JP2021098790A - Dispersion composition of modified polyolefin resin and method for producing the same - Google Patents
Dispersion composition of modified polyolefin resin and method for producing the same Download PDFInfo
- Publication number
- JP2021098790A JP2021098790A JP2019230730A JP2019230730A JP2021098790A JP 2021098790 A JP2021098790 A JP 2021098790A JP 2019230730 A JP2019230730 A JP 2019230730A JP 2019230730 A JP2019230730 A JP 2019230730A JP 2021098790 A JP2021098790 A JP 2021098790A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polyolefin resin
- modified polyolefin
- dispersion composition
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 239000006185 dispersion Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims abstract description 23
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims abstract description 16
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 32
- 239000000853 adhesive Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 20
- 239000011324 bead Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 4
- 239000002994 raw material Substances 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000002844 melting Methods 0.000 description 23
- 230000008018 melting Effects 0.000 description 23
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- -1 polypropylene Polymers 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000003849 aromatic solvent Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 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 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
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229940091181 aconitic acid Drugs 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 2
- 239000008199 coating composition Substances 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
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 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
- 239000000047 product Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-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
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-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
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-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
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 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
- 239000004593 Epoxy Chemical class 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- METIGIXCFPEQNM-UHFFFAOYSA-M amino-(2-bromoethyl)-dimethylazanium;bromide Chemical compound [Br-].C[N+](C)(N)CCBr METIGIXCFPEQNM-UHFFFAOYSA-M 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 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
- 239000002609 medium Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 150000002739 metals Chemical class 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、変性ポリオレフィン樹脂の分散体組成物と、その製造方法に関する。 The present invention relates to a dispersion composition of a modified polyolefin resin and a method for producing the same.
ポリプロピレンやポリエチレンといったポリオレフィン樹脂は、引張強さ、引裂強さ、衝撃強さ等の機械的性質や、耐水性、耐薬品性に優れている。また、軽量かつ安価であり、成形し易いといった多くの優れた性質も有しており、シート、フィルム、成形物等様々な用途に用いられている。但し、アクリル系樹脂やポリエステル系樹脂とは異なり、非極性かつ結晶性が良好であるため、塗装や接着が困難であるという欠点を有している。 Polyolefin resins such as polypropylene and polyethylene are excellent in mechanical properties such as tensile strength, tear strength, and impact strength, as well as water resistance and chemical resistance. In addition, it is lightweight, inexpensive, and has many excellent properties such as easy molding, and is used in various applications such as sheets, films, and molded products. However, unlike acrylic resins and polyester resins, it has the disadvantage that it is difficult to paint and adhere because it is non-polar and has good crystallinity.
非極性樹脂基材に対する付着性を向上させたポリオレフィン樹脂として、塩素化ポリオレフィン樹脂が広く用いられている。但し、塩素化ポリオレフィン樹脂は脱塩酸の問題があるので、ポリオレフィン樹脂と金属との接着には不適であるとされている。
従って、ポリオレフィン樹脂と金属との接着には、非水系ディスパーションタイプの酸変性したポリオレフィン系樹脂をベースとしたものが一般的に使用されている。
A chlorinated polyolefin resin is widely used as a polyolefin resin having improved adhesion to a non-polar resin substrate. However, since the chlorinated polyolefin resin has a problem of dehydrochloric acid, it is considered to be unsuitable for adhesion between the polyolefin resin and the metal.
Therefore, for the adhesion between the polyolefin resin and the metal, those based on the non-aqueous dispersion type acid-modified polyolefin resin are generally used.
さらに近年では、耐熱性が求められる用途が増加しつつあり、この問題の解決のために比較的融点の高い樹脂を用いることが知られている（例えば、特許文献１参照）。特許文献１に記載の技術では、高融点樹脂を含有することにより耐熱性が向上するけれども、溶液安定性が低下する場合がある。そこで、良好な溶液性状を有し、且つ耐熱性を有する変性ポリオレフィン樹脂が提案されている（例えば、特許文献２参照）。 Further, in recent years, applications requiring heat resistance are increasing, and it is known to use a resin having a relatively high melting point in order to solve this problem (see, for example, Patent Document 1). In the technique described in Patent Document 1, the heat resistance is improved by containing the refractory resin, but the solution stability may be lowered. Therefore, a modified polyolefin resin having good solution properties and heat resistance has been proposed (see, for example, Patent Document 2).
特許文献２に記載の変性ポリオレフィン樹脂は、良好な溶液性状を有し、且つ耐熱性を有するものの、柔軟性が劣っており、使用用途が限られていた。 Although the modified polyolefin resin described in Patent Document 2 has good solution properties and heat resistance, it is inferior in flexibility and its use is limited.
本発明の課題は、柔軟性や耐熱性、及び溶液安定性を具備し、付着性にも優れる変性ポリオレフィン樹脂の分散体組成物を提供することである。 An object of the present invention is to provide a dispersion composition of a modified polyolefin resin having flexibility, heat resistance, solution stability, and excellent adhesion.
本発明者らは、上記課題について鋭意検討した結果、エチレンプロピレンゴムを少なくとも含む原料成分をα，β−不飽和カルボン酸又はその誘導体を含む変性成分で変性した変性ポリオレフィン樹脂を少なくとも含み、粒子径を０．１〜５０μｍに調整した分散体組成物によって、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。 As a result of diligent studies on the above problems, the present inventors have at least a modified polyolefin resin in which the raw material component containing at least ethylene propylene rubber is modified with a modified component containing α, β-unsaturated carboxylic acid or a derivative thereof, and the particle size It was found that the above-mentioned problems can be solved by the dispersion composition adjusted to 0.1 to 50 μm, and the present invention has been completed.
即ち、本発明者らは、下記の〔１〕〜〔９〕を提供する。
〔１〕成分（Ａ）：ポリオレフィン樹脂と、成分（Ｂ）：エチレンプロピレンゴムと、を少なくとも含む成分（Ｃ）：原料成分が、成分（Ｄ）：α，β−不飽和カルボン酸又はその誘導体を含む変性成分で変性された成分（Ｅ）：変性ポリオレフィン樹脂を少なくとも含み、粒子径が０．１〜５０μｍである変性ポリオレフィン樹脂の分散体組成物。
〔２〕前記成分（Ｂ）の含有量が、前記成分（Ａ）及び前記成分（Ｂ）の合計量に対し１０〜７０重量％である上記〔１〕に記載の変性ポリオレフィン樹脂の分散体組成物。
〔３〕前記成分（Ｂ）の曲げ弾性率が２０〜２００ＭＰａである、上記〔１〕または〔２〕に記載の変性ポリオレフィン樹脂の分散体組成物。
〔４〕前記成分（Ｂ）の測定温度２３０℃、測定荷重２．１６ｋｇのメルトフローレート（ＭＦＲ）が０．１〜８．０ｇ／１０分である、上記〔１〕〜〔３〕のいずれかに記載の変性ポリオレフィン樹脂の分散体組成物。
〔５〕上記〔１〕〜〔４〕のいずれかに記載の変性ポリオレフィン樹脂の分散体組成物を含む、塗料。
〔６〕上記〔１〕〜〔４〕のいずれかに記載の変性ポリオレフィン樹脂の分散体組成物を含む、プライマー。
〔７〕上記〔１〕〜〔４〕のいずれかに記載の変性ポリオレフィン樹脂の分散体組成物を含む、バインダー。
〔８〕上記〔１〕〜〔４〕のいずれかに記載の変性ポリオレフィン樹脂の分散体組成物を含む、接着剤。
〔９〕バッチ式ビーズミル装置により、成分（Ａ）：ポリオレフィン樹脂と、
成分（Ｂ）：エチレンプロピレンゴムと、を少なくとも含む成分（Ｃ）：原料成分が、成分（Ｄ）：α，β−不飽和カルボン酸又はその誘導体を含む変性成分
で変性された成分（Ｅ）：変性ポリオレフィン樹脂の粉砕と溶剤分散を同時に行う工程を含む、変性ポリオレフィン樹脂の分散体組成物の製造方法。
That is, the present inventors provide the following [1] to [9].
[1] Component (A): Polyolefin resin, Component (B): Ethylene propylene rubber, and at least Component (C): Raw material component is Component (D): α, β-unsaturated carboxylic acid or a derivative thereof. Component (E) modified with a modified component containing: A dispersion composition of a modified polyolefin resin containing at least a modified polyolefin resin and having a particle size of 0.1 to 50 μm.
[2] The dispersion composition of the modified polyolefin resin according to the above [1], wherein the content of the component (B) is 10 to 70% by weight based on the total amount of the component (A) and the component (B). Stuff.
[3] The dispersion composition of the modified polyolefin resin according to the above [1] or [2], wherein the flexural modulus of the component (B) is 20 to 200 MPa.
[4] Any of the above [1] to [3], wherein the measurement temperature of the component (B) is 230 ° C. and the melt flow rate (MFR) of the measurement load of 2.16 kg is 0.1 to 8.0 g / 10 minutes. The dispersion composition of the modified polyolefin resin described in C.
[5] A coating material containing the dispersion composition of the modified polyolefin resin according to any one of the above [1] to [4].
[6] A primer containing the dispersion composition of the modified polyolefin resin according to any one of the above [1] to [4].
[7] A binder containing the dispersion composition of the modified polyolefin resin according to any one of the above [1] to [4].
[8] An adhesive containing the dispersion composition of the modified polyolefin resin according to any one of the above [1] to [4].
[9] By using a batch type bead mill device, the component (A): polyolefin resin and
Component (B): Component containing at least ethylene propylene rubber (C): Raw material component modified with a modified component containing α, β-unsaturated carboxylic acid or a derivative thereof (E) : A method for producing a dispersion composition of a modified polyolefin resin, which comprises a step of simultaneously pulverizing the modified polyolefin resin and dispersing the solvent.
本発明によれば、柔軟性と耐熱性、及び溶液安定性を具備し、付着性にも優れる変性ポリオレフィン樹脂の分散体組成物を提供することができる。 According to the present invention, it is possible to provide a dispersion composition of a modified polyolefin resin having flexibility, heat resistance, solution stability, and excellent adhesion.
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、本明細書中、「ＡＡ〜ＢＢ」と表記する場合、ＡＡ以上ＢＢ以下を表す。
Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof.
In addition, in this specification, when it is expressed as "AA-BB", it means AA or more and BB or less.
［１．変性ポリオレフィン樹脂の分散体組成物］
本発明の変性ポリオレフィン樹脂の溶剤分散体は、成分（Ａ）：ポリオレフィン樹脂と、成分（Ｂ）：エチレンプロピレンゴムと、を少なくとも含む成分（Ｃ）：原料成分が、成分（Ｄ）：α，β−不飽和カルボン酸又はその誘導体を含む変性成分で変性された成分（Ｅ）：変性ポリオレフィン樹脂を少なくとも含み、粒子径が０．１μｍ〜５０μｍである変性ポリオレフィン樹脂の分散体組成物である。
[1. Dispersion composition of modified polyolefin resin]
The solvent dispersion of the modified polyolefin resin of the present invention contains at least a component (A): a polyolefin resin and a component (B): ethylene propylene rubber. Component (E) modified with a modified component containing β-unsaturated carboxylic acid or a derivative thereof: A dispersion composition of a modified polyolefin resin containing at least a modified polyolefin resin and having a particle size of 0.1 μm to 50 μm.
成分（Ａ）に成分（Ｂ）を混ぜることにより、耐熱性と柔軟性を具備したポリオレフィン樹脂を製造する事ができる。
また、成分（Ｃ）を成分（Ｄ）でグラフト変性することで、ポリオレフィン樹脂の非極性樹脂基材に対する付着性を向上させる事ができる。
さらに、成分（Ｅ）を含む分散体組成物における粒子径を０．１〜５０μｍに調整することにより、溶液安定性を向上し得る。
By mixing the component (B) with the component (A), a polyolefin resin having heat resistance and flexibility can be produced.
Further, by graft-modifying the component (C) with the component (D), the adhesiveness of the polyolefin resin to the non-polar resin substrate can be improved.
Further, the solution stability can be improved by adjusting the particle size of the dispersion composition containing the component (E) to 0.1 to 50 μm.
本発明の変性ポリオレフィン樹脂の分散体組成物は、上記の変性ポリオレフィン樹脂と溶剤を含むものである。他の成分として、乳化剤、安定剤、及び中和剤等の成分をさらに含んでもよい。 The dispersion composition of the modified polyolefin resin of the present invention contains the above-mentioned modified polyolefin resin and a solvent. As other components, components such as emulsifiers, stabilizers, and neutralizers may be further contained.
溶剤としては、例えば、トルエン、キシレン等の芳香族溶剤；酢酸エチル、酢酸ブチル等のエステル溶剤；メチルエチルケトン、メチルブチルケトン、エチルシクロヘキサン等のケトン溶剤；シクロヘキサン、メチルシクロヘキサン、ノナン、デカン等の脂肪族又は脂環式炭化水素溶剤が挙げられる。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分散体組成物に含まれていてよい。環境問題の観点から、有機溶剤として、芳香族溶剤以外の溶剤を使用することが好ましく、脂環式炭化水素溶剤とエステル溶剤又はケトン溶剤との混合溶剤を使用することがより好ましい。 Examples of the solvent include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl butyl ketone and ethyl cyclohexane; aliphatic solvents such as cyclohexane, methylcyclohexane, nonane and decane. Alternatively, an alicyclic hydrocarbon solvent can be mentioned. These organic solvents may be used alone or may be contained in the dispersion composition as a mixed solvent of two or more kinds. From the viewpoint of environmental problems, it is preferable to use a solvent other than the aromatic solvent as the organic solvent, and it is more preferable to use a mixed solvent of the alicyclic hydrocarbon solvent and the ester solvent or the ketone solvent.
本発明の変性ポリオレフィン樹脂の分散体組成物における粒子径は、０．１〜５０μｍであることが好ましく、０．３〜３０μｍであることがより好ましい。粒子径が斯かる範囲にあることで、溶液安定性と適度な粘性を両立し得る。
なお、粒子径は、通常メジアン径であり、粒度分布測定装置にて測定することができる。
The particle size of the dispersion composition of the modified polyolefin resin of the present invention is preferably 0.1 to 50 μm, more preferably 0.3 to 30 μm. When the particle size is in such a range, both solution stability and appropriate viscosity can be achieved.
The particle size is usually a median size and can be measured with a particle size distribution measuring device.
本発明の変性ポリオレフィン樹脂の分散体組成物の固形分は、１０〜３０％であることが好ましい。固形分が斯かる範囲にあることで、溶液安定性が良好となり得る。 The solid content of the dispersion composition of the modified polyolefin resin of the present invention is preferably 10 to 30%. When the solid content is in such a range, the solution stability can be improved.
（成分（Ａ）：ポリオレフィン樹脂）
成分（Ａ）は、その共重合体の構成について特に限定されるものではない。但し、エチレン−プロピレン共重合体、プロピレン−１−ブテン共重合体、及びエチレン−プロピレン−１−ブテン共重合体からなる群より選ばれる少なくとも１種の共重合体であることが好ましい。なお、これら共重合体に占めるプロピレン成分の割合は、共重合体全体の５０モル％以上が好ましく、５５モル％以上がより好ましい。
なお、プロピレン成分等の成分（Ａ）の構成成分の割合は、共重合体を調製する際の各単量体の仕込み量で算出することができる。
(Component (A): Polyolefin resin)
The component (A) is not particularly limited in terms of the composition of the copolymer. However, it is preferably at least one copolymer selected from the group consisting of an ethylene-propylene copolymer, a propylene-1-butene copolymer, and an ethylene-propylene-1-butene copolymer. The proportion of the propylene component in these copolymers is preferably 50 mol% or more, more preferably 55 mol% or more of the total copolymer.
The ratio of the constituent components of the component (A) such as the propylene component can be calculated by the amount of each monomer charged when preparing the copolymer.
成分（Ａ）の重量平均分子量は、１０，０００〜２００，０００の範囲であることが好ましく、１５，０００〜１５０，０００の範囲であることがより好ましい。
なお、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（標準物質：ポリスチレン）により測定することができる。
The weight average molecular weight of the component (A) is preferably in the range of 10,000 to 200,000, more preferably in the range of 15,000 to 150,000.
The weight average molecular weight can be measured by gel permeation chromatography (standard substance: polystyrene).
成分（Ａ）の融点は、４０〜１２０℃が好ましく、より好ましくは４０〜１００℃であり、さらに好ましくは５０〜９０℃である。成分（Ａ）の融点が斯かる範囲にあることで、得られる変性ポリオレフィン樹脂の溶液安定性を向上し得る。
ＤＳＣによる融点の測定は、例えば以下の条件で行うことができる。ＪＩＳ Ｋ７１２１−１９８７に準拠し、ＤＳＣ測定装置（セイコー電子工業製）を用い、約５ｍｇの試料を２００℃で１０分間加熱融解状態を保持した後、１０℃／分の速度で降温して−５０℃で安定保持する。その後、更に１０℃／分で２００℃まで昇温して融解した時の融解ピーク温度を測定し、該温度を融点として評価する。尚、後述の実施例における融点は斯かる条件で測定されたものである。
The melting point of the component (A) is preferably 40 to 120 ° C, more preferably 40 to 100 ° C, and even more preferably 50 to 90 ° C. When the melting point of the component (A) is in such a range, the solution stability of the obtained modified polyolefin resin can be improved.
The melting point can be measured by DSC under the following conditions, for example. In accordance with JIS K7121-1987, using a DSC measuring device (manufactured by Seiko Electronics Co., Ltd.), a sample of about 5 mg was kept in a heat-melted state at 200 ° C. for 10 minutes, and then cooled at a rate of 10 ° C./min to -50. Holds stable at ° C. Then, the melting peak temperature when the temperature is further raised to 200 ° C. at 10 ° C./min and melted is measured, and the temperature is evaluated as the melting point. The melting point in the examples described later was measured under such conditions.
（成分（Ｂ）：エチレンプロピレンゴム）
成分（Ｂ）は、エチレンプロピレンゴムである。成分（Ｂ）がエチレンプロピレンゴムであると、成分（Ａ）との相溶性が良好となる。成分（Ｂ）のエチレンプロピレンゴムは、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。
(Component (B): Ethylene propylene rubber)
The component (B) is ethylene propylene rubber. When the component (B) is ethylene propylene rubber, the compatibility with the component (A) is good. The ethylene propylene rubber of the component (B) may be used alone or in combination of two or more.
成分（Ｂ）の曲げ弾性率は、２０〜２００ＭＰａが好ましく、３０〜１５０ＭＰａがより好ましく、４０〜１１０ＭＰａが更に好ましい。成分（Ｂ）の弾性率が斯かる範囲にあることで、得られる変性ポリオレフィン樹脂の柔軟性を向上し得る。
なお、曲げ弾性率は、ＪＩＳ Ｋ ７２０３：９ ５に則って測定することができる。
The flexural modulus of the component (B) is preferably 20 to 200 MPa, more preferably 30 to 150 MPa, and even more preferably 40 to 110 MPa. When the elastic modulus of the component (B) is in such a range, the flexibility of the obtained modified polyolefin resin can be improved.
The flexural modulus can be measured according to JIS K 7203: 95.
成分（Ｂ）の測定温度２３０℃、測定荷重２．１６ｋｇにおけるメルトフローレートは０．１〜８．０ｇ／１０分が好ましく、０．３〜５．０ｇ／１０分がより好ましく、０．５〜３．０ｇ／１０分が更に好ましい。成分（Ｂ）のメルトフローレートが斯かる範囲にあることで、得られる変性ポリオレフィン溶液安定性が向上し得る。
なお、メルトフローレートは、ＡＳＴＭ Ｄ１２３８に則って測定することができる。
The melt flow rate of the component (B) at a measurement temperature of 230 ° C. and a measurement load of 2.16 kg is preferably 0.1 to 8.0 g / 10 minutes, more preferably 0.3 to 5.0 g / 10 minutes, and 0.5. ~ 3.0 g / 10 minutes is more preferable. When the melt flow rate of the component (B) is in such a range, the stability of the obtained modified polyolefin solution can be improved.
The melt flow rate can be measured according to ASTM D1238.
成分（Ｂ）の融点は、１００〜２００℃が好ましく、より好ましくは１００〜１８０℃であり、さらに好ましくは１００〜１７０℃である。成分（Ｂ）の融点が斯かる範囲にあることで、得られる変性ポリオレフィン樹脂の耐熱性を向上し得る。
ＤＳＣによる融点の測定は、例えば以下の条件で行うことができる。ＪＩＳ Ｋ７１２１−１９８７に準拠し、ＤＳＣ測定装置（セイコー電子工業製）を用い、約５ｍｇの試料を２００℃で１０分間加熱融解状態を保持した後、１０℃／分の速度で降温して−５０℃で安定保持する。その後、更に１０℃／分で２００℃まで昇温して融解した時の融解ピーク温度を測定し、該温度を融点として評価する。尚、後述の実施例における融点は斯かる条件で測定されたものである。
The melting point of the component (B) is preferably 100 to 200 ° C, more preferably 100 to 180 ° C, and even more preferably 100 to 170 ° C. When the melting point of the component (B) is in such a range, the heat resistance of the obtained modified polyolefin resin can be improved.
The melting point can be measured by DSC under the following conditions, for example. In accordance with JIS K7121-1987, using a DSC measuring device (manufactured by Seiko Electronics Co., Ltd.), a sample of about 5 mg was kept in a heat-melted state at 200 ° C. for 10 minutes, and then cooled at a rate of 10 ° C./min to -50. Holds stable at ° C. Then, the melting peak temperature when the temperature is further raised to 200 ° C. at 10 ° C./min and melted is measured, and the temperature is evaluated as the melting point. The melting point in the examples described later was measured under such conditions.
（成分（Ｃ）：原料成分）
成分（Ｂ）の含有量は、成分（Ａ）及び成分（Ｂ）の合計量に対し１０〜７０重量％が好ましく、２０〜５０重量％がより好ましい。成分（Ｂ）の含有量が斯かる範囲にあることにより、良好な溶液安定性を有し、かつ耐熱性と耐衝撃性を具備したポリオレフィン樹脂を製造し得る。
なお、成分（Ｃ）における成分（Ａ）と成分（Ｂ）の割合は、成分（Ｃ）又は変性ポリオレフィンを製造する際の成分（Ａ）と成分（Ｂ）の仕込み量で算出することができる。
(Component (C): Raw material component)
The content of the component (B) is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, based on the total amount of the component (A) and the component (B). When the content of the component (B) is in such a range, a polyolefin resin having good solution stability and heat resistance and impact resistance can be produced.
The ratio of the component (A) to the component (B) in the component (C) can be calculated by the amount of the component (A) and the component (B) charged when producing the component (C) or the modified polyolefin. ..
成分（Ｃ）を調製するにあたり、成分（Ａ）及び成分（Ｂ）は、いずれも変性されていてもよく、いずれか一方が変性されていてもよい。 In preparing the component (C), both the component (A) and the component (B) may be modified, or one of them may be modified.
（成分（Ｄ）：α，β−不飽和カルボン酸又はその誘導体を含む変性成分）
成分（Ｄ）は、α，β−不飽和カルボン酸又はその誘導体を含む変性成分である。α，β−不飽和カルボン酸及びその誘導体としては、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、（メタ）アクリル酸等が挙げられる。中でも、無水マレイン酸、無水アコニット酸、無水イタコン酸が好ましく、無水マレイン酸がより好ましい。
成分（Ｄ）は、α，β−不飽和カルボン酸及びその誘導体から選ばれる１種以上の化合物であればよく、α，β−不飽和カルボン酸１種以上とその誘導体１種以上の組み合わせ、α，β−不飽和カルボン酸２種以上の組み合わせ、α，β−不飽和カルボン酸の誘導体２種以上の組み合わせであってもよい。
(Component (D): Modified component containing α, β-unsaturated carboxylic acid or its derivative)
The component (D) is a modified component containing an α, β-unsaturated carboxylic acid or a derivative thereof. Examples of α, β-unsaturated carboxylic acid and its derivatives include maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, (meth). ) Aconitic acid and the like can be mentioned. Among them, maleic anhydride, aconitic anhydride, and itaconic anhydride are preferable, and maleic anhydride is more preferable.
The component (D) may be any compound as long as it is one or more compounds selected from α, β-unsaturated carboxylic acid and its derivatives, and is a combination of one or more α, β-unsaturated carboxylic acids and one or more derivatives thereof. It may be a combination of two or more kinds of α, β-unsaturated carboxylic acid and a combination of two or more kinds of derivatives of α, β-unsaturated carboxylic acid.
変性ポリオレフィン樹脂中の成分（Ｄ）のグラフト重量は、変性ポリオレフィン樹脂を１００重量％とした場合に、好ましくは０．１〜２０重量％であり、より好ましくは０．５〜１５重量％であり、さらに好ましくは１〜１０重量％である。グラフト重量が０．１重量％以上であることにより、得られる変性ポリオレフィン系樹脂の、金属被着体に対する接着性を保つことができる。グラフト重量が２０重量％以下であることにより、グラフト未反応物の発生を防止することができ、樹脂被着体に対する十分な接着性を得ることができる。 The graft weight of the component (D) in the modified polyolefin resin is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, when the modified polyolefin resin is 100% by weight. , More preferably 1 to 10% by weight. When the graft weight is 0.1% by weight or more, the adhesiveness of the obtained modified polyolefin resin to the metal adherend can be maintained. When the graft weight is 20% by weight or less, it is possible to prevent the generation of unreacted graft products and obtain sufficient adhesiveness to the resin adherend.
α，β−不飽和カルボン酸又はその誘導体のグラフト重量％は、公知の方法で測定することができる。例えば、アルカリ滴定法やフーリエ変換赤外分光法によって求めることができる。尚、後述の実施例におけるグラフト重量％は、アルカリ滴定法で測定されたものである。 The graft weight% of α, β-unsaturated carboxylic acid or a derivative thereof can be measured by a known method. For example, it can be obtained by alkaline titration method or Fourier transform infrared spectroscopy. The weight% of the graft in the examples described later was measured by the alkaline titration method.
α，β−不飽和カルボン酸又はその誘導体以外の変性成分として、（メタ）アクリル酸エステルが好ましい。（メタ）アクリル酸エステルは、一般式（１）で表される化合物であることが好ましい。一般式（１）で表される化合物を用いて変性すると、変性ポリオレフィン樹脂の分子量分布を狭くすることができ、溶液の低温安定性、他樹脂との相溶性、接着性を向上させることができる。一般式（１）で表される（メタ）アクリル酸エステルは、１種単独で用いてもよく、複数種を任意の割合で混合して用いてもよい。 As a modifying component other than α, β-unsaturated carboxylic acid or a derivative thereof, (meth) acrylic acid ester is preferable. The (meth) acrylic acid ester is preferably a compound represented by the general formula (1). When modified with the compound represented by the general formula (1), the molecular weight distribution of the modified polyolefin resin can be narrowed, and the low temperature stability of the solution, compatibility with other resins, and adhesiveness can be improved. .. The (meth) acrylic acid ester represented by the general formula (1) may be used alone or in admixture of a plurality of types at an arbitrary ratio.
ＣＨ2＝Ｃ（Ｒ1）ＣＯＯＲ2・・・（１） CH 2 = C (R 1 ) COOR 2 ... (1)
一般式（１）中、Ｒ１は、Ｈ又はＣＨ３を表し、ＣＨ３が好ましい。Ｒ２は、ＣｎＨ２ｎ＋１を表す。ｎは、８〜１８の整数を表し、８〜１５が好ましく、８〜１４がより好ましく、８〜１３がさらに好ましい。式（１）で表される化合物としては、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）アクリレートが好ましく、ラウリルメタクリレート、オクチルメタクリレート、トリデシルメタクリレートがより好ましい。 In the general formula (1), R 1 represents H or CH 3 , and CH 3 is preferable. R 2 represents CnH 2n + 1. n represents an integer of 8 to 18, preferably 8 to 15, more preferably 8 to 14, and even more preferably 8 to 13. As the compound represented by the formula (1), lauryl (meth) acrylate, tridecylic (meth) acrylate and octyl (meth) acrylate are preferable, and lauryl methacrylate, octyl methacrylate and tridecylic methacrylate are more preferable.
用途や目的に応じて、本発明の特性を損なわない範囲で、上述したもの以外の他のグラフト成分を併用することができる。他のグラフト成分は、１種単独で用いてもよく、複数種を組み合わせて併用してもよい。但し、合計のグラフト重量が成分（Ｄ）の合計のグラフト重量を超えないことが好ましい。 Depending on the intended use and purpose, graft components other than those described above can be used in combination as long as the characteristics of the present invention are not impaired. The other graft components may be used alone or in combination of two or more. However, it is preferable that the total graft weight does not exceed the total graft weight of the component (D).
（成分（Ｅ）：変性ポリオレフィン樹脂）
成分（Ｅ）の変性ポリオレフィン樹脂は、上記の成分（Ｃ）を成分（Ｄ）でグラフト変性したものである。成分（Ｃ）を成分（Ｄ）でグラフト変性することにより、ポリオレフィン樹脂の非極性樹脂基材に対する付着性を向上し得る。
(Component (E): Modified Polyolefin Resin)
The modified polyolefin resin of the component (E) is obtained by graft-modifying the above component (C) with the component (D). By graft-modifying the component (C) with the component (D), the adhesiveness of the polyolefin resin to the non-polar resin substrate can be improved.
（成分（Ｆ）：ラジカル発生剤）
成分（Ｃ）の成分（Ｄ）によるグラフト変性は、成分（Ｆ）としてラジカル発生剤を用いて行うことができる。成分（Ｆ）は、公知のラジカル発生剤の中より適宜選択することができ、有機過酸化物系化合物が好ましい。有機過酸化物系化合物としては、例えば、ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイド、ｔ−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、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、１，４−ビス［（ｔ−ブチルパーオキシ）イソプロピル］ベンゼン、１，１−ビス（ｔ−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（ｔ−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、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−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が挙げられる。中でも、ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイド及びジラウリルパーオキサイドが好ましい。成分（Ｆ）は、１種単独のラジカル発生剤でもよいし、複数種のラジカル発生剤の組み合わせであってもよい。
(Component (F): Radical generator)
The graft modification of the component (C) by the component (D) can be carried out by using a radical generator as the component (F). The component (F) can be appropriately selected from known radical generators, and an organic peroxide compound is preferable. Examples of the organic peroxide compound include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, and t-butyl hydroper. Oxide, 1,4-bis [(t-butylperoxy) isopropyl] benzene, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butyl) Peroxy) -cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2 -Ethylhexanoate, t-butylperoxyisopropyl carbonate, cumylperoxyoctate can be mentioned. Of these, di-t-butyl peroxide, dicumyl peroxide and dilauryl peroxide are preferable. The component (F) may be a single radical generator or a combination of a plurality of radical generators.
グラフト変性反応における成分（Ｆ）の添加量は、成分（Ｄ）の添加量に対し、好ましくは１〜１００重量％であり、より好ましくは１０〜５０重量％である。１重量％以上であることにより、十分なグラフト効率を保持することができる。１００重量％以下であることにより、変性ポリオレフィン樹脂の重量平均分子量の低下を防止することができる。 The amount of the component (F) added in the graft modification reaction is preferably 1 to 100% by weight, more preferably 10 to 50% by weight, based on the amount of the component (D) added. When it is 1% by weight or more, sufficient graft efficiency can be maintained. When it is 100% by weight or less, it is possible to prevent a decrease in the weight average molecular weight of the modified polyolefin resin.
（物性）
成分（Ｅ）の変性ポリオレフィン樹脂のＤＳＣによる融点は、その融点ピークが成分（Ｂ）に由来する１００℃〜２００℃の範囲及び成分（Ａ）に由来する４０〜１２０℃の範囲の２つあることが好ましく、成分（Ｂ）に由来する１００℃〜１７０℃の範囲及び成分（Ａ）に由来する５０〜９０℃の範囲の２つあることがより好ましい。変性ポリオレフィン樹脂の融点が斯かる範囲にあることで、本発明の効果をより優れて発揮し得る。
(Physical characteristics)
The melting point of the modified polyolefin resin of the component (E) by DSC has two melting points, one in the range of 100 ° C. to 200 ° C. derived from the component (B) and the other in the range of 40 to 120 ° C. derived from the component (A). It is preferable that there are two, a range of 100 ° C. to 170 ° C. derived from the component (B) and a range of 50 to 90 ° C. derived from the component (A). When the melting point of the modified polyolefin resin is in such a range, the effect of the present invention can be exhibited more excellently.
一般的に、ゴム成分を含有させることで柔軟性や耐熱性に優れることは知られているが、融点が高くなるにつれて結晶性が高まるため、溶液安定性が悪くなる。
本発明は、変性ポリオレフィン樹脂を溶剤に溶かすのではなく、溶剤に分散させることによって、柔軟性や耐熱性を具備しながら長期の溶液安定性に優れることを発明し得たものである。
Generally, it is known that the inclusion of a rubber component is excellent in flexibility and heat resistance, but the crystallinity increases as the melting point increases, so that the solution stability deteriorates.
According to the present invention, it has been possible to invent that a modified polyolefin resin is not dissolved in a solvent but is dispersed in a solvent, so that the modified polyolefin resin is excellent in long-term solution stability while having flexibility and heat resistance.
（用途）
本発明の変性ポリオレフィン樹脂の分散体組成物は、付着性（接着性）が低く、塗料等の塗工が困難な基材のための中間媒体として有用であり、例えば、付着性（接着性）の乏しいポリプロピレン、ポリエチレン等のポリオレフィン系基材同士の接着剤として使用し得る。この際、基材がプラズマ、コロナ等により表面処理されているか否かを問わず用いることができる。また、ポリオレフィン系基材の表面に本発明の変性ポリオレフィン樹脂をホットメルト方式で積層し、更にその上に塗料等を塗工することにより、塗料の付着安定性等を向上させることもできる。
また、本発明の変性ポリオレフィン樹脂の分散体組成物は、金属と樹脂との優れた接着性をも発揮し得る。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。従って、本発明の変性ポリオレフィン樹脂は、接着剤、プライマー、塗料用バインダー及びインキ用バインダーとして、又はこれらの成分として、用いることができる。
(Use)
The dispersion composition of the modified polyolefin resin of the present invention has low adhesiveness (adhesiveness) and is useful as an intermediate medium for a base material such as a paint that is difficult to apply. For example, adhesiveness (adhesiveness) It can be used as an adhesive between polyolefin-based substrates such as polypropylene and polyethylene, which are scarce. At this time, it can be used regardless of whether or not the base material is surface-treated by plasma, corona, or the like. Further, by laminating the modified polyolefin resin of the present invention on the surface of a polyolefin-based substrate by a hot-melt method and further applying a paint or the like on the modified polyolefin resin, the adhesion stability of the paint or the like can be improved.
Further, the dispersion composition of the modified polyolefin resin of the present invention can also exhibit excellent adhesiveness between the metal and the resin. Examples of the metal include aluminum, aluminum alloy, nickel, and stainless steel. Examples of the resin include non-polar resins such as polyolefin resins, polyurethane resins, polyamide resins, acrylic resins, and polyester resins. Therefore, the modified polyolefin resin of the present invention can be used as an adhesive, a primer, a binder for paints and a binder for inks, or as a component thereof.
本発明の変性ポリオレフィン樹脂の分散体組成物は、他の成分と混合し、樹脂組成物としてよい。他の成分として、溶液、硬化剤、及び接着成分からなる群より選択される少なくとも１種の成分を含むものが好ましい。 The dispersion composition of the modified polyolefin resin of the present invention may be mixed with other components to obtain a resin composition. As the other component, those containing at least one component selected from the group consisting of a solution, a curing agent, and an adhesive component are preferable.
（溶液）
本発明の分散体組成物の一実施態様は、上記変性ポリオレフィン樹脂と溶液を含むものである。溶液としては、有機溶剤が挙げられる。有機溶剤としては、例えば、トルエン、キシレン等の芳香族溶剤；酢酸エチル、酢酸ブチル等のエステル溶剤；メチルエチルケトン、メチルブチルケトン、エチルシクロヘキサン等のケトン溶剤；シクロヘキサン、メチルシクロヘキサン、ノナン、デカン等の脂肪族又は脂環式炭化水素溶剤が挙げられる。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よい。環境問題の観点から、有機溶剤として、芳香族溶剤以外の溶剤を使用することが好ましく、脂環式炭化水素溶剤とエステル溶剤又はケトン溶剤との混合溶剤を使用することがより好ましい。
(solution)
One embodiment of the dispersion composition of the present invention comprises the modified polyolefin resin and solution. Examples of the solution include organic solvents. Examples of the organic solvent include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl butyl ketone and ethyl cyclohexane; and fats such as cyclohexane, methylcyclohexane, nonane and decane. Group or alicyclic hydrocarbon solvents can be mentioned. These organic solvents may be used alone or may be contained in the resin composition as a mixed solvent of two or more kinds. From the viewpoint of environmental problems, it is preferable to use a solvent other than the aromatic solvent as the organic solvent, and it is more preferable to use a mixed solvent of the alicyclic hydrocarbon solvent and the ester solvent or the ketone solvent.
また、分散体組成物の保存安定性を高めるために、アルコール（例、メタノール、エタノール、プロパノール、イソプロピルアルコール、ブタノール）、プロピレン系グリコールエーテル（例、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−ｔ−ブチルエーテル）を、１種単独で、又は２種以上混合して用いてもよい。この場合、上記有機溶剤に対して、１〜２０重量％添加することが好ましい。 Further, in order to enhance the storage stability of the dispersion composition, alcohol (eg, methanol, ethanol, propanol, isopropyl alcohol, butanol), propylene glycol ether (eg, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol). -T-butyl ether) may be used alone or in combination of two or more. In this case, it is preferable to add 1 to 20% by weight with respect to the organic solvent.
（硬化剤）
本発明の組成物の他の実施態様は、上記の変性ポリオレフィン樹脂の分散体組成物と硬化剤を含む組成物である。硬化剤としては、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、或いはそれらの官能基が保護基でブロックされた架橋剤が例示される。硬化剤は１種単独であってもよいし、複数種の組み合わせであってもよい。
(Hardener)
Another embodiment of the composition of the present invention is a composition containing the above-mentioned dispersion composition of the modified polyolefin resin and a curing agent. Examples of the curing agent include polyisocyanate compounds, epoxy compounds, polyamine compounds, polyol compounds, and cross-linking agents in which their functional groups are blocked by protecting groups. The curing agent may be used alone or in combination of two or more.
硬化剤の配合量は、成分（Ｅ）の変性ポリオレフィン樹脂中の成分（Ｄ）の含有量により適宜選択できる。また、硬化剤を配合する場合は、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することができる。 The blending amount of the curing agent can be appropriately selected depending on the content of the component (D) in the modified polyolefin resin of the component (E). When a curing agent is blended, a catalyst such as an organic tin compound or a tertiary amine compound can be used in combination depending on the purpose.
（接着成分）
本発明の組成物の更に他の実施態様は、上記の変性ポリオレフィン樹脂の分散体組成物と接着成分を含む組成物である。接着成分としては、所望の効果を阻害しない範囲で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を用いることができる。
(Adhesive component)
Yet another embodiment of the composition of the present invention is a composition containing the above-mentioned dispersion composition of the modified polyolefin resin and an adhesive component. As the adhesive component, a known adhesive component such as a polyester-based adhesive, a polyurethane-based adhesive, or an acrylic-based adhesive can be used as long as the desired effect is not impaired.
本発明の組成物は、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、接着剤、プライマー、塗料用バインダー及びインキ用バインダーとして用いることができ、例えば、アルミラミネートフィルム等のラミネートフィルムにおける接着剤として有用である。 Since the composition of the present invention is excellent in adhesion between non-polar resins such as polyolefin-based substrates and between non-polar resins and metals, it can be used as an adhesive, a primer, a binder for paints and a binder for inks, for example, aluminum. It is useful as an adhesive in a laminated film such as a laminated film.
（プライマー、バインダー）
本発明の変性ポリオレフィン樹脂の分散体組成物又は上記記載の樹脂組成物は、プライマー、塗料用バインダー又はインキ用バインダーに用いることができる。本発明の変性ポリオレフィン樹脂又は上記記載の樹脂組成物は、接着性、溶液安定性、耐熱性に優れており、自動車のバンパー等ポリオレフィン基材への上塗り塗装時のプライマー、上塗り塗料やクリアーとの付着性に優れる塗料用バインダーとして好適に利用することができる。
(Primer, binder)
The dispersion composition of the modified polyolefin resin of the present invention or the resin composition described above can be used as a primer, a binder for paints, or a binder for inks. The modified polyolefin resin of the present invention or the resin composition described above is excellent in adhesiveness, solution stability, and heat resistance, and can be used as a primer, a topcoat paint, or a clear material when topcoating a polyolefin substrate such as an automobile bumper. It can be suitably used as a binder for paints having excellent adhesiveness.
本発明の変性ポリオレフィン樹脂の分散体組成物又は樹脂組成物を含むプライマー、塗料用バインダー又はインキ用バインダーは、溶液、粉末、シート等、用途に応じた形態で使用できる。また、その際に必要に応じて添加剤、例えば、酸化防止剤、光安定剤、紫外線吸収剤、顔料、染料、無機充填剤等を配合できる。 The dispersion composition of the modified polyolefin resin of the present invention or the primer containing the resin composition, the binder for paint or the binder for ink can be used in a form such as a solution, a powder, a sheet, etc. according to the intended use. At that time, additives such as antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, inorganic fillers and the like can be blended as needed.
（積層体）
本発明の変性ポリオレフィン樹脂の分散体組成物又は上記記載の樹脂組成物は、積層体に用いることができる。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変性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変性ポリオレフィン樹脂又は組成物を含む層が挟持されている態様が例示される。本発明の積層体は、リチウムイオン二次電池、コンデンサー、電気二重層キャパシター等の外装材として用いられるものであってもよい。
(Laminated body)
The dispersion composition of the modified polyolefin resin of the present invention or the resin composition described above can be used for a laminate. The arrangement of the layers in the laminate is not particularly limited, but the metal layer and the resin layer are located so as to sandwich the layer containing the modified polyolefin resin or the composition, and the first resin layer and the second resin layer sandwich the metal layer. Exists, and an embodiment in which a layer containing a modified polyolefin resin or a composition is sandwiched between the metal layer and each resin layer is exemplified. The laminate of the present invention may be used as an exterior material for a lithium ion secondary battery, a capacitor, an electric double layer capacitor, or the like.
［２．変性ポリオレフィン樹脂の分散体組成物の製造方法］
本発明の変性ポリオレフィン樹脂の分散体組成物の製造方法は、成分（Ａ）：ポリオレフィン樹脂と、成分（Ｂ）：エチレンプロピレンゴムと、を少なくとも含む成分（Ｃ）：原料成分が、成分（Ｄ）：α，β−不飽和カルボン酸又はその誘導体を含む変性成分で変性された成分（Ｅ）：変性ポリオレフィン樹脂を少なくとも含み、粒子径が０．１〜５０μｍである変性ポリオレフィン樹脂の分散体組成物を製造する方法である。
各成分の詳細は、[１．変性ポリオレフィン樹脂の分散体組成物]に記載した内容と同様である。
[2. Method for Producing Dispersion Composition of Modified Polyolefin Resin]
The method for producing a dispersion composition of a modified polyolefin resin of the present invention comprises at least a component (A): a polyolefin resin and a component (B): ethylene propylene rubber, and a component (C): a raw material component is a component (D). ): Component modified with a modified component containing α, β-unsaturated carboxylic acid or a derivative thereof (E): Dispersion composition of a modified polyolefin resin containing at least a modified polyolefin resin and having a particle size of 0.1 to 50 μm. It is a method of manufacturing things.
For details of each component, see [1. The content is the same as that described in [Dispersion composition of modified polyolefin resin].
成分（Ｅ）の変性ポリオレフィン樹脂を得る方法としては、例えば、以下の方法が挙げられる。成分（Ａ）と成分（Ｂ）をそれらが反応する程度に溶解する有機溶剤（例えば、トルエン等）に加熱溶解し、成分（Ｃ）を得た後、成分（Ｄ）及び他のグラフト成分を加え反応させることで本発明の変性ポリオレフィン樹脂を得ることができる。また、成分（Ａ）、成分（Ｂ）、成分（Ｄ）、及び他のグラフト成分を予めそれらが反応する程度に溶解する有機溶剤に加熱溶解して反応させる溶液法や、バンバリーミキサー、ニーダー、押出機等を使用して、成分（Ａ）、成分（Ｂ）、成分（Ｄ）及び他のグラフト成分を加え反応させる溶融混練法等でも成分（Ｅ）の変性ポリオレフィン樹脂を得ることができる。 Examples of the method for obtaining the modified polyolefin resin of the component (E) include the following methods. The component (A) and the component (B) are dissolved by heating in an organic solvent (for example, toluene) that dissolves the component (A) to the extent that they react to obtain the component (C), and then the component (D) and other graft components are added. The modified polyolefin resin of the present invention can be obtained by additional reaction. Further, a solution method in which the component (A), the component (B), the component (D), and other graft components are previously heated and dissolved in an organic solvent that dissolves them to the extent that they react, and the reaction is carried out. The modified polyolefin resin of the component (E) can also be obtained by a melt-kneading method or the like in which the component (A), the component (B), the component (D) and other graft components are added and reacted by using an extruder or the like.
本発明の分散体組成物を得る方法としては、例えば、以下の方法が挙げられる。上記成分（Ｅ）の変性ポリオレフィン樹脂を溶剤に浸し膨潤させた後、該膨潤樹脂を該溶剤ごとバッチ式ビーズミル装置にて微粉砕しつつ、装置内を循環させることで本発明の変性ポリオレフィン樹脂の溶剤分散体を得ることができる。 Examples of the method for obtaining the dispersion composition of the present invention include the following methods. The modified polyolefin resin of the above component (E) is immersed in a solvent to swell, and then the swelling resin is finely pulverized together with the solvent in a batch type bead mill device and circulated in the device to obtain the modified polyolefin resin of the present invention. A solvent dispersion can be obtained.
溶剤としては、例えば、トルエン、キシレン等の芳香族溶剤；酢酸エチル、酢酸ブチル等のエステル溶剤；メチルエチルケトン、メチルブチルケトン、エチルシクロヘキサン等のケトン溶剤；シクロヘキサン、メチルシクロヘキサン、ノナン、デカン等の脂肪族又は脂環式炭化水素溶剤が挙げられる。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よい。環境問題の観点から、有機溶剤として、芳香族溶剤以外の溶剤を使用することが好ましく、脂環式炭化水素溶剤とエステル溶剤又はケトン溶剤との混合溶剤を使用することがより好ましい。 Examples of the solvent include aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl butyl ketone and ethyl cyclohexane; aliphatic solvents such as cyclohexane, methylcyclohexane, nonane and decane. Alternatively, an alicyclic hydrocarbon solvent can be mentioned. These organic solvents may be used alone or may be contained in the resin composition as a mixed solvent of two or more kinds. From the viewpoint of environmental problems, it is preferable to use a solvent other than the aromatic solvent as the organic solvent, and it is more preferable to use a mixed solvent of the alicyclic hydrocarbon solvent and the ester solvent or the ketone solvent.
成分（Ｅ）である変性ポリオレフィン樹脂の微粉砕、および溶剤へ分散させるために、バッチ式ビーズミル装置を用いることが好ましい。該装置を用いることで、変性ポリオレフィン樹脂の微粉砕と溶剤分散を同時に行うことができ、作業効率が向上し得る。 It is preferable to use a batch type bead mill device for finely pulverizing the modified polyolefin resin as the component (E) and dispersing it in a solvent. By using the apparatus, the modified polyolefin resin can be finely pulverized and the solvent can be dispersed at the same time, and the work efficiency can be improved.
バッチ式ビーズミル装置としては、例えば、バスケットミル、リングミル、ＡＤミル等が挙げられる。中でも、バスケットミルを用いることが好ましい。バスケットミルとしては、例えば浅田鉄工製のものを使用することができる。 Examples of the batch type bead mill device include a basket mill, a ring mill, an AD mill and the like. Above all, it is preferable to use a basket mill. As the basket mill, for example, one manufactured by Asada Iron Works can be used.
バッチ式ビーズミル装置内に充填するビーズとしては、例えばガラス、アルミナ、スチール、ジルコン、ジルコニアが挙げられる。これらビーズは１種単独で用いてもよく、２種以上含まれていてよい。分散体の平均粒子径をより小さくし、かつビーズ同士の衝突によるビーズの摩耗を軽減するため、ジルコニアビーズを用いることが好ましい。
ビーズ径に特に指定は無いが、０．１ｍｍ〜１００ｍｍが好ましく、０．５ｍｍ〜５０ｍｍがより好ましく、１ｍｍ〜１０ｍｍが更に好ましい。ビーズ径が０．１ｍｍ〜１００ｍｍだと、微粉砕にかかる時間も短く、微粉砕後の変性ポリオレフィン樹脂が分散に適した粒子径となる。
Examples of beads to be filled in the batch type bead mill device include glass, alumina, steel, zircon, and zirconia. These beads may be used alone or may contain two or more. It is preferable to use zirconia beads in order to reduce the average particle size of the dispersion and to reduce the wear of the beads due to collision between the beads.
Although the bead diameter is not particularly specified, it is preferably 0.1 mm to 100 mm, more preferably 0.5 mm to 50 mm, still more preferably 1 mm to 10 mm. When the bead diameter is 0.1 mm to 100 mm, the time required for pulverization is short, and the modified polyolefin resin after pulverization has a particle diameter suitable for dispersion.
バッチ式ビーズミル装置内下部の攪拌羽根の攪拌速度は、扱う樹脂や溶剤、及びそれらの添加量によって適宜調節し得る。 The stirring speed of the stirring blades at the lower part of the batch type bead mill device can be appropriately adjusted depending on the resin and solvent to be handled and the amount of their addition.
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、成分（Ａ）、成分（Ｂ）及び変性ポリオレフィン樹脂の物性値並びに変性ポリオレフィン樹脂の評価は、下記に記載した方法で行う。また、「部」は別途記載がない限り重量部を示す。 Hereinafter, the present invention will be described in detail with reference to Examples. The following examples are for the purpose of preferably explaining the present invention, and do not limit the present invention. The physical characteristics of the component (A), the component (B) and the modified polyolefin resin, and the evaluation of the modified polyolefin resin are carried out by the methods described below. In addition, "part" indicates a weight part unless otherwise specified.
［曲げ弾性率（ＭＰａ）］
ＪＩＳ Ｋ ７２０３：９ ５に準拠して測定した。
[Bending elastic modulus (MPa)]
Measured according to JIS K 7203: 95.
[メルトフローレート（ｇ／１０分）]
ＡＳＴＭ Ｄ１２３８に準拠し、２３０℃の測定温度、測定荷重２．１６ｋｇの条件でメルトフローレート試験機（安田精機製作所製）にて算出した。
[Melt flow rate (g / 10 minutes)]
It was calculated by a melt flow rate tester (manufactured by Yasuda Seiki Seisakusho) under the conditions of a measurement temperature of 230 ° C. and a measurement load of 2.16 kg in accordance with ASTM D1238.
［平均粒子径（ｎｍ）］
実施例及び比較例で得られる変性ポリオレフィン樹脂の分散体を、レーザー回折式粒度分布測定装置（Ｍａｌｖｅｒｎ Ｉｎｓｔｒｕｍｅｎｔｓ製、マスターサイザー３０００）の分散媒が循環する試料循環装置中に滴下して測定し、得られた粒度分布の体積累積５０％粒子径（メジアン径）を平均粒子径とした。
[Average particle size (nm)]
The dispersion of the modified polyolefin resin obtained in Examples and Comparative Examples was dropped into a sample circulation device in which a dispersion medium of a laser diffraction type particle size distribution measuring device (manufactured by Malvern Instruments, Mastersizer 3000) circulates and measured. The volume cumulative 50% particle size (median size) of the obtained particle size distribution was taken as the average particle size.
［粘度（ｍＰａ・ｓ）］
実施例及び比較例で得られる変性ポリオレフィン樹脂の分散体または溶液をガラス瓶内に密閉し、恒温槽にて２５℃に調温し、Ｂ型粘度計（東機産業社製、ＢＭＩＩ型粘度計）を用いて、回転速度６０ｒｐｍの条件で測定した。
[Viscosity (mPa · s)]
The dispersion or solution of the modified polyolefin resin obtained in Examples and Comparative Examples is sealed in a glass bottle, the temperature is adjusted to 25 ° C. in a constant temperature bath, and a B-type viscometer (BMII type viscometer manufactured by Toki Sangyo Co., Ltd.). Was measured under the condition of a rotation speed of 60 rpm.
［溶液安定性］
溶液試料を密閉したガラス瓶に入れ、５℃で７日間静置保管した後、目視にて外観を評価した。
○：組成物溶液の流動性が保たれている。
△：組成物溶液の流動性が若干低下するが、実用上問題はない。
×：組成物溶液の流動性が低下している。
[Solution stability]
The solution sample was placed in a closed glass bottle and stored at 5 ° C. for 7 days, and then the appearance was visually evaluated.
◯: The fluidity of the composition solution is maintained.
Δ: The fluidity of the composition solution is slightly lowered, but there is no problem in practical use.
X: The fluidity of the composition solution is low.
[ピール適性]
実施例及び比較例で得られる変性ポリオレフィン樹脂の分散体または溶液を、イソプロピルアルコールで脱脂した超高剛性ポリプロピレン基材表面へ１０μｍの膜厚となる様スプレー塗装し、室温で１０分間乾燥後、さらに上塗り塗料を１００μｍとなる様にスプレー塗装し、室温で１０分間乾燥後、８０℃で３０分間焼付を行った。恒温恒湿環境下（２３℃、５０％ＲＨ）にて３日間静置後、引張試験機にてピール強度を測定し、下記の基準にて評価を行った。
なお、ピール適性は、樹脂の柔軟性の指標として用いることができる。
○：５００ｇｆ／ｃｍ以上であり、ピール適性良好。
△：４００ｇｆ／ｃｍ以上５００ｇｆ／ｃｍ未満であり、ややピール適性に劣るものの、実用上問題無い。
×：４００ｇｆ／ｃｍ未満であり、ピール適性に劣る。
[Peel aptitude]
The dispersion or solution of the modified polyolefin resin obtained in Examples and Comparative Examples was spray-coated on the surface of an ultra-high-rigidity polypropylene base material degreased with isopropyl alcohol to a thickness of 10 μm, dried at room temperature for 10 minutes, and then further. The topcoat paint was spray-coated to a size of 100 μm, dried at room temperature for 10 minutes, and then baked at 80 ° C. for 30 minutes. After standing in a constant temperature and humidity environment (23 ° C., 50% RH) for 3 days, the peel strength was measured with a tensile tester and evaluated according to the following criteria.
The peel suitability can be used as an index of the flexibility of the resin.
◯: 500 gf / cm or more, and good peel suitability.
Δ: 400 gf / cm or more and less than 500 gf / cm, which is slightly inferior in peel suitability, but there is no problem in practical use.
X: It is less than 400 gf / cm and is inferior in peel suitability.
［耐熱性］
調製した変性ポリオレフィン樹脂塗料組成物を、ポリオレフィン系基材としてポリプロピレン（ＯＰＰ）にスプレー塗工した。該塗工面に表面処理がされていない超高剛性ＰＰ板を貼り合わせた後、ヒートシール（接着幅１０ｍｍ、０．２ＭＰａ、１６０℃、１０秒)し、試験片を得た。試験片のＯＰＰフィルム側に１００ｇのおもりを取り付け、ＯＰＰフィルム側を下にし、１００℃に設定した乾燥機の中に入れ、２時間後にＯＰＰの剥離状態を目視確認し、下記評価基準で評価した。
○：ＯＰＰフィルムの剥がれが無い。
×：ＯＰＰフィルムが超高剛性ＰＰ板から剥離している。
[Heat-resistant]
The prepared modified polyolefin resin coating composition was spray-coated on polypropylene (OPP) as a polyolefin-based substrate. An ultra-high rigidity PP plate without surface treatment was attached to the coated surface, and then heat-sealed (adhesion width 10 mm, 0.2 MPa, 160 ° C., 10 seconds) to obtain a test piece. A 100 g weight was attached to the OPP film side of the test piece, the OPP film side was turned down, and the test piece was placed in a dryer set at 100 ° C. Two hours later, the peeled state of the OPP was visually confirmed and evaluated according to the following evaluation criteria. ..
◯: There is no peeling of the OPP film.
X: The OPP film is peeled off from the ultra-high rigidity PP plate.
［付着性］
アルミ箔上に樹脂乾燥膜厚２μｍとなるように＃１６のマイヤーバーで調製した変性ポリオレフィン樹脂塗料組成物の溶液試料を接着剤として塗布し、１８０℃で１０秒間乾燥した。塗布済みのアルミ箔を無延伸ポリプロピレン（ＣＰＰ）シートと貼合し、１２０℃で３秒間、２００ｋＰａの条件で熱圧着を行った後、１５ｍｍ幅に切り出して試験片を作製した。試験片を２３℃、相対湿度５０％で２４時間恒温恒湿に保管した後、１８０度方向剥離、剥離速度１００ｍｍ／ｍｉｎの条件でラミネート接着強度を測定し、下記の基準にて評価を行った。
○：接着強度が５００ｇ／１５ｍｍ以上であり、接着性良好。
△：接着強度が３００ｇ／１５ｍｍ以上５００ｇ／１５ｍｍ未満であり、やや接着性に劣るものの、実用上問題無い。
×：接着強度が３００ｇ／１５ｍｍ未満であり、接着性に劣る。
[Adhesiveness]
A solution sample of the modified polyolefin resin coating composition prepared with a # 16 Meyer bar was applied as an adhesive on the aluminum foil so as to have a resin dry film thickness of 2 μm, and dried at 180 ° C. for 10 seconds. The coated aluminum foil was bonded to an unstretched polypropylene (CPP) sheet, thermocompression bonded at 120 ° C. for 3 seconds under the condition of 200 kPa, and then cut into a width of 15 mm to prepare a test piece. The test piece was stored at a constant temperature and humidity for 24 hours at 23 ° C. and a relative humidity of 50%, and then the laminate adhesive strength was measured under the conditions of 180 degree peeling and peeling speed of 100 mm / min, and evaluated according to the following criteria. ..
◯: Adhesive strength is 500 g / 15 mm or more, and adhesiveness is good.
Δ: The adhesive strength is 300 g / 15 mm or more and less than 500 g / 15 mm, and although the adhesive strength is slightly inferior, there is no problem in practical use.
X: The adhesive strength is less than 300 g / 15 mm, and the adhesiveness is inferior.
［成分：（Ｅ）変性ポリオレフィン樹脂］
（製造例１）
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、成分（Ａ−１）としてプロピレン−エチレン−１−ブテン共重合体（プロピレン成分６０モル％、エチレン成分１０モル％、１−ブテン成分３０モル％、Ｔｍ＝６５℃）５０部、及び成分（Ｂ−１）としてプロピレンエチレンゴム（エチレン成分３４モル％、曲げ弾性率５５ＭＰａ、ＭＦＲ２．０ｇ／１０分（２３０℃）、Ｔｍ＝１５３℃）５０部を、トルエン４００ｇに加熱溶解した。系内の温度を１１０℃に保持して撹拌しながら、成分（Ｄ）として無水マレイン酸７．０部、その他成分としてラウリルメタクリレート７．０部、および成分（Ｆ）としてジ−ｔ−ブチルパーオキサイド４．０部をそれぞれ３時間かけて滴下し、さらに１時間反応させた。反応後、室温まで冷却した反応物を大過剰のアセトン中に投入して精製し、無水マレイン酸のグラフト重量が５．７重量％、ラウリルメタクリレートのグラフト重量が６．２重量％の変性ポリオレフィン樹脂（成分（Ｅ−１））を得た。得られた変性ポリオレフィン樹脂のＤＳＣで測定した融点ピークは６３℃および１４６℃であった。
[Component: (E) Modified Polyolefin Resin]
(Manufacturing Example 1)
A propylene-ethylene-1-butene copolymer (60 mol% propylene component, 10 mol% ethylene component, 1-) as a component (A-1) in a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel. Butene component 30 mol%, Tm = 65 ° C.) 50 parts, and propylene ethylene rubber as component (B-1) (ethylene component 34 mol%, bending elasticity 55 MPa, MFR 2.0 g / 10 minutes (230 ° C), Tm = 50 parts (153 ° C.) was dissolved by heating in 400 g of toluene. While maintaining the temperature in the system at 110 ° C. and stirring, 7.0 parts of maleic anhydride as the component (D), 7.0 parts of lauryl methacrylate as the other component, and di-t-butylper as the component (F). 4.0 parts of the oxide was added dropwise over 3 hours, and the mixture was further reacted for 1 hour. After the reaction, the reaction product cooled to room temperature was put into a large excess of acetone for purification, and the modified polyolefin resin had a maleic anhydride graft weight of 5.7% by weight and a lauryl methacrylate graft weight of 6.2% by weight. (Component (E-1)) was obtained. The melting point peaks of the obtained modified polyolefin resin measured by DSC were 63 ° C. and 146 ° C.
（製造例２）
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、成分（Ａ−２）としてプロピレン−エチレン共重合体（プロピレン成分８９モル％、エチレン成分１１モル％、Ｔｍ＝６５℃）８０部、及び成分（Ｂ−１）としてプロピレンエチレンゴム（エチレン成分３４モル％、曲げ弾性率５５ＭＰａ、ＭＦＲ２．０ｇ／１０分（２３０℃）、Ｔｍ＝１５３℃）２０部を、トルエン４００ｇに加熱溶解した。系内の温度を１１０℃に保持して撹拌しながら、成分（Ｄ）として無水マレイン酸５．０部、その他成分としてオクチルメタクリレート５．０部、および成分（Ｆ）としてジ−ｔ−ブチルパーオキサイド１．０部をそれぞれ３時間かけて滴下し、さらに１時間反応させた。反応後、室温まで冷却した反応物を大過剰のアセトン中に投入して精製し、無水マレイン酸のグラフト重量が３．７重量％、オクチルメタクリレートのグラフト重量が３．２重量％の変性ポリオレフィン樹脂（成分（Ｅ−２））を得た。得られた変性ポリオレフィン樹脂のＤＳＣで測定した融点ピークは６５℃および１５０℃であった。
(Manufacturing Example 2)
Propylene-ethylene copolymer (propylene component 89 mol%, ethylene component 11 mol%, Tm = 65 ° C.) 80 as component (A-2) in a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel. 20 parts of propylene ethylene rubber (ethylene component 34 mol%, bending elasticity 55 MPa, MFR 2.0 g / 10 minutes (230 ° C.), Tm = 153 ° C.) as a part and component (B-1) are heat-dissolved in 400 g of toluene. did. While maintaining the temperature in the system at 110 ° C. and stirring, 5.0 parts of maleic anhydride as the component (D), 5.0 parts of octyl methacrylate as the other component, and di-t-butylper as the component (F). 1.0 part of the oxide was added dropwise over 3 hours, and the mixture was further reacted for 1 hour. After the reaction, the reaction product cooled to room temperature was put into a large excess of acetone for purification, and the modified polyolefin resin had a maleic anhydride graft weight of 3.7% by weight and an octyl methacrylate graft weight of 3.2% by weight. (Component (E-2)) was obtained. The melting point peaks of the obtained modified polyolefin resin measured by DSC were 65 ° C. and 150 ° C.
（製造例３）
成分（Ｂ−１）の代わりに成分（Ｂ−２）としてプロピレンエチレンゴム（エチレン成分４０モル％、曲げ弾性率１００ＭＰａ、ＭＦＲ０．６ｇ／１０分（２３０℃）、Ｔｍ＝１４２℃）を用いた以外は、製造例２と同様に反応した。反応後、室温まで冷却した反応物を大過剰のアセトン中に投入して精製し、無水マレイン酸のグラフト重量が５．５重量％、ラウリルメタクリレートのグラフト重量が６．０重量％の変性ポリオレフィン樹脂（成分（Ｅ−３））を得た。得られた変性ポリオレフィン樹脂のＤＳＣで測定した融点ピークは６３℃および１４３℃であった。
(Manufacturing Example 3)
Propylene ethylene rubber (ethylene component 40 mol%, flexural modulus 100 MPa, MFR 0.6 g / 10 minutes (230 ° C.), Tm = 142 ° C.) was used as the component (B-2) instead of the component (B-1). Except for the above, the reaction was the same as in Production Example 2. After the reaction, the reaction product cooled to room temperature was put into a large excess of acetone for purification, and the modified polyolefin resin had a maleic anhydride graft weight of 5.5% by weight and a lauryl methacrylate graft weight of 6.0% by weight. (Component (E-3)) was obtained. The melting point peaks of the obtained modified polyolefin resin measured by DSC were 63 ° C. and 143 ° C.
（製造例４）
成分（Ａ−２）を２５部、成分（Ｂ−１）を７５部とした以外は、製造例２と同様に反応した。反応後、室温まで冷却した反応物を大過剰のアセトン中に投入して精製し、無水マレイン酸のグラフト重量が５．６重量％、ラウリルメタクリレートのグラフト重量が５．９重量％の変性ポリオレフィン樹脂（成分（Ｅ−４））を得た。得られた変性ポリオレフィン樹脂のＤＳＣで測定した融点ピークは６５℃および１５０℃であった。
(Manufacturing Example 4)
The reaction was carried out in the same manner as in Production Example 2 except that the component (A-2) was 25 parts and the component (B-1) was 75 parts. After the reaction, the reaction product cooled to room temperature was put into a large excess of acetone for purification, and the modified polyolefin resin had a maleic anhydride graft weight of 5.6% by weight and a lauryl methacrylate graft weight of 5.9% by weight. (Component (E-4)) was obtained. The melting point peaks of the obtained modified polyolefin resin measured by DSC were 65 ° C. and 150 ° C.
（製造例５）
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、成分（Ａ−１）としてプロピレン−エチレン−１−ブテン共重合体（プロピレン成分６０モル％、エチレン成分１０モル％、１−ブテン成分３０モル％、Ｔｍ＝６５℃）５０部、及び成分（Ｂ−３）としてプロピレンエチレンゴム（エチレン成分４モル％、曲げ弾性率２８０ＭＰａ、ＭＦＲ１０．０ｇ／１０分（２３０℃）、Ｔｍ＝１３０℃）５０部を、トルエン４００ｇに加熱溶解した。系内の温度を１１０℃に保持して撹拌しながら、成分（Ｄ）として無水マレイン酸６．０部、その他成分としてオクチルメタクリレート６．０部、および成分（Ｆ）としてジ−ｔ−ブチルパーオキサイド１．０部をそれぞれ３時間かけて滴下し、さらに１時間反応させた。反応後、室温まで冷却した反応物を大過剰のアセトン中に投入して精製し、無水マレイン酸のグラフト重量が３．６重量％、オクチルメタクリレートのグラフト重量が３．３重量％の変性ポリオレフィン樹脂（成分（Ｅ−５））を得た。得られた変性ポリオレフィン樹脂のＤＳＣで測定した融点ピークは６３℃および１３１℃であった。
(Manufacturing Example 5)
A propylene-ethylene-1-butene copolymer (60 mol% propylene component, 10 mol% ethylene component, 1-) as a component (A-1) in a four-necked flask equipped with a stirrer, a cooling tube, and a dropping funnel. Butene component 30 mol%, Tm = 65 ° C.) 50 parts, and propylene ethylene rubber (ethylene component 4 mol%, bending elasticity 280 MPa, MFR 10.0 g / 10 minutes (230 ° C.), Tm = (130 ° C.) 50 parts were dissolved by heating in 400 g of toluene. While maintaining the temperature in the system at 110 ° C. and stirring, 6.0 parts of maleic anhydride as the component (D), 6.0 parts of octyl methacrylate as the other component, and di-t-butylper as the component (F). 1.0 part of the oxide was added dropwise over 3 hours, and the mixture was further reacted for 1 hour. After the reaction, the reaction product cooled to room temperature was put into a large excess of acetone for purification, and the modified polyolefin resin had a maleic anhydride graft weight of 3.6% by weight and an octyl methacrylate graft weight of 3.3% by weight. (Component (E-5)) was obtained. The melting point peaks of the obtained modified polyolefin resin measured by DSC were 63 ° C. and 131 ° C.
（製造例６）
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、成分（Ａ−１）としてプロピレン−エチレン−１−ブテン共重合体（プロピレン成分６０モル％、エチレン成分１０モル％、１−ブテン成分３０モル％、Ｔｍ＝６５℃）１００部を、トルエン４００ｇに加熱溶解した。系内の温度を１１０℃に保持して撹拌しながら、成分（Ｄ）として無水マレイン酸７．０部、その他成分としてオクチルメタクリレート７．０部、および成分（Ｆ）としてジ−ｔ−ブチルパーオキサイド１．０部をそれぞれ３時間かけて滴下し、さらに１時間反応させた。反応後、室温まで冷却した反応物を大過剰のアセトン中に投入して精製し、無水マレイン酸のグラフト重量が５．６重量％、オクチルメタクリレートのグラフト重量が５．３重量％の変性ポリオレフィン樹脂（成分（Ｅ−６））を得た。得られた変性ポリオレフィン樹脂の融点は６３℃であった。
(Manufacturing Example 6)
Propylene-ethylene-1-butene copolymer (60 mol% propylene component, 10 mol% ethylene component, 1-) as component (A-1) in a four-necked flask equipped with a stirrer, cooling tube, and dropping funnel. 100 parts of butene component (30 mol%, Tm = 65 ° C.) was dissolved by heating in 400 g of toluene. While maintaining the temperature in the system at 110 ° C. and stirring, 7.0 parts of maleic anhydride as the component (D), 7.0 parts of octyl methacrylate as the other component, and di-t-butylper as the component (F). 1.0 part of the oxide was added dropwise over 3 hours, and the mixture was further reacted for 1 hour. After the reaction, the reaction product cooled to room temperature was put into a large excess of acetone for purification, and the modified polyolefin resin had a maleic anhydride graft weight of 5.6% by weight and an octyl methacrylate graft weight of 5.3% by weight. (Component (E-6)) was obtained. The melting point of the obtained modified polyolefin resin was 63 ° C.
（実施例１）
５Ｌのステンレス製ビーカー中に製造例１で得た変性ポリオレフィン樹脂（成分（Ｅ−１））を３００g取り、メチルシクロヘキサン１３６０ｇおよびメチルエチルケトン３４０ｇを添加して蓋をし、２０℃に調温した恒温槽中に２時間静置して該ペレットを膨潤させた。該膨潤ペレットを該溶剤ごとバスケットミル分散装置（浅田鉄工製）の釜に移し、ジルコニアビーズ（１．５ｍｍ径）が充填された分散バスケットを下ろして、１分間窒素パージを行い、酸素濃度を爆発限界以下とした。その後、該バスケット内部ローターおよび該ローターに連動した下部撹拌羽の回転数を徐々に上げ、該膨潤ペレットを含む溶剤が該バスケットを循環、すなわち、該バスケット上部から内部に吸引され該バスケット側面および底部のスリットから排出され、再び該バスケット上部から吸引されるという流れが発生している事を確認した。その後、９００ｒｐｍで、液温が３０℃前後となる様適宜調整しながら、３時間該膨潤ペレットを該バスケット内に循環させ、微粉砕と溶剤への分散を行った。分散後、釜底部バルブからフェルト製ろ布を通して排出し、分散体を得た。得られた分散体の固形分は１４．９％、粘度は５０ｍＰａ・ｓ、粒子径（メジアン径）は０．６０μｍであった。
(Example 1)
300 g of the modified polyolefin resin (component (E-1)) obtained in Production Example 1 was taken in a 5 L stainless steel beaker, 1360 g of methylcyclohexane and 340 g of methylethylketone were added, the lid was closed, and the temperature was adjusted to 20 ° C. The pellet was swollen by allowing it to stand inside for 2 hours. The swollen pellets are transferred together with the solvent to a kettle of a basket mill disperser (manufactured by Asada Iron Works), a disperse basket filled with zirconia beads (1.5 mm diameter) is lowered, nitrogen purging is performed for 1 minute, and the oxygen concentration is exploded. It was below the limit. Then, the rotation speed of the inner rotor of the basket and the lower stirring blade linked to the rotor is gradually increased, and the solvent containing the swollen pellets circulates in the basket, that is, is sucked inward from the upper part of the basket, and the side surfaces and the bottom of the basket It was confirmed that a flow of being discharged from the slit of the basket and being sucked from the upper part of the basket again occurred. Then, at 900 rpm, the swollen pellets were circulated in the basket for 3 hours while appropriately adjusting the liquid temperature to about 30 ° C., and finely pulverized and dispersed in a solvent. After the dispersion, the mixture was discharged from the valve at the bottom of the kettle through a felt filter cloth to obtain a dispersion. The solid content of the obtained dispersion was 14.9%, the viscosity was 50 mPa · s, and the particle size (median diameter) was 0.60 μm.
（実施例２）
製造例２で得た変性ポリオレフィン樹脂（成分（Ｅ−２））を用いた以外は、実施例１と同様に製造した。得られた分散体の固形分は１５．１％、粘度は３７ｍＰａ・ｓ、粒子径（メジアン径）は０．５７μｍであった。
(Example 2)
It was produced in the same manner as in Example 1 except that the modified polyolefin resin (component (E-2)) obtained in Production Example 2 was used. The solid content of the obtained dispersion was 15.1%, the viscosity was 37 mPa · s, and the particle size (median diameter) was 0.57 μm.
（実施例３）
製造例３で得た変性ポリオレフィン樹脂（成分（Ｅ−３））を用いた以外は、実施例１と同様に製造した。得られた分散体の固形分は１５．０％、粘度は９０ｍＰａ・ｓ、粒子径（メジアン径）は２０．００μｍであった。
(Example 3)
It was produced in the same manner as in Example 1 except that the modified polyolefin resin (component (E-3)) obtained in Production Example 3 was used. The solid content of the obtained dispersion was 15.0%, the viscosity was 90 mPa · s, and the particle size (median diameter) was 20.00 μm.
（実施例４）
製造例４で得た変性ポリオレフィン樹脂（成分（Ｅ−４））を用いた以外は、実施例１と同様に製造した。得られた分散体の固形分は１５．２％、粘度は２２５ｍＰａ・ｓ、粒子径（メジアン径）は０．８９μｍであった。
(Example 4)
It was produced in the same manner as in Example 1 except that the modified polyolefin resin (component (E-4)) obtained in Production Example 4 was used. The solid content of the obtained dispersion was 15.2%, the viscosity was 225 mPa · s, and the particle size (median diameter) was 0.89 μm.
（実施例５）
製造例５で得た変性ポリオレフィン樹脂（成分（Ｅ−５））を用いた以外は、実施例１と同様に製造した。得られた分散体の固形分は１５．１％、粘度は７０ｍＰａ・ｓ、粒子径は３０．１０μｍであった。
(Example 5)
It was produced in the same manner as in Example 1 except that the modified polyolefin resin (component (E-5)) obtained in Production Example 5 was used. The solid content of the obtained dispersion was 15.1%, the viscosity was 70 mPa · s, and the particle size was 30.10 μm.
（比較例１）
ガラス瓶内にて、製造例１で得た変性ポリオレフィン樹脂（成分（Ｅ−１））を、メチルシクロヘキサン／メチルエチルケトン溶液（混合比８０／２０）に溶解して、１５重量％の濃度の変性ポリオレフィン樹脂溶液を調製した。得られた溶液の固形分は１５．０％、粘度は３００ｍＰａ・ｓであった。
(Comparative Example 1)
In a glass bottle, the modified polyolefin resin (component (E-1)) obtained in Production Example 1 is dissolved in a methylcyclohexane / methylethylketone solution (mixing ratio 80/20) to obtain a modified polyolefin resin having a concentration of 15% by weight. The solution was prepared. The solid content of the obtained solution was 15.0%, and the viscosity was 300 mPa · s.
（比較例２）
製造例２で得た変性ポリオレフィン樹脂（成分（Ｅ−２））を用いた以外は、比較例１と同様に溶液を調製した。得られた溶液の固形分は１５．０％、粘度は４０ｍＰａ・ｓであった。
(Comparative Example 2)
A solution was prepared in the same manner as in Comparative Example 1 except that the modified polyolefin resin (component (E-2)) obtained in Production Example 2 was used. The solid content of the obtained solution was 15.0%, and the viscosity was 40 mPa · s.
（比較例３）
製造例６で得た変性ポリオレフィン樹脂（成分（Ｅ−６））を用いた以外は、比較例１と同様に溶液を調製した。得られた溶液の固形分は１５．０％、粘度は４０ｍＰａ・ｓであった。
(Comparative Example 3)
A solution was prepared in the same manner as in Comparative Example 1 except that the modified polyolefin resin (component (E-6)) obtained in Production Example 6 was used. The solid content of the obtained solution was 15.0%, and the viscosity was 40 mPa · s.
表１の実施例１〜５から明らかなように、本発明の変性ポリオレフィン樹脂分散体組成物は溶液安定性、ピール適性、耐熱性および付着性をバランスよく有していた。
一方、比較例１および２のような溶剤に溶解させた形態では、溶液安定性が劣る。また、比較例３のように、成分（Ｂ）を配合しない場合、ピール適性や耐熱性が劣ることとなる。
As is clear from Examples 1 to 5 in Table 1, the modified polyolefin resin dispersion composition of the present invention had a good balance of solution stability, peelability, heat resistance and adhesiveness.
On the other hand, in the form dissolved in a solvent such as Comparative Examples 1 and 2, the solution stability is inferior. Further, when the component (B) is not blended as in Comparative Example 3, the peel suitability and heat resistance are inferior.
Claims (9)
成分（Ｂ）：エチレンプロピレンゴムと、
を少なくとも含む成分（Ｃ）：原料成分が、
成分（Ｄ）：α，β−不飽和カルボン酸又はその誘導体を含む変性成分
で変性された成分（Ｅ）：変性ポリオレフィン樹脂
を少なくとも含み、粒子径が０．１〜５０μｍである変性ポリオレフィン樹脂の分散体組成物。 Component (A): Polyolefin resin and
Ingredient (B): Ethylene propylene rubber and
Ingredient (C) containing at least
Component (D): Component modified with a modified component containing α, β-unsaturated carboxylic acid or a derivative thereof (E): A modified polyolefin resin containing at least a modified polyolefin resin and having a particle size of 0.1 to 50 μm. Dispersion composition.
成分（Ａ）：ポリオレフィン樹脂と、
成分（Ｂ）：エチレンプロピレンゴムと、
を少なくとも含む成分（Ｃ）：原料成分が、
成分（Ｄ）：α，β−不飽和カルボン酸又はその誘導体を含む変性成分
で変性された成分（Ｅ）：変性ポリオレフィン樹脂
の粉砕と溶剤分散を同時に行う工程を含む、変性ポリオレフィン樹脂の分散体組成物の製造方法。 By batch type bead mill device
Component (A): Polyolefin resin and
Ingredient (B): Ethylene propylene rubber and
Ingredient (C) containing at least
Component (D): Component modified with a modified component containing α, β-unsaturated carboxylic acid or a derivative thereof (E): Dispersion of modified polyolefin resin including a step of simultaneously pulverizing the modified polyolefin resin and dispersing the solvent. Method for producing the composition.
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| JPH09235319A (en) * | 1995-12-27 | 1997-09-09 | Nippon Poriorefuin Kk | Graft modified resin or its composition and laminate using the same |
| JP2011068912A (en) * | 2000-07-31 | 2011-04-07 | Mitsui Chemicals Inc | Aqueous dispersion composition for imparting chipping resistance |
| JP2003192855A (en) * | 2001-12-25 | 2003-07-09 | Mitsubishi Cable Ind Ltd | Heat reversible crosslinkable elastomer composition and molding thereof |
| JP2012136705A (en) * | 2005-12-28 | 2012-07-19 | Mitsui Chemicals Inc | Coating material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023204306A1 (en) * | 2022-04-22 | 2023-10-26 | 三井化学株式会社 | Resin composition and multilayer laminated film |
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