.
本願発明におけるイソシアネート基含有ウレタンプレポリマーは、一括仕込み反応法、多段階仕込み反応法のいずれでも合成できるが、プレポリマーの分子中にイソシアネート基を残す必要がある。有機ポリイソシアネートのイソシアネート基と高分子ポリオール、場合により更に鎖延長剤の活性水素（基）とのイソシアネート基／活性水素（基）の当量比は、１.１〜５.０／１.０が好ましく、更に１.３〜２.０／１.０が好ましい。このようにし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のイソシアネート基含有量は０.１〜１５.０質量％が好ましく、特に０.３〜１０.０質量％が好ましく、最も好ましくは０.４〜５.０質量％である。イソシアネート基含有量が０.１質量％未満の場合は、分子量が大きくなりすぎて粘度が増大し作業性が低下する。また、プレポリマー中の架橋点が少ないため、十分な接着性が得られない。イソシアネート基含有量が１５.０質量％を超える場合は、炭酸ガスによる発泡を防止することが困難になるため好ましくない。 The isocyanate group-containing urethane prepolymer in the present invention can be synthesized by either a batch charge reaction method or a multistage charge reaction method, but it is necessary to leave an isocyanate group in the molecule of the prepolymer. The isocyanate group / active hydrogen (group) equivalent ratio of the isocyanate group of the organic polyisocyanate and the polymer polyol, and optionally the active hydrogen (group) of the chain extender, is 1.1 to 5.0 / 1.0. It is preferably 1.3 to 2.0 / 1.0. The isocyanate group-containing urethane prepolymer thus obtained preferably has an isocyanate group content of 0.1 to 15.0% by mass, particularly preferably 0.3 to 10.0% by mass, and most preferably 0.4 to 5.0% by mass. When the isocyanate group content is less than 0.1% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Moreover, since there are few crosslinking points in a prepolymer, sufficient adhesiveness cannot be obtained. If the isocyanate group content exceeds 15.0% by mass, it is difficult to prevent foaming due to carbon dioxide gas, which is not preferable.
本願発明におけるイソシアネート基含有ウレタンプレポリマーの合成には、オクチル酸第一錫、オクテン酸錫などの、亜鉛、錫、鉛、ジルコニウム、ビスマス、コバルト、マンガン、鉄等の金属とオクチル酸、オクテン酸、ナフテン酸等の有機酸との塩、ジブチル錫ビス（アセチルアセトナート）、ジルコニウムテトラキス（アセチルアセトナート）、チタンテトラキス（アセチルアセトナート）などの金属キレート化合物、ジブチル錫ジラウレート、ジオクチル錫ジラウレート等の有機金属と有機酸との塩、トリエチレンジアミン、トリエチルアミン、トリ−n−ブチルアミン等の有機アミンやその塩などの公知のウレタン化触媒を用いることができる。これらのうち金属有機酸塩や有機金属と有機酸との塩が好ましい。また、更に公知の有機溶媒を用いることもできる。 For the synthesis of an isocyanate group-containing urethane prepolymer in the present invention, metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, iron, octyl acid, octenoic acid, such as stannous octylate, tin octenoate, etc. , Salts with organic acids such as naphthenic acid, metal chelate compounds such as dibutyltin bis (acetylacetonate), zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate), dibutyltin dilaurate, dioctyltin dilaurate, etc. Known urethanization catalysts such as organic metal and organic acid salts, organic amines such as triethylenediamine, triethylamine and tri-n-butylamine and salts thereof can be used. Of these, metal organic acid salts and salts of organic metals and organic acids are preferred. Further, a known organic solvent can also be used.
本発明において用いられる、実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂は、高分子量のため１００℃前後の高温雰囲気においても揮発することがなく、かつ高分子量であるにもかかわらず低粘度であり、さらにまたイソシアネート基含有ウレタンプレポリマーと相溶性に優れているため、これを配合することにより、得られるクリーンルーム用ウレタン系シーリング材組成物の粘度を下げる効果が大きなため、有機溶剤を使用しなくても押出しや充填塗布等の作業性を優れたものとすることができるとともに、硬化物の表面にブリードしないため、ブリードした液状物が半導体や食品に付着して汚染させてしまうということがないという効果を奏するものであり、具体的には、出発物質としてショ糖を使用し、そのショ糖の水酸基に対してアルキレンオキサイドを付加重合させた後、末端の水酸基をアルキルエーテル化して封鎖することにより得られるものである。ショ糖の水酸基に対するアルキレンオキサイドの付加重合は通常の方法で行うことができ、触媒（アルカリ触媒、アミン系触媒、酸性触媒）の存在下または不存在下に、常圧または加圧下に１段階または多段階で行われる。 The sucrose polyetherized resin having substantially no reactive functional group used in the present invention has a high molecular weight and does not volatilize even in a high temperature atmosphere of about 100 ° C. Regardless of its low viscosity, and also excellent compatibility with the isocyanate group-containing urethane prepolymer, by blending this, the effect of lowering the viscosity of the resulting clean room urethane sealant composition is great, Workability such as extrusion and filling and coating can be improved without using organic solvents, and since it does not bleed on the surface of the cured product, the bleed liquid adheres to and contaminates semiconductors and foods. Specifically, sucrose is used as a starting material, and the sucrose After addition polymerization of alkylene oxide relative to the hydroxyl group, it is obtained by blocking the terminal hydroxyl group by alkyl etherification. The addition polymerization of alkylene oxide to the hydroxyl group of sucrose can be carried out in the usual manner, in the presence or absence of a catalyst (alkali catalyst, amine-based catalyst, acidic catalyst), one step or under normal pressure or pressure. Performed in multiple stages.
なお、前記実質的に反応性を有しないとは、ショ糖の水酸基に対してアルキレンオキサイドを付加重合させたのち、末端の水酸基をアルキルエーテル化して封鎖した後も極めて少量の水酸基などのイソシアネート基に対して反応性を有する官能基が残存する場合があるが、この残存官能基とイソシアネート基含有ウレタンプレポリマーのイソシアネート基との反応は、硬化性組成物の製造時においても貯蔵中においても無視することができ、本願発明の目的を達成する上で影響がないことを意味する。 It should be noted that the term “substantially not reactive” means that an isocyanate group such as a very small amount of hydroxyl group is formed after addition polymerization of alkylene oxide to the hydroxyl group of sucrose, and then alkylating and blocking the terminal hydroxyl group. May remain, but the reaction between this residual functional group and the isocyanate group of the isocyanate group-containing urethane prepolymer is ignored both during production of the curable composition and during storage. This means that there is no influence in achieving the object of the present invention.
前記アルキレンオキサイドとしては、例えばエチレンオキサイド、プロピレンオキサイド、１，２−ブチレンオキサイド、２，３−ブチレンオキサイド、テトラヒドロフランなどが挙げられ、これらは単独で、或いは２種以上を組み合わせて用いることができる。これらのうち、得られる実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂の粘度が低く、イソシアネート基含有ウレタンプレポリマーとの相溶性に優れるため、これを含有するクリーンルーム用ウレタン系シーリング材組成物の粘度低下に効果があり作業性を良好なものとさせ、かつ硬化後のシーリング材表面にブリードしない点で、プロピレンオキサイド単独或いはプロビレンオキサイドとエチレンオキサイドとの併用が好ましく、特にプロピレンオキサイド単独が好ましい。なお、２種以上のアルキレンオキサイドを併用する場合、ランダム付加共重合でもよいし、ブロック付加共重合でもよい。
前記アルキルエーテル化のアルキルとしては、例えばメチル、エチル、ｎ−プロピル、ｎ−ブチル、ラウリル、イソプロピルなど１価の脂肪族炭化水素基が挙げられ、これらは単独で、或いは２種以上が併用されていてもよい。これらのうちメチル、エチル、ｎ−プロピル、ｎ−ブチルなどの炭素数１〜４の１価のアルキルが好ましい。
Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and tetrahydrofuran. These can be used alone or in combination of two or more. Of these, the sucrose polyetherized resin having substantially no reactive functional group is low in viscosity and excellent in compatibility with the isocyanate group-containing urethane prepolymer. In view of reducing the viscosity of the sealing material composition and improving the workability, and not bleeding to the surface of the sealing material after curing, propylene oxide alone or a combination of propylene oxide and ethylene oxide is preferable. Propylene oxide alone is preferred. In addition, when using together 2 or more types of alkylene oxides, random addition copolymerization may be sufficient and block addition copolymerization may be sufficient.
Examples of the alkyl etherified alkyl include monovalent aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, lauryl, and isopropyl. These may be used alone or in combination of two or more. It may be. Of these, monovalent alkyl having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, and n-butyl is preferable.
前記実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂の数平均分子量は、１，０００〜２０，０００の高分子量のものが好ましく、更に５，０００〜１０，０００が好ましく、１，０００を下回ると硬化物の表面にブリードし易くなり、２０，０００を超えると得られるクリーンルーム用ウレタン系シーリング材組成物の粘度が上がり作業性が悪化し好ましくない。 The number average molecular weight of the sucrose polyetherized resin having substantially no reactive functional group is preferably 1,000 to 20,000, more preferably 5,000 to 10,000, If it is less than 1,000, it tends to bleed on the surface of the cured product, and if it exceeds 20,000, the viscosity of the urethane sealant composition for clean room obtained is increased, and workability is deteriorated.
本発明において実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂の使用量は、イソシアネート基含有ウレタンプレポリマー１００重量部に対して、１〜３００重量部が好ましく、更に３０〜１５０重量部が好ましい。１重量部を下回るとシーリング材組成物の粘度低下効果が無くなり作業性が悪化し、３００重量部を超えるとシーリング材組成物の硬化後のゴム弾性物性が低下し好ましくない。
なお、実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂の市販品としては、三洋化成工業社製のサンフレックスＳＰＸ−８０が挙げられる。
In the present invention, the amount of the sucrose polyetherized resin having substantially no reactive functional group is preferably 1 to 300 parts by weight, more preferably 30 to 150 parts, per 100 parts by weight of the isocyanate group-containing urethane prepolymer. Part by weight is preferred. When the amount is less than 1 part by weight, the effect of reducing the viscosity of the sealing material composition is lost and workability is deteriorated. When the amount exceeds 300 parts by weight, the rubber elastic properties after curing of the sealing material composition are undesirably lowered.
In addition, as a commercial item of the sucrose polyether-ized resin which does not have a reactive functional group substantially, Sunflex SPX-80 by Sanyo Chemical Industries Ltd. is mentioned.
有機表面処理炭酸カルシウムは、クリーンルーム用ウレタン系シーリング材組成物に揺変性を付与して、クリーンルームの内壁などの垂直面に充填や塗布したときにタレ（スランプ）を起こさないようにする作用を有する。一般に揺変性付与剤として、たとえば、コロイダルシリカ、石綿粉、有機表面処理炭酸カルシウム（脂肪酸処理炭酸カルシウム）等の無機系揺変性付与剤、および有機ベントナイト、脂肪酸アマイド等の有機系揺変性付与剤が挙げられるが、これらのうちコロイダルシリカは少量の配合で揺変性を付与できるものの、クリーンルーム用ウレタン系シーリング材組成物の硬化速度を高めるため後述する硬化促進触媒を使用すると揺変性付与構造が破壊され、垂直面に充填や塗布したときにタレを起こすため使用が制限されてしまうことがある。しかしながら、有機表面処理炭酸カルシウムにはこのような欠点がなく、クリーンルーム用ウレタン系シーリング材組成物に安定した揺変性を付与することができるため、特に好ましい。 Organic surface-treated calcium carbonate has a function to prevent sagging (slump) when it is applied to a vertical surface such as an inner wall of a clean room by applying thixotropy to the urethane sealant composition for clean room. . In general, thixotropic agents include, for example, colloidal silica, asbestos powder, inorganic thixotropic agents such as organic surface-treated calcium carbonate (fatty acid-treated calcium carbonate), and organic thixotropic agents such as organic bentonite and fatty acid amide. Among them, colloidal silica can give thixotropy with a small amount of blending, but if a curing accelerator catalyst described later is used in order to increase the curing rate of the urethane sealant composition for clean rooms, the thixotropic structure is destroyed. In some cases, the use of the vertical surface may be limited because of sagging when filled or coated on the vertical surface. However, organic surface-treated calcium carbonate is particularly preferable because it does not have such disadvantages and can impart stable thixotropic properties to the urethane sealant composition for clean rooms.
前記有機表面処理炭酸カルシウムは、公知の方法で製造することができる。まず微粉末状の炭酸カルシウムは、たとえば石灰石を焼成炉で焼成し、炭酸ガスと生石灰に分解した後、生石灰は水を加えて水化精製し、石灰乳とし、炭酸ガスを吹き込んで反応させるか、または炭酸ガス気流中に石灰乳を噴務し向流または並流のかたちで接触させて反応させて製造することができ（一般に軽質炭酸カルシウムと称される）、次いでこの微粉末状炭酸カルシウムに揺変性付与能力を与える目的と二次凝集を防ぐ目的で脂肪酸金属塩や、ロジン酸等の樹脂酸の金属塩などで微粉末状炭酸カルシウムの表面を処理して脂肪酸表面処理炭酸カルシウムや樹脂酸表面処理炭酸カルシウムなどの有機表面処理炭酸カルシウムが得られる。ここで脂肪酸金属塩としては、好ましくは炭素数１０〜２５の脂肪酸のナトリウム、カリウム、カルシウム、アルミニウムの塩である。これらの市販品としては、例えば白艶華ＣＣ、白艶華ＣＣＲ、白艶華Ｒ０６、ＶＩＧＯＴ−１０、ＶＩＧＯＴ−１５、ＳＴＡＶＩＧＯＴ−１５Ａ（全て白石工業社製）、ＮＣＣ＃３０１０、ＮＣＣ＃１０１０（日東粉化工業社製）等が挙げられる。これらは単独であるいは２種以上を組み合わせて使用できるが、これらのうち揺変性付与効果が高い点で脂肪酸表面処理炭酸カルシウムが特に好ましい。
なお、重質炭酸カルシウムと呼ばれる天然の炭酸カルシウムを粉砕して微粉体状にしたものを脂肪酸金属塩や樹脂酸金属塩で処理したものも使用できる。
The organic surface-treated calcium carbonate can be produced by a known method. First of all, for powdered calcium carbonate, limestone is calcined in a baking furnace and decomposed into carbon dioxide and quick lime, then quick lime is hydrated and refined by adding water to lime milk, and carbon dioxide is blown into the reaction. , Or can be produced by spraying lime milk in a carbon dioxide stream and contacting it in countercurrent or cocurrent flow (generally referred to as light calcium carbonate), then this finely powdered calcium carbonate The surface of finely powdered calcium carbonate is treated with a fatty acid metal salt or a metal salt of a resin acid such as rosin acid for the purpose of imparting thixotropy imparting ability and preventing secondary aggregation. Organic surface treated calcium carbonate such as acid surface treated calcium carbonate is obtained. Here, the fatty acid metal salt is preferably a sodium, potassium, calcium or aluminum salt of a fatty acid having 10 to 25 carbon atoms. As these commercially available products, for example, white gloss flower CC, white gloss flower CCR, white gloss flower R06, VIGOT-10, VIGOT-15, STAVIGOT-15A (all manufactured by Shiroishi Kogyo Co., Ltd.), NCC # 3010, NCC # 1010 (manufactured by Nitto Flour Industry Co., Ltd.) ) And the like. These can be used alone or in combination of two or more. Of these, fatty acid surface-treated calcium carbonate is particularly preferred because of its high thixotropic effect.
In addition, what grind | pulverized the natural calcium carbonate called heavy calcium carbonate into the fine powder form, and processed with the fatty acid metal salt and the resin acid metal salt can also be used.
この有機表面処理炭酸カルシウムの平均粒径は、０.０１〜０．５μｍ、さらに０.０３〜０.１５μｍが好ましく、ＢＥＴ比表面積は５〜２００ｍ２／ｇ、さらに１０〜６０ｍ２／ｇが好ましい。
平均粒径が、０.０１μｍを下回るか、あるいはＢＥＴ比表面積が２００ｍ２／ｇを超えると得られるクリーンルーム用ウレタン系シーリング材組成物の粘度が上がり作業性は悪化し、平均粒径が０.５μｍを上回るか、あるいはＢＥＴ比表面積が５ｍ２／ｇを下回ると揺変性付与効果がなくなるため好ましくない。
The average particle size of the organic surface-treated calcium carbonate is preferably 0.01 to 0.5 μm, more preferably 0.03 to 0.15 μm, and the BET specific surface area is 5 to 200 m 2 / g, and further 10 to 60 m 2 / g. preferable.
When the average particle size is less than 0.01 μm or the BET specific surface area is more than 200 m 2 / g, the viscosity of the urethane sealant composition for clean room obtained is increased and the workability is deteriorated, and the average particle size is reduced to 0.0. If it exceeds 5 μm or the BET specific surface area is less than 5 m 2 / g, the thixotropic effect is lost, such being undesirable.
本願発明において、シーリング材組成物は、クリーンルーム内で製造あるいは使用される製品や精密機器類などを汚染させないため、揮発成分を実質的に含有しないことが必要である。この揮発成分は、クリーンルーム用ウレタン系シーリング材組成物を９０℃の高温雰囲気に３時間置いたときに質量の減少として測定される成分であり、主として有機溶剤などの低分子量で低沸点の有機化合物からなり、該質量の減少が前記クリーンルーム用ウレタン系シーリング材組成物の０．１質量％未満であることがとくに好ましい。
なお、本発明において揮発成分を実質的に含有しないという意味は、きわめて微量の揮発成分を含有していても本願発明の目的を達成する上でまったく悪影響がないことを示す。
In the present invention, the sealing material composition does not contaminate products or precision instruments manufactured or used in a clean room, and therefore needs to be substantially free of volatile components. This volatile component is a component measured as a decrease in mass when the urethane-based sealant composition for clean rooms is placed in a high temperature atmosphere at 90 ° C. for 3 hours, and is mainly a low molecular weight, low boiling point organic compound such as an organic solvent. It is particularly preferable that the decrease in the mass is less than 0.1 mass% of the urethane sealant composition for clean rooms.
In the present invention, the meaning that substantially no volatile component is contained means that there is no adverse effect on achieving the object of the present invention even if a very small amount of volatile component is contained.
つぎに、本願発明のクリーンルーム用ウレタン系シーリング材組成物において用いられる添加剤について説明する。 Below, the additive used in the urethane type sealing material composition for clean rooms of this invention is demonstrated.
本願発明における添加剤としては、耐候安定剤、充填剤、カップリング剤、保存安定性改良剤（脱水剤）、着色剤などが挙げられる。 Examples of the additive in the present invention include a weather resistance stabilizer, a filler, a coupling agent, a storage stability improving agent (dehydrating agent), and a coloring agent.
耐候安定剤としては、硬化樹脂の酸化や光劣化、熱劣化を防止して、耐候性だけでなく耐熱性を更に向上させるために使用されるものである。耐候安定剤としては具体的には、酸化防止剤、紫外線吸収剤、光硬化性化合物を挙げることができる。 The weather resistance stabilizer is used to prevent oxidation, photodegradation and thermal degradation of the cured resin and further improve not only the weather resistance but also the heat resistance. Specific examples of the weather resistance stabilizer include an antioxidant, an ultraviolet absorber, and a photocurable compound.
酸化防止剤としてはヒンダードアミン系やヒンダードフェノール系の酸化防止剤が挙げられ、ヒンダードアミン系酸化防止剤としては、例えば、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ブチルマロネート、メチル１，２，２，６，６−ペンタメチル−４−ピペリジルセバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、１−［２−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕エチル］−４−〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕−２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、旭電化工業社製の商品名アデカスタブシリーズのＬＡ−５２、ＬＡ−５７、ＬＡ−６２、ＬＡ−６７、ＬＡ−７７、ＬＡ−８２、ＬＡ−８７等の分子量１，０００未満の低分子量のヒンダードアミン系酸化防止剤、同じくアデカスタブシリーズのＬＡ−６３Ｐ、ＬＡ−６８Ｄ、あるいはチバ・スペシャルティ・ケミカルズ社製の商品名ＣＨＩＭＡＳＳＯＲＢシリーズの１１９ＦＬ、２０２０ＦＤＬ、９４４ＦＤ、９４４ＬＤ等の分子量１，０００以上の高分子量のヒンダードアミン系酸化防止剤などが挙げられる。 Antioxidants include hindered amine and hindered phenol antioxidants. Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis. (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2 , 6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] 2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, trade names ADK STAB series LA-52, LA-57, LA manufactured by Asahi Denka Kogyo Co., Ltd. -62, LA-67, LA-77, LA-82, LA-87 and other low molecular weight hindered amine antioxidants with a molecular weight of less than 1,000, LA-63P, LA-68D, or Ciba -High molecular weight hindered amine antioxidants having a molecular weight of 1,000 or more such as 119FL, 2020FDL, 944FD, and 944LD of trade names CHIMASSORB series manufactured by Specialty Chemicals.
ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリスリト−ル−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニルプロピオアミド］、ベンゼンプロパン酸３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシＣ７−Ｃ９側鎖アルキルエステル、２，４−ジメチル−６−（１−メチルペンタデシル）フェノールなどが挙げられる。 Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide], benzenepropane Examples include acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.
紫外線吸収剤としては、例えば、２−（３，５−ジ−ｔｅｒｔ−ブチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノール等のトリアジン系紫外線吸収剤、オクタベンゾン等のべンゾフェノン系紫外線吸収剤、２，４−ジ−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンゾエート等のベンゾエート系紫外線吸収剤が挙げられる。 Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and other triazine-based UV absorbers, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butyl Examples thereof include benzoate ultraviolet absorbers such as phenyl-3,5-di-tert-butyl-4-hydroxybenzoate.
光硬化性化合物としては、アクリロイル基やメタクリロイル基などの光によって反応硬化する基を分子内に１個以上含有する化合物が挙げられ、具体的には、例えば、イソシアネート基含有ウレタン樹脂に水酸基含有アクリレート化合物や水酸基含有メタクリレート化合物を反応させたウレタンアクリレートやウレタンメタクリレート、トリメチロールプロパントリアクリレートやトリメチロールプロパントリメタクリレートなどのエステルアクリレートやエステルメタクリレート、ポリエチレンアジペートポリオールのアクリレートやメタクリレートなどのポリエステルアクリレートやポリエステルメタクリレート、ポリエーテルポリオ−ルのアクリレートやメタクリレートなどのポリエーテルアクリレートやポリエーテルメタクリレート、あるいはポリケイ皮酸ビニル類、アジド化樹脂などが挙げられ、分子量１０，０００以下、更に分子量５，０００以下の単量体、オリゴマーが好ましく、特にアクリロイル基および／またはメタクリロイル基を１分子当たり平均して２個以上含有するものが好ましい。
これらの耐候安定剤は単独あるいは２種以上を組合わせて使用できる。
Examples of the photocurable compound include a compound containing one or more groups that are reactively cured by light such as an acryloyl group or a methacryloyl group in the molecule. Specifically, for example, an isocyanate group-containing urethane resin is added to a hydroxyl group-containing acrylate. Urethane acrylate and urethane methacrylate reacted with a compound and hydroxyl group-containing methacrylate compound, ester acrylate and ester methacrylate such as trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, polyester acrylate and polyester methacrylate such as acrylate and methacrylate of polyethylene adipate polyol, Polyether acrylate and polyether methacrylate such as polyether polyol acrylate and methacrylate Alternatively, polyvinyl cinnamates, azide resins, and the like can be mentioned. Monomers and oligomers having a molecular weight of 10,000 or less, and further a molecular weight of 5,000 or less are preferable. Particularly, acryloyl groups and / or methacryloyl groups are averaged per molecule. And those containing 2 or more are preferred.
These weather stabilizers can be used alone or in combination of two or more.
耐候安定剤は、イソシアネート基含有ウレタンプレポリマー（Ａ）１００重量部に対して、０．０１〜３０重量部、特に０．１〜１０重量部配合するのが好ましい。 The weathering stabilizer is preferably blended in an amount of 0.01 to 30 parts by weight, particularly 0.1 to 10 parts by weight, per 100 parts by weight of the isocyanate group-containing urethane prepolymer (A).
充填剤、カップリング剤、保存安定性改良剤（脱水剤）、着色剤は、それぞれ増量や補強、接着性向上、保存安定性（貯蔵安定性）の向上、着色などのために、本願発明のクリーンルーム用ウレタン系シーリング材組成物に配合して使用することができる。 Fillers, coupling agents, storage stability improvers (dehydrating agents), and colorants are used for the purpose of increasing or reinforcing, improving adhesion, improving storage stability (storage stability), coloring, etc. It can be used by blending with a urethane sealant composition for clean rooms.
充填剤としては、マイカ、カオリン、ゼオライト、グラファイト、珪藻土、白土、クレー、タルク、スレート粉、無水ケイ酸、石英微粉末、アルミニウム粉末、亜鉛粉末、沈降性シリカなどの合成シリカ、炭酸カルシウム、炭酸マグネシウム、アルミナ等の無機粉末状充填剤、アスベスト、ガラス繊維、炭素繊維等の繊維状充填剤、ガラスバルーン、シラスバルーン、シリカバルーン、セラミックバルーン等の無機系バルーン状充填剤などの無機系充填剤、あるいはこれらの表面を脂肪酸やシランカップリング剤等の有機物で処理した充填剤、木粉、クルミ穀粉、もみ殻粉、パルプ粉、木綿チップ、ゴム粉末、熱可塑性あるいは熱硬化性樹脂の微粉末、ポリエチレン等の粉末や中空体、サランマイクロバルーン等の有機系バルーン状充填剤などの有機系充填剤などの他、水酸化マグネシウムや水酸化アルミニウムなどの難燃性付与充填剤なども挙げられ、粒径０.０１〜１，０００μmのものが好ましい。これらは単独あるいは２種以上を組合わせて使用できる。 Fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, precipitated silica, synthetic silica, calcium carbonate, carbonic acid Inorganic fillers such as inorganic powder fillers such as magnesium and alumina, fibrous fillers such as asbestos, glass fibers and carbon fibers, inorganic balloon fillers such as glass balloons, shirasu balloons, silica balloons and ceramic balloons Or fillers whose surfaces are treated with organic substances such as fatty acids and silane coupling agents, wood flour, walnut flour, rice husk flour, pulp flour, cotton chips, rubber powder, thermoplastic or thermosetting resin fine powder Powders such as polyethylene, hollow bodies, and organic balloon fillers such as saran microballoons. Other organic fillers, include well as flame retardant fillers such as magnesium hydroxide and aluminum hydroxide, as a particle size 0.01~1,000μm are preferred. These can be used alone or in combination of two or more.
カップリング剤としては、シラン系、アルミニウム系、ジルコアルミネート系などの各種カップリング剤および／またはその部分加水分解縮合物を挙げることができ、このうちシラン系カップリング剤および／またはその部分加水分解物が接着性に優れているので好ましい。
このシラン系カップリング剤としては、具体的には、３−メタクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシランなどのアルコキシシリル基を含有する化合物および／またはこれらシラン系カップリング剤の１種または２種以上の部分加水分解縮合物を挙げることができる。これらは単独であるいは２種以上を組合せて使用できる。
Examples of the coupling agent include various coupling agents such as silane-based, aluminum-based, and zircoaluminate-based and / or partial hydrolysis condensates thereof. Of these, the silane-based coupling agent and / or partial hydrolysis thereof. The decomposed product is preferable because of its excellent adhesiveness.
Specific examples of the silane coupling agent include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3 -Compounds containing alkoxysilyl groups such as glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane and / or one or more partial hydrolysis condensates of these silane coupling agents Can be mentioned. These can be used alone or in combination of two or more.
保存安定性改良剤としては、組成物中に存在する水分と反応するビニルトリメトキシシラン、酸化カルシウム、ｐ−トルエンスルホニルイソシアネートなどが挙げられ、これらは単独あるいは２種以上を組合わせて使用できる。 Examples of the storage stability improver include vinyltrimethoxysilane that reacts with moisture present in the composition, calcium oxide, p-toluenesulfonyl isocyanate, and the like. These can be used alone or in combination of two or more.
着色剤としては、酸化チタンや酸化鉄などの無機系顔料、銅フタロシアニンなどの有機系顔料、カーボンブラックなどが挙げられる。
これらは単独あるいは２種以上を組合わせて使用できる。
Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.
These can be used alone or in combination of two or more.
充填剤、カップリング剤、保存安定性改良剤、および着色剤の合計の配合量は、イソシアネート基含有ウレタンプレポリマー（Ａ）１００重量部に対して０〜５００重量部、特に５〜３００重量部であることが好ましい。 The total amount of filler, coupling agent, storage stability improver, and colorant is 0 to 500 parts by weight, particularly 5 to 300 parts by weight, per 100 parts by weight of the isocyanate group-containing urethane prepolymer (A). It is preferable that
本願発明のクリーンルーム用ウレタン系シーリング材組成物において、前記各添加剤成分はそれぞれ１種類または２種以上を混合して使用することができる。 In the urethane sealant composition for a clean room of the present invention, each of the additive components can be used alone or in combination of two or more.
本願発明において、クリーンルーム用ウレタン系シーリング材組成物にさらに硬化促進触媒を添加することができる。
使用することができる硬化促進触媒としては、たとえば、テトラ−ｎ−ブチルチタネート等の金属のアルコキシド、オクチル酸第一錫、オクテン酸錫などの、亜鉛、錫、鉛、ジルコニウム、ビスマス、コバルト、マンガン、鉄等の金属とオクチル酸、オクテン酸、ナフテン酸等の有機酸との塩、ジブチル錫ビス（アセチルアセトナート）、ジルコニウムテトラキス（アセチルアセトナート）、チタンテトラキス（アセチルアセトナート）等の金属キレート化合物、ジブチル錫ジラウレート、ジオクチル錫ジラウレート等の有機金属と有機酸との塩、モルホリン等の有機アミンやその塩などが挙げられ、これらは単独あるいは２種以上を組合わせて使用できる。これらのうち硬化を促進する効果が高い点で有機金属と有機酸との塩が好ましく、さらにジブチル錫ジラウレートが好ましい。
In this invention, a hardening acceleration | stimulation catalyst can be further added to the urethane type sealing material composition for clean rooms.
Examples of the curing acceleration catalyst that can be used include zinc, tin, lead, zirconium, bismuth, cobalt, manganese, such as metal alkoxides such as tetra-n-butyl titanate, stannous octylate, and tin octenoate. , Salts of metals such as iron and organic acids such as octylic acid, octenoic acid and naphthenic acid, metal chelates such as dibutyltin bis (acetylacetonate), zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetonate) Examples thereof include a compound, a salt of an organic metal such as dibutyltin dilaurate and dioctyltin dilaurate and an organic acid, an organic amine such as morpholine and a salt thereof, and these can be used alone or in combination of two or more. Among these, a salt of an organic metal and an organic acid is preferable in that the effect of promoting curing is high, and dibutyltin dilaurate is more preferable.
なお、本願発明のクリーンルーム用ウレタン系シーリング材組成物は作業性の点から１液湿気硬化型として使用するのが好ましいが、本願発明のシーリング材組成物を主剤とし、水などの硬化剤を混合して硬化させる２液硬化型としても使用できる。 The urethane sealant composition for clean rooms of the present invention is preferably used as a one-component moisture-curing type from the viewpoint of workability. However, the sealant composition of the present invention is mainly used and a curing agent such as water is mixed. Then, it can be used as a two-component curable type that is cured.
本願発明のクリーンルーム用ウレタン系シーリング材組成物は、汚染防止性に優れ、かつ有機溶剤等の揮発性物質成分を含有しない１成分形湿気硬化型のウレタン系シーリング材として好適に用いられる。 The urethane sealant composition for clean rooms of the present invention is suitably used as a one-component moisture-curing urethane sealant that is excellent in antifouling properties and does not contain volatile components such as organic solvents.
本願発明は、イソシアネート基含有ウレタンプレポリマーと、実質的に反応性官能基を有しないショ糖のポリエーテル化樹脂と、有機表面処理炭酸カルシウムとを含有し、かつ揮発成分を含有しないクリーンルーム用ウレタン系シーリング材組成物であるから、大気中などの水分により硬化して、高い伸びと接着性を有する優れたゴム状弾性体となり、硬化途中ならびに硬化後においても、さらに周囲の雰囲気が常温においても、５０〜１００℃の高温においても揮発成分（ガス状有機物）が発生せず、かつ硬化物の表面に可塑剤等の液状物が移行（ブリード）することがないため、クリーンルーム内で製造あるいは使用される製品や精密機器類などを汚染することがない、さらには硬化促進触媒を添加して硬化速度を高めても充填塗布時にタレない（スランプしない）という優れた効果を奏する。 The present invention relates to a urethane for a clean room containing an isocyanate group-containing urethane prepolymer, a polyether resin of sucrose having substantially no reactive functional group, and organic surface-treated calcium carbonate, and containing no volatile components. Because it is a system sealant composition, it is cured by moisture in the atmosphere, etc., and becomes an excellent rubber-like elastic body having high elongation and adhesiveness. Even during and after curing, the ambient atmosphere is also at room temperature. , No volatile components (gaseous organic substances) are generated even at high temperatures of 50 to 100 ° C., and liquid materials such as plasticizers do not migrate (bleed) to the surface of the cured product. Products and precision instruments are not contaminated, and even when a curing accelerator is added to increase the curing speed, An excellent effect that there is no record (not slump).
以下に本願発明の実施例を示すが、本願発明がこれに限定されるものではない。 Examples of the present invention are shown below, but the present invention is not limited thereto.
〔合成例１〕
攪拌機、温度計、窯素シール管および加熱・冷却装置付き反応容器に、窒素ガスを流しながらポリオキシプロピレングリコール（三井武田ケミカル社製、Ｄｉｏｌ−３０００、数平均分子量３，０００）３３２ｇと、ポリオキシプロピレントリオール（三井武田ケミカル社製、ＭＮ−４０００、数平均分子景４，０００）６６ｇと、２，４−トルエンジイソシアネート（日本ポリウレタン工業社製、Ｔ−１００）４４ｇとを攪拌しながら仕込み、次いでジブチル錫ジラウレート０．４ｇを加え、８０℃で４時間攪拌して反応させた後、冷却してウレタンプレポリマーを合成した。
得られたウレタンプレポリマーは、滴定によるイソシアネート基含有量２．２質量％、２５℃における粘度１３，０００ｍＰａ・ｓの常温で粘稠な液体であった。
[Synthesis Example 1]
332 g of polyoxypropylene glycol (manufactured by Mitsui Takeda Chemical Co., Diol-3000, number average molecular weight 3,000) while flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, kiln seal tube and heating / cooling device, 66 g of oxypropylene triol (Mitsui Takeda Chemical Co., Ltd., MN-4000, number average molecular landscape 4,000) and 44 g of 2,4-toluene diisocyanate (Nippon Polyurethane Industry Co., Ltd., T-100) were charged with stirring. Next, 0.4 g of dibutyltin dilaurate was added, and the mixture was reacted by stirring at 80 ° C. for 4 hours, and then cooled to synthesize a urethane prepolymer.
The obtained urethane prepolymer was a viscous liquid at room temperature having an isocyanate group content of 2.2% by mass and a viscosity of 13,000 mPa · s at 25 ° C.
〔実施例１〕
加熱・冷却装置および窒素シール管付き混練容器に、窒素ガスを流しながら合成例１で得たイソシアネート基含有ウレタンプレポリマー３００ｇを仕込み、攪拌しながら（実質的に反応性官能基を有しない）ショ糖のポリエーテル化樹脂（三洋化成工業社製、サンフレックスＳＰＸ−８０、数平均分子量８，０００）２５０ｇ、ヒンダードフェノール系酸化防止剤（チバ・スペシャルテイ・ケミカルズ社製、ＩＲＧＡＮＯＸ１０１０、ペンタエリスリトールテトラキス〔３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕）５ｇ、予め乾燥した炭酸カルシウム２００ｇ、酸化チタン２０ｇおよび３−グリシドキシプロピルトリメトキシシラン（信越化学工業社製、ＫＢＭ４０３）１ｇを順次仕込み均一になるまで攪拌、混合した。次いで脂肪酸表面処理炭酸カルシウム（白石工業社製、白艶華ＣＣＲ）２５０ｇとｐ−トルエンスルフォニルイソシアネート５ｇとジブチル錫ジラウレート０.５ｇを仕込みさらに均一になるまで攪拌、混合し、次いで減庄脱泡し、容器に充填、密封してクリーンルーム用ウレタン系シーリング材組成物を調製した。
[Example 1]
In a kneading vessel equipped with a heating / cooling device and a nitrogen seal tube, 300 g of the isocyanate group-containing urethane prepolymer obtained in Synthesis Example 1 was charged while flowing nitrogen gas, and stirred (substantially free of reactive functional groups). Polyether resin of sugar (manufactured by Sanyo Chemical Industries, Sunflex SPX-80, number average molecular weight 8,000) 250 g, hindered phenol antioxidant (manufactured by Ciba Specialty Chemicals, IRGANOX 1010, pentaerythritol tetrakis) [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) 5 g, pre-dried calcium carbonate 200 g, titanium oxide 20 g and 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) , KBM403) 1g is sequentially charged and uniform. In stirring, and mixed. Next, 250 g of fatty acid surface-treated calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Shiraka Hana CCR), 5 g of p-toluenesulfonyl isocyanate and 0.5 g of dibutyltin dilaurate were charged and stirred until they became more uniform. And sealed and sealed to prepare a clean room urethane sealant composition.
〔比較例１〕
実施例１において、（実質的に反応性官能基を有しない）ショ糖のポリエーテル化樹脂２５０ｇを使用しないで、代わりにジオクチルフタレート２５０ｇを使用し、炭酸カルシウムの使用量を４２０ｇにし、さらに脂肪酸表面処理炭酸カルシウム２５０ｇを使用しないで、代わりにコロイダルシリカ（日本アエロジル杜製、ＡＥＲＯＳＩＬ２００）３０ｇを使用した以外は同様にしてシーリング材組成物を調製した。
[Comparative Example 1]
In Example 1, 250 g of dioctyl phthalate was used instead of 250 g of sucrose polyetherated resin (substantially having no reactive functional group), the amount of calcium carbonate used was 420 g, and fatty acid A sealant composition was prepared in the same manner except that 250 g of surface-treated calcium carbonate was not used and 30 g of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., AEROSIL 200) was used instead.
以上の結果を表１に示す
試験方法
（１）揮発分
ＪＩＳ Ｋ ６８３３（１９９４）「接着剤の一般試験方法」、６．４不揮発分の試験方法に準じ、平形はかり瓶５０×３０ｍｍの外壁に沿って同形に成形したアルミニウム箔の皿に、実施例１と比較例１で得たシーリング材組成物を試料として用い、試料１．５ｇを採り、その質量を量り、次いで９０℃の恒温槽に入れ３時間加熱乾燥した後とりだし放冷しその質量を量り、（１）に示す計算式により揮発分を求めた。
Ｖ＝（Ｗａ−Ｗｂ）／ Ｗａ×１００ （１）
ここに、Ｖ ：揮発分（質量％）
Ｗａ：乾操前の試料の質量（ｇ）
Ｗｂ：乾燥後の試料の質量（ｇ）
Test method (1) Volatile content JIS K 6833 (1994) “General test method of adhesive”, 6.4 Non-volatile content test method Aluminum foil formed in the same shape along the outer wall of a flat weighing bottle 50 × 30 mm Using the sealing material composition obtained in Example 1 and Comparative Example 1 as a sample, take 1.5 g of the sample, weigh the mass, then place it in a constant temperature bath at 90 ° C. and heat dry for 3 hours. After standing to cool, the mass was measured, and the volatile content was determined by the formula shown in (1).
V = (Wa−Wb) / Wa × 100 (1)
Where V: Volatile content (mass%)
Wa: Mass of the sample before drying (g)
Wb: mass of the sample after drying (g)
（２）押出し性
ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の試験方法」の「４．１４試験用カートリッジによる押出し試験」に準拠して測定した（測定温度２３℃）。押出し時間が５秒以下のものを○と評価した。
(2) Extrudability Measured in accordance with JIS A1439: 1997 “Testing method of sealing material for building” “4.14 Extrusion test with test cartridge” (measurement temperature 23 ° C.). Those having an extrusion time of 5 seconds or less were evaluated as ◯.
（３）スランプ
ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の試験方法」の「４．１スランプ試験」に準拠して、スランプ（縦）を測定した（測定温度２３℃）。
(3) Slump The slump (longitudinal) was measured in accordance with “4.1 slump test” in JIS A1439: 1997 “Testing method of sealing material for building” (measurement temperature: 23 ° C.).
（４）タックフリー
ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の試験方法」の「４．１９タックフリー試験」に準拠して測定した。タックフリー時間が５時間以内のものを○と評価した。
(4) Tack-free Measured in accordance with “4.19 Tack-free test” in JIS A1439: 1997 “Testing method of building sealing material”. A tack-free time of 5 hours or less was rated as “good”.
（５）汚染性
硬化後のシーリング材の表面に可塑剤等の液状成分が出てきていないことを評価するために、液状成分がブリードしていると硬化物表面が著しく粘着し、表面に塵埃が多量に付着して黒く汚れてしまうことに着目して、汚染性を試験した。
試験方法は、厚さ５ｍｍのスレート板を使用し、深さ５ｍｍ、幅２５ｍｍ、長さ１５０ｍｍの目地を作製し、その目地にシーリング材組成物を打設し、余分のシーリング材をヘラでかきとり、表面を平らにしたものを、２３℃、５０％相対湿度で１４日間養生し試験体を作製した。
養生後の試験体の表面に黒色珪砂（粒径７０〜１１０μｍ）をふりかけ、ただちに試験体を裏返し、底面を手で軽く叩き余分の黒色珪砂を落とした。表面に付着した残った黒色珪砂（汚れ）の状態を目視により観察して、以下の判定基準により養生後の汚染性を判定した。
○は液状成分が硬化後のシーリング材の表面にブリードしていないことを示している。
(5) Contamination To evaluate the absence of liquid components such as plasticizers on the surface of the sealing material after curing, if the liquid components are bleed, the surface of the cured product will remarkably adhere, and dust will adhere to the surface. Focusing on the fact that a large amount adheres and becomes black and dirty, the contamination property was tested.
The test method uses a slate plate with a thickness of 5 mm, a joint with a depth of 5 mm, a width of 25 mm, and a length of 150 mm is prepared, a sealing material composition is placed on the joint, and the excess sealing material is scraped off with a spatula. The test piece was prepared by curing the flattened surface at 23 ° C. and 50% relative humidity for 14 days.
Black quartz sand (particle size: 70 to 110 μm) was sprinkled on the surface of the test specimen after curing, and the specimen was immediately turned over, and the bottom surface was lightly tapped by hand to remove excess black silica sand. The state of the remaining black silica sand (dirt) adhering to the surface was visually observed, and the contamination after curing was determined according to the following criteria.
○ indicates that the liquid component does not bleed on the surface of the sealing material after curing.
〔実施例２〕
実施例１で調製したクリーンルーム用ウレタン系シーリング材組成物について、ガス状有機物が発生しないことを確認するために、ガス分析を行った。
[Example 2]
In order to confirm that no gaseous organic matter was generated with respect to the urethane sealant composition for clean room prepared in Example 1, gas analysis was performed.
（１）試験方法
実施例１で調製したクリーンルーム用ウレタン系シーリング材組成物を約１０×１０ｍｍ、厚さ約２ｍｍに整形塗布し、これを試料として、塗布直後のものと、２３℃、５０％相対湿度で７日間養生硬化させたものそれぞれについて、発生するガス状有機物の分析を行った。
試料を正常なガラスセル内に入れ、ガラスセル内に高純度窒素ガスを０．１Ｌ／ｍｉｎの流量で導入し、ガラスセルの出口に有機物ガス捕集用の吸着管を取り付け、常温で１時間、窒素ガスを流通させて試料から発生する有機物ガスを吸着管に吸着捕集する。この吸着管を、加熱脱着装置付のガスクロマトグラフ質量分析装置にセットし、吸着管に捕集されたガス状有機物を加熱脱着によってガスクロマトグラフ質量分析装置に導入して定性および定量分析を行う。
(1) Test method The urethane sealant composition for clean room prepared in Example 1 was shaped and applied to a thickness of about 10 × 10 mm and a thickness of about 2 mm, and this was used as a sample immediately after application, 23 ° C., 50%. For each of those cured and cured at a relative humidity for 7 days, the generated gaseous organic matter was analyzed.
Place the sample in a normal glass cell, introduce high-purity nitrogen gas into the glass cell at a flow rate of 0.1 L / min, attach an adsorption tube for collecting organic gas at the outlet of the glass cell, and keep at room temperature for 1 hour The organic gas generated from the sample is adsorbed and collected in the adsorption tube by circulating nitrogen gas. This adsorption tube is set in a gas chromatograph mass spectrometer equipped with a heat desorption device, and gaseous organic substances collected in the adsorption tube are introduced into the gas chromatograph mass spectrometer by heat desorption to perform qualitative and quantitative analysis.
（２）試験結果
分析結果を以下の表２に示す。同表に示している分析対象物質は、従来のシーリング材からガス発生が確認されている物質のうち、比較的揮発性が低く、そのために、シーリング材から長期間にわたって徐々にガス化して放散され、また、半導体製品等に吸着すると汚れとして残留し易く、製品不良の原因となりやすい成分である。
実施例１で調製したクリーンルーム用ウレタン系シーリング材組成物では表２に示したようにこれら成分のすべてが不検出あるいは定量下限値以下であることが判明した。したがって、ガス状有機物を発生してクリーンルームの清浄度を低下させる恐れがなく、クリ−ンルーム用として実用性が高いことが確認できた。
In the urethane sealant composition for clean room prepared in Example 1, as shown in Table 2, it was found that all of these components were not detected or were below the lower limit of quantification. Therefore, it has been confirmed that there is no risk of generating a gaseous organic substance and lowering the cleanliness of the clean room, and that the practicality for the clean room is high.
Claims (4)
前記揮発成分が、前記クリーンルーム用ウレタン系シーリング材組成物を９０℃の高温雰囲気に３時間置いたときに質量の減少として測定されるガス状有機物であり、
前記有機表面処理炭酸カルシウムが、平均粒径が０.０１〜０．５μｍであってＢＥＴ比表面積が５〜２００ｍ２／ｇであること、
を特徴とするクリーンルーム用一液湿気硬化型ウレタン系シーリング材組成物。 One liquid for clean room containing isocyanate group-containing urethane prepolymer, polyether resin of sucrose having substantially no reactive functional group, and organic surface-treated calcium carbonate, and substantially free of volatile components A moisture-curing urethane-based sealant composition,
The volatile component is a gaseous organic substance measured as a decrease in mass when the urethane-based sealant composition for clean rooms is placed in a high temperature atmosphere at 90 ° C. for 3 hours,
The organic surface-treated calcium carbonate has an average particle diameter of 0.01 to 0.5 μm and a BET specific surface area of 5 to 200 m 2 / g,
A one-part moisture-curing urethane-based sealing material composition for clean rooms.
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| JPH02150489A (en) * | 1988-11-30 | 1990-06-08 | Kanebo N S C Kk | Two-pack polyurethane-based sealant |
| JPH0995661A (en) * | 1995-07-27 | 1997-04-08 | Taisei Corp | Wet-sealing material, its production, clean room and local facility |
| JP2003301102A (en) * | 2002-04-10 | 2003-10-21 | Lonseal Corp | One-pack moisture curable polyurethane composition |
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| JPH02150489A (en) * | 1988-11-30 | 1990-06-08 | Kanebo N S C Kk | Two-pack polyurethane-based sealant |
| JPH0995661A (en) * | 1995-07-27 | 1997-04-08 | Taisei Corp | Wet-sealing material, its production, clean room and local facility |
| JP2003301102A (en) * | 2002-04-10 | 2003-10-21 | Lonseal Corp | One-pack moisture curable polyurethane composition |
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