JP2023139819A - Resin composition, modifier, and composition containing the modifier - Google Patents
Resin composition, modifier, and composition containing the modifier Download PDFInfo
- Publication number
- JP2023139819A JP2023139819A JP2022045541A JP2022045541A JP2023139819A JP 2023139819 A JP2023139819 A JP 2023139819A JP 2022045541 A JP2022045541 A JP 2022045541A JP 2022045541 A JP2022045541 A JP 2022045541A JP 2023139819 A JP2023139819 A JP 2023139819A
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- Prior art keywords
- resin composition
- ethylene
- acrylic acid
- resin
- copolymer
- 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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Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 105
- 239000003607 modifier Substances 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title description 35
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 40
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims description 60
- -1 polypropylene, ethylene-propylene copolymer Polymers 0.000 claims description 46
- 238000004898 kneading Methods 0.000 claims description 24
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 22
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 21
- 229920001684 low density polyethylene Polymers 0.000 claims description 15
- 239000004702 low-density polyethylene Substances 0.000 claims description 15
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 14
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 10
- 229940022769 d- lactic acid Drugs 0.000 claims description 10
- 229920002292 Nylon 6 Polymers 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 8
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 8
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 7
- 229920000571 Nylon 11 Polymers 0.000 claims description 7
- 229920000299 Nylon 12 Polymers 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 7
- 239000004700 high-density polyethylene Substances 0.000 claims description 7
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 7
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 229930182843 D-Lactic acid Natural products 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920001778 nylon Polymers 0.000 claims description 5
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 239000004626 polylactic acid Substances 0.000 claims description 5
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 229920002961 polybutylene succinate Polymers 0.000 claims description 4
- 239000004631 polybutylene succinate Substances 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 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 claims description 3
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 3
- 229920005668 polycarbonate resin Polymers 0.000 claims description 3
- 239000004431 polycarbonate resin Substances 0.000 claims description 3
- 229920005990 polystyrene resin Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 239000000155 melt Substances 0.000 description 27
- 238000002844 melting Methods 0.000 description 20
- 230000008018 melting Effects 0.000 description 20
- PZRHRDRVRGEVNW-UHFFFAOYSA-N milrinone Chemical compound N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C PZRHRDRVRGEVNW-UHFFFAOYSA-N 0.000 description 18
- 229960003574 milrinone Drugs 0.000 description 18
- 238000009864 tensile test Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 16
- 238000009863 impact test Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000013502 plastic waste Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000012773 agricultural material Substances 0.000 description 2
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920000118 poly(D-lactic acid) Polymers 0.000 description 2
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-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
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-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
- 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
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-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
- 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 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-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
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- JGDSPOCXKKSJTF-UHFFFAOYSA-N C(C)(C)(C)OOC1=CC(=C(C=C1C(C)C)C(C)C)OOC(C)(C)C Chemical compound C(C)(C)(C)OOC1=CC(=C(C=C1C(C)C)C(C)C)OOC(C)(C)C JGDSPOCXKKSJTF-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920003298 Nucrel® Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、該樹脂組成物およびその組成物からなる成形品に関するものである。 The present invention relates to the resin composition and a molded article made from the composition.
近年、プラスチックによる環境汚染問題への関心が高まっており、プラスチック製品のマテリアルリサイクルが促進されている。プラスチックのマテリアルリサイクルでは、回収したプラスチック廃棄物を溶融して原料ペレットに戻すか、パレットなどの消耗材料へ再生されることが多い。この時、回収したプラスチック廃棄物中に異種のプラスチックが混在した状態でリサイクルすると、互いの相溶性が悪いことからリサイクルされたプラスチックの物性が低下する問題が生じる。そのため、現在は回収したプラスチック廃棄物を素材毎に選別したのち、製品へと再生するという工程がとられている。 In recent years, there has been increasing interest in the problem of environmental pollution caused by plastics, and material recycling of plastic products has been promoted. In plastic material recycling, collected plastic waste is often melted back into raw material pellets or recycled into consumable materials such as pallets. At this time, if different types of plastics are recycled in a mixed state in the collected plastic waste, a problem arises in that the physical properties of the recycled plastics deteriorate due to poor compatibility with each other. Therefore, the current process is to sort collected plastic waste by material and then recycle it into products.
しかしながら、異種のプラスチックが積層された多層フィルムや多層容器などでは、素材毎に分別することが困難であることからリサイクルすることができず、埋立や焼却処理されているのが現状である。 However, multilayer films and multilayer containers made of different types of plastics cannot be recycled because it is difficult to separate them by material, so they are currently disposed of in landfills or incinerated.
このような背景の中、積層状態の複合樹脂をリサイクルする手段として、相溶化剤の添加が検討されている。例えば、アイオノマー樹脂を相溶化剤として用い、ポリエチレン(PE)-ポリエチレンテレフタレート(以下、PETと略すことがある。)、ポリプロピレン(以下、PPと略すことがある。)-ABSの複合リサイクルの検討がなされている(例えば、特許文献1参照。)。また、オキサゾリン系相溶化剤を用い、PE-PET等の複合リサイクルの検討がなされている(例えば、特許文献2参照。)。さらに、PE-エチレン・ビニルアルコール共重合体(以下、EVOHと略すことがある。)の複合リサイクルの検討もなされている(例えば、特許文献3参照。)。これら文献によれば、相溶化剤を添加することによりPEとPETやEVOHなどの複合物の物性を向上できることが示されている。しかし、これら方法により得られるリサイクル樹脂は機械特性が十分ではないため、さらなる機械特性の改善が可能な技術の開発が必要である。また、粘度増加や黄変、臭気の問題などにより繰り返しリサイクル性に劣ることや再生樹脂の使用用途に制限があった。 Against this background, the addition of a compatibilizer is being considered as a means of recycling composite resins in a laminated state. For example, using an ionomer resin as a compatibilizer, the combined recycling of polyethylene (PE) - polyethylene terephthalate (hereinafter sometimes abbreviated as PET), polypropylene (hereinafter sometimes abbreviated as PP) - ABS is being considered. (For example, see Patent Document 1.) In addition, studies have been made on composite recycling of PE-PET and the like using an oxazoline compatibilizer (see, for example, Patent Document 2). Further, studies have been made on the combined recycling of PE-ethylene vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH) (see, for example, Patent Document 3). These documents indicate that the physical properties of composites of PE, PET, EVOH, etc. can be improved by adding a compatibilizer. However, since the recycled resins obtained by these methods do not have sufficient mechanical properties, it is necessary to develop a technology that can further improve the mechanical properties. Furthermore, problems such as increased viscosity, yellowing, and odor lead to poor recyclability, and there are limits to the uses of recycled resin.
本発明は、上記課題に鑑みてなされたものであり、その目的は、リサイクル回収された異種材料の積層体のような複数の樹脂を含むプラスチック材料の脆性を克服し、耐衝撃性や破断伸度を改良することが可能な改質剤として使用することが可能な樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above problems, and its purpose is to overcome the brittleness of plastic materials containing multiple resins, such as recycled laminates of different materials, and to improve impact resistance and fracture elongation. It is an object of the present invention to provide a resin composition that can be used as a modifier that can improve the hardness.
本発明者らは、上記課題を解決すべく鋭意検討した結果、アクリル酸含有量が4mol%以下のエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%以下のエチレン-メタクリル酸共重合体と、アクリル酸含有量が4mol%より大きいエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%より大きいエチレン-メタクリル酸共重合体を含む樹脂組成物が、複数の樹脂成分からなる脆性材料の耐衝撃性や破断伸度を向上させることができる樹脂改質剤として好適に使用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 intensive studies to solve the above problems, the present inventors have found that an ethylene-acrylic acid copolymer with an acrylic acid content of 4 mol% or less, or an ethylene-methacrylic acid copolymer with a methacrylic acid content of 4 mol% or less and a resin composition containing an ethylene-acrylic acid copolymer having an acrylic acid content of more than 4 mol%, or an ethylene-methacrylic acid copolymer having a methacrylic acid content of more than 4 mol%, consisting of a plurality of resin components. The present inventors have discovered that the present invention can be suitably used as a resin modifier that can improve the impact resistance and elongation at break of brittle materials, and have completed the present invention.
本発明の各態様は、以下に示す[1]~[14]である。
[1] 下記成分(1)及び(2)を含む樹脂組成物(A)。
(1)アクリル酸含有量が4mol%以下のエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%以下のエチレン-メタクリル酸共重合体(a1)
(2)アクリル酸含有量が4mol%より大きいエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%より大きいエチレン-メタクリル酸共重合体(a2)
[2] さらに、前記(1)及び(2)と異なるアクリル酸又はメタクリル酸含有量であるエチレン-アクリル酸共重合体またはエチレン-メタクリル酸共重合体を含む上記[1]に記載の樹脂組成物(A)。
[3] 前記(1)及び(2)のアクリル酸又はメタクリル酸含有量の差が、1mol%以上6.5mol%以下である、上記[1]又は[2]に記載の樹脂組成物(A)。
[4] 架橋剤(a3)を含む上記[1]乃至[3]のいずれかに記載の樹脂組成物(A)。
[5] 上記[1]乃至[4]のいずれかに記載の樹脂組成物(A)を含む改質剤。
[6] 上記[1]乃至[4]のいずれかに記載の樹脂組成物(A)を1重量%以上50重量%以下、及び熱可塑性樹脂(B)を50重量%以上99重量%以下(ここで(B)及び(A)の合計は100重量%とする)含む樹脂組成物。
[7] 熱可塑性樹脂(B)がポリオレフィン系樹脂、アクリル酸系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリカーボネート樹脂、ポリスチレン樹脂及びスチレン-アクリロニトリル共重合体からなる群より選ばれる少なくとも1種である、上記[6]に記載の樹脂組成物。
[8] 熱可塑性樹脂(B)が高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレン-ビニルアルコール共重合体、ナイロン6、ナイロン6,6、ナイロン11、ナイロン12、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタラート樹脂、ポリブチレンテレフタレート、ポリ乳酸(ポリ-L-乳酸、ポリ-D-乳酸、L-乳酸とD-乳酸の共重合体、ポリL-乳酸とポリD-乳酸のステレオコンプレックスを含む)及びポリブチレンサクシネートからなる群より選ばれる少なくとも1種である、上記[6]に記載の樹脂組成物。
[9] 熱可塑性樹脂(B)が高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体からなる群より選ばれる少なくとも1種と、エチレン-ビニルアルコール共重合体、ナイロン6、ナイロン6,6、ナイロン11、ナイロン12、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタラート樹脂及びポリブチレンテレフタレートからなる群より選ばれる少なくとも1種をそれぞれ含む、上記[6]に記載の樹脂組成物。
[10] 熱可塑性樹脂(B)が2種以上の樹脂である、上記[6]乃至[9]のいずれかに記載の樹脂組成物。
[11] 熱可塑性樹脂(B)が使用済みの成形体である、上記[6]乃至[10]のいずれかに記載の樹脂組成物。
[12] 熱可塑性樹脂(B)と上記[5]に記載の改質剤を二軸押出機で混練する混練工程を有する上記[6]乃至[11]のいずれかに記載の樹脂組成物の製造方法。
[13] 混練工程を二軸押出機のスクリュ回転数が50rpm以上3000rpm以下の条件で行う、上記[12]に記載の樹脂組成物の製造方法。
[14] 上記[6]乃至[11]のいずれかに記載の樹脂組成物を成形して得られる成形体。
Each aspect of the present invention is [1] to [14] shown below.
[1] A resin composition (A) containing the following components (1) and (2).
(1) Ethylene-acrylic acid copolymer with acrylic acid content of 4 mol% or less, or ethylene-methacrylic acid copolymer with methacrylic acid content of 4 mol% or less (a1)
(2) Ethylene-acrylic acid copolymer with an acrylic acid content of more than 4 mol% or an ethylene-methacrylic acid copolymer with a methacrylic acid content of more than 4 mol% (a2)
[2] The resin composition according to [1] above, further comprising an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer having an acrylic acid or methacrylic acid content different from those in (1) and (2) above. Object (A).
[3] The resin composition (A ).
[4] The resin composition (A) according to any one of [1] to [3] above, containing a crosslinking agent (a3).
[5] A modifier comprising the resin composition (A) according to any one of [1] to [4] above.
[6] 1% to 50% by weight of the resin composition (A) according to any one of [1] to [4] above, and 50% to 99% by weight of the thermoplastic resin (B) ( Here, the total of (B) and (A) is 100% by weight).
[7] The thermoplastic resin (B) is at least one selected from the group consisting of polyolefin resins, acrylic acid resins, polyamide resins, polyester resins, polycarbonate resins, polystyrene resins, and styrene-acrylonitrile copolymers. , the resin composition according to [6] above.
[8] Thermoplastic resin (B) is high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, Nylon 11, Nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin, polybutylene terephthalate, polylactic acid (poly-L-lactic acid, poly-D-lactic acid, copolymer of L-lactic acid and D-lactic acid, poly-L-lactic acid) The resin composition according to the above [6], which is at least one selected from the group consisting of a stereocomplex of lactic acid and polyD-lactic acid) and polybutylene succinate.
[9] The thermoplastic resin (B) is at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, and ethylene-propylene copolymer, and ethylene-vinyl alcohol copolymer. The resin according to [6] above, each containing at least one member selected from the group consisting of nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin, and polybutylene terephthalate. Composition.
[10] The resin composition according to any one of [6] to [9] above, wherein the thermoplastic resin (B) is two or more kinds of resins.
[11] The resin composition according to any one of [6] to [10] above, wherein the thermoplastic resin (B) is a used molded article.
[12] The resin composition according to any one of [6] to [11] above, which has a kneading step of kneading the thermoplastic resin (B) and the modifier according to [5] above in a twin-screw extruder. Production method.
[13] The method for producing a resin composition according to [12] above, wherein the kneading step is performed under conditions where the screw rotation speed of the twin-screw extruder is 50 rpm or more and 3000 rpm or less.
[14] A molded article obtained by molding the resin composition according to any one of [6] to [11] above.
本発明によれば、耐衝撃性や破断伸度の改質効果に優れて、これらの物性を要求される樹脂成形品の改質剤として有用な樹脂組成物を提供することができる。特に、該樹脂組成物を用いることにより、複数の樹脂を含むプラスチック廃棄物のマテリアルリサイクルを有効に行うことが可能である。 According to the present invention, it is possible to provide a resin composition that is excellent in the effect of modifying impact resistance and elongation at break and is useful as a modifier for resin molded products that require these physical properties. In particular, by using the resin composition, it is possible to effectively perform material recycling of plastic waste containing a plurality of resins.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be explained in detail based on its preferred embodiments.
本発明の一態様である樹脂組成物(A)は、アクリル酸含有量が4mol%以下のエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%以下のエチレン-メタクリル酸共重合体(a1)(以下、「共重合体(a1)」という)と、アクリル酸含有量が4mol%より大きいエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%より大きいエチレン-メタクリル酸共重合体(a2)(以下、「共重合体(a2)」という)を含む。 The resin composition (A), which is an embodiment of the present invention, is an ethylene-acrylic acid copolymer having an acrylic acid content of 4 mol% or less, or an ethylene-methacrylic acid copolymer having a methacrylic acid content of 4 mol% or less ( a1) (hereinafter referred to as "copolymer (a1)"), and an ethylene-acrylic acid copolymer with an acrylic acid content of more than 4 mol%, or an ethylene-methacrylic acid copolymer with a methacrylic acid content of more than 4 mol%. Copolymer (a2) (hereinafter referred to as "copolymer (a2)").
エチレン-アクリル酸共重合体(以下、EAAと略すことがある。)は市販品の中から便宜選択することができ、SKグローバルケミカルからプリマコ-ルの商品名で、ハネウェルからA-Cの商品名で市販されている。 Ethylene-acrylic acid copolymer (hereinafter sometimes abbreviated as EAA) can be conveniently selected from commercially available products, such as SK Global Chemical under the trade name Primacol and Honeywell under the trade name A-C. It is marketed under the name
エチレン-メタクリル酸共重合体(以下、EMAAと略すことがある。)は市販品の中から便宜選択することができ、三井・ダウポリケミカル株式会社からニュクレルの商品名で販売されている。 Ethylene-methacrylic acid copolymer (hereinafter sometimes abbreviated as EMAA) can be conveniently selected from commercially available products, and is sold by Mitsui Dow Polychemical Co., Ltd. under the trade name Nucrel.
共重合体(a1)において、エチレン-アクリル酸共重合体のアクリル酸含有量、又はエチレン-メタクリル酸共重合体のメタクリル酸含有量は4mol%以下である。これにより、熱可塑性樹脂(B)中のポリオレフィンとの相溶性が向上する。 In the copolymer (a1), the acrylic acid content of the ethylene-acrylic acid copolymer or the methacrylic acid content of the ethylene-methacrylic acid copolymer is 4 mol% or less. This improves the compatibility with the polyolefin in the thermoplastic resin (B).
共重合体(a2)において、エチレン-アクリル酸共重合体のアクリル酸含有量、又はエチレン-メタクリル酸共重合体のメタクリル酸含有量は4mol%より大きく、好ましくは6mol%以上、更に好ましくは8mol%以上である。これにより、熱可塑性樹脂(B)中のポリエステルやポリアミド(以下、PAと略すことがある。)などの高極性成分との相溶性が向上する。 In the copolymer (a2), the acrylic acid content of the ethylene-acrylic acid copolymer or the methacrylic acid content of the ethylene-methacrylic acid copolymer is greater than 4 mol%, preferably 6 mol% or more, and more preferably 8 mol%. % or more. This improves compatibility with highly polar components such as polyester and polyamide (hereinafter sometimes abbreviated as PA) in the thermoplastic resin (B).
樹脂組成物(A)は、さらに前記(1)及び(2)と異なるアクリル酸又はメタクリル酸含有量であるエチレン-アクリル酸共重合体またはエチレン-メタクリル酸共重合体を含むことが好ましい。 It is preferable that the resin composition (A) further contains an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer having a different acrylic acid or methacrylic acid content from the above-mentioned (1) and (2).
樹脂組成物(A)において、各アクリル酸又はメタクリル酸の含有量差はすべて0.1mol%以上であることが好ましく、0.5mol%以上であることがさらに好ましい。これにより、樹脂組成物(A)を改質剤として熱可塑性樹脂(B)に配合した際に相溶性がより向上し、得られる組成物の耐衝撃性及び破断伸びが向上する。 In the resin composition (A), the difference in content of each acrylic acid or methacrylic acid is preferably 0.1 mol% or more, more preferably 0.5 mol% or more. Thereby, when the resin composition (A) is blended into the thermoplastic resin (B) as a modifier, the compatibility is further improved, and the impact resistance and elongation at break of the resulting composition are improved.
また、共重合体(a1)と共重合体(a2)のアクリル酸又はメタクリル酸含有量の差が、好ましくは1mol%以上6.5mol%以下、より好ましくは1mol%以上5.5mol%以下である。これにより、樹脂組成物(A)を改質剤として熱可塑性樹脂(B)に配合した際に相溶性がより向上し、得られる組成物の耐衝撃性及び破断伸びが向上する。 Further, the difference in acrylic acid or methacrylic acid content between copolymer (a1) and copolymer (a2) is preferably 1 mol% or more and 6.5 mol% or less, more preferably 1 mol% or more and 5.5 mol% or less. be. Thereby, when the resin composition (A) is blended into the thermoplastic resin (B) as a modifier, the compatibility is further improved, and the impact resistance and elongation at break of the resulting composition are improved.
樹脂組成物(A)において、共重合体(a1)と共重合体(a2)の混合比率は、共重合体(a1)を50重量%以上99重量%以下、共重合体(a2)を1重量%以上50重量%以下(ここで(a1)及び(a2)の合計は100重量%とする)含むことが好ましく、共重合体(a1)を60重量%以上90重量%以下、共重合体(a2)を10重量%以上40重量%以下(ここで(a1)及び(a2)の合計は100重量%とする)含むことが好ましい。これにより、配合した樹脂の相溶性および耐衝撃性をより向上させる。 In the resin composition (A), the mixing ratio of copolymer (a1) and copolymer (a2) is 50% to 99% by weight of copolymer (a1) and 1% to 99% by weight of copolymer (a2). It preferably contains 60% by weight or more and 50% by weight or less (here, the total of (a1) and (a2) is 100% by weight), and contains 60% by weight or more and 90% by weight or less of copolymer (a1). It is preferable that (a2) is contained in an amount of 10% by weight or more and 40% by weight or less (here, the total of (a1) and (a2) is 100% by weight). This further improves the compatibility and impact resistance of the blended resin.
樹脂組成物(A)において、(a1)及び(a2)の架橋変性処理を行っても良い。ここで架橋変性処理は、架橋剤を前記樹脂組成物(A)に添加し、溶融混練処理する方法、電子線照射による方法を例示することができ、溶融混錬する方法で処理した架橋変性体であることが好ましい。溶融混練法を用いる場合、架橋剤(a3)を含むことが好ましい。架橋剤(a3)としては、エポキシ化合物、有機過酸化物、多官能イソシアネート化合物、アジリジン基含有化合物、カルボジイミド、オキサゾリン、アミノ樹脂などが挙げられ、なかでもエポキシ化合物、有機過酸化物が反応性の観点から好ましく用いられる。 In the resin composition (A), the crosslinking modification treatments (a1) and (a2) may be performed. Here, examples of the crosslinking modification treatment include a method of adding a crosslinking agent to the resin composition (A) and melt-kneading the resin composition, and a method of electron beam irradiation. It is preferable that When using the melt-kneading method, it is preferable to include a crosslinking agent (a3). Examples of the crosslinking agent (a3) include epoxy compounds, organic peroxides, polyfunctional isocyanate compounds, aziridine group-containing compounds, carbodiimides, oxazolines, and amino resins, among which epoxy compounds and organic peroxides are reactive. It is preferably used from this point of view.
エポキシ化合物や有機過酸化物であれば特に限定されず、例えば、エポキシ化合物であれば、少なくとも1つのエポキシ基を有する化合物であれば、特に限定されない。エポキシ化合物としては、例えば、ビスフェノールAジグリシジルエーテル、ビスフェノールFジグリシジルエーテル、水添ビスフェノールAジグリシジルエーテル、水添ビスフェノールFジグリシジルエーテル、ノボラックグリシジルエーテル、グリセリンポリグリシジルエーテルなどが挙げられる。 It is not particularly limited as long as it is an epoxy compound or an organic peroxide. For example, if it is an epoxy compound, it is not particularly limited as long as it has at least one epoxy group. Examples of the epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, novolac glycidyl ether, and glycerin polyglycidyl ether.
有機過酸化物は、ジクミルペルオキシド、ジt-ブチルペルオキシド、2,5-ジメチル-2,5-ジ(t-ブチルペルオキシ)ヘキサン、1、1ージ(tーブチルペルオキシ)シクロヘキサン、2,5-ジメチル-2,5-ジ(t-ブチルペルオキシ)ヘキシン-3、1,3-ビス(t-ブチルペルオキシイソプロピル)ベンゼン、1,1-ビス(t-ブチルペルオキシ)-3,3,5-トリメチルシクロヘキサン、1,3-ジ-(t-ブチルペルオキシ)-ジイソプロピルベンゼン、n-ブチル-4,4-ビス(t-ブチルペルオキシ)バレレート、ベンゾイルペルオキシド、p-クロロベンゾイルペルオキシド、2,4-ジクロロベンゾイルペルオキシド、t-ブチルペルオキシベンゾエート、t-ブチルペルオキシイソプロピルカーボネート、ジアセチルペルオキシド、ラウロイルペルオキシド、t-ブチルクミルペルオキシドなどが挙げることができる。 The organic peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di(t-butylperoxy)cyclohexane, 2, 5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy)-3,3,5 -trimethylcyclohexane, 1,3-di-(t-butylperoxy)-diisopropylbenzene, n-butyl-4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4- Examples include dichlorobenzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and t-butyl cumyl peroxide.
これらは単独或いは2種類以上を混合して使用することができ、樹脂組成物(A)100部に対して、架橋剤(a3)の添加量は、0.001~10部の範囲で調整することが好ましい。 These can be used alone or in combination of two or more, and the amount of the crosslinking agent (a3) added is adjusted in the range of 0.001 to 10 parts with respect to 100 parts of the resin composition (A). It is preferable.
本発明の一態様である改質剤は、樹脂組成物(A)を含むものである。 A modifier that is one embodiment of the present invention contains a resin composition (A).
改質剤を配合する熱可塑性樹脂組成物(B)としては、改質剤との相容性に優れることから、ポリオレフィン系樹脂、アクリル酸系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリカーボネート樹脂、ポリスチレン樹脂及びスチレン-アクリロニトリル共重合体からなる群より選ばれる少なくとも1種が好ましく、少なくとも2種がより好ましい。 As the thermoplastic resin composition (B) in which the modifier is blended, polyolefin resins, acrylic acid resins, polyamide resins, polyester resins, polycarbonate resins, At least one kind selected from the group consisting of polystyrene resin and styrene-acrylonitrile copolymer is preferred, and at least two kinds are more preferred.
ポリオレフィン系樹脂としては、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレン-ビニルアルコール共重合体、エチレンーアクリル酸エステル共重合体、エチレンーメタクリル酸エステル共重合体、ポリブタジエン、ポリイソプレンなどが挙げられる。 Examples of polyolefin resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid ester copolymer, and ethylene-methacrylate. Examples include acid ester copolymers, polybutadiene, and polyisoprene.
アクリル酸系樹脂としては、ポリアクリル酸、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ブチル、ポリアクリル酸オクチル、ポリメタクリル酸、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ブチル、ポリメタクリル酸オクチルなどが挙げられる。 Examples of acrylic acid resins include polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyoctyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, Examples include polyoctyl methacrylate.
ポリアミド系樹脂としては、ナイロン6、ナイロン6,6、ナイロン11、ナイロン12などが挙げられる。 Examples of the polyamide resin include nylon 6, nylon 6,6, nylon 11, and nylon 12.
ポリエステル樹脂としては、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタラート樹脂(PETG樹脂)、ポリブチレンテレフタレート、ポリ乳酸(ポリ-L-乳酸、ポリ-D-乳酸、L-乳酸とD-乳酸の共重合体、ポリL-乳酸とポリD-乳酸のステレオコンプレックスを含む)、ポリブチレンサクシネート、ポリ(ブチレンサクシネート/アジペート)、ポリエチレンサクシネート、ポリ(ブチレンサクシネート/テレフタレート)、ポリ(ブチレンアジペート/テレフタレート)、ポリ(ヒドロキシブチレート/ヒドロキシヘキサノエート)、ポリグリコール酸、ポリ3-ヒドロキシブチレート、ポリカプロラクトンなどが挙げられる。 Examples of polyester resins include polyethylene terephthalate, glycol-modified polyethylene terephthalate resin (PETG resin), polybutylene terephthalate, polylactic acid (poly-L-lactic acid, poly-D-lactic acid, copolymer of L-lactic acid and D-lactic acid, poly(L-lactic acid and poly(D-lactic acid) stereocomplex), polybutylene succinate, poly(butylene succinate/adipate), polyethylene succinate, poly(butylene succinate/terephthalate), poly(butylene adipate/terephthalate) , poly(hydroxybutyrate/hydroxyhexanoate), polyglycolic acid, poly3-hydroxybutyrate, polycaprolactone, and the like.
この中で、樹脂組成物(A)とブレンドした場合に耐衝撃性や破断伸びの改良性が大きいことから、熱可塑性樹脂(B)を構成する熱可塑性樹脂としては、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレン-ビニルアルコール共重合体、ナイロン6、ナイロン6,6、ナイロン11、ナイロン12、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタラート樹脂(PETG樹脂)、ポリブチレンテレフタレート、ポリ乳酸(ポリ-L-乳酸、ポリ-D-乳酸、L-乳酸とD-乳酸の共重合体、ポリL-乳酸とポリD-乳酸のステレオコンプレックスを含む)及びポリブチレンサクシネートからなる群より選ばれる少なくとも1種が好ましい。 Among these, the thermoplastic resins constituting the thermoplastic resin (B) are high-density polyethylene, low-density polyethylene, and Polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, nylon 11, nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin ( PETG resin), polybutylene terephthalate, polylactic acid (including poly-L-lactic acid, poly-D-lactic acid, copolymers of L-lactic acid and D-lactic acid, stereocomplex of poly-L-lactic acid and poly-D-lactic acid) and at least one selected from the group consisting of polybutylene succinate.
より好ましくは、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体からなる群より選ばれる少なくとも1種と、エチレン-ビニルアルコール共重合体、ナイロン6、ナイロン6,6、ナイロン11、ナイロン12、ポリエチレンテレフタレート、グリコール変性ポリエチレンテレフタラート樹脂及びポリブチレンテレフタレートからなる群より選ばれる少なくとも1種をそれぞれ含むことが望ましい。
熱可塑性樹脂(B)は、未使用のバージン樹脂、使用済みの成形体を回収して得られた樹脂でもよい。すなわち、1種又は複数種の樹脂のすべてが未使用の樹脂である形態、1種又は複数種の樹脂のうちの少なくとも1種が使用済みの樹脂である形態が含まれ、1種又は複数種の樹脂のすべてが使用済みの樹脂である形態も含まれる。
More preferably, at least one selected from the group consisting of high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, and ethylene-propylene copolymer, and ethylene-vinyl alcohol copolymer, nylon 6, and nylon. It is desirable that the resin contains at least one selected from the group consisting of 6,6, nylon 11, nylon 12, polyethylene terephthalate, glycol-modified polyethylene terephthalate resin, and polybutylene terephthalate.
The thermoplastic resin (B) may be an unused virgin resin or a resin obtained by collecting used molded bodies. That is, it includes a form in which all of the one or more resins are unused resins, a form in which at least one of the one or more resins is a used resin, and one or more resins. This also includes a form in which all of the resin in the resin is used resin.
熱可塑性樹脂(B)は、使用済みの成形体を回収して得られた樹脂を使用する場合、複数種類の樹脂を含むことがある。この場合、不純物として塩ビ樹脂、ワックス、接着剤、可塑剤、酸化防止剤等の有機物の不純物として含む。一方、フィラーなどの無機不純物を含むこともある。 The thermoplastic resin (B) may contain a plurality of types of resins when a resin obtained by collecting used molded bodies is used. In this case, organic impurities such as vinyl chloride resin, wax, adhesive, plasticizer, and antioxidant are included as impurities. On the other hand, it may also contain inorganic impurities such as fillers.
樹脂組成物(A)と熱可塑性樹脂(B)との混合比率は、熱可塑性樹脂(B)を50重量%以上99重量%以下、樹脂組成物(A)を1重量%以上50重量%以下含むことが好ましい。熱可塑性樹脂(B)を99重量%以下含むことで得られる樹脂組成物は耐衝撃性に優れたものとなる。一方、熱可塑性樹脂(B)を50重量%以上含むことで得られる樹脂組成物が剛性に優れたものとなる。さらに好ましくは熱可塑性樹脂(B)を60重量%以上95重量%以下、樹脂組成物(A)を5重量%以上40重量%含み、またさらに好ましくは熱可塑性樹脂(B)を70重量%以上95重量%以下、樹脂組成物(A)を5重量%以上30重量%含む。 The mixing ratio of the resin composition (A) and the thermoplastic resin (B) is 50% to 99% by weight of the thermoplastic resin (B) and 1% to 50% by weight of the resin composition (A). It is preferable to include. A resin composition obtained by containing 99% by weight or less of the thermoplastic resin (B) has excellent impact resistance. On the other hand, a resin composition obtained by containing 50% by weight or more of the thermoplastic resin (B) has excellent rigidity. More preferably, the content of the thermoplastic resin (B) is 60% by weight or more and 95% by weight or less, the resin composition (A) is 5% by weight or more and 40% by weight, and even more preferably the thermoplastic resin (B) is 70% by weight or more. It contains 95% by weight or less, and 5% by weight or more and 30% by weight of the resin composition (A).
樹脂組成物(A)を含む改質剤を熱可塑性樹脂(B)に配合する場合、改質剤と熱可塑性樹脂(B)を混練する混練工程を有する製造方法により製造することができる。 When blending the modifier containing the resin composition (A) with the thermoplastic resin (B), it can be produced by a manufacturing method that includes a kneading step of kneading the modifier and the thermoplastic resin (B).
混練方法としては、改質剤と熱可塑性樹脂(B)を構成する各種材料を同時に混練装置で混練する方法と、改質剤のみを事前に混練し、その後熱可塑性樹脂(B)と混練した改質剤をブレンドし更に混練する方法が挙げられる。後者の方が、改質剤がより均一に混ざり、所望の物性が安定して得られることから好ましい。 As for the kneading method, the modifier and various materials constituting the thermoplastic resin (B) were kneaded simultaneously in a kneading device, and the modifier alone was kneaded in advance and then kneaded with the thermoplastic resin (B). Examples include a method of blending a modifier and further kneading. The latter is preferable because the modifier is mixed more uniformly and the desired physical properties can be stably obtained.
混練装置としては、各成分を均一に分散できれば特に制限はなく、通常用いられる樹脂の混練装置により製造することができる。例えば、単軸押出機、二軸押出機、多軸押出機、バンバリーミキサー、加圧ニーダ-、回転ロール、インターナルミキサーなどの混練装置が挙げられる。この中で、分散性および連続生産性に優れることから、二軸押出機がより好ましい。 The kneading device is not particularly limited as long as each component can be uniformly dispersed, and the kneading device can be manufactured using a commonly used resin kneading device. Examples include kneading devices such as a single screw extruder, a twin screw extruder, a multi-screw extruder, a Banbury mixer, a pressure kneader, a rotating roll, and an internal mixer. Among these, a twin-screw extruder is more preferred because it has excellent dispersibility and continuous productivity.
二軸押出機で混練を行う場合のスクリュ回転数は特に制限されないが、50rpm以上3000rpm以下で混練することが好ましく、より好ましくは300rpm以上3000rpm以下である。スクリュ回転数50rpm以上であれば混合した各成分の分散性が向上し、得られた樹脂の物性に優れるため好ましく、スクリュ回転数3000rpm以下であれば過剰なせん断発熱による樹脂の劣化が生じないことから、得られた樹脂の物性に優れるため好ましい。 The screw rotation speed when performing kneading with a twin-screw extruder is not particularly limited, but kneading is preferably performed at 50 rpm or more and 3000 rpm or less, more preferably 300 rpm or more and 3000 rpm or less. A screw rotation speed of 50 rpm or more is preferable because the dispersibility of each mixed component is improved and the resulting resin has excellent physical properties, and a screw rotation speed of 3000 rpm or less does not cause deterioration of the resin due to excessive shear heat generation. This is preferred because the resulting resin has excellent physical properties.
混練工程において押出機を使用する場合、押出機で混練した樹脂組成物、好ましくは前記50rpm以上3000rpm以下の高速せん断条件で混練した樹脂組成物を原料として用いることができる。また、そのまま押出機で押出成形することで得られる成形体を成形品として用いることができる。 When an extruder is used in the kneading step, a resin composition kneaded with an extruder, preferably a resin composition kneaded under the above-mentioned high-speed shearing conditions of 50 rpm or more and 3000 rpm or less, can be used as a raw material. Moreover, a molded article obtained by extrusion molding with an extruder as it is can be used as a molded article.
混練温度は熱可塑性樹脂(B)の中で最も融点が低い成分の融点または非晶性樹脂であればガラス転移温度~300℃程度が好ましい。 The kneading temperature is preferably the melting point of the component with the lowest melting point among the thermoplastic resins (B) or the glass transition temperature to about 300° C. if it is an amorphous resin.
樹脂組成物(A)と、熱可塑性樹脂(B)を含む樹脂組成物は、本発明の効果を損なわない範囲で、帯電防止剤、光安定剤、紫外線吸収剤、造核剤、滑剤、酸化防止剤、ブロッキング防止剤、流動性改良剤、離型剤、難燃剤、着色剤、無機系中和剤、塩酸吸収剤、充填剤導電剤、鎖長延長剤、加水分解防止剤等が用いられても良い。 The resin composition (A) and the resin composition containing the thermoplastic resin (B) may contain antistatic agents, light stabilizers, ultraviolet absorbers, nucleating agents, lubricants, and oxidation agents to the extent that the effects of the present invention are not impaired. Inhibitors, anti-blocking agents, fluidity improvers, mold release agents, flame retardants, colorants, inorganic neutralizers, hydrochloric acid absorbers, filler conductive agents, chain extenders, hydrolysis inhibitors, etc. are used. It's okay.
上記樹脂組成物が樹脂組成物(A)と熱可塑性樹脂(B)以外の成分を含む場合、その含有量は、(A)と(B)の合計を100重量部とし、その100重量部に対する添加量として表すことができる。換言すると、前記(A)、(B)の「~重量%」という表記は(A)、(B)の比率であり、それ以外の成分の比率は別に定義することができる。 When the resin composition contains components other than the resin composition (A) and the thermoplastic resin (B), the content is based on 100 parts by weight of the total of (A) and (B). It can be expressed as the amount added. In other words, the expression "~% by weight" in (A) and (B) above is the ratio of (A) and (B), and the ratios of other components can be defined separately.
また上記樹脂組成物は、ペレットやパウダーなどの任意の形態にしておいて使用することができる。 Further, the resin composition can be used in any form such as pellets or powder.
本発明の一態様である成形品は、上記樹脂組成物を成形して得られるものである。樹脂組成物の成形方法は任意であり、例えば異形押出、フィルム、シート、ブロー、射出、発泡、押出コーティング、回転成形などが挙げられる。成形品は、自動車部品、電気・電子部品の筐体、建材、土木部材、農業資材、容器、包装資材、接着剤、日用品など各種用途に利用することができる。 A molded article that is one embodiment of the present invention is obtained by molding the above resin composition. The resin composition may be formed by any method, including profile extrusion, film, sheet, blowing, injection, foaming, extrusion coating, rotational molding, and the like. Molded products can be used for various purposes such as automobile parts, housings for electrical and electronic parts, building materials, civil engineering materials, agricultural materials, containers, packaging materials, adhesives, and daily necessities.
以下、実施例および比較例により本発明を説明するが、本発明はこれらに限定されるものではない。
(1)メルトマスフローレイト(MFR)
エチレン-酢酸ビニル共重合体、エチレン-アクリル酸共重合体、エチレン-メタクリル酸共重合体、および熱可塑性樹脂(B)のMFRは、メルトインデクサー(宝工業製)にて190℃、2.16kg荷重の条件にて測定した。
(2)衝撃強度
衝撃強度はJIS P 8134に準拠して測定した。プレス成型した厚み0.1mmのシートをフィルムインパクトテスタ(東洋精機製、FT-M型)にて、試験容量3J、突き刺し先端半球状ハンマーの条件にて測定した。
(3)引張試験
プレス成型した厚み0.1mmのシートをASTM D-1822-L ダンベル状試験片に打ち抜いた。試験片のサイズは、全長63.5mm、平行部長さ9.53mm、平行部幅3.18mm、厚さ0.1mm、つかみ部幅9.53mmであった。試験片をテンシロン引張試験機(オリエンテック製、RTE-1210)にて、チャック間距離30mm、引張速度200mm/分の条件で測定した。試料が破断した点を破断伸度(破断伸度[%]=破断に要した引張長さ[mm]/チャック間距離30mm)、破断したときの応力を破断応力とした。
The present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
(1) Melt mass flow rate (MFR)
The MFR of the ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and thermoplastic resin (B) was measured at 190°C with a melt indexer (manufactured by Takara Kogyo) at 2. Measurement was performed under the condition of 16 kg load.
(2) Impact strength Impact strength was measured in accordance with JIS P 8134. A press-molded sheet with a thickness of 0.1 mm was measured using a film impact tester (manufactured by Toyo Seiki, Model FT-M) under the conditions of a test capacity of 3 J and a hemispherical hammer tip.
(3) Tensile test A press-molded sheet with a thickness of 0.1 mm was punched out into an ASTM D-1822-L dumbbell-shaped test piece. The size of the test piece was 63.5 mm in total length, 9.53 mm in parallel part length, 3.18 mm in parallel part width, 0.1 mm in thickness, and 9.53 mm in grip part width. The test piece was measured using a Tensilon tensile tester (manufactured by Orientec, RTE-1210) under conditions of a chuck distance of 30 mm and a tensile speed of 200 mm/min. The point at which the sample broke was taken as the elongation at break (elongation at break [%] = tensile length required for break [mm]/distance between chucks 30 mm), and the stress at the time of break was taken as the break stress.
実施例1
樹脂組成物(A)として、下記組成の樹脂組成物を用いた。
[樹脂組成物(A)]
・アクリル酸含有量2.6mol%、メルトマスフローレイト2.6g/10分であるエチレン-アクリル酸共重合体(a1-1)(SKグローバルケミカル(株)製 商品名PRIMACOR1321)65重量%
・アクリル酸含有量8.9mol%、メルトマスフローレイト300g/10分であるエチレン-アクリル酸共重合体(a2-1)(SKグローバルケミカル(株)製 商品名PRIMACOR5980I)35重量%
上記樹脂をドライブレンドし、スクリュ径が25mmである二軸押出機(テクノベル製 商品名ULTnano25TW)を用いて、樹脂温度160℃、スクリュ回転数150rpmの条件で溶融混練し、樹脂組成物(A)のペレットを得た。
Example 1
A resin composition having the following composition was used as the resin composition (A).
[Resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-1) having an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 1321) 65% by weight
- Ethylene-acrylic acid copolymer (a2-1) having an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 5980I) 35% by weight
The above resins were dry-blended and melt-kneaded using a twin-screw extruder with a screw diameter of 25 mm (trade name: ULTnano25TW, manufactured by Technovel) at a resin temperature of 160°C and a screw rotation speed of 150 rpm to obtain a resin composition (A). pellets were obtained.
熱可塑性樹脂(B)としては、下記組成の熱可塑性樹脂組成物を用いた。
[熱可塑性樹脂(B)の組成物]
・メルトマスフローレイト3g/10分、融点111℃である低密度ポリエチレン(B-1)(東ソー(株)製 商品名ペトロセン205)70重量%
・エチレン含量35mol%、融点177℃であるエチレン-ビニルアルコール共重合体(B-2)((株)クラレ社製 商品名エバール C109B)30重量%
熱可塑性樹脂(B)の組成物80重量%と樹脂組成物(A)20重量%をドライブレンドし、スクリュ径が25mmである二軸押出機(テクノベル製 商品名ULTnano25TW)を用いて、樹脂温度200℃、スクリュ回転数300rpmの条件で溶融混練し、樹脂組成物を得た。
As the thermoplastic resin (B), a thermoplastic resin composition having the following composition was used.
[Composition of thermoplastic resin (B)]
・Low density polyethylene (B-1) (manufactured by Tosoh Corporation, trade name Petrocene 205) with a melt mass flow rate of 3 g/10 minutes and a melting point of 111° C. 70% by weight
- Ethylene-vinyl alcohol copolymer (B-2) having an ethylene content of 35 mol% and a melting point of 177°C (manufactured by Kuraray Co., Ltd., trade name EVAL C109B) 30% by weight
80% by weight of the thermoplastic resin (B) composition and 20% by weight of the resin composition (A) were dry blended, and the resin temperature was adjusted to A resin composition was obtained by melt-kneading at 200° C. and a screw rotation speed of 300 rpm.
得られた樹脂組成物を、プレス成型機(神藤金属工業所製 AWFA-50型)を用いて、圧力10MPa、加熱温度200℃(一次加圧×3分、二次加圧×3分)、冷却温度25℃(4分)の条件にてプレス成型し、厚み0.1mmのプレスシートを得た。 The obtained resin composition was molded using a press molding machine (AWFA-50 model manufactured by Shindo Metal Industry Co., Ltd.) at a pressure of 10 MPa and a heating temperature of 200°C (primary pressure x 3 minutes, secondary pressure x 3 minutes), Press molding was performed at a cooling temperature of 25° C. (4 minutes) to obtain a pressed sheet with a thickness of 0.1 mm.
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表1に示す。 An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 1.
実施例2
樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は、実施例1と同様の手法によりプレスシートを得た。
[樹脂組成物(A)]
・アクリル酸含有量3.5mol%、メルトマスフローレイト7g/10分であるエチレン-アクリル酸共重合体(a1-2)(SKグローバルケミカル(株)製 商品名PRIMACOR3540)65重量%
・アクリル酸含有量8.9mol%、メルトマスフローレイト300g/10分であるエチレン-アクリル酸共重合体(a2-1)(SKグローバルケミカル(株)製 商品名PRIMACOR5980I)35重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表1に示す。
Example 2
A press sheet was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
[Resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-2) with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 3540) 65% by weight
- Ethylene-acrylic acid copolymer (a2-1) having an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 5980I) 35% by weight
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 1.
実施例3
樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は、実施例1と同様の手法によりプレスシートを得た。
[樹脂組成物(A)]
・アクリル酸含有量2.6mol%、メルトマスフローレイト2.6g/10分であるエチレン-アクリル酸共重合体(a1-1)(SKグローバルケミカル(株)製 商品名PRIMACOR1321)65重量%
・アクリル酸含有量3.5mol%、メルトマスフローレイト7g/10分であるエチレン-アクリル酸共重合体(a1-2)(SKグローバルケミカル(株)製 商品名PRIMACOR3540)10重量%
・アクリル酸含有量8.9mol%、メルトマスフローレイト300g/10分であるエチレン-アクリル酸共重合体(a2-1)(SKグローバルケミカル(株)製 商品名PRIMACOR5980I)25重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表1に示す。
Example 3
A press sheet was obtained in the same manner as in Example 1, except that a resin composition having the following composition was used as the resin composition (A).
[Resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-1) having an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 1321) 65% by weight
- Ethylene-acrylic acid copolymer (a1-2) having an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 3540) 10% by weight
- Ethylene-acrylic acid copolymer (a2-1) having an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 5980I) 25% by weight
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 1.
実施例4
熱可塑性樹脂(B)として下記組成の熱可塑性樹脂組成物を用いた。
[熱可塑性樹脂(B)の組成物]
・メルトマスフローレイト3g/10分、融点111℃である低密度ポリエチレン(B-1)(東ソー(株)製 商品名ペトロセン205)70重量%
・融点220℃であるナイロン6(B-3)(宇部興産(株)製 商品名UBEナイロン1022D)30重量%
熱可塑性樹脂(B)の組成物80重量%と実施例1に記載の樹脂組成物(A)20重量%をドライブレンドし、スクリュ径が25mmである二軸押出機(テクノベル製 商品名ULTnano25TW)を用いて、樹脂温度230℃、スクリュ回転数300rpmの条件で溶融混練し、樹脂組成物を得た。
Example 4
A thermoplastic resin composition having the following composition was used as the thermoplastic resin (B).
[Composition of thermoplastic resin (B)]
・Low density polyethylene (B-1) (manufactured by Tosoh Corporation, trade name Petrocene 205) with a melt mass flow rate of 3 g/10 minutes and a melting point of 111° C. 70% by weight
- Nylon 6 (B-3) with a melting point of 220°C (product name: UBE Nylon 1022D, manufactured by Ube Industries, Ltd.) 30% by weight
80% by weight of the thermoplastic resin (B) composition and 20% by weight of the resin composition (A) described in Example 1 were dry-blended using a twin-screw extruder with a screw diameter of 25 mm (product name: ULTnano25TW, manufactured by Technovel). A resin composition was obtained by melt-kneading under the conditions of a resin temperature of 230° C. and a screw rotation speed of 300 rpm.
得られた樹脂組成物を、プレス成型機(神藤金属工業所製 AWFA-50型)を用いて、圧力10MPa、加熱温度230℃(一次加圧×3分、二次加圧×3分)、冷却温度25℃(4分)の条件にてプレス成型し、厚み0.1mmのプレスシートを得た。 The obtained resin composition was molded using a press molding machine (AWFA-50 model manufactured by Shinto Metal Industry Co., Ltd.) at a pressure of 10 MPa and a heating temperature of 230°C (primary pressure x 3 minutes, secondary pressure x 3 minutes). Press molding was performed at a cooling temperature of 25° C. (4 minutes) to obtain a pressed sheet with a thickness of 0.1 mm.
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表1に示す。 An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 1.
実施例5
熱可塑性樹脂(B)として下記組成の熱可塑性樹脂組成物を用いた。
[熱可塑性樹脂(B)の組成物]
・メルトマスフローレイト3g/10分、融点111℃である低密度ポリエチレン(B-1)(東ソー(株)製 商品名ペトロセン205)70重量%
・融点255℃であるポリエチレンテレフタレート(Bー4)(ユニチカ(株)製 MA-2103)30重量%
熱可塑性樹脂(B)の組成物80重量%と実施例1に記載の樹脂組成物(A)20重量%をドライブレンドし、スクリュ径が25mmである二軸押出機(テクノベル製 商品名ULTnano25TW)を用いて、樹脂温度270℃、スクリュ回転数150rpmの条件で溶融混練し、樹脂組成物を得た。
Example 5
A thermoplastic resin composition having the following composition was used as the thermoplastic resin (B).
[Composition of thermoplastic resin (B)]
・Low density polyethylene (B-1) (manufactured by Tosoh Corporation, trade name Petrocene 205) with a melt mass flow rate of 3 g/10 minutes and a melting point of 111° C. 70% by weight
・30% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Co., Ltd. MA-2103) with a melting point of 255°C
80% by weight of the thermoplastic resin (B) composition and 20% by weight of the resin composition (A) described in Example 1 were dry-blended using a twin-screw extruder with a screw diameter of 25 mm (product name: ULTnano25TW, manufactured by Technovel). A resin composition was obtained by melt-kneading under the conditions of a resin temperature of 270° C. and a screw rotation speed of 150 rpm.
得られた樹脂組成物を、プレス成型機(神藤金属工業所製 AWFA-50型)を用いて、圧力10MPa、加熱温度230℃(一次加圧×3分、二次加圧×3分)、冷却温度25℃(4分)の条件にてプレス成型し、厚み0.1mmのプレスシートを得た。 The obtained resin composition was molded using a press molding machine (AWFA-50 model manufactured by Shinto Metal Industry Co., Ltd.) at a pressure of 10 MPa and a heating temperature of 230°C (primary pressure x 3 minutes, secondary pressure x 3 minutes). Press molding was performed at a cooling temperature of 25° C. (4 minutes) to obtain a pressed sheet with a thickness of 0.1 mm.
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表1に示す。 An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 1.
比較例1
下記の熱可塑性樹脂(B)の組成物のみを用いた以外は、実施例1と同様の手法によりプレスシートを得た。
[熱可塑性樹脂(B)の組成物]
・メルトマスフローレイト3g/10分、融点111℃である低密度ポリエチレン(B-1)(東ソー(株)製 商品名ペトロセン205)70重量%
・エチレン含量35mol%、融点177℃であるエチレン-ビニルアルコール共重合体(B-2)((株)クラレ社製 商品名エバール C109B)30重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表1に示す。
Comparative example 1
A press sheet was obtained in the same manner as in Example 1, except that only the composition of the thermoplastic resin (B) described below was used.
[Composition of thermoplastic resin (B)]
・Low density polyethylene (B-1) (manufactured by Tosoh Corporation, trade name Petrocene 205) with a melt mass flow rate of 3 g/10 minutes and a melting point of 111° C. 70% by weight
- Ethylene-vinyl alcohol copolymer (B-2) having an ethylene content of 35 mol% and a melting point of 177°C (manufactured by Kuraray Co., Ltd., trade name EVAL C109B) 30% by weight
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 1.
比較例2
下記の熱可塑性樹脂(B)の組成物のみを用いた以外は、実施例5と同様の手法によりプレスシートを得た。
[熱可塑性樹脂(B)の組成物]
・メルトマスフローレイト3g/10分、融点111℃である低密度ポリエチレン(B-1)(東ソー(株)製 商品名ペトロセン205)70重量%
・融点255℃であるポリエチレンテレフタレート(Bー4)(ユニチカ(株)製 MA-2103)30重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表1に示す。
Comparative example 2
A press sheet was obtained in the same manner as in Example 5, except that only the composition of the thermoplastic resin (B) described below was used.
[Composition of thermoplastic resin (B)]
・Low density polyethylene (B-1) (manufactured by Tosoh Corporation, trade name Petrocene 205) with a melt mass flow rate of 3 g/10 minutes and a melting point of 111° C. 70% by weight
・30% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Co., Ltd. MA-2103) with a melting point of 255°C
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 1.
実施例6
熱可塑性樹脂(B)として下記組成の熱可塑性樹脂組成物を用いた以外は、実施例5と同様の手法によりプレスシートを得た。
[熱可塑性樹脂(B)の組成物]
・メルトマスフローレイト3g/10分、融点111℃である低密度ポリエチレン(B-1)(東ソー(株)製 商品名ペトロセン205)70重量%
・エチレン含量35mol%、融点177℃であるエチレン-ビニルアルコール共重合体(B-2)((株)クラレ社製 商品名エバール C109B)10重量%
・融点220℃であるナイロン6(B-3)(宇部興産(株)製 商品名UBEナイロン1022D)10重量%
・融点255℃であるポリエチレンテレフタレート(Bー4)(ユニチカ(株)製 MA-2103)10重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。
Example 6
A press sheet was obtained in the same manner as in Example 5, except that a thermoplastic resin composition having the following composition was used as the thermoplastic resin (B).
[Composition of thermoplastic resin (B)]
・Low density polyethylene (B-1) (manufactured by Tosoh Corporation, trade name Petrocene 205) with a melt mass flow rate of 3 g/10 minutes and a melting point of 111° C. 70% by weight
- Ethylene-vinyl alcohol copolymer (B-2) having an ethylene content of 35 mol% and a melting point of 177°C (manufactured by Kuraray Co., Ltd., trade name EVAL C109B) 10% by weight
- Nylon 6 (B-3) with a melting point of 220°C (trade name: UBE Nylon 1022D, manufactured by Ube Industries, Ltd.) 10% by weight
・10% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Co., Ltd. MA-2103) with a melting point of 255°C
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
実施例7
熱可塑性樹脂(B)を65重量%、樹脂組成物(A)を35重量%とした以外は、実施例6と同様の手法によりプレスシートを得た。
Example 7
A press sheet was obtained in the same manner as in Example 6, except that the thermoplastic resin (B) was 65% by weight and the resin composition (A) was 35% by weight.
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。 An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
実施例8
樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は、実施例6と同様の手法によりプレスシートを得た。
[樹脂組成物(A)の組成物]
・アクリル酸含有量2.6mol%、メルトマスフローレイト2.6g/10分であるエチレン-アクリル酸共重合体(a1-1)(SKグローバルケミカル(株)製 商品名PRIMACOR1321)65重量%
・メタクリル酸含有量3.9mol%、メルトマスフローレイト8g/10分であるエチレン-メタクリル酸共重合体(a1-3)(三井・ダウ ポリケミカル(株)製 商品名ニュクレルN1108C)10重量%
・アクリル酸含有量8.9mol%、メルトマスフローレイト300g/10分であるエチレン-アクリル酸共重合体(a2-1)(SKグローバルケミカル(株)製 商品名PRIMACOR5980I)25重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。
Example 8
A press sheet was obtained in the same manner as in Example 6, except that a resin composition having the following composition was used as the resin composition (A).
[Composition of resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-1) having an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 1321) 65% by weight
- Ethylene-methacrylic acid copolymer (a1-3) having a methacrylic acid content of 3.9 mol% and a melt mass flow rate of 8 g/10 min (manufactured by Mitsui Dow Polychemical Co., Ltd., trade name Nuclell N1108C) 10% by weight
- Ethylene-acrylic acid copolymer (a2-1) having an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 5980I) 25% by weight
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
実施例9
樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は、実施例6と同様の手法によりプレスシートを得た。
[樹脂組成物(A)の組成物]
・アクリル酸含有量2.6mol%、メルトマスフローレイト2.6g/10分であるエチレン-アクリル酸共重合体(a1-1)(SKグローバルケミカル(株)製 商品名PRIMACOR1321)45重量%
・アクリル酸含有量3.5mol%、メルトマスフローレイト7g/10分であるエチレン-アクリル酸共重合体(a1-2)(SKグローバルケミカル(株)製 商品名PRIMACOR3540)30重量%
・アクリル酸含有量8.9mol%、メルトマスフローレイト300g/10分であるエチレン-アクリル酸共重合体(a2-1)(SKグローバルケミカル(株)製 商品名PRIMACOR5980I)25重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。
Example 9
A press sheet was obtained in the same manner as in Example 6, except that a resin composition having the following composition was used as the resin composition (A).
[Composition of resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-1) having an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 1321) 45% by weight
- Ethylene-acrylic acid copolymer (a1-2) with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 3540) 30% by weight
- Ethylene-acrylic acid copolymer (a2-1) having an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 5980I) 25% by weight
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
実施例10
樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は、実施例3と同様の手法によりプレスシートを得た。
[樹脂組成物(A)の組成物]
・アクリル酸含有量2.6mol%、メルトマスフローレイト2.6g/10分であるエチレン-アクリル酸共重合体(a1-1)(SKグローバルケミカル(株)製 商品名PRIMACOR1321)65重量%
・アクリル酸含有量3.5mol%、メルトマスフローレイト7g/10分であるエチレン-アクリル酸共重合体(a1-2)(SKグローバルケミカル(株)製 商品名PRIMACOR3540)10重量%
・アクリル酸含有量8.9mol%、メルトマスフローレイト300g/10分であるエチレン-アクリル酸共重合体(a2-1)(SKグローバルケミカル(株)製 商品名PRIMACOR5980I)25重量%
・ビスフェノールAグリシジルエーテル(D3415、Sigma-Aldrich製)0.5部
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。
比較例3
下記の熱可塑性樹脂(B)の組成物のみを用いた以外は、実施例6と同様の手法によりプレスシートを得た。
[熱可塑性樹脂(B)の組成物]
・メルトマスフローレイト3g/10分、融点111℃である低密度ポリエチレン(B-1)(東ソー(株)製 商品名ペトロセン205)70重量%
・エチレン含量35mol%、融点177℃であるエチレン-ビニルアルコール共重合体(B-2)((株)クラレ社製 商品名エバール C109B)10重量%
・融点220℃であるナイロン6(B-3)(宇部興産(株)製 商品名UBEナイロン1022D)10重量%
・融点255℃であるポリエチレンテレフタレート(Bー4)(ユニチカ(株)製 MA-2103)10重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。
Example 10
A press sheet was obtained in the same manner as in Example 3, except that a resin composition having the following composition was used as the resin composition (A).
[Composition of resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-1) having an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 1321) 65% by weight
- Ethylene-acrylic acid copolymer (a1-2) having an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 3540) 10% by weight
- Ethylene-acrylic acid copolymer (a2-1) having an acrylic acid content of 8.9 mol% and a melt mass flow rate of 300 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 5980I) 25% by weight
・Bisphenol A glycidyl ether (D3415, manufactured by Sigma-Aldrich) 0.5 part
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
Comparative example 3
A press sheet was obtained in the same manner as in Example 6, except that only the composition of the thermoplastic resin (B) described below was used.
[Composition of thermoplastic resin (B)]
・Low density polyethylene (B-1) (manufactured by Tosoh Corporation, trade name Petrocene 205) with a melt mass flow rate of 3 g/10 minutes and a melting point of 111° C. 70% by weight
- Ethylene-vinyl alcohol copolymer (B-2) having an ethylene content of 35 mol% and a melting point of 177°C (manufactured by Kuraray Co., Ltd., trade name EVAL C109B) 10% by weight
- Nylon 6 (B-3) with a melting point of 220°C (trade name: UBE Nylon 1022D, manufactured by Ube Industries, Ltd.) 10% by weight
・10% by weight of polyethylene terephthalate (B-4) (manufactured by Unitika Co., Ltd. MA-2103) with a melting point of 255°C
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
比較例4
樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は、実施例6と同様の手法によりプレスシートを得た。
[樹脂組成物(A)の組成物]
・アクリル酸含有量2.6mol%、メルトマスフローレイト2.6g/10分であるエチレン-アクリル酸共重合体(a1-1)(SKグローバルケミカル(株)製 商品名PRIMACOR1321)100重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。
Comparative example 4
A press sheet was obtained in the same manner as in Example 6, except that a resin composition having the following composition was used as the resin composition (A).
[Composition of resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-1) with an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 1321) 100% by weight
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
比較例5
樹脂組成物(A)として下記組成の樹脂組成物を用いた以外は、実施例6と同様の手法によりプレスシートを得た。
[樹脂組成物(A)の組成物]
・アクリル酸含有量2.6mol%、メルトマスフローレイト2.6g/10分であるエチレン-アクリル酸共重合体(a1-1)(SKグローバルケミカル(株)製 商品名PRIMACOR1321)65重量%
・アクリル酸含有量3.5mol%、メルトマスフローレイト7g/10分であるエチレン-アクリル酸共重合体(a1-2)(SKグローバルケミカル(株)製 商品名PRIMACOR3540)35重量%
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。
Comparative example 5
A press sheet was obtained in the same manner as in Example 6, except that a resin composition having the following composition was used as the resin composition (A).
[Composition of resin composition (A)]
- Ethylene-acrylic acid copolymer (a1-1) having an acrylic acid content of 2.6 mol% and a melt mass flow rate of 2.6 g/10 min (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 1321) 65% by weight
- Ethylene-acrylic acid copolymer (a1-2) with an acrylic acid content of 3.5 mol% and a melt mass flow rate of 7 g/10 minutes (manufactured by SK Global Chemical Co., Ltd., trade name PRIMACOR 3540) 35% by weight
An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
比較例6
熱可塑性樹脂(B)を40重量%、樹脂組成物(A)を60重量%とした以外は、実施例6と同様の手法によりプレスシートを得た。
Comparative example 6
A press sheet was obtained in the same manner as in Example 6, except that the thermoplastic resin (B) was 40% by weight and the resin composition (A) was 60% by weight.
得られたプレスシートを用いて、衝撃試験と引張試験を実施した。評価の結果を表2に示す。 An impact test and a tensile test were conducted using the obtained press sheet. The results of the evaluation are shown in Table 2.
本発明の樹脂組成物からなる成形品は、自動車部品、電気・電子部品の筐体、建材、土木部材、農業資材、容器、包装資材、接着剤、日用品など各種用途に利用することができる。 Molded articles made of the resin composition of the present invention can be used for various purposes such as automobile parts, housings for electrical and electronic parts, building materials, civil engineering members, agricultural materials, containers, packaging materials, adhesives, and daily necessities.
Claims (14)
(1)アクリル酸含有量が4mol%以下のエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%以下のエチレン-メタクリル酸共重合体(a1)
(2)アクリル酸含有量が4mol%より大きいエチレン-アクリル酸共重合体、又はメタクリル酸含有量が4mol%より大きいエチレン-メタクリル酸共重合体(a2) A resin composition (A) containing the following components (1) and (2).
(1) Ethylene-acrylic acid copolymer with acrylic acid content of 4 mol% or less, or ethylene-methacrylic acid copolymer with methacrylic acid content of 4 mol% or less (a1)
(2) Ethylene-acrylic acid copolymer with an acrylic acid content of more than 4 mol% or an ethylene-methacrylic acid copolymer with a methacrylic acid content of more than 4 mol% (a2)
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