JP2008075048A - Coating composition - Google Patents
Coating composition Download PDFInfo
- Publication number
- JP2008075048A JP2008075048A JP2006259006A JP2006259006A JP2008075048A JP 2008075048 A JP2008075048 A JP 2008075048A JP 2006259006 A JP2006259006 A JP 2006259006A JP 2006259006 A JP2006259006 A JP 2006259006A JP 2008075048 A JP2008075048 A JP 2008075048A
- Authority
- JP
- Japan
- Prior art keywords
- resistance
- coating composition
- duranate
- polycarbonate diol
- polyurethane particles
- 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
- 239000008199 coating composition Substances 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000004814 polyurethane Substances 0.000 claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 229920000515 polycarbonate Polymers 0.000 claims description 33
- 239000004417 polycarbonate Substances 0.000 claims description 33
- 150000002009 diols Chemical class 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 36
- 239000011248 coating agent Substances 0.000 abstract description 35
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 20
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000000704 physical effect Effects 0.000 description 19
- 239000003973 paint Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 13
- -1 tridendiisocyanate Chemical compound 0.000 description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 9
- 206010016322 Feeling abnormal Diseases 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002649 leather substitute Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- RJLZSKYNYLYCNY-UHFFFAOYSA-N ethyl carbamate;isocyanic acid Chemical compound N=C=O.CCOC(N)=O RJLZSKYNYLYCNY-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XSMIOONHPKRREI-UHFFFAOYSA-N undecane-1,11-diol Chemical compound OCCCCCCCCCCCO XSMIOONHPKRREI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 1
- RKIMETXDACNTIE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorocyclohexane Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F RKIMETXDACNTIE-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CJFUEPJVIFJOOU-UHFFFAOYSA-N 2-perfluorobutyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1CCCO1 CJFUEPJVIFJOOU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- JTDWCIXOEPQECG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCCCC(C)(C)C JTDWCIXOEPQECG-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical class NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229960002017 echothiophate Drugs 0.000 description 1
- BJOLKYGKSZKIGU-UHFFFAOYSA-N ecothiopate Chemical compound CCOP(=O)(OCC)SCC[N+](C)(C)C BJOLKYGKSZKIGU-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 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
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- AEDVWMXHRPMJAD-UHFFFAOYSA-N n,n,1,1,2,2,3,3,4,4,4-undecafluorobutan-1-amine Chemical compound FN(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AEDVWMXHRPMJAD-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical class CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical class C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229950011087 perflunafene Drugs 0.000 description 1
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical class OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical group C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical class NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は、1分子中に少なくとも2つ以上のイソシアナート基を有するポリイソシアナート化合物と、特定の構造式で表される、1分子中に少なくとも2つ以上の水酸基を有するポリカーボネートジオール、および特定の平均粒子径のポリウレタン粒子からなる硬化性塗料組成物に関するものである。 The present invention relates to a polyisocyanate compound having at least two isocyanate groups in one molecule, a polycarbonate diol having at least two hydroxyl groups in one molecule represented by a specific structural formula, and a specific The present invention relates to a curable coating composition comprising polyurethane particles having an average particle diameter of
従来、ポリウレタン樹脂は、合成皮革、人工皮革、接着剤、家具用塗料、自動車塗料等の幅広い領域で使用されており、イソシアネ−トと反応させるポリオール成分としてポリエーテルやポリエステルが用いられてきた(特許文献1〜2参照)。しかしながら、近年、耐熱性、耐候性、耐加水分解性、耐黴性、耐油性等、樹脂の耐性への要求の高度化や、さらには手触り感覚がソフトなソフトフィール塗料への要求が高まってきている。通常、耐性を向上させるためには、ポリマーへの架橋構造の導入が一般的であるが、この手段によると、塗料の塗膜は硬くなってしまうため、耐性に関するハイレベルの要求とソフトフィールを両立させることには困難があった。 Conventionally, polyurethane resins have been used in a wide range of areas such as synthetic leather, artificial leather, adhesives, furniture paints, and automobile paints, and polyethers and polyesters have been used as polyol components to react with isocyanates ( Patent References 1-2). However, in recent years, there has been an increase in demand for resin resistance, such as heat resistance, weather resistance, hydrolysis resistance, weather resistance, and oil resistance, and there has been an increasing demand for soft-feel paints with a soft hand feeling. ing. In general, in order to improve the resistance, it is common to introduce a crosslinked structure into the polymer. However, by this means, the coating film of the paint becomes hard, so that a high level of requirements regarding resistance and a soft feel are required. It was difficult to achieve both.
本発明は、塗膜硬度、柔軟性、耐酸性、耐アルカリ性、耐アルコール性、耐油性などの物性バランスに優れ、かつソフトタッチ感のある塗膜を形成可能にする硬化性塗料組成物を提供することを目的とする。 The present invention provides a curable coating composition that has an excellent balance of physical properties such as coating film hardness, flexibility, acid resistance, alkali resistance, alcohol resistance, and oil resistance, and that can form a coating film with a soft touch feeling. The purpose is to do.
本発明者らは、鋭意検討した結果、ポリイソシアナート硬化剤と特定構造のポリカーボネートジオール、および特定の平均粒子径のポリウレタン粒子を組み合わせることにより、所期目的を達成しうることを見出し本発明をなすに至った。
即ち、本発明は、
1.次の(a)、(b)および(c)を必須成分として含有することを特徴とする塗料用組成物。
(a)1分子中に少なくとも2つ以上のイソシアナート基を有するポリイソシアナート化合物。
(b)下記式(1)および(2)の繰り返し単位からなり、下記(1)と(2)の繰り返し単位の割合が(1)/(2)=90/10〜40/60(モル比)であり、末端基が水酸基であることを特徴とする脂肪族ポリカーボネートジオール。
As a result of intensive studies, the present inventors have found that a desired object can be achieved by combining a polyisocyanate curing agent, a polycarbonate diol having a specific structure, and polyurethane particles having a specific average particle diameter. It came to an eggplant.
That is, the present invention
1. A coating composition comprising the following (a), (b) and (c) as essential components:
(A) A polyisocyanate compound having at least two or more isocyanate groups in one molecule.
(B) It consists of repeating units of the following formulas (1) and (2), and the ratio of the repeating units of the following (1) and (2) is (1) / (2) = 90/10 to 40/60 (molar ratio). An aliphatic polycarbonate diol characterized in that the terminal group is a hydroxyl group.
(c)平均粒子径が2〜20μmのポリウレタン粒子:全固形分における添加量として3〜30重量%、
2.ポリイソシアナート化合物が、1分子中に少なくとも2.5以上のイソシアナート基を有することを特徴とする、1.記載の塗料組成物、
3.不活性有機溶剤を0〜90重量%含有することを特徴とする、1.又は2.記載の塗料組成物、である。
(C) Polyurethane particles having an average particle diameter of 2 to 20 μm: 3 to 30% by weight as an addition amount in the total solid content,
2. 1. The polyisocyanate compound has at least 2.5 or more isocyanate groups in one molecule. The coating composition according to the description,
3. 1. 0 to 90% by weight of an inert organic solvent is contained. Or 2. The coating composition as described.
本発明によれば、塗膜硬度、柔軟性、耐酸性、耐アルカリ性、耐アルコール性、耐油性などの物性バランスに優れた塗膜であって、手触り感覚がソフトなソフトフィール塗料を形成可能な硬化性塗料組成物を提供することができる。 According to the present invention, a coating film having a good balance of physical properties such as coating film hardness, flexibility, acid resistance, alkali resistance, alcohol resistance, oil resistance, and the like can be formed into a soft feel paint with a soft hand feeling. A curable coating composition can be provided.
以下、本発明について詳述する。本発明で用いる、1分子中に少なくとも2つ以上のイソシアナート基を有するポリイソシアナート化合物としては、トリレンジイソシアナート、ジフェニルメタンジイソシアナート、ジイソシアナートシクロヘキサン、トリデンジイソシアナート、ヘキサメチレンジイソシアナート、トリメチルヘキサンジイソシアナート,1.5−ナフタレンジイソシアナート、キシリレンジイソシアナート、2.6−ジイソシアナートメチルカプロエート、イソホロンジイソシアナート(IPDI)、メチルシクロヘキサン−2,4(又は2,6)−ジイソシアナート、4,4′メチレンビス(シクロヘキシルイソシアナート)などの芳香族、脂肪族、脂環族系イソシアナート、あるいはこれらのイソシアナートの単独又は混合物から誘導されるイソシアヌレート型ポリイソシアナート、ビュレット型イソシアナート及びこれらジイソシアナートとエチレングリコール、ポリエーテルポリオール(ポリエチレングリコール、ポリプロピレングリコール等)、カプロラクトンポリオール、ポリカーボネートポリオールやイソシアナート基と反応する官能基を有する低分子量のポリエステル樹脂(油変性タイプを含む)やアクリル系共重合体などとのランタン型付加物、あるいは、2−ヒドロキシプロピル(メタ)アクリレートとヘキサメチレンジイソシアナート等モル付加物、イソシアナートエチル(メタ)クリレートなどのイソシアナート基と共重合性不飽和基を有するビニル系モノマーを必須成分としたイソシアナート基を有する共重合体等が挙げられる。特に耐候性の点から、ヘキサメチレンジイソシアナート(HDI)、イソホロンジイソシアナート(IPDI)等の脂肪族脂環族ジイソシアナートから誘導されたポリイソシアナート類が望ましい。更には、これらのポリイソシアナートを、例えば、ブタノール、2−エチルヘキサノール等の低級アルコール、メチルエチルケトンオキシム、ラクタム類、フェノール類、イミダゾール類、活性メチレン化合物など公知のブロック剤でブロックした、いわゆるブロックドイソシアナート系硬化剤を用いることができる。これらポリイソシアナート化合物としては、スミジュール44S、44V70(いずれも住化バイエルウレタン製)、TDIとHDIのコポリマーであるディスモジュールHL(住化バイエルウレタン製)、旭化成ケミカルズ製の各種デュラネ−ト、すなわちデュラネート24A−100、デュラネート22A−75PX、デュラネート18H−70B、デュラネート21S−75E、デュラネートTHA−100、デュラネートTPA−100、デュラネートMFA−75X、デュラネートTSA−100、デュラネートTSS−100、デュラネートTSE−100、デュラネートD−101、デュラネートD−201、デュラネートP−301−75E、デュラネー
トE−402−90T、デュラネートE−402−90T、デュラネートE−405−80T、デュラネートME20−100、デュラネート17B−60PX、デュラネートTPA−B80X、デュラネートMF−B60X、デュラネートE−402−B80T、デュラネートME20−B80S、デュラネートWB40−100、デュラネートWB40−80D、デュラネートWT20−100、デュラネートWT30−100等として入手可能である。硬化塗膜の耐酸性、耐アルカリ性、耐アルコール性、耐油性、耐磨耗性、耐傷付き性を向上させるためには、ポリイソシアナート化合物が、1分子中に少なくとも2.5以上のイソシアナート基かつ/またはブロックドイソシアナート基を有することが好ましく、具体的にはビウレット、アロファナート、ウレチジンジオン、イソシアヌラート等のジイソシアネート誘導体、および多価アルコールアダクト型がより好ましい。
Hereinafter, the present invention will be described in detail. Polyisocyanate compounds having at least two or more isocyanate groups in one molecule used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, diisocyanate cyclohexane, tridendiisocyanate, hexamethylene diisocyanate. Narate, trimethylhexane diisocyanate, 1.5-naphthalene diisocyanate, xylylene diisocyanate, 2.6-diisocyanate methylcaproate, isophorone diisocyanate (IPDI), methylcyclohexane-2,4 (or 2,6) -diisocyanates, 4,4'methylenebis (cyclohexyl isocyanate) and other aromatic, aliphatic, alicyclic isocyanates, or isocyanates derived from these isocyanates alone or in mixtures Low molecular weight having functional groups that react with rate-type polyisocyanates, burette-type isocyanates and these diisocyanates and ethylene glycol, polyether polyols (polyethylene glycol, polypropylene glycol, etc.), caprolactone polyols, polycarbonate polyols and isocyanate groups Lanthanum type adducts with polyester resins (including oil-modified types) and acrylic copolymers, or molar adducts such as 2-hydroxypropyl (meth) acrylate and hexamethylene diisocyanate, isocyanate ethyl (meth) Examples thereof include a copolymer having an isocyanate group containing a vinyl monomer having an isocyanate group and a copolymerizable unsaturated group such as acrylate as an essential component. In particular, from the viewpoint of weather resistance, polyisocyanates derived from aliphatic alicyclic diisocyanates such as hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are desirable. Further, these polyisocyanates are blocked with known blocking agents such as lower alcohols such as butanol and 2-ethylhexanol, methyl ethyl ketone oximes, lactams, phenols, imidazoles, and active methylene compounds. An isocyanate curing agent can be used. Examples of these polyisocyanate compounds include Sumidur 44S and 44V70 (all manufactured by Sumika Bayer Urethane), Dismodule HL (manufactured by Sumika Bayer Urethane), which is a copolymer of TDI and HDI, and various duranates manufactured by Asahi Kasei Chemicals. That is, Duranate 24A-100, Duranate 22A-75PX, Duranate 18H-70B, Duranate 21S-75E, Duranate THA-100, Duranate TPA-100, Duranate MFA-75X, Duranate TSA-100, Duranate TSS-100, Duranate TSE-100 , Duranate D-101, Duranate D-201, Duranate P-301-75E, Duranate E-402-90T, Duranate E-402-90T, Duranet E-405-80T, Duranate ME20-100, Duranate 17B-60PX, Duranate TPA-B80X, Duranate MF-B60X, Duranate E-402-B80T, Duranate ME20-B80S, Duranate WB40-100, Duranate WB40-80D, Duranate Available as WT20-100, Duranate WT30-100, etc. In order to improve the acid resistance, alkali resistance, alcohol resistance, oil resistance, abrasion resistance and scratch resistance of the cured coating film, the polyisocyanate compound contains at least 2.5 or more isocyanate per molecule. And / or a blocked isocyanate group, specifically, diisocyanate derivatives such as biuret, allophanate, uretidinedione, isocyanurate, and polyhydric alcohol adducts are more preferable.
次に、本発明で用いるポリカーボネートジオールは、下記式(1)および(2)の繰り返し単位からなり、下記式(1)と(2)の繰り返し単位の割合が(1)/(2)=90/10〜40/60(モル比)であり、末端基が水酸基であることを特徴とする脂肪族ポリカーボネートジオールである。 Next, the polycarbonate diol used in the present invention comprises repeating units of the following formulas (1) and (2), and the ratio of the repeating units of the following formulas (1) and (2) is (1) / (2) = 90. / 10 to 40/60 (molar ratio), and an aliphatic polycarbonate diol characterized in that a terminal group is a hydroxyl group.
本発明者らは、各種ポリカーボネートジオールを本用途に検討した結果、上記特定の構造のカーボネートジオールを用いることにより、手触り感覚がソフトなソフトフィール塗料が得られることを見出した。本発明のポリカーボネートジオールは、Schell著、P olmer Review 第9巻、第9〜20ページ(1964年)に記載された種々の方法により、1,4−ブタンジオールと、1,6−ヘキサンジオールから合成される共重合ポリカーボネートジオールである。ポリカーボネートジオールを構成する繰り返し単位である上記式(1)と(2)の繰り返し単位の割合が(1)/(2)=90/10(モル比)を超えると、得られる塗膜のソフト感が損なわれるので好ましくない。また、ポリカーボネートジオールを構成する繰り返し単位である上記式(1)と(2)の繰り返し単位の割合が(1)/(2)=40/60(モル比)未満においても得られる塗膜のソフト感が損なわれるばかりではなく、耐油性、耐磨耗性も悪化するので好ましくない。より好ましいポリカーボネートジオールを構成する繰り返し単位である上記式(1)と(2)の割合は(1)/(2)=85/15〜50/50(モル比)、さらに好ましくは(1)/(2)=80/20〜60/40(モル比)である。 As a result of examining various polycarbonate diols for this application, the present inventors have found that a soft feel paint having a soft hand feeling can be obtained by using the carbonate diol having the above specific structure. The polycarbonate diol of the present invention can be obtained from 1,4-butanediol and 1,6-hexanediol by various methods described in Schell, Polymer Review Vol. 9, pages 9-20 (1964). It is a copolymerized polycarbonate diol to be synthesized. When the ratio of the repeating units of the above formulas (1) and (2) constituting the polycarbonate diol exceeds (1) / (2) = 90/10 (molar ratio), the softness of the resulting coating film Is unfavorable because it is damaged. Moreover, the coating film software obtained even when the ratio of the repeating units of the above formulas (1) and (2), which are the repeating units constituting the polycarbonate diol, is less than (1) / (2) = 40/60 (molar ratio) Not only the feeling is impaired, but also the oil resistance and wear resistance are deteriorated, which is not preferable. The ratio of the above formulas (1) and (2), which are repeating units constituting a more preferable polycarbonate diol, is (1) / (2) = 85/15 to 50/50 (molar ratio), more preferably (1) / (2) = 80/20 to 60/40 (molar ratio).
本発明で用いるポリカーボネートジオールは、1,4−ブタンジオールと、1,6−ヘキサンジオールから合成される共重合ポリカーボネートジオールであるが、その特徴を阻害しない範囲で、その他の低分子量ジオールを共重合成分として含有することができる。具体的に使用できるその他のジオールとしては、エチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,2−ブタンジオール、1、3−ブタンジオー
ル、1、5−ペンタンジオール、2−メチル−1,3−プロパンジオール、ネオペンチルグリコール、2,3−ブタンジオール、2,5−ヘキサンジオール、1,7−ヘプタンジオール、1,8−オクタンジオール、2−メチルー1,8−オクタンジオール、1,9−ノナンジオール、1,10−デカンジオール、1,11−ウンデカジオール、1,12−ドデカンジオール、1,4−シクロヘキサンジオール、1,4−シクロヘキサンジメタノール等が挙げられるが、それらジオールの割合は、1,4−ブタンジオールと、1,6−ヘキサンジオールを含む全モノマージオールに占める割合として、40重量%未満、好ましくは20重量%未満、さらに好ましくは10重量%未満である。
The polycarbonate diol used in the present invention is a copolymerized polycarbonate diol synthesized from 1,4-butanediol and 1,6-hexanediol, but other low molecular weight diols are copolymerized as long as the characteristics are not impaired. It can be contained as a component. Other diols that can be specifically used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, -Methyl-1,3-propanediol, neopentyl glycol, 2,3-butanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octane Examples include diol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. The ratio of these diols is the total amount of 1,4-butanediol and 1,6-hexanediol. As a percentage of merging all, less than 40 wt%, preferably less than 20 wt%, more preferably less than 10 wt%.
本発明における、ポリカーネートジオールの数平均分子量は500〜10000、好ましくは1000〜5000である。さらに好ましくは数平均分子量1500〜3000である。数平均分子量が500未満になると、塗膜の柔軟性が低下し、ソフト感が著しく損なわれる可能性がある。また、数平均分子量が10000を超えると、イソシアネートとの反応が著しく遅くなり、乾燥に長時間を要するばかりではなく、得られる塗料組成物の粘度が高くなり、実際の塗工が難しくなるので好ましくない。
本発明に用いられるポリカーボネートジオールのポリマ−末端は、実質的にすべてヒドロキシル基であることが望ましい。
In the present invention, the number average molecular weight of the polycarbonate diol is 500 to 10,000, preferably 1000 to 5,000. More preferably, the number average molecular weight is 1500 to 3000. When the number average molecular weight is less than 500, the flexibility of the coating film is lowered and the soft feeling may be significantly impaired. In addition, when the number average molecular weight exceeds 10,000, the reaction with the isocyanate is remarkably slow, and not only does it take a long time to dry, but also the viscosity of the resulting coating composition becomes high and actual coating becomes difficult, which is preferable. Absent.
It is desirable that the polymer ends of the polycarbonate diol used in the present invention are substantially all hydroxyl groups.
本発明においては、1,4−ブタンジオールと、1,6−ヘキサンジオール他に、1分子に3個以上のヒドロキシル基を持つ化合物、例えば、トリメチロールエタン、トリメチロールプロパン、ヘキサントリオール、ペンタエリスリトール、等を少量用いる事により、一分子中の平均水酸基数が2.5未満、好ましくは2.4未満の多官能化したポリカーボネートも含まれる。2.5以上に多官能化したポリカーボネートの場合、得られる塗料組成物の粘度が高くなり、実際の塗工が難しくなるばかりではなく、得られる塗膜が硬くなりソフト感が損なわれるので好ましくない。
前記ポリカーボネートジオールとポリイソシアナートとの配合比は、塗膜性能の点からOH/NCO=1/0.5〜1/1.5(当量比)、より好ましくはOH/NCO=1/0.8〜1/1.2(当量比) になる様に配合するのが好ましい。OH1当量に対してNCOが0.5当量未満では所定の塗膜物性が得られず、1.5当量を超えると硬化速度に問題があり好ましくない。
In the present invention, 1,4-butanediol, 1,6-hexanediol, and other compounds having three or more hydroxyl groups per molecule, such as trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol By using a small amount of these, a polyfunctionalized polycarbonate having an average number of hydroxyl groups in one molecule of less than 2.5, preferably less than 2.4 is also included. In the case of polycarbonate polyfunctionalized to 2.5 or more, the viscosity of the resulting coating composition is increased, and not only the actual coating becomes difficult, but also the resulting coating film becomes hard and soft feeling is impaired, which is not preferable. .
The blending ratio of the polycarbonate diol and the polyisocyanate is OH / NCO = 1 / 0.5 to 1 / 1.5 (equivalent ratio), more preferably OH / NCO = 1/0. It is preferable to blend so as to be 8 to 1 / 1.2 (equivalent ratio). If the NCO is less than 0.5 equivalent with respect to 1 equivalent of OH, the predetermined coating film properties cannot be obtained.
本発明では得られる塗膜のソフト感をより高めるためにポリウレタン粒子を用いる。このポリウレタン粒子としては、懸濁安定剤の存在下においてポリウレタンプレポリマーを水中に分散させた後重合し、洗浄、乾燥させて製造する方法(特開平1−185648号公報)、乳化剤の存在下に非水不活性液体中でポリウレタンを乳化重合する方法(特開平5−214054号公報、特開平7−97425号公報)、等で合成される球状のポリウレタン粒子である。このポリウレタン粒子の合成において、2官能以下イソシアナートウレタンプレポリマーを使用した場合は熱可塑性ウレタン粒子が得られ、2官能を超える末端イソシアナートウレタンプレポリマーを使用すると3次元架橋したウレタン粒子が得られる。本発明で使用するポリウレタン粒子としては、本塗料組成物により得られる塗膜の、耐酸性、耐アルカリ性、耐アルコール性、耐油性、耐熱性、耐磨耗性を向上させるために、3次元架橋したウレタン粒子がより好適に用いられる。用いるポリウレタン粒子の平均粒子径は2〜20μmである。平均粒子径が2μm未満では、得られる塗膜の光沢が高くなり、高級感が得られなくなるばかりではなく、ソフト感も低下するので好ましくない。一方、平均粒子径が20μmを超えると、得られる塗膜の磨耗性が低下し、また表面のソフト感が損なわれるので好ましくない。より好ましい平均粒子径は4〜15μm、さらに好ましくは5〜10μmである。 In the present invention, polyurethane particles are used in order to further enhance the soft feeling of the obtained coating film. As the polyurethane particles, a method in which a polyurethane prepolymer is dispersed in water in the presence of a suspension stabilizer and then polymerized, washed and dried (JP-A-1-185648), in the presence of an emulsifier. Spherical polyurethane particles synthesized by a method of emulsion polymerization of polyurethane in a non-aqueous inert liquid (JP-A-5-214054 and JP-A-7-97425). In the synthesis of this polyurethane particle, when a difunctional or lower isocyanate urethane prepolymer is used, a thermoplastic urethane particle is obtained, and when a terminal isocyanate urethane prepolymer exceeding 2 functions is used, a three-dimensionally crosslinked urethane particle is obtained. . The polyurethane particles used in the present invention include three-dimensional cross-linking in order to improve the acid resistance, alkali resistance, alcohol resistance, oil resistance, heat resistance, and wear resistance of the coating film obtained by the present coating composition. The urethane particles used are more preferably used. The average particle diameter of the polyurethane particles used is 2 to 20 μm. If the average particle diameter is less than 2 μm, the resulting coating film has high gloss, and not only does not give a high-quality feeling, but also the soft feeling is lowered. On the other hand, if the average particle diameter exceeds 20 μm, the wear properties of the resulting coating film are lowered and the softness of the surface is impaired, which is not preferable. A more preferable average particle diameter is 4 to 15 μm, and further preferably 5 to 10 μm.
本塗料組成部におけるポリウレタン粒子の添加量は、塗料組成物に含まれる全固形分の3〜30重量%である。ポリウレタン粒子の含有量が3重量%未満では、得られる塗膜の
ソフト感が得られず、またポリウレタン粒子の含有量が30重量%を超えると、得られる塗膜の磨耗性が極端に悪化するので好ましくない。好ましいポリウレタン粒子の添加量は5〜20%、さらに好ましくは8〜15重量%である。
本発明の硬化性塗料組成物には、各種用途に応じて硬化促進剤(触媒)、充填剤、難燃剤、染料、有機または無機顔料、離型剤、流動性調整剤、可塑剤、抗酸化剤、紫外線吸収剤、光安定剤、消泡剤、レベリング剤、着色剤、溶剤等を添加することができる。
The addition amount of the polyurethane particles in the coating composition part is 3 to 30% by weight of the total solid content contained in the coating composition. When the content of polyurethane particles is less than 3% by weight, the softness of the resulting coating film cannot be obtained, and when the content of polyurethane particles exceeds 30% by weight, the wear properties of the resulting coating film are extremely deteriorated. Therefore, it is not preferable. The amount of polyurethane particles added is preferably 5 to 20%, more preferably 8 to 15% by weight.
The curable coating composition of the present invention includes a curing accelerator (catalyst), a filler, a flame retardant, a dye, an organic or inorganic pigment, a release agent, a fluidity modifier, a plasticizer, and an antioxidant according to various uses. An agent, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a colorant, a solvent and the like can be added.
硬化促進剤としては、モノアミンであるトリエチルアミン、N,N−ジメチルシクロヘキシルアミン、ジアミンであるテトラメチルエチレンジアミン、その他トリアミン、環状アミン、ジメチルエタノールアミンのようなアルコールアミン、エーテルアミン、金属触媒としては酢酸カリウム、2エチルへキサン酸カリウム、酢酸カルシウム、オクチル酸鉛、ジブチル錫ジラウレート、オクチル酸錫、ビスマスネオデカノエート、ビスマスオキシカーボネート、ビスマス2−エチルヘキサノエート、オクチル酸亜鉛、亜鉛ネオデカノエート、ホスフィン、ホスホリン等、一般的に用いられるものが使用できる。
充填剤や顔料としては、織布、ガラス繊維、炭素繊維、ポリアミド繊維、雲母、カオリン、ベントナイト、金属粉、アゾ顔料、カーボンブラック、クレー、シリカ、タルク、石膏、アルミナ白、炭酸バリウム等一般的に用いられているものが使用できる。
離型剤や流動性調整剤、レベリング剤としては、シリコーン、エアロジル、ワックス、ステアリン酸塩、BYK−331(BYKケミカル社製)のようなポリシロキサン等が用いられる。
Curing accelerators include monoamine triethylamine, N, N-dimethylcyclohexylamine, diamine tetramethylethylenediamine, other triamines, cyclic amines, alcohol amines such as dimethylethanolamine, ether amines, and metal catalysts such as potassium acetate. Potassium 2-ethylhexanoate, calcium acetate, lead octylate, dibutyltin dilaurate, tin octylate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2-ethylhexanoate, zinc octylate, zinc neodecanoate, phosphine, Commonly used materials such as phospholine can be used.
As fillers and pigments, woven fabric, glass fiber, carbon fiber, polyamide fiber, mica, kaolin, bentonite, metal powder, azo pigment, carbon black, clay, silica, talc, gypsum, alumina white, barium carbonate, etc. Can be used.
As the mold release agent, fluidity adjusting agent, and leveling agent, silicone, aerosil, wax, stearate, polysiloxane such as BYK-331 (manufactured by BYK Chemical Co., Ltd.) and the like are used.
本発明に用いられる添加剤としては少なくとも酸化防止剤、光安定剤及び熱安定剤が用いられることが望ましい。これらの酸化防止剤としては燐酸、亜燐酸、の脂肪族、芳香族又はアルキル基置換芳香族エステルや次亜燐酸誘導体、フェニルホスホン酸、フェニルホスフィン酸、ジフェニルホスホン酸、ポリホスホネート、ジアルキルペンタエリスリトールジホスファイト、ジアルキルビスフェノールAジホスファイト等のリン化合物;フェノール系誘導体特にヒンダードフェノール化合物、チオエーテル系、ジチオ酸塩系、メルカプトベンズイミダゾール系、チオカルバニリド系、チオジプロピオン酸エステル等のイオウを含む化合物;スズマレート、ジブチルスズモノオキシド等のスズ系化合物を用いることができる。 As the additive used in the present invention, at least an antioxidant, a light stabilizer and a heat stabilizer are preferably used. These antioxidants include phosphoric acid, phosphorous acid, aliphatic, aromatic or alkyl group-substituted aromatic esters and hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diesters. Phosphites, phosphorous compounds such as dialkyl bisphenol A diphosphites; phenol derivatives, especially hindered phenol compounds, thioethers, dithioates, mercaptobenzimidazoles, thiocarbanilides, thiodipropionates, and other sulfur-containing compounds; Tin compounds such as dibutyltin monoxide can be used.
これらはこれらは単独で用いても2種以上組み合わせて用いてもよい。
本発明の塗料組成物には、塗装時の作業性を調整するために、必要に応じて不活性有機溶剤を0〜90重量%含有することができる。用いる不活性有機溶剤としては実質的にポリイソシアナート化合物に対して不活性な有機溶媒であり且つ活性水素を有しないものである。その例としはて、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、石油エーテル、石油ベンジン、リグロイン、石油スピリット、シクロヘキサン、メチルシクロヘキサン等の炭化水素類、トリクロロフルオロエタン、テトラクロロジフルオロエタン、パーフルオロエーテル等の弗素化油等の弗素系不活性液体、パーフルオロシクロヘキサン、パーフルオロブチルテトラヒドロフラン、パーフルオロデカリン、パーフルオロ−n−ブチルアミン、パーフルオロポリエーテル、ジメチルポリシロキサン等の単独又は混合物が挙げられる。さらには、メチルエチルケトン、アセトン、酢酸エチル、酢酸ブチル、トルエン、キシレン等の溶媒が挙げられる。
These may be used alone or in combination of two or more.
The coating composition of the present invention may contain 0 to 90% by weight of an inert organic solvent as necessary in order to adjust the workability during coating. The inert organic solvent used is an organic solvent which is substantially inert to the polyisocyanate compound and does not have active hydrogen. Examples include hydrocarbons such as pentane, hexane, heptane, octane, decane, petroleum ether, petroleum benzine, ligroin, petroleum spirit, cyclohexane, methylcyclohexane, trichlorofluoroethane, tetrachlorodifluoroethane, perfluoroether, etc. Fluorinated inert liquids such as fluorinated oils, perfluorocyclohexane, perfluorobutyltetrahydrofuran, perfluorodecalin, perfluoro-n-butylamine, perfluoropolyether, dimethylpolysiloxane and the like may be used alone or as a mixture. Furthermore, solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, xylene and the like can be mentioned.
本組成組成物の塗装方法としては、各々の成分を塗装直前に混合した後、スプレー、ロール、はけ等で基材に塗布する方法が用いられる。予め、硬化剤である(a)成分以外を混合しておき、塗布直前に(a)成分を添加し均一に混合した後、塗布する方法も可能である。
本発明の硬化性塗料組成物は、ソフトフィール塗料として、家電製品、OA製品、自動車内装部品、皮革の表面処理、合成皮革の表面処理、等に好ましく用いることができる。
As a coating method of this composition, after mixing each component just before coating, the method of apply | coating to a base material with a spray, a roll, a brush etc. is used. It is also possible to apply a method in which components other than the component (a), which is a curing agent, are mixed in advance, and the component (a) is added and mixed uniformly immediately before application, and then applied.
The curable coating composition of the present invention can be preferably used as a soft feel coating for home appliances, OA products, automobile interior parts, leather surface treatment, synthetic leather surface treatment, and the like.
以下、実施例などを用いて本発明を更に詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。また、以下の実施例および比較例において、各種ポリオールおよびそのポリウレタンフィルムの諸物性は、下記の試験方法に従って試験を実施した。
<試験方法>
1.不溶分率
ガラス板上に塗布液を塗布し、80℃で2時間加熱して膜厚40μmのフィルムを作製した。フィルムをガラス板から剥がし、約3cm×3cmに切り取ってから浸漬前のフィルム重量を秤量した。その後、フィルムを銅網に入れて、MEKに24時間浸漬した。銅網からフィルムを取り出して加熱乾燥してから浸漬後のフィルム重量を秤量し、下記式から不溶分率を算出した。
不溶分率[%]=100×(浸漬後のフィルム重量)/(浸漬前のフィルム重量)
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example etc., this invention is not limited at all by these examples. In the following Examples and Comparative Examples, various polyols and various physical properties of the polyurethane film were tested according to the following test methods.
<Test method>
1. Insoluble fraction The coating solution was applied onto a glass plate and heated at 80 ° C. for 2 hours to produce a film having a thickness of 40 μm. The film was peeled off from the glass plate, cut to about 3 cm × 3 cm, and then weighed before dipping. Thereafter, the film was put into a copper net and immersed in MEK for 24 hours. The film was taken out from the copper net, dried by heating, weighed after immersion, and the insoluble fraction was calculated from the following equation.
Insoluble fraction [%] = 100 × (film weight after immersion) / (film weight before immersion)
2.塗膜硬度
上記1.で形成したガラス板上のフィルムについて、ペンドラム式硬度計で測定した。ガラス板上に塗布した塗装サンプルを装置に置き、振幅が5°になった時点かから振幅が2°になるまでの時間を測定した(t)。塗装していないガラス板につき、同様の測定を行い振幅が5°になった時点かから振幅が2°になるまでの時間を測定した(t0)。硬度(X)は以下の式で計算した。
硬度:X=t/t0
3.耐磨耗性
上記1.で形成したガラス板上のフィルムについて、JIS K5600−5−8の方法に準じ、テーバー型磨耗試験機を用い測定した。磨耗試験前の重量と磨耗試験(500回転)後の塗膜板の重量変化を測定し表記した。
2. Coating film hardness The film on the glass plate formed in the above was measured with a pen drum type hardness meter. The coating sample applied on the glass plate was placed in the apparatus, and the time from when the amplitude reached 5 ° until the amplitude reached 2 ° was measured (t). The same measurement was performed on the uncoated glass plate, and the time from when the amplitude reached 5 ° to when the amplitude reached 2 ° was measured (t0). The hardness (X) was calculated by the following formula.
Hardness: X = t / t0
3. Abrasion resistance The film on the glass plate formed in the above was measured using a Taber type abrasion tester according to the method of JIS K5600-5-8. The weight before the abrasion test and the change in the weight of the coated film after the abrasion test (500 rotations) were measured and expressed.
4.光沢度
上記1.で形成したガラス板上のフィルムについて、JIS K5600−4−7の方法に準じ、85°での塗膜表面の光沢度を測定した。
5.ソフト感
上記1.で形成したガラス板上のフィルムについて、フィルム表面を手で触った時の感触によりソフト感を評価した。判定結果は以下の表記で表した。
○:良好なソフト感
△:比較的良好なソフト感
×:ソフトとは感じられない。
4). Glossiness With respect to the film on the glass plate formed in step 1, the glossiness of the coating film surface at 85 ° was measured according to the method of JIS K5600-4-7.
5. Soft feeling The soft feeling of the film on the glass plate formed in the above was evaluated by the touch when the film surface was touched by hand. Judgment results were expressed in the following notation.
○: Good soft feeling Δ: Relatively good soft feeling ×: It is not felt soft.
〔実施例1〕
ポリカーボネートジオール−1(PCDL−1:1,4−ブタンジオールと1,6−ヘキサンジオールとを70/30のモル比で共重合して得られたポリカーボネートジオールで、数平均分子量2000)200g、レベリング剤BYK−331(BYKケミカル社製)2.06g、ジブチル錫ジラウレート(Air Product社製)1.2g、ポリウレタン粒子(アートパール、C−800、平均粒子系=6μm、根上工業株式会社製)35gおよびシンナーとしてキシレン/酢酸ブチル(70/30)の混合溶媒356gを添加して拌機し塗料主剤を得た。これに硬化剤としてデュラネートTPA−100(旭化成ケミカルズ社製:ヘキサメチレンジイソシアナート系イソシアヌレート型硬化剤、NCO含量=23.1wt%)を38.2g添加、混合して塗布液を作製した。これをアクリロニトリル−ブタジエン−スチレン(ABS)樹脂板上に塗布した後、80℃で2時間加熱硬化させ膜厚み30〜40μmの塗膜を得た。その諸物性を表1に示した。
[Example 1]
200 g of polycarbonate diol-1 (PCDL-1: polycarbonate diol obtained by copolymerizing 1,4-butanediol and 1,6-hexanediol at a molar ratio of 70/30, number average molecular weight 2000), leveling Agent BYK-331 (BYK Chemical Co., Ltd.) 2.06 g, dibutyltin dilaurate (Air Product) 1.2 g, polyurethane particles (Art Pearl, C-800, average particle system = 6 μm, Negami Kogyo Co., Ltd.) 35 g As a thinner, 356 g of a mixed solvent of xylene / butyl acetate (70/30) was added and stirred to obtain a paint base. To this was added 38.2 g of Duranate TPA-100 (manufactured by Asahi Kasei Chemicals Corporation: hexamethylene diisocyanate-based isocyanurate type curing agent, NCO content = 23.1 wt%) as a curing agent, and a coating solution was prepared. This was coated on an acrylonitrile-butadiene-styrene (ABS) resin plate and then cured by heating at 80 ° C. for 2 hours to obtain a coating film having a film thickness of 30 to 40 μm. The physical properties are shown in Table 1.
〔実施例2〕
実施例1のポリカーボネートジオールの替わりにポリカーボネートジオール−2(PCDL−2:1,4−ブタンジオールと1,6−ヘキサンジオールとを87/13のモル比で共重合して得られたポリカーボネートジオールで、数平均分子量2000)を用いた以外は、実施例1と同様の方法で塗料を作成した。その諸物性を表1に示した。
〔実施例3〕
実施例1のポリカーボネートジオールの替わりにポリカーボネートジオール−3(PCDL−3:1,4−ブタンジオールと1,6−ヘキサンジオールとを70/30のモル比で共重合して得られたポリカーボネートジオールで、数平均分子量1000)を用い、デュラネートTPA−100の添加量を76.4gとした以外は、実施例1と同様の方法で塗料を作成した。その諸物性を表1に示した。
[Example 2]
In place of the polycarbonate diol of Example 1, polycarbonate diol-2 (PCDL-2: a polycarbonate diol obtained by copolymerizing 1,4-butanediol and 1,6-hexanediol at a molar ratio of 87/13) A paint was prepared in the same manner as in Example 1 except that the number average molecular weight 2000) was used. The physical properties are shown in Table 1.
Example 3
Instead of the polycarbonate diol of Example 1, polycarbonate diol-3 (PCDL-3: polycarbonate diol obtained by copolymerizing 1,4-butanediol and 1,6-hexanediol at a molar ratio of 70/30) The number average molecular weight 1000) was used, and a paint was prepared in the same manner as in Example 1 except that the amount of Duranate TPA-100 added was 76.4 g. The physical properties are shown in Table 1.
〔実施例4〕
実施例1の硬化剤の替わりに、デュラネート24A(旭化成ケミカルズ社製:ヘキサメチレンジイソシアナート系ビュレット型硬化剤、NCO含量=23.5wt%)を37.5gとした以外は実施例1と同様に塗料を作成した。その諸物性を表1に示した。
〔実施例5〕
実施例1のポリウレタン粒子の替わりに、DIAPLACOAT、RHU−5070D(大日精化工業株式会社製、ポリウレタン粒子、平均粒子系=7μm)を使用した以外は実施例1と同様に塗料を作成した。その諸物性を表1に示した。
〔実施例6〕
実施例1のポリウレタン粒子の替わりに、アートパール、C−400(根上工業株式会社製、ポリウレタン粒子、平均粒子系=14μm)を使用した以外は実施例1と同様に塗料を作成した。その諸物性を表1に示した。
Example 4
Instead of the curing agent of Example 1, Duranate 24A (Asahi Kasei Chemicals Co., Ltd .: hexamethylene diisocyanate burette type curing agent, NCO content = 23.5 wt%) was changed to 37.5 g, and was the same as Example 1. Created a paint. The physical properties are shown in Table 1.
Example 5
A paint was prepared in the same manner as in Example 1 except that DIAPLACOAT, RHU-5070D (manufactured by Dainichi Seika Kogyo Co., Ltd., polyurethane particles, average particle size = 7 μm) was used instead of the polyurethane particles of Example 1. The physical properties are shown in Table 1.
Example 6
A paint was prepared in the same manner as in Example 1 except that Art Pearl, C-400 (manufactured by Negami Kogyo Co., Ltd., polyurethane particles, average particle system = 14 μm) was used instead of the polyurethane particles of Example 1. The physical properties are shown in Table 1.
〔実施例7〕
窒素ガスで充分に置換し、乾燥させた2LオートクレーブにアデカポリエーテルG−700(旭電化工業株式会社製、グリセリンPO付加物、水酸基価225mg/KOHg)175gとヘキサメチレンジイソシアネート101gを仕込み、120℃で20時間撹拌、応させた。その後減圧下で未反応のヘキサメチレンジイソシアネートを除去した後トルエンを加えて不揮発分90%の合成物(I)を得た。2L撹拌機付きセパラブルフラスコに水970gを仕込み、この中ヘメトローズ90SH−100(信越化学株式会社製品;メチルセルロース)30gを溶解して分散媒を作成した。該分散媒を1000rpm撹拌下に合成物(I)250gをトルエン87gで希釈した溶液を加え、懸濁液を作成した。撹拌継続下に懸濁液を60℃に昇温し、1.5時間反応した後室温まで冷却し、固液分離し、水で充分洗浄した後70℃、20時間乾燥して平均粒子径4μmのウレタン粒子を得た。実施例1のポリウレタン粒子の替わりに、上記方法にて合成したポリウレタン粒子を使用した以外は実施例1と同様に塗料を作成した。その諸物性を表1に示した。
Example 7
A 2 L autoclave sufficiently substituted with nitrogen gas and dried was charged with 175 g of ADEKA polyether G-700 (manufactured by Asahi Denka Kogyo Co., Ltd., glycerin PO adduct, hydroxyl value 225 mg / KOHg) and 101 g of hexamethylene diisocyanate, and 120 ° C. And stirred for 20 hours. Thereafter, unreacted hexamethylene diisocyanate was removed under reduced pressure, and then toluene was added to obtain a compound (I) having a nonvolatile content of 90%. 970 g of water was charged into a separable flask equipped with a 2 L stirrer, and 30 g of Hemetroze 90SH-100 (manufactured by Shin-Etsu Chemical Co., Ltd .; methylcellulose) was dissolved therein to prepare a dispersion medium. A solution obtained by diluting 250 g of the compound (I) with 87 g of toluene was added to the dispersion medium while stirring at 1000 rpm to prepare a suspension. With continuous stirring, the suspension was heated to 60 ° C., reacted for 1.5 hours, cooled to room temperature, separated into solid and liquid, thoroughly washed with water, dried at 70 ° C. for 20 hours, and an average particle size of 4 μm. Of urethane particles were obtained. A paint was prepared in the same manner as in Example 1 except that the polyurethane particles synthesized by the above method were used instead of the polyurethane particles in Example 1. The physical properties are shown in Table 1.
〔実施例8〕
実施例1のポリウレタン粒子添加量を20gとした以外は実施例1と同様に塗料を作成した。その諸物性を表1に示した。
〔実施例9〕
実施例1のポリウレタン粒子添加量を55gとした以外は実施例1と同様に塗料を作成した。その諸物性を表1に示した。
Example 8
A coating material was prepared in the same manner as in Example 1 except that the amount of polyurethane particles added in Example 1 was 20 g. The physical properties are shown in Table 1.
Example 9
A paint was prepared in the same manner as in Example 1 except that the amount of polyurethane particles added in Example 1 was changed to 55 g. The physical properties are shown in Table 1.
〔比較例1〕
実施例1のポリカーボネートジオールの替わりにポリカーボネートジオール−2(PCDL−3:1,4−ブタンジオールと1,6−ヘキサンジオールとを30/70のモル比で共重合して得られたポリカーボネートジオールで、数平均分子量2000)を用いた以
外は、実施例1と同様の方法で塗料を作成した。その諸物性を表2に示した。
〔比較例2〕
実施例1のポリカーボネートジオールの替わりにポリカーボネートジオール−2(PCDL−3:1,4−ブタンジオールと1,6−ヘキサンジオールとを95/5のモル比で共重合して得られたポリカーボネートジオールで、数平均分子量2000)を用いた以外は、実施例1と同様の方法で塗料を作成した。その諸物性を表2に示した。
[Comparative Example 1]
Instead of the polycarbonate diol of Example 1, polycarbonate diol-2 (PCDL-3: 1,4-butanediol and 1,6-hexanediol copolymerized at a molar ratio of 30/70 was obtained. A paint was prepared in the same manner as in Example 1 except that the number average molecular weight 2000) was used. The physical properties are shown in Table 2.
[Comparative Example 2]
In place of the polycarbonate diol of Example 1, polycarbonate diol-2 (PCDL-3: 1,4-butanediol and 1,6-hexanediol copolymerized at a molar ratio of 95/5) A paint was prepared in the same manner as in Example 1 except that the number average molecular weight 2000) was used. The physical properties are shown in Table 2.
〔比較例3〕
実施例1のポリカーボネートジオールの替わりにポリカプロラクトン(PCL−1、プラクセル220N、数平均分子量2000、ダイセル化学工業製)を用いた以外は、実施例1と同様の方法で塗料を作成した。その諸物性を表2に示した。
〔比較例4〕
実施例1のポリウレタン粒子の替わりに、アートパール、C−200(根上工業株式会社製、ポリウレタン粒子、平均粒子系=30μm)を使用した以外は実施例1同様に塗料を作成した。その諸物性を表2に示した。
[Comparative Example 3]
A paint was prepared in the same manner as in Example 1 except that polycaprolactone (PCL-1, Plaxel 220N, number average molecular weight 2000, manufactured by Daicel Chemical Industries) was used in place of the polycarbonate diol of Example 1. The physical properties are shown in Table 2.
[Comparative Example 4]
A paint was prepared in the same manner as in Example 1 except that Art Pearl C-200 (manufactured by Negami Kogyo Co., Ltd., polyurethane particles, average particle size = 30 μm) was used instead of the polyurethane particles of Example 1. The physical properties are shown in Table 2.
〔比較例5〕
実施例1のポリウレタン粒子の替わりに、アクリル系樹脂粒子(アートパール、G−800T(根上工業株式会社製、平均粒子系=6μm)を使用した以外は実施例1同様に塗料を作成した。その諸物性を表2に示した。
〔比較例6〕
実施例1のポリウレタン粒子添加量を5gとした以外は実施例1と同様に塗料を作成した。その諸物性を表2に示した。
〔比較例7〕
実施例1のポリウレタン粒子添加量を130gとした以外は実施例1と同様に塗料を作成した。その諸物性を表2に示した。
[Comparative Example 5]
A coating material was prepared in the same manner as in Example 1 except that acrylic resin particles (Art Pearl, G-800T (manufactured by Negami Industrial Co., Ltd., average particle system = 6 μm)) were used instead of the polyurethane particles of Example 1. Various physical properties are shown in Table 2.
[Comparative Example 6]
A coating material was prepared in the same manner as in Example 1 except that the amount of polyurethane particles added in Example 1 was changed to 5 g. The physical properties are shown in Table 2.
[Comparative Example 7]
A coating material was prepared in the same manner as in Example 1 except that the amount of polyurethane particles added in Example 1 was changed to 130 g. The physical properties are shown in Table 2.
Claims (3)
(a)1分子中に少なくとも2つ以上のイソシアナート基を有するポリイソシアナート化合物。
(b)下記式(1)および(2)の繰り返し単位からなり、下記(1)と(2)の繰り返し単位の割合が(1)/(2)=90/10〜40/60(モル比)であり、末端基が水酸基であることを特徴とする脂肪族ポリカーボネートジオール。
(A) A polyisocyanate compound having at least two or more isocyanate groups in one molecule.
(B) It consists of repeating units of the following formulas (1) and (2), and the ratio of the repeating units of the following (1) and (2) is (1) / (2) = 90/10 to 40/60 (molar ratio). An aliphatic polycarbonate diol characterized in that the terminal group is a hydroxyl group.
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JP2008063395A (en) * | 2006-09-06 | 2008-03-21 | Asahi Kasei Chemicals Corp | Coating composition |
JP2009280665A (en) * | 2008-05-21 | 2009-12-03 | Asahi Kasei Chemicals Corp | Composition for curable coating material containing polycarbonate diol |
JP2010013529A (en) * | 2008-07-02 | 2010-01-21 | Asahi Kasei Chemicals Corp | Curable composition for soft feeling paint having high drying rate and improved in resistance |
WO2011076728A1 (en) * | 2009-12-23 | 2011-06-30 | Bayer Materialscience Ag | Polyurethane binder |
CN103287145A (en) * | 2013-06-08 | 2013-09-11 | 惠州市维尔康精密部件有限公司 | Processing method for shell pattern of television |
JP2017078150A (en) * | 2015-10-22 | 2017-04-27 | 旭化成株式会社 | Curable composition for a coating |
JP2017078149A (en) * | 2015-10-22 | 2017-04-27 | 旭化成株式会社 | Coating Composition |
JP2018083898A (en) * | 2016-11-24 | 2018-05-31 | トヨタ自動車株式会社 | Coating, and article and method for producing the same |
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JP2021075632A (en) * | 2019-11-08 | 2021-05-20 | 旭化成株式会社 | Coating composition |
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JP2008063395A (en) * | 2006-09-06 | 2008-03-21 | Asahi Kasei Chemicals Corp | Coating composition |
JP2009280665A (en) * | 2008-05-21 | 2009-12-03 | Asahi Kasei Chemicals Corp | Composition for curable coating material containing polycarbonate diol |
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WO2011076728A1 (en) * | 2009-12-23 | 2011-06-30 | Bayer Materialscience Ag | Polyurethane binder |
CN103287145A (en) * | 2013-06-08 | 2013-09-11 | 惠州市维尔康精密部件有限公司 | Processing method for shell pattern of television |
US10428236B2 (en) | 2014-07-07 | 2019-10-01 | Tosoh Corporation | Polyurethane urea resin composition exhibiting UV-absorption-agent resistance, moulded body using said composition, and coating material |
JP2017078150A (en) * | 2015-10-22 | 2017-04-27 | 旭化成株式会社 | Curable composition for a coating |
JP2017078149A (en) * | 2015-10-22 | 2017-04-27 | 旭化成株式会社 | Coating Composition |
JP2018083898A (en) * | 2016-11-24 | 2018-05-31 | トヨタ自動車株式会社 | Coating, and article and method for producing the same |
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