JP2004250680A - Styrene-based resin composition - Google Patents
Styrene-based resin composition Download PDFInfo
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- JP2004250680A JP2004250680A JP2004010382A JP2004010382A JP2004250680A JP 2004250680 A JP2004250680 A JP 2004250680A JP 2004010382 A JP2004010382 A JP 2004010382A JP 2004010382 A JP2004010382 A JP 2004010382A JP 2004250680 A JP2004250680 A JP 2004250680A
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 312
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 229920001577 copolymer Polymers 0.000 claims abstract description 80
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 229920001400 block copolymer Polymers 0.000 claims abstract description 58
- 150000001993 dienes Chemical class 0.000 claims abstract description 43
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 34
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000000465 moulding Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 229920006249 styrenic copolymer Polymers 0.000 claims description 14
- 229920001890 Novodur Polymers 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 description 62
- 238000000034 method Methods 0.000 description 33
- 238000002156 mixing Methods 0.000 description 26
- 230000000704 physical effect Effects 0.000 description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 14
- 238000012662 bulk polymerization Methods 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000012986 chain transfer agent Substances 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 229920006300 shrink film Polymers 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 229920000428 triblock copolymer Polymers 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 2
- KQJQPCJDKBKSLV-UHFFFAOYSA-N 1-bromo-3-ethenylbenzene Chemical compound BrC1=CC=CC(C=C)=C1 KQJQPCJDKBKSLV-UHFFFAOYSA-N 0.000 description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 2
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 2
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- GQEFPXSNRRKUHO-UHFFFAOYSA-N 4-methylpent-1-enylbenzene Chemical compound CC(C)CC=CC1=CC=CC=C1 GQEFPXSNRRKUHO-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- -1 fatty acid esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 2
- 239000012285 osmium tetroxide Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011049 pearl Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 101150041968 CDC13 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Containers Having Bodies Formed In One Piece (AREA)
- Packages (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、スチレン系樹脂と熱可塑性エラストマーとを混合してなる新規なスチレン系樹脂組成物に関する。 The present invention relates to a novel styrene resin composition obtained by mixing a styrene resin and a thermoplastic elastomer.
スチレン系樹脂は、成形加工性に優れる点からプラスチック容器に多く使用されている。近年、プラスチック容器の分野では環境負荷等の問題から塩化ビニル系樹脂からスチレン系樹脂への代替が進んでおり、特にスチレン系樹脂シートを真空成形、プレス成形して得られる成型用シートにおいてはスチレン系樹脂に熱可塑性エラストマーを配合した所謂耐衝撃性スチレン系樹脂組成物が多用されている。しかしながら、耐衝撃性スチレン系樹脂組成物は、前記熱可塑性エラストマーの配合割合を高めた場合には、耐衝撃性は向上するものの、成型用シートの剛性の低下を招き外部からの過重によって成型品が容易に変形するため、該内容物を梱包する容器の場合、該内容物が損傷を受けやすくなるものであった。一方、耐衝撃性スチレン系樹脂組成物中の熱可塑性エラストマー量を少なくした場合は、成型品の剛性は高まるものの、衝撃強度は低くなり、成型品にクラック、折れや割れが生じやすいものであった。そこで、従来より、このように相互に背反する成型品の剛性と耐衝撃性とのバランスを図る検討がなされており、例えばスチレンブロック量が65〜85質量%のスチレン−ブタジエンブロック共重合体、スチレン−アクリル酸ブチル共重合体、及びスチレンブロック量が10〜50質量%のスチレン−ブタジエンブロック共重合体を配合した透明耐衝撃性樹脂組成物が知られている(例えば、下記特許文献1参照)。
Styrene resins are widely used in plastic containers because of their excellent moldability. In recent years, in the field of plastic containers, the replacement of vinyl chloride-based resins with styrene-based resins has been progressing due to environmental load and other problems. A so-called impact-resistant styrene-based resin composition in which a thermoplastic elastomer is blended with a base resin is frequently used. However, when the proportion of the thermoplastic elastomer is increased, the impact-resistant styrenic resin composition improves the impact resistance, but reduces the rigidity of the molding sheet and causes a molded article due to external load. Are easily deformed, so that in the case of a container for packing the contents, the contents are easily damaged. On the other hand, when the amount of the thermoplastic elastomer in the impact-resistant styrenic resin composition is reduced, the rigidity of the molded product is increased, but the impact strength is reduced and the molded product is liable to crack, break or crack. Was. Therefore, conventionally, studies have been made to balance the rigidity and the impact resistance of such mutually contradictory molded products. For example, a styrene-butadiene block copolymer having a styrene block amount of 65 to 85% by mass, There is known a transparent impact-resistant resin composition containing a styrene-butyl acrylate copolymer and a styrene-butadiene block copolymer having a styrene block amount of 10 to 50% by mass (for example, see
しかし、上記透明耐衝撃性樹脂組成物は、該組成物の成型品において剛性と耐衝撃性とを兼備させることができるものの、成型品にした場合の面衝撃強度が未だ十分なものでなく、特に成型用シートを二次成形して得られるブリスターパッケージ、キャリアテープ、食品用容器等の各種二次成型品において、内容物を梱包した状態で、落下や運搬時における振動によって割れやクラックが生じやすいものであった。 However, although the transparent impact-resistant resin composition can have both rigidity and impact resistance in a molded product of the composition, the surface impact strength when molded is still insufficient. In particular, in the case of various secondary molded products such as blister packages, carrier tapes, food containers, etc. obtained by secondary molding of molding sheets, cracks and cracks occur due to vibration during dropping and transportation while the contents are packed It was easy.
本発明が解決しようとする課題は、耐衝撃性スチレン系樹脂組成物の成型品における面衝撃強度を飛躍的に改善し、面衝撃強度と剛性とのバランスを改善することにある。 The problem to be solved by the present invention is to dramatically improve the surface impact strength of a molded article of the impact-resistant styrene resin composition, and to improve the balance between the surface impact strength and the rigidity.
本発明者等は、上記課題を解決すべく鋭意検討を重ねた結果、スチレン系共重合体(A)と、スチレン系単量体の重合体ブロック(b1)、及び共役ジエン系単量体の重合体ブロック(b2)から構成されるブロック共重合体(B)とを含むスチレン系樹脂組成物であって、前記スチレン系共重合体(A)がスチレン系単量体(a)、アクリル酸ブチル(b)、及びメタクリル酸メチル(c)の3元共重合体であって、前記ブロック共重合体(B)が組成物中で所定のモルフォロジーを有し、更に、前記共役ジエン系単量体に由来する構造単位を原料質量比で前記スチレン系樹脂組成物中9〜25質量%の割合である場合、その成型品が優れた剛性を発現すると共に、面衝撃強度も飛躍的に向上することを見いだし、本発明を完成するに至った。 The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the styrene-based copolymer (A), the polymer block (b1) of the styrene-based monomer, and the conjugated diene-based monomer A styrene-based resin composition comprising a block copolymer (B) composed of a polymer block (b2), wherein the styrene-based copolymer (A) is a styrene-based monomer (a), acrylic acid A terpolymer of butyl (b) and methyl methacrylate (c), wherein the block copolymer (B) has a predetermined morphology in the composition, and the conjugated diene monomer When the structural unit derived from the body is 9 to 25% by mass in the styrenic resin composition in terms of the raw material mass ratio, the molded product exhibits excellent rigidity and the surface impact strength is dramatically improved. Have led to the completion of the present invention. .
即ち、本発明はスチレン系共重合体(A)と、スチレン系単量体の重合体ブロック(b1)及び共役ジエン系単量体の重合体ブロック(b2)から構成されるブロック共重合体(B)とを含むスチレン系樹脂組成物であって、
前記スチレン系共重合体(A)がスチレン系単量体(a)、アクリル酸ブチル(b)及びメタクリル酸メチル(c)の共重合体であり、
前記ブロック共重合体(B)が、前記重合体ブロック(b1)の層とジエン系単量体の前記重合体ブロック(b2)の層が交互に積層する多層構造を形成しており、かつ、
前記共役ジエン系単量体に由来する構造単位を原料質量比で前記スチレン系樹脂組成物中9〜25質量%の割合で含有する
ことを特徴とするスチレン系樹脂組成物に関する。
That is, the present invention provides a styrene-based copolymer (A), a styrene-based monomer polymer block (b1), and a conjugated diene-based polymer block (b2). A) a styrenic resin composition comprising:
The styrene-based copolymer (A) is a copolymer of a styrene-based monomer (a), butyl acrylate (b) and methyl methacrylate (c),
The block copolymer (B) has a multilayer structure in which layers of the polymer block (b1) and layers of the polymer block (b2) of diene-based monomers are alternately laminated; and
A styrene-based resin composition, comprising a structural unit derived from the conjugated diene-based monomer in a raw material mass ratio of 9 to 25% by mass in the styrene-based resin composition.
本発明は、更に前記スチレン系樹脂組成物からなる成型用シートに関する。 The present invention further relates to a molding sheet comprising the styrene resin composition.
本発明は、更に前記スチレン系樹脂組成物からなるブリスターパッケージに関する。 The present invention further relates to a blister package comprising the styrene resin composition.
本発明の透明性スチレン系樹脂組成物は、前記した通り、スチレン系共重合体(A)と、スチレン系単量体の重合体ブロック(b1)及び共役ジエン系単量体の重合体ブロック(b2)から構成されるブロック共重合体(B)とから構成され、かつ、前記スチレン系共重合体(A)がスチレン系単量体(a)、アクリル酸ブチル(b)、及びメタクリル酸メチル(c)から構成されるものである。そして、前記ブロック共重合体(B)は、該ブロック共重合体(B)中のスチレン系単量体の重合体ブロック(b1)の層と、共役ジエン系単量体の重合体ブロック(b2)の層とが交互に積層する多層構造を形成しており、前記スチレン系共重合体(A)は、該多層構造の層間に入り込んで連続層を形成している。ここで、前記スチレン系共重合体(A)が連続層を形成し、前記ブロック共重合体(B)が多層構造を形成するモルフォロジーは、具体的には図1で示される透過型電子顕微鏡写真(TEM)で確認することができる。該図1において黒く写る部分がブロック共重合体(B)中の共役ジエン系単量体の重合体ブロック(b2)の層に対応しており、この層で囲まれている白抜き部分がスチレン系単量体の重合体ブロック(b1)の層に対応している。 As described above, the transparent styrene-based resin composition of the present invention comprises a styrene-based copolymer (A), a styrene-based polymer block (b1), and a conjugated diene-based monomer block ( b2), and the styrene-based copolymer (A) is a styrene-based monomer (a), butyl acrylate (b), and methyl methacrylate. (C). The block copolymer (B) comprises a layer of a styrene monomer polymer block (b1) in the block copolymer (B) and a conjugated diene monomer polymer block (b2). ) Are alternately laminated to form a multilayer structure, and the styrene-based copolymer (A) penetrates into the layers of the multilayer structure to form a continuous layer. Here, the morphology in which the styrene-based copolymer (A) forms a continuous layer and the block copolymer (B) forms a multilayer structure is specifically shown in a transmission electron micrograph shown in FIG. (TEM). In FIG. 1, the black portion corresponds to the layer of the polymer block (b2) of the conjugated diene monomer in the block copolymer (B), and the white portion surrounded by this layer is styrene. This corresponds to the layer of the polymer block (b1) of the system monomer.
前記スチレン系単量体の重合体ブロック(b1)及び共役ジエン系単量体の重合体ブロック(b2)から構成されるブロック共重合体(B)は、それ自体、該ブロック共重合体(B)中の前記重合体ブロック(b1)の層と共役ジエン系単量体の重合体ブロック(b2)の層が交互に積層する多層構造を有している。本発明ではかかる多層構造をできるだけ崩すことなく、複数の共役ジエン系単量体の重合体ブロック(b2)の層の層間に前記スチレン系共重合体(A)を連続層として存在させることによって面衝撃強度を改善できたものである。これに対して、SBSをブロック共重合体として用い、かつ、スチレン系単量体とアクリル酸ブチルとの二元共重合体を連続層として用いる前記従来技術の場合、該共重合体とブロック共重合体とが相溶化し易い為に、SBSが有するモルフォロジーが破壊され、前記した成型品の面衝撃強度、特に成型用シートを二次成形した成型品の面衝撃強度が十分なレベルに達しないものであった。 The block copolymer (B) composed of the styrene monomer polymer block (b1) and the conjugated diene monomer polymer block (b2) is itself a block copolymer (B). ) Has a multilayer structure in which layers of the polymer block (b1) and layers of the polymer block (b2) of the conjugated diene monomer are alternately laminated. In the present invention, the styrene-based copolymer (A) is present as a continuous layer between layers of the polymer block (b2) of a plurality of conjugated diene-based monomers without breaking the multilayer structure as much as possible. The impact strength was improved. On the other hand, in the case of the above-mentioned prior art in which SBS is used as a block copolymer and a binary copolymer of a styrene monomer and butyl acrylate is used as a continuous layer, the copolymer and the block copolymer are used. Since the polymer is easily compatible with the polymer, the morphology of the SBS is destroyed, and the surface impact strength of the above-mentioned molded product, particularly the surface impact strength of the molded product obtained by secondary molding of the molding sheet, does not reach a sufficient level. Was something.
本発明では、特に連続層を形成するスチレン系共重合体(A)の単量体成分としてメタクリル酸メチル(c)を用いたこと、及び共役ジエン系単量体に由来する構造単位を原料質量比基準で前記スチレン系樹脂組成物中9〜25質量%となる割合にすることにより、前記した適切なモルフォロジーを発現させ面衝撃強度と剛性のバランスを図ることができたものである。尚、ここで共役ジエン系単量体に由来する構造単位とは、該共役ジエン系単量体が付加反応したアルキレン構造部位をいい、例えば、共役ジエン系単量体として1,3−ブタジエンを用いた場合には、ブタ−2−エン−1,4−ジイル、及びブタ−3−エン−1,2−ジイルを表す。 In the present invention, in particular, methyl methacrylate (c) was used as a monomer component of the styrene-based copolymer (A) forming the continuous layer, and the structural unit derived from the conjugated diene-based monomer was used as a raw material mass. By setting the ratio to 9 to 25% by mass in the styrene-based resin composition on a ratio basis, the above-described appropriate morphology can be developed and the balance between surface impact strength and rigidity can be achieved. Here, the structural unit derived from the conjugated diene-based monomer means an alkylene structure site obtained by the addition reaction of the conjugated diene-based monomer. For example, 1,3-butadiene is used as a conjugated diene-based monomer. When used, they represent but-2-ene-1,4-diyl and but-3-en-1,2-diyl.
また、このような適度なモルフォロジーを形成する為には、更にメタクリル酸メチル(c)に由来する構造単位を原料質量比基準で前記スチレン系樹脂組成物中1.5〜6質量%となる割合にすることが好ましい。ここでメタクリル酸メチル(c)に由来する構造単位とは、該メタクリル酸メチル(c)が付加反応した構造部位をいい、具体的には1−メチル−1−メチルオキシカルボニル−エチレンである。 Further, in order to form such an appropriate morphology, a ratio of the structural unit derived from methyl methacrylate (c) in the styrene resin composition to be 1.5 to 6% by mass based on the mass ratio of the raw materials. Is preferable. Here, the structural unit derived from methyl methacrylate (c) refers to a structural site where the methyl methacrylate (c) has undergone an addition reaction, specifically, 1-methyl-1-methyloxycarbonyl-ethylene.
更に、アクリル酸ブチル(b)に由来する構造単位の存在量も前記スチレン系樹脂組成物のモルフォロジー形成に影響しており、これが多くなるにつれて前記多層構造の割合が少なくなる傾向にある。一方、該構造単位が少なくなるにつれて前記多層構造の割合は多くなる傾向があるものの、剛性が低下する。よって、これらの点からアクリル酸ブチル(b)に由来する構造単位を原料質量比基準で前記スチレン系樹脂組成物中2.8〜8.5質量%となる割合にすることが好ましい。ここでアクリル酸ブチル(b)に由来する構造単位とは、該アクリル酸ブチル(b)が付加反応した構造部位をいい、具体的には1−ブチルオキシカルボニル−エチレンである。 Furthermore, the abundance of structural units derived from butyl acrylate (b) also affects the morphology formation of the styrenic resin composition, and as this increases, the proportion of the multilayer structure tends to decrease. On the other hand, as the number of the structural units decreases, the ratio of the multilayer structure tends to increase, but the rigidity decreases. Therefore, from these points, it is preferable that the ratio of the structural unit derived from butyl acrylate (b) be 2.8 to 8.5% by mass in the styrene resin composition based on the mass ratio of the raw materials. Here, the structural unit derived from butyl acrylate (b) refers to a structural site where the butyl acrylate (b) has undergone an addition reaction, specifically, 1-butyloxycarbonyl-ethylene.
ここでスチレン系樹脂組成物中の共役ジエン系単量体に由来する構造単位、メタクリル酸メチル(c)に由来する構造単位、及びアクリル酸ブチル(b)に由来する構造単位の含有率は、C13−NMRの測定における各構造単位に特徴的な炭素原子に対応するケミカルピークの面積比から求めることができる。例えば、メタクリル酸メチル(b)に由来する構造単位の場合、カルボニル炭素原子のケミカルシフト175ppm、アクリル酸ブチル(b)に由来する構造単位の場合、酸素原子に結合するブチル基の炭素原子のケミカルシフト63ppmのピークの面積比からこれらの構造単位の含有率を求めることができる。 Here, the content of the structural unit derived from the conjugated diene monomer, the structural unit derived from methyl methacrylate (c), and the structural unit derived from butyl acrylate (b) in the styrene-based resin composition is as follows: It can be determined from the area ratio of chemical peaks corresponding to carbon atoms characteristic of each structural unit in C 13 -NMR measurement. For example, in the case of the structural unit derived from methyl methacrylate (b), the chemical shift of the carbonyl carbon atom is 175 ppm, and in the case of the structural unit derived from butyl acrylate (b), the chemical unit of the carbon atom of the butyl group bonded to the oxygen atom is used. The content of these structural units can be determined from the area ratio of the peak at a shift of 63 ppm.
本発明の透明性スチレン系樹脂組成物において連続層を形成する前記スチレン系共重合体(A)は、前記した通りスチレン系単量体(a)、アクリル酸ブチル(b)、及びメタクリル酸メチル(c)の共重合体である。このようにスチレン系単量体(a)の共重合成分としてアクリル酸ブチル(b)を用いることで組成物自体に柔軟性を付与することができ、また、メタクリル酸メチル(c)を用いることで、前記スチレン−ブタジエンブロック共重合体(B)との相溶化を抑制し、前記ブロック共重合体(B)が有するモルフォロジーを保持することができる。 As described above, the styrene-based copolymer (A) that forms the continuous layer in the transparent styrene-based resin composition of the present invention includes a styrene-based monomer (a), butyl acrylate (b), and methyl methacrylate. It is a copolymer of (c). By using butyl acrylate (b) as a copolymer component of the styrene monomer (a), the composition itself can be imparted with flexibility, and using methyl methacrylate (c). Thus, the compatibility with the styrene-butadiene block copolymer (B) can be suppressed, and the morphology of the block copolymer (B) can be maintained.
ここで、スチレン系共重合体(A)を構成するスチレン系単量体は、スチレン、α−メチルスチレン、o−メチルスチレン、m−メチルスチレン、p−メチルスチレン、エチルスチレン、イソブチルスチレン、t−ブチルスチレン、o−ブロムスチレン、m−ブロムスチレン、p−ブロムスチレン、o−クロロスチレン、m−クロロスチレン、p−クロロスチレン等が挙げられる。これらのなかでも反応性が良好で重合が容易である等の理由からスチレンが好ましい。 Here, the styrene monomer constituting the styrene copolymer (A) is styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, isobutylstyrene, t -Butylstyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene and the like. Of these, styrene is preferred because of its good reactivity and easy polymerization.
また、前記スチレン系共重合体(A)は、スチレン系単量体(a)78〜85質量%、アクリル酸ブチル(b)6〜19質量%、及びメタクリル酸メチル(c)3〜16重量%の共重合体であることが好ましい。後述するように、成型品の面衝撃強度の点から前記ブロック共重合体(B)は該共重合体中のポリブタジエンブロックの含有量が20〜30質量%であることが好ましく、前記スチレン系共重合体(A)の原料単量体比率を前記した78〜85質量%なる割合とすることで、その成型品に優れた透明性を付与することができる。更に、面衝撃強度及び剛性のバランスも一層良好なものとなる。特に、成型品の透明性の点からは、上記比率の中でも前記ブロック共重合体(B)との屈折率の差が0.002以下となる様、適宜単量体比率を調節することが好ましい。また、メタクリル酸メチル(c)を前記した3〜16重量%なる割合で使用することにより、成型品に優れた耐熱性を付与することができ、気温の高い地方での使用、又は夏期の使用において優れた剛性と面衝撃強度とを発現させることができる。更に、メタクリル酸メチル(c)を前記割合で使用することにより、前記スチレン系共重合体(A)の分子量を比較的低く抑え乍らも溶融時に適度な流動性を発現させて、良好な成型加工性を発現させることができる。その為、連続層である前記スチレン系共重合体(A)が適度な柔軟性を有することになる結果、成型用シートの折り曲げ白化を良好に防止することができる。このような観点から前記スチレン系共重合体(A)の質量平均分子量は25×104〜35×104であるスチレン系共重合体であることが好ましく、また、メルトマスフローレイトは5〜12g/10minであることが好ましい。このように前記スチレン系共重合体(A)は分子量を低く抑えながら適当な流動性を発現させることができる為、前記スチレン系共重合体(A)と前記ブロック共重合体(B)とを溶融混練する際の温度条件を低く設定できる。その結果、溶融混練時にゲル化の発生を防止でき、最終的に得られる成型品の外観が優れたものとなる。 The styrene-based copolymer (A) contains 78 to 85% by weight of a styrene-based monomer (a), 6 to 19% by weight of butyl acrylate (b), and 3 to 16% by weight of methyl methacrylate (c). % Of the copolymer. As described later, the content of the polybutadiene block in the block copolymer (B) is preferably 20 to 30% by mass from the viewpoint of the surface impact strength of the molded product, and the styrene copolymer is preferably used. By setting the raw material monomer ratio of the polymer (A) to the above-mentioned ratio of 78 to 85% by mass, excellent transparency can be imparted to the molded product. Furthermore, the balance between surface impact strength and rigidity is further improved. In particular, from the viewpoint of the transparency of the molded product, it is preferable to appropriately adjust the monomer ratio so that the difference in the refractive index with the block copolymer (B) is 0.002 or less among the above ratios. . In addition, by using methyl methacrylate (c) in the above-mentioned ratio of 3 to 16% by weight, excellent heat resistance can be imparted to a molded product, and use in a high-temperature region or use in summer. In this case, excellent rigidity and surface impact strength can be exhibited. Furthermore, by using methyl methacrylate (c) in the above ratio, the styrene copolymer (A) can have a relatively low molecular weight while exhibiting an appropriate fluidity at the time of melting, and can be molded in good condition. Workability can be developed. Therefore, the styrene-based copolymer (A), which is a continuous layer, has appropriate flexibility, so that bending whitening of the molding sheet can be favorably prevented. From such a viewpoint, the styrene-based copolymer (A) is preferably a styrene-based copolymer having a mass average molecular weight of 25 × 10 4 to 35 × 10 4 , and the melt mass flow rate is 5 to 12 g. / 10 min is preferable. As described above, since the styrene-based copolymer (A) can exhibit appropriate fluidity while keeping the molecular weight low, the styrene-based copolymer (A) and the block copolymer (B) can be combined with each other. Temperature conditions for melt-kneading can be set low. As a result, the occurrence of gelation during melt-kneading can be prevented, and the appearance of the finally obtained molded article becomes excellent.
このようなスチレン系共重合体(A)は、スチレン系単量体(a)、アクリル酸ブチル(b)、及びメタクリル酸メチル(c)を所定の質量比で重合して得ることができる。重合方法は、懸濁重合重合法、塊状懸濁重合法、溶液重合法、及び塊状重合法が挙げられるが、生産性、コスト面及び組成の均一性の点から連続塊状重合法が好ましい。 Such a styrene-based copolymer (A) can be obtained by polymerizing a styrene-based monomer (a), butyl acrylate (b), and methyl methacrylate (c) at a predetermined mass ratio. Examples of the polymerization method include a suspension polymerization polymerization method, a bulk suspension polymerization method, a solution polymerization method, and a bulk polymerization method, and a continuous bulk polymerization method is preferable in terms of productivity, cost, and uniformity of composition.
本発明では、該連続塊状重合法のなかでも特に複数の管状反応器を直列に連結した重合ラインを有し、かつ、前記管状反応器の内部にミキシングエレメントを配設してなる重合装置を用いた連続塊状重合法が、均質なスチレン系共重合体(A)を効率的に生産できる点から好ましい。 In the present invention, the continuous bulk polymerization method particularly employs a polymerization apparatus having a polymerization line in which a plurality of tubular reactors are connected in series, and a mixing element disposed inside the tubular reactor. The continuous bulk polymerization method is preferred because a homogeneous styrene-based copolymer (A) can be efficiently produced.
尚、ここで用いるミキシングエレメントは、例えば管内に流入した重合液の流れの分割と流れ方向を変え、分割と合流を繰り返すことにより重合液を混合するものであり、SMX型、SMR型のスルザー式の管状ミキサー、ケニックス式のスタティックミキサー、東レ式の管状ミキサー等が挙げられる。 The mixing element used here is, for example, an SMX type or SMR type Sulzer type mixing element which changes the flow and direction of the flow of the polymerization liquid flowing into the pipe and repeats the division and merging. Tubular mixer, Kenix type static mixer, Toray type tubular mixer, and the like.
また、当該連続塊状重合法においては原料成分を前記重合装置に投入する前に予め攪拌式反応器を用い、各原料成分をこの攪拌式反応器内で予備重合した、次いで、連続的に前記連続塊状重合ラインを構成する重合装置に該重合液を投入することが得られるスチレン系共重合体(A)の均一性がより高まる点から好ましい。ここで使用し得る攪拌式反応器は、例えば攪拌式槽型反応器、攪拌式塔型反応器等が挙げられ、該攪拌器内の攪拌翼は、例えばアンカー型、タービン型、スクリュー型、ダブルヘリカル型、ログボーン型等の攪拌翼が何れも使用できる。 In addition, in the continuous bulk polymerization method, before the raw material components are introduced into the polymerization apparatus, a stirring reactor is used in advance, and each raw material component is preliminarily polymerized in the stirring reactor. It is preferable to charge the polymerization liquid into a polymerization apparatus constituting a bulk polymerization line, since the uniformity of the obtained styrene-based copolymer (A) is further improved. Stirring reactors that can be used here include, for example, a stirring tank reactor, a stirring tower reactor, and the like, and stirring blades in the stirrer include, for example, an anchor type, a turbine type, a screw type, and a double type. Any of helical type, log bone type, etc. stirring blades can be used.
かかる攪拌式反応器及び連続塊状重合装置を連結した連続重合ライン内で前記各原料成分の重合を行う際の温度条件は、重合転化率が35〜55質量%までの重合初期段階では120〜135℃、その後の重合後段では140〜160℃の範囲であることが好ましい。かかる温度条件を満たす場合、得られるスチレン系共重合体(A)の分子量の制御が容易になり、かつ、生産性も格段に向上する。 The temperature conditions for performing the polymerization of each of the raw material components in a continuous polymerization line connecting such a stirring type reactor and a continuous bulk polymerization apparatus are as follows: the polymerization conversion rate is 120 to 135 in the initial stage of polymerization at a polymerization conversion rate of 35 to 55% by mass. C., and preferably in the range of 140 to 160 C. in the subsequent stage of polymerization. When such a temperature condition is satisfied, the control of the molecular weight of the obtained styrenic copolymer (A) becomes easy, and the productivity is remarkably improved.
重合終了後は、重合溶液は予熱器内で予熱され、次いで脱揮発槽に送られ、減圧下にて未反応単量体および溶剤を除去した後、ペレット化することにより目的とするスチレン系共重合体(A)が得られる。 After completion of the polymerization, the polymerization solution is preheated in a preheater, then sent to a devolatilization tank, and after removing the unreacted monomers and the solvent under reduced pressure, pelletizing the styrene-based copolymer. The polymer (A) is obtained.
尚、上記連続塊状重合法においては、前記管状反応器内の上記重合溶液の粘性を低下させる為に溶剤を使用してもよい。この場合、その使用量は各原料成分の合計100質量部に対して5〜20質量部である。溶剤の種類としては、通常、塊状重合法で使用されているエチルベンゼン、トルエン、キシレン等が適している。また、スチレン系共重合体(A)の分子量調節のために連鎖移動剤を添加するのが好ましい。該連鎖移動剤の添加量は、通常原料モノマーの合計100重量部に対して0.005〜0.5質量部の範囲である。 In the continuous bulk polymerization method, a solvent may be used to reduce the viscosity of the polymerization solution in the tubular reactor. In this case, the used amount is 5 to 20 parts by mass based on 100 parts by mass of each raw material component in total. As the type of the solvent, ethylbenzene, toluene, xylene and the like which are usually used in the bulk polymerization method are suitable. It is preferable to add a chain transfer agent for controlling the molecular weight of the styrene copolymer (A). The amount of the chain transfer agent to be added is generally in the range of 0.005 to 0.5 parts by mass based on 100 parts by weight of the total amount of the raw material monomers.
また、スチレン系共重合体(A)の製造においては、適宜重合開始剤を用いることができる。当該重合開始剤は、汎用のパーオキサイド系重合開始剤が何れも使用できる。本発明においては、公知のパーオキサイド系重合開始剤の中でも、スチレン系共重合体(A)を三次元的に重合でき、シートの押出成形時のネックイン現象を良好に防止できる点から2,2−ビス(4,4−ジ−t−ブチルパーオキシシクロヘキシル)プロパンが好ましい。 In the production of the styrenic copolymer (A), a polymerization initiator can be appropriately used. As the polymerization initiator, any general-purpose peroxide-based polymerization initiator can be used. In the present invention, among known peroxide-based polymerization initiators, the styrene-based copolymer (A) can be three-dimensionally polymerized, and the neck-in phenomenon at the time of sheet extrusion molding can be favorably prevented. 2-Bis (4,4-di-t-butylperoxycyclohexyl) propane is preferred.
次に、スチレン系単量体の重合体ブロック(b1)及び共役ジエン系単量体の重合体ブロック(b2)から構成されるブロック共重合体(B)は、
1)スチレン系単量体の重合体ブロック(b1)と共役ジエン系単量体の重合体ブロック(b2)とからなるジブロックコポリマー、
2)スチレン系単量体の重合体ブロック(b1)と共役ジエン系単量体の重合体ブロック(b2)と、更にスチレン系単量体の重合体ブロック(b1)とから構成されるトリブロックコポリマー、
3)前記トリブロックコポリマーの水素添加物、
4)複数のスチレン系単量体の重合体ブロック(b1)とスチレン系単量体の重合体ブロック(b1)とからなるトリブロックを越える複数の重合体ブロックから構成される多ブロックコポリマー、及び
5)スチレン系単量体の重合体ブロック(b1)と共役ジエン系単量体の重合体ブロック(b2)に加え、ランダム共重合部分を有するブロック共重合体、
などが挙げられる。
Next, a block copolymer (B) composed of a polymer block (b1) of a styrene monomer and a polymer block (b2) of a conjugated diene monomer is as follows:
1) a diblock copolymer comprising a polymer block (b1) of a styrene monomer and a polymer block (b2) of a conjugated diene monomer;
2) A triblock composed of a polymer block (b1) of a styrene monomer, a polymer block (b2) of a conjugated diene monomer, and a polymer block (b1) of a styrene monomer. Copolymer,
3) a hydrogenated product of the triblock copolymer,
4) a multi-block copolymer comprising a plurality of polymer blocks exceeding a triblock consisting of a plurality of styrene monomer polymer blocks (b1) and a styrene monomer polymer block (b1); 5) a block copolymer having a random copolymerized portion in addition to the polymer block (b1) of the styrene monomer and the polymer block (b2) of the conjugated diene monomer,
And the like.
これらの中でも該ゴム質重合体(B)のモルフォロジー的に耐面衝撃性に優れる点から前記2)のトリブロックコポリマーが好ましい。尚、このトリブロックコポリマーについて、スチレン系単量体の重合体ブロック(b1)は、部分的に共役ジエン系単量体が共重合していてもよいし、また、共役ジエン系単量体の重合体ブロック(b2)は、部分的にスチレン系単量体が共重合していてもよい。 Among these, the triblock copolymer 2) is preferable because the rubbery polymer (B) has excellent morphologically excellent surface impact resistance. In the triblock copolymer, the styrene monomer polymer block (b1) may be partially copolymerized with a conjugated diene monomer, or may be a conjugated diene monomer. In the polymer block (b2), a styrene monomer may be partially copolymerized.
ここで、前記重合体ブロック(b1)を構成するスチレン系単量体は、スチレン、α−メチルスチレン、o−メチルスチレン、m−メチルスチレン、p−メチルスチレン、エチルスチレン、イソブチルスチレン、t−ブチルスチレン、o−ブロムスチレン、m−ブロムスチレン、p−ブロムスチレン、o−クロロスチレン、m−クロロスチレン、p−クロロスチレン等が挙げられる。本発明では特にスチレンが前記した交互積層状態を形成し易い点から好ましい。 Here, the styrene monomer constituting the polymer block (b1) includes styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, isobutylstyrene, and t-methylstyrene. Butylstyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene and the like. In the present invention, styrene is particularly preferred because it can easily form the above-mentioned alternately laminated state.
次に、前記重合体ブロック(b2)を構成する共役ジエン系単量体は、ブタジエン、クロロプレン、イソプレン、1,3−ペンタジエン等のジエン系単量体が挙げられる。これらのなかでも該重合体ブロック(b2)によって発現されるゴム弾性に優れ、最終的に得られる本発明のスチレン系樹脂組成物に優れた面衝撃強度を付与できる点からポリブタジエンブロックであることが好ましい。 Next, examples of the conjugated diene-based monomer constituting the polymer block (b2) include diene-based monomers such as butadiene, chloroprene, isoprene, and 1,3-pentadiene. Among these, the polybutadiene block is preferable because it is excellent in rubber elasticity expressed by the polymer block (b2) and can impart excellent surface impact strength to the finally obtained styrene resin composition of the present invention. preferable.
従って、前記ブロック共重合体(B)は、所謂スチレン−ブタジエン共重合体(SBR)、トリブロックタイプはスチレン−ブタジエン−スチレン共重合体(SBS)であることが好ましく、とりわけ面衝撃強度の点からスチレン−ブタジエン−スチレン共重合体(SBS)が好ましい。 Therefore, the block copolymer (B) is preferably a so-called styrene-butadiene copolymer (SBR), and the triblock type is preferably a styrene-butadiene-styrene copolymer (SBS). Styrene-butadiene-styrene copolymer (SBS) is preferred.
また、ブロック共重合体(B)中の共役ジエン系単量体の重合体ブロック(b2)の量が多くなると、ブロック共重合体(B)のゴム的性質が強くなり、成形加工時に塑性変形し難くなるため、ブロック共重合体(B)中の共役ジエン系単量体の重合体ブロック(b2)の含有率は20〜30質量%であることが好ましい。 Further, when the amount of the polymer block (b2) of the conjugated diene monomer in the block copolymer (B) increases, the rubber-like properties of the block copolymer (B) become strong, and plastic deformation occurs during molding. Since it is difficult to carry out, the content of the polymer block (b2) of the conjugated diene monomer in the block copolymer (B) is preferably 20 to 30% by mass.
以上詳述したブロック共重合体(B)は、スチレン系単量体と共役ジエン系単量体とを乳化重合や溶液重合など公知の方法に依って製造することができる。特に前記トリブロックコポリマーを製造する場合は、炭化水素系有機溶媒中で有機リチウム化合物等のアニオン系重合開始剤の存在下にスチレン系単量体及びジエン系単量体を溶液重合しトリブロックコポリマーを製造する方法がブロック共重合体(B)の高分子量化の調整が容易な点から好ましい。 The block copolymer (B) described in detail above can be produced from a styrene monomer and a conjugated diene monomer by a known method such as emulsion polymerization or solution polymerization. In particular, when the triblock copolymer is produced, a styrene monomer and a diene monomer are solution-polymerized in a hydrocarbon organic solvent in the presence of an anionic polymerization initiator such as an organic lithium compound to form a triblock copolymer. Is preferred from the viewpoint of easily adjusting the molecular weight of the block copolymer (B) to high.
本発明のスチレン系樹脂組成物は、前記スチレン系共重合体(A)と、前記ブロック共重合体(B)とを溶融混合することによって得られる。本発明ではこのように両者を溶融混合することにより、前記ブロック共重合体(B)が本来有するモルフォロジーを破壊することなく、スチレン系単量体の重合体ブロック(b1)の層と共役ジエン系単量体の重合体ブロック(b2)の層とが交互に積層された層間に前記スチレン系共重合体(A)を連続層として存在させることができる。 The styrene-based resin composition of the present invention is obtained by melt-mixing the styrene-based copolymer (A) and the block copolymer (B). In the present invention, by melting and mixing the two, the layer of the styrene-based monomer polymer block (b1) and the conjugated diene-based block can be formed without destroying the morphology inherent in the block copolymer (B). The styrene-based copolymer (A) can be present as a continuous layer between layers in which layers of the monomer polymer block (b2) are alternately laminated.
この際、前記スチレン系共重合体(A)と、前記ブロック共重合体(B)との混合比率は、前記した通り、ブロック共重合体(B)の原料成分である共役ジエン系単量体に由来する構造単位を原料質量比基準で前記スチレン系樹脂組成物中9〜25質量%となる割合である。本発明のスチレン系樹脂組成物中の共役ジエン系単量体に由来する構造単位の存在比が9質量%未満では、成型品に充分な面衝撃強度を付与することができない。一方、25質量%を超える場合は、組成物自体の剛性が不十分なものとなり成型用シートの二次成形時においてドローダウンを生じ易くなる。かかる範囲の中でも特に14〜25質量%の範囲が、面衝撃強度が改善効果が顕著な物となり好ましい。また、前記メタクリル酸メチル(c)に由来する構造単位を原料質量比基準で前記スチレン系樹脂組成物中1.5〜6質量%となる割合、更に前記アクリル酸ブチル(b)に由来する構造単位を原料質量比基準で前記スチレン系樹脂組成物中2.8〜9.5質量%となる割合となるように、前記スチレン系共重合体(A)及び前記ブロック共重合体(B)とを混合することが好ましい。 At this time, the mixing ratio of the styrene-based copolymer (A) and the block copolymer (B) is, as described above, a conjugated diene-based monomer which is a raw material component of the block copolymer (B). Is a ratio of 9 to 25% by mass in the styrene-based resin composition based on the mass ratio of the raw materials. If the abundance ratio of the structural unit derived from the conjugated diene-based monomer in the styrene-based resin composition of the present invention is less than 9% by mass, sufficient surface impact strength cannot be imparted to the molded product. On the other hand, if it exceeds 25% by mass, the rigidity of the composition itself becomes insufficient, and drawdown tends to occur during the secondary molding of the molding sheet. Among these ranges, a range of 14 to 25% by mass is particularly preferable because the surface impact strength is significantly improved. Further, the ratio of the structural unit derived from the methyl methacrylate (c) in the styrene resin composition is 1.5 to 6% by mass based on the mass ratio of the raw material, and the structure derived from the butyl acrylate (b). The styrene-based copolymer (A) and the block copolymer (B) are used so that the unit is 2.8 to 9.5% by mass in the styrene-based resin composition based on the raw material mass ratio. Is preferably mixed.
尚、ここで共役ジエン系単量体に由来する構造単位とは、該共役ジエン系単量体が付加反応したアルキレン構造部位をいい、例えば、共役ジエン系単量体として1,3−ブタジエンを用いた場合には、ブタ−2−エン−1,4−ジイル、及びブタ−3−エン−1,2−ジイルを表す。また、該構造単位のスチレン系樹脂組成物中の含有率は、C13−NMRの測定における各構造単位に特徴的な炭素原子に対応するケミカルピークの面積比から求めることができる。例えば、ブタ−3−エン−1,2−ジイルの場合、1,2−ビニル基を構成する末端炭素原子のケミカルシフト114ppm、ブタ−2−エン−1,4−ジイルの場合、末端炭素原子のケミカルシフト125〜132ppmのピークの面積比からこれらの構造単位の含有率を求めることができる。 Here, the structural unit derived from the conjugated diene-based monomer means an alkylene structure site obtained by the addition reaction of the conjugated diene-based monomer. For example, 1,3-butadiene is used as a conjugated diene-based monomer. When used, they represent but-2-ene-1,4-diyl and but-3-en-1,2-diyl. The content of the structural unit in the styrene-based resin composition can be determined from the area ratio of the chemical peak corresponding to the carbon atom characteristic to each structural unit in C 13 -NMR measurement. For example, in the case of but-3-ene-1,2-diyl, the chemical shift of the terminal carbon atom constituting the 1,2-vinyl group is 114 ppm, and in the case of but-2-ene-1,4-diyl, the terminal carbon atom is The content of these structural units can be determined from the area ratio of the peaks of the chemical shift of 125 to 132 ppm.
また、前記スチレン系共重合体(A)と、前記ブロック共重合体(B)とを溶融混合する具体的方法は、例えば、両者をミキサーで均一にドライブレンドした後、この混合物を押出機に投入し、溶融混練する方法、或いは、前記スチレン系共重合体(A)と前記ブロック共重合体(B)とを押出機に投入して溶融混練する方法が挙げられる。 In addition, a specific method of melt-mixing the styrene-based copolymer (A) and the block copolymer (B) is, for example, to uniformly dry-blend the two with a mixer, and then mix the mixture with an extruder. A method of charging and melt-kneading, or a method of charging the styrene-based copolymer (A) and the block copolymer (B) into an extruder and melt-kneading them.
例えば、スチレン系共重合体(A)、及びブロック共重合体(B)のペレット若しくはパールをバンバリーミキサー等のミキサーで予めドライブレンドし、得られた混合物を押出機に投入するか、又は前記ペレット若しくはパールを直接押出機に投入し、押出機にて190〜240℃で溶融混練する方法が挙げられる。溶融混練した混合物はそのままシート化しても良いし、一旦ペレット化した後に再度押出機で溶融シート化しても良い。また、溶融混練する方法としては、例えば、単軸及びニ軸押出機、ニーダー、オープンロールにより溶融混練する方法が挙げられる。尚、押出し時の樹脂温度は、ゲルの生成を抑制し、成型品外観を良好にするために前記スチレン系共重合体(A)及び前記ブロック共重合体(B)の溶融温度であって、かつ、210℃以下であることが好ましい。 For example, pellets or pearls of the styrene copolymer (A) and the block copolymer (B) are dry-blended in advance using a mixer such as a Banbury mixer, and the resulting mixture is charged into an extruder, or Alternatively, there is a method in which pearls are directly charged into an extruder and melt-kneaded at 190 to 240 ° C. by the extruder. The melt-kneaded mixture may be directly formed into a sheet, or may be formed into pellets once and then formed again into a molten sheet by an extruder. Examples of the method of melt-kneading include, for example, a method of melt-kneading with a single-screw and twin-screw extruder, a kneader, and an open roll. In addition, the resin temperature at the time of extrusion is a melting temperature of the styrene-based copolymer (A) and the block copolymer (B) in order to suppress gel formation and improve the appearance of a molded product, And it is preferable that it is 210 degrees C or less.
本発明では、前記スチレン系共重合体(A)、及び前記ブロック共重合体(B)を各原料成分から重合する際、或いは、両者を溶融混練する際に、適宜、酸化防止剤、離型剤、紫外線吸収剤、着色剤、熱安定剤、可塑剤、染料等の各種添加剤を混合してもよい。これら添加剤は、その混練の際、あるいは各重合体の重合中に添加することができる。かかる添加剤は、具体的には、ミネラルオイル、エステル系可塑剤、ポリエステル系可塑剤などの可塑剤、酸化防止剤、連鎖移動剤、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸の金属塩、シリコンオイルなどが挙げられ、これらの1種あるいは2種以上が組み合わせて用いられる。 In the present invention, when the styrene-based copolymer (A) and the block copolymer (B) are polymerized from each raw material component, or when both are melt-kneaded, an antioxidant and a mold release agent are appropriately used. Various additives such as an agent, an ultraviolet absorber, a colorant, a heat stabilizer, a plasticizer, and a dye may be mixed. These additives can be added during kneading or during polymerization of each polymer. Specific examples of such additives include mineral oils, plasticizers such as ester plasticizers and polyester plasticizers, antioxidants, chain transfer agents, higher fatty acids, higher fatty acid esters, metal salts of higher fatty acids, and silicon oil. And these may be used alone or in combination of two or more.
また、本発明では、面衝撃強度の一層の改善を目的としてスチレン系単量体の構造単位を50質量%以下に調節した、スチレン系単量体の重合体ブロックと共役ジエン系単量体の重合体ブロックとから構成されるブロック共重合体をスチレン系樹脂組成物中2〜15質量%の割合でスチレン系樹脂組成物に添加することができる。 In the present invention, in order to further improve the surface impact strength, the structural unit of the styrene monomer is adjusted to 50% by mass or less, and the polymer block of the styrene monomer and the conjugated diene monomer are adjusted. A block copolymer composed of a polymer block and a styrene resin composition can be added to the styrene resin composition at a ratio of 2 to 15% by mass in the styrene resin composition.
本発明のスチレン系樹脂組成物から成型用シートを製造する方法としては、前記した方法によって前記スチレン系共重合体(A)及び前記ブロック共重合体(B)を溶融混練した後、T−ダイから押出す方法やカレンダー成形法、インフレーション押出成形法にてシートを製膜する方法が挙げられる。この様にして厚み0.02〜3mm、好ましくは0.03〜1mmの二次成形に適したシートを製造することができる。 As a method for producing a molding sheet from the styrene-based resin composition of the present invention, the styrene-based copolymer (A) and the block copolymer (B) are melt-kneaded by the method described above, and then a T-die is used. And a method of forming a sheet by a calender molding method and an inflation extrusion molding method. In this way, a sheet having a thickness of 0.02 to 3 mm, preferably 0.03 to 1 mm, suitable for secondary molding can be produced.
このようにして得られた成型用シートは、透明性、面衝撃強度、剛性、耐折り曲げ白化性、成形加工性に優れたものとなる。例えば、透明性としては、JIS K7105に準拠した0.4mm厚シートを用いてのシート曇価が5以下となる。また、面衝撃強度は0.4mm厚シートでのデュポン衝撃強度で0.8J以上と従来にない性能を発現する。また、成型品の耐熱性も改善され、高温高湿条件(例えば、温度65℃、湿度80%、8時間静置)で変形しないものとなる。 The sheet for molding thus obtained is excellent in transparency, surface impact strength, rigidity, resistance to bending whitening, and moldability. For example, as for transparency, the sheet cloud value using a 0.4 mm thick sheet based on JIS K7105 is 5 or less. Further, the surface impact strength is 0.8 J or more in DuPont impact strength with a sheet having a thickness of 0.4 mm, exhibiting an unprecedented performance. Further, the heat resistance of the molded product is also improved, and the molded product does not deform under high temperature and high humidity conditions (for example, a temperature of 65 ° C., a humidity of 80%, and a standing time of 8 hours).
本発明では前記成型用シートを更に圧空成形、加熱加圧成形等により所望の形状に賦型することができる。該成型用シートは、耐折り曲げ白化性があり、面衝撃強度と剛性のバランスに優れ、且つ成形加工性が良好である為、例えば、ブリスターパッケージ、食品包装用トレー、蓋材、カップ、各種収納用トレー、キャリアテープ、シュリンクフィルム等の用途に適用することができ、とりわけ耐折り曲げ白化性に優れる点、また耐熱性も良好である点からブリスターパッケージとして有用である。 In the present invention, the molding sheet can be further shaped into a desired shape by air pressure molding, heat and pressure molding, or the like. Since the molding sheet has bending whitening resistance, is excellent in balance between surface impact strength and rigidity, and has good moldability, it can be used, for example, in blister packages, food packaging trays, lids, cups, and various types of containers. It can be applied to applications such as trays, carrier tapes, shrink films, etc., and is particularly useful as a blister package because of its excellent bending whitening resistance and good heat resistance.
一方、本発明のスチレン系樹脂組成物は上記したシート用途のみならず、シュリンクフィルムにも適用できる。シュリンクフィルムを製造する方法としては、本発明のスチレン系樹脂組成物を溶融混練後、押出し、少なくとも1方向に延伸する方法が挙げられる。 On the other hand, the styrene-based resin composition of the present invention can be applied not only to the above-mentioned sheet application but also to a shrink film. Examples of a method for producing a shrink film include a method in which the styrene-based resin composition of the present invention is melt-kneaded, extruded, and stretched in at least one direction.
また、上記シュリンクフィルムの製造方法における延伸方法としては、特に制限されず1軸または2軸に、同時或いは逐次で延伸する方法が好ましい。 The method of stretching the shrink film is not particularly limited, and a method of stretching uniaxially or biaxially, simultaneously or sequentially, is preferable.
ここで延伸方法は、フラット状の1軸延伸の場合は、加熱ロール間の速度差で押出方向に、或いはテンター等で押出方向と直角方向に主体的に延伸し、2軸延伸の場合は、加熱ロール間の速度差で押出方向に縦延伸した後テンター等で横方向に延伸するか、テンター内で縦横同時に延伸する方法が挙げられる。 Here, the stretching method is, in the case of flat uniaxial stretching, mainly stretching in the extrusion direction at a speed difference between heating rolls, or in the direction perpendicular to the extrusion direction with a tenter or the like, and in the case of biaxial stretching, A method in which the film is longitudinally stretched in the extrusion direction at a speed difference between the heating rolls and then horizontally stretched in a tenter or the like, or simultaneously stretched vertically and horizontally in a tenter.
環状の1軸延伸の場合は、円筒状に押し出されたシートのバブルの断面直径方向の膨張を抑制し乍ら押し出し方法に延伸してドラフトを調節する方法が挙げられ、環状の2軸延伸の場合は、押し出し方法に延伸すると共に、円筒状に押し出されたシートのバブル内部にエアーを吹き込みながらバブルの断面直径方向と同時或いは逐次延伸する方法が挙げられる。 In the case of annular uniaxial stretching, there is a method in which the draft is adjusted by stretching the sheet extruded in a cylindrical shape while suppressing expansion in the cross-sectional diametric direction of the bubble. In this case, there is a method in which the sheet is stretched by an extrusion method, and simultaneously or sequentially stretched in the sectional diameter direction of the bubble while blowing air into the inside of the bubble of the sheet extruded in a cylindrical shape.
また、本発明の透明スチレン系樹脂組成物は、上記シート及びシュリンクフィルムの各用途に加え、剛性、面衝撃性、更に成形性に富み、更に優れた透明性も発現し得る点から射出成形、異型押出成形、真空成形、圧空成形等の各種成形用途に適用することもでき、家電製品のハウジングや部品、OA機器の各種部品、文房具、雑貨等として用いることもできる。 Further, the transparent styrene-based resin composition of the present invention, in addition to the respective uses of the sheet and shrink film, rigidity, surface impact, rich in moldability, injection molding from the point that even more excellent transparency can be expressed, It can be applied to various molding applications such as profile extrusion molding, vacuum molding, air pressure molding and the like, and can also be used as housings and parts for home appliances, various parts for OA equipment, stationery, miscellaneous goods and the like.
本発明によれば、スチレン系樹脂組成物の成型品における面衝撃強度を飛躍的に改善し、面衝撃強度と剛性とのバランスを改善できる。 ADVANTAGE OF THE INVENTION According to this invention, the surface impact strength in the molded article of a styrene resin composition can be improved remarkably, and the balance between surface impact strength and rigidity can be improved.
更に、成型用シートにおける折曲げ加工時や衝撃時の白化による外観不良を防止できる他、該成型用シートの二次成型品に優れた透明性や耐熱性も付与できる。そのため、本発明のスチレン系樹脂組成物は、ブリスターパッケージ、食品包装用トレー、蓋材、カップ、各種収納用トレー、キャリアテープ、シュリンクフィルム等の用途に極めて有用である。 Furthermore, in addition to preventing appearance defects due to whitening at the time of bending or impact of the molding sheet, excellent transparency and heat resistance can be imparted to a secondary molded product of the molding sheet. Therefore, the styrene resin composition of the present invention is extremely useful for applications such as blister packages, food packaging trays, lids, cups, various storage trays, carrier tapes, shrink films, and the like.
次に実施例をもって本発明を具体的に説明するが、本発明はこれらの例に限定されるものではない。以下の「部」または「%」は特に断りがない限り、質量基準である。
[スチレン系共重合体(A)の製造]
スチレン系共重合体(A)の製造は、図3に示す工程図で示した重合ラインからなる連続重合装置を用いた。当該重合装置は、プランジャーポンプ(1)、攪拌式反応器(2)、ギアポンプ(3)、(7)、(11)、ミキシングエレメントを内部に配設してなる管状反応器(4)、(5)、(6)、(8)、(9)、及び(10)から構成される。図3において矢印は重合液の液流の方向を示しており、プランジャーポンプ(1)によって原料成分は、まず攪拌式反応器(2)へ送られ、攪拌下で初期グラフト重合させた後、ギアポンプ(3)により、管状反応器(4)、(5)、(6)、及びギアポンプ(7)で構成される循環式重合ライン(I)内に導入され、該循環式重合ライン(I)内で重合液を循環させなら重合を行う。一方、管状反応器(8)、(9)、(10)、及びギアポンプ(11)は非循環式の重合ライン(II)を形成しており、前記循環ライン(I)内の重合液の一部はこの重合ライン(II)に流れこみ該重合ライン(II)内で所望の重合度まで重合が行われる。
Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The “parts” or “%” below are based on mass unless otherwise specified.
[Production of styrenic copolymer (A)]
For the production of the styrene copolymer (A), a continuous polymerization apparatus comprising a polymerization line shown in the process diagram shown in FIG. 3 was used. The polymerization apparatus includes a plunger pump (1), a stirring reactor (2), a gear pump (3), (7), (11), a tubular reactor (4) having a mixing element disposed therein, (5), (6), (8), (9), and (10). In FIG. 3, the arrows indicate the direction of the flow of the polymerization liquid. The raw material components are first sent to the stirred reactor (2) by the plunger pump (1), and the initial graft polymerization is performed under stirring. By the gear pump (3), it is introduced into the circulation polymerization line (I) composed of the tubular reactors (4), (5), (6) and the gear pump (7), and the circulation polymerization line (I) If the polymerization solution is circulated inside, polymerization is performed. On the other hand, the tubular reactors (8), (9), (10) and the gear pump (11) form a non-circulating polymerization line (II), and one of the polymerization liquids in the circulation line (I) is formed. The part flows into the polymerization line (II), and polymerization is performed in the polymerization line (II) to a desired degree of polymerization.
ここで、該循環式重合ライン(I)での重合は、該循環式重合ライン(I)出口でのスチレン系単量体(a)とアクリル酸ブチル(b)、メタクリル酸メチル(c)の合計の重合転化率が、通常35〜55質量%、好ましくは40〜50質量%になる様に重合される。循環式重合ライン(I)内を循環する重合液の流量と、非循環式の重合ライン(II)へ流出する重合液の流量との比、還流比Rは、重合ライン(II)に流出せずに循環式重合ライン(I)内を還流する混合溶液の流量をF1 (リットル /時間)とし、循環重合ライン(I)から非循環の重合ライン(II)に流出する混合溶液の流量F2 (リットル/時間)とした場合、通常R=F1 /F2 が3〜15の範囲に調整される。 Here, the polymerization in the circulating polymerization line (I) is performed by reacting the styrene monomer (a) with butyl acrylate (b) and methyl methacrylate (c) at the outlet of the circulating polymerization line (I). The polymerization is carried out so that the total polymerization conversion is usually 35 to 55% by mass, preferably 40 to 50% by mass. The ratio of the flow rate of the polymerization liquid circulating in the circulation type polymerization line (I) to the flow rate of the polymerization liquid flowing out of the non-circulation type polymerization line (II), and the reflux ratio R, are output to the polymerization line (II). The flow rate of the mixed solution refluxing in the circulation polymerization line (I) is set to F1 (liter / hour), and the flow rate F2 of the mixed solution flowing from the circulation polymerization line (I) to the non-circulation polymerization line (II) is F2 ( Liter / hour), R = F1 / F2 is usually adjusted in the range of 3 to 15.
重合終了後、重合溶液はギアポンプ(11)により予熱器、次いで脱揮発槽に送られ、減圧下にて未反応単量体および溶剤を除去した後、ペレット化することにより目的とするスチレン系共重合体(A)が得られる。 After the polymerization is completed, the polymerization solution is sent to a preheater and then to a devolatilization tank by a gear pump (11), and after removing unreacted monomers and a solvent under reduced pressure, pelletizing the styrene-based copolymer. The polymer (A) is obtained.
(スチレン系共重合体(A−1)の製造)
スチレン(SM)82部、アクリル酸ブチル(BuA)12部、メタクリル酸メチル(MMA)6部、エチルベンゼン8部から成る混合溶液を調製し、重合開始剤として単量体混合物100部に対して0.025部の2,2−ビス(4,4−ジ−パーオキシシクロヘキシル)プロパン、連鎖移動剤として単量体混合物100部に対して0.01部のn−ドデシルメルカプタンを加え、前記重合装置を用い以下の条件下で連続的に塊状重合させた。
(Production of styrene-based copolymer (A-1))
A mixed solution comprising 82 parts of styrene (SM), 12 parts of butyl acrylate (BuA), 6 parts of methyl methacrylate (MMA), and 8 parts of ethylbenzene was prepared. 0.025 parts of 2,2-bis (4,4-di-peroxycyclohexyl) propane and 0.01 part of n-dodecylmercaptan as a chain transfer agent per 100 parts of the monomer mixture were added to the polymerization apparatus. Was used for continuous bulk polymerization under the following conditions.
攪拌式反応器(2)での反応温度:115℃
循環式重合ライン(I)での反応温度:132℃
重合ライン(II)での反応温度:150℃
次に、重合させて得られた混合溶液を熱交換器で215℃まで加熱し、減圧下で揮発成分を除去した後、ペレット化してスチレン系共重合体(A−1)を得た。得られたスチレン系共重合体の物性を表1に示した。
Reaction temperature in stirred reactor (2): 115 ° C
Reaction temperature in the circulation polymerization line (I): 132 ° C
Reaction temperature in polymerization line (II): 150 ° C
Next, the mixed solution obtained by the polymerization was heated to 215 ° C. with a heat exchanger to remove volatile components under reduced pressure, and then pelletized to obtain a styrene-based copolymer (A-1). Table 1 shows the physical properties of the obtained styrenic copolymer.
(スチレン系共重合体(A−2)の製造)
スチレン(SM)82部、アクリル酸ブチル(BuA)12部、メタクリル酸メチル(MMA)6部、エチルベンゼン9部から成る混合溶液に、重合開始剤として単量体混合物100部に対して0.025部の2,2−ビス(4,4−ジ−パーオキシシクロヘキシル)プロパン、連鎖移動剤として単量体混合物100部に対して0.02部のn−ドデシルメルカプタンを加えた以外はスチレン系共重合体(A−1)と同様にしてスチレン系共重合体(A−2)を得た。得られたスチレン系共重合体の物性を表1に示した。
(Production of styrene copolymer (A-2))
A mixed solution consisting of 82 parts of styrene (SM), 12 parts of butyl acrylate (BuA), 6 parts of methyl methacrylate (MMA) and 9 parts of ethylbenzene was added as a polymerization initiator in an amount of 0.025 to 100 parts of the monomer mixture. Parts of 2,2-bis (4,4-di-peroxycyclohexyl) propane and a styrene copolymer except that 0.02 parts of n-dodecyl mercaptan were added as a chain transfer agent to 100 parts of the monomer mixture. A styrenic copolymer (A-2) was obtained in the same manner as the polymer (A-1). Table 1 shows the physical properties of the obtained styrenic copolymer.
(スチレン系共重合体(A−3)の製造)
スチレン(SM)82部、アクリル酸ブチル(BuA)8部、メタクリル酸メチル(MMA)10部、エチルベンゼン9部から成る混合溶液に、重合開始剤として単量体混合物100部に対して0.025部の2,2−ビス(4,4−ジ−パーオキシシクロヘキシル)プロパン、連鎖移動剤として単量体混合物100部に対して0.03部のn−ドデシルメルカプタンを加えた以外はスチレン系共重合体(A−1)と同様にしてスチレン系共重合体(A−3)を得た。得られたスチレン系共重合体の物性を表1に示した。
(Production of styrene copolymer (A-3))
A mixed solution consisting of 82 parts of styrene (SM), 8 parts of butyl acrylate (BuA), 10 parts of methyl methacrylate (MMA) and 9 parts of ethylbenzene was used as a polymerization initiator in an amount of 0.025 to 100 parts of the monomer mixture. Parts of 2,2-bis (4,4-di-peroxycyclohexyl) propane and a styrene-based copolymer except that 0.03 part of n-dodecylmercaptan was added to 100 parts of the monomer mixture as a chain transfer agent. A styrenic copolymer (A-3) was obtained in the same manner as in the polymer (A-1). Table 1 shows the physical properties of the obtained styrenic copolymer.
(スチレン系共重合体(A−4)の製造)
スチレン(SM)82部、アクリル酸ブチル(BuA)5部、メタクリル酸メチル(MMA)13部、エチルベンゼン6部から成る混合溶液に、重合開始剤として単量体混合物100部に対して0.025部のt−ブチルパーオキシイソプロピルモノカーボネート、連鎖移動剤として単量体混合物100部に対して0.03部のn−ドデシルメルカプタンを加え、図3の工程図で示した重合ラインを用い以下の条件下で連続的に塊状重合させた。
(Production of styrene copolymer (A-4))
A mixed solution consisting of 82 parts of styrene (SM), 5 parts of butyl acrylate (BuA), 13 parts of methyl methacrylate (MMA), and 6 parts of ethylbenzene was added as a polymerization initiator in an amount of 0.025 to 100 parts of the monomer mixture. Part of t-butyl peroxyisopropyl monocarbonate, 0.03 part of n-dodecyl mercaptan was added to 100 parts of the monomer mixture as a chain transfer agent, and the polymerization line shown in the process diagram of FIG. Under the conditions, bulk polymerization was continuously performed.
攪拌式反応器(2)での反応温度:119℃
循環式重合ライン(I)での反応温度:124℃
重合ライン(II)での反応温度:150℃
重合させて得られた混合溶液を熱交換器で215℃まで加熱し、減圧下で揮発成分を除去した後、ペレット化してスチレン系共重合体(A−4)を得た。得られたスチレン系共重合体の物性を表1に示した。
Reaction temperature in the stirred reactor (2): 119 ° C
Reaction temperature in the circulation polymerization line (I): 124 ° C
Reaction temperature in polymerization line (II): 150 ° C
The mixed solution obtained by the polymerization was heated to 215 ° C. with a heat exchanger, volatile components were removed under reduced pressure, and then pelletized to obtain a styrene-based copolymer (A-4). Table 1 shows the physical properties of the obtained styrenic copolymer.
(スチレン系共重合体(A−5)の製造)
スチレン(SM)82部、アクリル酸ブチル(BuA)5部、メタクリル酸メチル(MMA)13部、エチルベンゼン9部から成る混合溶液に、重合開始剤として単量体混合物100部に対して0.025部の2,2−ビス(4,4−ジ−パーオキシシクロヘキシル)プロパン、連鎖移動剤として単量体混合物100部に対して0.03部のn−ドデシルメルカプタンを加えた以外はスチレン系共重合体(A−1)と同様にしてスチレン系共重合体(A−5)を得た。得られたスチレン系共重合体の物性を表1に示した。
(Production of styrene-based copolymer (A-5))
A mixed solution consisting of 82 parts of styrene (SM), 5 parts of butyl acrylate (BuA), 13 parts of methyl methacrylate (MMA) and 9 parts of ethylbenzene was added as a polymerization initiator in an amount of 0.025 to 100 parts of the monomer mixture. Parts of 2,2-bis (4,4-di-peroxycyclohexyl) propane and a styrene-based copolymer except that 0.03 part of n-dodecylmercaptan was added to 100 parts of the monomer mixture as a chain transfer agent. A styrenic copolymer (A-5) was obtained in the same manner as in the polymer (A-1). Table 1 shows the physical properties of the obtained styrenic copolymer.
(スチレン系共重合体(A−6)の製造)
スチレン(SM)82部、アクリル酸ブチル(BuA)18部、エチルベンゼン9部から成る混合溶液に、重合開始剤として単量体混合物100部に対して0.026部の2,2−ビス(4,4−ジ−パーオキシシクロヘキシル)プロパンを加え、図3の工程図で示した重合ラインを用い以下の条件下で連続的に塊状重合させた。
攪拌式反応器(2)での反応温度:115℃
循環重合ライン(I)での反応温度:132℃
非循環重合ライン(II)での反応温度:150℃
重合させて得られた混合溶液を熱交換器で215℃まで加熱し、減圧下で揮発成分を除去した後、ペレット化してスチレン系共重合体(A−6)を得た。得られたスチレン系共重合体の物性を表1に示した。
(Production of styrene-based copolymer (A-6))
In a mixed solution consisting of 82 parts of styrene (SM), 18 parts of butyl acrylate (BuA) and 9 parts of ethylbenzene, 0.026 parts of 2,2-bis (4 , 4-di-peroxycyclohexyl) propane was added, and continuous bulk polymerization was carried out using the polymerization line shown in the process diagram of FIG. 3 under the following conditions.
Reaction temperature in stirred reactor (2): 115 ° C
Reaction temperature in circulation polymerization line (I): 132 ° C
Reaction temperature in non-circulation polymerization line (II): 150 ° C
The mixed solution obtained by the polymerization was heated to 215 ° C. with a heat exchanger, volatile components were removed under reduced pressure, and the mixture was pelletized to obtain a styrene copolymer (A-6). Table 1 shows the physical properties of the obtained styrenic copolymer.
[スチレン系樹脂組成物の製造及び物性評価]
(スチレン−ブタジエン−スチレンブロック共重合体(B))
下記の各実施例及び比較例で使用したスチレン−ブタジエン−スチレンブロック共重合体(B)は、次の通りである。
[Production of styrene resin composition and evaluation of physical properties]
(Styrene-butadiene-styrene block copolymer (B))
The styrene-butadiene-styrene block copolymer (B) used in each of the following Examples and Comparative Examples is as follows.
スチレン−ブタジエン−スチレンブロック共重合体(B1):
シェブロンフィリップス社製SBS(商品名「KレジンKR05」)
スチレンに由来する構成単位の含有率 : 75質量%
ブタジエンに由来する構造単位の含有率 : 25質量%
MFR:7g/10min
Styrene-butadiene-styrene block copolymer (B1):
Chevron Phillips SBS (trade name “K Resin KR05”)
Content of structural units derived from styrene: 75% by mass
Content of structural units derived from butadiene: 25% by mass
MFR: 7g / 10min
スチレン−ブタジエン−スチレンブロック共重合体(B2)
シェブロンフィリップス社製SBS(商品名「KレジンDK11」
スチレンに由来する構成単位の含有率 : 75質量%、
ブタジエンに由来する構造単位の含有率 : 25質量%、
MFR:8g/10min。)
以下、前記スチレン−ブタジエン−スチレンブロック共重合体(B1)及び(B2)はそれぞれ「ブロック共重合体(B1)」及び「ブロック共重合体(B2)」と略記する。
Styrene-butadiene-styrene block copolymer (B2)
Chevron Phillips SBS (trade name “K Resin DK11”
Content of structural units derived from styrene: 75% by mass,
Content of structural units derived from butadiene: 25% by mass,
MFR: 8 g / 10 min. )
Hereinafter, the styrene-butadiene-styrene block copolymers (B1) and (B2) are abbreviated as “block copolymer (B1)” and “block copolymer (B2)”, respectively.
(C13−NMRによる測定)
各実施例及び比較例で得られたスチレン系樹脂組成物中の共役ジエン系単量体に由来する構造単位、メタクリル酸メチル(c)に由来する構造単位、及びアクリル酸ブチル(b)に由来する構造単位の含有率は、次の様にして測定した。
(Measured by C 13 -NMR)
Structural units derived from the conjugated diene-based monomer in the styrene-based resin compositions obtained in each of Examples and Comparative Examples, structural units derived from methyl methacrylate (c), and derived from butyl acrylate (b) The content of the structural unit to be measured was measured as follows.
各実施例又は比較例で得られたサンプル120mgをCDC13 0.5mlに溶解し、緩和試薬 約5mgを加えNMR測定試料管に充填した。日本電子製NMR「GSX−400」によりゲートカップリング法による定量13C-NMRを測定した。 120 mg of the sample obtained in each example or comparative example was dissolved in 0.5 ml of CDC13, and about 5 mg of a relaxation reagent was added to the solution and filled in a sample tube for NMR measurement. Quantitative 13 C-NMR was measured by a gate coupling method using NMR “GSX-400” manufactured by JEOL Ltd.
下記に示す炭素原子のケミカルピークの面積比から各構造単位の含有率を求めた。 The content of each structural unit was determined from the area ratio of the chemical peaks of carbon atoms shown below.
測定対象となる炭素原子とそれに対応するケミカルシフト
スチレンに由来する構造単位の場合、芳香族炭素原子:142〜146ppm
メチルメタクリレートに由来する構造単位の場合、カルボニル炭素原子:
175ppm
ブチルアクリレートに由来する構造単位の場合、酸素原子に結合するブチル基の炭素原子:63ppm
ブタジエンに由来する構造単位(ブタ−3−エン−1,2−ジイル)の場合、1,2−ビニル基を構成する末端炭素原子:114ppm
ブタジエンに由来する構造単位(ブタ−2−エン−1,4−ジイル)の場合、末端炭素原子:125〜132ppm
In the case of a carbon atom to be measured and a corresponding chemical shift styrene-derived structural unit, an aromatic carbon atom: 142 to 146 ppm
In the case of a structural unit derived from methyl methacrylate, a carbonyl carbon atom:
175ppm
In the case of a structural unit derived from butyl acrylate, the carbon atom of the butyl group bonded to the oxygen atom: 63 ppm
In the case of a structural unit derived from butadiene (but-3-ene-1,2-diyl), a terminal carbon atom constituting a 1,2-vinyl group: 114 ppm
In the case of a structural unit derived from butadiene (but-2-ene-1,4-diyl), a terminal carbon atom: 125 to 132 ppm
[物性評価方法]
下記の各実施例及び比較例における成型用シートの物性評価方法は以下の通りである。
[Physical property evaluation method]
The methods for evaluating the physical properties of the molding sheet in each of the following Examples and Comparative Examples are as follows.
(ヘイズの測定)
JIS K7105に準拠して、濁度、曇り度計(日本電色工業製)を用い、0.4mm厚みのシート試験片の透明性を表すヘイズ値を測定した。
(Haze measurement)
In accordance with JIS K7105, a haze value indicating the transparency of a 0.4 mm-thick sheet test piece was measured using a turbidity and haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).
(デュポン衝撃強度の測定)
デュポン衝撃試験機(東洋精機製作所製)を用い、重錘300g、撃芯先端半径6.3mm、受台半径6.3mmの条件で、厚み0.4mmのシート試験片の50%破壊エネルギーを求めた。
(Measurement of DuPont impact strength)
Using a DuPont impact tester (manufactured by Toyo Seiki Seisaku-Sho, Ltd.), the 50% breaking energy of a 0.4 mm-thick sheet test piece was determined under the conditions of a weight of 300 g, a tip radius of the shooting core of 6.3 mm, and a cradle radius of 6.3 mm. Was.
(引張弾性率の測定)
JIS K7161に準拠し、試験速度1mm/minで引張弾性率を測定した。
(Measurement of tensile modulus)
The tensile modulus was measured at a test speed of 1 mm / min in accordance with JIS K7161.
(メルトマスフローレートの測定)
JIS K7210に準拠し、温度200℃、荷重5Kgfでメルトマスフローレートを測定した。
(Measurement of melt mass flow rate)
Based on JIS K7210, the melt mass flow rate was measured at a temperature of 200 ° C. and a load of 5 kgf.
(折曲げ白化試験)
0.4mm厚シートを180°折り曲げ、次いでシーとを元の状態に戻した時の白化部分の太さをノギスにて実測した。
(Bending whitening test)
A 0.4 mm thick sheet was bent at 180 °, and then the thickness of the whitened portion when the sheet was returned to the original state was measured with a vernier caliper.
(シート外観の評価)
押出したシートに、フィッシュアイ、ハードスポット、シャークスキン等の外観不良が発生しなかった場合を○、発生した場合を×とした。
(Evaluation of sheet appearance)
The extruded sheet was evaluated as ○ when no appearance defects such as fish eyes, hard spots and sharkskin were generated, and evaluated as x when it did.
(耐熱性評価)
0.4mm厚シートを真空成形機により170×130×35(mm)の箱型に成形し、この成型品を温度65℃、湿度80%の恒温槽内に8時間放置し、成型品の変形を確認した。成型品に変形が認められなかった場合を○、変形した場合を×とした。
(Heat resistance evaluation)
A 0.4 mm thick sheet is formed into a 170 × 130 × 35 (mm) box by a vacuum forming machine, and the formed product is left in a constant temperature bath at a temperature of 65 ° C. and a humidity of 80% for 8 hours to deform the formed product. It was confirmed. The case where no deformation was observed in the molded product was evaluated as ○, and the case where it was deformed was evaluated as ×.
(ネックインの測定)
押出したシートの幅(W)を測定し、ダイ巾をW0として、次式よりネックインを算出した。
(Measurement of neck-in)
Extruded sheet of width (W) were measured, and the die width as W 0, was calculated neck-in from the following equation.
ネックイン(mm)=W0−W
Neck-in (mm) = W 0 -W
実施例1
スチレン系共重合体(A−1)に、下記のスチレン−ブタジエン−スチレンブロック共重合体(B1)を(A−1)/(B1)=50/50の質量割合で加え、押出成形して厚さ0.4mmのシートを作成した。
Example 1
The following styrene-butadiene-styrene block copolymer (B1) was added to the styrene-based copolymer (A-1) at a mass ratio of (A-1) / (B1) = 50/50, and extruded. A sheet having a thickness of 0.4 mm was prepared.
得られたシートを用いて各種物性を測定した。測定値を表3に示した。尚、シート成形条件は次の通りである。 Various physical properties were measured using the obtained sheet. The measured values are shown in Table 3. The sheet forming conditions are as follows.
シート成形機:ユニオンプラスチック株式会社製UEV型30mm押出機
シリンダー温度:210℃、Tダイ設定温度:210℃
T−ダイ リップ巾:200mm
引取り速度:1m/min
スクリュー回転数:65rpm
Sheet forming machine: UEV type 30mm extruder manufactured by Union Plastics Co., Ltd. Cylinder temperature: 210 ° C, T-die set temperature: 210 ° C
T-die lip width: 200mm
Pickup speed: 1m / min
Screw rotation speed: 65 rpm
実施例2
スチレン系共重合体(A−1)に、ブロック共重合体(B2)を(A−1)/(B2)=40/60の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表2に示した。
Example 2
The block copolymer (B2) was added to the styrene-based copolymer (A-1) at a mixing ratio of (A-1) / (B2) = 40/60, and the thickness was reduced to 0 under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 2.
実施例3
スチレン系共重合体(A−1)に、ブロック共重合体(B2)を(A−1)/(B2)=40/60の配合割合で、下記の押出条件にて厚さ0.4mmのシートを作成し、各種物性を測定した。
Example 3
The block copolymer (B2) was added to the styrene-based copolymer (A-1) at a mixing ratio of (A-1) / (B2) = 40/60 to a thickness of 0.4 mm under the following extrusion conditions. Sheets were prepared and various physical properties were measured.
<押出条件>
シート成形機:日立造船産業株式会社製120mm押出機
シリンダー温度:210℃、T−ダイ設定温度:210℃
T−ダイリップ巾:1030mm
引取り速度:22m/min
スクリュー回転数:60rpm
また、シートの一部を切り出し、四酸化オスミウムで染色後、ウルトラミクロトームでCD方向の断面から超薄切片を作製し、透過型電子顕微鏡(TEM)を撮影した。結果を図1に示す。
<Extrusion conditions>
Sheet forming machine: 120mm extruder manufactured by Hitachi Zosen Corporation Cylinder temperature: 210 ° C, T-die set temperature: 210 ° C
T-die lip width: 1030mm
Pickup speed: 22m / min
Screw rotation speed: 60rpm
Further, a part of the sheet was cut out, stained with osmium tetroxide, ultra-thin sections were prepared from a cross section in the CD direction with an ultramicrotome, and a transmission electron microscope (TEM) was photographed. The results are shown in FIG.
実施例4
スチレン系共重合体(A−1)に、ブロック共重合体(B2)を(A−1)/(B2)30/70の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表2に示した。
Example 4
The block copolymer (B2) was added to the styrene-based copolymer (A-1) at a mixing ratio of (A-1) / (B2) 30/70, and a thickness of 0.1 was obtained under the same conditions as in Example 1. A 4 mm sheet was prepared and various physical properties were measured. The measured values are shown in Table 2.
実施例5
スチレン系共重合体(A−2)に、ブロック共重合体(B1)を(A−3)/(B1)=50/50の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表3に示した。
Example 5
The block copolymer (B1) was added to the styrene-based copolymer (A-2) at a mixing ratio of (A-3) / (B1) = 50/50, and a thickness of 0 was obtained under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 3.
実施例6
スチレン系共重合体(A−3)に、ブロック共重合体(B1)を(A−4)/(B1)=50/50の質量割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表3に示した。
Example 6
The block copolymer (B1) was added to the styrene-based copolymer (A-3) at a mass ratio of (A-4) / (B1) = 50/50, and a thickness of 0 was obtained under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 3.
実施例7
スチレン系共重合体(A−1)に、ブロック共重合体(B1)と、スチレン系モノマー構成単位の含有率:43質量%、ブタジエンモノマー構造単位の含有率:57質量%のスチレン−ブタジエンブロック共重合体エラストマー(JSR社製「TR2003」)を(A−1)/(B1)/(TR2003)=40/50/10の配合の割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表3に示した。
Example 7
A block copolymer (B1) and a styrene-butadiene block having a styrene monomer structural unit content of 43% by mass and a butadiene monomer structural unit content of 57% by mass in a styrene copolymer (A-1). A copolymer elastomer ("TR2003" manufactured by JSR Corporation) was added at a ratio of (A-1) / (B1) / (TR2003) = 40/50/10, and a thickness of 0 was obtained under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 3.
実施例8
スチレン系共重合体(A−4)に、ブロック共重合体(B1)を(A−4)/(B1)=50/50の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表3に示した。
Example 8
The block copolymer (B1) was added to the styrene-based copolymer (A-4) at a mixing ratio of (A-4) / (B1) = 50/50, and a thickness of 0 was obtained under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 3.
実施例9
スチレン系共重合体(A−5)に、ブロック共重合体(B1)を(A−5)/(B1)=50/50の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表3に示した。
Example 9
The block copolymer (B1) was added to the styrene-based copolymer (A-5) at a mixing ratio of (A-5) / (B1) = 50/50, and a thickness of 0 was obtained under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 3.
実施例10
スチレン系共重合体(A−1)に、ブロック共重合体(B1)を(A−5)/(B1)=40/60の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表3に示した。
Example 10
The block copolymer (B1) was added to the styrene-based copolymer (A-1) at a mixing ratio of (A-5) / (B1) = 40/60, and the thickness was reduced to 0 under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 3.
比較例1
スチレン系共重合体(A−6)に、ブロック共重合体(B1)を(A−6)/(B1)=40/60の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表4に示した。
Comparative Example 1
The block copolymer (B1) was added to the styrene-based copolymer (A-6) at a mixing ratio of (A-6) / (B1) = 40/60, and the thickness was reduced to 0 under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 4.
比較例2
スチレン系共重合体(A−6)に、ブロック共重合体(B2)を(A−6)/(B1)=40/60の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表4に示した。
Comparative Example 2
The block copolymer (B2) was added to the styrene-based copolymer (A-6) at a mixing ratio of (A-6) / (B1) = 40/60, and the thickness was reduced to 0 under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 4.
尚、得られたシートの一部を切り出し、四酸化オスミウムで染色後、ウルトラミクロトームでCD方向の断面から超薄切片を作製し、透過型電子顕微鏡(TEM)を撮影した。結果を図2に示す。 In addition, a part of the obtained sheet was cut out, stained with osmium tetroxide, ultra-thin sections were prepared from a cross section in the CD direction using an ultramicrotome, and photographed with a transmission electron microscope (TEM). FIG. 2 shows the results.
比較例3
スチレン系共重合体(A−6)に、ブロック共重合体(B2)を(A−6)/(B1)=30/60の配合割合で加え、実施例1と同一の条件で厚さ0.4mmのシートを作成し、各種物性を測定した。測定値を表4に示した。
Comparative Example 3
The block copolymer (B2) was added to the styrene-based copolymer (A-6) at a mixing ratio of (A-6) / (B1) = 30/60, and a thickness of 0 was obtained under the same conditions as in Example 1. A sheet of 0.4 mm was prepared and various physical properties were measured. The measured values are shown in Table 4.
(尚、表中「TR2003」はJSR社製熱可塑性エラストマー「TR2003」(スチレン系モノマー構成単位の含有率:43質量%、ブタジエンモノマー構造単位の含有率:57質量%のスチレン−ブタジエンブロック共重合体)を表す。) (Note that "TR2003" in the table is a thermoplastic elastomer "TR2003" manufactured by JSR Corporation (styrene-butadiene block copolymer having a styrene monomer structural unit content of 43% by mass and a butadiene monomer structural unit content of 57% by mass). Union).)
(1):プランジャーポンプ
(2):攪拌式反応器
(3):ギヤポンプ
(4):ミキシングエレメントを内部に配設してなる管状反応器
(5):ミキシングエレメントを内部に配設してなる管状反応器
(6):ミキシングエレメントを内部に配設してなる管状反応器
(7):ギヤポンプ
(8):ミキシングエレメントを内部に配設してなる管状反応器
(9):ミキシングエレメントを内部に配設してなる管状反応器
(10):ミキシングエレメントを内部に配設してなる管状反応器
(11):ギアポンプ
(I):循環式重合ライン
(II):非循環式の重合ライン
(1): Plunger pump
(2): Stirred reactor
(3): Gear pump
(4): A tubular reactor having a mixing element disposed inside
(5): A tubular reactor having a mixing element disposed inside
(6): Tubular reactor having a mixing element disposed inside
(7): Gear pump
(8): Tubular reactor having a mixing element disposed inside
(9): A tubular reactor having a mixing element disposed inside
(10): tubular reactor having a mixing element disposed inside
(11): Gear pump
(I): Circulation polymerization line
(II): Non-circulation type polymerization line
Claims (8)
前記スチレン系共重合体(A)がスチレン系単量体(a)、アクリル酸ブチル(b)及びメタクリル酸メチル(c)の共重合体であり、
前記ブロック共重合体(B)が、前記重合体ブロック(b1)の層とジエン系単量体の前記重合体ブロック(b2)の層が交互に積層する多層構造を形成しており、かつ、
前記共役ジエン系単量体に由来する構造単位を原料質量比で前記スチレン系樹脂組成物中9〜25質量%の割合で含有する
ことを特徴とするスチレン系樹脂組成物。 A styrene-based copolymer (A) and a block copolymer (B) composed of a polymer block of a styrene-based monomer (b1) and a polymer block of a conjugated diene-based monomer (b2) are included. A styrenic resin composition,
The styrene-based copolymer (A) is a copolymer of a styrene-based monomer (a), butyl acrylate (b) and methyl methacrylate (c),
The block copolymer (B) has a multilayer structure in which layers of the polymer block (b1) and layers of the polymer block (b2) of diene-based monomers are alternately laminated; and
A styrene-based resin composition comprising a structural unit derived from the conjugated diene-based monomer in a ratio of 9 to 25% by mass in the styrene-based resin composition in terms of a raw material mass ratio.
A blister package comprising the styrene resin composition according to claim 1.
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WO2007020933A1 (en) * | 2005-08-16 | 2007-02-22 | Dainippon Ink And Chemicals, Inc. | Multilayer sheet and molded body using same |
JP2007126169A (en) * | 2005-11-02 | 2007-05-24 | Shin Etsu Polymer Co Ltd | Method for manufacturing electronic part storing member, and electronic part storing member |
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US8012539B2 (en) | 2008-05-09 | 2011-09-06 | Kraton Polymers U.S. Llc | Method for making sulfonated block copolymers, method for making membranes from such block copolymers and membrane structures |
US8445631B2 (en) | 2009-10-13 | 2013-05-21 | Kraton Polymers U.S. Llc | Metal-neutralized sulfonated block copolymers, process for making them and their use |
US8263713B2 (en) | 2009-10-13 | 2012-09-11 | Kraton Polymers U.S. Llc | Amine neutralized sulfonated block copolymers and method for making same |
US9394414B2 (en) | 2010-09-29 | 2016-07-19 | Kraton Polymers U.S. Llc | Elastic, moisture-vapor permeable films, their preparation and their use |
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US9365662B2 (en) | 2010-10-18 | 2016-06-14 | Kraton Polymers U.S. Llc | Method for producing a sulfonated block copolymer composition |
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JP2007126169A (en) * | 2005-11-02 | 2007-05-24 | Shin Etsu Polymer Co Ltd | Method for manufacturing electronic part storing member, and electronic part storing member |
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