JPH01245013A - Dispersant composition for nonaqueous dispersion polymerization and polyurethane composition using said composition - Google Patents
Dispersant composition for nonaqueous dispersion polymerization and polyurethane composition using said compositionInfo
- Publication number
- JPH01245013A JPH01245013A JP63071978A JP7197888A JPH01245013A JP H01245013 A JPH01245013 A JP H01245013A JP 63071978 A JP63071978 A JP 63071978A JP 7197888 A JP7197888 A JP 7197888A JP H01245013 A JPH01245013 A JP H01245013A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- dispersant
- polyurethane
- polyol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000012674 dispersion polymerization Methods 0.000 title claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 title claims description 49
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920000570 polyether Polymers 0.000 abstract description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 abstract description 3
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 2
- 230000000740 bleeding effect Effects 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- -1 alicyclic alcohols Chemical class 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000004970 Chain extender Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 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
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- GCWAFWMUTOXMIT-HWKANZROSA-N (e)-heptadec-2-ene Chemical compound CCCCCCCCCCCCCC\C=C\C GCWAFWMUTOXMIT-HWKANZROSA-N 0.000 description 1
- IICQZTQZQSBHBY-HWKANZROSA-N (e)-non-2-ene Chemical compound CCCCCC\C=C\C IICQZTQZQSBHBY-HWKANZROSA-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
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- HLMACKQLXSEXIY-UHFFFAOYSA-N 2-methyldec-1-ene Chemical compound CCCCCCCCC(C)=C HLMACKQLXSEXIY-UHFFFAOYSA-N 0.000 description 1
- PWRBDKMPAZFCSV-UHFFFAOYSA-N 2-methyldodec-1-ene Chemical compound CCCCCCCCCCC(C)=C PWRBDKMPAZFCSV-UHFFFAOYSA-N 0.000 description 1
- ZKRHEOXJNQPNQD-UHFFFAOYSA-N 2-methylheptadec-1-ene Chemical compound CCCCCCCCCCCCCCCC(C)=C ZKRHEOXJNQPNQD-UHFFFAOYSA-N 0.000 description 1
- YLZQHQUVNZVGOK-UHFFFAOYSA-N 2-methylnon-1-ene Chemical compound CCCCCCCC(C)=C YLZQHQUVNZVGOK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 1
- IICQZTQZQSBHBY-UHFFFAOYSA-N 2t-nonene Natural products CCCCCCC=CC IICQZTQZQSBHBY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000694851 Adipe Species 0.000 description 1
- GGBJHURWWWLEQH-UHFFFAOYSA-N Butyl-cyclohexane Natural products CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 description 1
- 241000951471 Citrus junos Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QFHYHYSMAHUARD-UHFFFAOYSA-N [S].CO Chemical compound [S].CO QFHYHYSMAHUARD-UHFFFAOYSA-N 0.000 description 1
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- 229940057995 liquid paraffin Drugs 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
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、非水分散重合法によりポリウレタン系粉末重
合体を製造する場合に用いる分散性の優れ次分散刑組成
物及び該組成物を用いたポリタレタン組成物に関するも
のである。Detailed Description of the Invention [Industrial Field of Application] The present invention provides a highly dispersible composition for producing a polyurethane powder polymer by a non-aqueous dispersion polymerization method, and a method for using the composition. This invention relates to a polytalethane composition.
非水分散重合法によるポリウレタン粉末の製造法は、既
に、松本ら（日本接着協会味、９．１８３゜１９７３年
）により基本的な重合法の解説がなされている。また、
特公昭５７−２９４８５号公報には、非水分散（エマル
ジ日ン）重合法によるポリウレタン粉末の製造法が述べ
られている。この重合法の最も重要なポイントは分散剤
の選択である。特公昭５７−２９４８５号公報では、分
散剤としてメタクリル酸ラウリルのような長鎖アルキル
をもったモノマーとメタクリル酸メチル、アクリルアミ
ドのようなモノマーとの共重合体を用いている。この分
散剤は、分散能力が低く、ポリウレタンの組成によって
は分散が不十分な場合があった。また、従来の分散剤は
、添加型であるので、ポリウレタン重合体の成形品は経
時による分散剤のしみ出しが発生し外観変化などの問題
が発生することがある。Regarding the method for producing polyurethane powder by non-aqueous dispersion polymerization, the basic polymerization method has already been explained by Matsumoto et al. (Japan Adhesive Association, 9.183°, 1973). Also,
Japanese Patent Publication No. 57-29485 describes a method for producing polyurethane powder by a non-aqueous dispersion (emulsion) polymerization method. The most important point in this polymerization method is the selection of the dispersant. In Japanese Patent Publication No. 57-29485, a copolymer of a monomer having a long chain alkyl such as lauryl methacrylate and a monomer such as methyl methacrylate or acrylamide is used as a dispersant. This dispersant has a low dispersing ability, and depending on the composition of the polyurethane, the dispersion may be insufficient. Further, since conventional dispersants are additive-type, problems such as a change in appearance may occur in molded articles of polyurethane polymers due to the dispersant exuding over time.
本発明者は、従来の分散剤の欠点である分散性能の悪さ
を改善するため、分散剤組成について鋭意研究、検討を
重ねた結果、ポリウレタンの原料の一つであるポリオー
ルに不飽和結合をもたせ、炭化水素側鎖を有するエチレ
ン性不飽和単量体をグラフト重合させた分散剤を見出し
、更に、該分散剤を非水分散重合法によりポリウレタン
系粉末重合体を製造する際に使用することにより、その
分散性を改善できることを見出し本発明を完成するに至
った。In order to improve the poor dispersion performance, which is a drawback of conventional dispersants, the inventors of the present invention have conducted intensive research and examination on the composition of dispersants, and as a result, they have created an unsaturated bond in polyol, which is one of the raw materials for polyurethane. , discovered a dispersant obtained by graft polymerization of an ethylenically unsaturated monomer having a hydrocarbon side chain, and furthermore, by using this dispersant in producing a polyurethane powder polymer by a non-aqueous dispersion polymerization method. The present inventors have discovered that the dispersibility can be improved and have completed the present invention.
即ち本発明は、
１、分子内に不飽和結合を有するポリオール１００重量
部に対して炭素数６以上の炭化水素基からなる側鎖を有
するエチレン性不飽和単量体２０から４００重量部を反
応せしめることを特徴とする分散剤組成物。That is, the present invention provides the following steps: 1. 20 to 400 parts by weight of an ethylenically unsaturated monomer having a side chain consisting of a hydrocarbon group having 6 or more carbon atoms is reacted with 100 parts by weight of a polyol having an unsaturated bond in the molecule. A dispersant composition characterized by:
２、非水分散重合法によりポリウレタン系粉末重合体を
製造する際、前記分散剤を重合体組成の一部として用い
ることを特徴とするポリウレタン組成物。2. A polyurethane composition characterized in that the dispersant is used as a part of the polymer composition when producing a polyurethane powder polymer by a non-aqueous dispersion polymerization method.
に関するものである。It is related to.
本発明の分散剤はあらゆる組成の非水分散重合によるポ
リウレタンの製造に有効に使用することが出来る。また
、非水分散重合によって得られたポリウレタンの成形物
は、分散剤がポリイソシアネートと反応しているため分
散剤のしみ出しなどによる経時変化がみられない。The dispersant of the present invention can be effectively used for producing polyurethane of any composition by non-aqueous dispersion polymerization. In addition, molded polyurethane obtained by non-aqueous dispersion polymerization does not change over time due to seepage of the dispersant because the dispersant reacts with the polyisocyanate.
本発明に用いることのできる分子内に不飽和結合を有す
るポリオールとしては、例えば、ポリエステルポリオー
ルの場合、原料のグリコール類、二塩基酸類などの一部
に不飽和基含有グリコールあるいは不飽和基含有ジカル
ボン酸を使用して製造したものなどがあげられる。また
、ポリエーテルポリオールの場合、出発物質として不飽
和基含有グリコールを用いて製造し友ものなどもあけら
れる。更に１分子量 ２０００以下の水酸基末端ポリエ
ステル、ポリエーテル、ポリカーボネートなどと不飽和
基含有ジカルボン酸とのエステル化によってえられるポ
リオールなどもめげられる。ここで述べた不飽和基含有
グリコールの例としては、２−プテンー１，４−ジオー
ル、グリセリンモノアリルエーテルなどがあげられる。Polyols having unsaturated bonds in the molecule that can be used in the present invention include, for example, in the case of polyester polyols, glycols containing unsaturated groups or dicarbonate containing unsaturated groups as part of the raw material glycols, dibasic acids, etc. Examples include those manufactured using acids. In addition, in the case of polyether polyols, products manufactured using unsaturated group-containing glycols as starting materials can also be used. Furthermore, polyols obtained by esterifying hydroxyl-terminated polyesters, polyethers, polycarbonates, etc. having a molecular weight of 2,000 or less with unsaturated group-containing dicarboxylic acids are also included. Examples of the unsaturated group-containing glycol mentioned here include 2-butene-1,4-diol, glycerin monoallyl ether, and the like.
また、不飽和基含有ジカルボン酸の例としてはマレイン
酸、イタコン酸などがある。本発明に用いることのでき
る分子内に不飽和結合を有するポリオールの分子量およ
び不飽和結合濃度は、特に制限はないが、分子量は３０
００以下、不飽和績＠濃度はポリオール１分子について
平均１０モル以下の不飽和基が望ましい。Examples of unsaturated group-containing dicarboxylic acids include maleic acid and itaconic acid. The molecular weight and unsaturated bond concentration of the polyol having an unsaturated bond in the molecule that can be used in the present invention are not particularly limited, but the molecular weight is 30
00 or less, and the unsaturated group concentration is desirably 10 moles or less on average per molecule of polyol.
本発明の分子内に不飽和結合を有するポリオールの製法
は通常のポリエステル、ポリエーテルなどの製造方法で
行うことができる。The polyol having an unsaturated bond in the molecule of the present invention can be produced by a conventional method for producing polyesters, polyethers, and the like.
本発明において分散剤の製造に用いられる炭素数６以上
の炭化水素基からなる側鎖を有するエチレン性不飽和４
Ｌ量体としては、例えば、ｌ−オクテン、ｌ−または２
−ノネン、１−または２−デセン、ｌ−ま次は２−ヘプ
タデセン、２−メチル−１−ノネン、２−メチル−１−
デセン、２−メチル−１−ドデセン、２−メチル−１−
へキサデセン、２−メチル−１−ヘプタデセンなどのビ
ニル、プロペニルまたはインプロベニル基含有脂肪族直
鎖型不飽和炭化水素、アクリル酸またはメタクリル酸と
２−エチルヘキシルアルコール、ヘキシルアルコールな
どの炭素数６以上の脂肪族アルコールまたはシクロヘキ
サノール、ノルボナノール、アダマンタノールなどの炭
素数６以上の脂環族アルコールとのエステルなどがあげ
られる。これらは単独あるいは２ね以上を併用すること
ができる。Ethylenically unsaturated 4 having a side chain consisting of a hydrocarbon group having 6 or more carbon atoms used in the production of a dispersant in the present invention
Examples of the L-mer include l-octene, l- or 2
-Nonene, 1- or 2-decene, 1- or 2-heptadecene, 2-methyl-1-nonene, 2-methyl-1-
Decene, 2-methyl-1-dodecene, 2-methyl-1-
Vinyl, propenyl or improbenyl group-containing aliphatic linear unsaturated hydrocarbons such as hexadecene and 2-methyl-1-heptadecene, acrylic acid or methacrylic acid and fats with 6 or more carbon atoms such as 2-ethylhexyl alcohol and hexyl alcohol. Examples include esters with group alcohols or alicyclic alcohols having 6 or more carbon atoms such as cyclohexanol, norbonanol, and adamantanol. These can be used alone or in combination of two or more.
本発明における不飽和結合を有するポリオールとエチレ
ン性不飽和単量体との反応は、特に制限はなく、反応開
始剤としてラジカル開始剤などを用いる通常のエチレン
性単量体の東金法が利用出来る。The reaction between the polyol having an unsaturated bond and the ethylenically unsaturated monomer in the present invention is not particularly limited, and the usual Togane method for ethylenic monomers using a radical initiator or the like as a reaction initiator can be used. .
本発明の反応に際しては、必要に応じて溶媒を用いるこ
とができる。例えば、酢酸ブチル、シクロヘキサン、ル
ーへブタンなど通常のエチレン性単量体の重合に用いる
溶媒はすべて用いることができる。In the reaction of the present invention, a solvent can be used as necessary. For example, all solvents commonly used in the polymerization of ethylenic monomers, such as butyl acetate, cyclohexane, and rougebutane, can be used.
更に、不飽和結合を有するポリオールと本発明のエチレ
ン性不飽和単量体の量比は１００／２０〜４００（重１
ｋｔ）が望ましい。ポリオール１００嵐量部に対してエ
チレン性不飽和単量体が２０重量部未満の場合は分散剤
としての性能が低下し、ポリウレタンを製造する際、分
散剤の仕込み量を多くする必要が生じ、経済的に不利と
なる。ポリオール１００重量部に対してエチレン性不飽
和単量体が４００重量部を超えると非水分散重合の際、
極性と非極性のバランスが失なわれ、分散剤としての効
果が発揮されなくなる。Furthermore, the quantitative ratio of the polyol having an unsaturated bond to the ethylenically unsaturated monomer of the present invention is 100/20 to 400 (by weight 1
kt) is desirable. If the amount of ethylenically unsaturated monomer is less than 20 parts by weight per 100 parts of polyol, the performance as a dispersant will deteriorate, and when producing polyurethane, it will be necessary to increase the amount of dispersant charged. It will be economically disadvantageous. If the amount of ethylenically unsaturated monomer exceeds 400 parts by weight per 100 parts by weight of polyol, during non-aqueous dispersion polymerization,
The balance between polarity and non-polarity is lost, and the effect as a dispersant is no longer exhibited.
本発明の非水分散重合用分散剤は、非水分散重合法でポ
リウレタンを製造する際の分散剤として使用することが
できるが、このポリウレタンとしては、通常の熱可塑性
ポリウレタン樹脂、必要に応じてインシアネート基ある
いは、ブロックイソシアネート基を含有させた不完全熱
可塑性ポリウレタン樹脂、あるいは熱硬化ポリウレタン
樹脂などである。The dispersant for non-aqueous dispersion polymerization of the present invention can be used as a dispersant when producing polyurethane by a non-aqueous dispersion polymerization method. These include incompletely thermoplastic polyurethane resins containing incyanate groups or blocked isocyanate groups, or thermosetting polyurethane resins.
ポリウレタン社基本的にポリオール、鎖延長剤およびポ
リイソシアネートから構成される。Polyurethanes are basically composed of polyols, chain extenders and polyisocyanates.
とれらポリウレタンを構成するポリオールとしては、少
なくとも２個の活性水素基を有する化合物を全て包含す
る。例としては、ポリエステルポリオール、ポリアルキ
レンエーテルポリオール、ポリカーボネートポリオール
およびこれらの混合物などがあげられる。The polyol constituting the polyurethane includes all compounds having at least two active hydrogen groups. Examples include polyester polyols, polyalkylene ether polyols, polycarbonate polyols, and mixtures thereof.
ポリウレタンを構成する鎖延長剤としては、１分子当り
少なくとも２個の活性水素基を含有し、約６０〜約３０
０の分子量をもつものが使用出来る。The chain extender constituting the polyurethane contains at least two active hydrogen groups per molecule, and has a molecular weight of about 60 to about 30.
Those with a molecular weight of 0 can be used.
ポリウレタンを構成するポリイソシアネートとしては、
少なくとも２個のイソシアネート基を有する化合物を使
用することが出来る。これらの例としては、トリレンジ
イソシアネート、キシリレンジイソシアネート、４．４
′−ジフェニルメタンジインシアネートなどの芳香族ジ
イソシアネー） 、１．．６−へキサメチレンジイソシ
アネート、ｊ、１２−ドデカンジインシアネートなどの
脂肪族ジイソシアネート、シクロヘキサン１，４−ジイ
ンシアネート、インホロンジイソシアネートなどの脂環
式ジイソシアネートなどがあけられる。また、これら化
合物と活性水素基含有化合物との反応によるイソシアネ
ート基末端化合物、カルボジイミド化反応、イソシアヌ
レート化反応などによるインシアネート変性体、アニリ
ンとホルムアルデヒドとの縮合物をホスゲン化したもの
などのポリイソシアネートなどもあげられる。また、メ
タノール、鴇−メタノール、ベンジルアルコール、ε−
カグロラクタム、メチルエチルケトンオキシム、フェノ
ール、クレゾールなどの活性水素を分子内に１個有する
適当なブロック剤で一部または全部を安定化したポリイ
ソシアネートなどを使用することもできる。The polyisocyanates that make up polyurethane include:
Compounds having at least two isocyanate groups can be used. Examples of these include tolylene diisocyanate, xylylene diisocyanate, 4.4
1. Aromatic diisocyanates such as '-diphenylmethane diincyanate), 1. ．． Aliphatic diisocyanates such as 6-hexamethylene diisocyanate and j,12-dodecane diisocyanate, and alicyclic diisocyanates such as cyclohexane 1,4-diisocyanate and inphorone diisocyanate can be used. In addition, polyisocyanates such as isocyanate group-terminated compounds obtained by the reaction of these compounds with active hydrogen group-containing compounds, incyanate modified products obtained by carbodiimidation reactions, isocyanurate reactions, etc., and phosgenated condensates of aniline and formaldehyde, etc. etc. can also be mentioned. In addition, methanol, sulfur-methanol, benzyl alcohol, ε-
It is also possible to use polyisocyanates partially or completely stabilized with a suitable blocking agent having one active hydrogen in the molecule, such as caglolactam, methyl ethyl ketone oxime, phenol, and cresol.
ホリウレタンを製造するためのポリオール、鎖延長剤お
よびポリイソシアネートの配合内容は、ポリウレタンの
使用目的により異なるので限定出来ないが、鎖延長剤と
ポリオールのモル比は通常１／１０からｌＯ／１の範囲
が好ましく、場合によっては鎖延長剤を使わないことも
ある。また、ポリイソシアネートのイソシアネート基と
ポリオールおよび鎖延長剤の活性水素基のモル比は通常
１．５から０．８の範囲が好ましい。これらポリウレタ
ンの製造に使用する本発明の分散剤は、活性水素基を有
しているので、ポリインシアネート配合量は分散剤の使
用量により調節する必要がある。分散剤の配合量は通常
ポリウレタンに対してｌから２０重量％である。The blending contents of polyol, chain extender and polyisocyanate for producing polyurethane cannot be limited as they vary depending on the intended use of the polyurethane, but the molar ratio of chain extender and polyol is usually from 1/10 to 1O/1. range is preferred, and in some cases, chain extenders may not be used. Further, the molar ratio of the isocyanate groups of the polyisocyanate to the active hydrogen groups of the polyol and chain extender is usually preferably in the range of 1.5 to 0.8. Since the dispersant of the present invention used for producing these polyurethanes has an active hydrogen group, the amount of polyinsyanate blended must be adjusted by the amount of the dispersant used. The amount of the dispersant added is usually 1 to 20% by weight based on the polyurethane.
非水分散重合法の基本となる技術は、特公昭４４−３０
７３６号公報によシ開示されておシ、ポリウレタンへの
応用は、特公昭５７−２９４８５号公報によシ開示され
ている。非水分散点合法を要約すれば、水以外の有機液
体を媒体として単量体を重合させ、有機媒体を述絖相と
して重合体を不連続の粒子状で生成させる方法である。The basic technology of the non-aqueous dispersion polymerization method is
Application to polyurethane is disclosed in Japanese Patent Publication No. 57-29485. To summarize, the non-aqueous dispersion point method is a method in which a monomer is polymerized using an organic liquid other than water as a medium, and the polymer is produced in the form of discontinuous particles using the organic medium as a precipitate phase.
この場合、分散剤を加えて安定した状態で重合体を生成
させる技術が用いられ、分散剤の選択は極めてＸ要であ
る。In this case, a technique is used in which a dispersant is added to form a polymer in a stable state, and the selection of the dispersant is extremely important.
本発明における非水分散重合法に用いられる有機媒体は
、生成する粒子状重合体に対して不溶性で、重合反応を
阻害しない不活性な性質を有するものである。本発明で
は、例えば、ルーへキサン、オクタン、ドデカン、流動
パラフィンなどの脂肪族または、シクロヘキサンのよう
な脂環族炭化水素類などが用いられる。反応温度を考慮
すると沸点が６０℃以上のものが好ましい。これらは単
独または２種以上の混合物で用いることができる。The organic medium used in the non-aqueous dispersion polymerization method of the present invention is insoluble in the particulate polymer produced and has inert properties that do not inhibit the polymerization reaction. In the present invention, for example, aliphatic hydrocarbons such as roohexane, octane, dodecane, liquid paraffin, and alicyclic hydrocarbons such as cyclohexane are used. Considering the reaction temperature, those having a boiling point of 60° C. or higher are preferred. These can be used alone or in a mixture of two or more.
連続相となる有機媒体と分散相となるポリウレタンとの
量比は、総量に対してポリウレタンが１０〜８０重量％
となる範囲が好ましい。生産効率、コスト上から４０重
量−以上が特に好ましい。The weight ratio of the organic medium serving as the continuous phase to the polyurethane serving as the dispersed phase is 10 to 80% by weight of polyurethane based on the total amount.
It is preferable that the range is as follows. From the viewpoint of production efficiency and cost, it is particularly preferable to have a weight of 40 mm or more.
ポリウレタンの反応速度を増加し、かつ反応を完全にす
るため、触媒を使用する仁とが望ましい。It is desirable to use a catalyst to increase the reaction rate of the polyurethane and to complete the reaction.
この触媒の例としては、ジプチルスズジラウレート、第
１スズオクトエート、Ｎ−メチルモルホリンおよびトリ
エチルアミンのよう々第三アミン、ナフテン酸鉛、鉛オ
クトエートなどである。これら触媒は触媒作用を与える
のに必要な量を用いるが、その量はポリウレタン組成に
対して通常０．０１−１重量−程度が好ましい。Examples of such catalysts are tertiary amines such as diptyltin dilaurate, stannous octoate, N-methylmorpholine and triethylamine, lead naphthenate, lead octoate, and the like. These catalysts are used in an amount necessary to provide a catalytic effect, and the amount is preferably about 0.01-1% by weight based on the polyurethane composition.
本発明における分散剤、ポリオール、鎖延長剤およびポ
リイソシアネートからなる反応体を有機媒体に分散させ
るためには公知のあらゆる形式の乳化装置を使用しても
よい。また、仕込法は、全ての原料を同時に仕込んでも
よく、目的に反して段階的に仕込んでもよい。段階的な
仕込み方として、
（１） 分散剤、ポリオール、鎖延長剤の混合物に有
機媒体を加え乳化（分散）し、ポリイックアネートを仕
込む
（２）分散剤、ポリオール、ポリインシアネートの混合
物に有機媒体を加え乳化し、その直後あるいは反応を進
行させた後鎖姑長剤を仕込む。Any type of emulsifying equipment known in the art may be used to disperse the reactants of the present invention, consisting of a dispersant, polyol, chain extender, and polyisocyanate, in an organic medium. Further, in the charging method, all the raw materials may be charged simultaneously, or may be charged in stages against the purpose. As a step-by-step preparation method, (1) Add an organic medium to the mixture of the dispersant, polyol, and chain extender, emulsify (disperse), and then add the polyicanate. (2) Add the polyicanate to the mixture of the dispersant, polyol, and polyincyanate. An organic medium is added and emulsified, and a chain lengthening agent is added immediately after or after the reaction has proceeded.
（３） 予め分散剤、ポリオールとポリインシアネー
トとを反応させ、プレポリマーにし、有機媒体を加え乳
化し、鎖延長剤を仕込む。(3) A dispersant, polyol, and polyincyanate are reacted in advance to form a prepolymer, an organic medium is added to emulsify, and a chain extender is added.
などの方法がある。触媒の仕込みはどの時点でも良いが
、全量の仕込みが終ってから仕込むのが好ましい。There are other methods. The catalyst may be added at any time, but it is preferable to add the catalyst after the entire amount has been added.
このようにして得られる粒子状ポリウレタンは、反応中
または反応後に必要に応じてメタノール、ｅ−カグロラ
クタム、メチルエチルケトンオキシム、フェノールなど
の活性水素を分子内に１個有する適当なブロック剤を添
加反応させて安定化させることが出来る。該分散体溶液
は、このままで塗料、接着剤として使用することもでき
る。The particulate polyurethane obtained in this way is reacted by adding a suitable blocking agent having one active hydrogen in the molecule, such as methanol, e-caglolactam, methyl ethyl ketone oxime, or phenol, as necessary during or after the reaction. It can be stabilized. The dispersion solution can also be used as it is as a paint or adhesive.
このようにして得られた粒子状ポリウレタンは、濾過ま
たはデカンテーショ／し、次いで常圧ま九は減圧下で乾
燥することによって分散溶液から回収できる。得られ良
ポリウレタン粉末は、平均粒子が０．１〜２０００μｍ
およびそれ以上の範囲にある粒子体である。該粉末は、
各徳成形用材料、粉体塗料、各種改質剤、充填剤など広
範囲に利用することができる。The particulate polyurethane thus obtained can be recovered from the dispersion solution by filtration or decantation and then drying under normal or reduced pressure. The obtained polyurethane powder has an average particle size of 0.1 to 2000 μm.
It is a particle body in the range of The powder is
It can be used in a wide range of applications, including molding materials, powder coatings, various modifiers, and fillers.
次に本発明について実施例によりさらに詳細に説明する
。Next, the present invention will be explained in more detail with reference to Examples.
実施例１゜
（１） 分子内に不飽和結合を有するポリオールの合
成
２１の４つロフラスコに、攪拌機、温度計、留出塔、Ｎ
、ガス導入管を付け、アジピン酸６６０Ｊ／。Example 1゜(1) Synthesis of polyol having unsaturated bonds in the molecule A four-hole flask was equipped with a stirrer, a thermometer, a distillation column, and N
, gas inlet tube attached, adipic acid 660J/.
無水マレインｆｆ１９８．ｌｉ！、エチレングリコール
４１０ｇ、オクテンｍ第１スズ０．０５，９を計りとり
、Ｎ、ガスを流しながら加熱混合する。１２０〜１６０
℃で縮合水を糸外に出した後、系内を徐々に減圧しなが
ら反応を続け、最終的に１９０℃、３０１１Ｈｐの条件
で４時間反応した後反応終了とした。得られたポリエス
テルは水酸基価１０４ ｒｐｒｆｌＫＯＨ／９、酸価２
．６ ｍ９ＫＯＨ／９であった。このポリエステルは分
子量１１７０で、１分子中に平均１モルの２亜結合を有
する。Anhydrous malein ff198. li! , 410 g of ethylene glycol, and 0.05.9 g of octene m stannous were weighed and mixed under heating while flowing N gas. 120-160
After condensation water was discharged from the filament at 190° C., the reaction was continued while gradually reducing the pressure inside the system, and the reaction was finally completed after 4 hours of reaction at 190° C. and 3011 Hp. The obtained polyester had a hydroxyl value of 104 rprflKOH/9 and an acid value of 2.
．． It was 6 m9KOH/9. This polyester has a molecular weight of 1170 and an average of 1 mole of 2 subbonds per molecule.
（２）分散剤の合成
５００ Ｆ＋１／の４つロフラスコに攪拌機、温度計、
滴下ロート、冷却器を付け、（１）で合成したポリオー
ル７４９と酢酸ブチル９９ｇを計りとる。Ｎ、ガスを滴
下ロートの上部から系内に流しながら加熱混合する。１
１０℃になりたとき、滴下ロートから２−エチルへキシ
ルメタアクリレート７４ｇとベンゾイルパーオキサイド
１．５ｇの溶解混合物を滴下開始する。(2) Synthesis of dispersant A stirrer, a thermometer, a 500 F+1/4-hole flask,
Attach a dropping funnel and a condenser, and weigh out 749 g of the polyol synthesized in (1) and 99 g of butyl acetate. N and gas are heated and mixed while flowing into the system from the top of the dropping funnel. 1
When the temperature reached 10°C, dropwise addition of a dissolved mixture of 74 g of 2-ethylhexyl methacrylate and 1.5 g of benzoyl peroxide was started from the dropping funnel.
１時間で滴下終了し、その後１３０℃で２時間反応させ
反応終了とした。この分散剤の水酸基価は４１ｍｙｘｏ
ｉｉ／ｇであった。The dropwise addition was completed in 1 hour, and the reaction was then continued at 130° C. for 2 hours to complete the reaction. The hydroxyl value of this dispersant is 41myxo
ii/g.
（３）ポリウレタン粉末の合成
５００ ｍｌの４つロセパラプルフラスコにプロペラ製
羽根の攪拌機、温度計、冷却器を付け、（２）で得られ
た分散剤９．１．９（０，００３モル）、６０℃に加熱
した分子量１０σ０のポリエチレンアジペー） ５７．
２９（０，０５７モル）、１．４−ブタンジオール５．
１ｇ（０，０５７モル）を仕込み均一に混合する。５０
°Ｃのジフェニルメタンジイソシアネート２９．３ｇ（
０，１１７モル）を加え、均一に混合した後、セルゾー
ル７１（５ｈｅｌｌ ｓｏｌ ７１シエル化学製、沸点
１７０〜２００°Ｃのパラフィン以下同じ） ｃｉｌｙ
を加え、高速に（約１００Ｏｒｐｍ）攪拌し乳化させる
。次いでジブチルスズジラウレートを０．０１ｊ９添加
し、攪拌同転数をおとして（約６００ｒｐｍ）１時間室
温で反応させた。７０℃に昇温し３時間反応させて、セ
ルゾール７１中に分散した粒子状のポリウレタン重合体
を得た。この分散体を静置し、デカンテーションにより
上置液を除去し、減圧下で乾燥してポリウレタン粉末を
得九。この粉末は主粒子径約２０〜１５０μｍであった
。(3) Synthesis of polyurethane powder Four 500 ml rosette parapul flasks were equipped with a propeller blade stirrer, a thermometer, and a condenser. ), polyethylene adipe with a molecular weight of 10σ0 heated to 60°C) 57.
29 (0,057 mol), 1,4-butanediol5.
Add 1 g (0,057 mol) and mix uniformly. 50
29.3 g of diphenylmethane diisocyanate at °C (
After adding 0,117 mol) and mixing uniformly, add Selsol 71 (5hell sol 71 manufactured by Shell Chemical, paraffin with a boiling point of 170 to 200°C and the same below) cily
and stir at high speed (approximately 100 rpm) to emulsify. Next, 0.01j9 of dibutyltin dilaurate was added, and the stirring speed was lowered (approximately 600 rpm) to allow reaction at room temperature for 1 hour. The temperature was raised to 70° C. and the mixture was reacted for 3 hours to obtain a particulate polyurethane polymer dispersed in Celsol 71. This dispersion was allowed to stand, the supernatant liquid was removed by decantation, and the dispersion was dried under reduced pressure to obtain a polyurethane powder. This powder had a main particle size of about 20-150 μm.
実施例２゜
（１）分子内に不飽和結合を有するポリオールの合成
実施例１０、（りで用いたのと同様のフラスコＫ、分子
量１０００のポリブチレンアジペート（曲品名二ツボラ
ン４００９ 、日本ポリウレタン工業製、水酸基価１１
０ ｍｆＫＯＨ／９ ） １０００ 、ｊｉ＋および無
水マイレｙｄ４９ｊ９を計シとり、Ｎ２ガスを流しなが
ら加熱混合する。Example 2゜(1) Synthesis of polyol having unsaturated bonds in the molecule Example 10, flask K similar to that used in (2), polybutylene adipate with a molecular weight of 1000 (product name Futsuboran 4009, Nippon Polyurethane Kogyo) made, hydroxyl value 11
0 mfKOH/9) 1000, ji+, and anhydrous Miley yd49j9 were weighed and heated and mixed while flowing N2 gas.
１４０〜１６０℃で縮合水を系外に出した後、系内を徐
々に減圧しながら反応を続け、最終的に１９０″Ｃ１３
９１１１１Ｈｐの条件で４時間反応した後反応終了とし
た。After letting the condensed water out of the system at 140-160℃, the reaction continued while gradually reducing the pressure inside the system, and finally the temperature was 190"C13.
The reaction was terminated after 4 hours of reaction under conditions of 91111 Hp.
ポリエステルは水酸基価５３ＦＩＩνＫＯＨ／ＩＩ％酸
価４．１ｍｐＫＯＨ／、ｊｉ！であった。このポリエス
テルは分子量２１００で、１分子中に平均１モルの２重
結合を有する。The polyester has a hydroxyl value of 53FIIνKOH/II% and an acid value of 4.1mpKOH/, ji! Met. This polyester has a molecular weight of 2100 and an average of 1 mole of double bonds in one molecule.
（２）分散剤の合成
実施例１ 、 （２）で用いたのと同様のフラスコに、
（１）で合成したポリオールを４４ｇおよび酢酸ブチル
を９９ｙ計りとる。Ｎ、ガスを滴下ロートの上部から系
内に流しながら加熱混合する。１１０℃になりたとき、
滴下ロートから２−エチルへキシルメタアクリレート５
１Ｊ、ラウリルメタアクリレート５１ｇおよびベンゾイ
ルパーオキサイド２Ｉの溶解混合物を滴下開始する。１
時間半で滴下終了し、その後１３０℃で２時間反応させ
反応終了とした。この分散剤の水酸基価は１１ゎ、ＫＯ
Ｈ７’ｇでめった。(2) Synthesis of dispersant Example 1 In a flask similar to that used in (2),
Weigh out 44g of the polyol synthesized in (1) and 99y of butyl acetate. N and gas are heated and mixed while flowing into the system from the top of the dropping funnel. When the temperature reached 110℃,
2-ethylhexyl methacrylate from the dropping funnel 5
1J, 51 g of lauryl methacrylate, and benzoyl peroxide 2I are started to be added dropwise. 1
The dropwise addition was completed in half an hour, and the reaction was then allowed to proceed at 130° C. for 2 hours to complete the reaction. The hydroxyl value of this dispersant is 11ゎ, KO
I got it at H7'g.
（３） ポリウレタン粉末の合成
実施例１． （３）で用いたのと同様のフラスコに、（
２）で得られた分散剤１８．２ ｇ （ｏ、Ｏｏｚモル
）、６０°Ｃに加熱したニラポラン４００９．５７．２
ｇ（０，０５６モル）、ｌ、４−プタンジオール５．
０ ｇ（０，０５６モル）を仕込み均一に混合する。５
０″Ｃのジフェニルメタンジイソシアネート２８．５ｇ
（０，１１４モル）を加え、均一に混合した後、ＩＰソ
ルベント１６２０ （出光石油化手製、沸点１７０〜２
００”Ｃのパラフィン）９０ｇを加え、高速に（約１０
１０００ｒｐ攪拌し乳化させる。次いでジブチルスズジ
ラウレートを０．０１ｇ添加し、攪拌回転数をおとして
（約６０Ｏｒｐｍ ） １時間室温で反応させた。７０
℃に昇温し３時間反応させて、ＩＰソルベント中に分散
した粒子状のポリウレタン重合体を得た。この分散体を
静置し、デカンテーションによシ上澄液を除去し、減圧
下で乾燥してポリウレタン粉末を得た。この粉末は主粒
子径約ｌＯ〜１３０μｍでありた。(3) Polyurethane powder synthesis example 1. In a flask similar to that used in (3), (
18.2 g (o, Ooz mol) of the dispersant obtained in 2), Niraporan 4009.57.2 heated to 60 °C
g (0,056 mol), 1,4-butanediol5.
Add 0 g (0,056 mol) and mix uniformly. 5
28.5g of 0″C diphenylmethane diisocyanate
(0,114 mol) and mixed uniformly, IP Solvent 1620 (manufactured by Idemitsu Petrochemical, boiling point 170-2
Add 90g of 00”C paraffin) and mix at high speed (approx.
Stir at 1000 rpm to emulsify. Next, 0.01 g of dibutyltin dilaurate was added, and the stirring rotation speed was reduced (approximately 60 rpm) to allow reaction at room temperature for 1 hour. 70
The temperature was raised to .degree. C. and the mixture was reacted for 3 hours to obtain a particulate polyurethane polymer dispersed in the IP solvent. This dispersion was allowed to stand, the supernatant liquid was removed by decantation, and the dispersion was dried under reduced pressure to obtain a polyurethane powder. This powder had a main particle size of about 10 to 130 μm.
実施例３゜
（１）分子内に不飽和結合を有するポリオールの合成
実施例１、（１）で用いたのと同様のフラスコに分子量
、１０００のポリへキサメチレンカーボネートジオ−／
Ｉ／（商品名ニラポラン９８１、日本ポリウレタン工業
製、水酸基価１１５ ｍ ｆＫＯＨ７ｇ ） ９８０．
９および無水マレイン酸４９ｇを計シとり、実施例１１
、（すと同じ方法で反応させた。得られたポリオールは
水酸基価５７町ＫＯＨ７ｇ、酸価４．２町ＫＯＨ／、９
でありた。Example 3゜(1) Synthesis of polyol having unsaturated bonds in the molecule Into a flask similar to that used in Example 1, (1) was added polyhexamethylene carbonate diol having a molecular weight of 1000.
I/(trade name Niraporan 981, manufactured by Nippon Polyurethane Industries, hydroxyl value 115 m fKOH7 g) 980.
Example 11
(The reaction was carried out in the same manner as above.The obtained polyol had a hydroxyl value of 57 KOH7g, an acid value of 4.2 KOH/, 9
It was.
このポリオールは分子量１９７０で、１分子中に平均１
モルの２重結合を有する。This polyol has a molecular weight of 1970, with an average of 1 per molecule.
It has moles of double bonds.
（２）分散剤の合成
実施例１ 、（２）で用いたのと同様のフラスコに、（
１）で合成したポリオールを４４９および酢酸ブチルを
９９９計りとる。Ｎ、ガスを滴下ロートの上部から系内
に流しながら加熱混合する。１１０°Ｃになりたとき、
滴下ロートからラウリルメタアクリレート１０３ｙおよ
びベンゾイルパーオキサイド２ｙの溶解混合物を滴下開
始する。１時間半で滴下終了し、その後１３０℃で２時
間反応させ反応終了とした。(2) Synthesis of dispersant Example 1 In a flask similar to that used in (2), (
Weigh out 449 g of the polyol synthesized in 1) and 999 g of butyl acetate. N and gas are heated and mixed while flowing into the system from the top of the dropping funnel. When the temperature reached 110°C,
A dissolved mixture of lauryl methacrylate 103y and benzoyl peroxide 2y is started dropping from the dropping funnel. The dropwise addition was completed in 1.5 hours, and the reaction was then allowed to proceed at 130° C. for 2 hours to complete the reaction.
この分散剤の水酸基価は１３ｍｇＫＯＨ／ｉでありた。The hydroxyl value of this dispersant was 13 mgKOH/i.
（３） ポリウレタン粉末の合成
実施例１ 、 （３）で用いたのと同様のフラスコＫ、
（２）で得られた分散剤９．１ｇ（０，００１モル）、
７０”ＣｌＩＣ加熱した分子量ｇｏｏｏのポリへキサメ
チレンカーボネートジオール（商品名ニラポラン９８０
、日本ポリウレタン工業製、水酸基価５６．９ ｍｇＫ
ＯＨ／ｇ）を、６７９ （０，０３４モル）、１．４−
ブタンジオール６．１．９ （０，０６８モル）を仕込
み、均一に混合する。ヘキサメチレンジイソシアネー）
１７．３．９（０，１０３モル）を加え、均一に混合
した後、セルゾール７１９０ｇを加え、高速に（約１０
００ ｒｐｍ ）攪拌し乳化させる。次いでジブチルス
ズジラウレートｔ−０，０３ｇ添加し、攪拌回転数をお
として（約６ｏｏｒｐｍ） １時間室温で反応させた
。(3) Polyurethane powder synthesis Example 1, flask K similar to that used in (3),
9.1 g (0,001 mol) of the dispersant obtained in (2),
70” ClIC heated polyhexamethylene carbonate diol (trade name Niraporan 980) with molecular weight gooo
, manufactured by Nippon Polyurethane Industries, hydroxyl value 56.9 mgK
OH/g), 679 (0,034 mol), 1.4-
Charge 6.1.9 (0,068 mol) of butanediol and mix uniformly. hexamethylene diisocyanate)
After adding 17.3.9 (0,103 mol) and mixing uniformly, add 7190 g of Celsol and mix at high speed (approximately 10
00 rpm) Stir to emulsify. Next, 0.03 g of dibutyltin dilaurate was added, and the stirring speed was reduced (about 6 oorpm) and the reaction was allowed to proceed at room temperature for 1 hour.
９０℃に昇温し、５時間反応させてセルゾール７１中に
分散した粒子状のポリウレタン重合体を得た。The temperature was raised to 90° C. and the mixture was reacted for 5 hours to obtain a particulate polyurethane polymer dispersed in Celsol 71.
この分散体を静置し、デカンテーションによシ上漬液を
除去し、減圧下で乾燥してポリウレタン粉末を４！４た
。この粉末の主粒子径は４０〜１５０μ属であった。次
に、粉末からシート・を成形した。シリコン糸離型剤を
塗布した２００ Ｘ ２００Ｈの鉄板を２００℃に加熱
しておき、この鉄板上に本発明のポリウレタン粉末勿落
し、溶融成形した。冷却後、シートをはがし、約１ ｉ
ｎ厚さの成形物をえた。この成形物を８０”Ｑ、２日間
加熱した後、成形物の表面状態を観察したが、分散剤な
どのブリードはみられなかりた。This dispersion was allowed to stand, the supernatant solution was removed by decantation, and the dispersion was dried under reduced pressure to obtain 4:4 polyurethane powder. The main particle diameter of this powder was 40 to 150 microns. Next, a sheet was formed from the powder. A 200 x 200H iron plate coated with a silicone thread mold release agent was heated to 200°C, and the polyurethane powder of the present invention was dropped onto the iron plate and melt-molded. After cooling, peel off the sheet and dry for about 1 i
A molded product with a thickness of n was obtained. After heating this molded product at 80''Q for 2 days, the surface condition of the molded product was observed, and no bleeding of the dispersant or the like was observed.
実施例４゜
実施例３で合成した分散剤を用いてポリウレタン粉末の
合成を行なった。Example 4 Using the dispersant synthesized in Example 3, polyurethane powder was synthesized.
実施例１． （３）で用いたのと同様のフラスコに、実
施例３． （２）で得られた分散剤９．１１Ｉ（０，０
０１モル八７０″ＯＫ加熱した分子量１０００のポリへ
キサメチレンカーボネートジオールにツボラン９８１．
水酸基価１１５町ＫＯＨ／ｇ）を５５．７．９ （０，
０５７モル）％１．４−ブタンジオール５．１９ （０
，０５７モル）を仕込み、均一に混合する。４，４′−
ジシクロヘキシルメタンジイソシアネ 一ト３０．
１ｇ（０，１１５モル）を加え、均一に混合した後、セ
ルゾール７１１００Ｊを加え、高速に（約１０００ ｒ
ｐｒｒり攪拌し乳化させる。次いでジブチルスズジラウ
レートトをｏ、ｏ３．ｙ添加し、攪拌回転数をおとして
（約６０゜ｒｐｍ）、１時間室温で反応させた。９０℃
に昇温し、６時間反応させてセルゾール７１中に分散し
た粒子状のポリウレタン重合体を得た。この分散体を減
圧下で溶媒を除去しポリウレタン粉末を得た。Example 1. In a flask similar to that used in (3), Example 3. Dispersant 9.11I (0,0
Tuborane 981.
Hydroxyl value 115 KOH/g) 55.7.9 (0,
057 mol)% 1.4-butanediol 5.19 (0
,057 mol) and mix uniformly. 4,4'-
Dicyclohexylmethane diisocyanate 30.
After adding 1 g (0,115 mol) and mixing uniformly, add Selsol 71100J and mix at high speed (approximately 1000 r
Stir to emulsify. Then dibutyltin dilaurate was added to o, o3. y was added, the stirring speed was reduced (approximately 60° rpm), and the reaction was allowed to proceed at room temperature for 1 hour. 90℃
The temperature was raised to 1, and the reaction was carried out for 6 hours to obtain a particulate polyurethane polymer dispersed in Celsol 71. The solvent was removed from this dispersion under reduced pressure to obtain polyurethane powder.
この粉末の主粒子径は２０〜１５０μｍでおった。この
ポリウレタン粉末を実施例ａ 、（３）と同じ方法でシ
ート成形した。更に、１６０〜１８０℃、１５〜２０ｋ
ｐ／ｃ＋＋ｆのプレス条件で５分間プレスし、厚さ０．
５１轟のプレスシートを得た。このシートをハ５Ｋ６７
２３の方法で機械的強度を求めたところ、引張９強さ５
３０’ｊ’／Ｌ１ｆｔ、伸び２８０％でる−）死。The main particle diameter of this powder was 20 to 150 μm. This polyurethane powder was formed into a sheet in the same manner as in Example a, (3). Furthermore, 160-180℃, 15-20k
Pressed for 5 minutes under press conditions of p/c++f to a thickness of 0.
A press sheet of 51 Todoroki was obtained. This sheet is 5K67
When the mechanical strength was determined using the method of 23, the tensile strength was 9 and 5.
30'j'/L1ft, elongation 280% -) Death.
実施例５゜
実施例２ 、 （３）で使用したジフェニルメタンジイ
ソシアネート２８．５ｇを１．４−シクロヘキシルジイ
ソシアネー） １８．９ｇ（０，１１４モル）にし、ジ
プテルスズジ２ウレートの量を０．０１ｇから０．０３
，９にし、また、７０℃、３時間の反応時間を９０℃６
時間にし九ほかは実施例２、（３）と同じようセしてボ
替ウレタン粉末の合成を行なった。このようにして得た
ポリウレタン粉末は主粒子径約１０〜１００μｍであっ
た。Example 5 28.5 g of diphenylmethane diisocyanate used in Examples 2 and (3) was changed to 18.9 g (0,114 mol) of 1,4-cyclohexyl diisocyanate, and the amount of diptertin di2urate was changed from 0.01 g to 0.03
, 9, and the reaction time was 90°C for 3 hours at 70°C.
A replacement urethane powder was synthesized in the same manner as in Examples 2 and (3) except for the following time. The polyurethane powder thus obtained had a main particle size of about 10 to 100 μm.
比較例 ｌ。Comparative example l.
（１） 分散剤の合成
実施例１、（２）で用いたのと同様のフラスコに、セル
ゾール？１．９７．７ｇを仕込み、Ｎ、ガスを滴下ロー
トの上部から系内に流しながら加熱した。あらかじめｔ
Ｉ４Ｍシたラウリルメタアクリレート１１９ｙ（０，４
７モル）、メチルメタクリレ−） ２７．５７（０，２
８モル）およびベンゾイルパーオキサイド２．５９の混
合物を攪拌しながら同温度で２時間かけて滴下した。１
４０℃に昇温し４時間反応させて分散剤を得た。(1) Synthesis of dispersant In a flask similar to that used in Example 1 and (2), add Celsol? 1.97.7 g was charged and heated while flowing N and gas into the system from the top of the dropping funnel. t in advance
I4M lauryl methacrylate 119y (0,4
7 mol), methyl methacrylate) 27.57 (0,2
A mixture of 8 mol) and 2.59 mol of benzoyl peroxide was added dropwise over 2 hours at the same temperature with stirring. 1
The temperature was raised to 40°C and the mixture was reacted for 4 hours to obtain a dispersant.
（２） ポリウレタン粉末の合成
分散剤として（１）の分散剤を９．１ｇ用いた以外は実
施例１ 、（３）と同じ方法で乳化させた。この結果、
反応体はセルゾール７１に分散が悪く塊状となった。(2) Synthesis of polyurethane powder Emulsification was carried out in the same manner as in Examples 1 and (3) except that 9.1 g of the dispersant of (1) was used as the dispersant. As a result,
The reactant was poorly dispersed in Celsol 71 and became lumpy.
本発明によって得られる非水分散重合用分散剤は、ポリ
ウレタン粉末の製造に於て優れた分散性能を有し、更に
構成成分であるポリインシアネートと反応するので、成
形品などにブリードすることがなく、優れた物性を有す
る。The dispersant for non-aqueous dispersion polymerization obtained by the present invention has excellent dispersion performance in the production of polyurethane powder, and furthermore, since it reacts with the constituent polyincyanate, it does not bleed into molded products etc. , has excellent physical properties.
また、該分散剤を用いたポリウレタン分散体は、分散体
溶液のままで塗料、接着剤として利用することが出来る
。本発明によって得られるポリウレタン粉末は、各柚成
形用材料、粉体塗料、各種改質剤、充填剤など広範囲な
用途がある。Further, a polyurethane dispersion using the dispersant can be used as a coating material or adhesive as a dispersion solution. The polyurethane powder obtained by the present invention has a wide range of uses, including various yuzu molding materials, powder coatings, various modifiers, and fillers.
Claims (1)
部に対して炭素数６以上の炭化水素基からなる側鎖を有
するエチレン性不飽和単量体２０から４００重量部を反
応せしめることを特徴とする非水分散重合用分散剤組成
物。 ２、非水分散重合法によりポリウレタン系粉末重合体を
製造するに際して１項の分散剤を重合体組成の一部とし
て用いることを特徴とするポリウレタン組成物。[Claims] 1. 20 to 400 parts by weight of an ethylenically unsaturated monomer having a side chain consisting of a hydrocarbon group having 6 or more carbon atoms per 100 parts by weight of a polyol having an unsaturated bond in the molecule. A dispersant composition for non-aqueous dispersion polymerization characterized by causing a reaction. 2. A polyurethane composition characterized in that the dispersant of item 1 is used as part of the polymer composition when producing a polyurethane powder polymer by a non-aqueous dispersion polymerization method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63071978A JPH01245013A (en) | 1988-03-28 | 1988-03-28 | Dispersant composition for nonaqueous dispersion polymerization and polyurethane composition using said composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63071978A JPH01245013A (en) | 1988-03-28 | 1988-03-28 | Dispersant composition for nonaqueous dispersion polymerization and polyurethane composition using said composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4236322A Division JPH0772221B2 (en) | 1992-08-13 | 1992-08-13 | Polyurethane composition using dispersant for non-aqueous dispersion polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01245013A true JPH01245013A (en) | 1989-09-29 |
| JPH0547564B2 JPH0547564B2 (en) | 1993-07-19 |
Family
ID=13476061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63071978A Granted JPH01245013A (en) | 1988-03-28 | 1988-03-28 | Dispersant composition for nonaqueous dispersion polymerization and polyurethane composition using said composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01245013A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0397711A (en) * | 1989-09-08 | 1991-04-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of polymeric granule |
| JPH03124717A (en) * | 1989-10-09 | 1991-05-28 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate microcapsule |
| JPH04132717A (en) * | 1990-09-26 | 1992-05-07 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate-based resin dispersion composition |
| JP2008163228A (en) * | 2006-12-28 | 2008-07-17 | Mitsui Chemicals Inc | Manufacturing method of biodegradable polymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036523A (en) * | 1983-08-09 | 1985-02-25 | Hitachi Chem Co Ltd | Manufacture of granular polymer |
-
1988
- 1988-03-28 JP JP63071978A patent/JPH01245013A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6036523A (en) * | 1983-08-09 | 1985-02-25 | Hitachi Chem Co Ltd | Manufacture of granular polymer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0397711A (en) * | 1989-09-08 | 1991-04-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of polymeric granule |
| JPH03124717A (en) * | 1989-10-09 | 1991-05-28 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate microcapsule |
| JPH04132717A (en) * | 1990-09-26 | 1992-05-07 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate-based resin dispersion composition |
| JP2008163228A (en) * | 2006-12-28 | 2008-07-17 | Mitsui Chemicals Inc | Manufacturing method of biodegradable polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0547564B2 (en) | 1993-07-19 |
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