JP5964227B2 - Method for producing polyurethane resin - Google Patents
Method for producing polyurethane resin Download PDFInfo
- Publication number
- JP5964227B2 JP5964227B2 JP2012285892A JP2012285892A JP5964227B2 JP 5964227 B2 JP5964227 B2 JP 5964227B2 JP 2012285892 A JP2012285892 A JP 2012285892A JP 2012285892 A JP2012285892 A JP 2012285892A JP 5964227 B2 JP5964227 B2 JP 5964227B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyol
- polyurethane resin
- content
- viewpoint
- 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 - Fee Related
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- 229920005749 polyurethane resin Polymers 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 150000003077 polyols Chemical class 0.000 claims description 77
- 229920005862 polyol Polymers 0.000 claims description 59
- 239000003054 catalyst Substances 0.000 claims description 33
- -1 organic acid salt Chemical class 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 229920000570 polyether Polymers 0.000 claims description 19
- 229920001228 polyisocyanate Polymers 0.000 claims description 18
- 239000005056 polyisocyanate Substances 0.000 claims description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- ZYCRBOCGBKATBL-UHFFFAOYSA-N 3-tert-butyl-6-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(C(C)(C)C)C(N)=C1N ZYCRBOCGBKATBL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- 150000005846 sugar alcohols Polymers 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000006082 mold release agent Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229930006000 Sucrose Natural products 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 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
- 239000003063 flame retardant Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 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
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- KUGVQHLGVGPAIZ-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KUGVQHLGVGPAIZ-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-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
- GPXSTLAIBOEFST-UHFFFAOYSA-N 1-[4-(2-hydroxypropyl)-3-methylpiperazin-1-yl]propan-2-ol Chemical compound CC(O)CN1CCN(CC(C)O)C(C)C1 GPXSTLAIBOEFST-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- WCDFMPVITAWTGR-UHFFFAOYSA-N 1-imidazol-1-ylpropan-2-ol Chemical compound CC(O)CN1C=CN=C1 WCDFMPVITAWTGR-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- UYHNDEQBDLNIJY-UHFFFAOYSA-N 2,2-diaminoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(N)N UYHNDEQBDLNIJY-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QHTUMQYGZQYEOZ-UHFFFAOYSA-N 2-(4-methylpiperazin-1-yl)ethanol Chemical compound CN1CCN(CCO)CC1 QHTUMQYGZQYEOZ-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
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- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 239000005715 Fructose Substances 0.000 description 1
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- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000007859 condensation product Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 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
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- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
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- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 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 1
- PLONEVHFXDFSLA-UHFFFAOYSA-N ethyl hexanoate;tin(2+) Chemical compound [Sn+2].CCCCCC(=O)OCC PLONEVHFXDFSLA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
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- 229960004337 hydroquinone Drugs 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 235000010355 mannitol Nutrition 0.000 description 1
- XPOXIRBXYPGDNE-UHFFFAOYSA-N methanediamine Chemical compound N[CH]N XPOXIRBXYPGDNE-UHFFFAOYSA-N 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- UNEXJVCWJSHFNN-UHFFFAOYSA-N n,n,n',n'-tetraethylmethanediamine Chemical compound CCN(CC)CN(CC)CC UNEXJVCWJSHFNN-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- DWEYPOWXNBAIDU-UHFFFAOYSA-N n,n-dichloromethanamine Chemical compound CN(Cl)Cl DWEYPOWXNBAIDU-UHFFFAOYSA-N 0.000 description 1
- YLISQABRPKFNCX-UHFFFAOYSA-N n,n-dimethyl-2-morpholin-4-yloxyethanamine Chemical compound CN(C)CCON1CCOCC1 YLISQABRPKFNCX-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 229920003986 novolac Polymers 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 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
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 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
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明はポリウレタン樹脂の製造方法に関するものである。さらに詳しくは、自動車用外装部品、特に一体成形窓用シールド材料に適したポリウレタン樹脂の製造方法に関するものである。 The present invention relates to a method for producing a polyurethane resin. More specifically, the present invention relates to a method for producing a polyurethane resin suitable for an automotive exterior part, particularly, an integrally molded window shielding material.
従来、窓用シールド材料としては、例えば、特定の分子量のポリオール類、特定の架橋剤（特定の分子量のポリオールとグリセリンの混合物）を、鉛又は錫等の有機酸塩の存在下、ポリイソシアネートと反応させる方法（特許文献１参照）等が知られている。 Conventionally, as a shielding material for windows, for example, a polyol having a specific molecular weight, a specific cross-linking agent (a mixture of a polyol having a specific molecular weight and glycerin), a polyisocyanate, and an organic acid salt such as lead or tin are used. A reaction method (see Patent Document 1) is known.
近年、コストダウンの観点から成形サイクルを短縮して生産性向上する要望が高まってきた。例えば、金型へ離型剤を塗布する回数を減らし、一回の塗布で連続数回成形することが望まれる。しかしながら、上記公報記載の方法では、脱型性が悪く、脱型毎に金型へ離型剤を塗布しなければならない。
したがって、本発明は、一体成形窓用シールド材料に適したポリウレタン樹脂の製造において、連続成形可能な製造方法を提供することを目的とする。
In recent years, from the viewpoint of cost reduction, there has been an increasing demand for improving the productivity by shortening the molding cycle. For example, it is desired to reduce the number of times the mold release agent is applied to the mold, and to perform continuous molding several times in one application. However, in the method described in the above publication, the mold release property is poor, and a mold release agent must be applied to the mold for each mold release.
Accordingly, an object of the present invention is to provide a production method capable of continuous molding in the production of a polyurethane resin suitable for an integrally molded window shielding material.
本発明者はこれら問題点を解決するため鋭意検討した結果、本発明を完成した。
すなわち本発明は、ポリオール組成物（Ａ）、下記芳香族ポリアミン（Ｂ）、ポリイソシアネート成分（Ｃ）及びウレタン化触媒（Ｄ）を含有する混合物を反応硬化するポリウレタン樹脂の製造方法であって、（Ａ）が、下記ポリエーテルポリオ−ル（ａ１）を含有し、（ａ１）の含有量が（Ａ）の合計重量を基準として５０〜１００重量％であり、（Ｃ）がジフェニルメタンジイソシアネートと低分子ポリオール（Ａ２）を反応させてなるＮＣＯ基末端ポリウレタンプレポリマー（Ｃ１）を含有し、密閉型枠内でこの混合物を反応硬化し、事前に密閉型枠内に挿入したガラスと一体成形する工程を有する自動車の窓用ポリウレタン樹脂の製造方法。
ポリエーテルポリオ−ル（ａ１）：ポリオキシエチレンポリオキシプロピレンポリオ−ルであって、数平均官能基数が７．８〜８．２であり、水酸基価が１０〜４０（ｍｇＫＯＨ／ｇ）であり、末端オキシエチレン単位の含有量が１０〜３０重量％であるポリエーテルポリオール。
芳香族ポリアミン（Ｂ）：ジエチルトルエンジアミン及び／又はターシャリーブチルトルエンジアミン。
As a result of intensive studies aimed at solving these problems, the present inventor has completed the present invention.
That is, the present invention is a method for producing a polyurethane resin by reaction-curing a mixture containing a polyol composition (A), the following aromatic polyamine (B), polyisocyanate component (C) and urethanization catalyst (D), (A) contains the following polyether polyol (a1), the content of (a1) is 50 to 100% by weight based on the total weight of (A), and (C) is low with diphenylmethane diisocyanate. A step of reacting the molecular polyol (A2) with an NCO group-terminated polyurethane prepolymer (C1), reacting and curing the mixture in a sealed mold, and integrally molding with glass previously inserted in the sealed mold The manufacturing method of the polyurethane resin for the windows of the motor vehicle which has this.
Polyether polyol (a1): Polyoxyethylene polyoxypropylene polyol having a number average functional group number of 7.8 to 8.2 and a hydroxyl value of 10 to 40 (mgKOH / g) A polyether polyol having a content of terminal oxyethylene units of 10 to 30% by weight.
Aromatic polyamine (B): diethyltoluenediamine and / or tertiary butyltoluenediamine.
本発明のポリウレタン樹脂の製造方法は、連続成形性が良好である。 The process for producing the polyurethane resin of the present invention has good continuous moldability.
本発明のポリウレタン樹脂の製造方法で用いられるポリオール組成物（Ａ）は、キュア性、連続成形性及び樹脂物性の観点から、ポリオキシエチレンポリオキシプロピレンポリオ−ルであって、数平均官能基数が７．８〜８．２であり、水酸基価が１０〜４０（ｍｇＫＯＨ／ｇ）であり、末端オキシエチレン単位の含有量が１０〜３０重量％であるポリエーテルポリオール（ａ１）を含有する。（ａ１）は２種以上を併用してもよい。 The polyol composition (A) used in the method for producing a polyurethane resin of the present invention is a polyoxyethylene polyoxypropylene polyol from the viewpoint of curing properties, continuous moldability and resin physical properties, and has a number average functional group number. A polyether polyol (a1) having a hydroxyl value of 7.8 to 8.2, a hydroxyl value of 10 to 40 (mg KOH / g), and a content of terminal oxyethylene units of 10 to 30% by weight is contained. (A1) may use 2 or more types together.
（ａ１）の数平均官能基数は７．８〜８．２であり、連続成形性及びキュア性の観点から、７．９〜８．１が好ましく、さらに好ましくは８．０である。
なお、本発明において、ポリエーテルポリオールの官能基数は、出発物質である活性水素含有化合物の官能基数と同一であるとみなす。
The number average functional group number of (a1) is 7.8 to 8.2, preferably 7.9 to 8.1, more preferably 8.0, from the viewpoint of continuous moldability and curing properties.
In the present invention, the number of functional groups of the polyether polyol is considered to be the same as the number of functional groups of the active hydrogen-containing compound that is the starting material.
（ａ１）の水酸基価は、１０〜４０（ｍｇＫＯＨ／ｇ）であり、連続成形性及び樹脂物性の観点から、１５〜３０（ｍｇＫＯＨ／ｇ）が好ましい。本発明における水酸基価は、ＪＩＳ Ｋ００７０（１９９２年版）に規定の方法で測定される。
（ａ１）の末端オキシエチレン単位の含有量は、１０〜３０重量％であり、連続成形性及びキュア性の観点から、１５〜２９重量％が好ましく、さらに好ましくは２０〜２５重量％である。
The hydroxyl value of (a1) is 10 to 40 (mg KOH / g), and 15 to 30 (mg KOH / g) is preferable from the viewpoint of continuous moldability and resin physical properties. The hydroxyl value in the present invention is measured by a method defined in JIS K0070 (1992 version).
The content of the terminal oxyethylene unit in (a1) is 10 to 30% by weight, preferably 15 to 29% by weight, more preferably 20 to 25% by weight from the viewpoint of continuous moldability and curing properties.
（ａ１）としては、後述の（Ａ１）の説明で記載する少なくとも２個の活性水素を有する化合物のうち、７．８〜８．２個の活性水素を含有する化合物に１，２−プロピレンオキサイド（以下、ＰＯと略記）次いでエチレンオキサイド（以下、ＥＯと略記）が付加された構造の化合物が挙げられる。
ＰＯ及びＥＯを付加する際に用いる触媒としては、アルカリ触媒（ＫＯＨ、ＣｓＯＨ等）の他、特開２０００−３４４８８１号公報に記載の触媒〔トリス（ペンタフルオロフェニル）ボラン等〕、特開平１１−１２０３００号公報に記載の触媒（過塩素酸マグネシウム等）を用いてもよい。
As (a1), among the compounds having at least two active hydrogens described in the description of (A1) described later, 1,2-propylene oxide is added to a compound containing 7.8 to 8.2 active hydrogens. (Hereinafter, abbreviated as PO) Next, a compound having a structure to which ethylene oxide (hereinafter abbreviated as EO) is added may be mentioned.
Catalysts used for adding PO and EO include alkali catalysts (KOH, CsOH, etc.), catalysts described in JP-A No. 2000-344881 [Tris (pentafluorophenyl) borane, etc.], JP-A No. 11- You may use the catalyst (magnesium perchlorate etc.) as described in 120300 gazette.
（ａ１）の含有量はポリオール組成物（Ａ）の合計重量を基準として、連続成形性の観点から、５０〜１００重量％であり、７０〜１００重量％が好ましい。 The content of (a1) is 50 to 100% by weight, preferably 70 to 100% by weight, from the viewpoint of continuous moldability, based on the total weight of the polyol composition (A).
本発明のポリオール組成物（Ａ）として、（ａ１）以外にもポリウレタン樹脂の製造に用いられる活性水素成分が使用できる。例えば（ａ１）以外のポリエーテルポリオール（Ａ１）、低分子ポリオール（Ａ２）、ポリエステルポリオール（Ａ３）及びこれらのポリオールの中でビニルモノマーを重合させて得られる重合体ポリオール（Ａ４）が挙げられる。 As the polyol composition (A) of the present invention, an active hydrogen component used for the production of a polyurethane resin can be used in addition to (a1). Examples thereof include polyether polyols (A1) other than (a1), low-molecular polyols (A2), polyester polyols (A3), and polymer polyols (A4) obtained by polymerizing vinyl monomers among these polyols.
ポリエーテルポリオール（Ａ１）としては、例えば、少なくとも２個の活性水素を含有する化合物（多価アルコール、アミン、多価フェノール、ポリカルボン酸、リン酸等）にアルキレンオキサイド（以下、ＡＯと略記）が付加された構造の化合物等が挙げられる。 Examples of the polyether polyol (A1) include compounds containing at least two active hydrogens (polyhydric alcohol, amine, polyhydric phenol, polycarboxylic acid, phosphoric acid, etc.) and alkylene oxide (hereinafter abbreviated as AO). And a compound having a structure to which is added.
多価アルコールとしては、炭素数２〜２０の２価アルコール｛脂肪族ジオール（例えば、エチレングリコール、プロピレングリコール、１，３−及び１，４−ブタンジオール、１，６−ヘキサンジオール及びネオペンチルグリコール等のアルキレングリコール；ジエチレングリコール及びジプロピレングリコール等のポリアルキレングリコール）及び脂環式ジオール（例えば、シクロヘキサンジオール及びシクロヘキサンジメタノール等のシクロアルキレングリコール）｝、炭素数３〜２０の３価アルコール｛脂肪族トリオール（例えば、グリセリン、トリメチロールプロパン、トリメチロールエタン及びヘキサントリオール等のアルカントリオール）｝；炭素数５〜２０の４〜８価又はそれ以上の多価アルコール｛脂肪族ポリオール（例えば、ペンタエリスリトール、ソルビトール、マンニトール、ソルビタン、ジグリセリン及びジペンタエリスリトール等のアルカンポリオール及びそれら又はアルカントリオールの分子内又は分子間脱水物；並びにショ糖、グルコース、マンノース、フルクトース及びメチルグルコシド等の糖及びその誘導体）｝等が挙げられる。これらの２種以上を併用してもよい。 As the polyhydric alcohol, a dihydric alcohol having 2 to 20 carbon atoms {aliphatic diol (for example, ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol). Alkylene glycols such as diethylene glycol and dipropylene glycol) and alicyclic diols (eg, cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol)}, trihydric alcohols having 3 to 20 carbon atoms {aliphatic Triols (e.g., alkanetriols such as glycerin, trimethylolpropane, trimethylolethane and hexanetriol)}; 4 to 8 or higher polyhydric alcohols having 5 to 20 carbon atoms {aliphatic polyols (eg, Alkane polyols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin and dipentaerythritol and intramolecular or intermolecular dehydrates of these or alkanetriols; and sugars such as sucrose, glucose, mannose, fructose and methyl glucoside and Derivatives thereof)} and the like. Two or more of these may be used in combination.
アミンとしては、活性水素の数が２〜８価又はそれ以上のものが挙げられ、アンモニア；脂肪族アミンとして、炭素数２〜２０のアルカノールアミン（例えば、モノエタノールアミン、ジエタノールアミン、イソプロパノールアミン及びアミノエチルエタノールアミン）、炭素数１〜２０のアルキルアミン（例えば、ｎ−ブチルアミン及びオクチルアミン）、炭素数２〜６のアルキレンジアミン（例えば、エチレンジアミン、プロピレンジアミン及びヘキサメチレンジアミン）、炭素数４〜２０のポリアルキレンポリアミン（アルキレン基の炭素数が２〜６のジアルキレントリアミン〜ヘキサアルキレンヘプタミン、例えば、ジエチレントリアミン及びトリエチレンテトラミン）が挙げられる。
また、炭素数６〜２０の芳香族モノ又はポリアミン（例えば、アニリン、フェニレンジアミン、トリレンジアミン、キシリレンジアミン、ジエチルトルエンジアミン、メチレンジアニリン及びジフェニルエーテルジアミン）；炭素数４〜２０の脂環式アミン（例えば、イソホロンジアミン、シクロヘキシレンジアミン及びジシクロヘキシルメタンジアミン）；炭素数４〜２０の複素環式アミン（例えば、ピペラジン、アミノエチルピペラジン及び特公昭５５−２１０４４号公報記載のもの）及びこれらの２種以上の併用などが挙げられる。
Examples of the amine include those having 2 to 8 or more active hydrogen atoms, ammonia; aliphatic amines having 2 to 20 carbon atoms such as monoethanolamine, diethanolamine, isopropanolamine and amino. Ethylethanolamine), alkylamines having 1 to 20 carbon atoms (for example, n-butylamine and octylamine), alkylenediamines having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine and hexamethylenediamine), and 4 to 20 carbon atoms. Polyalkylene polyamines (dialkylene triamines having 6 to 6 carbon atoms in the alkylene group to hexaalkylene heptamines such as diethylenetriamine and triethylenetetramine).
In addition, aromatic mono- or polyamines having 6 to 20 carbon atoms (for example, aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyl ether diamine); alicyclic having 4 to 20 carbon atoms Amines (for example, isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine); heterocyclic amines having 4 to 20 carbon atoms (for example, those described in piperazine, aminoethylpiperazine, and Japanese Examined Patent Publication No. 55-21044), and these 2 The combined use etc. of a seed or more is mentioned.
多価（２〜８価又はそれ以上）フェノールとしては、ピロガロール、ハイドロキノン及びフロログルシン等の単環多価フェノール；ビスフェノールＡ、ビスフェノールＦ及びビスフェノールスルホン等のビスフェノール；フェノールとホルムアルデヒドの縮合物（ノボラック）；例えば米国特許第３２６５６４１号明細書に記載のポリフェノール；並びにこれらの２種以上の併用などが挙げられる。 As polyvalent (2 to 8 or more) phenols, monocyclic polyphenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; condensates of phenol and formaldehyde (novolaks); Examples thereof include polyphenols described in US Pat. No. 3,265,641; and combinations of two or more thereof.
ポリカルボン酸としては、炭素数４〜１８の脂肪族ポリカルボン酸（コハク酸、アジピン酸、セバシン酸、グルタル酸、アゼライン酸、マレイン酸及びフマル酸等）、炭素数８〜１８の芳香族ポリカルボン酸（テレフタル酸、フタル酸、イソフタル酸及びトリメリット酸等）及びこれらの２種以上の混合物などが挙げられる。
ポリエーテルポリオール（Ａ１）の原料となるこれらの活性水素を含有する化合物は、単独で用いられても、２種以上が併用されてもよい。
これらの中で連続成形性の観点から多価アルコールが好ましく、キュア性の観点から、さらに好ましくは脂肪族多価アルコール及び脂環式多価アルコール、特に好ましくは脂肪族多価アルコールである。
Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), and aromatic polycarboxylic acids having 8 to 18 carbon atoms. Examples thereof include carboxylic acids (terephthalic acid, phthalic acid, isophthalic acid, trimellitic acid, etc.) and mixtures of two or more thereof.
These active hydrogen-containing compounds that serve as raw materials for the polyether polyol (A1) may be used alone or in combination of two or more.
Of these, polyhydric alcohols are preferable from the viewpoint of continuous moldability, and aliphatic polyhydric alcohols and alicyclic polyhydric alcohols are more preferable, and aliphatic polyhydric alcohols are particularly preferable from the viewpoint of curing properties.
活性水素を含有する化合物に付加されるＡＯとしては連続成形性の観点から、炭素数２〜８のものが好ましく、ＥＯ、ＰＯ、１，２−、１，３−、１，４−及び２，３−ブチレンオキサイド、スチレンオキサイド並びにこれらの２種以上の併用（ブロック及び／又はランダム付加）等が挙げられる。これらの中で成形性の観点から、ＰＯ並びにＰＯとＥＯとの併用が好ましく、さらに好ましくは、ＰＯとＥＯとの併用である。
ＡＯ付加時に用いる触媒としては、アルカリ触媒（ＫＯＨ、ＣｓＯＨ等）の他、特開２０００−３４４８８１号公報に記載の触媒〔トリス（ペンタフルオロフェニル）ボラン等〕、特開平１１−１２０３００号公報に記載の触媒（過塩素酸マグネシウム等）を用いてもよい。
AO added to the compound containing active hydrogen is preferably one having 2 to 8 carbon atoms from the viewpoint of continuous moldability, and includes EO, PO, 1,2-, 1,3-, 1,4- and 2 , 3-butylene oxide, styrene oxide, and combinations of two or more thereof (block and / or random addition). Among these, from the viewpoint of moldability, the combined use of PO and PO and EO is preferable, and the combined use of PO and EO is more preferable.
Catalysts used at the time of AO addition include alkali catalysts (KOH, CsOH, etc.), catalysts described in JP-A No. 2000-344881 [tris (pentafluorophenyl) borane, etc.], and JP-A No. 11-120300. A catalyst such as magnesium perchlorate may be used.
ポリエーテルポリオ−ル（Ａ１）の具体例としては、上記活性水素含有化合物にＰＯを付加したもの、ＰＯと他のＡＯ（好ましくはＥＯ）とを下記の様式で付加したもの、及びこれらの付加物とポリカルボン酸又はリン酸とのエステル化物等が挙げられる。なお、以下の記載において、ＡＯ＊はＰＯ以外のＡＯを意味する。
（１）ＰＯ−ＡＯ＊の順序でブロック付加したもの
（２）ＰＯ−ＡＯ＊−ＰＯ−ＡＯ＊の順序でブロック付加したもの
（３）ＡＯ＊−ＰＯ−ＡＯ＊の順序でブロック付加したもの
（４）ＰＯ−ＡＯ＊−ＰＯの順序でブロック付加したもの（活性セカンダリ−）
（５）ＰＯ及びＡＯ＊を混合付加したランダム付加物
（６）米国特許第４２２６７５６号明細書記載の順序でランダム又はブロック付加したもの
Specific examples of the polyether polyol (A1) include those obtained by adding PO to the active hydrogen-containing compound, those obtained by adding PO and another AO (preferably EO) in the following manner, and additions thereof. And an esterified product of the product with polycarboxylic acid or phosphoric acid. In the following description, AO * means AO other than PO.
(1) Block added in the order of PO-AO * (2) Block added in the order of PO-AO * -PO-AO * (3) Block added in the order of AO * -PO-AO * (4) Blocks added in the order of PO-AO * -PO (active secondary)
(5) Random adduct with mixed addition of PO and AO * (6) Random or block addition in the order described in US Pat. No. 4,226,756
低分子ポリオール（Ａ２）は、連続成形性の観点で、水酸基価２０００（ｍｇＫＯＨ／ｇ）未満〔好ましくは６０〜１９００（ｍｇＫＯＨ／ｇ）〕のポリオールが好ましく、例えば前記多価アルコール（エチレングリコール、ジエチレングリコール、１，４−ブタンジオール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール及びソルビトール等）、アルカノールアミン（トリエタノールアミン及びジエタノールアミン等）及びこれらの前記ＡＯ付加物などが挙げられる。これらの低分子ポリオール（Ａ２）は、単独又は併用して使用することができる。 The low molecular polyol (A2) is preferably a polyol having a hydroxyl value of less than 2000 (mgKOH / g) [preferably 60 to 1900 (mgKOH / g)] from the viewpoint of continuous moldability. For example, the polyhydric alcohol (ethylene glycol, Diethylene glycol, 1,4-butanediol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.), alkanolamines (triethanolamine, diethanolamine, etc.) and the AO adducts thereof. These low molecular polyols (A2) can be used alone or in combination.
ポリエステルポリオール（Ａ３）としては、前記の多価アルコール、ポリエーテルポリオール（Ａ１）及び／又は低分子ポリオール（Ａ２）と、前記ポリカルボン酸又はその無水物及び低級アルキル（アルキル基の炭素数：１〜４）エステル等のエステル形成性誘導体（例えば、アジピン酸、セバシン酸、無水マレイン酸、無水フタル酸、テレフタル酸ジメチル等）との縮合反応物；前記の多価アルコール、ポリエーテルポリオール及び／又は低分子ポリオールと、前記カルボン酸無水物及びＡＯとの縮合反応物；それら縮合反応物のＡＯ（ＥＯ、ＰＯ等）付加物；ポリラクトンポリオール、例えば前記多価アルコールを開始剤としてラクトン（ε−カプロラクトン等）を開環重合させることにより得られるもの；ポリカーボネートポリオール、例えば前記多価アルコールとアルキレンカーボネートとの反応物；等が挙げられる。
これらの中で連続成形性の観点で、前記の多価アルコール、ポリエーテルポリオール（Ａ１）及び／又は低分子ポリオール（Ａ２）と、前記ポリカルボン酸又はその無水物及び低級アルキル（アルキル基の炭素数：１〜４）エステル等のエステル形成性誘導体との縮合反応物や前記の多価アルコール、ポリエーテルポリオール及び／又は低分子ポリオールと、前記カルボン酸無水物及びＡＯとの縮合反応物；それら縮合反応物のＡＯ（ＥＯ、ＰＯ等）付加物が好ましい。
As the polyester polyol (A3), the polyhydric alcohol, the polyether polyol (A1) and / or the low molecular polyol (A2), the polycarboxylic acid or its anhydride, and a lower alkyl (the carbon number of the alkyl group: 1 -4) Condensation reaction products with ester-forming derivatives such as esters (for example, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.); the aforementioned polyhydric alcohols, polyether polyols and / or Condensation reaction product of a low molecular polyol, the carboxylic acid anhydride and AO; an AO (EO, PO, etc.) addition product of the condensation reaction product; a polylactone polyol, for example, a lactone (ε- Obtained by ring-opening polymerization of caprolactone, etc.); polycarbonate polyol , For example, a reaction product of the polyhydric alcohol and alkylene carbonate; and the like.
Among these, from the viewpoint of continuous moldability, the polyhydric alcohol, the polyether polyol (A1) and / or the low molecular polyol (A2), the polycarboxylic acid or its anhydride, and a lower alkyl (carbon of the alkyl group). Number: 1-4) Condensation reaction product with ester-forming derivative such as ester or the above-mentioned polyhydric alcohol, polyether polyol and / or low molecular polyol, condensation reaction product of carboxylic acid anhydride and AO; AO (EO, PO, etc.) adducts of condensation products are preferred.
重合体ポリオール（Ａ４）としては、ポリオール（Ａ１）及び（Ａ２）の少なくとも１種中で、ラジカル重合開始剤の存在下、エチレン性不飽和モノマー（ｄ）が重合され、得られた（ｄ）の重合体がポリオール中で安定分散されたものが挙げられる。（Ａ４）としては、（Ａ１）中で（ｄ）が重合されて得られるものが分散安定性の点で好ましい。重合方法の具体例としては、米国特許第３３８３３５１号明細書、特公昭３９−２５７３７号公報等に記載の方法が挙げられる。 The polymer polyol (A4) was obtained by polymerizing the ethylenically unsaturated monomer (d) in the presence of a radical polymerization initiator in at least one of the polyols (A1) and (A2) (d). In which a polymer is stably dispersed in a polyol. (A4) is preferably obtained by polymerizing (d) in (A1) from the viewpoint of dispersion stability. Specific examples of the polymerization method include those described in US Pat. No. 3,383,351, Japanese Examined Patent Publication No. 39-25737, and the like.
ラジカル重合開始剤としては、遊離基を生成して重合を開始させるものが使用でき、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）等のアゾ化合物；ジベンゾイルパーオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド及び過コハク酸等の有機過酸化物；過硫酸塩及び過ホウ酸塩等の無機過酸化物；等が挙げられる。なお、これらは２種以上を併用することができる。 As the radical polymerization initiator, one that generates a free radical and initiates polymerization can be used. 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Azo compounds such as 2,2′-azobis (2-methylbutyronitrile); organic peroxides such as dibenzoyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide and persuccinic acid; persulfates And inorganic peroxides such as perborate; In addition, these can use 2 or more types together.
エチレン性不飽和モノマー（ｄ）としては、不飽和ニトリル（ｄ１）、芳香環含有モノマー（ｄ２）、（メタ）アクリル酸エステル（ｄ３）、その他のエチレン性不飽和モノマー（ｄ４）及びこれらの２種以上の混合物等が挙げられる。
（ｄ１）としては、アクリロニトリル、メタクリロニトリルなどが挙げられる。
（ｄ２）としては、スチレン、α−メチルスチレン、ヒドロキシスチレン、クロルスチレンなどが挙げられる。
（ｄ３）としては、Ｃ、Ｈ及びＯ原子からなるもの、例えば、（メタ）アクリル酸アルキルエステル（アルキル基の炭素数が１〜２４）〔メチル（メタ）アクリレート、ブチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、エイコシル（メタ）アクリレート及びドコシル（メタ）アクリレート等〕、ヒドロキシアルキル（炭素数２〜５）（メタ）アクリレート〔ヒドロキシエチル（メタ）アクリレート等〕及びヒドロキシポリオキシアルキレンモノ（メタ）アクリレート〔アルキレン基の炭素数２〜４、ポリオキシアルキレン鎖の数平均分子量２００〜１０００等〕が挙げられる。
（ｄ４）としては、エチレン性不飽和カルボン酸及びその誘導体、具体的には（メタ）アクリル酸及び（メタ）アクリルアミド等；脂肪族又は脂環式炭化水素単量体、具体的にはアルケン（エチレン、プロピレン及びノルボルネン等）及びアルカジエン（ブタジエン等）等；フッ素系ビニル単量体、具体的には、フッ素含有（メタ）アクリレート（パーフルオロオクチルエチルメタクリレート及びパーフルオロオクチルエチルアクリレート等）等；塩素系ビニル単量体、具体的には塩化ビニリデン等；上記以外の窒素含有ビニル単量体、具体的には窒素含有（メタ）アクリレート（ジアミノエチルメタクリレート及びモルホリノエチルメタクリレート等）等；並びにビニル変性シリコーンなどが挙げられる。
これら（ｄ）中で、成形性の観点から、（ｄ１）及び（ｄ２）が好ましく、さらに好ましくはアクリロニトリル及び／又はスチレンである。
Examples of the ethylenically unsaturated monomer (d) include unsaturated nitrile (d1), aromatic ring-containing monomer (d2), (meth) acrylic acid ester (d3), other ethylenically unsaturated monomers (d4), and 2 A mixture of seeds or more may be mentioned.
Examples of (d1) include acrylonitrile and methacrylonitrile.
Examples of (d2) include styrene, α-methylstyrene, hydroxystyrene, chlorostyrene, and the like.
(D3) is composed of C, H and O atoms, for example, (meth) acrylic acid alkyl ester (alkyl group having 1 to 24 carbon atoms) [methyl (meth) acrylate, butyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, etc.], hydroxyalkyl (2 to 5 carbon atoms) (meth) acrylate [hydroxyethyl (meth) Acrylates and the like] and hydroxypolyoxyalkylene mono (meth) acrylates [alkylene group having 2 to 4 carbon atoms, polyoxyalkylene chain number average molecular weight of 200 to 1000, etc.].
(D4) includes ethylenically unsaturated carboxylic acids and derivatives thereof, specifically (meth) acrylic acid and (meth) acrylamide, etc .; aliphatic or alicyclic hydrocarbon monomers, specifically alkenes ( Ethylene, propylene, norbornene, etc.) and alkadienes (butadiene, etc.); fluorine-based vinyl monomers, specifically fluorine-containing (meth) acrylates (perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, etc.), etc .; chlorine -Based vinyl monomers, specifically vinylidene chloride, etc .; nitrogen-containing vinyl monomers other than those mentioned above, specifically nitrogen-containing (meth) acrylates (diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.); and vinyl-modified silicones Etc.
Among these (d), from the viewpoint of moldability, (d1) and (d2) are preferable, and acrylonitrile and / or styrene are more preferable.
エチレン性不飽和モノマー（ｄ）中の、（ｄ１）、（ｄ２）、（ｄ３）及び（ｄ４）の重量比率は、要求されるポリウレタンの物性等に応じて変えることができ、とくに限定されていないが、一例を示すと次の通りである。
（ｄ）の合計重量を基準として、（ｄ１）及び／又は（ｄ２）は、５０〜１００重量％が好ましく、さらに好ましくは８０〜１００重量％である。（ｄ１）と（ｄ２）の重量比はとくに限定されないが、好ましくは１００／０〜２０／８０である。（ｄ３）は、好ましくは０〜５０重量％、さらに好ましくは０〜２０重量％である。（ｄ４）は、好ましくは０〜１０重量％、さらに好ましくは０〜５重量％である。
The weight ratio of (d1), (d2), (d3) and (d4) in the ethylenically unsaturated monomer (d) can be changed according to the required physical properties of the polyurethane and is particularly limited. An example is as follows.
Based on the total weight of (d), (d1) and / or (d2) is preferably 50 to 100% by weight, more preferably 80 to 100% by weight. The weight ratio of (d1) and (d2) is not particularly limited, but is preferably 100/0 to 20/80. (D3) is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. (D4) is preferably 0 to 10% by weight, more preferably 0 to 5% by weight.
重合体ポリオール（Ａ４）中の（ｄ）の重合体の含有量は、（Ａ４）の合計重量を基準として、成形性の観点から、５０重量％以下が好ましく、さらに好ましくは３〜３０重量％である。 The content of the polymer (d) in the polymer polyol (A4) is preferably 50% by weight or less, more preferably 3 to 30% by weight, from the viewpoint of moldability, based on the total weight of (A4). It is.
ポリオール組成物（Ａ）中の（Ａ１）、（Ａ２）、（Ａ３）及び（Ａ４）の合計含有量は、（Ａ）の合計重量を基準として、成形性の観点から、０〜５０重量％が好ましく、さらに好ましくは０〜３０重量％である。 The total content of (A1), (A2), (A3) and (A4) in the polyol composition (A) is 0 to 50% by weight from the viewpoint of moldability, based on the total weight of (A). Is preferable, and more preferably 0 to 30% by weight.
本発明のポリウレタン樹脂の製造方法で用いる芳香族ポリアミン（Ｂ）は、連続成形性の観点から、ジエチルトルエンジアミン及び／又はターシャリーブチルトルエンジアミンである。 The aromatic polyamine (B) used in the method for producing a polyurethane resin of the present invention is diethyltoluenediamine and / or tertiary butyltoluenediamine from the viewpoint of continuous moldability.
芳香族ポリアミン（Ｂ）の含有量は、連続成形性及び硬さの観点から、ポリオール組成物（Ａ）の合計重量を基準として５〜３０重量％が好ましく、さらに好ましくは７〜２０重量％である。 The content of the aromatic polyamine (B) is preferably 5 to 30% by weight, more preferably 7 to 20% by weight, based on the total weight of the polyol composition (A), from the viewpoint of continuous moldability and hardness. is there.
本発明のポリウレタン樹脂の製造方法で用いるポリイソシアネ−ト成分（Ｃ）は、連続成形性の観点から、ジフェニルメタンジイソシアネート（以下、ＭＤＩと略記）と低分子ポリオール（Ａ２）を反応させてなるＮＣＯ基末端ポリウレタンプレポリマー（Ｃ１）を含有する。 The polyisocyanate component (C) used in the method for producing a polyurethane resin of the present invention has an NCO group terminal obtained by reacting diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and a low molecular polyol (A2) from the viewpoint of continuous moldability. Contains a polyurethane prepolymer (C1).
（Ｃ１）に使用されるＭＤＩとしては、４，４’−ＭＤＩ、２，４’−ＭＤＩ等が挙げられ、カルボジイミド化、ウレトンイミン化されたＭＤＩ等も使用できる。この中で、連続成形性の観点から、４，４’−ＭＤＩが好ましい。 Examples of the MDI used in (C1) include 4,4'-MDI, 2,4'-MDI and the like, and carbodiimidized and uretoniminated MDI can also be used. Among these, 4,4'-MDI is preferable from the viewpoint of continuous moldability.
（Ｃ１）に使用される低分子ポリオール（Ａ２）としては、連続成形性の観点から、水酸基価１００〜１９００（ｍｇＫＯＨ／ｇ）の低分子ポリオールが好ましい。例えば前記多価アルコール（エチレングリコール、ジエチレングリコール、１，４−ブタンジオール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール及びソルビトール等）、アルカノールアミン（トリエタノールアミン及びジエタノールアミン等）及びこれらの前記ＡＯ付加物などが好ましい。 The low molecular polyol (A2) used for (C1) is preferably a low molecular polyol having a hydroxyl value of 100 to 1900 (mgKOH / g) from the viewpoint of continuous moldability. For example, the polyhydric alcohols (ethylene glycol, diethylene glycol, 1,4-butanediol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.), alkanolamines (triethanolamine, diethanolamine, etc.) and their AOs Adducts are preferred.
（Ｃ１）の含有量は、連続成形性の観点から、ポリイソシアネ−ト成分（Ｃ）の合計重量を基準として３０〜１００重量％となるものが好ましく、さらに好ましくは５０〜１００重量％である。 The content of (C1) is preferably 30 to 100% by weight, more preferably 50 to 100% by weight, based on the total weight of the polyisocyanate component (C), from the viewpoint of continuous moldability.
本発明のポリイソシアネ−ト成分（Ｃ）としては、（Ｃ１）以外にもポリウレタン樹脂を製造する際に使用されるポリイソシアネートを用いることができる。例えば、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネート、これらの変性物（ウレタン基、カルボジイミド基、アロファネート基、ウレア基、ビューレット基、イソシアヌレート基及びオキサゾリドン基含有変性物等）及びこれらの２種以上の混合物が挙げられる。 As the polyisocyanate component (C) of the present invention, in addition to (C1), polyisocyanate used in producing a polyurethane resin can be used. For example, aromatic polyisocyanate, araliphatic polyisocyanate, modified products thereof (urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group and oxazolidone group-containing modified product) and these two kinds The above mixture is mentioned.
芳香族ポリイソシアネートとしては、炭素数（ＮＣＯ基中の炭素を除く；以下のポリイソシアネートも同様）６〜１６の芳香族ジイソシアネート、炭素数６〜２０の芳香族トリイソシアネート及びこれらのイソシアネートの粗製物等が挙げられる。具体例としては、１，３−及び１，４−フェニレンジイソシアネート、２，４−及び２，６−トリレンジイソシアネート（ＴＤＩ）、粗製ＴＤＩ、２，４’−及び４，４’−ＭＤＩ、ポリメチレンポリフェニレンポリイソシアネート（粗製ＭＤＩ）、ナフチレン−１，５−ジイソシアネート及びトリフェニルメタン−４，４’，４’’−トリイソシアネート等が挙げられる。 As aromatic polyisocyanate, C6-C16 aromatic diisocyanate, C6-C20 aromatic triisocyanate, and crude products of these isocyanates (excluding carbon in NCO group; the following polyisocyanates are also the same) Etc. Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and 4,4'-MDI, poly Examples include methylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate, and triphenylmethane-4,4 ′, 4 ″ -triisocyanate.
芳香脂肪族イソシアネートとしては、炭素数８〜１２の芳香脂肪族ジイソシアネート等が挙げられる。具体例としては、キシリレンジイソシアネート及びα，α，α’，α’−テトラメチルキシリレンジイソシアネート等が挙げられる。
変性ポリイソシアネートの具体例としては、カルボジイミド変性ＭＤＩ等が挙げられる。
Examples of the araliphatic isocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.
Specific examples of the modified polyisocyanate include carbodiimide-modified MDI.
これらの中で、反応性及び機械物性の観点から、芳香族ポリイソシアネートが好ましく、さらに好ましくは、ＭＤＩ、粗製ＭＤＩ、最も好ましくはＭＤＩである。 Among these, aromatic polyisocyanates are preferable from the viewpoint of reactivity and mechanical properties, more preferably MDI, crude MDI, and most preferably MDI.
ポリイソシアネ−ト成分（Ｃ）のＮＣＯ％含量は、（Ｃ）の合計重量を基準として、反応性及び機械物性の観点から、２０〜２８重量％が好ましく、さらに好ましくは２２〜２４重量％である。 The NCO% content of the polyisocyanate component (C) is preferably 20 to 28% by weight, more preferably 22 to 24% by weight, from the viewpoint of reactivity and mechanical properties, based on the total weight of (C). .
本発明のポリウレタン樹脂の製造方法に用いるウレタン化触媒（Ｄ）としては、ウレタン化反応を促進する触媒が使用でき、アミン触媒（Ｄ１）及び有機金属触媒（Ｄ２）等が挙げられる。 As the urethanization catalyst (D) used in the method for producing a polyurethane resin of the present invention, a catalyst for promoting the urethanization reaction can be used, and examples thereof include an amine catalyst (D1) and an organometallic catalyst (D2).
アミン触媒（Ｄ１）としては、１価脂肪族アミン［Ｎ，Ｎ−ジメチルシクロヘキシルアミン、Ｎ，Ｎ−ジクロヘキシルメチルアミン、Ｎ，Ｎ−ジメチルセチルアミン、トリエチルアミン及びＮ，Ｎ−ジメチルドデシルアミン等］；２価脂肪族アミン［Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチル−１，３−プロパンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサンジアミン、メチレンビス（ジメチルシクロヘキシルアミン）、３−ジメチルアミノ−Ｎ，Ｎ−ジメチルプロピオンアミド及びＮ，Ｎ，Ｎ’，Ｎ’−テトラエチルメチレンジアミン等］並びに３〜８価又はそれ以上の脂肪族アミン［Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ’’−ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ’’−ペンタメチルジプロピレンジアミン及びＮ，Ｎ，Ｎ’，Ｎ’−テトラ（３−ジメチルアミノプロピル）メタンジアミン等］の脂肪族アミン触媒、１価環状アミン［Ｎ−メチルモルホリン及びＮ−エチルモルホリン等］並びに２価以上の環状アミン［トリエチレンジアミン、Ｎ，Ｎ’−ジメチルピペラジン、Ｎ，Ｎ’−ジエチルピペラジン、Ｎ−メチル−Ｎ’−ジメチルアミノエトキシピペラジン、Ｎ−（２−ジメチルアミノエトキシ）モルホリン、１，２−ジメチルイミダゾール及び１，８−ジアザビシクロ［５，４，０］ウンデセン−７等］の環状アミン触媒、［ビス−２−ジメチルアミノエチルエーテル、２−（Ｎ，Ｎ−ジメチルアミノ）エチル−３−（Ｎ，Ｎ−ジメチルアミノ）プロピルエーテル、４，４’−オキシジエチレンジモルホリン及びエチレングリコールビス（３−ジメチルアミノプロピル）エーテル等］のエーテルジアミン触媒、［Ｎ，Ｎ−ジメチルアミノエタノール、Ｎ，Ｎ−ジメチルアミノエタノールのＥＯ付加物、Ｎ，Ｎ−テトラメチル−１，３−ジアミノ−２−プロパノール、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルエタノールアミン、Ｎ，Ｎ，Ｎ’−トリメチルアミノプロピルエタノールアミン、Ｎ−メチル−Ｎ’−（２−ヒドロキシエチル）ピペラジン、Ｎ−（２−ヒドロキシエチル）モルホリン、１−（２−ヒドロキシプロピル）イミダゾール、２，４，６−トリス（ジメチルアミノエチル）−フェノール及び１，４−ビス（２−ヒドロキシプロピル）−２−メチルピペラジン等］の水酸基含有アミン触媒等が挙げられる。 As the amine catalyst (D1), monovalent aliphatic amines [N, N-dimethylcyclohexylamine, N, N-dichloromethylamine, N, N-dimethylcetylamine, triethylamine, N, N-dimethyldodecylamine, etc.] Divalent aliphatic amine [N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N ′; -Tetramethylhexanediamine, methylenebis (dimethylcyclohexylamine), 3-dimethylamino-N, N-dimethylpropionamide and N, N, N ′, N′-tetraethylmethylenediamine, etc.] and 3 to 8 or more valences Aliphatic amine [N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ′, N ′ -Aliphatic amine catalyst such as pentamethyldipropylenediamine and N, N, N ', N'-tetra (3-dimethylaminopropyl) methanediamine], monovalent cyclic amine [N-methylmorpholine, N-ethylmorpholine, etc. And divalent or higher cyclic amines [triethylenediamine, N, N′-dimethylpiperazine, N, N′-diethylpiperazine, N-methyl-N′-dimethylaminoethoxypiperazine, N- (2-dimethylaminoethoxy) morpholine , 1,2-dimethylimidazole and 1,8-diazabicyclo [5,4,0] undecene-7 etc.], [bis-2-dimethylaminoethyl ether, 2- (N, N-dimethylamino) Ethyl-3- (N, N-dimethylamino) propyl ether, 4,4′-oxydiethylenedi Ruphorin and ethylene glycol bis (3-dimethylaminopropyl) ether etc.] ether diamine catalyst, [N, N-dimethylaminoethanol, EO adduct of N, N-dimethylaminoethanol, N, N-tetramethyl-1, 3-diamino-2-propanol, N, N, N′-trimethylaminoethylethanolamine, N, N, N′-trimethylaminopropylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, N -(2-hydroxyethyl) morpholine, 1- (2-hydroxypropyl) imidazole, 2,4,6-tris (dimethylaminoethyl) -phenol and 1,4-bis (2-hydroxypropyl) -2-methylpiperazine And the like, and the like.
有機金属触媒（Ｄ２）としては、有機錫触媒、有機ビスマス触媒等が挙げられる。
有機錫触媒としては、例えばジオクチル錫メルカプチド含有化合物（ドイツ公告特許１，７６９，３６７及びＵＳ特許３，６４５，９２７）及びカルボン酸の錫（II）塩、例えば酢酸錫（II）、オクタン酸錫（II）、エチルヘキサン酸錫（II）及びラウリン酸錫（II）並びに錫（IV）化合物、例えば、ジブチル錫ジラウレート、ジブチル錫ジオクテート、ジブチル錫ジクロライド、ジブチル錫ジアセテート、ジブチル錫マレエート及びジオクチル錫ジアセテートが挙げられる。
有機ビスマス触媒としては、ビスマスネオデカノエート、ビスマスバーサレート及びビスマスカルボキシレート等が挙げられる。
これらの中で、連続成形性及びキュア性の観点から、（Ｄ２）を含有することが好ましく、さらに好ましくは有機錫触媒、特に好ましくはジブチル錫ジラウレート、ジメチル錫ジラウレート及びそれらの混合物からなる群から選ばれるスズ（IV）化合物が好ましい。
Examples of the organometallic catalyst (D2) include an organic tin catalyst and an organic bismuth catalyst.
Examples of organotin catalysts include dioctyltin mercaptide-containing compounds (German Published Patent 1,769,367 and US Pat. No. 3,645,927) and tin (II) salts of carboxylic acids such as tin (II) acetate, tin octoate. (II), tin (II) ethylhexanoate and tin (II) laurate and tin (IV) compounds such as dibutyltin dilaurate, dibutyltin dioctate, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate and dioctyltin A diacetate is mentioned.
Examples of the organic bismuth catalyst include bismuth neodecanoate, bismuth versalate, and bismuth carboxylate.
Among these, from the viewpoint of continuous formability and curing properties, it is preferable to contain (D2), more preferably an organic tin catalyst, particularly preferably dibutyltin dilaurate, dimethyltin dilaurate, and a mixture thereof. The selected tin (IV) compound is preferred.
ウレタン化触媒（Ｄ）の使用量は、反応性の観点から、ポリオール組成物（Ａ）の合計重量を基準として、３級アミン（Ｄ１）が０．０５〜５重量％、有機金属触媒（Ｄ２）が０．０１〜３重量％であることが好ましく、さらに好ましくは、３級アミン（Ｄ１）が０．１〜３．０重量％、有機金属触媒（Ｄ２）が０．０１〜２重量％である。 The use amount of the urethanization catalyst (D) is 0.05 to 5% by weight of the tertiary amine (D1) and the organometallic catalyst (D2) based on the total weight of the polyol composition (A) from the viewpoint of reactivity. ) Is preferably 0.01 to 3% by weight, more preferably 0.1 to 3.0% by weight of the tertiary amine (D1) and 0.01 to 2% by weight of the organometallic catalyst (D2). It is.
本発明のポリウレタン樹脂の製造方法においては、必要により、補助成分を任意に使用してもよい。例えば、整泡剤（ジメチルシロキサン系、ポリエーテル変性ジメチルシロキサン系等）、着色剤（染料、顔料）、可塑剤（フタル酸エステル、アジピン酸エステル等）、有機充填剤（合成短繊維、熱可塑性もしくは熱硬化性樹脂からなる中空微小球等）、難燃剤（リン酸エステル、ハロゲン化リン酸エステル等）、老化防止剤（トリアゾール系、ベンゾフェノン系等）及び抗酸化剤（ヒンダードフェノール系、ヒンダードアミン系等）等公知の補助成分の存在下で反応させることができる。 In the method for producing a polyurethane resin of the present invention, auxiliary components may optionally be used as necessary. For example, foam stabilizer (dimethylsiloxane, polyether-modified dimethylsiloxane, etc.), colorant (dye, pigment), plasticizer (phthalate ester, adipic acid ester, etc.), organic filler (synthetic short fiber, thermoplastic) Or hollow microspheres made of thermosetting resins), flame retardants (phosphate esters, halogenated phosphate esters, etc.), anti-aging agents (triazoles, benzophenones, etc.) and antioxidants (hindered phenols, hindered amines) The reaction can be carried out in the presence of a known auxiliary component.
補助成分の使用量は、成形性の観点から、ポリオール組成物（Ａ）の合計重量を基準として、整泡剤は、好ましくは１０重量％以下、さらに好ましくは０．１〜５重量％である。着色剤は、好ましくは１０重量％以下、さらに好ましくは５重量％以下である。可塑剤は、好ましくは１０重量％以下、さらに好ましくは５重量％以下である。有機充填剤は、好ましくは５０重量％以下、さらに好ましくは３０重量％以下である。難燃剤は、好ましくは３０重量％以下、さらに好ましくは１〜２０重量％である。老化防止剤は、好ましくは５重量％以下、さらに好ましくは０．０１〜３重量％である。抗酸化剤は、好ましくは５重量％以下、さらに好ましくは０．０１〜３重量％である。 The amount of the auxiliary component used is preferably 10% by weight or less, more preferably 0.1 to 5% by weight based on the total weight of the polyol composition (A) from the viewpoint of moldability. . The colorant is preferably 10% by weight or less, more preferably 5% by weight or less. The plasticizer is preferably 10% by weight or less, more preferably 5% by weight or less. The organic filler is preferably 50% by weight or less, more preferably 30% by weight or less. The flame retardant is preferably 30% by weight or less, more preferably 1 to 20% by weight. The anti-aging agent is preferably 5% by weight or less, more preferably 0.01 to 3% by weight. The antioxidant is preferably 5% by weight or less, more preferably 0.01 to 3% by weight.
本発明のポリウレタン樹脂の製造方法に際してのイソシアネート指数〔（ＮＣＯ基／活性水素原子含有基）の当量比×１００〕（インデックス）は、好ましくは８５〜１２５、さらに好ましくは９０〜１２０、とくに好ましくは１００〜１１０である。イソシアネート指数が８５以上であると樹脂硬さが良好であり、１２５以下であると樹脂のキュア時間を短縮できる。 The isocyanate index [(NCO group / active hydrogen atom-containing group equivalent ratio × 100) (index) in the production method of the polyurethane resin of the present invention is preferably 85 to 125, more preferably 90 to 120, and particularly preferably. 100-110. When the isocyanate index is 85 or more, the resin hardness is good, and when it is 125 or less, the curing time of the resin can be shortened.
本発明のポリウレタン樹脂は、Ａ硬度が８５〜１００であると、自動車外装材料、特に自動車の窓用樹脂として適当な硬さであり好ましい。さらに好ましくはＡ硬度８８〜９８、特に好ましくはＡ硬度８９〜９７である。
Ａ硬度とは、押針を用いて行う押込み試験であり、剛性の一つの尺度である。ポリウレタンエラストマーに押針を定荷重で押付けた時の押込み深さを測定する方法であり、ＪＩＳ Ｋ６２５３に定義されている。
The polyurethane resin of the present invention preferably has an A hardness of 85 to 100, since it has a hardness suitable as an automobile exterior material, particularly an automobile window resin. More preferably, the A hardness is 88 to 98, and particularly preferably the A hardness is 89 to 97.
The A hardness is an indentation test performed using a push needle and is a measure of rigidity. This is a method of measuring the indentation depth when a push needle is pressed against a polyurethane elastomer with a constant load, and is defined in JIS K6253.
本発明に用いられる密閉型枠は、金属製又は樹脂製が挙げられ、好ましくは金属製である。 The hermetic mold used in the present invention may be made of metal or resin, and is preferably made of metal.
本発明に用いられる密閉型枠には事前に外部離型剤を塗布又は噴霧することが好ましい。
外部離型剤としては、ポリウレタン樹脂を製造する際用いられる外部離型剤が用いられ、フッ素離型剤、シリコーン離型剤、ワックス離型剤等が用いられる。
It is preferable to apply or spray an external mold release agent in advance on the closed mold used in the present invention.
As an external mold release agent, an external mold release agent used when producing a polyurethane resin is used, and a fluorine mold release agent, a silicone mold release agent, a wax mold release agent, and the like are used.
本発明においてポリウレタン樹脂と一体成形されるガラスは、自動車の窓用に用いられるものであれば、特に制限はない。 In the present invention, the glass integrally molded with the polyurethane resin is not particularly limited as long as it is used for automobile windows.
本発明においてポリウレタン樹脂と接するガラスの表面には、プライマーを塗布することが好ましい。プライマーとしては、シランカップリング剤及び／又はイソシアネート末端プレポリマーが好ましい。 In the present invention, it is preferable to apply a primer to the surface of the glass in contact with the polyurethane resin. As a primer, a silane coupling agent and / or an isocyanate terminal prepolymer are preferable.
本発明におけるポリウレタン樹脂の製造法の一例を示せば、以下の通りである。まず、ポリオール組成物（Ａ）、芳香族ポリアミン（Ｂ）、ウレタン化触媒（Ｄ）及び必要により整泡剤や着色剤等の補助成分を所定量混合する。次いで、ポリウレタン低圧もしくは高圧注入発泡機又は撹拌機を使用して、この混合物とポリイソシアネート成分（Ｃ）とをそれぞれ液温が１５〜６０℃で急速混合し、一体成形するガラスを挿入した密閉型枠、（型枠温度：１５〜１２５℃）中に注入し、ガラスと混合物が接触した状態でウレタン化反応を行わせ、所定時間（０．２分〜５分）硬化後、型から取り出すことで、ガラス一体成形ポリウレタン樹脂を得ることができる。 An example of the method for producing a polyurethane resin in the present invention is as follows. First, a predetermined amount of a polyol composition (A), an aromatic polyamine (B), a urethanization catalyst (D) and, if necessary, auxiliary components such as a foam stabilizer and a colorant are mixed. Next, using a polyurethane low-pressure or high-pressure injection foaming machine or a stirrer, this mixture and the polyisocyanate component (C) are rapidly mixed at a liquid temperature of 15 to 60 ° C., respectively, and a closed mold in which glass for integral molding is inserted. Pour into a frame, (form temperature: 15-125 ° C.), let the urethanation reaction take place with the glass in contact with the mixture, take out from the mold after curing for a predetermined time (0.2 minutes to 5 minutes) Thus, a glass-integrated polyurethane resin can be obtained.
以下、実施例により本発明を更に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.
実施例１〜８及び比較例１〜３
ガラス一体成形用試験型（２００×２００×３ｍｍ）に、フッ素離型剤〔（株）ネオス製「ＦＲＸ−ＡＳ２４」〕を型の内表面積に対し２０ｇ／ｍ２塗布した。プライマー〔ＬＯＲＤ社製「ＡＰ−１３４」〕を塗布したガラス片を試験型に設置し、高圧発泡機（ＰＥＣ社製ｍｉｎｉ−ＲＩＭ機）を用いて表１に示すポリオール成分とイソシアネート成分を混合し、試験型に注入し、ガラス一体成形を繰り返した。このとき各成分の液温は４０℃、型温は１１５℃で脱型時間は１分であった。脱型した際にウレタン樹脂が最初にモールドへ付着した時の成形回数を評価した。評価結果を表１に示す。
Examples 1-8 and Comparative Examples 1-3
A fluorine mold release agent [“FRX-AS24” manufactured by Neos Co., Ltd.] was applied to a glass integrated test mold (200 × 200 × 3 mm) at 20 g / m 2 with respect to the inner surface area of the mold. A glass piece coated with a primer (“AP-134” manufactured by LORD) was placed in a test mold, and the polyol component and isocyanate component shown in Table 1 were mixed using a high-pressure foaming machine (mini-RIM machine manufactured by PEC). Then, it was poured into a test mold and glass integral molding was repeated. At this time, the liquid temperature of each component was 40 ° C., the mold temperature was 115 ° C., and the demolding time was 1 minute. When the mold was removed, the number of moldings when the urethane resin first adhered to the mold was evaluated. The evaluation results are shown in Table 1.
＜使用原料の記号の説明＞
・ポリオール組成物（Ａ）
（ａ１−１）：ショ糖（数平均官能基数＝８）１モルに水酸化カリウムを触媒として、ＰＯ５３．９モルを付加し、さらに水酸化カリウムを触媒として、ＥＯ１８．２モルをブロック付加し、常法により水酸化カリウムを除去して得られたポリエーテルポリオール。水酸基価＝２８．０（ｍｇＫＯＨ／ｇ）、末端ＥＯ単位の含有量＝２０．０重量％。
（Ａ１−１）：グリセリン（数平均官能基数＝３）１モルに水酸化カリウムを触媒として、ＰＯ７６．３モルを付加し、さらに水酸化カリウムを触媒として、ＥＯ３３．７モルをブロック付加し、常法により水酸化カリウムを除去して得られたポリエーテルポリオール。水酸基価＝２８．０（ｍｇＫＯＨ／ｇ）、末端ＥＯ単位の含有量＝２４．７重量％。
（Ａ１−２）：プロピレングリコール（数平均官能基数＝２）１モルに水酸化カリウムを触媒として、ＰＯ５３．９モルを付加し、さらに水酸化カリウムを触媒として、ＥＯ１８．２モルをブロック付加し、常法により水酸化カリウムを除去して得られたポリエーテルポリオール。水酸基価＝２８．０（ｍｇＫＯＨ／ｇ）、末端ＥＯ単位の含有量＝２０．０重量％。
（Ａ２−１）：エチレングリコール
<Explanation of used raw material symbols>
Polyol composition (A)
(A1-1): 53.9 mol of PO is added to 1 mol of sucrose (number average functional group number = 8) using potassium hydroxide as a catalyst, and further 18.2 mol of EO is added as a block using potassium hydroxide as a catalyst. A polyether polyol obtained by removing potassium hydroxide by a conventional method. Hydroxyl value = 28.0 (mg KOH / g), content of terminal EO unit = 20.0% by weight.
(A1-1): 76.3 mol of PO was added to 1 mol of glycerin (number average functional group number = 3) using potassium hydroxide as a catalyst, and 33.7 mol of EO was added as a block using potassium hydroxide as a catalyst. A polyether polyol obtained by removing potassium hydroxide by a conventional method. Hydroxyl value = 28.0 (mgKOH / g), content of terminal EO unit = 24.7% by weight.
(A1-2): 5 mol of PO was added to 1 mol of propylene glycol (number average functional group = 2) using potassium hydroxide as a catalyst, and 18.2 mol of EO was added in blocks using potassium hydroxide as a catalyst. A polyether polyol obtained by removing potassium hydroxide by a conventional method. Hydroxyl value = 28.0 (mg KOH / g), content of terminal EO unit = 20.0% by weight.
(A2-1): Ethylene glycol
・芳香族ポリアミン（Ｂ）
（Ｂ−１）：ジエチルトルエンジアミン
（Ｂ−２）：ターシャリーブチルトルエンジアミン
・ Aromatic polyamine (B)
(B-1): Diethyltoluenediamine (B-2): Tertiary butyltoluenediamine
・ポリイソシアネート成分（Ｃ）
（Ｃ１−１）：４，４’−ＭＤＩとジプロピレングリコールを７８．９／２１．１（重量比）で反応させてなるイソシアネート基末端ウレタンプレポリマー（ＮＣＯ％＝７．６重量％）
（Ｃ−２）：４，４’−ＭＤＩ（ＮＣＯ％＝３３．６重量％）
（Ｃ−３）：ポリメリックＭＤＩ（ＮＣＯ％＝３１．０重量％）〔三洋化成（株）製「サンフォームＩＣ−４５１」〕
・ Polyisocyanate component (C)
(C1-1): Isocyanate group-terminated urethane prepolymer obtained by reacting 4,4′-MDI and dipropylene glycol at 78.9 / 21.1 (weight ratio) (NCO% = 7.6 wt%)
(C-2): 4,4′-MDI (NCO% = 33.6 wt%)
(C-3): Polymeric MDI (NCO% = 31.0% by weight) [“Sunform IC-451” manufactured by Sanyo Chemical Co., Ltd.]
・アミン触媒（Ｄ１）
（Ｄ１−１）：トリエチレンジアミン〔東ソー（株）製「ＴＥＤＡ」〕
・ジアルキル錫の有機酸塩（Ｄ２）
（Ｄ２−１）：ジブチル錫ジラウレート〔日東化成（株）製「ネオスタンＵ−１００」〕
・ Amine catalyst (D1)
(D1-1): Triethylenediamine [“TEDA” manufactured by Tosoh Corporation]
・ Organic acid salt of dialkyltin (D2)
(D2-1): Dibutyltin dilaurate [“Neostan U-100” manufactured by Nitto Kasei Co., Ltd.]
・他の添加剤
（Ｅ−１）：ジメチルポリシロキサン〔東レダウコーニングシリコーン（株）製「ＳＦ−８４１０」〕
（Ｆ−１）：黒トナー〔富士色素（株）製「フジＶＬブラック」〕
Other additive (E-1): dimethylpolysiloxane [“SF-8410” manufactured by Toray Dow Corning Silicone Co., Ltd.]
(F-1): Black toner (“Fuji VL Black” manufactured by Fuji Dye Co., Ltd.)
ポリウレタン樹脂の機械物性の測定方法及び単位を以下に示す。
密度：ＪＩＳ Ｋ７２２２に準拠。単位はｇ／ｃｍ３
Ａ硬度：ＪＩＳ Ｋ６２５３ に準拠。
引張強さ：ＪＩＳ Ｋ７３１２に準拠。単位はＭＰａ。
破断伸び：ＪＩＳ Ｋ７３１２に準拠。単位は％
The measuring method and unit of the mechanical properties of the polyurethane resin are shown below.
Density: Conforms to JIS K7222. The unit is g / cm 3
A hardness: Conforms to JIS K6253.
Tensile strength: Conforms to JIS K7312. The unit is MPa.
Elongation at break: according to JIS K7312. Units%
表１の結果から明らかなように、本発明の実施例は比較例と比べて、密度が同等であるにもかかわらず、Ａ硬度、引張強さ、破断伸び及び連続成形性の全ての項目において、優れた結果が得られる。 As is clear from the results in Table 1, the examples of the present invention were compared with the comparative examples in all items of A hardness, tensile strength, elongation at break and continuous formability, although the densities were equal. Excellent results are obtained.
本発明のポリウレタン樹脂の製造方法によれば、従来の方法によるものに比べて、離型剤の塗布回数が少なくても、連続成形性が良好なポリウレタン樹脂が得られる。したがって、特に、自動車の一体成形窓用シールド材料に極めて有用なポリウレタン樹脂が提供される。 According to the method for producing a polyurethane resin of the present invention, a polyurethane resin having good continuous moldability can be obtained even when the number of times of application of the release agent is small as compared with the conventional method. Therefore, in particular, a polyurethane resin that is extremely useful for a shield material for an integrally molded window of an automobile is provided.
Claims (2)
ポリエーテルポリオ−ル（ａ１）：ポリオキシエチレンポリオキシプロピレンポリオ−ルであって、数平均官能基数が７．８〜８．２であり、水酸基価が１０〜４０（ｍｇＫＯＨ／ｇ）であり、末端オキシエチレン単位の含有量が１０〜３０重量％であるポリエーテルポリオール。
芳香族ポリアミン（Ｂ）：ジエチルトルエンジアミン及び／又はターシャリーブチルトルエンジアミン。 A method for producing a polyurethane resin by reaction curing a mixture containing a polyol composition (A), the following aromatic polyamine (B), a polyisocyanate component (C) and a urethanization catalyst (D), wherein (A) is: The following polyether polyol (a1) is contained, the content of (a1) is 50 to 100% by weight based on the total weight of (A), and (C) is diphenylmethane diisocyanate and a low molecular polyol (A2) Containing NCO group-terminated polyurethane prepolymer (C1), and the content of NCO group-terminated polyurethane prepolymer (C1) is 26 to 100% by weight based on the total weight of the polyisocyanate component (C). there are, a motor vehicle having a reacting curing the mixture in a closed mold, integrally molded with glass inserted in a closed mold in the pre-process Method of manufacturing a window for the polyurethane resin.
Polyether polyol (a1): Polyoxyethylene polyoxypropylene polyol having a number average functional group number of 7.8 to 8.2 and a hydroxyl value of 10 to 40 (mgKOH / g) A polyether polyol having a content of terminal oxyethylene units of 10 to 30% by weight.
Aromatic polyamine (B): diethyltoluenediamine and / or tertiary butyltoluenediamine.
The method for producing a polyurethane resin according to claim 1, wherein the urethanization catalyst (D) contains an organic acid salt of dialkyltin.
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| JP6876185B1 (en) * | 2020-06-30 | 2021-05-26 | 株式会社イノアック技術研究所 | Urea resin composition and polyurea foam |
| JP6925554B1 (en) * | 2020-06-30 | 2021-08-25 | 株式会社イノアック技術研究所 | Polyurea foam |
| JP6876186B1 (en) * | 2020-06-30 | 2021-05-26 | 株式会社イノアック技術研究所 | Resin composition and foam |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60181115A (en) * | 1984-02-28 | 1985-09-14 | Sanyo Chem Ind Ltd | Production of polyurethane |
| JPS60197718A (en) * | 1984-03-21 | 1985-10-07 | Sanyo Chem Ind Ltd | Production of polyurethane |
| JPS60206819A (en) * | 1984-03-30 | 1985-10-18 | Sanyo Chem Ind Ltd | Production of polyurethane molding |
| JPS6142526A (en) * | 1984-08-03 | 1986-03-01 | Sanyo Chem Ind Ltd | Production of polyurethane molding |
| JPS61171720A (en) * | 1985-01-24 | 1986-08-02 | Sanyo Chem Ind Ltd | Production of polyurethane |
| JPS61232918A (en) * | 1985-04-09 | 1986-10-17 | Asahi Glass Co Ltd | Method of manufacturing window glass pane member |
| JPS6367128A (en) * | 1987-05-01 | 1988-03-25 | Asahi Glass Co Ltd | Method for forming molding of gasket |
| JPH0280420A (en) * | 1988-09-16 | 1990-03-20 | Sanyo Chem Ind Ltd | Production of polyurethane |
| JPH02296816A (en) * | 1989-05-12 | 1990-12-07 | Asahi Glass Co Ltd | Reaction injection molding |
| JPH03237117A (en) * | 1990-02-15 | 1991-10-23 | Mitsubishi Heavy Ind Ltd | Production of high molecular thermoplastic urethane elastomer and molding of high molecular thermoplastic urethane elastomer |
| JP3063288B2 (en) * | 1991-09-30 | 2000-07-12 | 日産自動車株式会社 | Method of forming window panel members |
| US5308880A (en) * | 1993-05-20 | 1994-05-03 | Air Products And Chemicals, Inc. | Tin catalysts for use in rim polyol blends containing acidic internal mold release agents and diethyltoluenediamine chain extender |
| JP5193415B2 (en) * | 2005-04-27 | 2013-05-08 | ベバスト ジャパン株式会社 | Vehicle roof panel |
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