JP2021080389A - ポリマー組成物 - Google Patents
ポリマー組成物 Download PDFInfo
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- JP2021080389A JP2021080389A JP2019209817A JP2019209817A JP2021080389A JP 2021080389 A JP2021080389 A JP 2021080389A JP 2019209817 A JP2019209817 A JP 2019209817A JP 2019209817 A JP2019209817 A JP 2019209817A JP 2021080389 A JP2021080389 A JP 2021080389A
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 125000005184 naphthylamino group Chemical group C1(=CC=CC2=CC=CC=C12)N* 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002465 nonacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
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- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
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- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000003138 primary alcohols Chemical class 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
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- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
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- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- IBYFOBGPNPINBU-UHFFFAOYSA-N tetradecenoic acid Natural products CCCCCCCCCCCC=CC(O)=O IBYFOBGPNPINBU-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- WXBXVVIUZANZAU-CMDGGOBGSA-N trans-2-decenoic acid Chemical compound CCCCCCC\C=C\C(O)=O WXBXVVIUZANZAU-CMDGGOBGSA-N 0.000 description 1
- IBYFOBGPNPINBU-OUKQBFOZSA-N trans-2-tetradecenoic acid Chemical compound CCCCCCCCCCC\C=C\C(O)=O IBYFOBGPNPINBU-OUKQBFOZSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FPBXRRDHCADTAL-UHFFFAOYSA-N triethoxy(3-nitropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC[N+]([O-])=O FPBXRRDHCADTAL-UHFFFAOYSA-N 0.000 description 1
- FJXRKYLOOJTENP-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyldisulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSCC[Si](OCC)(OCC)OCC FJXRKYLOOJTENP-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- URIYERBJSDIUTC-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltrisulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSCC[Si](OCC)(OCC)OCC URIYERBJSDIUTC-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- PTRSAJDNBVXVMV-UHFFFAOYSA-N triethoxy-[4-(4-triethoxysilylbutyldisulfanyl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCSSCCCC[Si](OCC)(OCC)OCC PTRSAJDNBVXVMV-UHFFFAOYSA-N 0.000 description 1
- NOPBHRUFGGDSAD-UHFFFAOYSA-N triethoxy-[4-(4-triethoxysilylbutyltetrasulfanyl)butyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCCSSSSCCCC[Si](OCC)(OCC)OCC NOPBHRUFGGDSAD-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- QPPXVBLDIDEHBA-UHFFFAOYSA-N trimethoxy(3-nitropropyl)silane Chemical compound CO[Si](OC)(OC)CCC[N+]([O-])=O QPPXVBLDIDEHBA-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- BNBXBRPOAJZBNB-UHFFFAOYSA-N trimethoxy-[4-(4-trimethoxysilylbutyldisulfanyl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCSSCCCC[Si](OC)(OC)OC BNBXBRPOAJZBNB-UHFFFAOYSA-N 0.000 description 1
- GSZUEPNJCPXEGU-UHFFFAOYSA-N trimethoxy-[4-(4-trimethoxysilylbutyltrisulfanyl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCSSSCCCC[Si](OC)(OC)OC GSZUEPNJCPXEGU-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
E*a/E*b≧1.3 (1)
TBa/FBa≧2.6 (2)
本発明のポリマー組成物は、ポリマー及びミクロフィブリル化植物繊維を含み、かつ前記式(1)、(2)を満たす。該ポリマー組成物は、粘弾性特性(E*、tanδ)、耐久性、耐衝撃性等の物性、ミクロフィブリル化植物繊維の配向性に優れている。
ポリマー及びミクロフィブリル化植物繊維を含む組成物が式(1)を満たす場合、ミクロフィブリル化植物繊維の配向によりE*の異方性が生じていると考えられるため、ポリマー中の該繊維の配向性が高いと推察される。更に式(2)を満たす場合、破断時応力が破断時伸びの50%時応力よりも2.6倍以上も高くなるので、配向方向に垂直な方向からの衝撃や振動に強くなっていると推察される。従って、前記ポリマー組成物は、粘弾性特性(E*(剛性)、tanδ(低燃費性))、耐衝撃性等の物性や、ミクロフィブリル化植物繊維の配向性に優れ、振動や衝撃に強い組成物を提供できると推察される。
E*a/E*b≧1.3 (1)
粘弾性特性(E*、tanδ)、耐久性、耐衝撃性等の物性、ミクロフィブリル化植物繊維の配向性の観点から、E*a/E*bは、1.4以上、1.5以上、1.8以上、2.0以上、2.2以上でもよい。上限は特に限定されないが、押出方向の耐亀裂成長性の観点から、E*a/E*bは、8.0以下、6.0以下、5.0以下でもよい。
TBa/FBa≧2.6 (2)
粘弾性特性(E*、tanδ)、耐久性、耐衝撃性等の物性、ミクロフィブリル化植物繊維の配向性の観点から、TBa/FBaは、3.0以上、3.1以上、3.2以上、3.4以上、3.5以上でもよい。上限は特に限定されないが、押出方向の耐振動性の観点から、TBa/FBaは、8.0以下、6.0以下、5.0以下でもよい。
1.0MPa≦E*a≦100MPa (1−1)
粘弾性特性(E*、tanδ)、耐久性、耐衝撃性等の物性、ミクロフィブリル化植物繊維の配向性の観点から、下限は1.2MPa以上、1.5MPa以上、6MPa以上、8MPa以上、10MPa以上、12MPa以上でもよい。上限は特に限定されないが、押出方向の耐衝撃性の観点から、90MPa以下がより好ましく、60MPa以下が更に好ましく、40MPa以下が特に好ましく、20MPa以下が最も好ましくい。
12MPa≦TBa≦50MPa (2−1)
粘弾性特性(E*、tanδ)、耐久性、耐衝撃性等の物性、ミクロフィブリル化植物繊維の配向性の観点から、下限は10MPa以上、15MPa以上、18MPa以上、20MPa以上、25MPa以上、30MPa以上でもよい。上限は特に限定されないが、押出方向の耐振動性の観点から、45MPa以下がより好ましい。
ポリマーとしては特に限定されず、例えば、ゴム、樹脂等の公知の高分子が挙げられる。これらのポリマーは単独で用いてもよく、2種以上を併用してもよい。
粘弾性特性(E*、tanδ)、耐久性、耐衝撃性等の物性、ミクロフィブリル化植物繊維の配向性及び分散性等の観点から、ポリマー組成物において、ポリマー100質量部に対して、ミクロフィブリル化植物繊維を0.5〜30質量部含むことが好ましい。下限は、1質量部以上がより好ましく、3質量部以上が更に好ましく、4質量部以上が特に好ましい。上限は、25質量部以下がより好ましく、20質量部以下が更に好ましく、15質量部以下が特に好ましい。
なお、上記平均アスペクト比は、下記式により算出することができる。
平均アスペクト比=平均繊維長/平均繊維径
オイルとしては特に限定されず、例えば、プロセスオイル、植物油脂、又はその混合物などの公知のオイルが挙げられる。プロセスオイルとしては、例えば、パラフィン系プロセスオイル、アロマ系プロセスオイル、ナフテン系プロセスオイル、TDAE、MES等の低PCA(多環式芳香族)プロセスオイルなどを使用できる。植物油脂としては、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、ロジン、パインオイル、パインタール、トール油、コーン油、こめ油、べに花油、ごま油、オリーブ油、ひまわり油、パーム核油、椿油、ホホバ油、マカデミアナッツ油、桐油等が挙げられる。これらは、1種を用いてもよいし、2種以上を組み合わせて用いてもよい。
下記式(A)の下限は、好ましくは100以上、より好ましくは120以上、更に好ましくは140以上、特に好ましくは150以上であり、上限は、好ましくは190以下、より好ましくは180以下、更に好ましくは170以下である。
80≦構成脂肪酸100質量%中の不飽和結合を1個有する1価不飽和脂肪酸の含有量(質量%)×1(不飽和結合数)+構成脂肪酸100質量%中の不飽和結合を2個有する2価不飽和脂肪酸の含有量(質量%)×2(不飽和結合数)+構成脂肪酸100質量%中の不飽和結合を3個有する3価不飽和脂肪酸の含有量(質量%)×3(不飽和結合数)≦200 式(A)
本明細書において、構成脂肪酸の平均炭素数は、以下の式(D)により算出される。
構成脂肪酸の平均炭素数=Σ構成脂肪酸100質量%中の炭素数nの脂肪酸の含有量(質量%)×n(炭素数)/100 式(D)
下限は特に限定されないが、好ましくは−100℃以上、より好ましくは−90℃以上である。
なお、グリセロール脂肪酸トリエステルの融点は、示差走査熱量測定(DSC)により測定できる。
なお、本明細書において、ヨウ素価とは、グリセロール脂肪酸トリエステル100gにハロゲンを反応させたとき、結合するハロゲンの量をヨウ素のグラム数に換算したものであり、電位差滴定法(JIS K0070)により測定した値である。
ミクロフィブリル化植物繊維及びオイルに有機酸アミンを添加することで、有機酸アミンの親水側がミクロフィブリル化植物繊維と相溶し、疎水側がオイルと相溶する。そして、これらの混合液を、ゴム、樹脂等のポリマーに配合した際、ポリマーに影響しないオイルを使用しているため、ポリマー中にオイルが分散すると共に、ミクロフィブリル化植物繊維の分散、配向効果も得られ、組成物の物性や配向性を向上できる。
なお、前記ポリマー組成物は、ミクロフィブリル化植物繊維以外の他のフィラーを配合してもよい。他のフィラーとしては、カーボンブラック、シリカ、炭酸カルシウム、タルク、アルミナ、クレー、水酸化アルミニウム、酸化アルミニウム、マイカなどが挙げられる。タイヤに適用する場合、カーボンブラック、シリカが好ましい。
なお、カーボンブラックの窒素吸着比表面積は、JIS K6217−2:2001によって求められる。
なお、シリカのN2SAは、ASTM D3037−93に準じてBET法で測定される値である。
シランカップリング剤としては、特に限定されず、例えば、ビス(3−トリエトキシシリルプロピル)テトラスルフィド、ビス(2−トリエトキシシリルエチル)テトラスルフィド、ビス(4−トリエトキシシリルブチル)テトラスルフィド、ビス(3−トリメトキシシリルプロピル)テトラスルフィド、ビス(2−トリメトキシシリルエチル)テトラスルフィド、ビス(2−トリエトキシシリルエチル)トリスルフィド、ビス(4−トリメトキシシリルブチル)トリスルフィド、ビス(3−トリエトキシシリルプロピル)ジスルフィド、ビス(2−トリエトキシシリルエチル)ジスルフィド、ビス(4−トリエトキシシリルブチル)ジスルフィド、ビス(3−トリメトキシシリルプロピル)ジスルフィド、ビス(2−トリメトキシシリルエチル)ジスルフィド、ビス(4−トリメトキシシリルブチル)ジスルフィド、3−トリメトキシシリルプロピル−N,N−ジメチルチオカルバモイルテトラスルフィド、2−トリエトキシシリルエチル−N,N−ジメチルチオカルバモイルテトラスルフィド、3−トリエトキシシリルプロピルメタクリレートモノスルフィド、などのスルフィド系、3−メルカプトプロピルトリメトキシシラン、2−メルカプトエチルトリエトキシシラン、Momentive社製のNXT、NXT−Zなどのメルカプト系、ビニルトリエトキシシラン、ビニルトリメトキシシランなどのビニル系、3−アミノプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシランなどのアミノ系、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、などのグリシドキシ系、3−ニトロプロピルトリメトキシシラン、3−ニトロプロピルトリエトキシシランなどのニトロ系、3−クロロプロピルトリメトキシシラン、3−クロロプロピルトリエトキシシランなどのクロロ系などがあげられる。市販品としては、デグッサ社、Momentive社、信越シリコーン(株)、東京化成工業(株)、アヅマックス(株)、東レ・ダウコーニング(株)等の製品を使用できる。これらは、単独で用いてもよく、2種以上を併用してもよい。
ポリテルペンは、テルペン化合物を重合して得られる樹脂及びそれらの水素添加物である。テルペン化合物は、(C5H8)nの組成で表される炭化水素及びその含酸素誘導体で、モノテルペン(C10H16)、セスキテルペン(C15H24)、ジテルペン(C20H32)などに分類されるテルペンを基本骨格とする化合物であり、例えば、α−ピネン、β−ピネン、ジペンテン、リモネン、ミルセン、アロオシメン、オシメン、α−フェランドレン、α−テルピネン、γ−テルピネン、テルピノレン、1,8−シネオール、1,4−シネオール、α−テルピネオール、β−テルピネオール、γ−テルピネオールなどが挙げられる。
また、固体状のアクリル系樹脂は、水酸基、カルボキシル基、シラノール基等を有していてよい。
加硫促進剤の含有量は特に制限はなく、要望する加硫速度や架橋密度に合わせて自由に決定すれば良いが、ポリマー100質量部に対して、通常、0.3〜10質量部、好ましくは0.5〜7質量部である。
ミクロフィブリル化植物繊維:(株)スギノマシン製のバイオマスナノファイバー(製品名「BiNFi−s セルロース」、固形分2質量%、水分98質量%、平均繊維径10〜50nm、平均繊維長2〜5μm)
オイル:日清オイリオ(株)製の大豆油(各特性を表1に示す。なお、表1中の脂肪酸の含有量は、構成脂肪酸100質量%中の各脂肪酸の含有量(質量%)を意味する。)
有機酸アミン1:カルボン酸アミン塩(Elementis社製FX600)
有機酸アミン2:脂肪酸アミン塩(キレスト(株)製キレスライトWR−6)
NRラテックス:Muhibbah LATEKS社から入手したフィールドラテックスを使用
SBRラテックス:日本ゼオン(株)製のLX110(E−SBR、ビニル含量18質量%、スチレン含量:37.5質量%、ゴムラテックス中のゴム成分の濃度40.5質量%)
NR:TSR20
SBR:日本ゼオン(株)製の市販品(S−SBR、スチレン含量41質量%)
カーボンブラック:三菱ケミカル(株)製のダイアブラックN550(N2SA41m2/g)
老化防止剤:大内新興化学工業(株)製のノクラック6C
酸化亜鉛:三井金属鉱業(株)製の酸化亜鉛2種
ステアリン酸:日油(株)製の椿
硫黄:日本乾溜工業(株)製のセイミ硫黄
加硫促進剤:大内新興化学工業(株)製のノクセラーNS
熱可塑性樹脂:クラレ社製Hybrar 7311F
(樹脂名等))
ミクロフィブリル化植物繊維500gに純水1000gを添加し、ミクロフィブリル化植物繊維の0.5質量%(固形分濃度)懸濁液を作製し、高速ホモジナイザー(IKAジャパン社製の「T50」、回転数:8000rpm)で約5分撹拌して均一な水分散液を調製した。
表2の配合処方に従って、オイル、上記調製した水分散液(ミクロフィブリル化植物繊維の乾燥質量(固形分)換算)、有機酸アミン1〜2を混合し、更にトルエンをオイル100質量部に対して100質量部添加して、混合した。得られた混合物に塩酸を少量添加し、80℃に加熱して共沸させて水分を除去した。水分除去後の混合物を高速ホモジナイザー(IKAジャパン社製の「T50」、回転数:8000rpm)を用いて50℃で5分撹拌、混合して、混合液1〜3を調製した。
表3の配合処方に従って、ゴム・ミクロフィブリル化植物繊維複合体を製造した。
具体的には、上記調製した水分散液(ミクロフィブリル化植物繊維の水分散液)、NRラテックス(ゴム(固形分)換算)又はSBRラテックス(ゴム(固形分)換算)を、高速ホモジナイザーを用いて室温で5分攪拌し、pH10.2の配合ラテックスを得た。次いで、室温下で2質量%ギ酸水溶液を加え、pH3〜4に調整し、凝固物を得た。得られた凝固物をろ過し、乾燥してゴム・ミクロフィブリル化植物繊維複合体(WB1、2)を得た。
<ゴムサンプルの作製>
表4〜5に示す配合処方に従い、1.7Lバンバリーミキサーを用いて、硫黄及び加硫促進剤以外の材料を150℃で4分間混練りした。次に、オープンロールを用いて、得られた混練り物に硫黄及び加硫促進剤を添加して80℃で4分間練り込み、未加硫ゴム組成物を得た。得られた未加硫ゴム組成物を170℃で20分間プレス成形し(加硫)、ゴムサンプル(加硫ゴム組成物)を作製した。
表6に示す配合処方に従い、材料を2軸押出機で混練、成形し、樹脂組成物(試験片)を得た。
前記ゴムサンプルの作製で製造されたゴムサンプルから採取した試験片(加硫ゴム組成物)、前記樹脂組成物の作製で製造された樹脂組成物から採取した試験片について、下記の物性測定、評価を行った。結果を表4〜6に示した。表4、5、6の基準比較例は、それぞれ比較例1−1、2−1、3−1である。
押出方向、押出方向に直行する方向に採取した試験片(サイズ:縦20mm、横3mm、厚さ2mm)を用い、GABO社製イプレクサーを用いて、温度70℃、周波数10Hz、初期歪10%及び動歪1%の条件下で、押出方向の複素弾性率E*a(MPa)、押出方向の直交方向の複素弾性率E*b(MPa)を測定した。
JIS K6251:2017「加硫ゴム及び熱可塑性ゴム−引張特性の求め方」に従って7号ダンベルサンプルを用いて引張試験を行い(標準試験温度(23±2℃))、押出方向伸長時の破断応力TBa(MPa)、押出方向伸長時における破断時伸びの50%伸長時の応力FBa(MPa)を測定した。
各ゴムサンプル(試験片)、各樹脂組成物(試験片)について、Izod衝撃試験機((株)東洋精機製作所製)を用いてIzod衝撃試験を実施した(ミクロフィブリル化植物繊維の配向方向に垂直な方向(押出方向に直行する方向)に衝撃入力)。試験片中央部に深さ2mmの切り欠き(ノッチ)を挿入した。5.5J−R試験では5.5Jのハンマーを用いてノッチと反対側を打撃し、ノッチのない成形品表面から亀裂を進展させ、その時の衝撃強度を算出した。基準比較例を100とし、各試験片を指数で表示した。指数が大きいほど、耐衝撃性(衝撃強さ)が大きい。
各ゴムサンプル(加硫ゴム組成物)について、GABO社製イプレクサーを用いて、温度70℃、周波数10Hz、初期歪10%及び動歪1%の条件下で、損失正接(tanδ)を測定し、基準比較例を100としたときの指数で表示した(ミクロフィブリル化植物繊維の配向方向(押出方向)に伸長変形)。指数が大きいほど、低燃費性に優れる。
各ゴムサンプル(加硫ゴム組成物)及び各樹脂組成物を用い、JIS K6260「加硫ゴム及び熱可塑性ゴム−デマッチャ屈曲亀裂試験方法」に基づいて各試験片を作製し、屈曲亀裂成長試験を行い、70%伸張を100万回繰り返してゴムシートを屈曲させたのち、発生した亀裂の長さを測定した(ミクロフィブリル化植物繊維の配向方向に垂直な方向(押出方向に直行する方向)に屈曲)。基準比較例の測定値(長さ)の逆数を100とし、指数表示した。指数が大きいほど、亀裂の成長が抑制され、耐屈曲亀裂成長性に優れることを示す。
各ゴムサンプル(加硫ゴム組成物)及び各樹脂組成物について、JIS K7391 3.3中央加振法に準拠し、振動性能を評価した。基準比較例の振動性能を100とし、指数表示した。指数が大きいほど、振動性能に優れることを示す。
各樹脂組成物(試験片)について、防湿容器中で23℃±2℃で24時間以上保持した。この試験片を防湿容器から取り出した後、速やか(15分以内)に、曲げ弾性率(MPa)をISO178に準じて測定した(ミクロフィブリル化植物繊維の配向方向に垂直な方向(押出方向に直行する方向)の曲げ弾性率を測定)。測定は、温度23℃、湿度50%RHで行った。基準比較例を100とし、各試験片を指数で表示した。指数が大きいほど、曲げ弾性率が大きい。
各樹脂組成物(試験片)について、JIS Z 2248に準拠する試験方法で曲げ強度(kgf/mm2)を測定した(ミクロフィブリル化植物繊維の配向方向に垂直な方向(押出方向に直行する方向)の曲げ強度を測定)。即ち、スパン間距離を200mmとし、2つの支えは円形でその半径が5mm、中間押金具は半径が5mmの半円断面の、3点曲げ方式とした。試験体は補強面を下とし、クロスヘッド速度は2mm/分とした。基準比較例を100とし、各試験片を指数で表示した。指数が大きいほど、曲げ強度が大きい。
Claims (8)
- ポリマー及びミクロフィブリル化植物繊維を含み、
押出方向の複素弾性率E*a(MPa)と該押出方向の直交方向の複素弾性率E*b(MPa)との比(E*a/E*b)が下記式(1)、押出方向伸長時の破断応力TBa(MPa)と該押出方向伸長時における破断時伸びの50%伸長時の応力FBa(MPa)との比(TBa/FBa)が下記式(2)を満たすポリマー組成物。
E*a/E*b≧1.3 (1)
TBa/FBa≧2.6 (2) - E*a/E*b≧1.5を満たす請求項1記載のポリマー組成物。
- E*a/E*b≧2.0を満たす請求項1記載のポリマー組成物。
- TBa/FBa≧3.0を満たす請求項1〜3のいずれかに記載のポリマー組成物。
- TBa/FBa≧3.4を満たす請求項1〜3のいずれかに記載のポリマー組成物。
- 前記ポリマー100質量部に対して、前記ミクロフィブリル化植物繊維を0.5〜30質量部含む請求項1〜5のいずれかに記載のポリマー組成物。
- 前記ポリマー組成物中における前記ミクロフィブリル化植物繊維の平均アスペクト比が10〜1000である請求項1〜6のいずれかに記載のポリマー組成物。
- 前記ポリマー組成物中における前記ミクロフィブリル化植物繊維の平均繊維径が10μm以下である請求項1〜7のいずれかに記載のポリマー組成物。
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US4414370A (en) | 1981-01-09 | 1983-11-08 | S. C. Johnson & Son, Inc. | Process for continuous bulk copolymerization of vinyl monomers |
US4529787A (en) | 1982-06-15 | 1985-07-16 | S. C. Johnson & Son, Inc. | Bulk polymerization process for preparing high solids and uniform copolymers |
US4546160A (en) | 1984-02-29 | 1985-10-08 | S. C. Johnson & Son, Inc. | Bulk polymerization process for preparing high solids and uniform copolymers |
US5010166A (en) | 1987-03-05 | 1991-04-23 | S. C. Johnson & Son, Inc. | Process and apparatus for producing polyol polymers and polyol polymers so produced |
US4988763A (en) | 1988-04-26 | 1991-01-29 | S. C. Johnson & Son, Inc. | Catalyzed bulk process for producing cyclic ester-modified acrylic polymers |
JP4286319B1 (ja) | 2008-02-01 | 2009-06-24 | 住友ゴム工業株式会社 | 空気入りタイヤ |
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