JP6443659B2 - Thermoplastic elastomer - Google Patents
Thermoplastic elastomer Download PDFInfo
- Publication number
- JP6443659B2 JP6443659B2 JP2014195456A JP2014195456A JP6443659B2 JP 6443659 B2 JP6443659 B2 JP 6443659B2 JP 2014195456 A JP2014195456 A JP 2014195456A JP 2014195456 A JP2014195456 A JP 2014195456A JP 6443659 B2 JP6443659 B2 JP 6443659B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- parts
- acrylic rubber
- examples
- monomer
- 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.)
- Expired - Fee Related
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 36
- 229920000800 acrylic rubber Polymers 0.000 claims description 62
- 229920000058 polyacrylate Polymers 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 47
- -1 polybutylene terephthalate Polymers 0.000 claims description 37
- 239000012792 core layer Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 16
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 description 19
- 229920001169 thermoplastic Polymers 0.000 description 18
- 239000004416 thermosoftening plastic Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical class ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-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
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- JSCFNQDWXBNVBP-UHFFFAOYSA-N 1,2-diphenylguanidine;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 JSCFNQDWXBNVBP-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical class CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- JDICEKWSLNPYSN-UHFFFAOYSA-N 2-(2,4-dinitrophenyl)-1,3-benzothiazole-4-thiol Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1C1=NC2=C(S)C=CC=C2S1 JDICEKWSLNPYSN-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-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
- DALNRYLBTOJSOH-UHFFFAOYSA-N 3,3,5,7,7-pentamethyl-1,2,4-trioxepane Chemical compound CC1CC(C)(C)OOC(C)(C)O1 DALNRYLBTOJSOH-UHFFFAOYSA-N 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- UCWBKJOCRGQBNW-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;dihydrate Chemical compound O.O.[Na+].OCS([O-])=O UCWBKJOCRGQBNW-UHFFFAOYSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- NEYNBSGIXOOZGZ-UHFFFAOYSA-L zinc;butoxymethanedithioate Chemical compound [Zn+2].CCCCOC([S-])=S.CCCCOC([S-])=S NEYNBSGIXOOZGZ-UHFFFAOYSA-L 0.000 description 1
- LAGTXXPOZSLGSF-UHFFFAOYSA-L zinc;n-butyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCCCN(C([S-])=S)C1=CC=CC=C1.CCCCN(C([S-])=S)C1=CC=CC=C1 LAGTXXPOZSLGSF-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、アクリルゴムと熱可塑性ポリエステルとを含む混合物を、架橋剤の存在下にて動的に架橋させてなる熱可塑性エラストマーに関する。 The present invention relates to a thermoplastic elastomer obtained by dynamically crosslinking a mixture containing an acrylic rubber and a thermoplastic polyester in the presence of a crosslinking agent.
近年、加硫ゴムに代わる材料として、加硫工程を必要とせず、熱可塑性樹脂と同様の成形加工性を有する熱可塑性エラストマーが、自動車、電気・電子、医療、食品、及び日用品等の分野で幅広く使用されている。特に、シール性が必要とされる分野においてはゴムと熱可塑性樹脂とを含む混合物を、架橋剤の存在下にて動的に架橋したタイプの熱可塑性エラストマーが使用されている。 In recent years, as an alternative to vulcanized rubber, thermoplastic elastomers that do not require a vulcanization process and have the same moldability as thermoplastic resins have been used in fields such as automobiles, electrical / electronics, medical, food, and daily necessities. Widely used. In particular, in a field where sealability is required, a thermoplastic elastomer of a type in which a mixture containing rubber and a thermoplastic resin is dynamically cross-linked in the presence of a cross-linking agent is used.
この種の熱可塑性エラストマーとしては、例えば下記特許文献１がある。特許文献１では、熱可塑性ポリエステルとアクリルゴムとを含む混合物を、架橋剤の存在下にて動的に架橋することで熱可塑性エラストマーを得ている。ここでのアクリルゴムは、アクリル酸アルキルエステル単量体及び／又はアクリル酸アルコキシアルキルエステル単量体が２０〜９９．９９質量％、ジシクロペンテニルオキシエチルアクリレート（ＤＣＰＥＡ）などの炭素−炭素二重結合を側鎖に有する単量体が０．０１〜２０質量％、不飽和アクリロニトリル単量体が０〜４０質量％、及びこれらと共重合可能な単量体が０〜３０質量％で構成されている。 As this kind of thermoplastic elastomer, for example, there is Patent Document 1 below. In Patent Document 1, a thermoplastic elastomer is obtained by dynamically crosslinking a mixture containing thermoplastic polyester and acrylic rubber in the presence of a crosslinking agent. The acrylic rubber here is 20 to 99.99% by mass of an acrylic acid alkyl ester monomer and / or an acrylic acid alkoxyalkyl ester monomer, and a carbon-carbon double such as dicyclopentenyloxyethyl acrylate (DCPEA). The monomer having a bond in the side chain is composed of 0.01 to 20% by mass, the unsaturated acrylonitrile monomer is 0 to 40% by mass, and the monomer copolymerizable therewith is 0 to 30% by mass. ing.
一般的に、特許文献１の様に側鎖に炭素−炭素二重結合を有する多官能単量体を使用すると、アクリルゴムの重合中に、当該単量体の側鎖の炭素−炭素二重結合も反応することでアクリルゴムがゲル化する。アクリルゴムがゲル化すると架橋点が失われることになる。一方、この種の熱可塑性エラストマーは、熱可塑性樹脂にゴム粒子が分散した、いわゆる海島構造となっている。特許文献１の熱可塑性エラストマーでは、側鎖に炭素−炭素二重結合を有する多官能単量体がアクリルゴム粒子全体に均一に存在している。この場合、アクリルゴム粒子全体が緻密なゲルを形成するため、熱可塑性ポリエステルとアクリルゴム粒子との分子レベルの絡み合いが起きず、相容性が低い。これらの問題から、最終的に得られる熱可塑性エラストマーの引張強度、引張伸び及び成形加工性が低いという課題を有する。 Generally, when a polyfunctional monomer having a carbon-carbon double bond in the side chain as in Patent Document 1 is used, the carbon-carbon double of the side chain of the monomer is polymerized during the polymerization of acrylic rubber. The acrylic rubber gels by reacting with the bond. When the acrylic rubber is gelled, the crosslinking point is lost. On the other hand, this type of thermoplastic elastomer has a so-called sea-island structure in which rubber particles are dispersed in a thermoplastic resin. In the thermoplastic elastomer of Patent Document 1, a polyfunctional monomer having a carbon-carbon double bond in the side chain is present uniformly throughout the acrylic rubber particles. In this case, since the entire acrylic rubber particles form a dense gel, the entanglement at the molecular level between the thermoplastic polyester and the acrylic rubber particles does not occur and the compatibility is low. From these problems, the thermoplastic elastomer finally obtained has a problem of low tensile strength, tensile elongation and molding processability.
そこで、本発明者らは上記課題を解決すべく鋭意検討した結果、側鎖に炭素−炭素二重結合を有する多官能単量体としてメタクリル酸アリル単量体を使用した場合に、アクリルゴムの重合中のゲル化の抑制が可能であることを見出した。さらに、メタクリル酸アリル単量体を含む内層部のコア層と、側鎖に炭素−炭素二重結合を有する多官能単量体を含まない表層部のシェル層とから構成される、コア−シェル構造のアクリルゴムを使用することで、熱可塑性ポリエステルとアクリルゴム粒子との相容性が向上することを見出した。すなわち本発明は、引張強度、引張伸び、成形加工性、耐熱性および耐油性に優れる熱可塑性エラストマーを提供することを目的とする。
Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that when an allyl methacrylate monomer is used as a polyfunctional monomer having a carbon-carbon double bond in the side chain, It has been found that gelation during polymerization can be suppressed. Furthermore, the core-shell is composed of an inner layer core layer containing allyl methacrylate monomer and a surface layer shell layer not containing a polyfunctional monomer having a carbon-carbon double bond in the side chain. It has been found that the compatibility between the thermoplastic polyester and the acrylic rubber particles is improved by using the acrylic rubber having the structure. That is, an object of the present invention is to provide a thermoplastic elastomer excellent in tensile strength, tensile elongation, moldability , heat resistance and oil resistance .
そのための手段として、本発明は、（Ａ）アクリルゴムと（Ｂ）ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエ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一種とを含む混合物を、（Ｃ）有機過酸化物の存在下で動的に架橋させてなる熱可塑性エラストマーの製法であって、（Ａ）アクリルゴムは、コア−シェル構造を有する。ここでのコア層は、（ａ−１）一般式（１）及び／又は一般式（２）で表される単量体から選ばれる少なくとも１種と、（ａ−２）アクリロニトリル単量体と、（ａ−３）メタクリル酸アリル単量体とを含む。一方、シェル層は、側鎖に炭素−炭素二重結合を有する多官能単量体を含まず、（ａ−４）一般式（１）及び／又は一般式（２）で表される単量体から選ばれる少なくとも１種と、（ａ−５）アクリロニトリル単量体と、（ａ−６）メタクリル酸グリシジル単量体とを含む。
（式中、ｎは０、１又は３である）
（式中、ｍは０又は１である）
As a means for that purpose, the present invention provides a mixture comprising (A) an acrylic rubber and (B) at least one selected from the group consisting of polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene terephthalate . a process for preparing a thermoplastic elastomer comprising by dynamically crosslinked in the presence of, (a) acrylic rubber, core - has a shell structure. The core layer here is (a-1) at least one selected from monomers represented by the general formula (1) and / or the general formula (2), and (a-2) an acrylonitrile monomer. (A-3) Allyl methacrylate monomer. On the other hand, the shell layer does not contain a polyfunctional monomer having a carbon-carbon double bond in the side chain, and is represented by (a-4) a single amount represented by the general formula (1) and / or the general formula (2). At least one selected from the body, (a-5) an acrylonitrile monomer, and (a-6) a glycidyl methacrylate monomer.
(Wherein n is 0, 1 or 3)
(Where m is 0 or 1)
（Ａ）アクリルゴムのコア層は、（ａ−１）＋（ａ−２）＝１００質量部として、（ａ−１）を８０〜１００質量部、（ａ−２）を０〜２０質量部含む。また、（ａ−１）と（ａ−２）の合計１００質量部に対して、（ａ−３）を０．１〜２質量部含む。 (A) The core layer of acrylic rubber is (a-1) + (a-2) = 100 parts by mass, (a-1) is 80 to 100 parts by mass, and (a-2) is 0 to 20 parts by mass. Including. Moreover, 0.1-2 mass parts of (a-3) is included with respect to a total of 100 mass parts of (a-1) and (a-2).
一方、（Ａ）アクリルゴムのシェル層は、（ａ−４）＋（ａ−５）＝１００質量部として、（ａ−４）を８０〜１００質量部、（ａ−５）を０〜２０質量部含み、且つ（ａ−４）と（ａ−５）の合計１００質量部に対して、（ａ−６）を０〜５質量部含む。 On the other hand, the shell layer of (A) acrylic rubber is (a-4) + (a-5) = 100 parts by mass, (a-4) is 80-100 parts by mass, and (a-5) is 0-20. Including 0 parts by mass of (a-6) with respect to a total of 100 parts by mass of (a-4) and (a-5).
また、本発明の熱可塑性エラストマーは、（Ａ）を１００質量部、（Ｂ）を１５〜７０質量部含む混合物を、（Ａ）１００質量部に対して（Ｃ）が０．１〜５質量部存在する条件下にて、動的に架橋させてなる。 The thermoplastic elastomer of the present invention is a mixture containing 100 parts by mass of (A) and 15 to 70 parts by mass of (B), and (C) is 0.1 to 5 parts by mass with respect to 100 parts by mass of (A). It is dynamically crosslinked under the existing conditions.
なお、本発明において数値範囲を示す「○○〜××」とは、その下限の数値（○○）及び上限の数値（××）も含む意味である。すなわち、正確に記載すれば「○○以上××以下」となる。 In the present invention, “OO to XX” indicating a numerical range means to include the lower limit numerical value (OO) and the upper limit numerical value (XX). That is, if it is accurately described, it will be “XX or more and XX or less”.
本発明によれば、（Ａ）アクリルゴムのコア層には、（ａ−３）メタクリル酸アリル単量体を含むため、（ａ−３）の側鎖のアリル基を架橋点として確保でき、得られる熱可塑性エラストマーの引張強度及び引張伸びを向上することができる。一方、シェル層は側鎖に炭素−炭素二重結合を有する多官能単量体を含まないため、当該シェル層にはゲルが形成されない。これにより、熱可塑性ポリエステルとアクリルゴム粒子との相容性が向上し、熱可塑性ポリエステルとアクリルゴム粒子との分散性が向上することで、得られる熱可塑性エラストマーの成形加工性を向上することができる。
According to the present invention, since the core layer of (A) acrylic rubber contains (a-3) allyl methacrylate monomer, the allyl group of the side chain of (a-3) can be secured as a crosslinking point, The tensile strength and tensile elongation of the resulting thermoplastic elastomer can be improved. On the other hand, since the shell layer does not contain a polyfunctional monomer having a carbon-carbon double bond in the side chain, no gel is formed in the shell layer. Thereby, the compatibility between the thermoplastic polyester and the acrylic rubber particles is improved, and the dispersibility between the thermoplastic polyester and the acrylic rubber particles is improved, thereby improving the molding processability of the obtained thermoplastic elastomer. it can.
以下、本発明について詳細に説明する。本発明の熱可塑性エラストマーは、（Ｂ）熱可塑性ポリエステルに（Ａ）アクリルゴム粒子が分散した、いわゆる海島構造となっている。 Hereinafter, the present invention will be described in detail. The thermoplastic elastomer of the present invention has a so-called sea-island structure in which (A) acrylic rubber particles are dispersed in (B) thermoplastic polyester.
≪（Ａ）アクリルゴム≫
（Ａ）アクリルゴムは、熱可塑性エラストマー中のソフトセグメントとして作用し、主として柔軟性、弾力性、シール性、耐熱性、及び耐油性等を付与する成分である。そのうえで、本発明の（Ａ）アクリルゴムは、内部にメタクリル酸アリル単量体を含むコア層と、該コア層を覆う、ゲル分を含まないシェル層とによって構成されたコア−シェル構造となっている。
≪ (A) Acrylic rubber≫
(A) Acrylic rubber is a component that acts as a soft segment in a thermoplastic elastomer and mainly imparts flexibility, elasticity, sealing properties, heat resistance, oil resistance, and the like. In addition, the acrylic rubber (A) of the present invention has a core-shell structure constituted by a core layer containing an allyl methacrylate monomer inside and a shell layer covering the core layer and not containing a gel component. ing.
＜コア層＞
コア層は、（ａ−１）一般式（１）及び／又は一般式（２）で表される単量体から選ばれる少なくとも１種と、（ａ−２）アクリロニトリル単量体と、（ａ−３）メタクリル酸アリル単量体とを含む。
<Core layer>
The core layer comprises (a-1) at least one selected from monomers represented by general formula (1) and / or general formula (2), (a-2) acrylonitrile monomer, (a -3) Allyl methacrylate monomer.
（ａ−１）
一般式（１）で表される単量体は、すなわち、アクリル酸メチル、アクリル酸エチル、アクリル酸−ｎ−ブチルである。これらは１種のみを使用することもできるし、２種以上を併用することもできる。これらの中でも、優れた柔軟性を発揮できるという点で、特に好ましいのはアルキル基の炭素数が２又は４のアクリル酸アルキルエステル単量体である。
(A-1)
The monomers represented by the general formula (1) are methyl acrylate, ethyl acrylate, and n-butyl acrylate. These can use only 1 type and can also use 2 or more types together. Among these, an acrylic acid alkyl ester monomer having an alkyl group having 2 or 4 carbon atoms is particularly preferable in that it can exhibit excellent flexibility.
一般式（２）で表される単量体は、すなわち、アクリル酸２−メトキシエチル、アクリル酸２−エトキシエチルである。これらは１種のみを使用することもできるし、２種以上を併用することもできる。これらの中でも、優れた耐油性を発揮できるという点で、特に好ましいのは、アクリル酸２−メトキシエチルである。 The monomers represented by the general formula (2) are 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate. These can use only 1 type and can also use 2 or more types together. Among these, 2-methoxyethyl acrylate is particularly preferable because it can exhibit excellent oil resistance.
コア層中、（ａ−１）の含有量は、後述の（ａ−２）との合計１００質量部に対して８０〜１００質量部であることが好ましい。（ａ−１）の含有量が８０質量部未満では、熱可塑性エラストマーの柔軟性等が低下する。一方、（ａ−１）の含有量が１００質量部を超えると、後述の（ａ−３）の含有量が相対的に少なくなり、アクリルゴムの架橋が十分に進行せず、得られる熱可塑性エラストマーの引張強度等が低下する。 In the core layer, the content of (a-1) is preferably 80 to 100 parts by mass with respect to 100 parts by mass in total with (a-2) described later. If content of (a-1) is less than 80 mass parts, the softness | flexibility etc. of a thermoplastic elastomer will fall. On the other hand, when the content of (a-1) exceeds 100 parts by mass, the content of (a-3) described later becomes relatively small, and crosslinking of acrylic rubber does not proceed sufficiently, and the resulting thermoplasticity The tensile strength of the elastomer is reduced.
（ａ−２）
コア層中、（ａ−２）の含有量は、（ａ−１）との合計１００質量部に対して０〜２０質量部であることが好ましい。すなわち、（ａ−２）は必須成分ではなく、必ずしもコア層中に含有されていなくてもよい。（ａ−２）アクリロニトリル単量体を含有していると、耐油性が向上する。但し、（ａ−２）の含有量が２０質量部を超えると、結果として得られる熱可塑性エラストマーの柔軟性等が低下する。
(A-2)
In the core layer, the content of (a-2) is preferably 0 to 20 parts by mass with respect to 100 parts by mass in total with (a-1). That is, (a-2) is not an essential component and may not necessarily be contained in the core layer. (A-2) Oil resistance improves when it contains the acrylonitrile monomer. However, if the content of (a-2) exceeds 20 parts by mass, the flexibility and the like of the resulting thermoplastic elastomer will decrease.
（ａ−３）
コア層中、（ａ−３）の含有量は、（ａ−１）と（ａ−２）の合計１００質量部に対して０．１〜２質量部であることが好ましい。（ａ−３）の含有量が０．１質量部未満では（Ａ）アクリルゴムの架橋が十分に進行せず、熱可塑性エラストマーにおいて優れた引張強度が得られない。一方、（ａ−３）の含有量が２質量部を超えると、（Ａ）アクリルゴムが過度に架橋するため、熱可塑性エラストマーの成形加工性が低下する。
(A-3)
In the core layer, the content of (a-3) is preferably 0.1 to 2 parts by mass with respect to 100 parts by mass in total of (a-1) and (a-2). When the content of (a-3) is less than 0.1 part by mass, the crosslinking of (A) acrylic rubber does not proceed sufficiently, and excellent tensile strength cannot be obtained in the thermoplastic elastomer. On the other hand, when the content of (a-3) exceeds 2 parts by mass, (A) the acrylic rubber is excessively crosslinked, so that the molding processability of the thermoplastic elastomer is lowered.
＜シェル層＞
シェル層は、（ａ−４）一般式（１）及び／又は一般式（２）で表される単量体から選ばれる少なくとも１種と、（ａ−５）アクリロニトリル単量体と、（ａ−６）メタクリル酸グリシジル単量体とを含む。但し、コア層とは異なり、側鎖に炭素−炭素二重結合を有する多官能単量体を含まない。したがって、アクリルゴムを重合した際、シェル層にはゲルが形成されない。
<Shell layer>
The shell layer comprises (a-4) at least one selected from monomers represented by general formula (1) and / or general formula (2), (a-5) acrylonitrile monomer, (a -6) glycidyl methacrylate monomer. However, unlike the core layer, a polyfunctional monomer having a carbon-carbon double bond in the side chain is not included. Therefore, no gel is formed in the shell layer when the acrylic rubber is polymerized.
（ａ−４・ａ−５・ａ−６）
（ａ−４）には、コア層の（ａ−１）と同種の単量体を使用すればよい。
(A-4 ・ a-5 ・ a-6)
For (a-4), the same type of monomer as (a-1) of the core layer may be used.
シェル層において、（ａ−４）・（ａ−５）の含有量も、それぞれコア層の（ａ−１）・（ａ−２）と同様の範囲でよい。具体的には、（ａ−４）と（ａ−５）の合計１００質量部に対して、（ａ−４）を８０〜１００質量部、（ａ−５）を０〜２０質量部含有していることが好ましい。 In the shell layer, the contents of (a-4) and (a-5) may be in the same ranges as (a-1) and (a-2) of the core layer, respectively. Specifically, with respect to a total of 100 parts by mass of (a-4) and (a-5), 80 to 100 parts by mass of (a-4) and 0 to 20 parts by mass of (a-5) are contained. It is preferable.
一方、（ａ−６）の含有量は、（ａ−４）と（ａ−５）の合計１００質量部に対して０〜５質量部とすることが好ましい。すなわち、（ａ−６）は必須成分ではなく、必ずしもシェル層中に含有されていなくてもよい。（ａ−６）メタクリル酸グリシジル単量体を含有していると、特に引張強度が向上する。 On the other hand, the content of (a-6) is preferably 0 to 5 parts by mass with respect to 100 parts by mass in total of (a-4) and (a-5). That is, (a-6) is not an essential component and may not necessarily be contained in the shell layer. (A-6) When the glycidyl methacrylate monomer is contained, the tensile strength is particularly improved.
〔アクリルゴムの重合〕
コア−シェル構造のアクリルゴムは、コア層を先に重合し、重合転化率が一定以上になった時点で、シェル層の単量体を続いて添加する方法で得ることができる。具体的には、先ず、（ａ−１）、（ａ−３）及び必要に応じて（ａ−２）を含む混合物を、ラジカル重合開始剤の存在下で共重合させることでコア層を形成する。続いて、当該コア層が分散された状態において、そのまま（ａ−４）、及び必要に応じて（ａ−５）、（ａ−６）を添加し、再度ラジカル重合開始剤の存在下で共重合させることで、コア層を覆うようにシェル層が形成される。重合方法としては、塊状重合、溶液重合、懸濁重合、乳化重合等の公知の方法が可能であるが、乳化重合が特に好ましい。
[Acrylic rubber polymerization]
The acrylic rubber having a core-shell structure can be obtained by a method in which the core layer is polymerized first and the monomer of the shell layer is subsequently added when the polymerization conversion rate becomes a certain level or more. Specifically, first, a core layer is formed by copolymerizing a mixture containing (a-1), (a-3) and, if necessary, (a-2) in the presence of a radical polymerization initiator. To do. Subsequently, in the state where the core layer is dispersed, (a-4) is added as it is, and (a-5) and (a-6) are added as necessary, and again in the presence of a radical polymerization initiator. By polymerizing, a shell layer is formed so as to cover the core layer. As the polymerization method, known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used, and emulsion polymerization is particularly preferable.
乳化重合に使用する乳化剤としては、例えば、アニオン系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤及び両性界面活性剤等が挙げられる。通常、アニオン系界面活性剤が多用され、例えば、炭素数１０以上の長鎖脂肪酸塩、ロジン酸塩等が使用される。具体的には、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、ステアリン酸のカリウム塩及びナトリウム塩等が挙げられる。これらの乳化剤は１種のみを使用してもよいし、２種以上を併用することもできる。 Examples of the emulsifier used in the emulsion polymerization include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Usually, anionic surfactants are frequently used. For example, long chain fatty acid salts having 10 or more carbon atoms, rosin acid salts and the like are used. Specific examples include capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and potassium and sodium salts of stearic acid. These emulsifiers may use only 1 type and can also use 2 or more types together.
ラジカル重合開始剤としては、例えば、ハイドロパーオキサイド、無機過酸化物、アゾ化合物等が挙げられる。ハイドロパーオキサイドとしては、例えば、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド等が挙げられる。無機過酸化物としては、例えば、過硫酸カリウム、過硫酸アンモニウム等が挙げられる。また、これら過酸化物と硫酸第一鉄とを組み合わせたレドックス系触媒を使用することもできる。アゾ化合物としては、例えば、アゾビスイソブチロニトリル、２，２’−アゾビス（２−（２−イミダゾリン−２−イル）プロパン）ジハイドロクロライド等が挙げられる。これらのラジカル重合開始剤は１種のみを使用してもよいし、２種以上を併用することもできる。（Ａ）アクリルゴムの分子量を調節するために連鎖移動剤を使用することもできる。連鎖移動剤としては、例えば、アルキルメルカプタン、四塩化炭素、チオグリコール類、ジテルペン、ターピノーレン及びγ−テルピネン類等が挙げられる。これらの連鎖移動剤は１種のみを使用することもできるし、２種以上を併用することもできる。 Examples of the radical polymerization initiator include hydroperoxide, inorganic peroxide, azo compound and the like. Examples of the hydroperoxide include t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like. Examples of inorganic peroxides include potassium persulfate and ammonium persulfate. Moreover, the redox catalyst which combined these peroxide and ferrous sulfate can also be used. Examples of the azo compound include azobisisobutyronitrile, 2,2′-azobis (2- (2-imidazolin-2-yl) propane) dihydrochloride, and the like. These radical polymerization initiators may be used alone or in combination of two or more. (A) A chain transfer agent can also be used to adjust the molecular weight of the acrylic rubber. Examples of the chain transfer agent include alkyl mercaptans, carbon tetrachloride, thioglycols, diterpenes, terpinolene, and γ-terpinenes. These chain transfer agents can be used alone or in combination of two or more.
（Ａ）アクリルゴムを共重合する際は、各単量体、乳化剤、及びラジカル重合開始剤等を反応容器に一括投入して重合を開始してもよいし、反応継続時に連続的あるいは間欠的に添加してもよい。重合は、窒素置換等酸素を除去した反応器を用いて０〜１００℃、好ましくは０〜８０℃で行うことができる。重合方式は連続式でもよいし、回分式であってもよい。重合時間は０．０１〜３０時間程度、好ましくは1〜１０時間程度である。（Ａ）アクリルゴムの重合終了後（コア−シェル構造の重合終了後）、反応生成物（ラテックス）を塩化ナトリウム、塩化カルシウム等の無機塩の水溶液に投入して凝固させ、水洗、乾燥することによりコア−シェル構造のアクリルゴムが得られる。 (A) When the acrylic rubber is copolymerized, the polymerization may be started by batch charging each monomer, emulsifier, radical polymerization initiator, etc. into the reaction vessel, or continuously or intermittently as the reaction continues. You may add to. Polymerization can be carried out at 0 to 100 ° C., preferably 0 to 80 ° C., using a reactor from which oxygen has been removed, such as nitrogen substitution. The polymerization method may be a continuous method or a batch method. The polymerization time is about 0.01 to 30 hours, preferably about 1 to 10 hours. (A) After completion of polymerization of acrylic rubber (after completion of polymerization of the core-shell structure), the reaction product (latex) is put into an aqueous solution of an inorganic salt such as sodium chloride or calcium chloride to be coagulated, washed with water and dried. Thus, an acrylic rubber having a core-shell structure is obtained.
≪（Ｂ）熱可塑性ポリエステル≫
（Ｂ）熱可塑性ポリエステルは、熱可塑性エラストマー中のハードセグメントとして作用し、主として熱可塑性エラストマーの引張強度、成形加工性、及び耐熱性等を向上させる成分である。
≪ (B) Thermoplastic polyester≫
(B) The thermoplastic polyester is a component that acts as a hard segment in the thermoplastic elastomer and mainly improves the tensile strength, molding processability, heat resistance, and the like of the thermoplastic elastomer.
（Ｂ）熱可塑性ポリエステルは、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンテレフタレートが挙げられる。この中でもポリブチレンテレフタレート、ポリトリメチレンテレフタレートがより好ましい。
Examples of the (B) thermoplastic polyester include polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene terephthalate. Among these, polybutylene terephthalate and polytrimethylene terephthalate are more preferable.
（Ｂ）熱可塑性ポリエステルの含有量は、（Ａ）アクリルゴム１００質量部に対して１５〜７０質量部とする。（Ｂ）熱可塑性ポリエステルの含有量が１５質量部未満では、熱可塑性エラストマーの成形加工性が低下する。一方、７０質量部を超えると、熱可塑性エラストマーの柔軟性が低下する。 (B) Content of thermoplastic polyester shall be 15-70 mass parts with respect to 100 mass parts of (A) acrylic rubber. (B) If content of thermoplastic polyester is less than 15 mass parts, the moldability of a thermoplastic elastomer will fall. On the other hand, when it exceeds 70 mass parts, the softness | flexibility of a thermoplastic elastomer will fall.
≪（Ｃ）架橋剤（有機過酸化物）≫
（Ｃ）架橋剤としての有機過酸化物は、（Ａ）アクリルゴムを架橋するために添加されるものであって、（Ａ）アクリルゴム中の（ａ−３）の側鎖のアリル基に作用しアクリルゴムを架橋する機能を有する。有機過酸化物としては、例えば、ジアルキルパーオキサイド、パーオキシケタール、ジアシルパーオキサイド、パーオキシエステル等が挙げられる。ジアルキルパーオキサイドとしては、例えば、ジクミルパーオキサイド、α，α’−ジ（ｔ−ブチルパーオキシ）ジイソプロピルベンゼン、ｔ−ブチルクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシン）ヘキシン−３、３，３，７，７−テトラメチル−１，２，４−トリオキセパン、３，３，５，７，７−ペンタメチル−１，２，４−トリオキセパン等が挙げられる。パーオキシケタールとしては、例えば、１，１−ジ（ｔ−ヘキシルパーオキシ）シクロヘキサン、１，１−ジ（ｔ−ブチルパーオキシ）シクロヘキサン、ｎ−ブチル−４，４−ジ（ｔ−ブチルパーオキシ）バレレート等が挙げられる。ジアシルパーオキサイドとしては、例えば、ベンゾイルパーオキサイド、ジ（４−メチルベンゾイル）パーオキサイド等が挙げられる。パーオキシエステルとしては、例えば、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ヘキシルパーオキシベンゾエート、ｔ−ヘキシルパーオキシ−３−メチルベンゾエート、ｔ−ブチルパーオキシベンゾエート等が挙げられる。この中でも、ジアルキルパーオキサイドが好ましい。これらの架橋剤は１種のみを使用してもよいし、２種以上を併用することもできる。
≪ (C) Crosslinking agent (organic peroxide) ≫
(C) The organic peroxide as a cross-linking agent is added to cross-link (A) acrylic rubber, and (A) the side chain allyl group of (a-3) in the acrylic rubber. It functions to crosslink acrylic rubber. Examples of organic peroxides include dialkyl peroxides, peroxyketals, diacyl peroxides, and peroxy esters. Examples of the dialkyl peroxide include dicumyl peroxide, α, α′-di (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxine) hexyne-3,3,3,7,7-tetramethyl-1,2,4-trioxepane, 3,3 5,7,7-pentamethyl-1,2,4-trioxepane and the like. Examples of the peroxyketal include 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, n-butyl-4,4-di (t-butylper). Oxy) valerate and the like. Examples of the diacyl peroxide include benzoyl peroxide and di (4-methylbenzoyl) peroxide. Examples of peroxyesters include 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-hexylperoxybenzoate, t-hexylperoxy-3-methylbenzoate, and t-butylperoxybenzoate. Etc. Among these, dialkyl peroxide is preferable. These crosslinking agents may be used alone or in combination of two or more.
（Ｃ）架橋剤の使用量は、できるだけ少ないことが好ましい。架橋剤の使用量が多いと、得られる熱可塑性エラストマーの成形加工性、柔軟性等が低下する。具体的には、（Ａ）アクリルゴム１００質量部に対して、０．１〜５質量部とする。 (C) The amount of the crosslinking agent used is preferably as small as possible. When the amount of the crosslinking agent used is large, the molding processability and flexibility of the resulting thermoplastic elastomer are lowered. Specifically, it is 0.1 to 5 parts by mass with respect to 100 parts by mass of (A) acrylic rubber.
（Ｃ）架橋剤の使用に際しては、架橋促進剤や架橋助剤を使用することもできる。架橋促進剤としては、例えば、スルフェンアミド系化合物、チアゾ−ル系化合物、グアニジン化合物、アルデヒドアミン又はアルデヒド−アンモニア系化合物、イミダゾリン系化合物、チオユリア系化合物、チウラム系化合物、ジチオ酸塩系化合物、ザンテ−ト系化合物等が挙げられる。スルフェンアミド系化合物としては、例えば、Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、Ｎ−オキシジエチレン−２−ベンゾチアゾリルスルフェンアミド、Ｎ，Ｎ−ジイソプロピル−２−ベンゾチアゾリルスルフェンアミド等が挙げられる。チアゾ−ル系化合物としては、例えば、２−メルカプトベンゾチアゾ−ル、２−（２’，４’−ジニトロフェニル）メルカプトベンゾチアゾ−ル、２−（４’−モルホリノジチオ）ベンゾチアゾ−ル、ジベンゾチアジルジスルフィド等が挙げられる。グアニジン化合物としては、例えば、ジフェニルグアニジン、ジオルソトリルグアニジン、ジオルソニトリルグアニジン、オルソニトリルバイグアナイド、ジフェニルグアニジンフタレ−ト等が挙げられる。アルデヒドアミン又はアルデヒド−アンモニア系化合物としては、例えば、アセトアルデヒド−アニリン反応物、ブチルアルデヒド−アニリン縮合物、ヘキサメチレンテトラミン、アセトアルデヒドアンモニア等が挙げられる。イミダゾリン化合物としては、例えば、２−メルカプトイミダゾリン等が挙げられる。チオユリア系化合物としては、例えば、チオカルバニリド、ジエチルチオユリア、ジブチルチオユリア、トリメチルチオユリア、ジオルソトリルチオユリア等が挙げられる。チウラム系化合物としては、例えば、テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、テトラオクチルチウラムジスルフィド、ペンタメチレンチウラムテトラスルフィド等が挙げられる。ジチオ酸塩系化合物としては、例えば、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジ−ｎ−ブチルジチオカルバミン酸亜鉛、エチルフェニルジチオカルバミン酸亜鉛、ブチルフェニルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸ナトリウム、ジメチルジチオカルバミン酸セレン、ジメチルジチオカルバミン酸テルル等が挙げられる。ザンテ−ト系化合物としては、例えば、ジブチルキサントゲン酸亜鉛等が挙げられる。これらの架橋促進剤は１種のみを使用してもよいし、２種以上を併用することもできる。 (C) When using a crosslinking agent, a crosslinking accelerator or a crosslinking aid can also be used. Examples of the crosslinking accelerator include sulfenamide compounds, thiazole compounds, guanidine compounds, aldehyde amines or aldehyde-ammonia compounds, imidazoline compounds, thiourea compounds, thiuram compounds, dithioate compounds, Examples thereof include xanthate compounds. Examples of the sulfenamide compound include N-cyclohexyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N, N-diisopropyl-2-benzothiazolylsulfene. Examples include amides. Examples of thiazol compounds include 2-mercaptobenzothiazol, 2- (2 ′, 4′-dinitrophenyl) mercaptobenzothiazol, and 2- (4′-morpholinodithio) benzothiazol. And dibenzothiazyl disulfide. Examples of the guanidine compound include diphenyl guanidine, diorthotolyl guanidine, diorthonitrile guanidine, orthonitrile biguanide, diphenyl guanidine phthalate and the like. Examples of the aldehyde amine or aldehyde-ammonia compound include acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia, and the like. Examples of the imidazoline compound include 2-mercaptoimidazoline. Examples of the thiourea compound include thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diortholylthiourea and the like. Examples of thiuram compounds include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetraoctylthiuram disulfide, pentamethylenethiuram tetrasulfide and the like. Examples of the dithioate-based compound include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate. And tellurium dimethyldithiocarbamate. Examples of the xanthate compound include zinc dibutylxanthate. These crosslinking accelerators may be used alone or in combination of two or more.
架橋助剤としては、例えば、キノンジオキシム系化合物、メタクリレ−ト系化合物、アリル系化合物、マレイミド系化合物等が挙げられる。キノンジオキシム系化合物としては、例えば、ｐ−キノンジオキシム等が挙げられる。メタクリレ−ト系化合物としては、例えば、ポリエチレングリコールジメタクリレ−ト等が挙げられる。アリル系化合物としては、例えば、ジアリルフタレ−ト、トリアリルシアヌレ−ト等が挙げられる。マレイミド系化合物としては、例えば、ｍ−フェニレンビスマレイミド等が挙げられる。これらの架橋助剤は１種のみを使用してもよいし、２種以上を併用することもできる。 Examples of the crosslinking aid include quinone dioxime compounds, methacrylate compounds, allyl compounds, maleimide compounds, and the like. Examples of the quinone dioxime compound include p-quinone dioxime. Examples of the methacrylate compound include polyethylene glycol dimethacrylate. Examples of allylic compounds include diallyl phthalate and triallyl cyanurate. Examples of maleimide compounds include m-phenylene bismaleimide. These crosslinking aids may be used alone or in combination of two or more.
≪その他の添加剤≫
なお、（Ａ）アクリルゴムには、本発明の効果を阻害しない範囲で、可塑剤、軟化剤、充填剤、補強剤、金属酸化物、老化防止剤、加工助剤、難燃剤、又は紫外線吸収剤等のその他の添加剤を添加することもできる。その他の各添加剤は、下記に示す具体的材料のうち１種のみを使用してもよいし、２種以上を併用することもできる。
≪Other additives≫
In addition, (A) acrylic rubber has a plasticizer, a softening agent, a filler, a reinforcing agent, a metal oxide, an anti-aging agent, a processing aid, a flame retardant, or an ultraviolet absorber within a range that does not impair the effects of the present invention. Other additives such as an agent can also be added. As each of the other additives, only one kind of the specific materials shown below may be used, or two or more kinds may be used in combination.
可塑剤としては、例えば、フタル酸エステル類、脂肪酸エステル類、トリメリット酸エステル類、アジピン酸系ポリエステル類、ポリエーテルエステル類、エポキシ化大豆油等が挙げられる。フタル酸エステル類としては、例えば、ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジイソブチルフタレート、ジオクチルフタレート、ブチルオクチルフタレート、ジ（２−エチルヘキシル）フタレート、ジイソオクチルフタレート、ジイソデシルフタレート等が挙げられる。脂肪酸エステル類としては、例えば、ジメチルアジペート、ジイソブチルアジペート、ジ（２−エチルヘキシル）アジペート、ジイソオクチルアジペート、ジイソデシルアジペート、オクチルデシルアジペート、ジ（２−エチルヘキシル）アゼレート、ジイソオクチルアゼレート、ジイソブチルアゼレート、ジブチルセバケート、ジ（２−エチルヘキシル）セバケート、ジイソオクチルセバケート等が挙げられる。トリメリット酸エステル類としては、例えば、トリメリット酸イソデシルエステル、トリメリット酸オクチルエステル、トリメリット酸ｎ−オクチルエステル、トリメリット酸系イソノニルエステル等が挙げられる。 Examples of the plasticizer include phthalic acid esters, fatty acid esters, trimellitic acid esters, adipic acid polyesters, polyether esters, epoxidized soybean oil, and the like. Examples of the phthalic acid esters include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di (2-ethylhexyl) phthalate, diisooctyl phthalate, diisodecyl phthalate, and the like. Examples of fatty acid esters include dimethyl adipate, diisobutyl adipate, di (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl aze Rate, dibutyl sebacate, di (2-ethylhexyl) sebacate, diisooctyl sebacate and the like. Examples of trimellitic acid esters include trimellitic acid isodecyl ester, trimellitic acid octyl ester, trimellitic acid n-octyl ester, trimellitic acid isononyl ester, and the like.
軟化剤としては、例えば、石油系軟化剤、植物油系軟化剤、サブ等が挙げられる。石油系軟化剤としては、例えば、アロマティック系、ナフテン系、パラフィン系軟化剤等が挙げられる。植物系軟化剤としては、例えば、ひまし油、綿実油、あまに油、なたね油、大豆油、パーム油、やし油、落花生油、木ろう等が挙げられる。サブとしては、例えば、黒サブ、白サブ、飴サブ等が挙げられる。 Examples of the softener include petroleum-based softeners, vegetable oil-based softeners, subs, and the like. Examples of petroleum softeners include aromatic, naphthenic, and paraffinic softeners. Examples of plant softeners include castor oil, cottonseed oil, rapeseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, and wax. Examples of the sub include a black sub, a white sub, and a dark blue sub.
充填剤としては、例えば、シリカ、重質炭酸カルシウム、胡粉、軽微性炭酸カルシウム、極微細活性化炭酸カルシウム、特殊炭酸カルシウム、塩基性炭酸マグネシウム、カオリンクレー、焼成クレー、パイロフライトクレー、シラン処理クレー、合成ケイ酸カルシウム、合成ケイ酸マグネシウム、合成ケイ酸アルミニウム、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、酸化マグネシウム、カオリン、セリサイト、タルク、微粉タルク、ウォラスナイト、ゼオライト、ゾーノトナイト、アスベスト、ＰＭＦ（Ｐｒｏｃｅｓｓｅｄ Ｍｉｎｅｒａｌ Ｆｉｂｅｒ）、セピオライト、チタン酸カリウム、エレスタダイト、石膏繊維、ガラスバルン、シリカバルン、ハイドロタルサイト、フライアシュバルン、シラスバルン、カーボン系バルン、アルミナ、硫酸バリウム、硫酸アルミニウム、硫酸カルシウム、二硫化モリブデン等が挙げられる。 Examples of fillers include silica, heavy calcium carbonate, pepper, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, pyroflight clay, and silane-treated clay. , Synthetic calcium silicate, synthetic magnesium silicate, synthetic aluminum silicate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, sericite, talc, fine talc, wollastonite, zeolite, zonotonite, asbestos, PMF (Processed Mineral Fiber), sepiolite, potassium titanate, elastadite, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, shirasu balun, carbo System balun, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, and the like.
補強剤としては、例えば、ＳＡＦカーボンブラック、ＩＳＡＦカーボンブラック、ＨＡＦカーボンブラック、ＦＥＦカーボンブラック、ＧＰＦカーボンブラック、ＳＲＦカーボンブラック、ＦＴカーボンブラック、ＭＴカーボンブラック、アセチレンカーボンブラック、ケッチェンブラック等が挙げられる。 Examples of the reinforcing agent include SAF carbon black, ISAF carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, acetylene carbon black, ketjen black and the like. .
金属酸化物としては、例えば、亜鉛華、活性亜鉛華、表面処理亜鉛華、炭酸亜鉛、複合亜鉛華、複合活性亜鉛華、表面処理酸化マグネシウム、酸化マグネシウム、水酸化カルシウム、極微細水酸化カルシウム、一酸化鉛、鉛丹、鉛白等が挙げられる。 Examples of the metal oxide include zinc white, activated zinc white, surface-treated zinc white, zinc carbonate, composite zinc white, composite active zinc white, surface-treated magnesium oxide, magnesium oxide, calcium hydroxide, ultrafine calcium hydroxide, Lead monoxide, red lead, white lead, etc. are mentioned.
老化防止剤としては、例えば、ナフチルアミン系、ジフェニルアミン系、ｐ−フェニレンジアミン系、キノリン系、ヒドロキノン誘導体系、モノ、ビス、トリス、ポリフェノール系、チオビスフェノール系、ヒンダートフェノール系、亜リン酸エステル系、イミダゾール系、ジチオカルバミン酸ニッケル塩系、リン酸系等が挙げられる。 Antiaging agents include, for example, naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivative, mono, bis, tris, polyphenol, thiobisphenol, hindered phenol, phosphite Imidazole, nickel dithiocarbamate, phosphoric acid and the like.
加工助剤としては、例えば、ステアリン酸、オレイン酸、ラウリル酸、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸カリウム、ステアリン酸ナトリウム、ステアリルアミン等が挙げられる。 Examples of the processing aid include stearic acid, oleic acid, lauric acid, zinc stearate, calcium stearate, potassium stearate, sodium stearate, stearylamine and the like.
また、本発明の熱可塑性エラストマーには、ゴム成分として（Ａ）アクリルゴム以外のゴムを配合することもできる。例えば、スチレン−ブタジエン共重合ゴム、ブタジエンゴム、イソプレンゴム、ブタジエン−イソプレン共重合ゴム、スチレン−ブタジエン−イソプレン共重合ゴム、アクリロニトリル−ブタジエン共重合ゴム、ブチルゴム、天然ゴム、クロロプレンゴム等が挙げられる。 Moreover, rubber other than (A) acrylic rubber can also be mix | blended with the thermoplastic elastomer of this invention as a rubber component. Examples thereof include styrene-butadiene copolymer rubber, butadiene rubber, isoprene rubber, butadiene-isoprene copolymer rubber, styrene-butadiene-isoprene copolymer rubber, acrylonitrile-butadiene copolymer rubber, butyl rubber, natural rubber, chloroprene rubber and the like.
〔熱可塑性エラストマーの合成〕
熱可塑性エラストマーは、（Ａ）アクリルゴム１００質量部と、（Ｂ）熱可塑性ポリエステル１５〜７０質量部とを含む溶融混合物を、（Ｃ）架橋剤の存在下において動的架橋させて得られる。動的架橋とは、（Ａ）アクリルゴムと、（Ｂ）熱可塑性ポリエステルとを含む混合物を混練しながら架橋を進行させることをいう。
[Synthesis of thermoplastic elastomer]
The thermoplastic elastomer is obtained by dynamically crosslinking a molten mixture containing (A) 100 parts by mass of acrylic rubber and (B) 15 to 70 parts by mass of a thermoplastic polyester in the presence of (C) a crosslinking agent. Dynamic cross-linking means that cross-linking proceeds while kneading a mixture containing (A) acrylic rubber and (B) thermoplastic polyester.
（Ａ）アクリルゴムと、（Ｂ）熱可塑性ポリエステルとの溶融混練は、（Ｂ）熱可塑性ポリエステルの融点より高く、（Ａ）アクリルゴムの分解開始温度程度、具体的には１００〜３５０℃、好ましくは１５０〜３００℃、より好ましくは１８０〜２８０℃で行えばよい。 The melt kneading of (A) acrylic rubber and (B) thermoplastic polyester is higher than the melting point of (B) thermoplastic polyester, (A) about the decomposition start temperature of acrylic rubber, specifically 100 to 350 ° C, Preferably it may be carried out at 150 to 300 ° C, more preferably 180 to 280 ° C.
（Ａ）アクリルゴムと（Ｂ）熱可塑性ポリエステルとを含む混合物の混練には、一軸押出機、二軸押出機、二軸ローター型押出機等の連続式押出機や、加圧型ニーダー、バンバリーミキサー、ブラベンダーミキサー等の密閉式混練機を使用することができる。通常、こうして動的に架橋された（Ａ）アクリルゴムは、熱可塑性ポリエステルのマトリックス相に微分散される。このような相構造を形成することにより、（Ａ）アクリルゴムが架橋されているにも関わらず、エラストマーは熱可塑性（流動性）を有する。従って、熱可塑性エラストマーは、押出成形法、射出成形法、ブロー成形法、圧縮成形法等、公知の熱可塑性樹脂の成形方法により所定形状に成形加工することができる。 For kneading of a mixture containing (A) acrylic rubber and (B) thermoplastic polyester, continuous extruders such as a single screw extruder, twin screw extruder, twin screw rotor type extruder, pressure kneader, and Banbury mixer A closed kneader such as a Brabender mixer can be used. Usually, the dynamically crosslinked (A) acrylic rubber is finely dispersed in the matrix phase of the thermoplastic polyester. By forming such a phase structure, the elastomer has thermoplasticity (fluidity) even though (A) the acrylic rubber is crosslinked. Therefore, the thermoplastic elastomer can be molded into a predetermined shape by a known thermoplastic resin molding method such as an extrusion molding method, an injection molding method, a blow molding method, or a compression molding method.
本発明の熱可塑性エラストマーは、良好な耐油性や耐熱性を有し、強度、伸び、及びシール性などに優れる。そのため、当該熱可塑性エラストマーは、オイルクーラーホース、エアーダクトホース、パワーステアリングホース、コントロールホース、インタークーラーホース、トルコンホース、オイルリターンホース、耐熱ホース等の各種ホース材、燃料ホース材、ベアリングシール、バルクステムシール、各種オイルシール、Ｏ−リング、パッキン、ガスケット等のシール材、各種ダイヤフラム、ゴム板、ベルト、オイルレベルゲージ、ホースマスキング、配管断熱材等の被覆材、ロール等に好適に利用することができる。 The thermoplastic elastomer of the present invention has good oil resistance and heat resistance, and is excellent in strength, elongation, sealability and the like. Therefore, the thermoplastic elastomers are oil cooler hose, air duct hose, power steering hose, control hose, intercooler hose, torque converter hose, oil return hose, heat-resistant hose and other various hose materials, fuel hose materials, bearing seals, bulk stems. It can be suitably used for sealing materials such as seals, various oil seals, O-rings, packings, gaskets, various diaphragms, rubber plates, belts, oil level gauges, hose masking, piping insulation materials, rolls, etc. it can.
以下、本発明の具体的な実施例について説明するが、本発明はこれに限られることはない。 Hereinafter, although the specific Example of this invention is described, this invention is not limited to this.
＜（Ａ）アクリルゴムの重合＞
水２００質量部、ラウリル硫酸ナトリウム１質量部、硫酸第一鉄０．０１質量部、エチレンジアミン四酢酸ナトリウム０．０３質量部、ヒドロキシメタンスルフィン酸ナトリウム二水和物０．０５質量部を、窒素置換したステンレス製反応器に仕込み、コア用単量体として表１又は表２に示す材料を表１又は表２に示す割合で、１，１，３，３−テトラメチルブチルハイドロパーオキサイド０．１質量部と共に２時間かけて滴下し、反応温度３０℃で乳化重合させた。重合転化率が１００％に達したところで、シェル単量体として表１又は表２に示す材料を表１又は表２に示す割合で、１，１，３，３−テトラメチルブチルハイドロパーオキサイド０．１質量部と共に３０分かけて滴下し、反応温度３０℃で乳化重合させた。
<(A) Polymerization of acrylic rubber>
200 parts by weight of water, 1 part by weight of sodium lauryl sulfate, 0.01 part by weight of ferrous sulfate, 0.03 part by weight of sodium ethylenediaminetetraacetate, 0.05 part by weight of sodium hydroxymethanesulfinate dihydrate were replaced with nitrogen. 1,1, 3,3-tetramethylbutyl hydroperoxide 0.1% of the materials shown in Table 1 or 2 as the core monomer in the ratio shown in Table 1 or 2 It was added dropwise over 2 hours together with parts by mass, and emulsion polymerization was carried out at a reaction temperature of 30 ° C. When the polymerization conversion rate reached 100%, the materials shown in Table 1 or Table 2 as shell monomers in the proportions shown in Table 1 or Table 2, with 1,1,3,3-tetramethylbutyl hydroperoxide 0 .1 part by mass over 30 minutes and emulsion polymerization at a reaction temperature of 30 ° C.
得られた、反応生成物(ラテックス)を１％塩化カルシウム水溶液に滴下し、アクリルゴムを凝固させた。この凝固物を十分に水洗した後、８０℃で２４時間乾燥させることにより、（Ａ）アクリルゴムＡ−１〜Ａ−５(実施例用)及びＡ’−１〜Ａ’−１１(比較例用)を得た。 The obtained reaction product (latex) was dropped into a 1% calcium chloride aqueous solution to coagulate the acrylic rubber. After thoroughly washing the coagulated product with water and drying at 80 ° C. for 24 hours, (A) acrylic rubbers A-1 to A-5 (for examples) and A′-1 to A′-11 (comparative examples) Obtained).
なお、表１又は表２に示す数値は質量部であり、表１又は表２に示す材料の具体名は、次の通りである
ＥＡ：アクリル酸エチル
ＢＡ：アクリル酸ブチル
ＭＥＡ：アクリル酸２−メトキシエチル
ＡＮ：アクリロニトリル
ＡＭＡ：メタクリル酸アリル
ＤＣＰＥＡ：アクリル酸ジシクロペンテニルオキシエチル
ＶＡ：アクリル酸ビニル
ＰＥＧＤＡ：ポリエチレングリコールジアクリレート（エチレングリコール単位＝４）
ＤＶＢ：ジビニルベンゼン
ＧＭＡ：メタクリル酸グリシジル
The numerical values shown in Table 1 or Table 2 are parts by mass, and the specific names of the materials shown in Table 1 or Table 2 are as follows: EA: ethyl acrylate BA: butyl acrylate MEA: acrylic acid 2- Methoxyethyl AN: Acrylonitrile AMA: Allyl methacrylate DCPEA: Dicyclopentenyloxyethyl acrylate VA: Vinyl acrylate PEGDA: Polyethylene glycol diacrylate (ethylene glycol unit = 4)
DVB: divinylbenzene GMA: glycidyl methacrylate
＜熱可塑性エラストマーの合成＞
（Ａ）アクリルゴム及び（Ｂ）熱可塑性ポリエステルとして表３又は表４に示す材料を表３又は表４に示す量で使用し、温度２５０℃、ブレード回転数１００ｒｐｍに設定したバンバリーミキサーに投入し、トルクが一定になるまで混練を行った。次に（Ｃ）架橋剤として表３又は表４に示す材料を表３又は表４に示す量追加投入し、トルクが一定になるまで混練を行い、熱可塑性エラストマー（実施例１〜９、比較例１〜１１）を合成した。なお、表３又は表４に示す数値は質量部であり、表３又は表４に示す材料表示の具体名は次の通りである。
ＰＢＴ：ポリブチレンテレフタレート
ＰＴＴ：ポリトリメチレンテレフタレート
ＰＥＴ：ポリエチレンテレフタレート
Ｈ２５Ｂ：２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）−ヘキサン
ＤＣＰ：ジクミルパーオキサイド
ＰＭＴＯＰ：３，３，５，７，７−ペンタメチル−１，２，４−トリオキセパン
<Synthesis of thermoplastic elastomer>
(A) Acrylic rubber and (B) Thermoplastic polyester The materials shown in Table 3 or Table 4 are used in the amounts shown in Table 3 or Table 4, and charged into a Banbury mixer set at a temperature of 250 ° C. and a blade rotation speed of 100 rpm. The kneading was continued until the torque became constant. Next, (C) the materials shown in Table 3 or Table 4 as the cross-linking agent were added in the amount shown in Table 3 or Table 4 and kneaded until the torque became constant. Thermoplastic elastomers (Examples 1 to 9, comparison) Examples 1 to 11) were synthesized. In addition, the numerical value shown in Table 3 or Table 4 is a mass part, and the specific name of the material display shown in Table 3 or Table 4 is as follows.
PBT: Polybutylene terephthalate PTT: Polytrimethylene terephthalate PET: Polyethylene terephthalate H25B: 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane DCP: Dicumyl peroxide PMTOP: 3, 3, 5 , 7,7-Pentamethyl-1,2,4-trioxepane
得られた各実施例及び比較例の熱可塑性エラストマーをバンバリーミキサーから取り出し、フィーダールーダーに投入し、ペレット化した。このペレットをシリンダ温度２５０℃に設定した射出成形機によって長さ１５０ｍｍ、幅３０ｍｍ、厚さ２ｍｍのシート状に成形し、その成形加工性及び機械的物性（引張強度、引張伸び、硬度）を評価した。その結果も表３又は表４に示す。なお、各性能の評価方法は次の通りである。 The obtained thermoplastic elastomers of Examples and Comparative Examples were taken out from the Banbury mixer, put into a feeder ruder, and pelletized. This pellet was formed into a sheet of 150 mm length, 30 mm width and 2 mm thickness by an injection molding machine set at a cylinder temperature of 250 ° C., and its molding processability and mechanical properties (tensile strength, tensile elongation, hardness) were evaluated. did. The results are also shown in Table 3 or Table 4. In addition, the evaluation method of each performance is as follows.
＜成形加工性＞
射出成形したシートを目視により観察し、フローマーク又はブツが確認されない場合を○、フローマーク又はブツが確認される場合を×とした。
＜引張強度・伸び＞
ＪＩＳ Ｋ ６２５１に準拠し、試験速度５００ｍｍ／ｍｉｎにて引張強度(ＭＰａ)、引張伸び(％)を測定した。
＜硬度＞
ＪＩＳ Ｋ ６２５３に準拠し、スプリング硬さ試験機Ａ形によって硬度を測定した。
＜耐熱性＞
ＪＩＳ Ｋ ６２５７に準拠し、試験片を１５０℃に設定したギヤーオーブン中に７０時間放置した後の引張強度(ＭＰａ)及び引張伸び(％)を測定し、引張強度の変化率（％）及び引張伸びの変化率（％）を算出した。
＜耐油性＞
ＪＩＳ Ｋ ６２５８に準拠し、試験片をＩＲＭ９０３試験油に浸漬した状態で１５０℃に設定したギヤーオーブン中に７０時間放置した後の質量（ｇ）を測定し、質量変化率を（％）算出した。
<Molding processability>
The injection-molded sheet was visually observed, and the case where no flow mark or irregularity was confirmed was marked with ◯, and the case where a flow mark or irregularity was confirmed was marked with ×.
<Tensile strength / elongation>
Based on JIS K 6251, tensile strength (MPa) and tensile elongation (%) were measured at a test speed of 500 mm / min.
<Hardness>
In accordance with JIS K 6253, the hardness was measured with a spring hardness tester A type.
<Heat resistance>
In accordance with JIS K 6257, the tensile strength (MPa) and tensile elongation (%) after the specimen was left in a gear oven set at 150 ° C. for 70 hours were measured, and the rate of change (%) in tensile strength and tensile strength were measured. The percent change in elongation was calculated.
<Oil resistance>
Based on JIS K 6258, the mass (g) after being left in a gear oven set at 150 ° C. for 70 hours in a state where the test piece was immersed in IRM903 test oil was measured, and the mass change rate was calculated (%). .
表３の結果から、実施例１〜９は、メタクリル酸アリル単量体を含むコア層と、多官能単量体を含んでいないシェル層から構成されるコア−シェル構造のアクリルゴムを使用したので、成形加工性、引張強度、及び引張伸びが優れていた。実施例１〜５、及び実施例８〜９は、アクリロニトリル単量体を含むアクリルゴムを使用したので、特に耐油性に優れていた。実施例１〜３、及び実施例５は、シェル層にメタクリル酸グリシジル単量体を含むアクリルゴムを使用したので、特に引張強度に優れていた。 From the result of Table 3, Examples 1-9 used the acrylic rubber of the core-shell structure comprised from the core layer containing an allyl methacrylate monomer, and the shell layer which does not contain a polyfunctional monomer. Therefore, the moldability, tensile strength, and tensile elongation were excellent. Examples 1 to 5 and Examples 8 to 9 were particularly excellent in oil resistance because acrylic rubber containing an acrylonitrile monomer was used. Examples 1 to 3 and Example 5 were particularly excellent in tensile strength because acrylic rubber containing a glycidyl methacrylate monomer was used in the shell layer.
表４の結果から、比較例１は、コア層にメタクリル酸アリル単量体を含まないアクリルゴムを使用したので、成形加工性、引張強度、及び引張伸びが劣っていた。比較例２は、コア層にメタクリル酸アリル単量体を過剰に含むアクリルゴムを使用したので、成形加工性、引張伸び、及び硬度が劣っていた。比較例３〜７は、コア層に多官能単量体を含むアクリルゴムを使用したので、成形加工性、引張強度、及び引張伸びが劣っていた。比較例８〜９は、シェル層に多官能単量体を含むアクリルゴムを使用したので、成形加工性が劣っていた。比較例１０は、シェル層を有さず、全体にメタクリル酸アリルを含むアクリルゴムを使用したので、成形加工性が劣っていた。比較例１１は、コア層にメタクリル酸アリル単量体を含まず、シェル層にメタクリル酸アリル単量体を含むアクリルゴムを使用したので、成形加工性、引張強度、及び引張伸びが劣っていた。 From the result of Table 4, since the comparative example 1 used the acrylic rubber which does not contain an allyl methacrylate monomer in a core layer, molding processability, tensile strength, and tensile elongation were inferior. In Comparative Example 2, since acrylic rubber containing an excessive amount of allyl methacrylate monomer in the core layer was used, molding processability, tensile elongation, and hardness were inferior. Since Comparative Examples 3 to 7 used acrylic rubber containing a polyfunctional monomer in the core layer, the moldability, tensile strength, and tensile elongation were inferior. Since the comparative examples 8-9 used the acrylic rubber containing a polyfunctional monomer for a shell layer, the moldability was inferior. Since Comparative Example 10 did not have a shell layer and used acrylic rubber containing allyl methacrylate as a whole, the molding processability was inferior. Since the comparative example 11 used the acrylic rubber which does not contain an allyl methacrylate monomer in a core layer and contains an allyl methacrylate monomer in a shell layer, molding processability, tensile strength, and tensile elongation were inferior. .
Claims (1)
（Ａ）アクリルゴムは、コア−シェル構造を有し、
コア層は、
（ａ−１）一般式（１）及び／又は一般式（２）で表される単量体から選ばれる少なくとも１種を８０〜１００質量部と、
（ａ−２）アクリロニトリル単量体を０〜２０質量部と、
（ａ−３）メタクリル酸アリル単量体を、（ａ−１）と（ａ−２）の合計１００質量部に対して０．１〜２質量部とを含み、
シェル層は、
側鎖に炭素−炭素二重結合を有する多官能単量体を含まず、
（ａ−４）一般式（１）及び／又は一般式（２）で表される単量体から選ばれる少なくとも１種を８０〜１００質量部と、
（ａ−５）アクリロニトリル単量体を０〜２０質量部と、
（ａ−６）メタクリル酸グリシジル単量体を、（ａ−４）と（ａ−５）の合計１００質量部に対して０〜５質量部とを含み、
（Ｃ）有機過酸化物が（ａ−３）メタクリル酸アリル単量体の側鎖のアリル基に作用して（Ａ）アクリルゴムを架橋することを特徴とする、熱可塑性エラストマーの製造方法。
（式中、ｎは０、１又は３である）
（式中、ｍは０又は１である）
(A) A mixture containing 100 parts by mass of acrylic rubber and (B) 15 to 70 parts by mass of (B) at least one selected from the group consisting of polybutylene terephthalate, polytrimethylene terephthalate and polyethylene terephthalate. A method for producing a thermoplastic elastomer by dynamically crosslinking in the presence of 0.1 to 5 parts by mass of (C) an organic peroxide ,
(A) Acrylic rubber has a core-shell structure,
The core layer is
(A-1) 80 to 100 parts by mass of at least one selected from monomers represented by general formula (1) and / or general formula (2);
(A-2) 0-20 parts by mass of acrylonitrile monomer;
(A-3) The allyl methacrylate monomer includes 0.1 to 2 parts by mass with respect to 100 parts by mass in total of (a-1) and (a-2),
The shell layer
Does not contain polyfunctional monomer having a carbon-carbon double bond in the side chain,
(A-4) 80 to 100 parts by mass of at least one selected from monomers represented by general formula (1) and / or general formula (2);
(A-5) 0-20 parts by mass of acrylonitrile monomer;
The (a-6) glycidyl methacrylate monomer, saw including a 0-5 parts by weight per 100 parts by weight of (a-4) and (a-5),
(C) An organic peroxide acts on the allyl group of the side chain of (a-3) allyl methacrylate monomer to crosslink (A) acrylic rubber, A method for producing a thermoplastic elastomer.
(Wherein n is 0, 1 or 3)
(Where m is 0 or 1)
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