JP2011126945A - Aqueous polyurethane resin composition and aqueous coating composition using the same - Google Patents
Aqueous polyurethane resin composition and aqueous coating composition using the same Download PDFInfo
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- JP2011126945A JP2011126945A JP2009284543A JP2009284543A JP2011126945A JP 2011126945 A JP2011126945 A JP 2011126945A JP 2009284543 A JP2009284543 A JP 2009284543A JP 2009284543 A JP2009284543 A JP 2009284543A JP 2011126945 A JP2011126945 A JP 2011126945A
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- JP
- Japan
- Prior art keywords
- polyurethane resin
- resin composition
- aqueous
- chlorinated
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 115
- 239000011342 resin composition Substances 0.000 title claims abstract description 69
- 239000008199 coating composition Substances 0.000 title claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 52
- 229920000570 polyether Polymers 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920005862 polyol Polymers 0.000 claims abstract description 34
- 150000003077 polyols Chemical class 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000012736 aqueous medium Substances 0.000 claims abstract description 15
- 125000001033 ether group Chemical group 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000004970 Chain extender Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 abstract description 50
- 239000011248 coating agent Substances 0.000 abstract description 48
- 239000000463 material Substances 0.000 abstract description 16
- 229920003023 plastic Polymers 0.000 abstract description 15
- 239000004033 plastic Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 34
- 239000000047 product Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 20
- -1 polypropylene Polymers 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 229920000098 polyolefin Polymers 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 239000003973 paint Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- UKXROSORAUTSSH-UHFFFAOYSA-N 2-(1,2-dichloroethyl)oxirane Chemical compound ClCC(Cl)C1CO1 UKXROSORAUTSSH-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 235000015278 beef Nutrition 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 239000006059 cover glass Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 235000013772 propylene glycol Nutrition 0.000 description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003760 tallow Substances 0.000 description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 3
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- LAKPAFZLNCJMEN-UHFFFAOYSA-L (2,3,4,5,6-pentafluorophenyl)aluminum(2+);difluoride Chemical compound [F-].[F-].FC1=C(F)C(F)=C([Al+2])C(F)=C1F LAKPAFZLNCJMEN-UHFFFAOYSA-L 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical class CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- AQSVMUCTNYYCRW-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)-3,4,5-trimethylbenzene Chemical class CC1=CC(CN=C=O)=C(CN=C=O)C(C)=C1C AQSVMUCTNYYCRW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VOGHDWQJCXXBMH-UHFFFAOYSA-N 1,2-dichlorobut-2-ene Chemical compound CC=C(Cl)CCl VOGHDWQJCXXBMH-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
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- POHPFVPVRKJHCR-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)alumane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Al](C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F POHPFVPVRKJHCR-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- HWWBSHOPAPTOMP-UHFFFAOYSA-N tritert-butylborane Chemical compound CC(C)(C)B(C(C)(C)C)C(C)(C)C HWWBSHOPAPTOMP-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
【課題】 プラスティック基材等への付着性に優れ、且つ耐油性及び耐水性に優れた塗膜の形成を可能とする水性ポリウレタン樹脂組成物を提供すること。
【解決手段】 （ａ）下記式（１）で表される塩素化エーテル残基を繰り返し単位として含む塩素化ポリエーテル、（ｂ）ポリイソシアネート、（ｃ）ポリオール及び（ｄ）親水基導入剤を反応させて得られたポリウレタン樹脂が、水性媒体中に分散していることを特徴とする水性ポリウレタン樹脂組成物。
【化１】
【選択図】 なしPROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin composition capable of forming a coating film excellent in adhesion to a plastic base material and the like and excellent in oil resistance and water resistance.
SOLUTION: (a) A chlorinated polyether containing a chlorinated ether residue represented by the following formula (1) as a repeating unit, (b) a polyisocyanate, (c) a polyol, and (d) a hydrophilic group introducing agent. An aqueous polyurethane resin composition, wherein a polyurethane resin obtained by reaction is dispersed in an aqueous medium.
[Chemical 1]
[Selection figure] None
Description
本発明は、水性ポリウレタン樹脂組成物並びにそれを用いた水性塗料組成物に関する。 The present invention relates to an aqueous polyurethane resin composition and an aqueous coating composition using the same.
従来より、オレフィン基材（特にポリプロピレン）、ゴム成分複合基材（特にアクリロニトリルブタジエンスチレン共重合（ＡＢＳ）樹脂）等のプラスティック基材は、優れた成形性、軽量性等を有していることから、多種多様な分野において用いられてきた。しかし、これらのプラスティック基材は極性が小さいことから、塗料等の付着性が十分でないという問題があった。 Conventionally, plastic base materials such as olefin base materials (particularly polypropylene) and rubber component composite base materials (particularly acrylonitrile butadiene styrene copolymer (ABS) resin) have excellent moldability, light weight and the like. Have been used in a wide variety of fields. However, since these plastic substrates have a small polarity, there is a problem that adhesion of paints and the like is not sufficient.
また、塗料においては、有機溶剤がもたらす環境汚染等の問題から、有機溶剤を含む有機溶剤型から有機溶剤を含まない水性型への切り替えが望まれ、塗膜性能に優れた水性塗料の開発が進められている。 In paints, it is desired to switch from organic solvent-containing organic solvents to organic-free water-based paints due to problems such as environmental pollution caused by organic solvents. It is being advanced.
そこで、プラスティック基材等に対する付着性を向上させる水性塗料としては以下のような組成物が開示されている。 Therefore, the following compositions are disclosed as water-based paints that improve adhesion to plastic substrates and the like.
すなわち、例えば、特開２００１−２９７７号公報（特許文献１）には、水性塗料において、プラスティック基材等に対する付着付与剤として塩素化ポリオレフィン（ＣＰＯ）エマルションを用いることが開示されている。ＣＰＯエマルションとは、塩素化ポリプロピレン樹脂を外部乳化剤を用いて水に強制的に分散させたものであり、塗装の際にはＣＰＯエマルション中の塩素原子が加熱乾燥時にラジカル化し、プラスティック基材の炭化水素の水素を引き抜くことにより、プラスティック基材の表面が極性化することで水性塗料との付着性を向上させるものである。しかしながら、ＣＰＯエマルションは油成分（牛脂、ラード、高級脂肪酸等）に溶解しやすいため、ＣＰＯエマルションを含有する塗膜は耐油性の点において劣ったものであった。さらに、ＣＰＯエマルションは製造時に多量の外部乳化剤を使用するため、ＣＰＯエマルションを含有する塗膜は耐水性の点においても劣ったものであった。 That is, for example, JP-A-2001-2777 (Patent Document 1) discloses that a chlorinated polyolefin (CPO) emulsion is used as an adhesion-imparting agent for a plastic substrate or the like in an aqueous coating material. A CPO emulsion is a chlorinated polypropylene resin that is forcibly dispersed in water using an external emulsifier. During coating, chlorine atoms in the CPO emulsion are radicalized during heating and drying, and carbonization of the plastic substrate is performed. By pulling out hydrogen from hydrogen, the surface of the plastic substrate is polarized, thereby improving adhesion to the water-based paint. However, since the CPO emulsion is easily soluble in oil components (beef tallow, lard, higher fatty acids, etc.), the coating film containing the CPO emulsion was inferior in oil resistance. Furthermore, since a large amount of an external emulsifier is used during production of the CPO emulsion, the coating film containing the CPO emulsion is inferior in terms of water resistance.
また、特開平６−１７２６３７号公報（特許文献２）には、塩素化されたポリオールと、カルボン酸基を有するポリオールと、ジイソシアネートとを反応させ、更に塩基性化合物で中和して水に分散させることで得られる水性ポリウレタン樹脂組成物を用いることにより、水性塗料の基材との付着性が向上することが開示されている。しかしながら、ポリオールに塩素基を導入する方法として、ポリオールと塩素基を有するジカルボン酸又は無水酸とを反応させる方法をとるため、生じたポリエステルは加水分解を受けやすく、このような水性ポリウレタン樹脂組成物を含有する塗膜は耐水性の点において劣ったものであった。 In JP-A-6-172737 (Patent Document 2), a chlorinated polyol, a polyol having a carboxylic acid group, and a diisocyanate are reacted, further neutralized with a basic compound, and dispersed in water. It is disclosed that the adhesion of the water-based paint to the base material is improved by using the water-based polyurethane resin composition obtained by the above. However, since the method of introducing a chlorine group into a polyol is a method of reacting a polyol with a dicarboxylic acid or anhydride having a chlorine group, the resulting polyester is susceptible to hydrolysis, and such an aqueous polyurethane resin composition is used. The coating film containing was inferior in terms of water resistance.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、プラスティック基材等への付着性に優れ、且つ耐油性及び耐水性に優れた塗膜の形成を可能とする水性ポリウレタン樹脂組成物、並びにそれを用いた水性塗料組成物を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and is an aqueous polyurethane resin that is excellent in adhesion to a plastic substrate and the like, and can form a coating film excellent in oil resistance and water resistance. It is an object of the present invention to provide a composition, and an aqueous coating composition using the composition.
本発明者らは、特定の塩素化ポリエーテルを用いて得られた水性ポリウレタン樹脂組成物は、プラスティック基材等への付着性に優れ、且つ耐油性及び耐水性に優れた塗膜の形成を可能とすることを見出し、本発明を完成するに至った。 The inventors of the present invention have formed an aqueous polyurethane resin composition obtained using a specific chlorinated polyether, which has excellent adhesion to a plastic substrate and the like, and is excellent in oil resistance and water resistance. The inventors have found that it is possible to complete the present invention.
すなわち、本発明の水性ポリウレタン樹脂組成物は、（ａ）下記式（１）で表される塩素化エーテル残基を繰り返し単位として含む塩素化ポリエーテル、（ｂ）ポリイソシアネート、（ｃ）ポリオール及び（ｄ）親水基導入剤を反応させて得られたポリウレタン樹脂が、水性媒体中に分散していることを特徴とするものである。 That is, the aqueous polyurethane resin composition of the present invention comprises (a) a chlorinated polyether containing a chlorinated ether residue represented by the following formula (1) as a repeating unit, (b) a polyisocyanate, (c) a polyol and (D) A polyurethane resin obtained by reacting a hydrophilic group introducing agent is dispersed in an aqueous medium.
本発明にかかる（ａ）塩素化ポリエーテルとしては、数平均分子量が２００〜１００００である塩素化ポリエーテルが好ましい。なお、本発明における数平均分子量とは、テトラヒドロフランを溶媒とし、ゲル・パーミエイション・クロマトグラフィーを用いて、ポリスチレン換算で測定した値のことである。 As the (a) chlorinated polyether according to the present invention, a chlorinated polyether having a number average molecular weight of 200 to 10,000 is preferable. In the present invention, the number average molecular weight is a value measured in terms of polystyrene using tetrahydrofuran as a solvent and gel permeation chromatography.
また、本発明にかかる（ａ）塩素化ポリエーテルとしては、水酸基価が１〜１０００ｍｇＫＯＨ／ｇである塩素化ポリエーテルが好ましい。なお、本発明における（ａ）塩素化ポリエーテルの水酸基価はＪＩＳ−Ｋ１５５７に記載の方法に従って算出した値のことである。 Moreover, as (a) chlorinated polyether concerning this invention, the chlorinated polyether whose hydroxyl value is 1-1000 mgKOH / g is preferable. The hydroxyl value of (a) chlorinated polyether in the present invention is a value calculated according to the method described in JIS-K1557.
さらに、本発明にかかるポリウレタン樹脂としては、（ａ）塩素化ポリエーテル、（ｂ）ポリイソシアネート、（ｃ）ポリオール及び（ｄ）親水基導入剤と、更に（ｅ）鎖延長剤とを反応させて得られたものであることが好ましい。 Furthermore, as the polyurethane resin according to the present invention, (a) a chlorinated polyether, (b) a polyisocyanate, (c) a polyol, (d) a hydrophilic group introducing agent, and (e) a chain extender are reacted. It is preferable that it is obtained.
また、本発明の水性塗料組成物は、前記本発明の水性ポリウレタン樹脂組成物を含有することを特徴とするものである。 The aqueous coating composition of the present invention is characterized by containing the aqueous polyurethane resin composition of the present invention.
本発明によれば、プラスティック基材等への付着性に優れ、且つ耐油性及び耐水性に優れた塗膜の形成を可能とする水性ポリウレタン樹脂組成物、並びにそれを用いた水性塗料組成物を提供することが可能となる。 According to the present invention, an aqueous polyurethane resin composition having excellent adhesion to a plastic substrate and the like and capable of forming a coating film excellent in oil resistance and water resistance, and an aqueous coating composition using the same It becomes possible to provide.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
本発明の水性ポリウレタン樹脂組成物は、（ａ）下記式（１）で表される塩素化エーテル残基を繰り返し単位として含む塩素化ポリエーテル、（ｂ）ポリイソシアネート、（ｃ）ポリオール及び（ｄ）親水基導入剤を反応させて得られたポリウレタン樹脂が、水性媒体中に分散していることを特徴とするものである。 The aqueous polyurethane resin composition of the present invention comprises (a) a chlorinated polyether containing a chlorinated ether residue represented by the following formula (1) as a repeating unit, (b) a polyisocyanate, (c) a polyol, and (d ) A polyurethane resin obtained by reacting a hydrophilic group introducing agent is dispersed in an aqueous medium.
先ず、本発明において用いられる（ａ）塩素化ポリエーテルについて説明する。本発明において用いられる（ａ）塩素化ポリエーテルは、（ａ）前記式（１）で表される塩素化エーテル残基を繰り返し単位として含むものである。 First, (a) chlorinated polyether used in the present invention will be described. The (a) chlorinated polyether used in the present invention includes (a) a chlorinated ether residue represented by the formula (1) as a repeating unit.
本発明において用いられる（ａ）塩素化ポリエーテルとしては、分子鎖末端に水酸基を有している必要があり、本発明の水性ポリウレタン樹脂組成物の原料として、（ａ）塩素化ポリエーテルの水酸基価は１〜１０００（ｍｇＫＯＨ／ｇ）であることが好ましく、１８〜２５０（ｍｇＫＯＨ／ｇ）であることがより好ましい。（ａ）塩素化ポリエーテルの水酸基価が前記下限未満だと後述の（ｂ）ポリイソシアネートとの反応が不十分となるため、後述の本発明の水性塗料組成物からなる塗膜の耐久性が乏しくなる傾向にあり、他方、前記上限を超えると後述のポリウレタン樹脂の粘度が高くなるため、水性媒体中への分散が困難になる傾向にある。 The (a) chlorinated polyether used in the present invention must have a hydroxyl group at the end of the molecular chain. As a raw material for the aqueous polyurethane resin composition of the present invention, (a) the hydroxyl group of the chlorinated polyether The value is preferably 1-1000 (mgKOH / g), more preferably 18-250 (mgKOH / g). (A) If the hydroxyl value of the chlorinated polyether is less than the lower limit, the reaction with the polyisocyanate described later (b) is insufficient, so that the durability of the coating film comprising the aqueous coating composition of the present invention described later is improved. On the other hand, when the above upper limit is exceeded, the viscosity of the polyurethane resin described later tends to be high, so that dispersion in an aqueous medium tends to be difficult.
また、本発明において用いられる（ａ）塩素化ポリエーテルとしては、数平均分子量２００〜１００００を有するものであることが好ましく、数平均分子量４５０〜６０００を有するものであることがより好ましい。前記塩素化ポリエーテルの数平均分子量が前記下限未満だと後述の本発明の水性塗料組成物からなる塗膜がもろくなり、また前記塗膜中の塩素含有量が少なくなるため、前記塗膜の付着性が乏しくなる傾向となる。他方、前記塩素化ポリエーテルの数平均分子量が前記上限を超えると前記塗膜の耐油性が乏しくなり、また前記塩素化ポリエーテルを希釈剤により２０％に希釈して用いる場合、希釈された前記塩素化ポリエーテルの粘度は２５０００ｍＰａ・ｓ ａｔ ２５℃を超えるため、後述の本発明にかかるポリウレタン樹脂の合成が困難になる傾向にある。 In addition, the (a) chlorinated polyether used in the present invention preferably has a number average molecular weight of 200 to 10,000, and more preferably has a number average molecular weight of 450 to 6,000. If the number average molecular weight of the chlorinated polyether is less than the lower limit, the coating film made of the aqueous coating composition of the present invention described later becomes brittle, and the chlorine content in the coating film is reduced. Adhesion tends to be poor. On the other hand, when the number average molecular weight of the chlorinated polyether exceeds the upper limit, the oil resistance of the coating film becomes poor, and when the chlorinated polyether is diluted to 20% with a diluent, Since the viscosity of the chlorinated polyether exceeds 25000 mPa · s at 25 ° C., synthesis of a polyurethane resin according to the present invention described later tends to be difficult.
前記式（１）で表される塩素化エーテル残基を繰り返し単位として含む重合体としては、前記式（１）で表される塩素化エーテル残基のみを繰り返し単位とする単独重合体或いは重合体中の主鎖及び／又は側鎖に前記式（１）で表される塩素化エーテル残基以外のモノマーを含む共重合体であってもよい。 The polymer containing the chlorinated ether residue represented by the formula (1) as a repeating unit is a homopolymer or polymer having only the chlorinated ether residue represented by the formula (1) as a repeating unit. It may be a copolymer containing monomers other than the chlorinated ether residue represented by the formula (1) in the main chain and / or side chain.
また、前記式（１）で表される塩素化エーテル残基を繰り返し単位として含む共重合体に含まれる前記式（１）で表される塩素化エーテル残基以外のモノマーとしては、例えば、エチレンオキサイド、プロピレンオキサイド、メチルアクリレート、メチルメタクリレート、ブチルメタクリレート、エチルアクリレート、シクロヘキシルアクリレート、アクリル酸、ヒドロキシエチルメタクリレート、エチレン、ブタジエン、プロピレン、酢酸ビニル、ビニルアルコールが挙げられ、前記共重合体における前記モノマーの含有量としては、５〜５０質量％であることが好ましく、１０〜４０質量％であることがより好ましい。 Examples of the monomer other than the chlorinated ether residue represented by the formula (1) contained in the copolymer containing the chlorinated ether residue represented by the formula (1) as a repeating unit include, for example, ethylene Oxide, propylene oxide, methyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate, cyclohexyl acrylate, acrylic acid, hydroxyethyl methacrylate, ethylene, butadiene, propylene, vinyl acetate, vinyl alcohol, and the monomers in the copolymer As content, it is preferable that it is 5-50 mass%, and it is more preferable that it is 10-40 mass%.
本発明において用いられる塩素化ポリエーテルの製造方法としては、前記式（１）で表される塩素化エーテル残基を繰り返し単位として含む塩素化ポリエーテルを製造することが可能な方法であればよく、特に制限はされない。 The method for producing the chlorinated polyether used in the present invention may be any method that can produce a chlorinated polyether containing the chlorinated ether residue represented by the formula (1) as a repeating unit. There are no particular restrictions.
本発明において用いられる塩素化ポリエーテルの製造方法としては、例えば、含活性水素化合物を重合開始剤として用い、酸触媒の存在下、下記式（２）で表される塩素化エポキシ化合物の開環重合を行う方法が挙げられる。なお、前記式（１）で表される塩素化エーテル残基は、下記式（２）で表される塩素化エポキシ化合物のα開裂及び／又はβ開裂により生成され、α開裂とβ開裂の頻度は、使用する含活性水素化合物や酸触媒の種類、重合条件によって変化する。 As a method for producing a chlorinated polyether used in the present invention, for example, ring opening of a chlorinated epoxy compound represented by the following formula (2) in the presence of an acid catalyst using an active hydrogen-containing compound as a polymerization initiator. Examples include a method of performing polymerization. The chlorinated ether residue represented by the formula (1) is generated by α-cleavage and / or β-cleavage of the chlorinated epoxy compound represented by the following formula (2), and the frequency of α-cleavage and β-cleavage. Varies depending on the active hydrogen-containing compound used, the type of acid catalyst, and the polymerization conditions.
前記重合開始剤としては、例えば、ヒドロキシ化合物、アミン化合物、カルボン酸化合物、フェノール化合物、燐酸やチオール化合物等の含活性水素化合物が挙げられる。より具体的には、エチレングルコール、ジエチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、グリセリン、トリメチロールプロパン、ヘキサントリオール、ペンタエリスリトール、ジグリセリン、ソルビトール、シュークローズ等のヒドロキシ化合物、エチレンジアミン等のアミン化合物、安息香酸、アジピン酸等のカルボン酸化合物、ビスフェノールＡ等のフェノール化合物、エタンジチオール、ブタンジチオール等のチオール化合物、水が挙げられる。このような重合開始剤は、単独で又は２種類以上を混合して用いてもよい。 Examples of the polymerization initiator include active hydrogen-containing compounds such as hydroxy compounds, amine compounds, carboxylic acid compounds, phenol compounds, phosphoric acid and thiol compounds. More specifically, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, hexanetriol, pentaerythritol, diglycerin, sorbitol, shoelace, etc. Examples include hydroxy compounds, amine compounds such as ethylenediamine, carboxylic acid compounds such as benzoic acid and adipic acid, phenolic compounds such as bisphenol A, thiol compounds such as ethanedithiol and butanedithiol, and water. Such polymerization initiators may be used alone or in admixture of two or more.
また、前記重合開始剤の使用量としては、特に制限はなく、目的とする塩素化ポリエーテルの数平均分子量に合わせて前記式（２）で表される塩素化エポキシ化合物と重合開始剤の比により調整すればよい。本発明の水性ポリウレタン樹脂組成物の原材料として適した（ａ）塩素化ポリエーテルが得られるという観点からは、前記式（２）で表される塩素化エポキシ化合物１ｍｏｌに対して前記重合開始剤における活性水素含有量が０．０２〜２ｍｏｌとなるような量で前記重合開始剤を用いることが好ましい。 Further, the amount of the polymerization initiator used is not particularly limited, and the ratio of the chlorinated epoxy compound represented by the formula (2) to the polymerization initiator according to the number average molecular weight of the target chlorinated polyether. It may be adjusted by. From the viewpoint that (a) a chlorinated polyether suitable as a raw material of the aqueous polyurethane resin composition of the present invention is obtained, the polymerization initiator is used in 1 mol of the chlorinated epoxy compound represented by the formula (2). The polymerization initiator is preferably used in such an amount that the active hydrogen content is 0.02 to 2 mol.
前記酸触媒としては、公知の酸触媒を用いることができ、特に制限はされないが、例えば、硫酸、燐酸、塩酸等の鉱酸、三フッ化ホウ素、三塩化ホウ素等のハロゲン化ホウ素化合物、塩化アルミニウム、臭化アルミニウム等のハロゲン化アルミニウム化合物、フッ化アンチモン、塩化アンチモン等のアンチモン化合物、塩化第二鉄等の鉄化合物、五フッ化燐等の燐化合物、塩化亜鉛等のハロゲン化亜鉛化合物、四塩化チタン等のチタン化合物、塩化ジルコニウム等のジルコニウム化合物、塩化ベリリウム等のベリリウム化合物、トリフェニルホウ素、トリ（ｔ−ブチル）ホウ素、トリス（ペンタフルオロフェニル）ホウ素、ビス（ペンタフルオロフェニル）−ｔ−ブチルホウ素、ビス（ペンタフルオロフェニル）フッ化ホウ素、ジ（ｔ−ブチル）フッ化ホウ素、（ペンタフルオロフェニル）２フッ化ホウ素等の有機ホウ素化合物、トリエチルアルミニウム、トリフェニルアルミニウム、ジフェニル−t−ブチルアルミニウム、トリス（ペンタフルオロフェニル）アルミニウム、ビス（ペンタフルオロフェニル）−t−ブチルアルミニウム、ビス（ペンタフルオロフェニル）フッ化アルミニウム、ジ（ｔ−ブチル）フッ化アルミニウム、(ペンタフルオロフェニル)２フッ化アルミニウム、（ｔ−ブチル）２フッ化アルミニウム等の有機アルミニウム化合物、ジエチル亜鉛等の有機亜鉛化合物が挙げられる。 As the acid catalyst, known acid catalysts can be used, and are not particularly limited. For example, mineral acids such as sulfuric acid, phosphoric acid and hydrochloric acid, boron halide compounds such as boron trifluoride and boron trichloride, chloride Aluminum halide compounds such as aluminum and aluminum bromide, antimony compounds such as antimony fluoride and antimony chloride, iron compounds such as ferric chloride, phosphorus compounds such as phosphorus pentafluoride, zinc halide compounds such as zinc chloride, Titanium compounds such as titanium tetrachloride, zirconium compounds such as zirconium chloride, beryllium compounds such as beryllium chloride, triphenylboron, tri (t-butyl) boron, tris (pentafluorophenyl) boron, bis (pentafluorophenyl) -t -Butyl boron, bis (pentafluorophenyl) boron fluoride, di (t-butyl) ) Organic boron compounds such as boron fluoride, (pentafluorophenyl) boron difluoride, triethylaluminum, triphenylaluminum, diphenyl-t-butylaluminum, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t -Organoaluminum compounds such as butylaluminum, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) aluminum fluoride, (pentafluorophenyl) aluminum difluoride, (t-butyl) aluminum difluoride, diethyl Organic zinc compounds such as zinc can be mentioned.
さらに、ハロゲン化ホウ素化合物、ハロゲン化アルミニウム化合物、フッ化アンチモン、アンチモン化合物等のルイス酸を前記酸触媒として用いる場合、単独で使用してもよいし、種々の有機化合物との錯体として使用してもよい。ルイス酸と有機化合物の錯体としては、例えば、ジメチルエーテル錯体、ジエチルエーテル錯体、ＴＨＦ（テトラヒドロフラン）錯体等のエーテル錯体、酢酸錯体等のカルボン酸錯体、アルコール錯体、アミン錯体、フェノール錯体が挙げられる。また、このような酸触媒は２種以上を併用してもよい。 Further, when a Lewis acid such as a boron halide compound, an aluminum halide compound, antimony fluoride, or an antimony compound is used as the acid catalyst, it may be used alone or as a complex with various organic compounds. Also good. Examples of the complex of Lewis acid and an organic compound include ether complexes such as dimethyl ether complex, diethyl ether complex, and THF (tetrahydrofuran) complex, carboxylic acid complexes such as acetic acid complex, alcohol complexes, amine complexes, and phenol complexes. Such acid catalysts may be used in combination of two or more.
また、前記酸触媒の使用量としては、特に制限はないが、本発明において用いられる（ａ）塩素化ポリエーテルを効率良く製造できるという観点から、前記式（２）で表される塩素化エポキシ化合物１ｍｏｌに対して１×１０−５〜０．１ｍｏｌの範囲となるように前記酸触媒を用いることが好ましい。 The amount of the acid catalyst used is not particularly limited. From the viewpoint that (a) the chlorinated polyether used in the present invention can be efficiently produced, the chlorinated epoxy represented by the formula (2) is used. The acid catalyst is preferably used so as to be in the range of 1 × 10 −5 to 0.1 mol with respect to 1 mol of the compound.
また、本発明において用いられる塩素化ポリエーテルを製造する際には、溶媒中又は無溶媒下のどちらで製造を行ってもよく、粘性の高い高分子量の塩素化ポリエーテルを製造する際には、溶媒を用いたほうが好ましく、無溶媒で重合を行った後に溶媒を添加することもできる。 Further, when producing the chlorinated polyether used in the present invention, it may be produced either in a solvent or in the absence of a solvent, and when producing a high viscosity, high molecular weight chlorinated polyether. It is preferable to use a solvent, and the solvent can be added after polymerization without solvent.
前記溶媒としては、前記開環重合を阻害しないものであればよく、例えば、ヘキサン、ヘプタン等の炭化水素、トルエン、キシレン等の芳香族化合物、塩化メチレン、クロロホルム、ジクロロエタン、トリクロロエタン、ジクロロベンゼン等の塩素化物、エチルエーテル等のエーテル類、ニトロメタン、ニトロベンゼン等のニトロ化合物、二硫化炭素等の硫化物、プロピレングリコールジメチルエーテル等のアルキレングリコールジアルキルエーテルが、前記溶媒として挙げられる。また、このような溶媒は単独で又は２種類以上を混合して用いてもよい。 The solvent may be any solvent that does not inhibit the ring-opening polymerization, for example, hydrocarbons such as hexane and heptane, aromatic compounds such as toluene and xylene, methylene chloride, chloroform, dichloroethane, trichloroethane, dichlorobenzene, and the like. Examples of the solvent include chlorinated compounds, ethers such as ethyl ether, nitro compounds such as nitromethane and nitrobenzene, sulfides such as carbon disulfide, and alkylene glycol dialkyl ethers such as propylene glycol dimethyl ether. Moreover, you may use such a solvent individually or in mixture of 2 or more types.
さらに、前記溶媒の使用量としては、特に制限はないが、本発明において用いられる塩素化ポリエーテルの重合系からの回収効率の観点から、前記式（２）で表される塩素化エポキシ化合物の質量に対して１０倍以下の質量であることが好ましい。 Further, the amount of the solvent used is not particularly limited, but from the viewpoint of recovery efficiency from the polymerization system of the chlorinated polyether used in the present invention, the chlorinated epoxy compound represented by the formula (2) is used. The mass is preferably 10 times or less of the mass.
また、前記製造の条件としては、前記式（２）で表される塩素化エポキシ化合物の開環重合が可能であれば、特に制限されることはない。例えば、開環重合の際の温度としては−７８〜１５０℃の範囲とし、重合時間としては１０分〜４８時間の範囲とすることができる。さらに、品質に優れた塩素化ポリエーテルが得られるという観点から、前記製造の条件において、開環重合の際の温度としては−５０〜１２０℃の範囲とし、重合時間は３０分〜２４時間の範囲とすることが好ましい。 The production conditions are not particularly limited as long as ring-opening polymerization of the chlorinated epoxy compound represented by the formula (2) is possible. For example, the temperature during ring-opening polymerization can be in the range of −78 to 150 ° C., and the polymerization time can be in the range of 10 minutes to 48 hours. Furthermore, from the viewpoint of obtaining a chlorinated polyether having excellent quality, the temperature during ring-opening polymerization is in the range of −50 to 120 ° C., and the polymerization time is 30 minutes to 24 hours, in the above production conditions. It is preferable to be in the range.
次に、本発明において用いられる（ｂ）ポリイソシアネートについて説明する。本発明において用いられる（ｂ）ポリイソシアネートは、１分子中に２個以上イソシアネート基を含有する化合物であればよく、ポリウレタン樹脂の原材料として公知のもの、例えば、脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香族ジイソシアネートが挙げられる。 Next, (b) polyisocyanate used in the present invention will be described. The polyisocyanate (b) used in the present invention may be a compound containing two or more isocyanate groups in one molecule, and is known as a raw material of polyurethane resin, for example, aliphatic diisocyanate, alicyclic diisocyanate, Aromatic diisocyanates are mentioned.
本発明において用いることが可能な脂肪族ジイソシアネートとしては、例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、２−メチルペンタン−１，５−ジイソシアネート、３−メチルペンタン−１，５−ジイソシアネート、２，２，４−トリメチルヘキサメチレン−１，６−ジイソシアネート、２，４，４−トリメチルヘキサメチレン−１，６−ジイソシアネートが挙げられる。 Examples of the aliphatic diisocyanate that can be used in the present invention include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2 2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate.
また、本発明において用いることが可能な脂環族ジイソシアネートとしては、例えば、イソホロンジイソシアネート、シクロヘキシルジイソシアネート、水素添加キシリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加トリメチルキシリレンジイソシアネートが挙げられる。 Examples of the alicyclic diisocyanate that can be used in the present invention include isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated trimethylxylylene diisocyanate.
さらに、本発明において用いることが可能な芳香族ジイソシアネートとしては、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、キシレン−１，４−ジイソシアネート、キシレン−１，３−ジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルエーテルジイソシアネート、２，２’−ジフェニルプロパン−４，４’−ジイソシアネート、３，３’−ジメチルジフェニルメタン−４，４’−ジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、ナフチレン−１，４−ジイソシアネートが挙げられる。 Furthermore, examples of the aromatic diisocyanate that can be used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4 Examples include '-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and naphthylene-1,4-diisocyanate.
このようなポリイソシアネートは、単独で用いてもよく、又は２種以上を混合して用いてもよく、さらに、これらの変性体、例えば、アロファネート変性体、カルボジイミド変性体、ビュレット変性体、ウレトジオン変性体、ウレトイミン変性体、イソシアヌレート変性体を用いてもよい。 Such polyisocyanates may be used alone or in admixture of two or more, and further, these modified products, for example, allophanate modified products, carbodiimide modified products, burette modified products, uretdione modified products. Body, uretoimine modified body, isocyanurate modified body may be used.
本発明において用いられる（ｂ）ポリイソシアネートとしては、後述の本発明の水性塗料組成物からなる塗膜の紫外線による黄変を避けるという観点から、脂肪族ジイソシアネート又は脂環族ジイソシアネートが好ましい。 The (b) polyisocyanate used in the present invention is preferably an aliphatic diisocyanate or an alicyclic diisocyanate from the viewpoint of avoiding yellowing due to ultraviolet rays of a coating film comprising the aqueous coating composition of the present invention described later.
次に、本発明において用いられる（ｃ）ポリオールについて説明する。本発明において用いられる（ｃ）ポリオールとしては、ポリマー末端、分子鎖末端等に水酸基を有していればよく、ポリウレタン樹脂の原材料として公知のもの、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオールが挙げられる。 Next, (c) polyol used in the present invention will be described. The (c) polyol used in the present invention is only required to have a hydroxyl group at the polymer terminal, molecular chain terminal, etc., and is known as a raw material for polyurethane resin, for example, polyester polyol, polyether polyol, polycarbonate polyol, A polyolefin polyol is mentioned.
本発明において用いることが可能なポリエステルポリオールとしては、例えば、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、コハク酸、マロン酸、アジピン酸、１，４−シクロヘキシルジカルボン酸、マレイン酸、フマル酸、その他の二塩基酸等と、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、１，９−ノナンジオール、３，３−ジメチロールヘプタン、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、シクロヘキサン−１，４−ジオール等のジオール類又はグリセリン、トリメチロールプロパン、ペンタエリスリトール等のポリオール類とを重縮合反応させることにより得られるポリエステルポリオールが挙げられる。さらに、このようなポリエステルポリオールとしては、ε−カプロラクトン等の環状エステル、ジオールの一部をヘキサメチレンジアミンやイソホロンジアミン等のアミン類に変更したポリエステルアミドポリオールが挙げられる。 Examples of the polyester polyol that can be used in the present invention include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, and fumaric acid. , Other dibasic acids and the like, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 Diols such as hexanediol, 1,8-octanediol, 1,9-nonanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, or glycerin, Trimethylolpropane, pentaerythris Polyester polyols obtained by polycondensation reaction of a polyol such as tall like. Furthermore, examples of such polyester polyols include cyclic esters such as ε-caprolactone, and polyester amide polyols in which a part of the diol is changed to amines such as hexamethylene diamine and isophorone diamine.
本発明において用いることが可能なポリエーテルポリオールとしては、例えば、前記ジオール類、前記ポリオール類と、又はこれらと共にエチレンジアミン、プロピレンジアミン、トルエンジアミン、メタフェニレンジアミン、ジフェニルメタンジアミン等のアミン類と、エチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイド、メチルグリシジルエーテル、フェニルグリシジルエーテル等のアルキル又はアリールグリシジルエーテル、テトラヒドロフラン等の環状エーテル等とを付加重合することにより得られるポリエーテルポリオールが挙げられる。 Examples of the polyether polyol that can be used in the present invention include the diols, the polyols, or amines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, and diphenylmethanediamine, and ethylene oxide. And polyether polyols obtained by addition polymerization of alkylene oxides such as propylene oxide, alkyl or aryl glycidyl ethers such as methyl glycidyl ether and phenyl glycidyl ether, and cyclic ethers such as tetrahydrofuran.
本発明において用いることが可能なポリカーボネートポリオールとしては、例えば、前記ジオール類又は前記ポリオール類と、エチレンカーボネート、ジエチルカーボネート又はジフェニルカーボネート等との反応により得られるポリカーボネートポリオールが挙げられる。 Examples of the polycarbonate polyol that can be used in the present invention include polycarbonate polyols obtained by reacting the diols or polyols with ethylene carbonate, diethyl carbonate, diphenyl carbonate, or the like.
本発明において用いることが可能なポリオレフィンポリオールとしては、例えば、水酸基を２個以上有する、ポリブタジエンや水素添加ポリブタジエン及びポリイソプレンや水素添加ポリイソプレンが挙げられる。 Examples of the polyolefin polyol that can be used in the present invention include polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene having two or more hydroxyl groups.
さらに、目標とする物性を有する本発明の水性ポリウレタン樹脂組成物を得るために、前記ポリオールは適宜選択して用いることができる。例えば、低温特性及び機械強度の向上の観点からはポリテトラメチレンエーテルグリコールを、柔軟性及び低温特性の向上又は安価であるという観点からはポリプロピレングリコールを、可撓性、耐候性及び低温特性の向上の観点からはポリカプロラクトンポリオールを、耐熱性、耐候性、耐水性、機械強度及び耐加水分解性の観点からはポリカーボネートポリオールを、付着性及び密着性の向上の観点からはポリエステルポリオールを、（ｃ）ポリオールとして選択することができる。 Furthermore, in order to obtain the aqueous polyurethane resin composition of the present invention having target physical properties, the polyol can be appropriately selected and used. For example, polytetramethylene ether glycol is used from the viewpoint of improving low-temperature characteristics and mechanical strength, and polypropylene glycol is used from the viewpoint of improving flexibility and low-temperature characteristics or inexpensive, and flexibility, weather resistance, and low-temperature characteristics are improved. From the viewpoint of heat resistance, weather resistance, water resistance, mechanical strength and hydrolysis resistance, polycarbonate polyol, polyester polyol from the viewpoint of improving adhesion and adhesion, ) Can be selected as a polyol.
次に、本発明において用いられる（ｄ）親水基導入剤について説明する。本発明において用いられる（ｄ）親水基導入剤としては、後述のポリウレタン樹脂に組み込まれても分子内に遊離のカルボキシル基等の親水基を有しており、後述のポリウレタン樹脂の水性媒体中への分散性を向上させることが可能なものであればよい。このような（ｄ）親水基導入剤としては、例えば、ジメチロールプロピオン酸、ジメチロールブタン酸、乳酸、アルキロキシポリエチレングリコール、ポリエチレングリコール、Ｎ−（２−アミノメチル）−２−アミノエタンスルホン酸が挙げられる。 Next, (d) a hydrophilic group introducing agent used in the present invention will be described. The (d) hydrophilic group-introducing agent used in the present invention has a hydrophilic group such as a free carboxyl group in the molecule even when incorporated in the polyurethane resin described later, and into the aqueous medium of the polyurethane resin described later. What is necessary is just to be able to improve the dispersibility. Examples of such (d) hydrophilic group-introducing agent include dimethylolpropionic acid, dimethylolbutanoic acid, lactic acid, alkyloxypolyethylene glycol, polyethylene glycol, and N- (2-aminomethyl) -2-aminoethanesulfonic acid. Is mentioned.
次に、本発明にかかるポリウレタン樹脂について説明する。本発明にかかるポリウレタン樹脂は、前記（ａ）塩素化ポリエーテル、前記（ｂ）ポリイソシアネート、前記（ｃ）ポリオール及び前記（ｄ）親水基導入剤を反応させて得られたものである。 Next, the polyurethane resin according to the present invention will be described. The polyurethane resin according to the present invention is obtained by reacting the (a) chlorinated polyether, the (b) polyisocyanate, the (c) polyol and the (d) hydrophilic group introducing agent.
また、このようなポリウレタン樹脂としては、目標とする分子量、物性を有する本発明の水性ポリウレタン樹脂組成物が得られるという観点から、前記（ａ）塩素化ポリエーテル、前記（ｂ）ポリイソシアネート、前記（ｃ）ポリオール及び前記（ｄ）親水基導入剤と、更に（ｅ）鎖延長剤とを反応させて得られたものであることが好ましい。 In addition, as such a polyurethane resin, from the viewpoint that the aqueous polyurethane resin composition of the present invention having a target molecular weight and physical properties can be obtained, (a) the chlorinated polyether, (b) the polyisocyanate, (C) It is preferable to be obtained by reacting a polyol and the above-mentioned (d) hydrophilic group-introducing agent with (e) a chain extender.
本発明において用いることが可能な（ｅ）鎖延長剤としては、前記（ａ）塩素化ポリエーテルと前記（ｂ）ポリイソシアネート等とが反応して得られた生成物中のイソシアネート基と反応し、ウレア結合で連結し、前記生成物を高分子量化できるものであればよく、例えば、エチレンジアミン、ヘキサメチレンジアミン、キシリレンジアミン、イソホロンジアミン、ジエチレントリアミン、Ｎ−アミノエチル−Ｎ−エタノールアミン等のアミン類、水が挙げられ、これらを単独で用いてもよいし、２種以上を併用してもよい。また、このような（ｅ）鎖延長剤とイソシアネート基との反応は、急激な反応による発熱、本発明にかかるポリウレタン樹脂のゲル化を抑制するという観点から、２０〜５０℃下で行われることが好ましい。 Examples of the (e) chain extender that can be used in the present invention include a reaction with an isocyanate group in a product obtained by reacting the (a) chlorinated polyether with the (b) polyisocyanate. Any amines such as ethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, diethylenetriamine, N-aminoethyl-N-ethanolamine can be used as long as they can be linked with urea bonds to increase the molecular weight of the product. And water, and these may be used alone or in combination of two or more. In addition, such a reaction between the chain extender (e) and the isocyanate group is performed at 20 to 50 ° C. from the viewpoint of suppressing heat generation due to rapid reaction and gelation of the polyurethane resin according to the present invention. Is preferred.
また、本発明にかかるポリウレタン樹脂としては、水性媒体における高い分散性を有するポリウレタン樹脂が得られるという観点から、前記（ａ）塩素化ポリエーテル、前記（ｂ）ポリイソシアネート、前記（ｃ）ポリオール及び前記（ｄ）親水基導入剤と、更に中和剤とを反応させて得られたものであることも好ましい。 Moreover, as a polyurethane resin concerning this invention, from a viewpoint that the polyurethane resin which has the high dispersibility in an aqueous medium is obtained, said (a) chlorinated polyether, said (b) polyisocyanate, said (c) polyol and It is also preferred that it is obtained by reacting the above (d) hydrophilic group introducing agent with a neutralizing agent.
本発明において用いることが可能な中和剤としては、前記（ａ）塩素化ポリエーテルと前記（ｂ）ポリイソシアネート等とが反応して得られた生成物中のカルボキシル基等と反応して、本発明において用いられるポリウレタン樹脂の水性媒体における分散性を向上させることが可能なものであればよく、例えば、第三級アミン、水酸化ナトリウム、水酸化カリウム、アンモニア等のアルカリが挙げられ、これらを単独で用いてもよいし、２種以上を併用してもよい。 As a neutralizing agent that can be used in the present invention, it reacts with a carboxyl group or the like in a product obtained by reacting the (a) chlorinated polyether and the (b) polyisocyanate, Any polyurethane resin can be used as long as it can improve the dispersibility of the polyurethane resin used in the present invention in an aqueous medium. Examples include alkalis such as tertiary amines, sodium hydroxide, potassium hydroxide, and ammonia. May be used alone or in combination of two or more.
このようなアルカリとしては、後述の本発明の水性塗料樹脂組成物からなる塗膜の耐水性や耐候性を向上させるという観点から、アンモニア、エチルアミン、トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン、トリエタノールアミン、トリイソプロパノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−フェニルジエタノールアミン、モノエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、モルホリン、Ｎ−メチルモルホリン等のアミン系中和剤が好ましい。 Examples of such alkalis include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, tributylamine and trimethylamine from the viewpoint of improving the water resistance and weather resistance of a coating film comprising the aqueous paint resin composition of the present invention described later. Amine-based neutralizers such as ethanolamine, triisopropanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, morpholine, N-methylmorpholine Is preferred.
本発明にかかるポリウレタン樹脂の製造方法としては、特に制限されることはなく、公知の手法を用いることができ、前記（ａ）塩素化ポリエーテル、前記（ｂ）ポリイソシアネート、前記（ｃ）ポリオール、前記（ｄ）親水基導入剤等を一度に反応させてもよいし、多段階的に反応させてもよい。 The method for producing the polyurethane resin according to the present invention is not particularly limited, and a known method can be used. The (a) chlorinated polyether, the (b) polyisocyanate, and the (c) polyol The (d) hydrophilic group-introducing agent and the like may be reacted at a time or may be reacted in a multistage manner.
また、このようなポリウレタン樹脂の製造の際に、前記（ｂ）ポリイソシアネートと前記（ａ）塩素化ポリエーテル又は前記（ｃ）ポリオールとの均一な相溶性を付与するという観点から、共溶剤を添加してもよい。このような共溶剤としては、例えば、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルを挙げることができ、これらを単独で用いてもよいし、２種以上を併用してもよい。 Further, in the production of such a polyurethane resin, from the viewpoint of imparting uniform compatibility between the (b) polyisocyanate and the (a) chlorinated polyether or the (c) polyol, a co-solvent is used. It may be added. Examples of such a co-solvent include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether. These may be used alone or in combination of two or more. You may use together.
さらに、このようなポリウレタン樹脂の製造の際に、反応速度を向上させる又は反応温度を低くするという観点から、反応触媒を添加してもよい。このような反応触媒としては、例えば、ジブチルチンジラウレート、ナフテン酸亜鉛、ジオクチルチンジラウレート等の有機金属化合物や、トリエチレンジアミン、Ｎ−メチルモルホリン等の有機アミンやその塩が挙げられる。 Furthermore, in the production of such a polyurethane resin, a reaction catalyst may be added from the viewpoint of improving the reaction rate or lowering the reaction temperature. Examples of such a reaction catalyst include organic metal compounds such as dibutyltin dilaurate, zinc naphthenate and dioctyltin dilaurate, organic amines such as triethylenediamine and N-methylmorpholine, and salts thereof.
また、本発明にかかるポリウレタン樹脂の製造の際の温度としては、６０〜９０℃であることが好ましい。ポリウレタン樹脂の製造の際の温度が前記下限未満だと反応時間が長くなるため、本発明にかかるポリウレタン樹脂の生産性が悪くなる傾向にあり、他方、前記上限を超えると原料劣化や（ｂ）ポリイソシアネートのアロファネート化、ビュレット化、ダイマー化等の副反応による品質不良の原因や本発明にかかるポリウレタン樹脂の物性のばらつきの原因となる傾向にある。 Moreover, as temperature at the time of manufacture of the polyurethane resin concerning this invention, it is preferable that it is 60-90 degreeC. When the temperature during the production of the polyurethane resin is less than the lower limit, the reaction time becomes longer, so the productivity of the polyurethane resin according to the present invention tends to be deteriorated. It tends to cause poor quality due to side reactions such as allophanatization, buretization, dimerization and the like of polyisocyanate and variation in physical properties of the polyurethane resin according to the present invention.
次に、本発明の水性ポリウレタン樹脂組成物について説明する。本発明の水性ポリウレタン樹脂組成物は前記ポリウレタン樹脂が水性媒体中に分散しているものであることを特徴とするものである。なお、本発明において用いられる水性媒体とは水を主成分とする媒体であり、前記ポリウレタン樹脂を分散させられるものであればよい。 Next, the aqueous polyurethane resin composition of the present invention will be described. The aqueous polyurethane resin composition of the present invention is characterized in that the polyurethane resin is dispersed in an aqueous medium. The aqueous medium used in the present invention is a medium mainly composed of water as long as it can disperse the polyurethane resin.
本発明の水性ポリウレタン樹脂組成物における前記ポリウレタン樹脂は、数平均分子量が５０００〜５００００のものであることが好ましい。ポリウレタン樹脂の数平均分子量が前記下限未満だと後述の水性塗料組成物からなる塗膜の耐久性が乏しくなる傾向にあり、他方、前記上限を超えると、粘度が高くなり過ぎ、塗膜が均一にならない等、後述の水性塗料組成物を用いて塗装することが困難になる傾向にある。 The polyurethane resin in the aqueous polyurethane resin composition of the present invention preferably has a number average molecular weight of 5000 to 50000. If the number average molecular weight of the polyurethane resin is less than the above lower limit, the durability of the coating film made of an aqueous coating composition described later tends to be poor. On the other hand, if the upper limit is exceeded, the viscosity becomes too high and the coating film is uniform. However, it tends to be difficult to paint using a water-based paint composition described later.
また、本発明の水性ポリウレタン樹脂組成物における前記ポリウレタン樹脂の含有量（不揮発分）は、２０〜５０質量％であることが好ましい。水性ポリウレタン樹脂組成物における不揮発分が前記下限未満だと後述の本発明の水性塗料組成物の配合設計の自由度が狭くなる傾向にあり、他方、前記上限を超えると、本発明の水性塗料組成物及び水性ポリウレタン樹脂組成物の液粘度が高くなるため、混合不良が生じる傾向にある。 Moreover, it is preferable that content (non-volatile content) of the said polyurethane resin in the aqueous | water-based polyurethane resin composition of this invention is 20-50 mass%. If the non-volatile content in the aqueous polyurethane resin composition is less than the lower limit, the degree of freedom in blending design of the aqueous paint composition of the present invention described later tends to be narrowed. Since the liquid viscosity of the product and the aqueous polyurethane resin composition increases, mixing failure tends to occur.
また、本発明の水性ポリウレタン樹脂組成物において、前記ポリウレタン樹脂における塩素含有量は、５〜９質量％であることが好ましい。前記ポリウレタン樹脂における塩素含有量が前記下限未満だと後述の水性塗料組成物からなる塗膜の基材への付着性が乏しくなる傾向にあり、他方、前記上限を超えると、後述の水性塗料組成物からなる塗膜の耐油性及び耐水性が乏しくなる傾向にある。なお、前記塩素含有量とはＪＩＳ−Ｋ７２２９に記載の方法に従って算出した値のこと、すなわち、前記ポリウレタン樹脂を酸素雰囲気下で燃焼させ、発生させた塩素ガスをイオンクロマトグラフィーを用いて定量した値のことをいう。 Moreover, the aqueous polyurethane resin composition of this invention WHEREIN: It is preferable that the chlorine content in the said polyurethane resin is 5-9 mass%. If the chlorine content in the polyurethane resin is less than the lower limit, the adhesion of the coating film made of the aqueous coating composition described later tends to be poor, whereas if the upper limit is exceeded, the aqueous coating composition described later is used. There exists a tendency for the oil resistance and water resistance of a coating film made of a product to be poor. The chlorine content is a value calculated according to the method described in JIS-K7229, that is, a value obtained by quantifying the generated chlorine gas using ion chromatography by burning the polyurethane resin in an oxygen atmosphere. I mean.
また、本発明の水性ポリウレタン樹脂組成物における前記ポリウレタン樹脂の平均粒径は２０〜１５０ｎｍであることが好ましい。ポリウレタン樹脂の平均粒径が前記下限未満だと本発明の水性樹脂組成物（分散体）の粘度が高くなるため、作業性が悪くなる傾向にあり、前記上限を超えると水性媒体中においてポリウレタン樹脂の沈殿が生じ易くなる傾向にある。なお、前記平均粒径とは動的光散乱法にて測定した値をキュムラント法にて解析した値のことをいう。 Moreover, it is preferable that the average particle diameter of the said polyurethane resin in the water-based polyurethane resin composition of this invention is 20-150 nm. If the average particle size of the polyurethane resin is less than the lower limit, the viscosity of the aqueous resin composition (dispersion) of the present invention is increased, and therefore the workability tends to be deteriorated. Tends to occur. In addition, the said average particle diameter means the value which analyzed the value measured by the dynamic light scattering method by the cumulant method.
また、水性ポリウレタン樹脂組成物の２５℃における粘度は１０００ｍＰａ・ｓ以下であることが好ましい。水性ポリウレタン樹脂組成物の２５℃における粘度が前記上限を超えると後述の水性塗料としての使用が困難になる傾向にある。なお、前記粘度とはＢ型粘度計及び番号Ｎｏ．２のロ―タを用い、回転速度６０ｒｐｍにおいて測定した値のことをいう。 The viscosity of the aqueous polyurethane resin composition at 25 ° C. is preferably 1000 mPa · s or less. If the viscosity of the aqueous polyurethane resin composition at 25 ° C. exceeds the upper limit, it tends to be difficult to use as a water-based paint described later. The viscosity is a B-type viscometer and number No. The value measured at a rotational speed of 60 rpm using a rotor No. 2.
また、水性ポリウレタン樹脂組成物におけるポリウレタン樹脂において、前記（ａ）塩素化ポリエーテル、前記（ｃ）ポリオール及び前記（ｄ）親水基導入剤由来の水酸基量（Ｘ）と前記（ｂ）ポリイソシアネート由来のイソシアネート基量（Ｙ）との当量比は、Ｘ：Ｙ＝１：１．２〜１：１．５が好ましい。前記（ａ）塩素化ポリエーテル等由来の水酸基量が前記下限未満だと、前記ポリウレタン樹脂の末端がイソシアネートのままのものが多くなり、水との反応により炭酸ガスを生じさせながら、アミンとなる傾向にあり、ひいては発泡及び前記アミンと前記中和剤との競合により、前記ポリウレタン樹脂組成物の水性媒体おける分散状態が不安定になる傾向にある。他方、前記（ａ）塩素化ポリエーテル等由来の水酸基量が前記上限を超えると、本発明にかかるポリウレタン樹脂の液粘度が著しく高くなり、水性媒体への分散が困難になるため、良好な本発明の水性ポリウレタン樹脂組成物（分散体）が得られなくなる傾向にある。なお、前記水酸基量はＪＩＳ−Ｋ１５５７に記載の方法に従って算出した値のことをいい、前記イソシアネート基量はＪＩＳ−Ｋ１５５６に記載の方法に従って算出した値のことをいう。 Further, in the polyurethane resin in the aqueous polyurethane resin composition, the amount of hydroxyl group (X) derived from (a) chlorinated polyether, (c) polyol and (d) hydrophilic group introducing agent and (b) derived from polyisocyanate. The equivalent ratio with the isocyanate group amount (Y) is preferably X: Y = 1: 1.2 to 1: 1.5. When the amount of the hydroxyl group derived from the (a) chlorinated polyether is less than the lower limit, the end of the polyurethane resin remains as an isocyanate, and becomes an amine while generating carbon dioxide gas by reaction with water. Therefore, the dispersion state of the polyurethane resin composition in the aqueous medium tends to become unstable due to foaming and competition between the amine and the neutralizing agent. On the other hand, when the amount of the hydroxyl group derived from the (a) chlorinated polyether exceeds the upper limit, the liquid viscosity of the polyurethane resin according to the present invention becomes remarkably high and it becomes difficult to disperse in an aqueous medium. It tends to be impossible to obtain the aqueous polyurethane resin composition (dispersion) of the invention. The hydroxyl group amount refers to a value calculated according to the method described in JIS-K1557, and the isocyanate group amount refers to a value calculated according to the method described in JIS-K1556.
また、本発明の水性ポリウレタン樹脂組成物を製造する方法としては、特に制限されることなく、予め親水基が導入されているポリウレタン樹脂を水性媒体中に分散させるための公知の方法を用いることができ、例えば、（ａ）塩素化ポリエーテル、（ｂ）ポリイソシアネート、（ｃ）ポリオール及び（ｄ）親水基導入剤を反応させて得られた生成物と（ｅ）鎖延長剤と中和剤とを攪拌し分散させながら水性媒体中にて反応させる方法、前記生成物と中和剤とを攪拌しながら水性媒体中にて反応及び分散させた後、さらに（ｅ）鎖延長剤と反応させる方法、前記生成物と中和剤とを反応し得られた物を水性媒体中に攪拌しながら分散させた後、さらに（ｅ）鎖延長剤と反応させる方法が挙げられる。 In addition, the method for producing the aqueous polyurethane resin composition of the present invention is not particularly limited, and a known method for dispersing a polyurethane resin into which a hydrophilic group has been introduced in advance in an aqueous medium is used. For example, (a) chlorinated polyether, (b) polyisocyanate, (c) polyol and (d) a product obtained by reacting a hydrophilic group introducing agent, (e) a chain extender and a neutralizing agent And the product and the neutralizing agent are reacted and dispersed in the aqueous medium while stirring, and then further reacted with the chain extender (e). Examples of the method include a method in which a product obtained by reacting the product with the neutralizing agent is dispersed in an aqueous medium while stirring, and then (e) a method of reacting with a chain extender.
次に、本発明の水性塗料組成物について説明する。本発明の水性塗料組成物は前記水性ポリウレタン樹脂組成物を含有しているものであり、水性塗料組成物の物性をより高め、また各種物性を付与するために、水性塗料において添加剤として公知のものを添加してもよい。このような本発明の水性塗料組成物においては、前記水性ポリウレタン樹脂組成物の含有量は２０〜４０質量％であることが好ましい。前記水性ポリウレタン樹脂組成物の含有量が前記下限未満だと塗膜にヒビ、割れ、クラック等が生じるため、塗膜自体が形成されにくくなる傾向にあり、他方、前記上限を超えると、塗工時の作業性悪化が生じる傾向にある。 Next, the aqueous coating composition of the present invention will be described. The water-based coating composition of the present invention contains the water-based polyurethane resin composition, and is known as an additive in water-based coatings in order to enhance the physical properties of the water-based coating composition and to impart various physical properties. Things may be added. In such an aqueous coating composition of the present invention, the content of the aqueous polyurethane resin composition is preferably 20 to 40% by mass. If the content of the aqueous polyurethane resin composition is less than the lower limit, cracks, cracks, cracks and the like are generated in the coating film, and thus the coating film itself tends to be difficult to be formed. There is a tendency for workability to deteriorate at times.
本発明の水性塗料組成物に用いることのできる添加剤としては、例えば、顔料、染料、成膜剤、粘度調節剤、ゲル化防止剤、難燃剤、可塑剤、酸化防止剤、紫外線吸収剤、抗菌剤、充填剤、内部離型剤、補強材、艶消し剤、導電性付与剤、帯電制御剤、帯電防止剤、滑剤、消泡剤、沈降防止剤、香料が挙げられる。 Examples of additives that can be used in the aqueous coating composition of the present invention include pigments, dyes, film-forming agents, viscosity modifiers, anti-gelling agents, flame retardants, plasticizers, antioxidants, ultraviolet absorbers, Examples include antibacterial agents, fillers, internal mold release agents, reinforcing materials, matting agents, conductivity-imparting agents, charge control agents, antistatic agents, lubricants, antifoaming agents, antisettling agents, and fragrances.
また、本発明の水性塗料組成物は、本発明の効果を損なわない限り、他の樹脂組成物を混合して使用することもでき、例えば、アクリルエマルジョン、ポリエステルエマルジョン、ポリオレフィンエマルジョン、ラテックスが挙げられる。 In addition, the aqueous coating composition of the present invention can be used by mixing with other resin compositions as long as the effects of the present invention are not impaired. Examples thereof include acrylic emulsion, polyester emulsion, polyolefin emulsion, and latex. .
本発明の水性塗料組成物を用いた塗装方法は、特に制限されることはなく、公知の方法を用いることができ、例えば、エアスプレーによる塗装、エアレススプレーによる塗装、ローラーによる塗装、刷毛による塗装、静電塗装を用いて行うことができる。 The coating method using the aqueous coating composition of the present invention is not particularly limited, and a known method can be used. For example, coating by air spray, coating by airless spray, coating by roller, coating by brush Can be performed using electrostatic coating.
また、本発明の水性塗料組成物を用いて塗装することができる基材（被塗装基材）としては、特に制限されることはなく、例えば、プラスティック、金属、木材、石材が挙げられる。さらに、このような被塗装基材としては、化成処理、下塗り塗装、中塗り塗装等を予め施したものであってもよい。また、被塗装基材に本発明の水性塗料組成物を塗布した後、既知の塗料を塗布することもできる。 In addition, the substrate (substrate to be coated) that can be coated using the aqueous coating composition of the present invention is not particularly limited, and examples thereof include plastic, metal, wood, and stone. Furthermore, as such a base material to be coated, chemical conversion treatment, undercoat coating, intermediate coating, or the like may be performed in advance. Moreover, after apply | coating the water-based coating composition of this invention to a to-be-coated base material, a known coating material can also be apply | coated.
さらに、本発明の水性塗料組成物を用いた塗装後の乾燥方法としては、特に制限されることはなく、例えば、常温乾燥、加温乾燥、焼き付けが挙げられ、本発明の水性塗料組成物の組成に応じて適宜温度等の調整をしながら用いることができる。 Furthermore, the drying method after coating using the aqueous coating composition of the present invention is not particularly limited, and examples thereof include room temperature drying, heating drying, baking, and the like. It can be used while appropriately adjusting the temperature or the like according to the composition.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
（合成例１）
＜塩素化エポキシブタンの合成＞
攪拌機、冷却管、温度計、窒素導入管を取り付けた４つ口フラスコ（容積：５Ｌ）に、７０％ｍ−クロロ過安息香酸１０００ｇ（４．０６ｍｏｌ）とクロロホルム１３６０ｍｌを仕込み、攪拌してｍ−クロロ過安息香酸を溶解した。得られたｍ−クロロ過安息香酸溶液に３，４−ジクロロ−２−ブテン４２６ｇ（３．４４ｍｏｌ）を加え、４０℃で２４時間反応を行った後、スラリー溶液を濾過し、濾液のクロロホルムをエバポレーターで除去し、３，４−ジクロロ−１，２−エポキシブタン粗生成物を得た。得られた３，４−ジクロロ−１，２−エポキシブタン粗生成物をさらに減圧蒸留し、３３５ｇの３，４−ジクロロ−１，２−エポキシブタン（精製物）を得た。
(Synthesis Example 1)
<Synthesis of chlorinated epoxy butane>
A four-necked flask (volume: 5 L) equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube was charged with 1000 g (4.06 mol) of 70% m-chloroperbenzoic acid and 1360 ml of chloroform, and the mixture was stirred. Chloroperbenzoic acid was dissolved. To the obtained m-chloroperbenzoic acid solution, 426 g (3.44 mol) of 3,4-dichloro-2-butene was added and reacted at 40 ° C. for 24 hours. Then, the slurry solution was filtered, and the chloroform of the filtrate was filtered. Removal with an evaporator gave a crude 3,4-dichloro-1,2-epoxybutane product. The obtained 3,4-dichloro-1,2-epoxybutane crude product was further distilled under reduced pressure to obtain 335 g of 3,4-dichloro-1,2-epoxybutane (purified product).
（合成例２）
＜塩素化ポリエーテルの合成＞
攪拌機、冷却管、温度計、窒素導入管を取り付けた４つ口フラスコ（容積：２００ｍｌ）を減圧下で加熱乾燥し、窒素置換を行った後、重合開始剤としてプロピレングリコール２．７ｇ（３６ｍｍｏｌ）、酸触媒として三フッ化ホウ素エーテル錯体０．５２ｇ、重合溶媒として塩化メチレン３０ｇ、合成例１で得られた３，４−ジクロロ−１，２−エポキシブタン（精製物）３０ｇ（２１４ｍｍｏｌ）を仕込み、氷水浴下で攪拌を行いながら１時間重合反応を行った。得られた反応液に１％水酸化ナトリウム水溶液２５ｍｌを加え３０分攪拌し、油水分離を行った後、得られた有機層を無水硫酸ナトリウムにより乾燥し、無水硫酸ナトリウム、塩化メチレンを除去することにより粘性液体３１ｇを得た。
(Synthesis Example 2)
<Synthesis of chlorinated polyether>
A four-necked flask (volume: 200 ml) equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube was heated and dried under reduced pressure to perform nitrogen substitution, and then 2.7 g (36 mmol) of propylene glycol as a polymerization initiator. In addition, 0.52 g of boron trifluoride ether complex as an acid catalyst, 30 g of methylene chloride as a polymerization solvent, and 30 g (214 mmol) of 3,4-dichloro-1,2-epoxybutane (purified product) obtained in Synthesis Example 1 were charged. The polymerization reaction was carried out for 1 hour while stirring in an ice-water bath. After adding 25 ml of 1% sodium hydroxide aqueous solution to the obtained reaction solution and stirring for 30 minutes, oil / water separation was performed, and then the obtained organic layer was dried over anhydrous sodium sulfate to remove anhydrous sodium sulfate and methylene chloride. As a result, 31 g of a viscous liquid was obtained.
得られた粘性液体は１Ｈ−ＮＭＲ測定から、１．２ｐｐｍにプロピレングリコールのメチル基、３．４〜４．４ｐｐｍにプロピレングリコールのメチレン及びメチンと３，４−ジクロロ−１，２−エポキシブタンが開環したメチレンとメチンのプロトンが観測されたことから、３，４−ジクロロ−１，２−エポキシブタンが開環重合した塩素化ポリエーテル（３，４−ジクロロ−１，２−エポキシブタン共重合体）であることが確認された。 From the 1 H-NMR measurement, the resulting viscous liquid was found to be 1.2 ppm of methyl group of propylene glycol, 3.4 to 4.4 ppm of methylene and methine of propylene glycol and 3,4-dichloro-1,2-epoxybutane. As a result of the observation of the protons of methylene and methine that were ring-opened, 3,4-dichloro-1,2-epoxybutane was subjected to ring-opening polymerization (3,4-dichloro-1,2-epoxybutane). Copolymer).
さらに、ＪＩＳ−Ｋ１５５７に記載の方法に従った解析及び前述のゲル・パーミエイション・クロマトグラフィーを用いた解析により、得られた塩素化ポリエーテルは、水酸基価１２０、数平均分子量８００の塩素化ポリエーテルであることも確認された。 Furthermore, the chlorinated polyether obtained by the analysis according to the method described in JIS-K1557 and the analysis using the gel permeation chromatography described above was chlorinated with a hydroxyl value of 120 and a number average molecular weight of 800. It was also confirmed to be a polyether.
（合成例３）
＜ＨＤＩアロファネートの合成＞
攪拌機、温度計、冷却器及び窒素ガス導入管のついた反応器（容積：１Ｌ）に、ヘキサメチレンジイソシアネート（ＨＤＩ）を９５０ｇ、３−メチル−１，５−ペンタンジオール（ＭＰＤ）を５０ｇ、２−エチルヘキサン酸ジルコニウムを０．２ｇ仕込み、１１０℃にて５時間反応させた。得られた生成物は、ＦＴ−ＩＲ及び１３Ｃ−ＮＭＲの分析から、ウレタン基は有しておらず、アロファネート基を有していることが確認された。前記反応器にさらにリン酸を０．１ｇ仕込み５０℃で１時間停止反応を行った。停止反応後の生成物のイソシアネート含量は４０．４質量％であった。さらに、停止反応後の生成物につき、１３０℃、０．０４ｋＰａの条件にて薄膜蒸留を行い、収率：３１．３％、数平均分子量：１１００、イソシアネート含量：１９．２％、粘度：１７２０ｍＰａ・ｓ ａｔ ２５℃、平均官能基数：４．９、遊離のＨＤＩ含有量：０．２％、アロファネート基含有量：２．７ｍｍｏｌ／ｇのＨＤＩアロファネートを得た。得られたＨＤＩアロファネートをＦＴ−ＩＲ及び１３Ｃ−ＮＭＲにて分析したところ、ウレタン基の存在は認められず、アロファネート基の存在が確認され、また、ウレトジオン基及びイソシアヌレート基は痕跡程度の存在が確認された。
(Synthesis Example 3)
<Synthesis of HDI allophanate>
To a reactor (volume: 1 L) equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, 950 g of hexamethylene diisocyanate (HDI), 50 g of 3-methyl-1,5-pentanediol (MPD), 2 -0.2 g of zirconium ethylhexanoate was charged and reacted at 110 ° C for 5 hours. From the analysis of FT-IR and 13 C-NMR, it was confirmed that the obtained product did not have a urethane group but had an allophanate group. The reactor was further charged with 0.1 g of phosphoric acid, and stopped at 50 ° C. for 1 hour. The isocyanate content of the product after the termination reaction was 40.4% by mass. Further, the product after the termination reaction was subjected to thin film distillation under conditions of 130 ° C. and 0.04 kPa, yield: 31.3%, number average molecular weight: 1100, isocyanate content: 19.2%, viscosity: 1720 mPa -The HDI allophanate of sat25 degreeC, average functional group number: 4.9, free HDI content: 0.2%, allophanate group content: 2.7 mmol / g was obtained. When the obtained HDI allophanate was analyzed by FT-IR and 13 C-NMR, the presence of urethane groups was not confirmed, the presence of allophanate groups was confirmed, and uretdione groups and isocyanurate groups were present in trace amounts. Was confirmed.
（実施例１）
攪拌機、冷却管、温度計、窒素導入管を取り付けた反応器（容積：５００ｍｌ）に、合成例２で得られた３，４−ジクロロ−１，２−エポキシブタン共重合体と、ヘキサメチレンジイソシアネート（ＨＤＩ）及びイソホロンジイソシアネート（ＩＰＤＩ）と、エチレングリコール、ネオペンチルグリコール、アジピン酸、イソフタル酸からなるポリエステルポリオール（フタル酸系ポリエステルポリオール、日本ポリウレタン工業株式会社製、製品名：ニッポラン５７１１）と、親水基導入剤としてジメチロールプロピオン酸（ＤＭＰＡ）と、共溶剤としてジプロピレングリコールジメチルエーテル（ＤＰＧＤＭＥ）及びトリエチレングリコールジメチルエーテル（ＴＥＧＤＭＥ）とを表１に示した分量で各々仕込み、８５℃に加温し、同温度で４時間反応させた。得られた生成物に、中和剤としてトリエチルアミン（ＴＥＡ）をＤＭＰＡと同モル量になるよう仕込み、生成物中のカルボキシル基を中和した後、攪拌しながら脱イオン水を３５０ｇ仕込み、中和した生成物を水中に分散させた。さらに、分散後３０分以内に、水中に分散させた生成物に鎖延長剤としてアミン水（エチレンジアミン０．９６ｍｏｌを脱イオン水０．２４ｍｏｌに溶かしたもの）を仕込み、鎖延長反応を３０℃にて１２時間行い、水性ポリウレタン樹脂組成物を得た。
Example 1
3,4-Dichloro-1,2-epoxybutane copolymer obtained in Synthesis Example 2 and hexamethylene diisocyanate in a reactor (volume: 500 ml) equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube (HDI) and isophorone diisocyanate (IPDI), a polyester polyol composed of ethylene glycol, neopentyl glycol, adipic acid, and isophthalic acid (phthalic polyester polyol, manufactured by Nippon Polyurethane Industry Co., Ltd., product name: NIPPOLAN 5711), hydrophilic Dimethylolpropionic acid (DMPA) as a group introducing agent and dipropylene glycol dimethyl ether (DPGDME) and triethylene glycol dimethyl ether (TEGDME) as co-solvents were respectively charged in the amounts shown in Table 1, and heated to 85 ° C., Same temperature In was reacted for 4 hours. The resulting product was charged with triethylamine (TEA) as a neutralizing agent in the same molar amount as DMPA, neutralized with carboxyl groups in the product, and then charged with 350 g of deionized water with stirring. The product obtained was dispersed in water. Further, within 30 minutes after dispersion, the product dispersed in water was charged with amine water (0.96 mol of ethylenediamine dissolved in 0.24 mol of deionized water) as a chain extender, and the chain extension reaction was brought to 30 ° C. For 12 hours to obtain an aqueous polyurethane resin composition.
得られた水性ポリウレタンン樹脂組成物の性状については、下記に示す方法にて確認した。得られた結果を表２に示す。 About the property of the obtained water-based polyurethane resin composition, it confirmed by the method shown below. The obtained results are shown in Table 2.
＜塩素含有量＞
得られた水性ポリウレタン樹脂組成物中のポリウレタン樹脂における塩素含有量（質量％）は、ＪＩＳ−Ｋ７２２９に記載の方法に従って、得られたポリウレタン樹脂を燃焼させ、発生させた塩素ガスをイオンクロマトグラフィー（株式会社島津製作所製、製品名：ＣＬＡＳＳ−ｖｐ ｖｅｒ５．０３２）を用いて定量することにより求めた。
<Chlorine content>
The chlorine content (% by mass) in the polyurethane resin in the obtained aqueous polyurethane resin composition is determined by burning the obtained polyurethane resin in accordance with the method described in JIS-K7229, and the generated chlorine gas is subjected to ion chromatography ( It was determined by quantification using Shimadzu Corporation product name: CLASS-vp ver5.032.
＜不揮発分＞
得られた水性ポリウレタン樹脂組成物及びそれに含有されるポリウレタン樹脂、各々の質量を測定し、水性ポリウレタン樹脂組成物の質量に対するポリウレタン樹脂質量の比率を算出し、得られた水性ポリウレタン樹脂組成物の不揮発分（質量％）を求めた。
<Nonvolatile content>
The obtained aqueous polyurethane resin composition and the polyurethane resin contained therein, each mass was measured, the ratio of the polyurethane resin mass to the mass of the aqueous polyurethane resin composition was calculated, and the non-volatile property of the obtained aqueous polyurethane resin composition Minute (mass%) was determined.
＜粘度＞
得られた水性ポリウレタン樹脂組成物を、その液温が２５℃になるように調整した後、Ｂ型粘度計（東機産業株式会社製、製品名：ＴＶＢ−２２Ｌ、使用したローター番号：Ｎｏ．２）を用いて、回転速度６０ｒｐｍにおいて測定し、得られた水性ポリウレタン樹脂組成物の粘度（ｍＰａ・ｓ ａｔ ２５℃）を求めた。
<Viscosity>
After adjusting the obtained aqueous polyurethane resin composition so that the liquid temperature was 25 ° C., a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: TVB-22L, used rotor number: No. 2), the viscosity (mPa · s at 25 ° C.) of the aqueous polyurethane resin composition obtained was measured at a rotational speed of 60 rpm.
＜平均粒径＞
得られた水性ポリウレタン樹脂組成物を光散乱光度計（大塚電子株式会社製、製品名：ＥＬＳ−８００）にかけ、キュムラント法にて解析し、得られた水性ポリウレタン樹脂組成物中のポリウレタン樹脂の平均粒径を求めた。
<Average particle size>
The obtained aqueous polyurethane resin composition was subjected to a light scattering photometer (manufactured by Otsuka Electronics Co., Ltd., product name: ELS-800), analyzed by the cumulant method, and the average of the polyurethane resin in the obtained aqueous polyurethane resin composition The particle size was determined.
得られた水性ポリウレタン樹脂組成物については、ＡＢＳ（株式会社ユーコウ商会製、ＡＢＳ−Ｎ−ＷＮ）からなる基材上にアプリケータを用いて、乾燥膜厚で２０μｍとなるように均一に塗装し、７０℃で０．５時間かけ乾燥させ試験片を作製した。得られた試験片については下記に示す塗膜評価を行った。得られた結果を表３に示す。 About the obtained water-based polyurethane resin composition, it apply | coated uniformly so that it might become a dry film thickness of 20 micrometers using an applicator on the base material which consists of ABS (the Yuko Co., Ltd. make, ABS-N-WN). The test piece was prepared by drying at 70 ° C. for 0.5 hour. About the obtained test piece, the coating-film evaluation shown below was performed. The obtained results are shown in Table 3.
＜付着性試験＞
得られた試験片の塗膜の付着性については、ＪＩＳ−Ｋ５６００−５−６に準じて評価した。すなわち、試験片の塗膜面に１ｍｍ間隔で各６本の切り込みを縦横に入れて、計２５個のマス目を得た。得られた２５個のマス目の全面に粘着性テープ（ニチバン株式会社製、商品名：セロテープ（登録商標））を貼り付けて一気に剥がし、残ったマス目の数を数えた。そして、残ったマス目の数が１３個（５０％）以上であるものを「○」と評価し、５０％未満であるものを「×」と評価した。
<Adhesion test>
About the adhesiveness of the coating film of the obtained test piece, it evaluated according to JIS-K5600-5-6. That is, six cuts were made vertically and horizontally at 1 mm intervals on the coating surface of the test piece to obtain a total of 25 squares. Adhesive tape (manufactured by Nichiban Co., Ltd., trade name: cello tape (registered trademark)) was attached to the entire surface of the 25 squares thus obtained and peeled off at once, and the number of the remaining squares was counted. Then, those having 13 (50%) or more of the remaining squares were evaluated as “◯”, and those having less than 50% were evaluated as “x”.
＜耐油性試験＞
得られた試験片の塗膜面の上に牛脂を置き、さらにカバーガラスを牛脂上に押しつけながらかぶせた。カバーガラス及び牛脂で被覆した試験片を８０℃下で３時間放置した後に、カバーガラスを取り、試験片の塗膜の変化について下記基準を用いて視覚や触覚による官能評価を行った。
５点…カバーグラスを外した後、外観上、塗膜から牛脂をふき取っても塗膜に変化が全くない状態
４点…爪で塗膜面に触れて、塗膜の軟化がやや生じていることが分かった状態
３点…爪で塗膜面に触れて、塗膜の軟化が明らかに生じていることが分かった状態
２点…外観上、塗膜にブリスターやクラックが発生していた状態
１点…カバーグラスを外したときに、外観上、塗膜が基材から剥がれた（膨潤により塗膜が浮き、容易に基材から剥がれてしまった）状態。
<Oil resistance test>
The beef tallow was placed on the coating surface of the obtained test piece, and further covered with a cover glass pressed against the beef tallow. The test piece covered with the cover glass and beef tallow was allowed to stand at 80 ° C. for 3 hours, and then the cover glass was taken, and the sensory evaluation by visual or tactile sensation was performed using the following criteria for the change in the coating film of the test piece.
5 points: After removing the cover glass, there is no change in the coating film even if the beef tallow is wiped off from the coating film. 4 points: Touching the coating film surface with a nail causes a slight softening of the coating film. 3 points where it was found that touching the surface of the coating with a nail, 2 points where it was found that softening of the coating was clearly occurring. State where blisters and cracks were generated in the coating 1 point: When the cover glass was removed, the coating film was peeled from the base material in appearance (the coating film floated due to swelling and was easily peeled off from the base material).
＜耐水性試験＞
得られた試験片を、室温（２３℃）下で１日、さらに６０℃下で１日養生した後に、４０℃の水に浸漬した。そして、浸漬してから２４時間後に試験片の塗膜について、全く変化がなかった場合は「○」、変化があった場合は「×」として、視覚による官能評価を行った。
<Water resistance test>
The obtained test piece was cured at room temperature (23 ° C.) for 1 day and further at 60 ° C. for 1 day, and then immersed in water at 40 ° C. Then, after 24 hours of immersion, the test piece coating was visually evaluated as “◯” when there was no change and “X” when there was a change.
（実施例２及び比較例１）
実施例２においては、ＨＤＩ及びＩＰＤＩの代わりに、合成例３で得られたＨＤＩアロファネートを用いた以外は実施例１と同様にして水性ポリウレタン樹脂組成物を作製した。また、比較例１においては、ＨＤＩ及びＩＰＤＩの代わりに合成例３で得られたＨＤＩアロファネートを、さらに３，４−ジクロロ−１，２−エポキシブタン共重合体を用いなかった以外は実施例１と同様にして水性ポリウレタン樹脂組成物を作製した。得られた各々の水性ポリウレタン樹脂組成物の性状については実施例１と同様に解析した。得られた結果を表２に示す。また、得られた各々の水性ポリウレタン樹脂組成物を用いて実施例１と同様にして各試験片を作製し、塗膜評価を行った。得られた結果を表３に示す。
(Example 2 and Comparative Example 1)
In Example 2, an aqueous polyurethane resin composition was prepared in the same manner as in Example 1 except that the HDI allophanate obtained in Synthesis Example 3 was used instead of HDI and IPDI. Further, in Comparative Example 1, Example 1 except that HDI allophanate obtained in Synthesis Example 3 was not used in addition to 3,4-dichloro-1,2-epoxybutane copolymer in place of HDI and IPDI. In the same manner, an aqueous polyurethane resin composition was produced. About the property of each obtained water-based polyurethane resin composition, it analyzed similarly to Example 1. FIG. The obtained results are shown in Table 2. Moreover, each test piece was produced like Example 1 using each obtained water-based polyurethane resin composition, and coating-film evaluation was performed. The obtained results are shown in Table 3.
（比較例２〜４）
比較例２においては塩素化ポリオレフィン（東洋化成工業株式会社製、製品名：ＥＷ−５５０４）と比較例１で得られた水性ポリウレタン樹脂組成物とを塩素化ポリオレフィン：水性ポリウレタン樹脂（質量比）＝２５：７５の割合で混合し、比較例３においては前記塩素化ポリオレフィンと比較例１で得られた水性ポリウレタン樹脂組成物とを塩素化ポリオレフィン：水性ポリウレタン樹脂（質量比）＝６０：４０の割合で混合し、各々水性ポリウレタン樹脂組成物を作製した。また、比較例４においては前記塩素化ポリオレフィンを比較例１で得られた水性ポリウレタン樹脂組成物と混合することなく用意した。得られた各々の水性ポリウレタン樹脂組成物及び塩素化ポリオレフィンの性状については実施例１と同様に解析した。得られた結果を表２に示す。また、得られた各々の水性ポリウレタン樹脂組成物及び塩素化ポリオレフィンを用いて実施例１と同様にして各試験片を作製し、塗膜評価を行った。得られた結果を表３に示す。
(Comparative Examples 2 to 4)
In Comparative Example 2, chlorinated polyolefin (manufactured by Toyo Kasei Kogyo Co., Ltd., product name: EW-5504) and the aqueous polyurethane resin composition obtained in Comparative Example 1 were chlorinated polyolefin: aqueous polyurethane resin (mass ratio) = In the comparative example 3, the chlorinated polyolefin and the aqueous polyurethane resin composition obtained in the comparative example 1 were mixed in a ratio of 25:75. The ratio of chlorinated polyolefin: aqueous polyurethane resin (mass ratio) = 60: 40 Were mixed with each other to prepare aqueous polyurethane resin compositions. In Comparative Example 4, the chlorinated polyolefin was prepared without mixing with the aqueous polyurethane resin composition obtained in Comparative Example 1. The properties of each obtained aqueous polyurethane resin composition and chlorinated polyolefin were analyzed in the same manner as in Example 1. The obtained results are shown in Table 2. Moreover, each test piece was produced like Example 1 using each obtained water-based polyurethane resin composition and chlorinated polyolefin, and coating-film evaluation was performed. The obtained results are shown in Table 3.
表３に示した結果から明らかなように、本発明の水性ポリウレタン樹脂組成物を用いた場合（実施例１〜２）は、塗膜のプラスティック基材への付着性、耐油性及び耐水性が優れたものであった。一方、本発明にかかる（ａ）塩素化ポリエーテルを用いることなく作製された水性ポリウレタン樹脂組成物を用いた場合（比較例１）及び２５質量％の塩素化ポリオレフィンを含有する水性ポリウレタン樹脂組成物を用いた場合（比較例２）においては、塗膜のプラスティック基材への付着性及び耐水性の点で本発明の水性ポリウレタン樹脂組成物と比して劣っており、また、６０質量％の塩素化ポリオレフィンを含有する水性ポリウレタン樹脂組成物を用いた場合（比較例３）及び塩素化ポリオレフィンのみを用いた場合（比較例４）においては、塗膜の耐油性及び耐水性の点で本発明の水性ポリウレタン樹脂組成物と比して劣ったものであった。 As is clear from the results shown in Table 3, when the aqueous polyurethane resin composition of the present invention was used (Examples 1 and 2), the adhesion of the coating film to the plastic substrate, oil resistance and water resistance were It was excellent. On the other hand, when (a) the aqueous polyurethane resin composition produced without using the chlorinated polyether according to the present invention is used (Comparative Example 1) and the aqueous polyurethane resin composition containing 25% by mass of chlorinated polyolefin (Comparative Example 2) is inferior to the aqueous polyurethane resin composition of the present invention in terms of adhesion of the coating film to the plastic substrate and water resistance, and 60% by mass. In the case of using a water-based polyurethane resin composition containing chlorinated polyolefin (Comparative Example 3) and in the case of using only chlorinated polyolefin (Comparative Example 4), the present invention in terms of oil resistance and water resistance of the coating film. It was inferior compared with the aqueous polyurethane resin composition.
以上説明したように、本発明によれば、プラスティック基材等への付着性に優れ、且つ耐油性及び耐水性に優れた塗膜の形成を可能とする水性ポリウレタン樹脂組成物、並びにそれを用いた水性塗料組成物を提供することが可能となる。 As described above, according to the present invention, an aqueous polyurethane resin composition that is excellent in adhesion to a plastic substrate and the like, and that can form a coating film that is excellent in oil resistance and water resistance, and uses the same. It is possible to provide a water-based paint composition.
したがって、本発明の水性塗料組成物は、非極性の素材からなる基材への付着性に特に優れた塗膜を形成するため、オレフィン基材（特にポリプロピレン）、ゴム成分複合基材（特にアクリロニトリルブタジエンスチレン共重合（ＡＢＳ）樹脂）等のプラスティック基材用の水性塗料組成物として特に有用である。 Therefore, the water-based coating composition of the present invention forms a coating film that is particularly excellent in adhesion to a base material made of a non-polar material, so that an olefin base material (particularly polypropylene), a rubber component composite base material (particularly acrylonitrile). It is particularly useful as an aqueous coating composition for plastic substrates such as butadiene styrene copolymer (ABS) resin.
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| JP2018513233A (en) * | 2015-03-12 | 2018-05-24 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Aqueous polyurethane dispersion |
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