JP7657599B2 - Method for producing acid-modified chlorinated polyolefin resin - Google Patents
Method for producing acid-modified chlorinated polyolefin resin Download PDFInfo
- Publication number
- JP7657599B2 JP7657599B2 JP2021014533A JP2021014533A JP7657599B2 JP 7657599 B2 JP7657599 B2 JP 7657599B2 JP 2021014533 A JP2021014533 A JP 2021014533A JP 2021014533 A JP2021014533 A JP 2021014533A JP 7657599 B2 JP7657599 B2 JP 7657599B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polyolefin resin
- weight
- modified chlorinated
- chlorinated polyolefin
- 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.)
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- 229920005672 polyolefin resin Polymers 0.000 title claims description 140
- 238000004519 manufacturing process Methods 0.000 title claims description 63
- 239000002253 acid Substances 0.000 claims description 107
- 238000005660 chlorination reaction Methods 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000003999 initiator Substances 0.000 claims description 28
- 238000007348 radical reaction Methods 0.000 claims description 28
- 238000012986 modification Methods 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 22
- 238000006011 modification reaction Methods 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- -1 isodecyl Chemical group 0.000 description 39
- 239000011347 resin Substances 0.000 description 32
- 229920005989 resin Polymers 0.000 description 32
- 238000000034 method Methods 0.000 description 31
- 229920001577 copolymer Polymers 0.000 description 30
- 239000000203 mixture Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Chemical class 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000005456 alcohol based solvent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- 229920001384 propylene homopolymer Polymers 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000011230 binding agent Substances 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
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229940113083 morpholine Drugs 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 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
- 239000008096 xylene Substances 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- LHXNVCCLDTYJGT-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)propan-2-ol Chemical compound CC(O)COCC1CO1 LHXNVCCLDTYJGT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- GVJRTUUUJYMTNQ-UHFFFAOYSA-N 2-(2,5-dioxofuran-3-yl)acetic acid Chemical compound OC(=O)CC1=CC(=O)OC1=O GVJRTUUUJYMTNQ-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-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
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- NPKKFQUHBHQTSH-UHFFFAOYSA-N 2-(decoxymethyl)oxirane Chemical compound CCCCCCCCCCOCC1CO1 NPKKFQUHBHQTSH-UHFFFAOYSA-N 0.000 description 1
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 1
- ZXJBWUAALADCRI-UHFFFAOYSA-N 2-(octadecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCCCCCOCC1CO1 ZXJBWUAALADCRI-UHFFFAOYSA-N 0.000 description 1
- CUGZWHZWSVUSBE-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethanol Chemical compound OCCOCC1CO1 CUGZWHZWSVUSBE-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- WAPRZVXVTPSWEB-UHFFFAOYSA-N 2-[(2-butan-2-ylphenoxy)methyl]oxirane Chemical compound CCC(C)C1=CC=CC=C1OCC1OC1 WAPRZVXVTPSWEB-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、ポリオレフィン樹脂を原料とする酸変性塩素化ポリオレフィン樹脂の製造方法に関する。 The present invention relates to a method for producing acid-modified chlorinated polyolefin resin using polyolefin resin as a raw material.
これまで、ポリオレフィン樹脂を酸変性及び塩素化する際、一般的に酸成分及びラジカル反応開始剤を押出機等の混練機に添加し混練する溶融法を用いて酸変性を行い、その後反応タンクに移し替えて塩素化する方法が用いられてきた。 Until now, when polyolefin resins were acid-modified and chlorinated, the acid modification was generally carried out using a melting method in which an acid component and a radical reaction initiator were added to a kneader such as an extruder and kneaded, and then the resin was transferred to a reaction tank for chlorination.
しかしながら、溶融法を用いる方法では、混練時に、ポリオレフィン樹脂内部の二重結合（不飽和部）の増加や、残留モノマーのオリゴマー化等により、生成する樹脂に強い着色が生じてしまうという課題があった。このように、得られる樹脂の着色が強いと、例えば、白色塗料や白色インクに使用できないなど、樹脂の適用範囲が狭くなるという問題が生じ得る。 However, the melting method has the problem that the resulting resin becomes strongly colored during kneading due to an increase in double bonds (unsaturated parts) inside the polyolefin resin and oligomerization of residual monomers. If the resulting resin is strongly colored in this way, it can cause problems such as narrowing the range of application of the resin, making it impossible to use it in white paints or white inks.
また、着色を抑制するため、溶融法以外の方法を用いることも考えられるが、グラフト効率の低下などが懸念されることから、これまで、あまり検討が行われてこなかった。 In addition, in order to suppress coloration, it is possible to use methods other than the melting method, but due to concerns about a decrease in grafting efficiency, this has not been studied much up to now.
本発明の課題は、得られる酸変性塩素化ポリオレフィン樹脂の色味を抑えることができる酸変性塩素化ポリオレフィン樹脂の製造方法を提供することである。 The object of the present invention is to provide a method for producing an acid-modified chlorinated polyolefin resin that can suppress the color of the resulting acid-modified chlorinated polyolefin resin.
本発明者らは、上記課題について鋭意検討した結果、同一の反応タンク内で、ポリオレフィン樹脂に対し、酸成分による酸変性反応と、塩素化反応とを任意の順で連続して行うことにより、上記の課題を解決できることを見出し、本発明を完成するに至った。即ち、本発明者らは、下記の［１］～［６］を提供する。
［１］ ポリオレフィン樹脂に対し、同一の反応タンク内で、酸成分による酸変性反応と、塩素化反応とを任意の順で連続して行う酸変性塩素化工程を含む、酸変性塩素化ポリオレフィン樹脂の製造方法であって、
酸変性塩素化ポリオレフィン樹脂の酸成分のグラフト量が０．１重量％～１０重量％であり、且つ塩素のグラフト量が１０重量％～７０重量％である、酸変性塩素化ポリオレフィン樹脂の製造方法。
［２］ 酸変性塩素化工程が、ポリオレフィン樹脂に対し、同一の反応タンク内で、酸成分による酸変性反応と、塩素化反応とをこの順で連続して行う酸変性塩素化工程である、上記［１］に記載の酸変性塩素化ポリオレフィン樹脂の製造方法。
［３］ 酸変性塩素化工程において酸成分の投入後にラジカル反応開始剤を投入する、上記［２］に記載の酸変性塩素化ポリオレフィン樹脂の製造方法。
［４］ 酸成分の投入量が、ポリオレフィン樹脂１００重量部に対して、１０重量部以下である、上記［１］～［３］の何れかに記載の酸変性塩素化ポリオレフィン樹脂の製造方法。
［５］ 酸変性塩素化工程においてラジカル反応開始剤を投入することを含み、
ラジカル反応開始剤の投入量が、酸成分１重量部に対して、０．１重量部以上である、上記［１］～［４］の何れかに記載の酸変性塩素化ポリオレフィン樹脂の製造方法。
［６］ 酸変性塩素化工程においてラジカル反応開始剤を投入することを含み、
ラジカル反応開始剤の投入量が、酸成分１重量部に対して、２重量部以下である、上記［１］～［５］の何れかに記載の酸変性塩素化ポリオレフィン樹脂の製造方法。
As a result of intensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by continuously carrying out an acid modification reaction with an acid component and a chlorination reaction in any order on a polyolefin resin in the same reaction tank, and have thus completed the present invention. That is, the present inventors provide the following [1] to [6].
[1] A method for producing an acid-modified chlorinated polyolefin resin, comprising an acid-modified chlorination step in which an acid modification reaction with an acid component and a chlorination reaction are continuously carried out in any order on a polyolefin resin in the same reaction tank,
A method for producing an acid-modified chlorinated polyolefin resin, in which the graft amount of an acid component of the acid-modified chlorinated polyolefin resin is 0.1% by weight to 10% by weight, and the graft amount of chlorine is 10% by weight to 70% by weight.
[2] The method for producing an acid-modified chlorinated polyolefin resin according to the above [1], wherein the acid-modified chlorination step is an acid-modified chlorination step in which an acid modification reaction with an acid component and a chlorination reaction are continuously carried out in this order on a polyolefin resin in the same reaction tank.
[3] The method for producing an acid-modified chlorinated polyolefin resin according to the above [2], wherein a radical reaction initiator is added after the addition of an acid component in the acid-modified chlorination step.
[4] The method for producing an acid-modified chlorinated polyolefin resin according to any one of the above [1] to [3], wherein the amount of the acid component added is 10 parts by weight or less per 100 parts by weight of the polyolefin resin.
[5] The method includes adding a radical reaction initiator in the acid-modified chlorination step,
The method for producing an acid-modified chlorinated polyolefin resin according to any one of the above [1] to [4], wherein the amount of the radical reaction initiator added is 0.1 parts by weight or more per 1 part by weight of the acid component.
[6] The method includes adding a radical reaction initiator in the acid-modified chlorination step,
The method for producing an acid-modified chlorinated polyolefin resin according to any one of the above [1] to [5], wherein the amount of the radical reaction initiator added is 2 parts by weight or less per 1 part by weight of the acid component.
本発明によれば、色味を抑えた酸変性塩素化ポリオレフィン樹脂を製造することができる。 According to the present invention, it is possible to produce an acid-modified chlorinated polyolefin resin with reduced color.
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。なお、「ＡＡ～ＢＢ％」という表記は、ＡＡ％以上ＢＢ％以下を示す。 The present invention will be described in detail below with reference to preferred embodiments. Note that the notation "AA-BB%" indicates AA% or more and BB% or less.
［１．酸変性塩素化ポリオレフィン樹脂の製造方法］
本発明の酸変性塩素化ポリオレフィン樹脂の製造方法は、ポリオレフィン樹脂に対し、同一の反応タンク内で、酸成分の投入による酸変性反応と、塩素化反応とを任意の順で連続して行う酸変性塩素化工程を含むことを特徴とする。「連続して行う」とは、反応別に反応タンクの移し替え等を行わずに、ある反応から異なる反応に進めることを意味する。
[1. Method for producing acid-modified chlorinated polyolefin resin]
The method for producing an acid-modified chlorinated polyolefin resin of the present invention is characterized by comprising an acid-modified chlorination step in which an acid modification reaction by adding an acid component and a chlorination reaction are carried out continuously in any order on a polyolefin resin in the same reaction tank. "Continuously" means that a reaction is carried out from one reaction to another without transferring the reaction tank for each reaction.
酸変性塩素化工程は、酸変性反応から塩素化反応の順に連続して行う方法（製造方式Ｂ又は製造方式Ｃ）を用いてもよいし、塩素化反応から酸変性反応の順に連続して行う方法（製造方式Ａ）を用いてもよいが、色味をより一層抑える観点から、酸変性反応から塩素化反応の順に連続して行う方法が好ましい。したがって、酸変性塩素化工程は、ポリオレフィン樹脂に対し、同一の反応タンク内で、酸成分の投入による酸変性反応と、塩素化反応とをこの順で連続して行う酸変性塩素化工程であることが好ましい。 The acid-modified chlorination process may be carried out in a manner in which the acid modification reaction is carried out in succession in the order of chlorination reaction (manufacturing method B or manufacturing method C), or in a manner in which the chlorination reaction is carried out in succession in the order of acid modification reaction (manufacturing method A). However, from the viewpoint of further suppressing color, the method in which the acid modification reaction is carried out in succession in the order of chlorination reaction is preferred. Therefore, the acid-modified chlorination process is preferably an acid-modified chlorination process in which the acid modification reaction by adding an acid component and the chlorination reaction are carried out in succession in the same reaction tank on the polyolefin resin.
酸変性反応は、反応タンク内に酸成分を投入して、ポリオレフィン樹脂を酸成分と反応させることにより行う。酸変性反応から塩素化反応の順に連続して行う場合、反応タンク内への酸成分の投入は、一実施形態において、通常、ポリオレフィン樹脂投入と同時、もしくは樹脂の投入後に行う。 The acid modification reaction is carried out by adding an acid component to a reaction tank and reacting the polyolefin resin with the acid component. When the acid modification reaction and the chlorination reaction are carried out consecutively, in one embodiment, the acid component is usually added to the reaction tank simultaneously with the addition of the polyolefin resin or after the resin is added.
酸成分は、例えば、α，β－不飽和カルボン酸、及びその誘導体（例えば、α，β－不飽和カルボン酸エステル、α，β－不飽和カルボン酸無水物）であり、具体的には、マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、無水シトラコン酸、メサコン酸、イタコン酸、無水イタコン酸、アコニット酸、無水アコニット酸、無水ハイミック酸、（メタ）アクリル酸、（メタ）アクリル酸エステルが挙げられる。（メタ）アクリル酸エステルは、（メタ）アクリル酸基と炭化水素基とからなるエステルが好ましく、例えば、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソデシル（メタ）アクリレートが挙げられる。酸成分は、１種以上の化合物であってもよく、２種以上の化合物の組み合わせであってもよい。このような酸成分は、ポリオレフィン樹脂の主鎖に対してグラフト共重合により導入でき得る。酸成分は、ポリオレフィン樹脂へのグラフト性を考慮すると、無水マレイン酸が好ましい。 The acid component is, for example, an α,β-unsaturated carboxylic acid and its derivatives (for example, an α,β-unsaturated carboxylic acid ester and an α,β-unsaturated carboxylic acid anhydride), and specifically includes maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, hymic anhydride, (meth)acrylic acid, and (meth)acrylic acid esters. The (meth)acrylic acid ester is preferably an ester consisting of a (meth)acrylic acid group and a hydrocarbon group, and examples thereof include lauryl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, and isodecyl (meth)acrylate. The acid component may be one or more compounds, or a combination of two or more compounds. Such an acid component can be introduced into the main chain of the polyolefin resin by graft copolymerization. In consideration of the graftability to the polyolefin resin, the acid component is preferably maleic anhydride.
酸成分の投入量は、ポリオレフィン樹脂１００重量部に対して、好ましくは０．０５重量部以上、より好ましくは０．１重量部以上、さらに好ましくは０．３重量部以上、特に好ましくは０．５重量部以上である。投入量が０．０５重量部以上であることにより、酸変性塩素化ポリオレフィン樹脂の金属被着体に対する接着性を保つことができる。酸成分の投入量の上限値は、ポリオレフィン樹脂１００重量部に対して、好ましくは１５重量部以下、より好ましくは１０重量部以下、さらに好ましくは７重量部以下、特に好ましくは５重量部以下である。投入量が１５重量部以下であることにより、樹脂被着体に対する十分な接着性を得ることができる。投入量が１０重量部以下であることにより、より優れたグラフト効率を達成できる。 The amount of the acid component added is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, even more preferably 0.3 parts by weight or more, and particularly preferably 0.5 parts by weight or more, per 100 parts by weight of the polyolefin resin. By adding an amount of 0.05 parts by weight or more, the adhesion of the acid-modified chlorinated polyolefin resin to the metal adherend can be maintained. The upper limit of the amount of the acid component added is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 7 parts by weight or less, and particularly preferably 5 parts by weight or less, per 100 parts by weight of the polyolefin resin. By adding an amount of 15 parts by weight or less, sufficient adhesion to the resin adherend can be obtained. By adding an amount of 10 parts by weight or less, better grafting efficiency can be achieved.
塩素化反応は、ポリオレフィン樹脂に対して塩素を導入するための公知の方法を用いることができ、例えば、反応タンク内への塩素ガスの吹込みにより行う。 The chlorination reaction can be carried out using known methods for introducing chlorine into polyolefin resins, for example, by blowing chlorine gas into a reaction tank.
塩素化反応では、塩素のグラフト量が、ポリオレフィン樹脂の種類、反応スケール、反応装置等の要素の違いに依存することから、塩素のグラフト量の調節を、例えば、塩素の吹き込み量や塩素化反応の時間をモニタリングしながら行い得る。 In the chlorination reaction, the amount of chlorine grafted depends on factors such as the type of polyolefin resin, the reaction scale, and the reaction apparatus, so the amount of chlorine grafted can be adjusted, for example, by monitoring the amount of chlorine blown in and the time of the chlorination reaction.
塩素化反応を塩素ガスの吹込みにより行う場合は、塩素化反応後に、窒素ガスなどの不活性ガスの吹き込みなどにより、副生した塩化水素を除去することが望ましい。 When the chlorination reaction is carried out by blowing in chlorine gas, it is desirable to remove the by-product hydrogen chloride after the chlorination reaction by blowing in an inert gas such as nitrogen gas.
酸変性反応及び塩素化反応は、反応タンク内にラジカル反応開始剤を投入することにより、ラジカル反応開始剤の存在下にて行うことが好ましい。 The acid modification reaction and the chlorination reaction are preferably carried out in the presence of a radical reaction initiator by adding the radical reaction initiator to the reaction tank.
ラジカル反応開始剤としては、例えば、有機過酸化物系化合物及びアゾニトリル類が挙げられる。有機過酸化物系化合物としては、例えば、ジ－ｔｅｒｔ－ブチルパーオキサイド、ジクミルパーオキサイド、ｔｅｒｔ－ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、ジラウリルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルペルオキシ）ヘキサン、クメンハイドロパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－３，５，５－トリメチルシクロヘキサン、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－シクロヘキサン、シクロヘキサノンパーオキサイド、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシイソブチレート、ｔｅｒｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシイソプロピルカーボネート、クミルパーオキシオクトエートなどが挙げられる。アゾニトリル類としては、例えば、２，２－アゾビス（２－メチルブチロニトリル）、２，２－アゾビスイソブチロニトリル、２，２－アゾビス（２，４－ジメチルバレロニトリル）、２，２－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）が挙げられる。ラジカル反応開始剤としては、中でも、有機過酸化物系化合物が好ましく、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートが特に好ましい。 Examples of radical reaction initiators include organic peroxide compounds and azonitriles. Examples of organic peroxide compounds include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butylperoxybenzoate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisopropyl carbonate, and cumyl peroxyoctoate. Examples of azonitriles include 2,2-azobis(2-methylbutyronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile). As the radical reaction initiator, organic peroxide compounds are preferred, and tert-butylperoxy-2-ethylhexanoate is particularly preferred.
ラジカル反応開始剤の酸成分に対する投入量は、酸成分１重量部に対して、０．０１重量部以上であることが好ましく、０．１重量部以上であることがより好ましく、０．５重量部以上であることがさらに好ましい。投入量が０．１重量部以上であることにより、さらに一層十分なグラフト効率を保持し得る。ラジカル反応開始剤の酸成分に対する投入量の上限値は、酸成分１重量部に対して、５重量部以下であることが好ましく、２重量部以下であることがより好ましく、１．５重量部以下であることがさらに好ましい。投入量が２重量部以下であることにより、酸変性塩素化ポリオレフィン樹脂の分子量を低く抑えることができる。分子量が増大すると、溶剤溶解性の低下や、凝集物が形成しやすくなるといった不具合が生じ得る。 The amount of radical reaction initiator added to the acid component is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and even more preferably 0.5 parts by weight or more, per 1 part by weight of the acid component. By adding an amount of 0.1 parts by weight or more, it is possible to maintain even more sufficient grafting efficiency. The upper limit of the amount of radical reaction initiator added to the acid component is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, and even more preferably 1.5 parts by weight or less, per 1 part by weight of the acid component. By adding an amount of 2 parts by weight or less, it is possible to keep the molecular weight of the acid-modified chlorinated polyolefin resin low. If the molecular weight increases, problems such as a decrease in solvent solubility and a tendency to form aggregates may occur.
ラジカル反応開始剤のポリオレフィン樹脂に対する投入量は、ポリオレフィン樹脂１００重量部に対して、０．０５重量部以上であることが好ましく、０．１重量部以上であることがより好ましく、０．５重量部以上であることがさらに好ましい。投入量が０．５重量部以上であることにより、さらに一層十分なグラフト効率を保持し得る。ラジカル反応開始剤のポリオレフィン樹脂に対する投入量の上限値は、ポリオレフィン樹脂１００重量部に対して、２０重量部以下であることが好ましく、１０重量部以下であることがより好ましく、５重量部以下であることがさらに好ましい。投入量が５重量部以下であることにより、グラフト効率を維持することができ、且つ酸変性塩素化ポリオレフィン樹脂の分子量を低く抑えることができる。 The amount of radical reaction initiator added to the polyolefin resin is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and even more preferably 0.5 parts by weight or more, per 100 parts by weight of the polyolefin resin. By adding an amount of 0.5 parts by weight or more, it is possible to maintain even more sufficient graft efficiency. The upper limit of the amount of radical reaction initiator added to the polyolefin resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less, per 100 parts by weight of the polyolefin resin. By adding an amount of 5 parts by weight or less, it is possible to maintain graft efficiency and keep the molecular weight of the acid-modified chlorinated polyolefin resin low.
ポリオレフィン樹脂に対し、同一の反応タンク内で、酸成分による酸変性反応と、塩素化反応とをこの順で連続して行う場合において、ラジカル反応開始剤を用いる場合、反応タンク内への酸成分の投入後にラジカル反応開始剤を投入してもよいし（製造方式Ｃ）、反応タンク内へのラジカル反応開始剤の投入後に酸成分を投入してもよいが（製造方式Ｂ）、グラフト効率をより向上させる観点から、反応タンク内への酸成分の投入後にラジカル反応開始剤を投入することが好ましい。 When a polyolefin resin is subjected to an acid modification reaction using an acid component and a chlorination reaction in the same reaction tank in that order, if a radical reaction initiator is used, the radical reaction initiator may be added after the acid component is added to the reaction tank (production method C), or the acid component may be added after the radical reaction initiator is added to the reaction tank (production method B). However, from the viewpoint of further improving the grafting efficiency, it is preferable to add the radical reaction initiator after the acid component is added to the reaction tank.
酸変性反応及び塩素化反応は、溶液法等の公知の方法に従って行えばよい。溶液法によれば、副反応が少なく均一な酸変性物を得ることができる。溶液法は、例えば、ポリオレフィン樹脂を有機溶剤に溶解させた後、酸変性反応及び塩素化反応を行う方法であり得る。 The acid modification reaction and the chlorination reaction may be carried out according to a known method such as a solution method. The solution method allows for the production of a uniform acid modification product with few side reactions. The solution method may be, for example, a method in which a polyolefin resin is dissolved in an organic solvent and then the acid modification reaction and the chlorination reaction are carried out.
有機溶剤としては、例えば、クロロホルム、塩化メチレン等の塩素系溶剤、ベンゼン、トルエン、キシレン、エチルベンゼン、トリメチルベンゼン等の芳香族系溶剤等が挙げられ、中でも、塩素系溶剤が好ましく、クロロホルムがより好ましい。 Examples of organic solvents include chlorine-based solvents such as chloroform and methylene chloride, and aromatic solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. Among these, chlorine-based solvents are preferred, and chloroform is more preferred.
酸変性反応では、反応タンク内の圧力は、常圧で行ってもよいし、加圧下で行ってもよい。塩素化反応は、常圧であってもよいし、加圧下であってもよいが、加圧下で行うことが好ましく、例えば、１ＭＰａ以下、特に好ましくは０．２５ＭＰａ以下に調整して行う。 In the acid modification reaction, the pressure in the reaction tank may be normal pressure or may be under pressure. The chlorination reaction may be performed at normal pressure or under pressure, but is preferably performed under pressure, for example, adjusted to 1 MPa or less, and particularly preferably 0.25 MPa or less.
酸変性反応及び塩素化反応は、それぞれ、加熱して行うことが好ましく、温度範囲としては、例えば、５０～１４０℃であり、好ましくは６０～１３０℃であり、より好ましくは７０～１２０℃である、さらに好ましくは８０～１１０℃である。酸変性反応と塩素化反応とは、同一温度で行ってもよいし、上記の範囲内で異なる温度で行ってもよい。溶液法を用いる場合、例えば、ポリオレフィン樹脂を上記の範囲内の温度に加熱して有機溶剤に溶解させた後、上記の範囲内の温度で酸変性反応及び塩素化反応を行う。 The acid modification reaction and the chlorination reaction are preferably carried out by heating, and the temperature range is, for example, 50 to 140°C, preferably 60 to 130°C, more preferably 70 to 120°C, and even more preferably 80 to 110°C. The acid modification reaction and the chlorination reaction may be carried out at the same temperature or at different temperatures within the above range. When using a solution method, for example, the polyolefin resin is heated to a temperature within the above range to dissolve it in an organic solvent, and then the acid modification reaction and the chlorination reaction are carried out at a temperature within the above range.
本発明の酸変性塩素化ポリオレフィン樹脂の製造方法は、溶液法を用いる場合などにおいて、さらに酸変性塩素化ポリオレフィン樹脂を含む溶液を濃縮する濃縮工程を含んでもいてもよい。濃縮方法としては、例えば、加熱濃縮法、減圧濃縮法などを用いることができる。 When the method for producing the acid-modified chlorinated polyolefin resin of the present invention uses a solution method, the method may further include a concentration step of concentrating the solution containing the acid-modified chlorinated polyolefin resin. Examples of the concentration method that can be used include a heat concentration method and a reduced pressure concentration method.
［１－１．ポリオレフィン樹脂］
ポリオレフィン樹脂は、特に限定されるものではなく、１種のオレフィンの単独重合体であってもよく、２種以上のオレフィンの共重合体であってもよい。また、共重合体である場合、ランダム共重合体であってもよく、ブロック共重合体であってもよい。オレフィンとしては、α－オレフィンが好適に用いられる。α－オレフィンとしては、エチレン、プロピレン、１－ブテン等が挙げられる。
[1-1. Polyolefin resin]
The polyolefin resin is not particularly limited, and may be a homopolymer of one type of olefin, or a copolymer of two or more types of olefins. In addition, when it is a copolymer, it may be a random copolymer or a block copolymer. As the olefin, an α-olefin is preferably used. Examples of the α-olefin include ethylene, propylene, and 1-butene.
ポリオレフィン樹脂は、例えば、プロピレン単独重合体、エチレン－プロピレン共重合体、水素化ポリブタジエン、エチレン－ブテン共重合体、エチレン－オクテン共重合体、プロピレン－ブテン共重合体、エチレン－プロピレン－ブテン共重合体、α－オレフィン誘導体が挙げられる。なお、これらは市販品であってもよい。また、ポリオレフィン樹脂は、１種単独であってもよく、２種以上を併用してもよい。ポリオレフィン樹脂は、中でも、プロピレン単独重合体、エチレン－プロピレン共重合体、プロピレン－ブテン共重合体、エチレン－プロピレン－ブテン共重合体が好ましい。 Examples of polyolefin resins include propylene homopolymers, ethylene-propylene copolymers, hydrogenated polybutadiene, ethylene-butene copolymers, ethylene-octene copolymers, propylene-butene copolymers, ethylene-propylene-butene copolymers, and α-olefin derivatives. These may be commercially available products. The polyolefin resin may be one type alone or two or more types may be used in combination. Of these, the polyolefin resins preferably include propylene homopolymers, ethylene-propylene copolymers, propylene-butene copolymers, and ethylene-propylene-butene copolymers.
プロピレン単独重合体は、プロピレン由来の構成単位からなる重合体を表す。エチレン－プロピレン共重合体とは、構成単位がエチレン由来の構成単位及びプロピレン由来の構成単位である共重合体を表す。プロピレン－ブテン共重合体とは、構成単位がプロピレン由来の構成単位及び１－ブテン由来の構成単位である共重合体を表す。エチレン－プロピレン－ブテン共重合体とは、基本単位がエチレン由来の構成単位、構成単位がプロピレン由来の構成単位及び１－ブテン由来の構成単位である共重合体を表す。プロピレン単独重合体、エチレン－プロピレン共重合体、プロピレン－ブテン共重合体、及びエチレン－プロピレン－ブテン共重合体は、それぞれ、上記構成単位以外の他のオレフィン由来の構成単位を少量含有していてもよい。この含有量は、樹脂本来の性能を著しく損なわない量であればよい。 Propylene homopolymer refers to a polymer consisting of structural units derived from propylene. Ethylene-propylene copolymer refers to a copolymer whose structural units are structural units derived from ethylene and structural units derived from propylene. Propylene-butene copolymer refers to a copolymer whose structural units are structural units derived from propylene and structural units derived from 1-butene. Ethylene-propylene-butene copolymer refers to a copolymer whose base unit is a structural unit derived from ethylene, and whose structural units are structural units derived from propylene and structural units derived from 1-butene. Propylene homopolymer, ethylene-propylene copolymer, propylene-butene copolymer, and ethylene-propylene-butene copolymer may each contain a small amount of structural units derived from olefins other than the above structural units. This content may be an amount that does not significantly impair the inherent performance of the resin.
ポリオレフィン樹脂は、プロピレン由来の構成単位（プロピレン含有量）を含むことが好ましく、ポリオレフィン樹脂のプロピレン由来の構成単位（プロピレン含有量）の含有割合は、全構成単位１００モル％中、５０モル％以上であることが好ましく、６０モル％以上であることがより好ましい。プロピレン由来の構成単位を上記範囲で含むと、非極性樹脂（例えば、プロピレン樹脂）等の基材又は成型品に対する付着性を確保し得る。ポリオレフィン樹脂のプロピレン由来の構成単位（プロピレン含有量）の含有割合の上限は、特に限定されるものではないが、例えば、全構成単位１００モル％中、１００モル％（すなわちプロピレン単独重合体の場合）、９５モル％以下（例えばエチレン－プロピレン共重合体、プロピレン－ブテン共重合体、及びエチレン－プロピレン－ブテン共重合体等の場合）等であればよい。 The polyolefin resin preferably contains a propylene-derived structural unit (propylene content), and the content of the propylene-derived structural unit (propylene content) of the polyolefin resin is preferably 50 mol% or more, more preferably 60 mol% or more, of 100 mol% of all structural units. When the propylene-derived structural unit is contained within the above range, adhesion to a substrate or molded product such as a non-polar resin (e.g., propylene resin) can be ensured. The upper limit of the content of the propylene-derived structural unit (propylene content) of the polyolefin resin is not particularly limited, but may be, for example, 100 mol% (i.e., in the case of a propylene homopolymer) or 95 mol% or less (e.g., in the case of an ethylene-propylene copolymer, a propylene-butene copolymer, and an ethylene-propylene-butene copolymer, etc.) of 100 mol% of all structural units.
ポリオレフィン樹脂としては、重合触媒としてメタロセン触媒を用いて得られるポリオレフィン樹脂が、下記の特徴を有するので好ましい。メタロセン触媒を用いて得られるポリオレフィン樹脂は、分子量分布が狭い。また、ポリオレフィン樹脂が共重合体の場合は、ランダム共重合性に優れ、組成分布が狭く、さらには、共重合し得るコモノマーの範囲が広い。メタロセン触媒としては、公知のものが使用できる。メタロセン触媒は、好ましくは、以下に述べる成分（１）及び（２）と、さらに必要に応じて（３）とを組み合わせて得られる。
・成分（１）；共役五員環配位子を少なくとも一個有する周期律表４～６族の遷移金属化合物であるメタロセン錯体
・成分（２）；イオン交換性層状ケイ酸塩
・成分（３）；有機アルミニウム化合物
As the polyolefin resin, a polyolefin resin obtained using a metallocene catalyst as a polymerization catalyst is preferred because it has the following characteristics. The polyolefin resin obtained using a metallocene catalyst has a narrow molecular weight distribution. In addition, when the polyolefin resin is a copolymer, it has excellent random copolymerization properties, a narrow composition distribution, and a wide range of comonomers that can be copolymerized. As the metallocene catalyst, a known one can be used. The metallocene catalyst is preferably obtained by combining the following components (1) and (2), and further (3) as necessary.
Component (1): A metallocene complex which is a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand. Component (2): An ion-exchangeable layered silicate. Component (3): An organoaluminum compound.
ポリオレフィン樹脂の構造は、通常の高分子化合物が取り得るアイソタクチック構造、アタクチック構造、シンジオタクチック構造等のいずれであってもよい。これらの構造の中でも、ポリオレフィン基材への付着性、特に低温乾燥での付着性を考慮すると、メタロセン触媒を用いた場合にとり得る、アイソタクチック構造のポリオレフィン樹脂が好ましい。 The structure of the polyolefin resin may be any of the isotactic, atactic, syndiotactic, and other structures that ordinary polymer compounds can have. Among these structures, polyolefin resins with an isotactic structure, which can be obtained when a metallocene catalyst is used, are preferred in terms of adhesion to polyolefin substrates, particularly adhesion during low-temperature drying.
ポリオレフィン樹脂の重量平均分子量の下限値は、１０，０００以上が好ましく、２０，０００以上がより好ましい。これにより樹脂が凝集力を発揮し得るので、樹脂組成物が基材への付着性をより発現し得る。重量平均分子量の上限値は、３００，０００以下が好ましく、２５０，０００以下がより好ましい。これにより、樹脂組成物の他樹脂との相溶性及び溶剤への溶解性をより向上させることができる。重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により、標準ポリスチレン検量線から求め得る。 The lower limit of the weight average molecular weight of the polyolefin resin is preferably 10,000 or more, more preferably 20,000 or more. This allows the resin to exert cohesive force, so that the resin composition can better exhibit adhesion to the substrate. The upper limit of the weight average molecular weight is preferably 300,000 or less, more preferably 250,000 or less. This allows the resin composition to have better compatibility with other resins and better solubility in solvents. The weight average molecular weight can be determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC).
［１－２．酸変性塩素化ポリオレフィン樹脂］
酸変性塩素化ポリオレフィン樹脂の酸成分のグラフト量（酸成分の導入量）は、原料のポリオレフィン樹脂１００重量％に対し、０．１重量％～１０重量％であり、好ましくは０．３重量％～７重量％、さらに好ましくは０．５重量％～５重量％である。酸成分のグラフト量が０．１重量％以上であることにより、酸変性塩素化ポリオレフィン樹脂の金属被着体に対する接着性を保つことができる。酸成分のグラフト量が１０重量％以下であることにより、樹脂被着体に対する十分な接着性を得ることができる。
[1-2. Acid-modified chlorinated polyolefin resin]
The graft amount of the acid component of the acid-modified chlorinated polyolefin resin (the amount of the acid component introduced) is 0.1% by weight to 10% by weight, preferably 0.3% by weight to 7% by weight, and more preferably 0.5% by weight to 5% by weight, based on 100% by weight of the raw material polyolefin resin. By setting the graft amount of the acid component to 0.1% by weight or more, the adhesiveness of the acid-modified chlorinated polyolefin resin to a metal adherend can be maintained. By setting the graft amount of the acid component to 10% by weight or less, sufficient adhesiveness to a resin adherend can be obtained.
酸成分のグラフト量とは、原料のポリオレフィン樹脂を１００重量％とした場合のポリオレフィン樹脂に対して導入された酸成分の重量（重量％）を意味する。酸成分のグラフト量は、例えば、１Ｈ－ＮＭＲを用いる方法、アルカリ滴定法、又はフーリエ変換赤外分光法等により求められる。 The graft amount of the acid component means the weight (% by weight) of the acid component introduced to the polyolefin resin when the raw material polyolefin resin is taken as 100% by weight. The graft amount of the acid component can be determined, for example, by a method using 1H -NMR, an alkali titration method, or a Fourier transform infrared spectroscopy.
酸変性塩素化ポリオレフィン樹脂の酸成分のグラフト効率は、製造コストを抑える観点から５０％以上が好ましく、７０％以上がより好ましく、８０％以上が特に好ましい。 From the viewpoint of reducing production costs, the grafting efficiency of the acid component of the acid-modified chlorinated polyolefin resin is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more.
酸成分のグラフト効率は、投入した酸成分のうちポリオレフィン樹脂にグラフトした酸成分の重量割合（％）を示し、酸変性塩素化ポリオレフィン樹脂の酸成分のグラフト量の数値（重量％）を、原料のポリオレフィン樹脂１００重量部に対する酸成分の投入量の数値（重量部）で除し、得られる数値をさらに１００倍して算出できる。 The grafting efficiency of the acid component indicates the weight percentage (%) of the acid component grafted to the polyolefin resin out of the total acid components added, and can be calculated by dividing the graft amount (weight %) of the acid component of the acid-modified chlorinated polyolefin resin by the amount (parts by weight) of the acid component added per 100 parts by weight of the raw polyolefin resin, and then multiplying the resulting value by 100.
酸変性塩素化ポリオレフィン樹脂の塩素のグラフト量（塩素含有量）は、酸変性塩素化ポリオレフィン樹脂１００重量％に対し、１０重量％～７０重量％であり、１５重量％～５５重量％が好ましく、２０重量％～４５重量％がより好ましい。塩素のグラフト量を上記範囲にすることで、酸変性塩素化ポリオレフィン樹脂の極性を一定範囲に調整し得る。それにより、塗料中の他樹脂との相溶性が良くなり、さらにはポリオレフィン基材等の非極性基材に対する十分な接着性を得ることができる。 The amount of chlorine grafted (chlorine content) of the acid-modified chlorinated polyolefin resin is 10% by weight to 70% by weight, preferably 15% by weight to 55% by weight, and more preferably 20% by weight to 45% by weight, relative to 100% by weight of the acid-modified chlorinated polyolefin resin. By setting the amount of chlorine grafted within the above range, the polarity of the acid-modified chlorinated polyolefin resin can be adjusted to a certain range. This improves compatibility with other resins in the paint, and further allows sufficient adhesion to non-polar substrates such as polyolefin substrates to be obtained.
塩素のグラフト量とは、酸変性塩素化ポリオレフィン樹脂を１００重量％とした場合の、酸変性塩素化ポリオレフィン樹脂中における塩素化反応により導入された塩素の重量（重量％）を意味する。なお、塩素のグラフト量は、例えば、ＪＩＳ－Ｋ７２２９に基づいて測定した値であり得る。 The grafted amount of chlorine means the weight (wt%) of chlorine introduced into the acid-modified chlorinated polyolefin resin by the chlorination reaction, assuming that the acid-modified chlorinated polyolefin resin is 100 wt%. The grafted amount of chlorine may be a value measured, for example, based on JIS-K7229.
酸変性塩素化ポリオレフィン樹脂の重量平均分子量の下限値は、２，０００以上が好ましく、１０，０００以上がより好ましく、２０，０００以上がさらに好ましい。これにより、酸変性塩素化ポリオレフィン樹脂の凝集力を向上でき、基材への付着性を発現し得る。上限値は、２５０，０００以下が好ましく、２００，０００以下がより好ましく、１００，０００以下がさらに好ましく、８０、０００以下がとりわけ好ましい。これにより、他樹脂との相溶性及び溶剤への溶解性を向上させることができる。 The lower limit of the weight average molecular weight of the acid-modified chlorinated polyolefin resin is preferably 2,000 or more, more preferably 10,000 or more, and even more preferably 20,000 or more. This can improve the cohesive force of the acid-modified chlorinated polyolefin resin and can exhibit adhesion to the substrate. The upper limit is preferably 250,000 or less, more preferably 200,000 or less, even more preferably 100,000 or less, and especially preferably 80,000 or less. This can improve compatibility with other resins and solubility in solvents.
［２．酸変性塩素化ポリオレフィン樹脂の用途等］
酸変性塩素化ポリオレフィン樹脂は、他の成分との組み合わせにおいて組成物としても利用できる。このような組成物の製造方法は、酸変性塩素化工程に加えて、例えば、酸変性塩素化ポリオレフィン樹脂を他の成分と混合する工程を含み得る。
[2. Uses of acid-modified chlorinated polyolefin resin]
The acid-modified chlorinated polyolefin resin can also be used as a composition in combination with other components. In addition to the acid-modified chlorination step, the method for producing such a composition can include, for example, a step of mixing the acid-modified chlorinated polyolefin resin with other components.
他の成分としては、例えば、水、有機溶剤、硬化剤、接着成分、安定化剤、塩基性物質、乳化剤、架橋剤、希釈剤、酸化防止剤、光安定剤、紫外線吸収剤、顔料、染料、無機充填剤、その他のポリオレフィン樹脂等が挙げられ、用途に応じて選択できる。 Other components include, for example, water, organic solvents, curing agents, adhesive components, stabilizers, basic substances, emulsifiers, crosslinking agents, diluents, antioxidants, light stabilizers, UV absorbers, pigments, dyes, inorganic fillers, other polyolefin resins, etc., and can be selected according to the application.
硬化剤としては、例えば、ポリイソシアネート化合物、エポキシ化合物、ポリアミン化合物、ポリオール化合物等が挙げられる。硬化剤の含有量は、酸変性塩素化ポリオレフィン樹脂の含有量により適宜選択すればよい。硬化剤を用いる場合、硬化触媒として、目的に応じて、有機スズ化合物、第三級アミン化合物等の触媒を併用してもよい。 Examples of curing agents include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, etc. The content of the curing agent may be appropriately selected depending on the content of the acid-modified chlorinated polyolefin resin. When a curing agent is used, a catalyst such as an organotin compound or a tertiary amine compound may be used in combination as a curing catalyst depending on the purpose.
接着成分としては、例えば、ポリエステル系接着剤、ポリウレタン系接着剤、アクリル系接着剤等の公知の接着成分が挙げられる。 Examples of adhesive components include known adhesive components such as polyester adhesives, polyurethane adhesives, and acrylic adhesives.
安定化剤としては、例えば、エポキシ系安定化剤等のエポキシ環を含む化合物が挙げられる。エポキシ系安定化剤としては、例えば、エポキシ当量が１００から５００程度であり、一分子中にエポキシ基を１個以上含むエポキシ化合物が挙げられる。エポキシ系安定化剤としては、より詳細には、天然の不飽和基を有する植物油を過酢酸等の過酸でエポキシ化したエポキシ化大豆油やエポキシ化アマニ油；オレイン酸、トール油脂肪酸、大豆油脂肪酸等の不飽和脂肪酸をエポキシ化したエポキシ化脂肪酸エステル類；エポキシ化テトラヒドロフタレートに代表されるエポキシ化脂環式化合物；ビスフェノールＡや多価アルコールとエピクロロヒドリンとを縮合した、例えば、ビスフェノールＡグリシジルエーテル、エチレングリコールグリシジルエーテル、プロピレングリコールグリシジルエーテル、グリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル；ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、デシルグリシジルエーテル、ステアリルグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシジルエーテル、ｓｅｃ－ブチルフェニルグリシジルエーテル、ｔｅｒｔ－ブチルフェニルグリシジルエーテル、フェノールポリエチレンオキサイドグリシジルエーテル等に代表されるモノエポキシ化合物類等が挙げられる。安定化剤は、エポキシ環を含まない化合物でもよく、例えば、ポリ塩化ビニル樹脂の安定化剤として使用されている、ステアリン酸カルシウム、ステアリン酸鉛等の金属石鹸類；ジブチル錫ジラウレート、ジブチルマレート等の有機金属化合物類；ハイドロタルサイト類化合物が挙げられる。 Examples of stabilizers include compounds containing an epoxy ring, such as epoxy-based stabilizers. Examples of epoxy-based stabilizers include epoxy compounds that have an epoxy equivalent of about 100 to 500 and contain one or more epoxy groups in one molecule. More specifically, examples of the epoxy stabilizer include epoxidized soybean oil and linseed oil obtained by epoxidizing vegetable oils having natural unsaturated groups with peracids such as peracetic acid; epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid; epoxidized alicyclic compounds such as epoxidized tetrahydrophthalate; monoepoxy compounds such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, and sorbitol polyglycidyl ether obtained by condensing bisphenol A or polyhydric alcohol with epichlorohydrin; and monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, and phenol polyethylene oxide glycidyl ether. The stabilizer may be a compound that does not contain an epoxy ring, and examples of such stabilizers include metal soaps such as calcium stearate and lead stearate, which are used as stabilizers for polyvinyl chloride resins; organometallic compounds such as dibutyltin dilaurate and dibutyl maleate; and hydrotalcite compounds.
安定化剤の含有量は、酸変性塩素化ポリオレフィン樹脂１００重量％に対し、好ましくは０．１重量％以上、より好ましくは１重量％以上、更に好ましくは２重量％以上である。これにより、安定化効果が良好に発現し得る。上限は、好ましくは１５重量％以下、より好ましくは１２重量％以下、更に好ましくは１０重量％以下である。これにより、ポリオレフィン等の基材に対する接着性を良好に発現させることができる。 The content of the stabilizer is preferably 0.1% by weight or more, more preferably 1% by weight or more, and even more preferably 2% by weight or more, based on 100% by weight of the acid-modified chlorinated polyolefin resin. This allows the stabilizing effect to be well expressed. The upper limit is preferably 15% by weight or less, more preferably 12% by weight or less, and even more preferably 10% by weight or less. This allows the adhesion to substrates such as polyolefins to be well expressed.
有機溶剤としては、例えば、トルエン、キシレン等の芳香族系溶剤；酢酸メチル、酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ブチル等のエステル系溶剤；アセトン、メチルエチルケトン、メチルブチルケトン等のケトン系溶剤；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環系溶剤；ペンタン、ヘキサン等の脂肪族系溶剤；エチレングリコール、エチルセロソルブ、ブチルセロソルブ等のグリコール系溶剤；メタノール、エタノール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、ｓｅｃ－ブチルアルコール、ｔｅｒｔ－ブチルアルコール、２－エチル－ヘキサノール等のアルコール系溶剤；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノイソプロピルエーテル、プロピレングリコールモノブチルエーテル等のグリコールモノエーテル系溶剤が挙げられる。これら有機溶剤は、１種単独で用いてもよく、２種以上の混合溶剤として樹脂組成物に含まれていてもよい。環境問題の観点から、芳香族溶剤以外の溶剤を選択することが好ましく、脂環系溶剤とエステル溶剤又はケトン系溶剤との混合溶剤がより好ましい。また、有機溶剤を用いる場合、組成物の保存安定性を高めるために、アルコール系溶剤（例えば、上述の脂肪族アルコール系溶剤、グリコールモノエーテル系溶剤）を用いることが好ましい。その場合、アルコール系溶剤の含有量は、好ましくは、有機溶剤１００重量％に対し１～２０重量％である。 Examples of organic solvents include aromatic solvents such as toluene and xylene; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone; alicyclic solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane; aliphatic solvents such as pentane and hexane; glycol solvents such as ethylene glycol, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and 2-ethyl-hexanol; and glycol monoether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, and propylene glycol monobutyl ether. These organic solvents may be used alone or may be included in the resin composition as a mixed solvent of two or more types. From the viewpoint of environmental issues, it is preferable to select a solvent other than an aromatic solvent, and a mixed solvent of an alicyclic solvent and an ester solvent or a ketone solvent is more preferable. In addition, when an organic solvent is used, it is preferable to use an alcohol-based solvent (for example, the above-mentioned aliphatic alcohol-based solvent or glycol monoether-based solvent) in order to improve the storage stability of the composition. In that case, the content of the alcohol-based solvent is preferably 1 to 20% by weight relative to 100% by weight of the organic solvent.
組成物の成分として水や親水性有機溶媒（例えば、アルコール系溶剤、グリコール系溶剤、ケトン系溶剤、エステル系溶剤）を用いる場合には、組成物は塩基性物質を含むことが好ましい。これにより、溶剤への樹脂の分散性をより高めることができる。塩基性物質としては例えば、水酸化ナトリウム、水酸化カリウム、アンモニア、メチルアミン、プロピルアミン、ヘキシルアミン、オクチルアミン、エタノールアミン、プロパノールアミン、ジエタノールアミン、Ｎ－メチルジエタノールアミン、ジメチルアミン、ジエチルアミン、トリエチルアミン、Ｎ，Ｎ－ジメチルエタノールアミン、２－ジメチルアミノ－２－メチル－１－プロパノール、２－アミノ－２－メチル－１－プロパノール、モルホリン、ジメチルエタノールアミンなどが挙げられ、好ましくはアンモニア、トリエチルアミン、２－アミノ－２－メチル－１－プロパノール、モルホリン、ジメチルエタノールアミンなどが挙げられる。塩基性物質の含有量は、酸変性塩素化ポリオレフィン樹脂中の酸性成分の量に応じて、任意の量に調整することができる。酸変性塩素化ポリオレフィン樹脂組成物のｐＨが、通常は５以上、好ましくは６以上となる量である。これにより、十分に中和がされ、安定な分散性が保たれ得る。上限は通常、ｐＨ１０以下となる量である。これにより、他成分との相溶性、作業上の安全性を良好に保持できる。 When water or a hydrophilic organic solvent (e.g., an alcohol-based solvent, a glycol-based solvent, a ketone-based solvent, or an ester-based solvent) is used as a component of the composition, it is preferable that the composition contains a basic substance. This can further improve the dispersibility of the resin in the solvent. Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N,N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, and dimethylethanolamine, and preferably ammonia, triethylamine, 2-amino-2-methyl-1-propanol, morpholine, and dimethylethanolamine. The content of the basic substance can be adjusted to any amount depending on the amount of the acidic component in the acid-modified chlorinated polyolefin resin. The amount is such that the pH of the acid-modified chlorinated polyolefin resin composition is usually 5 or more, and preferably 6 or more. This allows sufficient neutralization and stable dispersibility to be maintained. The upper limit is usually an amount that results in a pH of 10 or less. This allows compatibility with other components and operational safety to be maintained well.
組成物の成分として水や親水性有機溶媒を用いる場合には、組成物は乳化剤を含むことが好ましい。これにより、酸変性塩素化ポリオレフィン樹脂を水性化して水系分散液とした際、樹脂成分の粒子径を調整でき、分散性を安定化させ耐湿性等の安定性に関する性能を向上させることができる。乳化剤としては例えば、ノニオン界面活性剤、アニオン界面活性剤等の界面活性剤が挙げられ、ノニオン界面活性剤が好ましい。 When water or a hydrophilic organic solvent is used as a component of the composition, it is preferable that the composition contains an emulsifier. This allows the particle size of the resin component to be adjusted when the acid-modified chlorinated polyolefin resin is made aqueous to form an aqueous dispersion, stabilizing dispersibility and improving performance related to stability such as moisture resistance. Examples of emulsifiers include surfactants such as nonionic surfactants and anionic surfactants, with nonionic surfactants being preferred.
ノニオン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ポリオキシプロピレンアルキルエーテル、ポリオキシエチレン誘導体、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン多価アルコール脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンポリオール、ソルビタン脂肪酸エステル、ポリオキシエチレン硬化ひまし油、ポリオキシアルキレン多環フェニルエーテル、ポリオキシエチレンアルキルアミン、アルキルアルカノールアミド、ポリアルキレングリコール（メタ）アクリレートなどが挙げられる。好ましくは、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脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミンである。 Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene derivatives, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene polyoxypropylene polyols, sorbitan fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ethers, polyoxyethylene alkylamines, alkyl alkanolamides, and polyalkylene glycol (meth)acrylates. Preferred are polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkylamines.
アニオン界面活性剤としては、例えば、アルキル硫酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、α－オレフィンスルホン酸塩、メチルタウリル酸塩、スルホコハク酸塩、エーテルスルホン酸塩、エーテルカルボン酸塩、脂肪酸塩、ナフタレンスルホン酸ホルマリン縮合物、アルキルアミン塩、第四級アンモニウム塩、アルキルベタイン、アルキルアミンオキシドなどが挙げられる。好ましくは、ポリオキシエチレンアルキルエーテル硫酸塩、スルホコハク酸塩である。 Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl tauryl salts, sulfosuccinates, ether sulfonates, ether carboxylates, fatty acid salts, naphthalenesulfonate-formaldehyde condensates, alkylamine salts, quaternary ammonium salts, alkyl betaines, and alkylamine oxides. Preferred are polyoxyethylene alkyl ether sulfates and sulfosuccinates.
組成物の成分として水や親水性有機溶媒を用いる場合には、組成物は、架橋剤を含むことが好ましい。架橋剤は、組成物中に存在する、水酸基、カルボキシル基、アミノ基等の基と反応し、架橋構造を形成し得る化合物であればよく、水溶性の架橋剤、及び、架橋剤の水分散体（何らかの方法で水に分散されている状態の架橋剤）のいずれでもよい。架橋剤としては、例えば、ブロックイソシアネート化合物、脂肪族又は芳香族のエポキシ化合物、アミン系化合物、アミノ樹脂などが挙げられる。架橋剤は、１種単独でも、２種以上の組み合わせでもよい。架橋剤の添加方法は特に限定されず、添加は、水性化工程途中、或いは水性化後のいずれでもよい。 When water or a hydrophilic organic solvent is used as a component of the composition, it is preferable that the composition contains a crosslinking agent. The crosslinking agent may be any compound capable of reacting with groups present in the composition, such as hydroxyl groups, carboxyl groups, and amino groups, to form a crosslinked structure, and may be either a water-soluble crosslinking agent or an aqueous dispersion of a crosslinking agent (a crosslinking agent dispersed in water by some method). Examples of crosslinking agents include blocked isocyanate compounds, aliphatic or aromatic epoxy compounds, amine compounds, and amino resins. The crosslinking agent may be used alone or in combination of two or more types. There is no particular limitation on the method of adding the crosslinking agent, and it may be added during or after the aqueous conversion process.
組成物の成分として疎水性有機溶媒（例えば、芳香族系溶剤、脂環系溶剤、脂肪族系溶剤）を用いる場合、組成物は希釈剤を含むことが好ましい。これにより、保存安定性が向上し得る。希釈剤としては、例えば、アルコール、プロピレン系グリコールエーテルが挙げられる。アルコールとしては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノールが挙げられる。プロピレン系グリコールエーテルとしては、例えば、プロピレングリコールメチルエーテル、プロピレングリコールエチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテルが挙げられる。 When a hydrophobic organic solvent (e.g., aromatic solvent, alicyclic solvent, aliphatic solvent) is used as a component of the composition, it is preferable that the composition contains a diluent. This can improve storage stability. Examples of diluents include alcohol and propylene-based glycol ethers. Examples of alcohols include methanol, ethanol, propanol, isopropanol, and butanol. Examples of propylene-based glycol ethers include propylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol tert-butyl ether.
酸変性塩素化ポリオレフィン樹脂及び組成物は、ポリオレフィン系基材等の非極性樹脂同士や非極性樹脂と金属の接着に優れるので、プライマー、接着剤、塗料用バインダー、インキ用バインダー等の各種用途において利用可能である。 Acid-modified chlorinated polyolefin resins and compositions have excellent adhesion between non-polar resins such as polyolefin substrates and between non-polar resins and metals, and can be used in a variety of applications such as primers, adhesives, paint binders, and ink binders.
酸変性塩素化ポリオレフィン樹脂及び組成物は、積層体を構成する層の材料として利用できる。積層体は、酸変性塩素化ポリオレフィン樹脂又は組成物を含む層、金属層及び樹脂層を含み得る。金属としては、例えば、アルミニウム、アルミニウム合金、ニッケル、ステンレスが挙げられる。樹脂としては、例えば、ポリオレフィン樹脂（例えば、低密度ポリエチレン樹脂、直鎖状低密度ポリエチレン樹脂、高密度ポリエチレン樹脂等のポリエチレン樹脂；無延伸ポリプロピレン樹脂等のポリプロピレン樹脂）等の非極性樹脂、ポリウレタン系樹脂、ポリアミド系樹脂、アクリル系樹脂、ポリエステル系樹脂が挙げられる。積層体における層の配置は特に限定されないが、金属層及び樹脂層が酸変性塩素化ポリオレフィン樹脂又は組成物を含む層を挟んで位置する態様、金属層を挟んで第１の樹脂層と第２の樹脂層が存在し、金属層と各樹脂層の間に酸変性塩素化ポリオレフィン樹脂の組成物を含む層が挟持されている態様が例示される。積層体の用途としては、トイレタリー用品の詰め替え用パウチが挙げられる。 The acid-modified chlorinated polyolefin resin and the composition can be used as a material for the layers constituting the laminate. The laminate may include a layer containing the acid-modified chlorinated polyolefin resin or composition, a metal layer, and a resin layer. Examples of metals include aluminum, aluminum alloys, nickel, and stainless steel. Examples of resins include non-polar resins such as polyolefin resins (e.g., polyethylene resins such as low-density polyethylene resins, linear low-density polyethylene resins, and high-density polyethylene resins; polypropylene resins such as unstretched polypropylene resins), polyurethane resins, polyamide resins, acrylic resins, and polyester resins. The arrangement of layers in the laminate is not particularly limited, but examples include a mode in which a metal layer and a resin layer are positioned with a layer containing the acid-modified chlorinated polyolefin resin or composition sandwiched therebetween, and a mode in which a first resin layer and a second resin layer are present with a metal layer sandwiched therebetween, and a layer containing the acid-modified chlorinated polyolefin resin composition is sandwiched between the metal layer and each resin layer. Examples of uses of the laminate include refill pouches for toiletries.
以下、本発明を実施例により詳細に説明する。以下の実施例は、本発明を好適に説明するためのものであって、本発明を限定するものではない。なお、物性値等の測定方法は、別途記載がない限り、上記に記載した測定方法である。また、「部」とは、特に断りがない限り、重量部を意味する。また、特に温度の指定が無い場合の温度条件は、常温（２５℃）であり、特に圧力の指定が無い場合の圧力条件は、常圧（０．１ＭＰａ）である。 The present invention will be described in detail below with reference to examples. The following examples are provided to better explain the present invention, but are not intended to limit the present invention. The methods for measuring physical properties and the like are as described above unless otherwise specified. Furthermore, "parts" refers to parts by weight unless otherwise specified. Furthermore, unless a particular temperature is specified, the temperature condition is normal temperature (25°C), and unless a particular pressure is specified, the pressure condition is normal pressure (0.1 MPa).
（実施例１：製造方式Ａ（塩素化→酸変性を連続）によるポリオレフィン樹脂の製造）
ポリオレフィン樹脂としてエチレン－プロピレン共重合体（分子量６万、エチレン含有量１０％）４ｋｇ、および反応溶剤としてクロロホルム２４Ｌを、グラスライニングされた反応釜に投入し、温度９５℃にて十分に溶融した後に撹拌を開始した。ラジカル反応開始剤としてｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートを１６０ｇ加え、上記釜内圧を常圧以上０．２５ＭＰａ以下に制御しながら、塩素ガスを吹き込んだ後、窒素ガスを吹き込み、副生した塩化水素を除去してポリオレフィン樹脂の塩素化を行った。
(Example 1: Production of polyolefin resin by production method A (sequential chlorination → acid modification))
4 kg of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as polyolefin resin and 24 L of chloroform as reaction solvent were charged into a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95° C. 160 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to normal pressure or higher and 0.25 MPa or lower, chlorine gas was blown in, followed by nitrogen gas, to remove the by-produced hydrogen chloride, thereby chlorinating the polyolefin resin.
次いで、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートを４ｇ追添し、酸成分として無水マレイン酸を１２０ｇ投入し、内温８５℃、内圧０．２ＭＰａにて４時間保持して、塩素化ポリオレフィン樹脂の酸変性を行い、重量平均分子量６．８万の酸変性塩素化ポリオレフィン樹脂を得た。 Next, 4 g of tert-butylperoxy-2-ethylhexanoate was added, and 120 g of maleic anhydride was added as the acid component. The mixture was then held at an internal temperature of 85°C and an internal pressure of 0.2 MPa for 4 hours to acid-modify the chlorinated polyolefin resin, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 68,000.
（実施例２：製造方式Ｂ（酸変性（酸後投入）→塩素化を連続）によるポリオレフィン樹脂の製造）
ポリオレフィン樹脂としてエチレン－プロピレン共重合体（分子量６万、エチレン含有量１０％）４ｋｇ、および反応溶剤としてクロロホルム２４Ｌを、グラスライニングされた反応釜に投入し、温度９５℃にて十分に溶融した後に撹拌を開始した。ラジカル反応開始剤としてｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートを１６０ｇ、酸成分として無水マレイン酸を１２０ｇ投入し、内温８５℃、内圧０．２ＭＰａにて４時間保持して、ポリオレフィン樹脂の酸変性を行った。
(Example 2: Production of polyolefin resin by production method B (sequential acid modification (adding acid after) → chlorination))
4 kg of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as polyolefin resin and 24 L of chloroform as reaction solvent were charged into a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95° C. 160 g of tert-butylperoxy-2-ethylhexanoate as a radical reaction initiator and 120 g of maleic anhydride as an acid component were charged, and the mixture was maintained at an internal temperature of 85° C. and an internal pressure of 0.2 MPa for 4 hours to perform acid modification of the polyolefin resin.
次いで、内温を９５℃にて、上記釜内圧を常圧以上０．２５ＭＰａ以下に制御しながら、塩素ガスを吹き込んだ後、窒素ガスを吹き込み、副生した塩化水素を除去して酸変性ポリオレフィン樹脂の塩素化を行い、重量平均分子量６．４万の酸変性塩素化ポリオレフィン樹脂を得た。 Next, at an internal temperature of 95°C, while controlling the internal pressure of the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride and chlorinate the acid-modified polyolefin resin, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 64,000.
（実施例３：製造方式Ｃ（酸変性（酸先仕込み）→塩素化を連続）によるポリオレフィン樹脂の製造）
ポリオレフィン樹脂としてエチレン－プロピレン共重合体（分子量６万、エチレン含有量１０％）４ｋｇ、酸成分として無水マレイン酸を１２０ｇ、および反応溶剤としてクロロホルムを２４Ｌ、グラスライニングされた反応釜に投入し、温度９５℃にて十分に溶融した後に撹拌を開始した。ラジカル反応開始剤としてｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートを１６０ｇ投入し、内温８５℃、内圧０．２ＭＰａにて４時間保持して、ポリオレフィン樹脂の酸変性を行った。
(Example 3: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination))
4 kg of ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as polyolefin resin, 120 g of maleic anhydride as acid component, and 24 L of chloroform as reaction solvent were charged into a glass-lined reaction vessel, and stirring was started after sufficient melting at a temperature of 95° C. 160 g of tert-butylperoxy-2-ethylhexanoate was charged as a radical reaction initiator, and the mixture was maintained at an internal temperature of 85° C. and an internal pressure of 0.2 MPa for 4 hours to perform acid modification of the polyolefin resin.
次いで、内温を９５℃にて、上記釜内圧を常圧以上０．２５ＭＰａ以下に制御しながら、塩素ガスを吹き込んだ後、窒素ガスを吹き込み、副生した塩化水素を除去して酸変性ポリオレフィン樹脂の塩素化を行い、重量平均分子量６．４万の酸変性塩素化ポリオレフィン樹脂を得た。 Next, at an internal temperature of 95°C, while controlling the internal pressure of the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride and chlorinate the acid-modified polyolefin resin, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 64,000.
（実施例４：製造方式Ｃ（酸変性（酸先仕込み）→塩素化を連続）によるポリオレフィン樹脂の製造）
無水マレイン酸（ＭＡＨ）の投入量を１２０ｇから４０ｇに変更し、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートの投入量を１６０ｇから５２ｇに変更した以外は、実施例３と同様にして、重量平均分子量６．４万の酸変性塩素化ポリオレフィン樹脂を得た。
(Example 4: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination))
The amount of maleic anhydride (MAH) added was changed from 120 g to 40 g, and the amount of tert-butylperoxy-2-ethylhexanoate added was changed from 160 g to 52 g, but the same procedure as in Example 3 was repeated to obtain an acid-modified chlorinated polyolefin resin having a weight average molecular weight of 64,000.
（実施例５：製造方式Ｃ（酸変性（酸先仕込み）→塩素化を連続）によるポリオレフィン樹脂の製造）
ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートの投入量を１６０ｇから６ｇに変更した以外は、実施例３と同様にして、重量平均分子量６．０万の酸変性塩素化ポリオレフィン樹脂を得た。
(Example 5: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination))
An acid-modified chlorinated polyolefin resin having a weight average molecular weight of 60,000 was obtained in the same manner as in Example 3, except that the amount of tert-butylperoxy-2-ethylhexanoate added was changed from 160 g to 6 g.
（実施例６：製造方式Ｃ（酸変性（酸先仕込み）→塩素化を連続）によるポリオレフィン樹脂の製造）
ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートの投入量を１６０ｇから３６０ｇに変更した以外は、実施例３と同様にして、重量平均分子量１５．０万の酸変性塩素化ポリオレフィン樹脂を得た。
(Example 6: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination))
An acid-modified chlorinated polyolefin resin having a weight average molecular weight of 150,000 was obtained in the same manner as in Example 3, except that the amount of tert-butylperoxy-2-ethylhexanoate added was changed from 160 g to 360 g.
（実施例７：製造方式Ｃ（酸変性（酸先仕込み）→塩素化を連続）によるポリオレフィン樹脂の製造）
無水マレイン酸の投入量を１２０ｇから６００ｇに変更し、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートの投入量を１６０ｇから６００ｇに変更した以外は、実施例３と同様にして、重量平均分子量６．０万の酸変性塩素化ポリオレフィン樹脂を得た。
(Example 7: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination))
The amount of maleic anhydride added was changed from 120 g to 600 g, and the amount of tert-butylperoxy-2-ethylhexanoate added was changed from 160 g to 600 g, but the same procedure as in Example 3 was repeated to obtain an acid-modified chlorinated polyolefin resin having a weight average molecular weight of 60,000.
（実施例８：製造方式Ｃ（酸変性（酸先仕込み）→塩素化を連続）によるポリオレフィン樹脂の製造）
使用するポリオレフィン樹脂をエチレン－プロピレン共重合体（分子量２万、エチレン含有量１０％）に変更した以外は、実施例３と同様にして、重量平均分子量２．０万の酸変性塩素化ポリオレフィン樹脂を得た。
(Example 8: Production of polyolefin resin by production method C (sequential acid modification (acid first charged) → chlorination))
An acid-modified chlorinated polyolefin resin having a weight average molecular weight of 20,000 was obtained in the same manner as in Example 3, except that the polyolefin resin used was changed to an ethylene-propylene copolymer (molecular weight 20,000, ethylene content 10%).
（比較例１：製造方式Ｄ（酸変性（押出）→塩素化を不連続）によるポリオレフィン樹脂の製造）
ポリオレフィン樹脂としてエチレン－プロピレン共重合体（分子量６万、エチレン含有量１０％）１００部に、無水マレイン酸３．５重量部、ジクミルパーオキサイドを３部加え、反応ゾーン温度を３００℃に設定した二軸押出機に供給することで熱減成を行い、酸変性ポリオレフィンＡを得た。
(Comparative Example 1: Production of polyolefin resin by production method D (discontinuous acid modification (extrusion) → chlorination))
100 parts of an ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as a polyolefin resin was added with 3.5 parts by weight of maleic anhydride and 3 parts of dicumyl peroxide, and the mixture was fed into a twin-screw extruder with the reaction zone temperature set at 300°C for thermal degradation to obtain an acid-modified polyolefin A.
得られた酸変性ポリオレフィンＡを４ｋｇ、および反応溶剤としてクロロホルムを２４Ｌ、グラスライニングされた反応釜に投入し、温度９５℃にて十分に溶融した後に撹拌を開始した。ラジカル反応開始剤としてｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートを４ｇ加え、上記釜内圧を常圧以上０．２５ＭＰａ以下に制御しながら、塩素ガスを吹き込んだ後、窒素ガスを吹き込み、副生した塩化水素を除去して、重量平均分子量６．０万の酸変性塩素化ポリオレフィン樹脂を得た。 4 kg of the obtained acid-modified polyolefin A and 24 L of chloroform as a reaction solvent were placed in a glass-lined reaction vessel, and after sufficient melting at a temperature of 95°C, stirring was started. 4 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 60,000.
（比較例２：製造方式Ｅ（酸変性（溶融）→塩素化を不連続）によるポリオレフィン樹脂の製造）
攪拌機、冷却管、及び滴下漏斗を取り付けた四つ口フラスコ中で、ポリオレフィン樹脂としてエチレン－プロピレン共重合体（分子量６万、エチレン含有量１０％）１００部を、１８０℃の油浴中で完全に溶解した。フラスコ内の窒素置換を約１０分間行った後、撹拌を行いながら無水マレイン酸４．７部を約５分間かけて投入し、ヘプタン１６部に溶解したジ－ｔｅｒｔ－ブチルパーオキサイド１６部を滴下ロートから約３０分かけて投入した。その後、系内を１８０℃に保ち、更に一時間反応を継続した後、アスピレーターでフラスコ内を減圧しながら約１時間かけて未反応の無水マレイン酸を取り除き、酸変性ポリオレフィンＢを得た。
(Comparative Example 2: Production of polyolefin resin by production method E (discontinuous acid modification (melting) → chlorination))
In a four-neck flask equipped with a stirrer, a cooling tube, and a dropping funnel, 100 parts of an ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) was completely dissolved in an oil bath at 180° C. as a polyolefin resin. After nitrogen replacement in the flask for about 10 minutes, 4.7 parts of maleic anhydride was added over about 5 minutes while stirring, and 16 parts of di-tert-butyl peroxide dissolved in 16 parts of heptane was added from the dropping funnel over about 30 minutes. Thereafter, the system was kept at 180° C., and the reaction was continued for another hour. After that, the unreacted maleic anhydride was removed over about 1 hour while reducing the pressure in the flask with an aspirator, and an acid-modified polyolefin B was obtained.
得られた酸変性ポリオレフィンＢを４ｋｇ、および反応溶剤としてクロロホルムを２４Ｌ、グラスライニングされた反応釜に投入し、温度９５℃にて十分に溶融した後に撹拌を開始した。ラジカル反応開始剤としてｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートを４ｇ加え、上記釜内圧を常圧以上０．２５ＭＰａ以下に制御しながら、塩素ガスを吹き込んだ後、窒素ガスを吹き込み、副生した塩化水素を除去して、重量平均分子量６．０万の酸変性塩素化ポリオレフィン樹脂を得た。 4 kg of the obtained acid-modified polyolefin B and 24 L of chloroform as a reaction solvent were placed in a glass-lined reaction vessel, and after sufficient melting at a temperature of 95°C, stirring was started. 4 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 60,000.
（比較例３：製造方式Ｄ（酸変性（押出）→塩素化を不連続）によるポリオレフィン樹脂の製造）
ポリオレフィン樹脂としてエチレン－プロピレン共重合体（分子量６万、エチレン含有量１０％）１００部に、無水マレイン酸１重量部、ジクミルパーオキサイドを３部加え、反応ゾーン温度を３００℃に設定した二軸押出機に供給することで熱減成を行い、酸変性ポリオレフィンＣを得た。
(Comparative Example 3: Production of polyolefin resin by production method D (discontinuous acid modification (extrusion) → chlorination))
100 parts of an ethylene-propylene copolymer (molecular weight 60,000, ethylene content 10%) as a polyolefin resin was added with 1 part by weight of maleic anhydride and 3 parts of dicumyl peroxide, and the mixture was fed into a twin-screw extruder with the reaction zone temperature set at 300°C for thermal degradation to obtain acid-modified polyolefin C.
得られた酸変性ポリオレフィンＣを４ｋｇ、および反応溶剤としてクロロホルムを２４Ｌ、グラスライニングされた反応釜に投入し、温度９５℃にて十分に溶融した後に撹拌を開始した。ラジカル反応開始剤としてｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエートを４ｇ加え、上記釜内圧を常圧以上０．２５ＭＰａ以下に制御しながら、塩素ガスを吹き込んだ後、窒素ガスを吹き込み、副生した塩化水素を除去して、重量平均分子量９．０万の酸変性塩素化ポリオレフィン樹脂を得た。 4 kg of the obtained acid-modified polyolefin C and 24 L of chloroform as a reaction solvent were placed in a glass-lined reaction vessel, and after sufficient melting at a temperature of 95°C, stirring was started. 4 g of tert-butylperoxy-2-ethylhexanoate was added as a radical reaction initiator, and while controlling the pressure inside the vessel to between normal pressure and 0.25 MPa, chlorine gas was blown in, followed by nitrogen gas, to remove the by-product hydrogen chloride, yielding an acid-modified chlorinated polyolefin resin with a weight-average molecular weight of 90,000.
（試験例１：酸変性塩素化ポリオレフィン樹脂の着色の評価）
得られた酸変性塩素化ポリオレフィンとトルエンをガラス瓶に入れ、２０％のトルエン溶液を調製した。その後、白紙を背景として、溶液の色調を目視評価した。
評価基準は以下の通りである。
Ａ：ほぼ着色が見られない
Ｂ：ごく微かに赤色の着色がみられる
Ｃ：赤色の着色が付いているが、溶液は透明性を保っている
Ｄ：赤色の着色により溶液が濁っている
(Test Example 1: Evaluation of Coloration of Acid-Modified Chlorinated Polyolefin Resin)
The acid-modified chlorinated polyolefin and toluene were placed in a glass bottle to prepare a 20% toluene solution, after which the color of the solution was visually evaluated against a white paper background.
The evaluation criteria are as follows:
A: Almost no coloring is observed. B: Very slight red coloring is observed. C: Red coloring is observed, but the solution remains transparent. D: The solution is cloudy due to red coloring.
（重量平均分子量（Ｍｗ））
製造例で製造した樹脂について、ＧＰＣにより下記条件に従い測定した。
装置：ＨＬＣ－８３２０ＧＰＣ（東ソー（株）製）
カラム：ＴＳＫ－ｇｅｌ Ｇ－６０００ＨＸＬ，Ｇ－５０００ＨＸＬ，Ｇ－４０００ＨＸＬ，Ｇ－３０００ＨＸＬ，Ｇ－２０００ＨＸＬ（東ソー（株）製）
溶離液：テトラヒドロフラン
流速：１ｍＬ／ｍｉｎ
温度：ポンプオーブン、カラムオーブン４０℃
注入量：１００μＬ
標準物質：ポリスチレン ＥａｓｉＣａｌ ＰＳ－１（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｙ（株）製）
(Weight average molecular weight (Mw))
The resins produced in the Production Examples were measured by GPC under the following conditions.
Apparatus: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: TSK-gel G-6000HXL, G-5000HXL, G-4000HXL, G-3000HXL, G-2000HXL (manufactured by Tosoh Corporation)
Eluent: tetrahydrofuran Flow rate: 1 mL/min
Temperature: Pump oven, column oven 40°C
Injection volume: 100 μL
Standard material: Polystyrene EasiCal PS-1 (Agilent Technology, Inc.)
（酸成分のグラフト量（重量％）及びグラフト効率（％））
アルカリ滴定法を用いて、ＪＩＳ－Ｋ００７０：１９９２に準じた方法で測定を行い、算出した。
(Amount of grafted acid component (wt%) and grafting efficiency (%))
Measurements were carried out using an alkali titration method in accordance with JIS-K0070:1992, and calculations were made.
（塩素のグラフト量（重量％））
ＪＩＳ－Ｋ７２２９：１９９５に準じた方法で測定を行った。
(Grafted amount of chlorine (wt%))
The measurement was carried out according to a method in accordance with JIS-K7229:1995.
実施例及び比較例における、酸成分及びラジカル反応開始剤の投入量、得られた酸変性塩素化ポリオレフィン樹脂の重量平均分子量（Ｍｗ）、塩素のグラフト量、酸成分のグラフト量、酸成分のグラフト効率、及び着色評価の結果を下記表１に示す。 The amounts of acid component and radical reaction initiator added, the weight average molecular weight (Mw) of the resulting acid-modified chlorinated polyolefin resin, the graft amount of chlorine, the graft amount of acid component, the graft efficiency of the acid component, and the results of color evaluation in the examples and comparative examples are shown in Table 1 below.
・製造方式
製造方式Ａ：本発明の製造方法（塩素化→酸変性を連続）
製造方式Ｂ：本発明の製造方法（酸変性（酸後投入）→塩素化を連続）
製造方式Ｃ：本発明の製造方法（酸変性（酸先仕込み）→塩素化を連続）
製造方式Ｄ：従来の製造方法（酸変性（押出）→塩素化を不連続）
製造方式Ｅ：従来の製造方法（酸変性（溶融）→塩素化を不連続）
Manufacturing method Manufacturing method A: Manufacturing method of the present invention (chlorination → acid modification in succession)
Production method B: Production method of the present invention (acid modification (adding acid after) → chlorination in succession)
Production method C: Production method of the present invention (acid modification (acid first) → chlorination in succession)
Manufacturing method D: Conventional manufacturing method (acid modification (extrusion) → discontinuous chlorination)
Manufacturing method E: Conventional manufacturing method (acid modification (melting) → discontinuous chlorination)
表１から、同一の反応タンク内で酸変性反応と塩素化反応とを連続して行って製造した酸変性塩素化ポリオレフィン樹脂（実施例１～８）は、従来の溶融法を用いて製造したもの（比較例１～３）に比べ、色味が抑えられていることがわかる。 From Table 1, it can be seen that the acid-modified chlorinated polyolefin resins (Examples 1 to 8) produced by successively carrying out the acid modification reaction and the chlorination reaction in the same reaction tank have a less pronounced color than those produced using the conventional melting method (Comparative Examples 1 to 3).
よって、本願発明の製造方法を用いて製造した塩素化ポリオレフィン樹脂は、色味が抑えられているため、白色塗料や白色インキなどを含め、これまで以上に幅広い用途で使用することができる。 The chlorinated polyolefin resin produced using the manufacturing method of the present invention has a subdued color and can therefore be used in a wider range of applications than ever before, including white paints and white inks.
Claims (6)
酸変性塩素化ポリオレフィン樹脂の酸成分のグラフト量が０．１重量％～１０重量％であり、且つ塩素のグラフト量が１０重量％～７０重量％であり、
酸変性塩素化工程において、酸成分投入後にラジカル反応開始剤を投入する、
酸変性塩素化ポリオレフィン樹脂の製造方法。 A method for producing an acid-modified chlorinated polyolefin resin, comprising an acid-modified chlorination step in which a polyolefin resin is subjected to an acid modification reaction with an acid component in the presence of a chloroform solvent and a chlorination reaction in the presence of a chloroform solvent in the same reaction tank in this order,
the graft amount of the acid component of the acid-modified chlorinated polyolefin resin is 0.1% by weight to 10% by weight, and the graft amount of the chlorine is 10% by weight to 70% by weight;
In the acid-modified chlorination step, a radical reaction initiator is added after the acid component is added.
A method for producing an acid-modified chlorinated polyolefin resin.
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| WO1999007758A1 (en) | 1997-08-04 | 1999-02-18 | Nippon Bee Chemical Co., Ltd. | Emulsion and process for preparing the same |
| JP2008516053A (en) | 2004-10-06 | 2008-05-15 | イーストマン ケミカル カンパニー | Modified chlorinated carboxylated polyolefins and their use as adhesion promoters |
| WO2020022251A1 (en) | 2018-07-25 | 2020-01-30 | 日本製紙株式会社 | Chlorinated polyolefin resin and method for producing same |
| WO2020138117A1 (en) | 2018-12-27 | 2020-07-02 | 日本製紙株式会社 | Chlorinated polyolefin resin composition and use thereof |
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| JP2652297B2 (en) * | 1992-02-26 | 1997-09-10 | 三洋化成工業株式会社 | Resin composition, coating agent and adhesive |
| JPH0790145A (en) * | 1993-09-21 | 1995-04-04 | Sanyo Chem Ind Ltd | Water-based resin composition and coating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999007758A1 (en) | 1997-08-04 | 1999-02-18 | Nippon Bee Chemical Co., Ltd. | Emulsion and process for preparing the same |
| JP2008516053A (en) | 2004-10-06 | 2008-05-15 | イーストマン ケミカル カンパニー | Modified chlorinated carboxylated polyolefins and their use as adhesion promoters |
| WO2020022251A1 (en) | 2018-07-25 | 2020-01-30 | 日本製紙株式会社 | Chlorinated polyolefin resin and method for producing same |
| WO2020138117A1 (en) | 2018-12-27 | 2020-07-02 | 日本製紙株式会社 | Chlorinated polyolefin resin composition and use thereof |
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