JPS62191119A - Manufacture of thermosetting polyurethane and/or polyurea sheet - Google Patents
Manufacture of thermosetting polyurethane and/or polyurea sheetInfo
- Publication number
- JPS62191119A JPS62191119A JP61032923A JP3292386A JPS62191119A JP S62191119 A JPS62191119 A JP S62191119A JP 61032923 A JP61032923 A JP 61032923A JP 3292386 A JP3292386 A JP 3292386A JP S62191119 A JPS62191119 A JP S62191119A
- Authority
- JP
- Japan
- Prior art keywords
- die head
- raw material
- sheet
- extruder die
- cooling
- 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.)
- Pending
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 16
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 8
- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000007765 extrusion coating Methods 0.000 claims abstract description 4
- 238000001125 extrusion Methods 0.000 claims description 25
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000007788 liquid Substances 0.000 abstract description 14
- 238000001879 gelation Methods 0.000 abstract description 8
- 239000003507 refrigerant Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 229910001369 Brass Inorganic materials 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010951 brass Substances 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 125000003277 amino group Chemical group 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- -1 Mizutomi Chemical compound 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000004292 cyclic ethers Chemical group 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 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
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- PFFIDZXUXFLSSR-UHFFFAOYSA-N 1-methyl-N-[2-(4-methylpentan-2-yl)-3-thienyl]-3-(trifluoromethyl)pyrazole-4-carboxamide Chemical compound S1C=CC(NC(=O)C=2C(=NN(C)C=2)C(F)(F)F)=C1C(C)CC(C)C PFFIDZXUXFLSSR-UHFFFAOYSA-N 0.000 description 1
- IFFLKGMDBKQMAH-UHFFFAOYSA-N 2,4-diaminopyridine Chemical compound NC1=CC=NC(N)=C1 IFFLKGMDBKQMAH-UHFFFAOYSA-N 0.000 description 1
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 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 1
- 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 1
- 229910000737 Duralumin Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass 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
- 239000011810 insulating material Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010721 machine oil Substances 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
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
Ｃ産業上の利用分野〕
本発明は、熱硬化性ウレタンおよび／またはユリア樹脂
の原料液が押し出しダイヘッド内でゲル化することがな
く、表面平滑性、均一性に優れた熱硬化性ポリウレタン
および／またはボリュリアシートの製造方法に関する。Detailed Description of the Invention C. Industrial Field of Application The present invention provides a thermosetting urethane and/or urea resin raw material solution that does not gel in the extrusion die head and has excellent surface smoothness and uniformity. The present invention relates to a method for producing thermosetting polyurethane and/or Voluria sheet.
従来、熱硬化性ポリウレタンおよび／またはボリュリア
シートの製造方法として押し出しコーティング法が行な
われてきた。しかし熱硬化性ポリウレタンやポリュリア
の原料液は、室温下でも徐々にゲル反応進み、押し出し
ダイヘッド内でゲル化を生じコーター出口の目づまりを
引き起こすので連続製造は困難であった。また、押し出
しダイヘッドの中で生じ流延されたゲル化物はシートの
中で粒となり、得られるシートの表面平滑性、均一性を
失わせる。更に甚だしい場合押し出しダイヘッドの中で
急速に硬化し製造装置が使用不能となることもあった。Conventionally, an extrusion coating method has been used as a method for producing thermosetting polyurethane and/or Voluria sheets. However, raw material liquids for thermosetting polyurethane and polyurea gradually undergo a gel reaction even at room temperature, causing gelation in the extrusion die head and clogging the coater outlet, making continuous production difficult. Moreover, the gelled material produced and cast in the extrusion die head becomes grains in the sheet, causing the resulting sheet to lose its surface smoothness and uniformity. Furthermore, in extreme cases, the resin may harden rapidly in the extrusion die head, rendering the manufacturing equipment unusable.
ゲル化を抑制するために触媒を減少すると硬化不足を生
じたり、硬化速度が遅くなるため均一なフィルムを得る
ことは難しかった。また、多量の溶剤で原料を希釈して
ゲル化反応を抑制することも可能であるが、流延した後
に多量の溶剤を完全に除くことは不可能であり、シート
中に残った溶剤が加熱硬化時に発泡するので表面平滑性
に優れたシートを得ることは困難であった・
ゲル化反応を防止する手段として、イソシアネ−ト基を
フェノール、メチルエチルケトンオキシムなどでブロッ
クしたものを原料に用いる方法があるが、シートの厚み
が大きいと加熱硬化時にブロック剤がうまく抜けず、発
生したブロック剤の蒸発による発泡を生じる問題がある
。またブロック剤を使用すると硬化温度、硬化時間が大
きくなる問題もあった。If the catalyst is reduced in order to suppress gelation, curing may be insufficient or the curing speed may be slow, making it difficult to obtain a uniform film. It is also possible to dilute the raw material with a large amount of solvent to suppress the gelation reaction, but it is impossible to completely remove the large amount of solvent after casting, and the solvent remaining in the sheet may be heated. It was difficult to obtain sheets with excellent surface smoothness because they foamed during curing. As a means of preventing gelation reactions, a method of using raw materials with isocyanate groups blocked with phenol, methyl ethyl ketone oxime, etc. However, if the sheet is too thick, the blocking agent cannot be removed properly during heat curing, resulting in foaming due to evaporation of the generated blocking agent. There is also the problem that the use of a blocking agent increases the curing temperature and curing time.
本発明の目的は、押し出しダイヘッド内でのポリウレタ
ンおよび／またはボリュリアの原料液のゲル化反応を抑
制し、表面平滑性、均一性に優れたシートを連続的に製
造する方法を提供することにある。An object of the present invention is to provide a method for continuously manufacturing sheets with excellent surface smoothness and uniformity by suppressing the gelation reaction of polyurethane and/or Voluria raw material liquid in an extrusion die head. .
本発明者らは、従来の押し出しコーティング法が持つ上
記の問題を解決する手段として押し出しダイヘッドを３
０℃以下に冷却しつつ原料を流延することにより、押し
出しダイヘッドの中でのゲル化反応を抑制しうろことを
見出し、本発明に到った。The present inventors developed an extrusion die head with three
It was discovered that the gelation reaction in the extrusion die head can be suppressed by casting the raw material while cooling it to 0° C. or lower, leading to the present invention.
すなわち、本発明は、熱硬化性ポリウレタンおよび／ま
たはポリユリアシートを押し出しコーティング法によっ
て製造するに際し、押し出しダイヘッドを３０℃以下に
冷却しつつ原料を流延し、次いで加熱硬化させることを
特徴とする熱硬化性ポリウレタンおよび／またはポリユ
リアシートの製造方法である。That is, the present invention is characterized in that when producing a thermosetting polyurethane and/or polyurea sheet by an extrusion coating method, the raw material is cast while cooling the extrusion die head to 30° C. or less, and then heated and cured. This is a method for producing a thermosetting polyurethane and/or polyurea sheet.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
冷却手段としては、押し出しダイヘッドの本体に冷媒が
流れる冷却板、冷却管などを取りつける手段、クーリン
グファンにより空冷する手段、電気的あるいは電子的な
冷却機器を取りつける手段などが可能であるが、押し出
しダイヘッドを構成するブロック内に冷媒を流す手段が
冷却効果が高く最も好ましい。Possible cooling means include attaching a cooling plate or cooling pipe through which a refrigerant flows to the main body of the extrusion die head, air cooling with a cooling fan, or attaching an electric or electronic cooling device. A means for flowing a refrigerant into the blocks constituting the is most preferable because it has a high cooling effect.
また、マニーホールドダイなどの空隙部分が大きい形状
の押し出しダイヘッドの場合は、空隙部分を貫通する構
造の冷却管を取りつける事によっても良い。Further, in the case of an extrusion die head having a large gap such as a manifold die, a cooling pipe having a structure that penetrates the gap may be attached.
さらに冷却効果を高めるために原料タンク、混合装置、
原料供給配管も冷却を行う事も推奨される。To further enhance the cooling effect, raw material tanks, mixing equipment,
It is also recommended that raw material supply piping be cooled.
冷媒としては、液体、気体の何れでも良いが、熱容量が
大きい液体を用いた方が冷媒の量は少量ですむので好ま
しい、液体の冷媒としては、例えば、水、シリコーン油
、各種の機械油、グリセリン、水富艮、メタノール、エ
タノール、ｎ−プロピルアルコール、ｎ−ブチルアルコ
ールなどが挙ケられ、中でも冷媒の安定性、経済性から
水が好ましい、気体としては、例えば、空気、窒素、炭
酸ガス、メタンガス、エタンガス、プロパンガス、フロ
ンガス、アンモニアなどが用いうる。The refrigerant may be either liquid or gas, but it is preferable to use a liquid with a large heat capacity because the amount of refrigerant required is small. Examples of liquid refrigerants include water, silicone oil, various machine oils, Examples include glycerin, Mizutomi, methanol, ethanol, n-propyl alcohol, n-butyl alcohol, among others, water is preferred from the viewpoint of refrigerant stability and economic efficiency.As for gases, for example, air, nitrogen, carbon dioxide gas, etc. , methane gas, ethane gas, propane gas, chlorofluorocarbon gas, ammonia, etc. can be used.
冷却温度は、３０℃以下でなくてはならない、３０℃以
上の温度では、押し出しダイヘッドの中でゲル化反応を
生じ易い、冷却温度は低いほど好ましいが、冷却温度が
低すぎると原料液の粘度が増大し流延時に支持体表面と
原料液の間に空気を巻き込み後の加熱硬化時に発泡など
の問題を生じ、シートの表面平滑性、均一性が失われる
ことがあるので３０．０００ｃｐｓ以下の粘度を原料液
が有する温度とする。また結晶性の原料液を用いる場合
は、該原料液の結晶温度以上にする。The cooling temperature must be below 30°C. Temperatures above 30°C tend to cause a gelation reaction in the extrusion die head. The lower the cooling temperature, the better; however, if the cooling temperature is too low, the viscosity of the raw material liquid will increase. 30,000 cps or less, air may be drawn in between the support surface and the raw material liquid during casting, causing problems such as foaming during heat curing after casting, and the surface smoothness and uniformity of the sheet may be lost. The viscosity is defined as the temperature of the raw material liquid. In addition, when a crystalline raw material liquid is used, the temperature is higher than the crystallization temperature of the raw material liquid.
冷却効果を高める押出ダイヘッドの材質としては、熱伝
導率が高い金属、例えば、真鍮、銅、アルミニウム、ア
ルミニウムシリカ合金、ジュラルミンなどが挙げられる
。原料あるいは冷媒により金属表面が侵される場合は、
表面をフッ素樹脂などにより保護しておいてもよい、ま
た、セラミックを用いる事も可能である０例えば、ベリ
リア、炭化ケイ素、窒化アルミニウムなどが熱伝導率が
高く好ましい、押出ダイヘッドの温度の低下に伴う水滴
の付着により製膜作業、あるいは得られるフィルム、シ
ート類に悪影響を及ぼす場合は、押出ダイヘッドの外側
に断熱材を取りつけたり、作業室内の除湿を行うとよい
。Examples of the material of the extrusion die head that enhances the cooling effect include metals with high thermal conductivity, such as brass, copper, aluminum, aluminum-silica alloy, and duralumin. If the metal surface is attacked by the raw material or refrigerant,
The surface may be protected with fluororesin, etc., or ceramic may also be used.For example, beryllia, silicon carbide, aluminum nitride, etc. have high thermal conductivity and are preferred for lowering the temperature of the extrusion die head. If the adhesion of accompanying water droplets adversely affects the film forming operation or the obtained films and sheets, it is recommended to attach a heat insulating material to the outside of the extrusion die head or dehumidify the work chamber.
押出ダイヘッドへの原料の供給手段としては、通常のギ
ヤアボンブ、デシプロポンプなどが利用できる。２液硬
化型のポリウレタンおよび／またはボリュリア原料液を
用いる場合は、主剤及び硬化剤をそれぞれ別々のポンプ
により、スタテンクミキサーなどの混合装置を介して、
押出ダイヘッドに供給するとよい、この場合も温度をで
きるだけ低く、好ましくは３０℃以下にしておく、混合
装置と押出コーター間の配管は短いほど好ましい。As a means for supplying raw materials to the extrusion die head, an ordinary gear bomb, deciprop pump, etc. can be used. When using a two-component curing type polyurethane and/or Voluria raw material liquid, the main agent and curing agent are mixed using separate pumps and a mixing device such as a Statenk mixer.
It is preferable to supply the mixture to an extrusion die head. In this case as well, the temperature is kept as low as possible, preferably below 30° C., and the shorter the piping between the mixing device and the extrusion coater, the better.
また、スタテックミキサーなどの混合機構を有する押出
コーターを利用することも可能である。It is also possible to use an extrusion coater having a mixing mechanism such as a static mixer.
押出ダイヘッド内で原料溶液は、すばやく必要な巾に分
散することが好ましい、巾広く分散する形状としては、
フィッシュテールダイ、コートハンガーダイ、マニホー
ルダイなどが挙げられる。It is preferable that the raw material solution is quickly dispersed in the required width within the extrusion die head.
Examples include fishtail dies, coat hanger dies, and manifold dies.
得られるフィルム、シート類の厚み、押し出しダイヘッ
ドへの原料の供給量と流延された原料を支える支持体の
移動速度により決定されるが、さらに均一な厚みの層を
得るためには、押出ダイヘッドの出口にブレードあるい
はドクターナイフを取り付けることが好ましい。The thickness of the resulting film or sheet is determined by the amount of raw material supplied to the extrusion die head and the moving speed of the support supporting the cast raw material. Preferably, a blade or doctor knife is attached to the outlet of the tube.
原料を流延させる支持体、硬化炉は、通常の熱硬化性樹
脂のコーテング方法において利用されるものが利用でき
る。支持体としては、金属板、プラスチックフィルム、
紙、ガラス板などが例示できる。また、支持体の耐熱温
度は、硬化温度よりも少なくとも１０℃以上高い事が望
まれる。As the support for casting the raw material and the curing furnace, those used in ordinary thermosetting resin coating methods can be used. Supports include metal plates, plastic films,
Examples include paper and glass plates. Further, it is desirable that the support has a heat resistance temperature that is at least 10° C. higher than the curing temperature.
加熱硬化した後、支持体からシートを剥がす場合は、支
持体の表面に離型剤を塗布し離型処理を行うとよい、Ｉ
ＩＩＩｌ型剤としては、リン酸系、シリコン系、フン素
糸などの離型剤が利用しできる。硬化炉としては、熱風
炉、赤外線炉あるいはこれらを組み合わせたものが挙げ
られる。加熱温度としては、原料溶液の硬化温度により
決定されるが、好ましくは、支持体の耐熱温度および得
られるシートの耐熱温度よりも少なくとも１０℃以下に
設定することが望ましい、加熱時間は、得られるシート
の表面がべとつかなくなるまで加熱した後、少なくとも
３分間後硬化を連続して行う方が好ましい。When peeling off the sheet from the support after heating and curing, it is recommended to apply a mold release agent to the surface of the support and perform mold release treatment.
As the III type agent, phosphoric acid type, silicone type, fluorine-based mold release agents, etc. can be used. Examples of the curing oven include a hot air oven, an infrared oven, or a combination thereof. The heating temperature is determined by the curing temperature of the raw material solution, but is preferably set to at least 10°C or lower than the heat-resistant temperature of the support and the heat-resistant temperature of the sheet obtained.The heating time is determined by the curing temperature of the raw material solution. After heating until the surface of the sheet is no longer tacky, it is preferable to continue post-curing for at least 3 minutes.
本発明による熱硬化性ポリウレタンおよび／またはポリ
ユリアシートの製造方法では、少なくとも分子内に２個
以上水酸基および／またはアミノ基を有する化合物と少
なくとも分子内に２個以上のイソシアネート基を有する
化合物が原料とじて用いる。In the method for producing thermosetting polyurethane and/or polyurea sheets according to the present invention, the raw materials are a compound having at least two or more hydroxyl groups and/or amino groups in the molecule and a compound having at least two or more isocyanate groups in the molecule. Use by closing.
分子中に２個以上水酸基を有する化合物としてポリエチ
レングリコール、ポリプロピレングリコール、カテコー
ル、レゾルシノール、ヒドロキノン、４．４’−ヒドロ
キシフェニルメタン、ビスフェノールＡ１グリセリン、
トリメチロールプロパン、ヘキサントリオール、トリメ
チロールエタン、トリメチロールブタン、ペンタエリス
リトール、２゜３．４− ）ジヒドロキシ−１−ブタノ
ール、２．３．４．５−テトラヒドロキシ−１−ペンタ
ノール、ソルビトール、シュクロースなどが挙げられる
。また、末端に水酸基を有するポリエーテルポリオール
、ポリエステルポリオール、塩基性ポリオールも利用で
きる。末端に水酸基を有するポリエーテルポリオールの
例としては、前記水酸基を有する化合物を開始剤として
、エチレンオキサイド、プロピレンオキサイド、テトラ
ヒドロフランなどの環状エーテル基を含む化合物との付
加重合により得られるものが挙げられる。末端に水酸基
を育するポリエステルポリオールの例としては、前記水
酸基を有する化合物とジカルボン酸とのエステル重合に
より得られるものが挙げられる。ジカルボン酸としては
、マロン酸、スクシン酸、ゲルタール酸、スペリン酸、
セバシン酸、三量化リルイン酸、マレイン酸、アジピン
酸、フタル酸、シェラ酸などが挙げられる。末端に水酸
基を有する塩基性ポリオールの例としては、エチレンジ
アミン、ベンゼンスルホンアミド、２−アミノエタノー
ル、Ｎ−メチルジェタノールアミン、ジエチレントリア
ミンなどのアミンを開始剤として、前記環状エーテル基
を有する化合物との付加重合により得られるものが挙げ
られる。Compounds having two or more hydroxyl groups in the molecule include polyethylene glycol, polypropylene glycol, catechol, resorcinol, hydroquinone, 4,4'-hydroxyphenylmethane, bisphenol A1 glycerin,
Trimethylolpropane, hexanetriol, trimethylolethane, trimethylolbutane, pentaerythritol, 2.3.4-) dihydroxy-1-butanol, 2.3.4.5-tetrahydroxy-1-pentanol, sorbitol, Examples include Claus. Furthermore, polyether polyols, polyester polyols, and basic polyols having hydroxyl groups at the ends can also be used. Examples of polyether polyols having a hydroxyl group at the terminal include those obtained by addition polymerization with a compound containing a cyclic ether group such as ethylene oxide, propylene oxide, or tetrahydrofuran using the compound having the hydroxyl group as an initiator. Examples of polyester polyols having hydroxyl groups at their terminals include those obtained by ester polymerization of a compound having a hydroxyl group and a dicarboxylic acid. Dicarboxylic acids include malonic acid, succinic acid, geltaric acid, speric acid,
Examples include sebacic acid, trimerized lyluic acid, maleic acid, adipic acid, phthalic acid, and Schellaic acid. Examples of basic polyols having a hydroxyl group at the terminal include addition with a compound having a cyclic ether group using an amine such as ethylenediamine, benzenesulfonamide, 2-aminoethanol, N-methyljetanolamine, or diethylenetriamine as an initiator. Examples include those obtained by polymerization.
分子中に２個以上のアミノ基を有′する化合物の例とし
ては、ジアミノビフェニル、２．４−ピリジンジアミン
、エチレンジアミン、ジエチレントリアミン、１．６．
１２−ドデカントリアミン、１．６．１１−ラブカント
リアミン、１．５．１０−デカントリアミン、１．５．
９−ノナントリアミン、２．４− ）リレンジアミン、
メタキシリレンジアミン、１．５−ナフチレンジアミ７
．４．４’−ジフェニルメタンジアミン、さらに次式で
示される縮合アミンなどが挙げられる。Examples of compounds having two or more amino groups in the molecule include diaminobiphenyl, 2,4-pyridinediamine, ethylenediamine, diethylenetriamine, 1.6.
12-dodecanetriamine, 1.6.11-labcantriamine, 1.5.10-decanetriamine, 1.5.
9-nonantriamine, 2.4-)lylenediamine,
metaxylylenediamine, 1,5-naphthylenediamine 7
．． Examples include 4.4'-diphenylmethanediamine and condensed amines represented by the following formula.
（式中、ｎは０以上である）
分子中に２個以上のイソシアネートａを有する化合物と
しては、例えば、２．４−）リレンジイソシアネート、
４．４°−ジフェニルメタンジイソシアネート、１．５
−ナフチレンジイソシアネート、ヘキサメチレンジイソ
シアネート、メタキシリレンジイソシアネート、ジアニ
シジンジイソシアネート、トリデンジイソシアネート、
２．６−ジイツシアネートメルカプロエート、イソホロ
ンジイソシアネート、トリフェニルメタントリイソシア
ネート、ポリメチレンポリフェニルイソシアネート、ボ
リメリンクイソシアネートなどが挙げられる。また前記
イソシアネート基を有する化合物と水あるいは先に記載
した水酸基やアミノ基を有する化合物と反応して得られ
るアダクト体（変性品）も利用できる。(In the formula, n is 0 or more) Examples of compounds having two or more isocyanates a in the molecule include 2.4-)lylene diisocyanate,
4.4°-diphenylmethane diisocyanate, 1.5
- Naphthylene diisocyanate, hexamethylene diisocyanate, metaxylylene diisocyanate, dianisidine diisocyanate, tridene diisocyanate,
Examples include 2.6-dicyanate mercaproate, isophorone diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenylisocyanate, and polymeline isocyanate. Further, an adduct (modified product) obtained by reacting the compound having an isocyanate group with water or the above-mentioned compound having a hydroxyl group or an amino group can also be used.
水酸基および／またはアミノ基を存する化合物とイソシ
アネート基を有する化合物の混合比としては、イソシア
ネート基と水酸基および／またはアミノ基の割合が１；
１．２〜１：０．８の範囲であることが望ましい。The mixing ratio of a compound having a hydroxyl group and/or an amino group and a compound having an isocyanate group is such that the ratio of the isocyanate group to the hydroxyl group and/or amino group is 1;
The ratio is preferably in the range of 1.2 to 1:0.8.
また、硬化速度が遅い場合は、触媒を添加する事が望ま
しい、触媒としては、通常の熱硬化型ウレタン用の触媒
が利用できる０例えば、トリエチルアミン、トリエチレ
ンジアミン、スフナスオクトエート、ジブチル錫ジー２
−エチルヘキソエート、ジブチル錫ジラウレート、オク
チル酸鉛、カリウムオレート、テトラ（２−エチルヘキ
シル）チタネート、塩化第二錫、塩化第二鉄、ナフテン
酸亜鉛、コバルト２−エチルヘキソエートなどが挙げら
れる。In addition, if the curing speed is slow, it is desirable to add a catalyst. As a catalyst, a normal catalyst for thermosetting urethane can be used. For example, triethylamine, triethylenediamine, sufnus octoate, dibutyltin
-Ethylhexoate, dibutyltin dilaurate, lead octylate, potassium oleate, tetra(2-ethylhexyl)titanate, stannic chloride, ferric chloride, zinc naphthenate, cobalt 2-ethylhexoate, etc. .
以下、実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例１
第１図及び第２図にしめした押出ダイヘッドを用い熱硬
化性ポリウレタンシートの連続製造を行った。ブレード
１２の全長は３０＋ｍｓ、 Ｒは１２０“、厚みＤは０
．４ｍｍに調整した。支持体としては、シリコーン処理
（離型処理）したポリエチレンテレツクレートのフィル
ムを用いた。冷却管９．ｌＯの直径は８ｍｌ＋であり、
その中に４℃の水を５００ｍ１／分で通液した。Example 1 A thermosetting polyurethane sheet was continuously manufactured using the extrusion die head shown in FIGS. 1 and 2. The total length of the blade 12 is 30+ms, R is 120", and thickness D is 0.
．． Adjusted to 4mm. A silicone-treated (release-treated) polyethylene tereclate film was used as the support. Cooling pipe 9. The diameter of lO is 8ml+,
Water at 4° C. was passed through it at a rate of 500 ml/min.
イソシアネート化合物としてヘキサメチレンジイソシア
ネートのとュウレット変性品″ＮＰＩ１００”（三井東
圧化学側製、遊離イソシアネート含有量２３．１％）
１２．１ｇ／分を、ヒドロキシル化合物としてトリオー
ルポリエーテル°ＭＮ４５０″（三井東圧化学■製、水
酸基価４５０＋ｏｇＸＯ，Ｈ／ｇ） ８．３ｇ／分を、
触媒としてオクチル酸鉛０．０４１ｇ／分を、レベリン
グ剤としてシリコーンオイル’ＹＦ３９１０”（東芝シ
リコーン■製）０．１ｇ／分をスタテックミキサーを介
して連続的に供給し、支持体上に流延し、次いで１３０
℃に保ったギャアオーブン中で１０分間硬化し、０．３
２ｍｍの厚みを持つシートを連続的に製造した。シート
製造中に得られたシートの表面状態を目視により観察し
た。その結果を表−１に示す。The isocyanate compound is a Tulett-modified product of hexamethylene diisocyanate "NPI100" (manufactured by Mitsui Toatsu Chemical Co., Ltd., free isocyanate content 23.1%)
12.1 g/min, and 8.3 g/min of triol polyether °MN450'' (manufactured by Mitsui Toatsu Chemical ■, hydroxyl value 450+ogXO, H/g) as a hydroxyl compound.
0.041 g/min of lead octylate as a catalyst and 0.1 g/min of silicone oil 'YF3910'' (manufactured by Toshiba Silicone ■) as a leveling agent were continuously supplied via a static mixer and cast onto the support. and then 130
Cured for 10 minutes in a Gaia oven kept at 0.3
Sheets with a thickness of 2 mm were produced continuously. The surface condition of the sheet obtained during sheet production was visually observed. The results are shown in Table-1.
実施例２
ヘキサメチレンジイソシアネートのビュウレット変性品
”ＮＰｌｌｏｏ” ８．８ｇ／分、４．４°−ジアミノ
ジフェニルメタン（アミノ基含有量１６．１重量％、分
子量１９８）のキシレン溶液（４１，５重量％） １１
．６ｇ／分およびシリコーンオイル０．１ｇ／分の割合
で用い、実施例１と同様の方法により０．２＋ｎｍの厚
みを持つシートを得た。Example 2 Biuret modified product of hexamethylene diisocyanate "NPlloo" 8.8 g/min, xylene solution (41.5% by weight) of 4.4°-diaminodiphenylmethane (amino group content 16.1% by weight, molecular weight 198) 11
．． A sheet having a thickness of 0.2+nm was obtained in the same manner as in Example 1 using a ratio of 6 g/min and silicone oil 0.1 g/min.
実施例１と同様にシート製造中に得られたシートの表面
状態を目視により観察した。その結果を表−１に示す。As in Example 1, the surface condition of the sheet obtained during sheet production was visually observed. The results are shown in Table-1.
実施例３
ヘキサメチレンジイソシアネートのビュウレット変性品
”ＮＰｌｌｏｏ“１７．５ｇ／分、２−アミノエタノー
ル（０８価７２０、アミノ基含有量２６．３重量％、分
子１ｉ６１）２．９ｇ／分、オクチル酸鉛０．０５ｇ／
分およびシリコーンオイル０．１ｇ／分の割合で用い、
実施例１と同様の方法により０ 、３５ａ＋ｍの厚みを
持つシートを得た。Example 3 Biuret modified product of hexamethylene diisocyanate "NPlloo" 17.5 g/min, 2-aminoethanol (08 valence 720, amino group content 26.3% by weight, molecule 1i61) 2.9 g/min, lead octylate 0.05g/
minutes and silicone oil at a rate of 0.1 g/minute,
A sheet having a thickness of 0.35 a+m was obtained in the same manner as in Example 1.
実施例１と同様にシート製造中に得られたシートの表面
状態を目視により観察した。その結果を表−１に示す。As in Example 1, the surface condition of the sheet obtained during sheet production was visually observed. The results are shown in Table-1.
比較例１
冷却水の温度を４０℃に変えた以外は実施例１と同じ条
件で熱硬化性ポリウレタンシートの連続製造を行った。Comparative Example 1 A thermosetting polyurethane sheet was continuously produced under the same conditions as in Example 1 except that the temperature of the cooling water was changed to 40°C.
開始後２０分に得られるウレタンシートの表面が荒れ出
し、６０分後には押出ダイヘッドの出口にゲル化物が詰
まり、得られるポリウレタンシートの表面に著しい表面
荒れを住した。The surface of the urethane sheet obtained became rough 20 minutes after the start, and after 60 minutes, the exit of the extrusion die head was clogged with gelled material, resulting in significant surface roughness on the surface of the polyurethane sheet obtained.
実施例１と同様にシート製造中に得られたシートの表面
状態を目視により観察した。その結果を表＝１に示す。As in Example 1, the surface condition of the sheet obtained during sheet production was visually observed. The results are shown in Table 1.
×；著しい表面荒れを生じる
（発明の効果〕
本発明のシートの製造方法では、熱硬化性ポリウレタン
および／またはポリュリアの原料液が押出ダイヘッドの
中でゲル化することがなく、表面平滑性、均一性に優れ
たシートの製造が可能である。またブロック剤などを使
用する必要がなく、発泡や硬化不足の問題を生じ龍く、
その産業上の利用可能性は大きい。×: Significant surface roughness occurs (effect of the invention) In the sheet manufacturing method of the present invention, the raw material liquid of thermosetting polyurethane and/or Polylia does not gel in the extrusion die head, and the surface smoothness and uniformity are maintained. It is possible to manufacture sheets with excellent properties.In addition, there is no need to use blocking agents, which may cause problems such as foaming or insufficient curing.
Its industrial applicability is great.
第１図は、本体ブロック内に冷却管を持つ押出ダイヘッ
ドの断面図、第２図は第１図のＡ−Ａ’綿上での断面図
を示す０図においては、１は支持体、２は梁、３は梁へ
本体を固定するボルト、４はロール、５．６は金属ブロ
ック、９．１０は冷却管、１１は原料供給用アダプター
、１２はブレード、１３はブレードの取付用ボルト、Ｅ
は支持体の移動方向、Ｒはブレードの角度、Ｄは流延厚
み、Ｐはダイヘッド内での液の流れをそれぞれ示す。Fig. 1 is a cross-sectional view of an extrusion die head having a cooling pipe in the main body block, and Fig. 2 is a cross-sectional view taken on the line A-A' of Fig. 1. In Fig. 0, 1 is a support, 2 3 is a beam, 3 is a bolt for fixing the main body to the beam, 4 is a roll, 5.6 is a metal block, 9.10 is a cooling pipe, 11 is an adapter for raw material supply, 12 is a blade, 13 is a bolt for attaching the blade, E
represents the moving direction of the support, R represents the angle of the blade, D represents the casting thickness, and P represents the flow of liquid within the die head.
Claims (1)
を押し出しコーティング法によって製造するに際し、押
し出しダイヘッドを３０℃以下に冷却しつつ原料を流延
し、次いで加熱硬化させることを特徴とする熱硬化性ポ
リウレタンおよび／またはポリユリヤシートの製造方法
。When producing a thermosetting polyurethane and/or polyurea sheet by an extrusion coating method, the thermosetting polyurethane and/or polyurea sheet is characterized in that the raw material is cast while cooling the extrusion die head to 30° C. or less, and then heated and cured. Or a method for manufacturing polyurethane sheets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61032923A JPS62191119A (en) | 1986-02-19 | 1986-02-19 | Manufacture of thermosetting polyurethane and/or polyurea sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61032923A JPS62191119A (en) | 1986-02-19 | 1986-02-19 | Manufacture of thermosetting polyurethane and/or polyurea sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62191119A true JPS62191119A (en) | 1987-08-21 |
Family
ID=12372425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61032923A Pending JPS62191119A (en) | 1986-02-19 | 1986-02-19 | Manufacture of thermosetting polyurethane and/or polyurea sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62191119A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0248921A (en) * | 1988-08-11 | 1990-02-19 | Diafoil Co Ltd | Manufacture of polymer film |
| US5102489A (en) * | 1988-12-22 | 1992-04-07 | Huels Aktiengesellschaft | Method of covulcanizing polyesters and ep(d)m rubbers |
| JP2022107398A (en) * | 2021-01-08 | 2022-07-21 | 日本碍子株式会社 | Extrusion molding die and extrusion molding machine |
-
1986
- 1986-02-19 JP JP61032923A patent/JPS62191119A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0248921A (en) * | 1988-08-11 | 1990-02-19 | Diafoil Co Ltd | Manufacture of polymer film |
| US5102489A (en) * | 1988-12-22 | 1992-04-07 | Huels Aktiengesellschaft | Method of covulcanizing polyesters and ep(d)m rubbers |
| JP2022107398A (en) * | 2021-01-08 | 2022-07-21 | 日本碍子株式会社 | Extrusion molding die and extrusion molding machine |
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