JPS6345743B2 - - Google Patents
Info
- Publication number
- JPS6345743B2 JPS6345743B2 JP58180729A JP18072983A JPS6345743B2 JP S6345743 B2 JPS6345743 B2 JP S6345743B2 JP 58180729 A JP58180729 A JP 58180729A JP 18072983 A JP18072983 A JP 18072983A JP S6345743 B2 JPS6345743 B2 JP S6345743B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- group
- carbon atoms
- parts
- block copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims description 32
- 229920001400 block copolymer Polymers 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 16
- 239000000194 fatty acid Substances 0.000 claims description 16
- 229930195729 fatty acid Natural products 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 150000001993 dienes Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005041 acyloxyalkyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 235000019646 color tone Nutrition 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002900 organolithium compounds Chemical class 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OQEBBZSWEGYTPG-UHFFFAOYSA-N 3-aminobutanoic acid Chemical group CC(N)CC(O)=O OQEBBZSWEGYTPG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- APMOEFCWQRJOPS-UHFFFAOYSA-N 5-ethenyl-1,5-dimethylcyclohexa-1,3-diene Chemical compound CC1=CC=CC(C)(C=C)C1 APMOEFCWQRJOPS-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005647 hydrohalogenation reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid 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
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
（産業上の利用分野）
本発明は、耐候性及び色調に優れたブロツク共
重合体組成物に関する。
（従来の技術）
共役ジエンとビニル芳香族炭化水素からなるブ
ロツク共重合体は、比較的ビニル芳香族炭化水素
含有量が少ない場合、加硫をしなくても加硫され
た天然ゴム或いは合成ゴムと同様の弾性を常温に
て有し、しかも高温で熱可塑性樹脂と同様の加工
性を有することから、履物、プラスチツク改質、
アスフアルト、粘接着分野等で広く利用されてい
る。又、比較的ビニル芳香族炭化水素含有量が多
い場合は、透明で耐衝撃性に優れた熱可塑性樹脂
が得られることから、食品包装容器分野を中心に
近年その使用量が増加すると同時に用途も多様化
しつつある。
（発明が解決しようとする課題）
しかしながら、かかるブロツク共重合体は耐候
性に劣り、長期間屋外で使用する用途には利用で
きないという問題点を有している。耐候性を改良
する方法としてはベンゾフエノン系化合物やベン
ゾトリアゾール系化合物を添加する方法が一般に
知られているが、かかる化合物はその改良効果が
充分でなくその改良が要望されている。
（課題を解決するための手段）
本発明者らはかかる現状に鑑み、ブロツク共重
合体の耐候性を改良方法について鋭意検討を進め
た結果、ヒンダードアミン系化合物と高級脂肪酸
を組合せることにより耐候性及び色調に優れた組
成物の得られることを見い出し、本発明を完成す
るに至つた。
すなわち、本発明は、
ビニル芳香族炭化水素の含有量が５〜95重量％
である共役ジエンとビニル芳香族炭化水素とから
成るブロツク共重合体100重量部に対して、
(a) 炭素数が10〜26の高級脂肪酸0.05〜５重量部
(b) 分子内に少なくとも１個の次式〔〕で示さ
れる基を有するヒンダードアミン系化合物
0.005〜３重量部
を含有するブロツク共重合体組成物。
（式中R1，R2，R3及びR4は同一又は異なり、
炭素原子数１〜12の直鎖または分枝鎖アルキル基
を表わすか、或いはR1とR2が一緒になつて、そ
れらが結合している炭素原子と共に、炭素原子数
４〜12のシクロアルキル基もしくは
(Industrial Application Field) The present invention relates to a block copolymer composition with excellent weather resistance and color tone. (Prior art) When a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon has a relatively low vinyl aromatic hydrocarbon content, it can be used as a vulcanized natural rubber or synthetic rubber without vulcanization. It has the same elasticity at room temperature as thermoplastic resin, and has the same processability as thermoplastic resin at high temperatures, so it is useful for footwear, plastic modification,
Widely used in asphalt, adhesive and other fields. In addition, when the vinyl aromatic hydrocarbon content is relatively high, a thermoplastic resin that is transparent and has excellent impact resistance can be obtained, so its usage has increased in recent years, mainly in the food packaging container field, and its applications have also expanded. It is becoming more diverse. (Problems to be Solved by the Invention) However, such block copolymers have a problem that they have poor weather resistance and cannot be used outdoors for long periods of time. As a method for improving weather resistance, a method of adding a benzophenone compound or a benzotriazole compound is generally known, but the improvement effect of such compounds is not sufficient and improvement thereof is desired. (Means for Solving the Problems) In view of the current situation, the present inventors have conducted intensive studies on methods for improving the weather resistance of block copolymers. The inventors have also discovered that a composition with excellent color tone can be obtained, and have completed the present invention. That is, the present invention has a vinyl aromatic hydrocarbon content of 5 to 95% by weight.
For 100 parts by weight of a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon, (a) 0.05 to 5 parts by weight of a higher fatty acid having 10 to 26 carbon atoms (b) At least one fatty acid in the molecule A hindered amine compound having a group represented by the following formula []
A block copolymer composition containing 0.005 to 3 parts by weight. (In the formula, R 1 , R 2 , R 3 and R 4 are the same or different,
represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or R 1 and R 2 together, together with the carbon atom to which they are attached, represents a cycloalkyl group having 4 to 12 carbon atoms; base or
【式】〔R′1，R′2，R′3及びR′4は同一
又は異なり、炭素原子数１〜12の直鎖または分枝
鎖アルキル基を表わす〕を形成していることを表
わす。Ｘ及びX′は水素または酸素原子を表わす
か、或いは炭素原子数１〜20の直鎖もしくは分枝
鎖アルキル基、炭素原子数３〜12のアルケニル基
もしくはアルキニル基、炭素原子数７〜13のアル
キル基、ニトロソ基を表わすか、更にはアリール
基で置換されているかいないヒドロキシアルキル
基、アルコキシアルキル基、アシロキシアルキル
基を表わす。）
を提供する。
本発明の組成物は、ブロツク共重合体とヒンダ
ードアミン系化合物のみを組合せた場合にみられ
る激しい黄変がほとんどなく、しかも耐候性が優
れているため長期間屋外で使用される様な各種用
途分野における素材として好適に利用できる。
以下本発明を詳細に説明する。
本発明で使用される共役ジエンとビニル芳香族
炭化水素とから成るブロツク共重合体は、ビニル
芳香族炭化水素の含有量が５〜95重量％、好まし
くは10〜90重量％、更に好ましくは15〜85重量％
のものである。かかるブロツク共重合体はビニル
芳香族炭化水素の含有量が60重量％以下、好まし
くは55重量％以下の場合は熱可塑性弾性体として
の特性を示し、ビニル芳香族炭化水素の含有量が
60重量％を超える場合、好ましくは65重量％以上
の場合は熱可塑性樹脂としての特性を示す。
本発明で使用されるブロツク共重合体の製造方
法としては、例えば特公昭36−19286号公報、特
公昭43−14979号公報、特公昭49−36957号公報、
特公昭48−2423号公報、特公昭48−4106号公報な
どに記載された方法があげられる。これらはすべ
て、炭化水素溶剤中で有機リチウム化合物等のア
ニオン重合開始剤を用い、共役ジエンとビニル芳
香族炭化水素をブロツク共重合する方法であり、
一般式
（Ａ−Ｂ）o、Ａ（―Ｂ−Ａ）o、Ｂ（―Ａ−Ｂ）o
（上式において、Ａはビニル芳香族炭化水素を
主とする重合体ブロツクであり、Ｂは共役ジエン
を主とする重合体ブロツクである。Ａブロツクと
Ｂブロツクとの境界は必ずしも明瞭に区別される
必要はない。又、ｎは１以上の整数で、一般には
１〜５の整数である。）
で表わされる線状ブロツク共重合体、あるいは一
般式
〔（Ｂ−Ａ）o〕−n+2Ｘ、
〔（Ａ−Ｂ）o〕−n+2Ｘ
〔（Ｂ−Ａ（―oＢ−〕n+2Ｘ
〔（Ａ−Ｂ（―oＡ−〕n+2Ｘ
（上式において、Ａ、Ｂは前記と同じであり、
Ｘは例えば四塩化ケイ素、四塩化スズ、エポキシ
化大豆油などのカツプリング剤の残基又は多官能
有機リチウム化合物等の開始剤の残基を示す。ｍ
及びｎは１以上の整数で、一般には１〜５の整数
である。）
で表わされるラジアルブロツク共重合体として得
られる。尚、上式において、ビニル芳香族炭化水
素を主とする重合体ブロツクとはビニル芳香族炭
化水素を50重量％以上含有するビニル芳香族炭化
水素と共役ジエンとの共重合体ブロツク又はビニ
ル芳香族炭化水素単独重合体ブロツク或いはそれ
らの組合せからなる重合体ブロツクを示し、共役
ジエンを主とする重合体ブロツクとは共役ジエン
を50重量％を超える量で含有する共役ジエンとビ
ニル芳香族炭化水素との共重合体ブロツク又は共
役ジエン単独重合体ブロツク或いはそれらの組合
せからなる重合体ブロツクを示す。共重合体ブロ
ツク中のビニル芳香族炭化水素は均一に分布して
いても、又テーパー状に分布していてもよい。
本発明の方法で用いるビニル芳香族炭化水素と
してはスチレン、ｏ―メチルスチレン、ｐ―メチ
ルスチレン、ｐ―tert―ブチルスチレン、１，３
―ジメチルスチレン、α―メチルスチレン、ビニ
ルナフタレン、ビニルアントラセンなどがある
が、特に一般的なものとしてはスチレンが挙げら
れる。これらは１種のみならず２種以上混合して
使用してもよい。
本発明で用いる共役ジエンとは、１対の共役二
重結合を有するジオレフインであり、たとえば
１，３―ブタジエン、２―メチル―１，３―ブタ
ジエン（イソプレン）、２，３―ジメチル―１，
３―ブタジエン、１，３―ペンタジエン、１，３
―ヘキサジエンなどであるが、特に一般的なもの
としては１，３―ブタジエン、イソプレンが挙げ
られる。これらは１種のみならず２種以上混合し
て使用してもよい。
本発明で使用するブロツク共重合体の分子量は
5000〜1000000、好ましくは10000〜800000、さら
に好ましくは30000〜500000である。また、ブロ
ツク共重合体はその基本的な特性を損わない範囲
内で水素添加、ハロゲン化、ハロゲン化水素化、
あるいは化学反応により水酸基、チオール基、ニ
トリル基、スルホン酸基、アミノ基等の官能基の
導入を行うなどの改質が行われていてもよい。
本発明で使用する成分(a)の高級脂肪酸は、炭素
数が10〜26、好ましくは炭素数12〜22の高級脂肪
酸である。通常高級脂肪酸は動物または植物油脂
を原料として得られるが、本発明においては、そ
の他ジカルボン酸、トリカルボン酸などでもよ
い。かかる高級脂肪酸の具体例としては、カプリ
ン酸、ラウリン酸、ミリスチン酸、パルミチン
酸、ステアリン酸、オレイン酸、リノール酸、リ
ノレン酸、リシノール酸、ベヘニン酸、牛脂脂肪
酸、ヒマシ硬化脂肪酸、あるいはこれらの混合物
があげられる。高級脂肪酸は、ブロツク共重合体
100重量部に対して0.05〜５重量部、好ましくは
0.1〜１重量部配合される。高級脂肪酸の配合量
が0.05重量部未満の場合はヒンダードアミン系化
合物の使用による黄変が防止できず、また５重量
部を超える場合は成形品の表面に高級脂肪酸がブ
リードして外観特性を低下させるため好ましくな
い。
本発明で使用する成分(b)のヒンダードアミン系
化合物は、分子内に少なくとも１個の次式〔〕
で示される基
（式中R1，R2，R3及びR4は同一又は異なり、
炭素原子数１〜12の直鎖または分枝鎖アルキル基
を表わすか、或いはR1とR2が一緒になつて、そ
れらが結合している炭素原子と共に、炭素原子数
４〜12のシクロアルキル基もしくは
[Formula] [R' 1 , R' 2 , R' 3 and R' 4 are the same or different and represent a straight or branched alkyl group having 1 to 12 carbon atoms]. . X and X' represent hydrogen or oxygen atoms, or straight-chain or branched alkyl groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 3 to 12 carbon atoms, or It represents an alkyl group, a nitroso group, or a hydroxyalkyl group, an alkoxyalkyl group, or an acyloxyalkyl group which is not substituted with an aryl group. ) I will provide a. The composition of the present invention has almost no severe yellowing that occurs when only a block copolymer and a hindered amine compound are combined, and has excellent weather resistance, so it can be used in various fields where it is used outdoors for a long time. It can be suitably used as a material for. The present invention will be explained in detail below. The block copolymer composed of a conjugated diene and a vinyl aromatic hydrocarbon used in the present invention has a vinyl aromatic hydrocarbon content of 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15% by weight. ~85% by weight
belongs to. Such a block copolymer exhibits properties as a thermoplastic elastomer when the content of vinyl aromatic hydrocarbons is 60% by weight or less, preferably 55% by weight or less;
If it exceeds 60% by weight, preferably 65% by weight or more, it exhibits properties as a thermoplastic resin. The method for producing the block copolymer used in the present invention includes, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-14979, Japanese Patent Publication No. 49-36957,
Examples include methods described in Japanese Patent Publication No. 48-2423 and Japanese Patent Publication No. 48-4106. All of these methods involve block copolymerization of a conjugated diene and a vinyl aromatic hydrocarbon using an anionic polymerization initiator such as an organolithium compound in a hydrocarbon solvent.
General formula (A-B) o , A(-B-A) o , B(-A-B) o (In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbon, and B is It is a polymer block mainly composed of conjugated diene.The boundary between A block and B block does not necessarily need to be clearly distinguished.Also, n is an integer of 1 or more, and generally an integer of 1 to 5. ) or the general formula [(B-A) o ]- n+2 X, [(A-B) o ]- n+2 X [(B-A(- o B-] n+2 X [(A-B(- o A-)] n+2 X (In the above formula, A and B are the same as above,
X represents, for example, a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, or epoxidized soybean oil, or a residue of an initiator such as a polyfunctional organolithium compound. m
and n is an integer of 1 or more, generally an integer of 1 to 5. ) is obtained as a radial block copolymer represented by: In the above formula, the polymer block mainly composed of vinyl aromatic hydrocarbons refers to a copolymer block of vinyl aromatic hydrocarbons and conjugated diene containing 50% by weight or more of vinyl aromatic hydrocarbons, or vinyl aromatic hydrocarbons. It refers to a polymer block consisting of a hydrocarbon homopolymer block or a combination thereof, and a polymer block mainly composed of a conjugated diene is a polymer block consisting of a conjugated diene containing more than 50% by weight of a conjugated diene, a vinyl aromatic hydrocarbon, This shows a polymer block consisting of a copolymer block, a conjugated diene homopolymer block, or a combination thereof. The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed or tapered. Vinyl aromatic hydrocarbons used in the method of the present invention include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3
- Dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, etc., but styrene is particularly common. These may be used not only alone, but also as a mixture of two or more. The conjugated diene used in the present invention is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,
3-butadiene, 1,3-pentadiene, 1,3
-hexadiene, etc., but particularly common ones include 1,3-butadiene and isoprene. These may be used not only alone, but also as a mixture of two or more. The molecular weight of the block copolymer used in the present invention is
5,000 to 1,000,000, preferably 10,000 to 800,000, and more preferably 30,000 to 500,000. In addition, the block copolymer may be subjected to hydrogenation, halogenation, hydrohalogenation, etc. within the range that does not impair its basic properties.
Alternatively, modification may be performed such as introduction of functional groups such as hydroxyl groups, thiol groups, nitrile groups, sulfonic acid groups, and amino groups through chemical reactions. The higher fatty acid of component (a) used in the present invention is a higher fatty acid having 10 to 26 carbon atoms, preferably 12 to 22 carbon atoms. Higher fatty acids are usually obtained from animal or vegetable oils and fats, but in the present invention, other fatty acids such as dicarboxylic acids and tricarboxylic acids may also be used. Specific examples of such higher fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, behenic acid, tallow fatty acid, castor hydrogenated fatty acid, or mixtures thereof. can be given. Higher fatty acids are block copolymers
0.05 to 5 parts by weight per 100 parts by weight, preferably
It is blended in an amount of 0.1 to 1 part by weight. If the amount of higher fatty acids is less than 0.05 parts by weight, yellowing due to the use of hindered amine compounds cannot be prevented, and if it exceeds 5 parts by weight, higher fatty acids will bleed onto the surface of the molded product and deteriorate the appearance characteristics. Therefore, it is undesirable. The hindered amine compound used in the present invention as component (b) has at least one compound of the following formula [] in the molecule.
The group represented by (In the formula, R 1 , R 2 , R 3 and R 4 are the same or different,
represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or R 1 and R 2 together, together with the carbon atom to which they are attached, represents a cycloalkyl group having 4 to 12 carbon atoms; base or
【式】〔R′1，R′2，R′3及びR′4は同一
又は異なり、炭素原子数１〜12の直鎖または分枝
鎖アルキル基を表わす〕を形成していることを表
わす。Ｘ及びX′は水素または酸素原子を表わす
か、或いは炭素原子数１〜20の直鎖もしくは分枝
鎖アルキル基、炭素原子数３〜12のアルケニル基
もしくはアルキニル基、炭素原子数７〜13のアル
キル基、ニトロソ基を表わすか、更にはアリール
基で置換されているかいないヒドロキシアルキル
基、アルコキシアルキル基、アシロキシアルキル
基を表わす。）
を有する化合物である。上記〔〕で示される基
を有する化合物としては、例えば
（式中R5は、ｍが１のとき：脂肪族、芳香族
もしくは複素環式モノカルボン酸から誘導される
アシル基、Ｎ―置換カルバミン酸もしくはＮ―置
換チオカルバミン酸から誘導されるＮ―置換カル
バモイル基もしくはＮ―置換チオカルバモイル
基、スルフイン酸、スルホン酸、リン酸、亜リン
酸もしくはほう酸のような酸素酸から１個の水酸
基を除去して得られる１価の基、メチルもしくは
ステアリルのようなアルキル基、シクロヘキシル
のようなシクロアルキル基、ベンジルのようなア
ラルキル基、フエニル、クロルフエニル、トリル
もしくはナフチルのようなアリール基または基
[Formula] [R' 1 , R' 2 , R' 3 and R' 4 are the same or different and represent a straight or branched alkyl group having 1 to 12 carbon atoms]. . X and X' represent hydrogen or oxygen atoms, or straight-chain or branched alkyl groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 3 to 12 carbon atoms, or It represents an alkyl group, a nitroso group, or a hydroxyalkyl group, an alkoxyalkyl group, or an acyloxyalkyl group which is not substituted with an aryl group. ) is a compound having the following. Examples of compounds having the group represented by [] above include: (In the formula, R 5 is an acyl group derived from an aliphatic, aromatic or heterocyclic monocarboxylic acid, an N- derived from an N-substituted carbamic acid or an N-substituted thiocarbamic acid when m is 1) Substituted carbamoyl or N-substituted thiocarbamoyl groups, monovalent groups obtained by removing one hydroxyl group from oxyacids such as sulfinic acid, sulfonic acid, phosphoric acid, phosphorous acid or boric acid, methyl or stearyl alkyl groups such as, cycloalkyl groups such as cyclohexyl, aralkyl groups such as benzyl, aryl groups or groups such as phenyl, chlorophenyl, tolyl or naphthyl.
窒素ガス雰囲気下において、１，３―ブタジエ
ン15重量部とスチレン20重量部を含むｎ―ヘキサ
ン溶液にｎ―ブチルリチウムを0.11重量部添加
し、70℃で２時間重合した後、さらに１，３―ブ
タジエン45重量部とスチレン20重量部を含むｎ―
ヘキサン溶液を加えて70℃で２時間重合した。得
られた重合体は、スチレン含有量40重量％のＢ―
Ａ―Ｂ―Ａ構造のブロツク共重合体であつた。
〔ブロツク共重合体 (B)〕
窒素ガス雰囲気下において、スチレン30重量部
を含むシクロヘキサン溶液にｎ―ブチルリチウム
を0.35重量部添加し、70℃で１時間重合した後、
１，３―ブタジエン70重量部含むシクロヘキサン
溶液を加えて70℃で２時間重合した。その後テト
ラクロルシランを、使用したｎ―ブチルリチウム
の1/4当量添加して、スチレン含有量30重量％の
（Ａ−Ｂ）4Si構造のブロツク共重合体を得た。
〔ブロツク共重合体 (C)〕
窒素ガス雰囲気下において、スチレン30重量部
とテトラヒドロフラン0.3重量部を含むシクロヘ
キサン溶液にｎ―ブチルリチウムを0.07重量部添
加し、70℃で１時間重合した後、更に１，３―ブ
タジエン15重量部とスチレン55重量部を含むシク
ロヘキサン溶液を加えて70℃で２時間重合した。
得られた重合体はスチレン含有量85重量％のＡ―
Ｂ―Ａ構造のブロツク共重合体であつた。
〔ブロツク共重合体 (D)〕
窒素ガス雰囲気下において、ブタジエン15重量
部を含むシクロヘキサン溶液にｎ―ブチルリチウ
ムを0.08重量部添加し、70℃で１時間重合した
後、順次スチレン20重量部、ブタジエン15重量
部、スチレン50重量部をそれぞれ添加して重合し
た。尚、各ステツプにおける重合温度は70℃、重
合時間はそれぞれ１時間とした。得られた重合体
はスチレン含有量70重量％のＢ―Ａ―Ｂ―Ａ構造
のブロツク共重合体であつた。
尚、各ブロツク共重合体には安定剤として
BHT及びTNPをブロツク共重合体100重量部に
対してそれぞれ0.5重量部添加した。
実施例１〜15及び比較例１〜23
表１に示した配合処法に従つて作製したブロツ
ク共重合体組成物の圧縮成形片を用いて耐候性及
び色調を調べ、結果を表１に示した。
次に比較例９〜23として、高級脂肪酸を使用し
ない以外は実施例１〜15と同様の圧縮成形片を用
いて耐候性及び色調を調べた。その結果これらの
比較例サンプルは耐候性は実施例１〜15と同等の
性能を有するものの、いずれも色調が極めて悪く
（評価ランクでは△又は×）実用上問題のあるも
のであつた。
以上の結果より、ブロツク共重合体に高級脂肪
酸及びヒンダードアミン系化合物を配合すること
により耐候性及び色調に優れた組成物の得られる
ことが明らかになつた。
In a nitrogen gas atmosphere, 0.11 parts by weight of n-butyllithium was added to an n-hexane solution containing 15 parts by weight of 1,3-butadiene and 20 parts by weight of styrene, and after polymerization at 70°C for 2 hours, further 1,3 parts by weight of n-butyllithium was added. -Contains 45 parts by weight of butadiene and 20 parts by weight of styrene-
A hexane solution was added and polymerization was carried out at 70°C for 2 hours. The obtained polymer was B- with a styrene content of 40% by weight.
It was a block copolymer with an ABA structure. [Block copolymer (B)] In a nitrogen gas atmosphere, 0.35 parts by weight of n-butyllithium was added to a cyclohexane solution containing 30 parts by weight of styrene, and after polymerization at 70°C for 1 hour,
A cyclohexane solution containing 70 parts by weight of 1,3-butadiene was added and polymerized at 70°C for 2 hours. Thereafter, tetrachlorosilane was added in an amount equivalent to 1/4 of the n-butyllithium used to obtain a block copolymer having an (A-B) 4 Si structure with a styrene content of 30% by weight. [Block copolymer (C)] In a nitrogen gas atmosphere, 0.07 parts by weight of n-butyllithium was added to a cyclohexane solution containing 30 parts by weight of styrene and 0.3 parts by weight of tetrahydrofuran, and after polymerization at 70°C for 1 hour, further A cyclohexane solution containing 15 parts by weight of 1,3-butadiene and 55 parts by weight of styrene was added and polymerized at 70°C for 2 hours.
The obtained polymer had a styrene content of 85% by weight.
It was a block copolymer with a BA structure. [Block copolymer (D)] In a nitrogen gas atmosphere, 0.08 parts by weight of n-butyllithium was added to a cyclohexane solution containing 15 parts by weight of butadiene, and after polymerization at 70°C for 1 hour, 20 parts by weight of styrene, Polymerization was carried out by adding 15 parts by weight of butadiene and 50 parts by weight of styrene. The polymerization temperature in each step was 70°C, and the polymerization time was 1 hour. The obtained polymer was a block copolymer having a BABA structure with a styrene content of 70% by weight. In addition, each block copolymer contains a stabilizer.
0.5 parts by weight of each of BHT and TNP were added to 100 parts by weight of the block copolymer. Examples 1 to 15 and Comparative Examples 1 to 23 Weather resistance and color tone were investigated using compression molded pieces of block copolymer compositions produced according to the formulation shown in Table 1, and the results are shown in Table 1. Ta. Next, as Comparative Examples 9 to 23, weather resistance and color tone were examined using compression molded pieces similar to those in Examples 1 to 15, except that higher fatty acids were not used. As a result, although these comparative samples had weather resistance performance equivalent to that of Examples 1 to 15, all of them had extremely poor color tones (ranked as Δ or × in the evaluation rank) and were problematic in practice. From the above results, it has become clear that a composition with excellent weather resistance and color tone can be obtained by blending a higher fatty acid and a hindered amine compound with a block copolymer.
【表】【table】
【表】【table】
【表】
実施例 16〜21
ブロツク共重合体にポリスチレン等を配合した
混合物に高級脂肪酸及びヒンダードアミン系化合
物を添加し、圧縮成形片を作製した。得られた各
サンプルの耐候性及び色調を調べ、結果を第２表
に示した。[Table] Examples 16 to 21 A compression molded piece was produced by adding a higher fatty acid and a hindered amine compound to a mixture of a block copolymer and polystyrene. The weather resistance and color tone of each sample obtained were examined, and the results are shown in Table 2.
【表】【table】
Claims (1)
％である共役ジエンとビニル芳香族炭化水素とか
ら成るブロツク共重合体100重量部に対して、 (a) 炭素数が10〜26の高級脂肪酸0.05〜５重量部 (b) 分子内に少なくとも１個の次式〔〕で示さ
れる基を有するヒンダードアミン系化合物
0.005〜３重量部 を含有するブロツク共重合体組成物。 （式中R1，R2，R3及びR4は同一又は異なり、
炭素原子数１〜12の直鎖または分枝鎖アルキル基
を表わすか、或いはR1とR2が一緒になつて、そ
れらが結合している炭素原子と共に、炭素原子数
４〜12のシクロアルキル基もしくは
【式】〔R′1，R′2，R′3及びR′4は同一 又は異なり、炭素原子数１〜12の直鎖または分枝
鎖アルキル基を表わす〕を形成していることを表
わす。Ｘ及びX′は水素または酸素原子を表わす
か、或いは炭素原子数１〜20の直鎖もしくは分枝
鎖アルキル基、炭素原子数３〜12のアルケニル基
もしくはアルキニル基、炭素原子数７〜13のアル
キル基、ニトロソ基を表わすか、更にはアリール
基で置換されているかいないヒドロキシアルキル
基、アルコキシアルキル基、アシロキシアルキル
基を表わす。）[Scope of Claims] 1. Based on 100 parts by weight of a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon in which the vinyl aromatic hydrocarbon content is 5 to 95% by weight, (a) number of carbon atoms; 0.05 to 5 parts by weight of higher fatty acid having 10 to 26 (b) Hindered amine compound having at least one group represented by the following formula [] in the molecule
A block copolymer composition containing 0.005 to 3 parts by weight. (In the formula, R 1 , R 2 , R 3 and R 4 are the same or different,
represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms, or R 1 and R 2 together, together with the carbon atom to which they are attached, represents a cycloalkyl group having 4 to 12 carbon atoms; Forming a group or [Formula] [R' 1 , R' 2 , R' 3 and R' 4 are the same or different and represent a straight or branched alkyl group having 1 to 12 carbon atoms] represents. X and X' represent hydrogen or oxygen atoms, or straight-chain or branched alkyl groups having 1 to 20 carbon atoms, alkenyl or alkynyl groups having 3 to 12 carbon atoms, or It represents an alkyl group, a nitroso group, or a hydroxyalkyl group, an alkoxyalkyl group, or an acyloxyalkyl group which is not substituted with an aryl group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18072983A JPS6072953A (en) | 1983-09-30 | 1983-09-30 | Block copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18072983A JPS6072953A (en) | 1983-09-30 | 1983-09-30 | Block copolymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6072953A JPS6072953A (en) | 1985-04-25 |
| JPS6345743B2 true JPS6345743B2 (en) | 1988-09-12 |
Family
ID=16088279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18072983A Granted JPS6072953A (en) | 1983-09-30 | 1983-09-30 | Block copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6072953A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0615655B2 (en) * | 1985-06-03 | 1994-03-02 | 旭有機材工業株式会社 | Resin molding material for injection molding |
| JPH0615654B2 (en) * | 1985-06-03 | 1994-03-02 | 旭有機材工業株式会社 | Resin molding material for injection molding |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5253957A (en) * | 1975-10-28 | 1977-04-30 | Shell Int Research | Block copolymers composition |
| JPS5262363A (en) * | 1975-11-18 | 1977-05-23 | Asahi Chem Ind Co Ltd | Blcok copolymer compositions with excellent thermal stability |
| JPS5318657A (en) * | 1976-08-05 | 1978-02-21 | Asahi Chem Ind Co Ltd | Ordorless resin composition |
-
1983
- 1983-09-30 JP JP18072983A patent/JPS6072953A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5253957A (en) * | 1975-10-28 | 1977-04-30 | Shell Int Research | Block copolymers composition |
| JPS5262363A (en) * | 1975-11-18 | 1977-05-23 | Asahi Chem Ind Co Ltd | Blcok copolymer compositions with excellent thermal stability |
| JPS5318657A (en) * | 1976-08-05 | 1978-02-21 | Asahi Chem Ind Co Ltd | Ordorless resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6072953A (en) | 1985-04-25 |
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