JPH0489832A - Aqueous dispersion - Google Patents
Aqueous dispersionInfo
- Publication number
- JPH0489832A JPH0489832A JP20557790A JP20557790A JPH0489832A JP H0489832 A JPH0489832 A JP H0489832A JP 20557790 A JP20557790 A JP 20557790A JP 20557790 A JP20557790 A JP 20557790A JP H0489832 A JPH0489832 A JP H0489832A
- Authority
- JP
- Japan
- Prior art keywords
- olefin copolymer
- copolymer
- aqueous dispersion
- modified
- adhesion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 50
- 239000004711 α-olefin Substances 0.000 claims abstract description 57
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 56
- 229920001577 copolymer Polymers 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- -1 monoolefin dicarboxylic acids Chemical class 0.000 claims description 29
- 238000007334 copolymerization reaction Methods 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 229920001038 ethylene copolymer Polymers 0.000 claims description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 abstract description 31
- 238000000576 coating method Methods 0.000 abstract description 31
- 239000003960 organic solvent Substances 0.000 abstract description 20
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 9
- 150000005673 monoalkenes Chemical class 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 4
- 229920000647 polyepoxide Polymers 0.000 abstract description 4
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 4
- 239000005061 synthetic rubber Substances 0.000 abstract description 4
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000003973 paint Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229920000578 graft copolymer Polymers 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007870 radical polymerization initiator Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-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
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MPKIZIGHGVKHDY-UHFFFAOYSA-N 2-tert-butyl-5-methylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1O MPKIZIGHGVKHDY-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- BEQGRRJLJLVQAQ-UHFFFAOYSA-N 3-methylpent-2-ene Chemical compound CCC(C)=CC BEQGRRJLJLVQAQ-UHFFFAOYSA-N 0.000 description 1
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000728 ammonium alginate Substances 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000006083 mineral thickener Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940080314 sodium bentonite Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- XCPXWEJIDZSUMF-UHFFFAOYSA-M sodium;dioctyl phosphate Chemical compound [Na+].CCCCCCCCOP([O-])(=O)OCCCCCCCC XCPXWEJIDZSUMF-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は水分散体に関し、特に各種の樹脂成形品に下塗
りして成形品の表面への塗料の付着性を向上させること
かできるとともに、有機溶媒を含有しないため、作業環
境を良好に保つことができる、ブライマーとして好適な
水分散体に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to an aqueous dispersion, and in particular can be used to undercoat various resin molded products to improve the adhesion of paint to the surface of the molded product. The present invention relates to an aqueous dispersion suitable as a brimer that can maintain a good working environment because it does not contain an organic solvent.
〈従来の技術〉
従来、ポリプロピレン等のポリオレフィンの成形品の表
面に塗装を施したり、他の樹脂層を形設したりして、そ
の付加価値を高めることが行われている。 しかし、
一般にポリオレフィンは、極性に乏しく、一般の塗料や
他の樹脂との付着性か悪い。 そのため、従来は予め成
形品の表面を、クロム酸、火炎、コロナ放電、プラズマ
、溶剤等で処理して該表面の極性を高めることにより、
塗料の付着性を改善することか試みられてきた。 し
かし、これらの処理においては、複雑な処理を要したり
、腐食性の薬品を使用するため危険を伴なったりする難
点かある。 また、安定した処理効果を得るためには、
厳しい工程管理か必要であるという欠点かある。<Prior Art> Conventionally, the added value of polyolefin molded products such as polypropylene has been increased by painting the surface or forming other resin layers. but,
Polyolefins generally have poor polarity and have poor adhesion to common paints and other resins. Therefore, conventionally, the surface of the molded product is treated in advance with chromic acid, flame, corona discharge, plasma, solvent, etc. to increase the polarity of the surface.
Attempts have been made to improve the adhesion of paints. However, these treatments have disadvantages in that they require complicated treatments and are dangerous due to the use of corrosive chemicals. In addition, in order to obtain stable treatment effects,
The drawback is that it requires strict process control.
そこで、ごわらの欠点を改良する有効な手段として、成
形品等の表面をブライマーで塗布処理する方法があり、
そのブライマーとして、本出願人は、先に、特定のプロ
ピレン・エチレン共重合体にマルイン酸またはその無水
物をグラフト共重合させてなる変性重合体を有機溶媒に
溶解してなる表面処理剤を提案した。(特公昭62−2
1027号公報) また、X線回折によって測定される
結晶化度か20%以下のαオレフィン共重合体に、モノ
オレフィンシカルホン酸モノアルキルエステルを05〜
15重王%グラフト共重合してなる変性重合体を有機溶
媒に溶解してなる表面処理剤を提案した。Therefore, as an effective means to improve the defects of Gowara, there is a method of coating the surface of molded products with a brimer.
As a primer, the applicant previously proposed a surface treatment agent made by dissolving a modified polymer obtained by graft copolymerizing marinic acid or its anhydride on a specific propylene/ethylene copolymer in an organic solvent. did. (Tokuko Showa 62-2
No. 1027) In addition, monoolefin cyclophonic acid monoalkyl ester is added to an α-olefin copolymer having a crystallinity of 20% or less as measured by X-ray diffraction.
We have proposed a surface treatment agent made by dissolving a modified polymer obtained by graft copolymerization of 15% heavy king in an organic solvent.
(特公昭61−11250号公報)
〈発明か解決しようとする課題〉
しかし、前屈に提案された表面処理剤は、良好な付着性
および保存安定性を有し、ブライマーとして有用である
か、いずれも有機溶媒を含有している。 ところで、近
年、揮発性有機溶媒の使用量を低減させ、工場内の作業
環境を良好に保つために、有機溶媒を含有しない、ある
いは有機溶媒を含有していても、その含有量が少量であ
る表面処理剤か、強く要望されている。 そのため、前
記の表面処理剤では、このような要望に応えることが困
難である。(Japanese Patent Publication No. 61-11250) <Problem to be solved by the invention> However, it is unclear whether the surface treatment agent proposed for forward bending has good adhesion and storage stability and is useful as a brimer. Both contain organic solvents. By the way, in recent years, in order to reduce the amount of volatile organic solvents used and maintain a good working environment in factories, there have been efforts to reduce the amount of volatile organic solvents used and to maintain a good working environment in factories. There is a strong demand for surface treatment agents. Therefore, it is difficult for the above-mentioned surface treatment agents to meet such demands.
そこて本発明の目的は、樹脂成形品、例えは、ポリプロ
ピレン等のポリオレフィン、合成ゴム、不飽和ポリエス
テル、エポキシ樹脂、ポリウレタン樹脂等、あるいはこ
れらの複合樹脂等の各種の樹脂からなる成形品との付着
性に優れるため、これらの成形品の表面に’48して十
分な剥離強度および密着性を有する塗膜を得ることがて
ぎ、さらに保存安定性が良好であるとともに、有機溶媒
を含有しない水系であるため、作業環境を良好に保つこ
とかできる、ブライマーとして好適な水分散体を提供す
ることにある。Therefore, it is an object of the present invention to mold resin products, for example, molded products made of various resins such as polyolefins such as polypropylene, synthetic rubber, unsaturated polyesters, epoxy resins, polyurethane resins, or composite resins thereof. Because of its excellent adhesion, it is necessary to obtain a coating film with sufficient peel strength and adhesion on the surface of these molded products, and it also has good storage stability and does not contain organic solvents. The object of the present invention is to provide an aqueous dispersion suitable as a brimer, which can maintain a good working environment because it is aqueous.
〈課題を解決するための手段〉
本発明は、前記課題を解決するために、結晶化度か20
%以下のα−オレフィン共重合体に、モノオレフィンジ
カルボン酸およびその無水物並ひにモノオレフィンジカ
ルボン酸のモノアルキルエステルから運ばれる少なくと
も1種を05〜15重量%含むようにグラフト共重合さ
せてなる変性共重合体を、さらに塩素化して得られる塩
素含有率10〜50重量%の塩素化変性α−オレフィン
共重合体を水に分散させてなる水分散体であって、該塩
素化変性α−オレフィン共重合体5〜70重量部に対し
て、水95〜30重量部を含む水分散体を提供するもの
である。<Means for Solving the Problems> In order to solve the above problems, the present invention provides crystallinity of 20
% or less of an α-olefin copolymer is graft copolymerized to contain from 05 to 15% by weight of at least one species carried from a monoolefin dicarboxylic acid and its anhydride as well as a monoalkyl ester of the monoolefin dicarboxylic acid. An aqueous dispersion obtained by dispersing in water a chlorinated modified α-olefin copolymer with a chlorine content of 10 to 50% by weight obtained by further chlorinating a modified copolymer, the chlorinated modified α-olefin copolymer having a chlorine content of 10 to 50% by weight. - An aqueous dispersion containing 95 to 30 parts by weight of water to 5 to 70 parts by weight of the olefin copolymer is provided.
また、前記α−オレフィン共重合体が、プロピレン・エ
チレン共重合体およびプロピレン・ブテン・エチレン共
重合体から選ばれる少なくとも1種であると、好ましい
。Further, it is preferable that the α-olefin copolymer is at least one selected from a propylene/ethylene copolymer and a propylene/butene/ethylene copolymer.
以下、本発明の水分散体について詳細に説明する。Hereinafter, the aqueous dispersion of the present invention will be explained in detail.
本発明の水分散体の生成分である塩素化変性α−オレフ
ィン共重合体は、α−オレフィン共重合体にモノオレフ
ィンジカルボン酸およびその無水物並びにモノオレフィ
ンジカルボン酸のモノアルキルエステルから選ばれる少
なくとも1種をグラフト共重合させてなる変性共重合体
を、さらに塩素化してなるものである。The chlorinated modified α-olefin copolymer, which is a product of the aqueous dispersion of the present invention, includes an α-olefin copolymer and at least one selected from monoolefin dicarboxylic acids and their anhydrides, and monoalkyl esters of monoolefin dicarboxylic acids. It is obtained by further chlorinating a modified copolymer obtained by graft copolymerizing one type of copolymer.
この塩素化変性α−オレフィン共重合体の主要構成成分
であるα−オレフィン共重合体は、プロピレンおよび/
またはエチレンを主成分とするものであり、例えは、プ
ロピレン・エチレン共重合体、あるいはプロピレンおよ
び/またはエチレンと、他のα−オレフィンとの共重合
体である。 このα−オレフィン共重合体において、プ
ロピレンの含有量は、通常、30〜90モル%程度であ
り、またエチレンの含有量は、通常、30〜90モル%
程度である。 また、このα−オレフィン共重合体が、
プロピレンとエチレンを共に含有する場合、プロピレン
/エチレンの含有割合は、通常、モル比て9515〜5
/95程度である。 また、他のα−オレフィンとして
は、例えは、1−ブテン、1−ペンテン、1−ヘキセン
、4−メチル−1−ペンテン、1−オクテン等が挙げら
れる。 本発明において、これらの他のα−オレフィン
の1種または2種以上が、α−オレフィン共重合体に含
まれていてもよい。 α−オレフィン共重合体か、こ
の他のα−オレフィンを含む場合、その含有量は、通常
、40モル%以下、好ましくは30モル%以下である。The α-olefin copolymer, which is the main component of this chlorinated modified α-olefin copolymer, consists of propylene and/or
Alternatively, the main component is ethylene, such as a propylene/ethylene copolymer or a copolymer of propylene and/or ethylene with another α-olefin. In this α-olefin copolymer, the propylene content is usually about 30 to 90 mol%, and the ethylene content is usually 30 to 90 mol%.
That's about it. Moreover, this α-olefin copolymer is
When both propylene and ethylene are contained, the propylene/ethylene content ratio is usually 9515 to 5 in terms of molar ratio.
/95. Examples of other α-olefins include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In the present invention, one or more of these other α-olefins may be contained in the α-olefin copolymer. When the α-olefin copolymer or other α-olefin is contained, its content is usually 40 mol% or less, preferably 30 mol% or less.
このα−オレフィン共重合体は、有機溶媒に溶解できる
ため溶液状態におけるグラフト共重合が容易となり、ま
た、後記の溶媒置換法によろ水分散体の調製が容易とな
る点て、結晶化度か20%以下、好ましくは2〜20%
、特に好ましくは5〜18%のものである。 この結晶
化度はX線回折によって測定される値である。This α-olefin copolymer can be dissolved in organic solvents, making it easy to perform graft copolymerization in a solution state.Also, it is easy to prepare a filtrate dispersion using the solvent replacement method described later, and its crystallinity is 20% or less, preferably 2-20%
, particularly preferably 5 to 18%. This crystallinity is a value measured by X-ray diffraction.
また、このα−オレフィン共重合体の分子!は、135
℃デカリン中で測定される極限粘度[η]が、通常、0
3〜20i/g程度、特に好ましくは0.5〜12dI
l/g程度のものである。Also, the molecule of this α-olefin copolymer! is 135
℃ The intrinsic viscosity [η] measured in decalin is usually 0.
About 3 to 20 i/g, particularly preferably 0.5 to 12 dI
It is about 1/g.
これらのα−オレフィン共重合体の中でも、エチレン・
プロピレン共重合体、およびフロピレン・ブテン・エチ
レン共重合体か好ましい。 本発明において、変性共重
合体を得るために、前記のようなα−オレフィン共重合
体に、グラフト共重合されるモノオレフィンジカルボン
酸およびその無木物並ひにモノオレフィンジカルボン酸
のモノアルキルエステルから選はれる少なくとも1種(
以下、車に「グラフト共重合単位」という)か、グラフ
ト共重合される。 モノオレフィンジカルボン酸とじて
は、例えば、マレイン酸、シトラコン酸、イタコン酸、
グルタコン酸、3−メチル−2−ペンテン・二酸、2−
メチル−2−ペンテン・二酸、2−ヘキセン・二酸等が
挙げられる。Among these α-olefin copolymers, ethylene
Propylene copolymers and propylene-butene-ethylene copolymers are preferred. In the present invention, in order to obtain a modified copolymer, a monoolefin dicarboxylic acid and its non-woody substance and a monoalkyl ester of a monoolefin dicarboxylic acid are graft-copolymerized to the α-olefin copolymer as described above. At least one type selected from (
(hereinafter referred to as "graft copolymerization unit") or graft copolymerization. Examples of monoolefin dicarboxylic acids include maleic acid, citraconic acid, itaconic acid,
Glutaconic acid, 3-methyl-2-pentene diacid, 2-
Examples include methyl-2-pentene diacid and 2-hexene diacid.
また、これらのモノオレフィンジカルボン酸の無水物お
よびそのカルボキシル基の1つかアルキルアルコールに
よりエステル化されたもの、すなわちモノオレフィンジ
カルボン酸のモノアルキルエステルも同様に挙げられる
。Also included are anhydrides of these monoolefin dicarboxylic acids and those obtained by esterifying one of their carboxyl groups with an alkyl alcohol, that is, monoalkyl esters of monoolefin dicarboxylic acids.
モノオレフィンジカルボン酸のモノアルキルエステルに
おいては、エステル化率(完全ジエステル化率を200
%とする)が、水分散体が十分な貯蔵安定性を有し、良
好な耐水性を有する塗膜が得られる点で、好ましくは4
5〜100%、さらに好ましくは80〜100%である
ものが望ましい。 また、モノアルキルエステルのアル
キル基としては、CnH2n(jlの一般式で表わされ
るものであり、例えは、メチル基、エチル基、n−プロ
ピル基、n−ブチル基、イソプロピル基等が挙げられる
。For monoalkyl esters of monoolefin dicarboxylic acids, the esterification rate (complete diesterification rate is 200
%) is preferably 4, since the aqueous dispersion has sufficient storage stability and a coating film with good water resistance can be obtained.
It is desirable that the content is 5 to 100%, more preferably 80 to 100%. Further, the alkyl group of the monoalkyl ester is represented by the general formula CnH2n (jl), and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, and the like.
本発明で用いられる変性共重合体の内で、グラフト共重
合単位としてモノオレフィンジカルボン酸のモノアルキ
ルエステルを有する変性共重合体は、例えは、モノオレ
フインシカルホン酸モノアルキルエステルをα−オレフ
ィン共重合体にグラフト共重合する方法、モノオレフィ
ンジカルボン酸もしくはその無水物を、α−オレフィン
共重合体にグラフト共重合させた後、アルキルアルコー
ルによりカルホキシル基の1つをエステル化する方法に
よって得ることができる。Among the modified copolymers used in the present invention, a modified copolymer having a monoalkyl ester of a monoolefin dicarboxylic acid as a graft copolymer unit is, for example, a monoalkyl ester of a monoolefin dicarboxylic acid copolymerized with an α-olefin. It can be obtained by graft copolymerizing a monoolefin dicarboxylic acid or its anhydride onto an α-olefin copolymer, and then esterifying one of the carboxyl groups with an alkyl alcohol. can.
この変性共重合体は、本発明の水分散体を81脂成形品
の表面に塗布して得られる塗膜か塗料等との付着性を十
分に有し、またその塗膜か十分な耐揮発油性を有する点
て、変性共重合体中におけるグラフト共重合単位のグラ
フト量、すなわちグラフト共重合単位の含有量か、05
〜15重量%、好ましくは1〜10重量%であるもので
ある。This modified copolymer has sufficient adhesion to the coating film obtained by applying the aqueous dispersion of the present invention to the surface of the 81 resin molded product, and has sufficient volatilization resistance. In terms of oiliness, the graft amount of the graft copolymer units in the modified copolymer, that is, the content of the graft copolymer units, 05
-15% by weight, preferably 1-10% by weight.
また、この変性共重合体の結晶化度は、グラフト共重合
前のα−オレフィン共重合体の結晶化度に比してほとん
ど同じか、わずかに小さい程度である。Further, the crystallinity of this modified copolymer is almost the same or slightly smaller than the crystallinity of the α-olefin copolymer before graft copolymerization.
前言己α−オレフィン共重合体にグラフト共重合単位を
グラフト共重合させて、変性共重合体を製造する方法と
しては、種々の公知の方法か挙げられる。 例えは、α
−オレフィン共重合体を有機溶媒に熔解し、前記グラフ
ト共重合単位およびラジカル重合開始剤を添加して加熱
攪拌することによりグラフト共重合反応を行なう方法、
α−オレフィン共重合体を加熱して溶融し、得られる熔
融物にグラフト共重合単位およびラジカル重合開始剤を
添加し攪拌することによりグラフト共重合反応を行なう
方法:あるいは各成分を押出機に供給して加熱混練しな
からグラフト共重合反応させる方法、α−オレフィン共
重合体のパウダーに前記グラフト共重合単位およびラジ
カル重合開始剤を有機溶媒に溶解してなる溶液を含浸さ
せた後、パウダーか熔解しない温度まで加熱し、グラフ
ト共重合反応させる方法などが挙げられる。 これら
の方法の中でも、さらに好適な具体例として、有機溶媒
1℃に対してα−オレフィン共重合体を0.01〜0.
5Kg、好ましくは01〜04にgの割合で溶解してな
る共重合体溶液に、前記グラフト共重合単位を1〜10
0m m o fl / m i n / K g−
共重合体、好ましくは2〜20 mmoll / m
in / Kg−共重合体の割合で逐次滴下する。 こ
のとき、同時に、ラジカル重合開始剤も、5×10−5
〜50 mmollm i n / K g−共重合体
、特に好ましくはIXl 0−2〜5 mmofl/
min / Kg−共重合体の添加速度で逐次滴下し
てグラフト共重合反応させる方法が挙げられる。Various known methods can be used to produce a modified copolymer by graft copolymerizing a graft copolymer unit onto the α-olefin copolymer. For example, α
- A method of performing a graft copolymerization reaction by dissolving an olefin copolymer in an organic solvent, adding the graft copolymerization unit and a radical polymerization initiator, and heating and stirring;
A method in which a graft copolymerization reaction is carried out by heating and melting an α-olefin copolymer, adding a graft copolymerization unit and a radical polymerization initiator to the resulting melt, and stirring: Alternatively, each component is fed to an extruder. In this method, a powder of α-olefin copolymer is impregnated with a solution obtained by dissolving the graft copolymer unit and a radical polymerization initiator in an organic solvent, and then the powder is mixed with heat and then subjected to a graft copolymerization reaction. Examples include a method of heating to a temperature at which it does not melt and causing a graft copolymerization reaction. Among these methods, as a more preferred specific example, the α-olefin copolymer is mixed at 0.01 to 0.0° C. with respect to 1° C. of the organic solvent.
1 to 10 of the graft copolymer units are added to a copolymer solution prepared by dissolving 5 kg of 0.01 to 0.04 g of the graft copolymer units.
0m m o fl / min / K g-
Copolymer, preferably 2-20 mmol/m
in/Kg-copolymer dropwise. At this time, at the same time, the radical polymerization initiator also
~50 mmolmin/K g-copolymer, particularly preferably IXl 0-2-5 mmofl/
An example of a method is to carry out a graft copolymerization reaction by sequentially dropping the copolymer at an addition rate of min/Kg.
グラフト共重合反応におけるラジカル重合開始剤/グラ
フト共重合単位の使用割合は、通常、モル比て、1/1
00〜60/100、好ましくは1/20〜1/2の範
囲である。The ratio of radical polymerization initiator/graft copolymerization unit used in the graft copolymerization reaction is usually 1/1 in terms of molar ratio.
It is in the range of 00 to 60/100, preferably 1/20 to 1/2.
反応温度は、α−オレフィン共重合体の融点以上、特に
120〜160℃の範囲か好ましく、反応時間は2〜1
0時間程度である。The reaction temperature is preferably higher than the melting point of the α-olefin copolymer, particularly preferably in the range of 120 to 160°C, and the reaction time is 2 to 1
It takes about 0 hours.
上記グラフト共重合に用いられるラジカル重合開始剤と
しては、例えは、ベンゾイルベルオキシト、ジクロルヘ
ンシイルベルオキシト、ジクミルペルオキシド、シーt
−ブチルペルオキシド、2.5−ジメチル−2,5〜シ
(ベルオキシヘンゾエート)ヘキシン−3,1,4−ヒ
ス(t−ブチルペルオキシイソプロピル)ベンゼン、ラ
ウロイルペルオキシド、2,5−ジメチル−2,5−ジ
(t−ブチルペルオキシ)ヘキシン−3,2,5−ジメ
チル−2,5−シ(t−ブチルペルオキシ)−ヘキサン
等の有機ペルオキシド、t−ブチルベルアセテート、t
−プチルベルヘンゾエート、t−ブチルベルフェニルア
セテート、t−ブチルベルイソブチレート、t−ブチル
ベルー5ee−オクトエート、t−ブチルベルピバレー
ト、クミルベルビバレート、t−ブチルベルジエチルア
セテート等の有機ベルエステル、アゾヒスイソブチロニ
トリル、ジメチルアゾイソブチロニトリル等のアゾ化合
物等か挙げられる。 これらのうちでは、有機ペルオキ
シドおよび有機ベルエステルか好ましく、特に、ジクミ
ルペルオキシド、シーt−ブチルペルオキシド、2.5
−ジメチル−2,5−ジ(t−ブチルペルオキシ)ヘキ
シン−3,2,5−ジメチル−2,5−シ(t−ブチル
ペルオキシ)ヘキサン、1.4−ヒス(t−ブチルペル
オキシイソプロピル)ベンゼン等のジアルキルペルオキ
シドか好ましい。Examples of the radical polymerization initiator used in the graft copolymerization include benzoyl peroxide, dichlorohensyl peroxide, dicumyl peroxide, sheet t
-butylperoxide, 2,5-dimethyl-2,5-cy(beroxyhenzoate)hexyne-3,1,4-his(t-butylperoxyisopropyl)benzene, lauroylperoxide, 2,5-dimethyl-2, Organic peroxides such as 5-di(t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(t-butylperoxy)-hexane, t-butylberacetate, t
- Organic bers such as butylberhenzoate, t-butylberphenylacetate, t-butylberisobutyrate, t-butylber-5ee-octoate, t-butylberpivalate, cumylberbivalate, t-butylberdiethyl acetate, etc. Examples include esters, azo compounds such as azohisisobutyronitrile, and dimethylazoisobutyronitrile. Among these, organic peroxides and organic peresters are preferred, especially dicumyl peroxide, t-butyl peroxide, 2.5
-dimethyl-2,5-di(t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,4-his(t-butylperoxyisopropyl)benzene Dialkyl peroxides such as are preferred.
有機溶媒を用いる場合、その有機溶媒の具体例としては
、ベンゼン、トルエン、キシレン等の芳香族系炭化水素
:ヘキサン、ヘプタン、オクタン、デカン等の脂肪族系
炭化水素;トリクロルエチレン、パークロルエチレン、
ジクロルエチレン、クロルベンゼン等のハロゲン化炭化
水素などが挙げられ、これらの中でも、芳香族系炭化水
素が好ましく、特にアルキル基置換芳香族系炭化水素が
好ましい。When using an organic solvent, specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; trichlorethylene, perchlorethylene,
Examples include halogenated hydrocarbons such as dichloroethylene and chlorobenzene. Among these, aromatic hydrocarbons are preferred, and alkyl group-substituted aromatic hydrocarbons are particularly preferred.
本発明の水分散体は、前記のようにして得られる変性共
重合体をさらに塩素化して得られる塩素化変性α−オレ
フィン共重合体を主成分とするものである。 この塩素
化変性α−オレフィン共重合体は、溶媒に溶解し易く、
後記の溶媒置換法による水分散体の製造が容易であり、
また成形品に塗布して塗料の付着性が高い塗膜を得るこ
とができる水分散体が得られる点て、塩素含有量が10
〜50重量%、好ましくは12〜30重量%のものであ
る。 また、この塩素化変性α−オレフィン共重合体の
極限粘度[η]は、水への分散か容易で、接着性が良好
である点で、通常、0. 1〜20 6fl/g、好ま
しくは0.2〜10du/g程度である。The aqueous dispersion of the present invention has as its main component a chlorinated modified α-olefin copolymer obtained by further chlorinating the modified copolymer obtained as described above. This chlorinated modified α-olefin copolymer is easily soluble in a solvent,
It is easy to produce an aqueous dispersion by the solvent substitution method described later,
In addition, the water dispersion that can be applied to molded products to obtain a coating film with high paint adhesion is obtained because the chlorine content is 10%.
-50% by weight, preferably 12-30% by weight. In addition, the intrinsic viscosity [η] of this chlorinated modified α-olefin copolymer is usually 0.00, since it is easily dispersed in water and has good adhesive properties. It is about 1 to 206 fl/g, preferably about 0.2 to 10 du/g.
この塩素化変性α−オレフィン共重合体の製造は、前記
変性共重合体を適当な有機溶媒に溶解または分散させた
後、塩素カスと反応させることによって行なうことがで
きる。 この反応は、通常、50〜120℃程度で、約
0.5〜5時間で行なうのが一般的である。 また、反
応を効率的に進行させるために、紫外線や可視光線を照
射したり、あるいはラジカル発生剤を使用してもよい。The chlorinated modified α-olefin copolymer can be produced by dissolving or dispersing the modified copolymer in a suitable organic solvent and then reacting it with chlorine scum. This reaction is generally carried out at about 50 to 120°C for about 0.5 to 5 hours. Furthermore, in order to make the reaction proceed efficiently, ultraviolet rays or visible light may be irradiated, or a radical generator may be used.
用いられる有機溶媒としては、例えは、ヘキサン、ヘプ
タン、オクタン、デカン、ドデカン、テトラドデカン等
の脂肪族炭化水素、メチルシクロペンタン、シクロヘキ
サン、メチルシクロヘキサン、シクロオクタン、シクロ
ドデカン等の脂環式炭化水素;ベンゼン、トルエン、キ
シレン、エチルベンゼン、クメン、エチルトルエン、ト
リメチルベンゼン、シイソフロビルヘンゼン等の芳香族
炭化水素;クロロベンゼン、ブロモヘンセン、0−シク
ロヘキサン、四塩化炭素、四臭化炭素、クロロホルム、
ブロモホルム、トリクロロエタン、トリクロロエチレン
、テトラクロロエタン、テトラクロロエチレン等のハロ
ゲン化炭化水素なとか挙げられる。 これらは1種単独
でも2種以上を組合せて用いてもよい。Examples of organic solvents used include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and tetradodecane, and alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclododecane. ; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cyisoflovirhenzene; chlorobenzene, bromohensen, 0-cyclohexane, carbon tetrachloride, carbon tetrabromide, chloroform,
Examples include halogenated hydrocarbons such as bromoform, trichloroethane, trichloroethylene, tetrachloroethane, and tetrachloroethylene. These may be used alone or in combination of two or more.
本発明の水分散体は、以上のようにして得られる塩素化
変性α−オレフィン共重合体を木に分散させて得られる
。 塩素化変性α−オレフィン共重合体を水に分散させ
て、本発明の水分散体を製造する方法としては、例えは
、該塩素化変性α−オレフィン共重合体、水および界面
活性剤を一括して混合して乳化させるドラム乳化法:予
め粉砕しておいた塩素化変性α−オレフィン共重合体を
界面活性剤とともに水中に投入して分散させる粉砕法:
有機溶媒に溶解した塩素化変性α−オレフィン共重合体
と界面活性剤および水とを混合した後、有機溶媒を除去
する溶媒置換法、ホモミキサーを用いて分散を行なうホ
モミキサー法:転相法等が挙げられ、使用する塩素化変
性α−オレフィン共重合体の物性に応じて適宜選択され
る。The aqueous dispersion of the present invention is obtained by dispersing the chlorinated modified α-olefin copolymer obtained as described above in wood. As a method for producing the aqueous dispersion of the present invention by dispersing a chlorinated modified α-olefin copolymer in water, for example, the chlorinated modified α-olefin copolymer, water, and a surfactant are mixed together. Drum emulsification method in which a chlorinated modified α-olefin copolymer that has been ground in advance is poured into water together with a surfactant and dispersed:
A solvent substitution method in which a chlorinated modified α-olefin copolymer dissolved in an organic solvent is mixed with a surfactant and water, and then the organic solvent is removed; a homomixer method in which dispersion is performed using a homomixer; a phase inversion method etc., and is appropriately selected depending on the physical properties of the chlorinated modified α-olefin copolymer used.
用いられる界面活性剤としては、非イオン系およびアニ
オン系界面活性剤を挙げることがてきる。 非イオン系
界面活性剤としては、例えば、ポリオキシエチレンアル
キルエーテル、ポリオキシエチレンアルキルフリルエー
テル、ポリオキシエチレンソルビタンエステル、ポリオ
キシエチレンアルキルアミンエーテル等か挙げられる。As the surfactants used, mention may be made of nonionic and anionic surfactants. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylfuryl ether, polyoxyethylene sorbitan ester, and polyoxyethylene alkylamine ether.
アニオン系界面活性剤としては、例えは、脂肪酸塩、
高級アルコール硫酸エステル、アルキルヘンセンスルホ
ン酸ナトリウム、ナフタリンスルホン酸ホルマリン縮合
物、ポリオキシエチレンアルキルエーテルサルフェート
等が挙げられ、特にアルキルヘンセンスルホン酸ナトリ
ウムが好ましい。Examples of anionic surfactants include fatty acid salts,
Examples include higher alcohol sulfuric esters, sodium alkylhensensulfonate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, and sodium alkylhensensulfonate is particularly preferred.
この界面活性剤の使用量は、塩素化変性αオレフィン共
重合体の分散状態が良好で、かつ得られる水分散体の成
形品との密着性か良好となる点て、通常、塩素化変性α
−オレフィン共重合体に対して005〜10重量%程度
か好ましく、特に0.1〜7重量%か好ましい。The amount of surfactant to be used is usually determined so that the dispersion state of the chlorinated modified α-olefin copolymer is good and the resulting aqueous dispersion has good adhesion to the molded product.
- It is preferably about 0.05 to 10% by weight, particularly preferably 0.1 to 7% by weight, based on the olefin copolymer.
本発明の水分散体中における塩素化変性α−オレフィン
共重合体と水の配合割合は、塩素化変性α−オレフィン
共重合体5〜70重量部に対して、水95〜30重量部
の割合の範囲の中で、適宜選択される。 特に、本発明
の水分散体を噴露塗布する場合には、塗布面に塗つむら
が生しにくく、塗膜の付着性のばらつきが生しにくく、
また、形成される塗膜の層が厚くならないため、例えは
、ブライマーとして使用した場合に塗装後の塗膜の平滑
性が良好となる点て3〜45重量%か好ましい。The blending ratio of the chlorinated modified α-olefin copolymer and water in the aqueous dispersion of the present invention is 95 to 30 parts by weight of water to 5 to 70 parts by weight of the chlorinated modified α-olefin copolymer. be selected as appropriate within the range. In particular, when spray-coating the aqueous dispersion of the present invention, uneven coating is less likely to occur on the coated surface, and variations in the adhesion of the coating film are less likely to occur.
In addition, since the layer of the coating film formed does not become thick, for example, when used as a brimer, the smoothness of the coating film after painting is improved, so it is preferable to use 3 to 45% by weight.
また、本発明の水分散体には、必要に応して、増粘剤、
塩基性物質、消泡剤等を添加することもできる。 さら
に、塗布される素材との濡れ性を改善するために、必要
に応じて少量の有機溶媒を添加してもよい。In addition, the aqueous dispersion of the present invention may contain a thickener,
Basic substances, antifoaming agents, etc. can also be added. Furthermore, in order to improve the wettability with the material to be coated, a small amount of organic solvent may be added as necessary.
増粘剤としては、例えは、アルギン酸アンモニウム、ア
ルギン酸ナトリウム、ベントナイトクレー等の鉱物性増
粘剤;ポリアクリル酸ナトリウム、ポリアクリル酸アン
モニウム、アクリルエマルジョンコポリマー架橋アクリ
ルエマルションコポリマー等のアクリル酸系増粘剤;カ
ルホキシルメチルセルロース、メチル°セルロース、ヒ
ドロキシプロピルメチルセルロース、ヒドロキシエチル
セルロース等の1&維素銹導体等を挙げることができ、
特にカルボキシメチルセルロースが好ましい。Examples of thickeners include mineral thickeners such as ammonium alginate, sodium alginate, and bentonite clay; acrylic acid thickeners such as sodium polyacrylate, ammonium polyacrylate, and crosslinked acrylic emulsion copolymers. ; Examples include 1&fiber conductors such as carboxyl methyl cellulose, methyl ° cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose;
Particularly preferred is carboxymethylcellulose.
消泡剤としては、例えは、ヒマシ油、大豆油、アマニ油
等の植物油;スピンドル油、流動パラフィン等の鉱物油
;ステアリン酸、オレイン酸等の脂肪酸ニオレイルアル
コール、ポリオキシアルキレングリコール、オクチルア
ルコール等のアルコール類:エチレングリコールシステ
アレート、ポリオキシエチレンソルヒタンモノラウレー
ト等の脂肪酸エステル:トリブチルホスフェート、ナト
リウムオクチルホスフェート等のリン酸エステル:ポリ
オキシアルキレンアミド等のアミド類;ステアリン酸ア
ルミニウム、オレイン酸カリウム、ステアリン酸カルシ
ウム等の金属石鹸;ジメチルシリコン、ポリエーテル変
性シリコン等のシリコン類、シアミルアミン、ポリオキ
シフロピレンアルキルアミン等のアミン類等か挙げられ
る。Examples of antifoaming agents include vegetable oils such as castor oil, soybean oil, and linseed oil; mineral oils such as spindle oil and liquid paraffin; fatty acids such as stearic acid and oleic acid, nioleyl alcohol, polyoxyalkylene glycol, and octyl alcohol. Alcohols such as ethylene glycol cystearate, polyoxyethylene solhitane monolaurate, etc. Fatty acid esters such as tributyl phosphate, sodium octyl phosphate, etc. Amides such as polyoxyalkylene amide; Aluminum stearate, olein Examples include metal soaps such as potassium acid and calcium stearate; silicones such as dimethyl silicone and polyether-modified silicone; and amines such as cyamylamine and polyoxyfuropylene alkylamine.
さらに、本発明の水分散体は、上記以外に、必要に応じ
て酸化防止剤、耐候安定剤、耐熱防止剤等の各種安定剤
、酸化チタン、有機顔料等の着色剤:カーボンブラック
、フェライト等の導電性付与剤などを含有していてもよ
い。Furthermore, in addition to the above, the aqueous dispersion of the present invention may optionally contain various stabilizers such as antioxidants, weather-resistant stabilizers, and heat-resistant inhibitors, titanium oxide, coloring agents such as organic pigments: carbon black, ferrite, etc. The conductivity imparting agent may be contained.
本発明の水分散体は、α−オレフィン共重合体やその他
の重合体からなる成形品の表面に塗布し、その表面への
塗料の付着性を改善するためのブライマー等として用い
ることができる。 特に、本発明の水分散体は、例えば
、高圧法ポリエチレン、中低圧法ポリエチレン、ポリプ
ロピレン、ポリ−4−メチル−1−ペンテン、ポリ−1
−ブテン、ポリスチレン等のα−オレフィン共重合体;
エチレン・フロピレン共重合体、エチレン・ブテン共重
合体、フロピレン・ブテン共重合体等のオレフィン共重
合体などからなる成形品に好適に用いることができる。The aqueous dispersion of the present invention can be applied to the surface of a molded article made of an α-olefin copolymer or other polymer, and used as a brimer or the like to improve the adhesion of paint to the surface. In particular, the aqueous dispersion of the present invention can be used, for example, in high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1
-α-olefin copolymers such as butene and polystyrene;
It can be suitably used for molded articles made of olefin copolymers such as ethylene/propylene copolymer, ethylene/butene copolymer, and propylene/butene copolymer.
さらに、本発明の水分散体は、上記のα−オレフィン共
重合体やその共重合体以外にも、ポリプロピレンと合成
ゴムとからなる成形品、ポリアミド樹脂、不飽和ポリエ
ステル樹脂、ポリブチレンテレフタレート樹脂、ポリカ
ーボネート樹脂等からなる成形品、例えば、自動車用バ
ンパー等の成形品、さらには、鋼板や電着処理用鋼板等
の表面処理にも用いることかできる。 また、ポリウレ
タン樹脂、脂肪酸変性ポリエステル樹脂、オイルフリー
ポリエステル樹脂、メラミン樹脂、エポキシ樹脂等を主
成分とする塗料、ブライマー、接着剤等を塗布した表面
に下塗りし、その表面への塗料等の付着性を改善すると
共に、鮮映性、低温衝撃性等にも優れる塗膜を形成する
ためにも用いられる。Furthermore, in addition to the above-mentioned α-olefin copolymer and its copolymer, the aqueous dispersion of the present invention also includes molded articles made of polypropylene and synthetic rubber, polyamide resins, unsaturated polyester resins, polybutylene terephthalate resins, It can also be used for surface treatment of molded products made of polycarbonate resin or the like, such as molded products such as automobile bumpers, and furthermore, steel plates and steel plates for electrodeposition treatment. In addition, undercoat the surface coated with paints, primers, adhesives, etc. whose main components are polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, etc. to improve the adhesion of the paint, etc. to the surface. It is also used to improve the image quality and form coating films with excellent image clarity and low-temperature impact resistance.
また、本発明の水分散体が通用される成形品は、上記の
各種重合体あるいは樹脂が、射出成形、圧縮成形、中空
成形、押出成形、回転成形等の公知の成形法のいずれの
方法によって成形されたものであってもよい。In addition, the molded products to which the aqueous dispersion of the present invention can be used include the above-mentioned various polymers or resins formed by any of the known molding methods such as injection molding, compression molding, blow molding, extrusion molding, and rotary molding. It may be molded.
本発明の水分散体は、これを適用する成形品が、タルク
、亜鉛華、ガラス繊維、チタン白、硫酸マグネシウム等
の無機充填剤、顔料等か配合されている場合にも、特に
塗膜の付着性の良いブライマー塗膜を形成することかで
きる。The aqueous dispersion of the present invention can be applied to molded products that contain inorganic fillers such as talc, zinc white, glass fiber, titanium white, magnesium sulfate, pigments, etc. It is possible to form a brimer coating film with good adhesion.
また、本発明の水分散体を塗布する成形品は、上記以外
に、種々の安定剤、紫外線吸収剤、塩酸吸収剤等を含有
していてもよい。Moreover, the molded article coated with the aqueous dispersion of the present invention may contain various stabilizers, ultraviolet absorbers, hydrochloric acid absorbers, etc. in addition to the above.
好ましく用いられる安定剤としては、例えば、2.6−
ジーt−ブチル−4−メチルフェノール、テトラキス[
メチレン(3,5−ジ−t−ブチル−4−ヒドロキシヒ
ドロシンナメート)]メタン、メタオクタデシル−3−
(4’−ヒドキシ−3,5−シーt−ブチルフェニル)
プロピオネート、2.2′ −メチレンビス(4−メチ
ル−6−t−ブチルフェノール)、4.4′−ブチリデ
ンビス(3−メチル−6−七−ブチルフェノール)、1
4.4’ −チオビス(3−メチル−6−t−ブチルフ
ェノール)、2.2−チオビス(4−メチル−6−t−
ブチルフェノール) 1,3.5−トリメチル−2
,4,6−1−リス(3,5−シーt−ブチル−4−ヒ
ドロキシヘンシル)ベンゼン、1゜3.5−トリス(2
−メチル−4−ヒドロキシ−5−t−ブチルフェノール
)ブタン等のフェノール系安定剤、ジラウリルチオジプ
ロピオネート、ジステアリルチオジプロピオネート等の
イオウ系安定剤、トリデシルホスファイト、トリノニル
フェニルホスファイト等のリン系安定剤などを挙げるこ
とができる。Preferably used stabilizers include, for example, 2.6-
Di-t-butyl-4-methylphenol, tetrakis [
Methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane, metaoctadecyl-3-
(4'-Hydoxy-3,5-sheet-t-butylphenyl)
Propionate, 2.2'-methylenebis(4-methyl-6-t-butylphenol), 4.4'-butylidenebis(3-methyl-6-7-butylphenol), 1
4.4'-thiobis(3-methyl-6-t-butylphenol), 2.2-thiobis(4-methyl-6-t-
butylphenol) 1,3,5-trimethyl-2
, 4,6-1-lis(3,5-t-butyl-4-hydroxyhensyl)benzene, 1°3,5-tris(2
- Phenol stabilizers such as methyl-4-hydroxy-5-t-butylphenol) butane, sulfur stabilizers such as dilaurylthiodipropionate and distearylthiodipropionate, tridecyl phosphite, trinonylphenyl phosphite, etc. Examples include phosphorus stabilizers such as Phite.
また、用いられる紫外線吸収剤としては、例えば、2−
ヒドロキシ−4−オクトキシヘンソフェノン、2−エチ
ルへキシル−2−シアノ−3,3−ジフェニルアクリレ
ート、バラオクチルフェニルサリチレート等か挙げられ
る。Further, as the ultraviolet absorber used, for example, 2-
Examples include hydroxy-4-octoxyhensophenone, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and paraoctylphenyl salicylate.
塩酸吸収剤としては、例えば、ステアリン酸カルシウム
等が挙げられる。Examples of the hydrochloric acid absorbent include calcium stearate.
本発明の水分散体を成形品の表面に適用する方法として
は、噴露塗布が好適であり、例えは、スプレーガンにて
成形品の表面に吹き付けられる。 成形品への塗布は常
温で行なえは良く、塗布した後、自然乾燥や加熱強制乾
燥等、適宜の方法によって乾燥され、塗膜を形成するこ
とができる。As a method for applying the aqueous dispersion of the present invention to the surface of a molded article, spray coating is suitable; for example, it is sprayed onto the surface of the molded article using a spray gun. The coating on the molded article can be carried out at room temperature, and after coating, it can be dried by an appropriate method such as natural drying or forced drying under heat to form a coating film.
以上のように、成形品の表面に本発明の水分散体を塗布
し、乾燥させた後、該成形品の表面には、静電塗装、吹
き付は塗装、刷毛塗り等の方法によって、塗料を塗布す
ることができる。As described above, after the aqueous dispersion of the present invention is applied to the surface of a molded article and dried, the surface of the molded article is coated with paint by electrostatic coating, spray painting, brush coating, etc. can be applied.
塗料の塗布は、下塗りした後、上塗りする方法で行なっ
てもよい。 塗料を塗布した後、ニクロム線、赤外線、
高周波等によって加熱する通常の方法に従って塗膜を硬
化させて、所望の塗膜を表面に有する成形品を得ること
ができる。 塗膜を硬化させる方法は、成形品の材質、
形状、使用する塗料の性状等によって適宜選はれる。The paint may be applied by applying an undercoat and then a topcoat. After applying the paint, use nichrome wire, infrared rays,
A molded article having a desired coating film on its surface can be obtained by curing the coating film according to a conventional heating method using high frequency waves or the like. The method of curing the coating film depends on the material of the molded product,
Appropriate selection is made depending on the shape, properties of the paint used, etc.
また、本発明の水分散体は、付着性、剥離強度および耐
水性に優れる特徴を生かして、上記の成形品のブライマ
ーとしての用途以外にも、広範囲の用途に適用可能なも
のであり、例えば、接着剤や塗料のための添加剤等の用
途にも適用可能であることはもちろんである。In addition, the aqueous dispersion of the present invention can be applied to a wide range of applications in addition to the above-mentioned applications as a brimer for molded products, taking advantage of its excellent adhesion, peel strength, and water resistance. Of course, it can also be used as an additive for adhesives and paints.
〈実施例〉
以下、本発明の実施例および比較例を挙げ、本発明を具
体的に説明するか、本発明はこれら実施例により何ら限
定されるものではない。<Examples> Hereinafter, the present invention will be specifically explained by giving Examples and Comparative Examples of the present invention, but the present invention is not limited in any way by these Examples.
また、以下において、塗膜の物性は下記の方法に従って
評価した。Further, in the following, the physical properties of the coating film were evaluated according to the following method.
基盤目試験
JIS K5400に記載されている基盤目試験の方
法に準じて、基盤目を付けた試験片を作成し、セロテー
プにチバン■製、商品名)を試験片の基盤目上に貼り付
けた後、これを速やかに90°の方向に引っ張って剥離
させ、基盤目100の内で剥離されなかった基盤目の数
を数え、付着性の指標とした。Base grain test A test piece with a base grain was prepared according to the method of the base grain test described in JIS K5400, and a piece of sellotape made by Chiban (trade name) was pasted on the base grain of the test piece. Thereafter, this was quickly pulled in a 90° direction to peel it off, and the number of base grains that were not peeled out of 100 base grains was counted and used as an index of adhesion.
rl」離強度
基材上に塗膜を調製し、1 cm幅にカッター刃で基材
に刃か到達するまで切れ目を入れ、端部を剥離させた後
、その剥離した塗膜の端部を50+nm/分の速度で1
80°の方向に塗膜か剥離するまで引っ張って剥離強度
を測定した。Prepare a coating film on the base material, make a 1 cm wide cut with a cutter blade until the blade reaches the base material, peel off the edge, and then cut the edge of the peeled coating film. 1 at a speed of 50+nm/min
The peel strength was measured by pulling the coating in an 80° direction until it peeled off.
耐水性
試験片を40℃の水中に240時間浸漬させた後、基盤
目試験に供し、付着性を評価する。The water resistance test piece was immersed in water at 40° C. for 240 hours and then subjected to a substrate test to evaluate adhesion.
(実施例1)
加圧反応容器に、プロピレン・エチレン共重合体(プロ
ピレン含有量:60モル%、極限粘度[ηコ (デカリ
ン135℃)・193dfl/g、X線回折による結晶
化度・12%)75gおよびトルエン240 mρを
仕込み、反応容器内の窒素置換を1時間行なった。
145℃に加熱してプロピレン・エチレン共重合体を完
全に溶解させた後、無水マレイン酸6,9gをトルエン
30m9に溶解してなる溶液と、シーt−ブチルパーオ
キシド2.4gをトルエン3omUに溶解してなる溶液
とを、同時に4時間かけて連続して滴下した。 滴下終
了後、温度を145℃に保って2時間反応させ、反応混
合物として、生成した変性共重合体を含むトルエン溶液
を得た。 反応終了後、反応混合物に大量のアセトンを
加え、生成した変性共重合体を析出させてf別し、アセ
トンてH7し洗浄した後、減圧乾燥した。(Example 1) In a pressurized reaction vessel, a propylene/ethylene copolymer (propylene content: 60 mol%, intrinsic viscosity [η(decalin 135°C)) 193 dfl/g, crystallinity determined by X-ray diffraction 12 %) and 240 mρ of toluene were charged, and the inside of the reaction vessel was replaced with nitrogen for 1 hour.
After heating to 145°C to completely dissolve the propylene/ethylene copolymer, a solution of 6.9 g of maleic anhydride dissolved in 30 m of toluene and 2.4 g of sheet t-butyl peroxide were dissolved in 3 omU of toluene. The resulting solution was simultaneously added dropwise continuously over 4 hours. After the dropwise addition was completed, the temperature was maintained at 145° C. and the reaction was allowed to proceed for 2 hours to obtain a toluene solution containing the produced modified copolymer as a reaction mixture. After the reaction was completed, a large amount of acetone was added to the reaction mixture, and the resulting modified copolymer was precipitated and separated, washed with H7 with acetone, and then dried under reduced pressure.
得られた変性共重合体中の無水マレイン酸の含有量を測
定したところ、4.2重量%であった。The content of maleic anhydride in the obtained modified copolymer was measured and found to be 4.2% by weight.
上記に得られた変性共重合体を、クロロヘンゼン溶媒中
、110℃に加熱して完全に熔解させ、温度を保ちなが
ら、光を完全に遮断し、塩素ガスを供給して、約2時間
反応させた。 得られた反応混合物に大過剰のメタノー
ルを加えて、反応生成物を析出させ、これをf別し、メ
タノールで繰返し洗浄した後、減圧乾燥して塩素化変性
共重合体を得た。 得られた塩素化変性共重合体の塩素
含有量を測定したところ、30重量%であった。The modified copolymer obtained above was heated to 110°C in a chlorohenzene solvent to completely melt it, and while maintaining the temperature, light was completely blocked and chlorine gas was supplied to react for about 2 hours. Ta. A large excess of methanol was added to the resulting reaction mixture to precipitate a reaction product, which was separated, washed repeatedly with methanol, and dried under reduced pressure to obtain a chlorinated modified copolymer. The chlorine content of the obtained chlorinated modified copolymer was measured and found to be 30% by weight.
次に、得られた塩素化変性共重合体をトルエンに溶解し
、ポリマー濃度125g/JZの溶イ夜を調製した。
このポリマー熔ン夜500g、蒸留水500g お
よびトデシルヘンゼンスルホン酸ナトリウム(花王■製
、ネオペレックスF−25)1.44gを、回転数10
00Orpmで15分間攪拌して混合させた。 次いで
、ポリアクリル酸(和光純薬■製、ハイヒスワコ−30
4)0.72gを加え、攪拌、混合して乳化液を得た。Next, the obtained chlorinated modified copolymer was dissolved in toluene to prepare a solution having a polymer concentration of 125 g/JZ.
500 g of this polymer melt, 500 g of distilled water, and 1.44 g of sodium todecylhenzenesulfonate (Neoperex F-25, manufactured by Kao ■) were mixed at a rotational speed of 10
The mixture was mixed by stirring at 00 rpm for 15 minutes. Next, polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., Hihiswako-30)
4) 0.72g was added and stirred and mixed to obtain an emulsion.
得られた乳化液中のトルエンをエバポレーターで減圧
留去し、ポリマー濃度20重量%の水分散体を得た。Toluene in the obtained emulsion was distilled off under reduced pressure using an evaporator to obtain an aqueous dispersion with a polymer concentration of 20% by weight.
この水分散体を、1,1.1−1−リクロルエタン蒸気
で洗浄したポリプロピレン(X440.三井石油化学工
業株式会社製)製角板に、塗布量が200g7m2とな
るように噴露塗布した。次に、この角板をエアオープン
中で100℃で30分間加熱乾燥させた後、基盤目試験
、剥離強度の測定および耐水性の評価に供した。 結果
を表1に示す。This aqueous dispersion was applied by spraying onto a square plate made of polypropylene (X440, manufactured by Mitsui Petrochemical Industries, Ltd.) which had been washed with 1,1.1-1-lichloroethane vapor in an amount of 200 g and 7 m 2 . Next, this square plate was heat-dried at 100° C. for 30 minutes in an open air environment, and then subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.
(実施例2)
実施例1と同様に、ポリプロピレン製角板に水分散体を
塗布、乾燥した後、ざらにウレタン系塗料(日本ビーケ
ミカル@製、R−271)を乾燥膜厚60μmになるよ
うに上塗りした。(Example 2) In the same manner as in Example 1, a water dispersion was applied to a polypropylene square plate, and after drying, a urethane paint (R-271, manufactured by Nippon B Chemical @) was applied to Zara to a dry film thickness of 60 μm. I painted it like this.
次に、100℃のエアオーブン中で30分間焼付を行な
い、塗膜試料を得た。Next, baking was performed in an air oven at 100° C. for 30 minutes to obtain a coating film sample.
得られた塗膜試料を基盤目試験、ff1lJ m強度の
測定および耐水性の評価に供した。 結果を表1に示す
。The obtained coating film sample was subjected to a base grain test, measurement of ff1lJ m strength, and evaluation of water resistance. The results are shown in Table 1.
(実施例3)
実施例1で製造した変性共重合体のトルエン溶液300
mllに、メタノール5.smRを添加し、145℃
で2時間加熱、攪拌して反応させ、マレイン酸モノメチ
ルエステルグラフト変性共重合体のトルエン溶液を得た
。(Example 3) Toluene solution of the modified copolymer produced in Example 1 300
ml of methanol. Add smR and heat to 145°C
The reaction mixture was heated and stirred for 2 hours to obtain a toluene solution of a maleic acid monomethyl ester graft-modified copolymer.
得られたマレイン酸モノメチルエステルグラフト変性共
重合体の赤外線吸収スペクトルを測定し、そのエステル
化率を求めたところ、エステル化IE1oo%のマレイ
ン酸モノメチルエステルかグラフト共重合されているこ
とか確証された。 次いで、このマレイン酸モノメチル
エステルグラフト変性共重合体を、実施例1と同様にし
て塩素化し、さらに水分散体を調製した。 得られた水
分散体を用いて、実施例2と同様にして塗膜試料を作製
し、これを基盤目試験、剥離強度の測定および耐水性の
評価に供した。 結果を表1に示す。When the infrared absorption spectrum of the obtained maleic acid monomethyl ester graft modified copolymer was measured and its esterification rate was determined, it was confirmed that maleic acid monomethyl ester with an esterification rate of 10% IE was graft copolymerized. . Next, this maleic acid monomethyl ester graft-modified copolymer was chlorinated in the same manner as in Example 1 to prepare an aqueous dispersion. Using the obtained aqueous dispersion, a coating film sample was prepared in the same manner as in Example 2, and the sample was subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.
(実施例4)
プロピレン/ブテン/エチレンのモル比が65/25/
10であるα−オレフィン共重合体3Kg、無水マレイ
ン酸120gおよび29.5ジメチル−2,5−ジ(t
−ブチルペルオキシ)へキーサン12gを、ヘンシェル
ミキサーで予め混合した後、2軸押出機(池貝鉄工所製
、PCM−45)に供給して、加熱温度230℃、回転
数260 rpmで混練しながら押出して反応させ、変
性共重合体を得た。(Example 4) The molar ratio of propylene/butene/ethylene is 65/25/
10, 3 kg of α-olefin copolymer, 120 g of maleic anhydride, and 29.5 dimethyl-2,5-di(t
-Butylperoxy) Hexane (12 g) was mixed in advance with a Henschel mixer, then supplied to a twin-screw extruder (manufactured by Ikegai Iron Works, PCM-45) and extruded while kneading at a heating temperature of 230°C and a rotation speed of 260 rpm. A modified copolymer was obtained.
得られた変性共重合体の無水マレイン酸の含有量(グラ
フト量)を測定したところ、2.9重量%であった。
この変性共重合体を実施例1と同様にして塩素化した後
、水分散体を調製し、実施例2と同様に塗膜試料を作製
して基盤目試験、剥離強度の測定および耐水性の評価に
供した。 結果を表1に示す。The maleic anhydride content (grafting amount) of the obtained modified copolymer was measured and found to be 2.9% by weight.
After chlorinating this modified copolymer in the same manner as in Example 1, an aqueous dispersion was prepared, and a coating film sample was prepared in the same manner as in Example 2 to conduct a substrate surface test, peel strength measurement, and water resistance test. It was submitted for evaluation. The results are shown in Table 1.
(実施例5)
プロピレン・エチレン共重合体の代わりに、実施例4で
使用したα−オレフィン共重合体を用いる以外は、実施
例1と同様にして水分散体を調製した。 水分散体の調
製の途中で製造された変性共重合体の無水マレイン酸の
含有量(グラフト量)は、4.0重量%であった。(Example 5) An aqueous dispersion was prepared in the same manner as in Example 1, except that the α-olefin copolymer used in Example 4 was used instead of the propylene-ethylene copolymer. The maleic anhydride content (grafting amount) of the modified copolymer produced during the preparation of the aqueous dispersion was 4.0% by weight.
得られた水分散体を用いて実施例2と同様にして塗膜試
料を作製し、基盤目試験、剥離強度の測定および耐水性
の評価に供した。 結果を表1に示す。A coating film sample was prepared in the same manner as in Example 2 using the obtained aqueous dispersion, and subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.
(比較例1)
変性共重合体の塩素化を行なわない以外は、実施例1と
同様にして水分散体を調製し、これを用いて、実施例2
と同様にして塗膜試料を作製し、これを基盤目試験、剥
離強度の測定および耐水性の評価に供した。 結果を表
1に示す。(Comparative Example 1) An aqueous dispersion was prepared in the same manner as in Example 1 except that the modified copolymer was not chlorinated, and using this, Example 2
A coating film sample was prepared in the same manner as above, and was subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.
(比較例2)
水分散体を塗布しない以外は、実施例2と同様にして塗
膜試料を作製し、これを基盤目試験、剥離強度の測定お
よび耐水性の評価に供した。 結果を表1に示す。(Comparative Example 2) A coating film sample was prepared in the same manner as in Example 2, except that the water dispersion was not applied, and this sample was subjected to a base grain test, peel strength measurement, and water resistance evaluation. The results are shown in Table 1.
表 1
〈発明の効果〉
本発明の水分散体は、樹脂成形品、例えば、ポリプロピ
レン等のα−オレフィン共重合体、合成ゴム、不飽和ポ
リエステル、エポキシ樹脂、ポリウレタン樹脂等、ある
いはこれらの複合樹脂等の各種の樹脂からなる成形品と
の付着性に優れるため、これらの成形品の表面に塗布し
て十分な剥離強度および密着性を有する塗膜を得ること
ができるとともに、有機溶媒を含有しない水系であるた
め、作業環境を良好に保つことができる、プライマーと
して好適なものである。Table 1 <Effects of the Invention> The aqueous dispersion of the present invention can be applied to resin molded products, such as α-olefin copolymers such as polypropylene, synthetic rubbers, unsaturated polyesters, epoxy resins, polyurethane resins, etc., or composite resins thereof. Because it has excellent adhesion to molded products made of various resins such as, it can be applied to the surface of these molded products to obtain a coating film with sufficient peel strength and adhesion, and it does not contain organic solvents. Since it is water-based, it is suitable as a primer because it can maintain a good working environment.
剥離強度: g / 10 m mPeel strength: g/10mm
Claims (2)
に、モノオレフィンジカルボン酸およびその無水物並び
にモノオレフィンジカルボン酸のモノアルキルエステル
から選ばれる少なくとも1種を0.5〜15重量%含む
ようにグラフト共重合させてなる変性共重合体を、さら
に塩素化して得られる塩素含有率10〜50重量%の塩
素化変性α−オレフィン共重合体を水に分散させてなる
水分散体であって、該塩素化変性α−オレフィン共重合
体5〜70重量部に対して、水95〜30重量部を含む
水分散体。(1) 0.5 to 15% by weight of at least one selected from monoolefin dicarboxylic acids, their anhydrides, and monoalkyl esters of monoolefin dicarboxylic acids to an α-olefin copolymer with a crystallinity of 20% or less. An aqueous dispersion obtained by dispersing in water a chlorinated modified α-olefin copolymer with a chlorine content of 10 to 50% by weight obtained by further chlorinating a modified copolymer obtained by graft copolymerization so as to contain An aqueous dispersion containing 95 to 30 parts by weight of water to 5 to 70 parts by weight of the chlorinated modified α-olefin copolymer.
チレン共重合体およびプロピレン・ブテン・エチレン共
重合体から選ばれる少なくとも1種である請求項1に記
載の水分散体。(2) The aqueous dispersion according to claim 1, wherein the α-olefin copolymer is at least one selected from propylene/ethylene copolymers and propylene/butene/ethylene copolymers.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20557790A JPH0489832A (en) | 1990-08-02 | 1990-08-02 | Aqueous dispersion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20557790A JPH0489832A (en) | 1990-08-02 | 1990-08-02 | Aqueous dispersion |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0489832A true JPH0489832A (en) | 1992-03-24 |
Family
ID=16509191
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20557790A Pending JPH0489832A (en) | 1990-08-02 | 1990-08-02 | Aqueous dispersion |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0489832A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0782179A2 (en) | 1995-12-27 | 1997-07-02 | Shin-Etsu Handotai Co., Ltd | Method of manufacturing semiconductor mirror wafers |
WO2000026310A1 (en) * | 1998-10-30 | 2000-05-11 | Nippon Paper Industries Co., Ltd. | Binder resin for polyolefin resin, process for producing the same, and uses thereof |
EP1065245A1 (en) * | 1999-01-18 | 2001-01-03 | Nippon Paper Industries Co., Ltd. | Binder resin composition and process for the production thereof |
-
1990
- 1990-08-02 JP JP20557790A patent/JPH0489832A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0782179A2 (en) | 1995-12-27 | 1997-07-02 | Shin-Etsu Handotai Co., Ltd | Method of manufacturing semiconductor mirror wafers |
WO2000026310A1 (en) * | 1998-10-30 | 2000-05-11 | Nippon Paper Industries Co., Ltd. | Binder resin for polyolefin resin, process for producing the same, and uses thereof |
US6586525B1 (en) | 1998-10-30 | 2003-07-01 | Nippon Paper Industries Co., Ltd. | Binder resin for polyolefin resin, process for producing the same, and uses thereof |
EP1065245A1 (en) * | 1999-01-18 | 2001-01-03 | Nippon Paper Industries Co., Ltd. | Binder resin composition and process for the production thereof |
EP1065245A4 (en) * | 1999-01-18 | 2002-10-02 | Jujo Paper Co Ltd | Binder resin composition and process for the production thereof |
US6555621B1 (en) | 1999-01-18 | 2003-04-29 | Nippon Paper Industries Co., Ltd. | Binder resin composition and process for the production thereof |
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