JPH04277549A - Rubber-modified styrenic resin excellent in low-temperature moldability - Google Patents
Rubber-modified styrenic resin excellent in low-temperature moldabilityInfo
- Publication number
- JPH04277549A JPH04277549A JP3861991A JP3861991A JPH04277549A JP H04277549 A JPH04277549 A JP H04277549A JP 3861991 A JP3861991 A JP 3861991A JP 3861991 A JP3861991 A JP 3861991A JP H04277549 A JPH04277549 A JP H04277549A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin
- styrene
- styrenic resin
- rubber
- 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.)
- Granted
Links
- 229920001890 Novodur Polymers 0.000 title claims description 92
- 239000002245 particle Substances 0.000 claims abstract description 41
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- -1 polysiloxane Polymers 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 abstract description 87
- 239000011347 resin Substances 0.000 abstract description 87
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000000806 elastomer Substances 0.000 abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 232
- 239000000047 product Substances 0.000 description 53
- 238000000465 moulding Methods 0.000 description 45
- 239000006260 foam Substances 0.000 description 39
- 238000000034 method Methods 0.000 description 33
- 230000000704 physical effect Effects 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 18
- 229920002223 polystyrene Polymers 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 13
- 239000013013 elastic material Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000005187 foaming Methods 0.000 description 12
- 239000004014 plasticizer Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 208000002260 Keloid Diseases 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 238000004904 shortening Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 210000001117 keloid Anatomy 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000035900 sweating Effects 0.000 description 4
- 238000009966 trimming Methods 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010097 foam moulding Methods 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 241000004297 Draba Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical group Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-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
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000252229 Carassius auratus Species 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 206010023330 Keloid scar Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- QPFMBZIOSGYJDE-UHFFFAOYSA-N acetylene tetrachloride Natural products ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は強度、透明性、低温成形
性に優れたゴム変性スチレン系樹脂に関するものである
。さらに詳しくは、本発明は特定の割合からなるスチレ
ン系構造単位とアクリル酸エステル（メタクリル酸エス
テル）系構造単位とメチルメタクリレート構造単位とか
らなるスチレン系重合体を連続相とし、ビニル芳香族炭
化水素重合体ブロックと共役ジエンを主体とする重合体
ブロックからなるゴム状弾性体を分散相とする強度、低
温成形性に優れたスチレン系樹脂に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-modified styrenic resin having excellent strength, transparency, and low-temperature moldability. More specifically, the present invention uses a styrenic polymer consisting of a styrene structural unit, an acrylic acid ester (methacrylic acid ester) structural unit, and a methyl methacrylate structural unit in a specific ratio as a continuous phase, and a vinyl aromatic hydrocarbon. The present invention relates to a styrenic resin having excellent strength and low-temperature moldability and having a dispersed phase of a rubber-like elastic body composed of a polymer block and a polymer block mainly composed of a conjugated diene.
【０００２】更に詳細には、本発明は■上記の新規なス
チレン系樹脂から得られた、真空成形性、圧空成形時の
成形サイクルを短縮させると共に、強靱性を高めて成形
品のトリミング時の抜き割れ防止を付与した、透明性の
優れた新規なスチレン系樹脂シート及び二軸延伸スチレ
ン系樹脂シート；■上記の新規なスチレン系樹脂を成形
してなる透明性、強度に優れた新規なスチレン系樹脂成
形体；■上記の新規なスチレン系樹脂から得られる、加
熱二次発泡成形性に優れ、発泡成形品の強度に優れた新
規なスチレン系樹脂発泡体を提供するものである。[0002] More specifically, the present invention provides (1) a product obtained from the above-mentioned novel styrene-based resin that has improved vacuum formability, shortened the molding cycle during pressure molding, and improved toughness to improve trimming of the molded product. A new styrene resin sheet with excellent transparency and biaxially oriented styrenic resin sheet that is resistant to punching and cracking;■ New styrene with excellent transparency and strength formed by molding the above new styrenic resin Resin molded article: (1) A novel styrenic resin foam obtained from the above-mentioned novel styrenic resin, which has excellent secondary foaming moldability and excellent strength of the foamed molded product.
【０００３】0003
【発明が解決しようとする課題】スチレン系樹脂は透明
性、成形性、剛性に優れた樹脂であるところから、家庭
用品、電気製品、包装等の成形材料として広く用いられ
てきた。利用分野が拡大するに従い、スチレン系樹脂の
強度向上、成形性向上が強く求められるようになった。
強度の高いスチレン系樹脂を得るには平均分子量を大き
くすればよいことは公知の事実であるが、分子量を大き
くすることにより成形性の低下は免れ得ない。又、成形
性の低下を補う為に可塑剤の添加も公知の事実であるが
、可塑剤を添加すると、強度、剛性が低下する。又、成
形時、可塑剤が成形品表面又は金型に付着する現象、い
わゆるスエッティング現象が生じ、成形品の品質低下、
生産性低下を招く。[Problems to be Solved by the Invention] Styrenic resins have been widely used as molding materials for household goods, electrical products, packaging, etc. because they are resins with excellent transparency, moldability, and rigidity. As the fields of use have expanded, there has been a strong demand for improved strength and moldability of styrene resins. Although it is a well-known fact that a styrenic resin with high strength can be obtained by increasing the average molecular weight, increasing the molecular weight inevitably reduces moldability. It is also a well-known fact that plasticizers are added to compensate for deterioration in moldability, but adding plasticizers reduces strength and rigidity. Additionally, during molding, a phenomenon in which the plasticizer adheres to the surface of the molded product or the mold, the so-called sweating phenomenon, occurs, resulting in a decrease in the quality of the molded product.
This results in decreased productivity.
【０００４】スチレン系樹脂の強度向上の為には、ゴム
状弾性体を分散粒子として含有するスチレン系重合体、
すなわちゴム補強スチレン系樹脂（ＨＩＰＳ）があるが
、この樹脂はシート、フィルムに成形しても不透明であ
り、透明性を要求される分野では使用できない。食品包
装用途では、スチレン系樹脂のシート、フィルムが多用
されている。塩化ビニル樹脂のシート、フィルムは成形
性が良好であり、成形体の強度も優れているが、最近の
環境問題から、塩化ビニル樹脂代替樹脂が求められてい
る。スチレン系単量体だけからなるスチレン系樹脂の改
良が種々行われているが、未だ市場要求を満足させるこ
とは出来ていない。In order to improve the strength of styrenic resins, styrene polymers containing rubber-like elastic bodies as dispersed particles,
Specifically, there is rubber reinforced styrene resin (HIPS), but this resin is opaque even when formed into a sheet or film, and cannot be used in fields where transparency is required. Styrene resin sheets and films are widely used in food packaging applications. Sheets and films made of vinyl chloride resin have good moldability and the strength of molded products is excellent, but due to recent environmental issues, there is a demand for substitute resins for vinyl chloride resin. Although various improvements have been made to styrenic resins consisting only of styrene monomers, they have not yet been able to satisfy market demands.
【０００５】一方、ポリスチレンとスチレン−ブタジエ
ンブロック共重合体をブレンドしたスチレン系樹脂は市
場要求をかなり満足しているので、現在市場で多用され
ている。しかし、このスチレン系樹脂は、成形時の配向
に対する強度の方向依存性が非常に大きいという欠点を
有している。又、シート、フィルム等をリワーク使用す
る為、スチレン−ブタジエンブロック共重合体が架橋し
、いわゆるゲル状物質が生成し、シート、フィルムの表
面特性を著しく悪化させるという欠点もある。そして、
厳しい透明性が要求される分野では問題がある。
又、この樹脂は非常にコストが高いという欠点もある。[0005] On the other hand, styrenic resins made by blending polystyrene and styrene-butadiene block copolymers are currently widely used in the market because they fairly satisfy market requirements. However, this styrenic resin has the drawback that its strength has a very large directional dependence on orientation during molding. In addition, since sheets, films, etc. are reworked, the styrene-butadiene block copolymer is crosslinked, producing a so-called gel-like substance, which significantly deteriorates the surface properties of the sheets and films. and,
This is problematic in fields where strict transparency is required. Another disadvantage of this resin is that it is extremely expensive.
【０００６】ポリスチレンを用いている限り、耐熱性等
の観点から、成形サイクルの短縮には限界がある。この
限界を打破する為に、スチレン系単量体と共重合可能な
第二の単量体を導入し、耐熱性を下げることは公知であ
る。この樹脂とゴム状弾性体、例えば、スチレン−ブタ
ジエンブロック共重合体をブレンドすることにより、市
場の要求を満足させることが可能であると期待されるが
、実際はポリスチレンにゴム状弾性体をブレンドしたも
のより強度が低く、実用的でない。そして、前述のスチ
レン−ブタジエンブロック共重合体に起因する同様な欠
点を有している。As long as polystyrene is used, there is a limit to the shortening of the molding cycle from the viewpoint of heat resistance and the like. In order to overcome this limit, it is known to introduce a second monomer copolymerizable with the styrene monomer to lower the heat resistance. It is expected that market demands can be met by blending this resin with a rubber-like elastic material, such as a styrene-butadiene block copolymer, but in reality, it is possible to meet market demands by blending a rubber-like elastic material with polystyrene. It is weaker than other materials and is not practical. It also has the same drawbacks as those caused by the styrene-butadiene block copolymer described above.
【０００７】特開昭６２−１６９８１２号公報では、ス
チレン、アクリル酸ブチル、メタクリル酸メチル及びス
チレン−ブタジエンブロック共重合体からなる混合溶液
を重合する方法の記載がある。しかし、かかる方法で重
合された熱可塑性樹脂は透明であり、高い伸びを示して
いるが、アイゾット衝撃強度に見られるように、ゴム補
強の効果は全く認められない。すなわち、透明性、伸び
は改良されても、強度は改良されていない。JP-A-62-169812 describes a method for polymerizing a mixed solution of styrene, butyl acrylate, methyl methacrylate and a styrene-butadiene block copolymer. However, although the thermoplastic resin polymerized by this method is transparent and exhibits high elongation, no effect of rubber reinforcement is observed as seen in the Izod impact strength. That is, although transparency and elongation have been improved, strength has not.
【０００８】＜スチレン系樹脂シート＞従来のスチレン
系樹脂シートは腰の強さ、透明性、成形性に優れている
等の理由で食品収納容器用の軽量容器等に多用されてい
る。スチレン系樹脂シートは真空成形、圧空成形機によ
り各種容器に熱成形されるが、熱成形する際の成形サイ
クルの短縮は生産性を向上させるので、成形の短縮でき
るスチレン系樹脂シートが要望されている。<Styrenic Resin Sheet> Conventional styrene resin sheets are widely used in lightweight food storage containers and the like because of their excellent stiffness, transparency, and moldability. Styrenic resin sheets are thermoformed into various containers using vacuum forming and pressure forming machines, but shortening the molding cycle during thermoforming improves productivity, so there is a demand for styrene resin sheets that can shorten the molding process. There is.
【０００９】二軸延伸シートでは、成形サイクルを短縮
させるために、延伸による分子配向を小さくし、配向緩
和応力を低くした二軸延伸スチレン系樹脂シート、分子
量を小さくした二軸延伸スチレン系樹脂シート等が試み
られているが、成形品を重ねてトリミングした際、成形
品が割れるという問題点があった。成形サイクルを短縮
させるために、内部潤滑剤を添加したスチレン系樹脂シ
ート、二軸延伸スチレン系樹脂シートが試みられている
が、大きな改善効果は認められない。[0009] In order to shorten the molding cycle, biaxially oriented styrenic resin sheets have a biaxially oriented styrenic resin sheet with reduced molecular orientation due to stretching and low orientation relaxation stress, and biaxially oriented styrenic resin sheets with a reduced molecular weight. However, there was a problem in that the molded products would break when they were overlapped and trimmed. In order to shorten the molding cycle, attempts have been made to use styrenic resin sheets to which an internal lubricant is added and biaxially oriented styrene resin sheets, but no significant improvement has been observed.
【００１０】又、第二の共重合可能な単量体、例えばブ
チルアクリレート、との共重合が試みられているが、成
形品の強度が著しく劣るものである。ポリスチレンとス
チレンーブタジエンブロック共重合体をブレンドした樹
脂を用いたスチレン系樹脂シートも同じ理由で成形サイ
クルの短縮に関して問題を有している。Copolymerization with a second copolymerizable monomer, such as butyl acrylate, has also been attempted, but the strength of the molded product is significantly inferior. A styrenic resin sheet using a resin blended with polystyrene and a styrene-butadiene block copolymer also has a problem in shortening the molding cycle for the same reason.
【００１１】食品収納容器として、硬質塩化ビニル樹脂
シートが多用されているが、最近の環境問題から、代替
え樹脂が求められているが、硬質塩化ビニル樹脂シート
と同等の条件で成形できるものがないのが現状である。
＜スチレン系樹脂発泡体＞ポリスチレン系樹脂発泡体は
加熱により、二次発泡し、容易に所望の形状に成形でき
、かつ得られた成形体は軽量で、機械的強度に優れ、外
観が美しく、疎水性に富み、断熱性に優れているため、
箱、トレー、カップ等の食品包装剤や簡易容器に使用さ
れている。最近、生産性の向上、不良率の減少の観点か
ら、二次発泡成形性の良好な、そして可能な限り低温で
成形できるスチレン系樹脂発泡体が望まれている。[0011] Rigid vinyl chloride resin sheets are often used as food storage containers, but due to recent environmental issues, alternative resins are required, but there is no one that can be molded under the same conditions as rigid vinyl chloride resin sheets. is the current situation. <Styrene resin foam> Polystyrene resin foam undergoes secondary foaming by heating and can be easily molded into a desired shape, and the resulting molded product is lightweight, has excellent mechanical strength, and has a beautiful appearance. Because it is highly hydrophobic and has excellent heat insulation properties,
It is used in food packaging such as boxes, trays, and cups, as well as simple containers. Recently, from the viewpoint of improving productivity and reducing the defective rate, there has been a demand for styrenic resin foams that have good secondary foaming moldability and can be molded at as low a temperature as possible.
【００１２】又、包装用トレー等では、自動包装する時
に成形品に大きな力が加わる為に成形品が割れるという
ことがしばしば生じる。又、最近の環境問題から、絶対
量を減らす、すなわち成形品の薄肉化が指向されている
。このため、スチレン系樹脂発泡体の強度の改良が求め
られている。シート状のポリスチレン系発泡体を加熱炉
で加熱処理して発泡させ、次いで加熱炉から取り出して
金型で成形する一連の加熱二次発泡成形体の製造に於い
て、加熱炉内の温度が不均一であることや外気温による
炉内温度の変動の為に、シートの一部又は全部が加熱不
良となり、成形時にシートが破れたり、型決まり性が悪
くなったり、逆に加熱過剰になって、成形品表面にケロ
イド状が発生したり、成形品の厚さが変動する等の現象
が生じる。[0012] Furthermore, when packaging trays and the like are automatically packaged, a large force is applied to the molded products, which often causes the molded products to crack. Furthermore, due to recent environmental issues, there is a trend toward reducing the absolute amount, that is, making molded products thinner. Therefore, there is a need to improve the strength of styrenic resin foams. In the production of a series of heated secondary foamed products in which sheet-shaped polystyrene foam is heat-treated in a heating furnace to foam, then taken out of the heating furnace and molded in a mold, the temperature inside the heating furnace is constant. Due to uniformity and fluctuations in the temperature inside the furnace depending on the outside temperature, part or all of the sheet may be insufficiently heated, resulting in the sheet being torn during molding, having poor moldability, or conversely being overheated. , phenomena such as the formation of keloids on the surface of the molded product and fluctuations in the thickness of the molded product occur.
【００１３】ケロイド状の発生を防ぐ為に、スチレン系
重合体基材の分子量を上げたり、シート表面にフィルム
を貼ったり、樹脂密度の大きい層、いわゆるスキン層を
形成したりする方法が知られているが、かかる方法では
型決まり性の良い発泡体が得られ難く、深絞り成形品の
場合には、シート破れが生じ易い。又、型決まり性の良
い発泡体を得る為に、スチレン系重合体基材に可塑剤、
滑剤等を添加する方法が知られているが、二次成形時の
加熱過剰時に発生するケロイド状の不良現象が起きやす
い。In order to prevent the formation of keloids, there are known methods such as increasing the molecular weight of the styrene polymer base material, attaching a film to the sheet surface, and forming a layer with high resin density, the so-called skin layer. However, with this method, it is difficult to obtain a foam with good shapeability, and in the case of a deep-drawn product, sheet tearing is likely to occur. In addition, in order to obtain a foam with good shapeability, a plasticizer,
A method of adding a lubricant or the like is known, but it tends to cause keloid-like defects that occur during overheating during secondary molding.
【００１４】ケロイド状の発生を抑え、型決まり性の良
好なスチレン系樹脂発泡体を得る方法として、分子量分
布の広いスチレン系樹脂発泡体を使用することが有効で
あることが特開昭６２−２２８３４号公報に記載されて
いるが、かかる分子量分布の広いポリスチレン系発泡体
の成形品は本質的に強度が弱いという欠点を有している
。[0014] As a method for suppressing the formation of keloids and obtaining a styrene resin foam with good shapeability, it was disclosed in Japanese Patent Application Laid-Open No. 1983-1983 that it is effective to use a styrene resin foam with a wide molecular weight distribution. Although it is described in Japanese Patent No. 22834, molded articles made of polystyrene foam having a wide molecular weight distribution inherently have a drawback of low strength.
【００１５】又、成形体の生産性を高めるために、成形
温度を下げるには限界がある。可塑剤の添加により耐熱
性を下げることは可能であるが、前述の理由で良好な成
形品が得られない。コモノマー、例えばブチルアクリレ
ートを共重合すると、耐熱性が低下することは良く知ら
れた事実であるが、この共重合体は強度が弱く、実用的
に用いることが出来ない。Furthermore, there is a limit to lowering the molding temperature in order to increase the productivity of molded products. Although it is possible to lower the heat resistance by adding a plasticizer, good molded products cannot be obtained for the reasons mentioned above. It is a well-known fact that copolymerization with a comonomer such as butyl acrylate reduces heat resistance, but this copolymer has low strength and cannot be used practically.
【００１６】又、この共重合体にスチレンーブタジエン
ブロック共重合体を添加すると、強度は向上するが、ス
チレン系樹脂発泡体を成形したあと、二次加熱成形する
までの間に発泡剤が飛散し、スチレン系樹脂発泡体中の
発泡剤量が時間、環境の変化と共に変化し、二次加熱成
形時に安定して成形品が得られないという致命的欠陥を
有している。[0016] Furthermore, when a styrene-butadiene block copolymer is added to this copolymer, the strength is improved, but the blowing agent is scattered during the period after the styrene resin foam is molded and before the secondary heat molding. However, the amount of blowing agent in the styrenic resin foam changes with time and changes in the environment, resulting in a fatal flaw in that a molded product cannot be stably obtained during secondary heat molding.
【００１７】＜スチレン系樹脂成形体＞スチレン系樹脂
は安価であり、透明性、成形性、剛性に優れていること
から、オーディオカセットハーフ、カセットハーフを収
納するプラスチックケース等のオーディオ製品、書類等
を収納するトレー等の事務用品、金魚鉢、洋服を収納す
るトレー、鳥籠、飲料用カップ、等の日常雑貨用品等多
岐に渡って使用されている。<Styrenic resin molded article> Styrene resin is inexpensive and has excellent transparency, moldability, and rigidity, so it can be used for audio products such as audio cassette halves, plastic cases for housing cassette halves, documents, etc. It is used in a wide variety of applications, including office supplies such as trays for storing things, fish bowls, trays for storing clothes, bird cages, drinking cups, and other daily miscellaneous goods.
【００１８】近年、各用途で成形体に対する要求性能が
高度化してきている。例えば、カセットハーフ、プラス
チックケースの場合に、コストダウンの要請から成形サ
イクルを極限迄短縮して生産性を高め、かつ成形品の厚
みを極限迄縮めコスト低減を計る等の方策が検討されて
おり、このために、スチレン系樹脂成形体の強度向上が
要求されている。収納箱のトレー等も大型化の方向を指
向し、これに対応する為に、成形体の強度向上が求めら
れている。[0018] In recent years, the performance requirements for molded products have become more sophisticated for various uses. For example, in the case of cassette halves and plastic cases, measures are being considered to reduce costs by shortening the molding cycle to the maximum extent possible to increase productivity, and by reducing the thickness of the molded product to the maximum extent possible. Therefore, it is required to improve the strength of styrene resin molded bodies. Storage box trays and the like are also becoming larger, and in order to accommodate this trend, improvements in the strength of molded bodies are required.
【００１９】これまで、強度の高い成形体を得るために
は、強度の高いスチレン系樹脂が用いられてきた。強度
の高いスチレン系樹脂を得るには、平均分子量を大きく
すれば良いことは公知の事実である。しかし、平均分子
量を大きくすることにより、成形性が低下し、ハイサイ
クル成形性が要望されている分野では問題があった。
又、流動性低下の結果、成形品に大きな成形歪みを与え
る結果、高分子量化による強度向上効果が低下する。Hitherto, in order to obtain molded articles with high strength, styrene resins with high strength have been used. It is a well-known fact that in order to obtain a styrenic resin with high strength, it is sufficient to increase the average molecular weight. However, increasing the average molecular weight reduces moldability, which is a problem in fields where high cycle moldability is desired. Further, as a result of the decrease in fluidity, large molding distortion is imparted to the molded article, and as a result, the effect of improving strength by increasing the molecular weight is decreased.
【００２０】この欠点を補う為に、可塑剤の使用も公知
である。可塑剤としてミネラル・オイルが一般的に多用
されている。しかし、可塑剤を添加すると、強度の低下
が大きく、高分子量化して強度向上を計った効果を大き
く低下させることになる。又、可塑剤を添加すると、成
形時にモールドスエッティング現象が生じ、成形体の外
観不良、金型清掃等による生産性の低下を招くことにな
る。[0020] In order to compensate for this drawback, the use of plasticizers is also known. Mineral oil is commonly used as a plasticizer. However, when a plasticizer is added, the strength decreases significantly, and the effect of increasing the molecular weight to improve strength is greatly reduced. Furthermore, when a plasticizer is added, a mold sweating phenomenon occurs during molding, resulting in poor appearance of the molded product and a decrease in productivity due to mold cleaning, etc.
【００２１】強度と成形性を改良するために、例えば、
成形性を向上させる為には、ブチルアクリレートを導入
すればよいことはよくしられている。しかし、従来のス
チレンーブチルアクリレート共重合体はブチルアクリレ
ートの含有量を増やしていくにつれて流動性は向上する
が、成形体の強度は流動性に反比例して低下するという
欠点を有していた。[0021] In order to improve strength and formability, for example,
It is well known that butyl acrylate can be introduced to improve moldability. However, conventional styrene-butyl acrylate copolymers have the disadvantage that although the fluidity improves as the content of butyl acrylate increases, the strength of the molded product decreases in inverse proportion to the fluidity.
【００２２】スチレンーブタジエンブロック共重合体と
ポリスチレンを混合したスチレン系樹脂はシート、フィ
ルムにすると高い強度、使用可能な程度の透明性を有す
るが射出成形すると、強度の配向依存性が大きい為、シ
ート、フィルムの場合ほど高い強度を示さない。又、射
出成形品は透明と言える範疇に入らないほど悪化し、実
使用には向かない。[0022] Styrenic resin, which is a mixture of styrene-butadiene block copolymer and polystyrene, has high strength and usable transparency when made into sheets or films, but when injection molded, the strength is highly dependent on orientation. It does not exhibit as high strength as sheets and films. In addition, the injection molded product deteriorates to such an extent that it cannot be called transparent, making it unsuitable for practical use.
【００２３】[0023]
【課題を解決する為の手段】本発明者らはかかる現状を
鑑がみ、鋭意検討した結果、スチレン系単量体と共重合
可能な第二、三の単量体として、アクリル酸エステル（
メタクリル酸エステル）系単量体、メチルメタアクリレ
ートを導入し、これらの単量体からなる重合体を連続相
とし、ゴム状弾性体を分散相とするスチレン系樹脂で、
かつ分散相のゴム状弾性体の粒子系を最適化し、適量の
有機ポリシロキサンを含有させることにより、■透明性
、成形性、強度のバランスに優れた新規なスチレン系樹
脂が得られること、このスチレン系樹脂を成形したシー
ト、フィルム、発泡体は低温で成形でき、かつ、成形体
の強度が優れたスチレン系樹脂が得られることを見出し
特に■二次加熱成形時形の成形サイクルを短縮させると
共に、強靱性を高めて成形品のトリミング時の抜き割れ
防止を付与した、透明性の優れたスチレン系樹脂シート
が得られること、■二次加熱成形性、ケロイド状の発生
を抑え、型決まり性良好であり、かつ、発泡成形品の強
度が優れ、低温で成形できるスチレン系樹脂発泡体が得
られること、■透明性、強度に優れた成形体が得られる
ことを見出し、本発明を完成するに至った。[Means for Solving the Problems] In view of the current situation, the present inventors have made extensive studies and have determined that acrylic ester (
methacrylic acid ester) type monomer and methyl methacrylate, a polymer made of these monomers is used as a continuous phase, and a rubber-like elastic body is used as a dispersed phase.
By optimizing the particle system of the rubber-like elastic material in the dispersed phase and incorporating an appropriate amount of organic polysiloxane, a new styrenic resin with an excellent balance of transparency, moldability, and strength can be obtained. It was discovered that sheets, films, and foams molded from styrene resin can be molded at low temperatures, and the molded product can be made from a styrenic resin with excellent strength.In particular, ■ shortening the molding cycle during secondary heat molding. At the same time, it is possible to obtain a styrenic resin sheet with excellent transparency that has increased toughness and prevents punching and cracking during trimming of molded products, ■Secondary heat moldability, suppresses the formation of keloids, and improves moldability. The present invention was completed after discovering that it is possible to obtain a styrenic resin foam that has good properties, excellent strength of the foamed molded product, and can be molded at low temperatures. I ended up doing it.
【００２４】すなわち本発明は、ゴム状弾性体を分散粒
子として含有するゴム変性スチレン系樹脂に於いて（ア
）連続相が
下記化学式（Ａ）；That is, in the present invention, in a rubber-modified styrenic resin containing a rubber-like elastic body as dispersed particles, (a) the continuous phase has the following chemical formula (A);
【００２５】[0025]
【化４】[C4]
【００２６】下記化学式（Ｂ）；The following chemical formula (B);
【００２７】[0027]
【化５】[C5]
【００２８】下記化学式（Ｃ）；The following chemical formula (C);
【００２９】[0029]
【化６】[C6]
【００３０】で示される構成からなり、構成単位（Ａ）
、（Ｂ）、（Ｃ）割合が
（Ａ）：２０〜７０ 重量％
（Ｂ）：０．５〜２０ 重量％
（Ｃ）：２９．５〜７９．５ 重量％（但し、（Ａ）
＋（Ｂ）＋（Ｃ）＝１００重量％）であり、（イ）分散
相の分散粒子径が０．１〜１．２μｍ、ゴム状弾性体の
含有量が１〜２０重量％であり、（ウ）ゴム変性スチレ
ン系樹脂１００重量部当たり０．００２〜０．３重量部
の有機ポリシロキサンを含有することを特徴とする強度
、透明性、成形性に優れたゴム変性スチレン系樹脂を提
供するものである。Consisting of the structure shown below, the structural unit (A)
, (B), (C) proportions are (A): 20-70% by weight (B): 0.5-20% by weight (C): 29.5-79.5% by weight (however, (A)
+ (B) + (C) = 100% by weight), (a) the dispersed particle diameter of the dispersed phase is 0.1 to 1.2 μm, and the content of the rubbery elastic body is 1 to 20% by weight, (c) To provide a rubber-modified styrenic resin with excellent strength, transparency, and moldability, which is characterized by containing 0.002 to 0.3 parts by weight of organic polysiloxane per 100 parts by weight of the rubber-modified styrenic resin. It is something to do.
【００３１】なお、本発明は下記の実施の態様をも含有
するものである。■ 上記構成単位（Ａ）、（Ｂ）、
（Ｃ）、ゴム状弾性体から構成され、上記に示された構
成単位（Ａ）、（Ｂ）、（Ｃ）の割合、及びゴム状弾性
体が上記に示された範囲の粒子径を有し、分散粒子とし
て存在し、上記に示された含有量を有し、そして上記に
示された有機ポリシロキサンを上記に示された量を含有
するゴム変性スチレン系樹脂によって形成される、新規
なスチレン系樹脂シート■ 上記構成単位（Ａ）、（
Ｂ）、（Ｃ）、ゴム状弾性体から構成され、上記に示さ
れた構成単位（Ａ）、（Ｂ）、（Ｃ）の割合、及びゴム
状弾性体が上記に示された範囲の粒子径を有し、分散粒
子として存在し、上記に示された含有量を有し、そして
上記に示された有機ポリシロキサンを上記に示された量
を含有するゴム変性スチレン系樹脂を成形してなる、二
次発泡成形性、発泡成形品の強度に優れた新規なスチレ
ン系樹脂発泡体。■ スチレン系樹脂発泡体の厚さが
０．１ｍｍ〜１０ｍｍ、密度０．０３〜０．５ｇ／ｃｃ
のシート状である。前記第■項記載の二次発泡成形性、
発泡成形品の強度に優れた新規なスチレン系樹脂発泡体
。■ 上記構成単位（Ａ）、（Ｂ）、（Ｃ）、ゴム状
弾性体から構成され、上記に示された構成単位（Ａ）、
（Ｂ）、（Ｃ）の割合、及びゴム状弾性体が上記に示さ
れた範囲の粒子径を有し、分散粒子として存在し、上記
に示された含有量を有し、そして上記に示された有機ポ
リシロキサンを上記に示された量を含有するゴム変性ス
チレン系樹脂を成形してなる、透明性、強度に優れた新
規なスチレン系樹脂成形体。The present invention also includes the following embodiments. ■ The above structural units (A), (B),
(C) is composed of a rubber-like elastic body, and has the proportions of the structural units (A), (B), and (C) shown above, and the rubber-like elastic body has a particle size within the range shown above. a rubber-modified styrenic resin, present as dispersed particles, having the content as indicated above, and containing the organopolysiloxane as indicated above in the amount indicated above. Styrenic resin sheet■ The above structural units (A), (
B), (C), particles composed of a rubbery elastic body, the ratio of the structural units (A), (B), (C) shown above, and the rubbery elastic body within the range shown above. molding a rubber-modified styrenic resin having a diameter, present as dispersed particles, having the content indicated above, and containing the organopolysiloxane indicated above in the amount indicated above. A new styrene resin foam with excellent secondary foam moldability and strength of foam molded products. ■ Thickness of styrene resin foam is 0.1 mm to 10 mm, density 0.03 to 0.5 g/cc
It is in the form of a sheet. Secondary foaming moldability as described in the above item (■),
A new styrene resin foam with excellent strength for foam molded products. ■ The above-mentioned structural units (A), (B), (C), the above-mentioned structural unit (A), which is composed of a rubber-like elastic body,
The proportions of (B) and (C) and the rubber-like elastomer have a particle size in the range indicated above, are present as dispersed particles, have the content indicated above, and A novel styrenic resin molded article having excellent transparency and strength, which is obtained by molding a rubber-modified styrenic resin containing the above-mentioned organic polysiloxane in the amount shown above.
【００３２】以下、本発明を詳細に説明する。連続相を
形成する構成単位（Ｂ）の量は０．５〜２０重量％の範
囲である。より好ましくは２〜１７重量％の範囲である
。２０重量％を越える場合は、耐熱性が低くなる結果、
シート、発泡体、成形体の実用範囲が非常に狭くなり好
ましくない。又、０．５重量％未満の場合は、スチレン
系樹脂の耐熱性が高くなる為、成形サイクルの短縮効果
、深絞り性向上効果が小さく、かつ強度の優れたシート
発泡体、成形体が得られない。The present invention will be explained in detail below. The amount of structural unit (B) forming the continuous phase ranges from 0.5 to 20% by weight. More preferably, it is in the range of 2 to 17% by weight. If it exceeds 20% by weight, the heat resistance will decrease,
This is undesirable because the practical range of sheets, foams, and molded products becomes extremely narrow. If the amount is less than 0.5% by weight, the heat resistance of the styrene resin will increase, so the effect of shortening the molding cycle and improving deep drawability will be small, and sheet foams and molded products with excellent strength will be obtained. I can't do it.
【００３３】構成単位（Ｃ）の量は２９．５〜７９．５
重量％の範囲である。より好ましくは３０〜７０重量％
である。この範囲以外では、スチレン系樹脂の透明性が
低下し好ましくない。本発明に於いては、連続相の屈折
率は特に制約されるものではないが、分散相を形成する
ゴム状弾性体の屈折率との差が０．０１以内に制御する
ことが透明性の観点から好ましい。特に、成形体の場合
は０．００８以内が好ましい。[0033] The amount of structural unit (C) is 29.5 to 79.5
% by weight. More preferably 30 to 70% by weight
It is. If it is outside this range, the transparency of the styrene resin will decrease, which is not preferable. In the present invention, although the refractive index of the continuous phase is not particularly restricted, it is important to control the difference between the refractive index of the rubber-like elastic body forming the dispersed phase and the refractive index within 0.01 in order to improve transparency. Preferable from this point of view. In particular, in the case of a molded article, it is preferably within 0.008.
【００３４】構成単位（Ｂ）の量はスチレン系樹脂の樹
脂物性設計値から決まるため、構成単位（Ａ）、構成単
位（Ｃ）で連続相の屈折率を制御することが必要である
。本発明のスチレン系樹脂の連続相の重合度は特に限定
されるものではないが、スチレン系樹脂、シート、フィ
ルム、発泡体、成形体の形状、使用目的等を考慮して、
２５℃における１０重量％トルエン溶液の粘度で１５セ
ンチポイズ〜８０センチポイズの領域で、より好ましく
は２０センチポイズ〜７０センチポイズの領域で設定す
ることが出来る。Since the amount of the structural unit (B) is determined by the resin physical property design values of the styrene resin, it is necessary to control the refractive index of the continuous phase using the structural unit (A) and the structural unit (C). The degree of polymerization of the continuous phase of the styrenic resin of the present invention is not particularly limited, but it may be determined by taking into account the shape of the styrenic resin, sheet, film, foam, molded product, purpose of use, etc.
The viscosity of a 10% by weight toluene solution at 25° C. can be set in the range of 15 centipoise to 80 centipoise, more preferably in the range of 20 centipoise to 70 centipoise.
【００３５】本発明のスチレン系樹脂中のスチレン系単
量体、アクリル酸（メタクリル酸）エステル単量体、メ
チルメタクリレート単量体、重合溶媒の総量は０．１５
重量％以下、好ましくは０．１重量％以下である。０．
１５重量％を越える場合は食品衛生上好ましくない。
又、これら三種の単量体から作られる二量体、三量体、
および三種の単量体、重合溶媒の総量は０．８重量％以
下、好ましくは０．７重量％以下、より好ましくは０．
６重量％以下である。これら低分子量化合物の総量が０
．８重量％を越える場合、シート成形時、発泡体成形時
、成形体成形時にモールドスエット現象の原因となり、
又、強度を低下させる因子として働く為、好ましくない
。The total amount of styrene monomer, acrylic acid (methacrylic acid) ester monomer, methyl methacrylate monomer, and polymerization solvent in the styrenic resin of the present invention is 0.15
It is not more than 0.1% by weight, preferably not more than 0.1% by weight. 0.
If it exceeds 15% by weight, it is unfavorable in terms of food hygiene. In addition, dimers and trimers made from these three types of monomers,
The total amount of the three types of monomers and polymerization solvent is 0.8% by weight or less, preferably 0.7% by weight or less, more preferably 0.8% by weight or less.
It is 6% by weight or less. The total amount of these low molecular weight compounds is 0
．． If it exceeds 8% by weight, it may cause mold sweat phenomenon during sheet molding, foam molding, and molding.
Moreover, it is not preferable because it acts as a factor that reduces strength.
【００３６】本発明に於いて、構成単位（Ａ）としては
、例えば次に示す構造のものが挙げられる。In the present invention, examples of the structural unit (A) include those having the following structure.
【００３７】[0037]
【化７】[C7]
【００３８】本発明において、構成単位（Ｂ）としては
、例えば次に示す構造のものが挙げられる。In the present invention, examples of the structural unit (B) include those having the following structure.
【００３９】[0039]
【化８】[Chemical formula 8]
【００４０】本発明の分散相としては、常温でゴム的性
質を示すものであればよく、例えばポリブタジエン類、
スチレンーブタジエン共重合体類、スチレン−ブタジエ
ンブロック共重合体類、イソプレン重合体類が用いられ
る。より好ましいものとしては、スチレン−ブタジエン
共重合体類、スチレン−ブタジエンブロック共重合体類
である。特にスチレン含有量は１０〜５０重量％である
ものが好ましい。又、ゴム状弾性体の分子量や分岐度等
は限定されるものではない。The dispersed phase of the present invention may be any phase as long as it exhibits rubbery properties at room temperature, such as polybutadiene,
Styrene-butadiene copolymers, styrene-butadiene block copolymers, and isoprene polymers are used. More preferred are styrene-butadiene copolymers and styrene-butadiene block copolymers. In particular, the styrene content is preferably 10 to 50% by weight. Moreover, the molecular weight, degree of branching, etc. of the rubber-like elastic body are not limited.
【００４１】本発明の分散相の粒子径は０．１〜１．２
μｍの範囲であることが必要であるより好ましくは０．
２〜０．９μｍである。分散粒子径が０．１μｍ未満の
時は強度補強効果が発現しない。あるいは、効果が非常
に小さい。一方、分散粒子径が１．２μｍを越える場合
は、強度補強効果は大きいが、透明性が悪くなり好まし
くない。本発明で言う粒子径は特に断らない限り数平均
粒子径を意味する。[0041] The particle size of the dispersed phase of the present invention is 0.1 to 1.2.
It is necessary to be in the range of μm, more preferably 0.
It is 2 to 0.9 μm. When the dispersed particle size is less than 0.1 μm, no strength reinforcing effect is exhibited. Or the effect is very small. On the other hand, if the dispersed particle size exceeds 1.2 μm, the strength reinforcing effect is great, but the transparency deteriorates, which is not preferable. The particle size referred to in the present invention means a number average particle size unless otherwise specified.
【００４２】粒子径分布状態は特に制限はないが次の二
つのタイプが好ましい。一つは粒子径分布（重量平均粒
子径／数平均粒子径）が３．０以下である分布状態、他
は双山分布を有する分布状態である。この時、大小の粒
子径の各々の分布は２．０以下あり、粒子径は本発明の
構成要件である０．１〜１．２μｍの範囲にあることが
必要である。Although there are no particular restrictions on the particle size distribution, the following two types are preferred. One is a distribution state in which the particle size distribution (weight average particle diameter/number average particle diameter) is 3.0 or less, and the other is a distribution state in which the particle size distribution is a double peak distribution. At this time, the distribution of large and small particle diameters must be 2.0 or less, and the particle diameter must be in the range of 0.1 to 1.2 μm, which is a constituent requirement of the present invention.
【００４３】本発明のゴム変性スチレン系樹脂中のゴム
状弾性体の量は１〜２０重量％である。好ましくは１〜
１５重量％である。ゴム状弾性体の量が１重量％未満の
時は強度補強効果が発現しない。又、２０重量％を越え
る場合は、透明性が低下し、使用用途が大きく限定され
るので好ましくない。又、剛性も低下する為このましく
ない。The amount of rubbery elastomer in the rubber-modified styrenic resin of the present invention is 1 to 20% by weight. Preferably 1~
It is 15% by weight. When the amount of the rubber-like elastic body is less than 1% by weight, no strength reinforcing effect is exhibited. Moreover, if it exceeds 20% by weight, transparency decreases and the usage is greatly limited, which is not preferable. Furthermore, this is not desirable since the rigidity will also decrease.
【００４４】スチレン系樹脂シートの場合、二軸延伸ス
チレン系樹脂シートとして用いる場合はゴム状弾性体の
量は１〜１０重量％、より好ましくは１〜７重量％であ
る。二軸に延伸がかかっているので、含有量が１０重量
％を越えると、強度向上効果が小さくなる。無延伸シー
トとして用いる場合は、１〜２０重量％の範囲である。In the case of a styrene resin sheet, when it is used as a biaxially oriented styrenic resin sheet, the amount of rubbery elastic material is 1 to 10% by weight, more preferably 1 to 7% by weight. Since biaxial stretching is applied, if the content exceeds 10% by weight, the strength improvement effect will be reduced. When used as a non-stretched sheet, the amount is in the range of 1 to 20% by weight.
【００４５】スチレン系樹脂発泡体の場合は１〜５重量
％の範囲が好ましい。５重量％を越える場合は、本発明
のゴム状弾性体を用い、分散粒子径を本発明の構成要件
範囲に制御しても、スチレン系樹脂発泡体中に存在する
発泡剤の含有量が時間、環境の変化により変動しやすく
なり、二次加熱成形時の安定性に悪影響を与える傾向に
なり好ましくない。In the case of styrene resin foam, the amount is preferably in the range of 1 to 5% by weight. If it exceeds 5% by weight, even if the rubber-like elastic body of the present invention is used and the dispersed particle size is controlled within the range of constituent requirements of the present invention, the content of the blowing agent present in the styrenic resin foam will increase over time. This is undesirable because it tends to fluctuate due to changes in the environment and has a tendency to adversely affect stability during secondary heat molding.
【００４６】スチレン系樹脂成形体の場合は、１〜２０
重量％の範囲で使用出来るが、剛性の観点から１〜１５
重量％の範囲がより好ましい。本発明で使用する有機ポ
リシロキサンは一般式[0046] In the case of styrene resin molded articles, 1 to 20
It can be used in the range of 1 to 15% by weight, but from the viewpoint of rigidity.
A weight percent range is more preferred. The organic polysiloxane used in the present invention has the general formula
【００４７】[0047]
【化９】[Chemical formula 9]
【００４８】で示される単位の繰り返しを骨格に含む重
合体である。例えば、ポリジメチルシロキサン、ポリメ
チルフェニルシロキサン、ポリジフェニルシロキサン及
びこれらの重合体の末端あるいは分子鎖中にエポキシ基
、水酸基、カルボキシル基、ビニル基、アミノ基、アル
コキシ基、フッ素等を導入したものが使用できる。有機
ポリシロキサンの分子量は特に限定されるものではない
。This is a polymer containing repeating units represented by the following in its skeleton. For example, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, and polymers thereof with epoxy groups, hydroxyl groups, carboxyl groups, vinyl groups, amino groups, alkoxy groups, fluorine, etc. introduced into the terminals or molecular chains. Can be used. The molecular weight of the organic polysiloxane is not particularly limited.
【００４９】有機ポリシロキサンの含有量はゴム変性ス
チレン系樹脂１００重量部当たり、０．００２〜０．３
重量部である。より好ましくは０．００５〜０．２重量
部である。０．００２重量部未満の場合は強度補強効果
が発現せず、０．３重量部を越える場合は強度補強効果
が小さくなり、透明性も低下し、又、剛性も低下するの
で好ましくない。The content of organic polysiloxane is 0.002 to 0.3 per 100 parts by weight of rubber-modified styrenic resin.
Parts by weight. More preferably, it is 0.005 to 0.2 parts by weight. If the amount is less than 0.002 parts by weight, the strength reinforcing effect will not be exhibited, and if it exceeds 0.3 parts by weight, the strength reinforcing effect will be reduced, the transparency will be lowered, and the rigidity will also be lowered, which is not preferable.
【００５０】本発明のスチレン系樹脂を得るには、ゴム
補強ポリスチレン（ＨＩＰＳ樹脂）の製造で多用されて
いる方法を用いることが出来る。すなわち、ゴム状弾性
体をスチレン系単量体そして／又はアクリル酸エステル
（メタクリル酸エステル）単量体そして／又はメチルメ
タアクリレートそして／又は重合溶媒そして／又は重合
開始剤からなる原料溶液に溶解し、このゴム状弾性体が
溶解した原料溶液を攪拌機付反応機に供給し重合を行う
。分散粒子の粒子径の制御は一般式に行われている方法
、攪拌羽根の攪拌数を変化させることにより制御される
。又、透明性を維持する方法として、一般的な方法、例
えば重合途中に必要に応じて単量体を添加するか、ある
いは連続的に追添加する等の方法が用いられる。[0050] In order to obtain the styrenic resin of the present invention, a method frequently used in the production of rubber-reinforced polystyrene (HIPS resin) can be used. That is, a rubber-like elastic body is dissolved in a raw material solution consisting of a styrene monomer and/or an acrylic ester (methacrylic ester) monomer and/or methyl methacrylate and/or a polymerization solvent and/or a polymerization initiator. The raw material solution in which the rubber-like elastic body is dissolved is supplied to a reactor equipped with a stirrer to carry out polymerization. The particle diameter of the dispersed particles is controlled by the general method of changing the stirring number of stirring blades. Further, as a method for maintaining transparency, a general method such as adding a monomer as necessary during polymerization or continuously adding a monomer may be used.
【００５１】ゴム状弾性体の含有量は、目標とする含有
量になるように原材料、重合率を調製することにより達
成することもできるが、高濃度のゴム状弾性体を含むス
チレン系樹脂を上記の方法で製造し、別に製造したゴム
状弾性体を含まないスチレン系樹脂と混合することによ
っても達成できる。但し、本発明の構成要件を全て満た
すことは当然のことである。The content of the rubbery elastic material can be achieved by adjusting the raw materials and polymerization rate so as to reach the target content, but it is possible to achieve the content of the rubbery elastic material by adjusting the raw materials and polymerization rate to achieve the target content. This can also be achieved by mixing the resin produced by the above method with a separately produced styrene resin that does not contain a rubber-like elastic body. However, it is a matter of course that all the constituent requirements of the present invention are satisfied.
【００５２】この時、重合溶媒、例えばエチルベンゼン
、トルエン、キシレン等を用いることも可能である。
又、スチレン系重合体の重合に常用されている有機過酸
化物を用いても、又、途中添加してもよい。重合方法は
スチレン系重合体の製法で常用されている塊状重合法、
又は溶液重合法が用いられる。回分式重合法、連続式重
合法いずれの方法も用いることができる。At this time, it is also possible to use a polymerization solvent such as ethylbenzene, toluene, xylene, etc. Furthermore, organic peroxides commonly used in the polymerization of styrenic polymers may be used, or may be added during the polymerization. The polymerization method is the bulk polymerization method, which is commonly used in the production of styrenic polymers.
Alternatively, a solution polymerization method is used. Either a batch polymerization method or a continuous polymerization method can be used.
【００５３】本発明のスチレン系単量体としては、スチ
レン、α−メチルスチレン、ｐ−ｔ−ブチルスチレン、
ｐ−メチルスチレン等が使用できる。これらスチレン系
単量体単独又は混合して使用することも出来る。アクリ
ル酸エステル（メタクリル酸エステル）単量体としては
、ブチルアクリレート、ブチルメタクリレート等が使用
できる。これらアクリル酸エステル（メタクリル酸エス
テル）単量体単独又は混合して使用できる。[0053] Examples of the styrenic monomer of the present invention include styrene, α-methylstyrene, pt-butylstyrene,
p-methylstyrene etc. can be used. These styrenic monomers can be used alone or in combination. As the acrylic ester (methacrylic ester) monomer, butyl acrylate, butyl methacrylate, etc. can be used. These acrylic ester (methacrylic ester) monomers can be used alone or in combination.
【００５４】反応機を出た重合溶液は回収装置に導かれ
る。回収装置はスチレン系樹脂の製造で常用されている
装置、例えばフラシュタンクシステム、多段ベント付き
押出機等を用いることができる。操作条件もスチレン系
樹脂の製造と同等の条件を用いることが出来る。有機ポ
リシロキサンの添加方法は、原料溶液に添加して重合系
へ供給する方法重合途中で重合系へ供給する方法、回収
系の前又は後で添加する方法、ゴム変性スチレン系樹脂
と有機ポリシロキサンを押出機で混合する方法、あるい
はゴム変性スチレン系樹脂と有機ポリシロキサンをブレ
ンドし、射出成形機、シート押出機、低発泡シート押出
機等で成形品を成形する時に混合する方法等が用いるこ
とができる。[0054] The polymerization solution leaving the reactor is led to a recovery device. As the recovery device, devices commonly used in the production of styrenic resins, such as a flash tank system, an extruder with a multi-stage vent, etc., can be used. As for the operating conditions, the same conditions as in the production of styrenic resin can be used. Methods for adding organic polysiloxane include adding it to the raw material solution and supplying it to the polymerization system, supplying it to the polymerization system during polymerization, adding it before or after the recovery system, and rubber-modified styrenic resin and organic polysiloxane. A method of mixing in an extruder, or a method of blending a rubber-modified styrenic resin and an organic polysiloxane and mixing them when molding a molded product using an injection molding machine, sheet extruder, low-foam sheet extruder, etc. can be used. Can be done.
【００５５】未反応単量体及び／又は重合溶媒を回収す
る前又は後の任意の段階でスチレン系重合体に慣用され
ている添加剤、例えば酸化防止剤、滑剤、可塑剤、着色
剤、帯電防止剤等を添加できる。このようにして得られ
たスチレン系樹脂は、一般式に、熱可塑性樹脂の成形に
用いられている公知の方法、例えば射出成形、押出成形
、圧縮成形等の方法によって各種成形体に成形される。Additives commonly used for styrenic polymers, such as antioxidants, lubricants, plasticizers, colorants, electrostatic charges, may be added at any stage before or after recovering unreacted monomers and/or polymerization solvents. Inhibitors etc. can be added. The styrenic resin thus obtained is generally molded into various molded products by known methods used for molding thermoplastic resins, such as injection molding, extrusion molding, and compression molding. .
【００５６】又、本発明では、フィルム、二軸延伸フィ
ルム、シート、発泡シート、発泡ビズ等に形成された後
、所望の成形体に成形することが出来る。又、得られた
スチレン系樹脂成形体、特にフィルム、シート、発泡体
の表面特性を改良するために帯電防止剤、シリコン等の
滑剤を表面に塗布してもよい。又、本発明で意図する目
的を損なわない範囲で、本発明で使用する特定のスチレ
ン系樹脂と他のスチレン系樹脂等を混合して使用するこ
とも可能である。Further, in the present invention, after being formed into a film, biaxially stretched film, sheet, foamed sheet, foamed biz, etc., it can be molded into a desired molded article. Further, in order to improve the surface characteristics of the obtained styrene resin molded article, especially a film, sheet, or foam, an antistatic agent or a lubricant such as silicone may be applied to the surface. Further, it is also possible to mix and use the specific styrene resin used in the present invention with other styrene resins, etc., within a range that does not impair the intended purpose of the present invention.
【００５７】＜スチレン系樹脂シート＞本発明に係わる
二軸延伸スチレン系樹脂シートを作成するには、押出機
によってスチレン系樹脂をシート状に押出した後、一般
に知られたテンター方式、インフレーション方式等を採
用して延伸し、延伸倍率は２〜５倍にするのが好ましい
本発明に係わる二軸延伸スチレン系樹脂シートはＡＳＴ
Ｍ Ｄ−１５０４に準拠して測定した配向緩和応力が
１〜１５ｋｇ／ｃｍ２ 、より好ましくは２〜１０ｋｇ
／ｃｍ２ の範囲となるように二軸延伸されているもの
が好ましい。配向緩和応力が上記範囲以上になると、一
般の成形機では成形が困難で、型再現性の悪い成形品し
か得られない。上記範囲以下ではシートの強度が弱く、
トリミング時の割れの現象が生じ好ましくない。<Styrenic resin sheet> In order to produce the biaxially oriented styrene resin sheet according to the present invention, the styrenic resin is extruded into a sheet shape using an extruder, and then a generally known tenter method, inflation method, etc. The biaxially stretched styrenic resin sheet according to the present invention is preferably stretched at a stretching ratio of 2 to 5 times.
Orientation relaxation stress measured in accordance with MD-1504 is 1 to 15 kg/cm2, more preferably 2 to 10 kg
It is preferable that the film be biaxially stretched so as to be within the range of /cm2. If the orientation relaxation stress exceeds the above range, it will be difficult to mold using a general molding machine, and only molded products with poor mold reproducibility will be obtained. Below the above range, the strength of the sheet will be weak.
This is undesirable because cracking occurs during trimming.
【００５８】又、本発明に係わるスチレン系樹脂シート
を作成するには、従来から多用されている一般的な方法
、例えば押出機で溶融した後、Ｔダイから押出す等の方
法が用いられる。シートの厚みは特に限定されるもので
はないが０．１〜３０ｍｍの範囲のものが用いられる。
本発明に係わるスチレン系樹脂シート（二軸延伸スチレ
ン系樹脂シート）は、成形性が良好で、ストレート法、
ドレーブ法によって、真空成形、又は熱板圧空成形（接
触加熱圧空成形）もしくはストレート法、ドレーブ法、
プラグアシスト法による間接加熱圧空成形によって軽量
容器、蓋等を成形する際に成形サイクルを短縮すること
ができる。[0058] In order to produce the styrenic resin sheet according to the present invention, a general method that has been widely used in the past, such as melting the resin in an extruder and then extruding it from a T-die, can be used. Although the thickness of the sheet is not particularly limited, a thickness in the range of 0.1 to 30 mm is used. The styrenic resin sheet (biaxially oriented styrenic resin sheet) according to the present invention has good moldability, and can be
By the drave method, vacuum forming, hot plate pressure forming (contact heating pressure forming), straight method, drave method,
Indirect heating and pressure forming using the plug assist method can shorten the molding cycle when molding lightweight containers, lids, etc.
【００５９】本発明のスチレン系樹脂シート（二軸延伸
スチレン系樹脂シート）は、シートの強度が強く、トリ
ミング時に成形品の抜き割れが生じない。又構成単位（
Ｂ）の量を増やすことにより、スチレン系樹脂シートの
ガラス転移温度が低下するので、硬質塩化ビニル樹脂シ
ートと同等の成形条件で成形することも可能である。
＜スチレン系樹脂発泡体＞スチレン系樹脂発泡体は、ス
チレン系樹脂にプロパン、ブタン、ペンタン、ヘキサン
等の低級炭化水素や塩化メチル、ジクロロメタン、トリ
クロロモノフルオロメタン、ジクロロジフルオロメタン
等のハロゲン化炭化水素等の発泡剤を含浸させ、押出機
に供給するか、スチレン系樹脂を押出機に供給した後、
押出機中に上記発泡剤を圧入し、発泡剤とスチレン系樹
脂を押出機中で溶融、混練させ、Ｔダイ又はサーキュラ
ーダイ等から押出す等公知の方法により、厚さ０．１ｍ
ｍ〜１０ｍｍ、密度０．０３〜０．５ｇ／ｃｃのシート
状のスチレン系樹脂発泡体が製造される。The styrenic resin sheet (biaxially oriented styrene resin sheet) of the present invention has high strength and does not cause cracks in the molded product during trimming. Also, the constituent unit (
By increasing the amount of B), the glass transition temperature of the styrenic resin sheet is lowered, so it is also possible to mold it under the same molding conditions as a hard vinyl chloride resin sheet. <Styrenic resin foam> Styrenic resin foam is made of styrene resin with lower hydrocarbons such as propane, butane, pentane, hexane, etc., or halogenated hydrocarbons such as methyl chloride, dichloromethane, trichloromonofluoromethane, dichlorodifluoromethane. After impregnating a foaming agent such as and feeding it to an extruder, or feeding a styrene resin to an extruder,
The foaming agent is press-fitted into an extruder, the foaming agent and styrene resin are melted and kneaded in the extruder, and the mixture is extruded from a T-die or circular die to a thickness of 0.1 m.
A sheet-like styrenic resin foam having a size of 10 mm to 10 mm and a density of 0.03 to 0.5 g/cc is produced.
【００６０】シートの厚さは０．１〜１０ｍｍが好まし
い。厚さが０．１ｍｍより薄いと二次発泡時にシートが
破損したり、十分な成形品強度を有しない。又、厚さが
１０ｍｍを越えると、二次成形が困難になる。密度は０
．０３〜０．５ｇ／ｃｃが好ましい。密度が０．０３ｇ
／ｃｃ未満の時は二次発泡成形にシートが破れたり、成
形品強度十分でなく、０．５ｇ／ｃｃを越える場合は発
泡成形品としてメリットが減じるので好ましくない。[0060] The thickness of the sheet is preferably 0.1 to 10 mm. If the thickness is less than 0.1 mm, the sheet may be damaged during secondary foaming or the molded product will not have sufficient strength. Moreover, if the thickness exceeds 10 mm, secondary molding becomes difficult. Density is 0
．． 03 to 0.5 g/cc is preferable. Density is 0.03g
If it is less than 0.5 g/cc, the sheet may be torn during secondary foam molding or the molded product will not have sufficient strength, and if it exceeds 0.5 g/cc, the merits of the foam molded product will be reduced, which is not preferable.
【００６１】スチレン系樹脂を発泡させ、スチレン系樹
脂発泡体を得るに当たり、発泡セル径を制御するタルク
、炭酸カリシュウム等の造核剤、可塑剤、滑剤、顔料、
帯電防止剤、難燃剤等を必要に応じて混合使用してもよ
い。以上のようにして得られたスチレン系樹脂発泡体を
加熱二次発泡成形するにはスチレン系樹脂発泡体を加熱
炉に入れて、軟化、二次発泡させた後、加熱炉から取り
出し、直ちにプレス成形して成形体にするのが一般的で
ある。In foaming the styrene resin to obtain a styrene resin foam, nucleating agents such as talc and potassium carbonate to control the foam cell diameter, plasticizers, lubricants, pigments,
Antistatic agents, flame retardants, etc. may be used in combination as necessary. To perform secondary foam molding on the styrene resin foam obtained as described above, the styrene resin foam is placed in a heating furnace, softened and subjected to secondary foaming, and then taken out of the heating furnace and immediately pressed. It is common to mold it into a molded body.
【００６２】＜スチレン系樹脂成形体＞本発明の成形体
は、強度に優れている点に特徴がある。成形体の形状に
ついては特に制限はないが、本発明のスチレン系樹脂は
流動性−強度のバランスが優れていることから、大型成
形品、例えば、事務機器用収納トレー、用紙収納トレー
コピー用紙受け、金魚鉢、鳥籠、飼育箱、衣装ケース、
食品収納ケース、オーディオ製品収納ケース、玩具、コ
ンピューター用テープ収納機器、電気冷蔵庫クリスパー
、事務機部品、オーディオ機器部品、化粧品収納ケース
等に最適に用いられる。又、記録媒体収納容器、例えば
、オーディオテープ、ビデオテープ、の収納容器、オー
ディオカセット、ビデオカセットテープ、オーディオデ
ィスク、ビデオディスク、フロッピーディスク等の収納
ケース等にも好適に用いられる。<Styrenic resin molded article> The molded article of the present invention is characterized by excellent strength. There are no particular restrictions on the shape of the molded product, but since the styrene resin of the present invention has an excellent balance between fluidity and strength, it can be used for large molded products, such as storage trays for office equipment, paper storage trays, and copy paper trays. , goldfish bowls, bird cages, breeding boxes, costume cases,
Ideal for use in food storage cases, audio product storage cases, toys, computer tape storage equipment, electric refrigerator crispers, office machine parts, audio equipment parts, cosmetic storage cases, etc. It can also be suitably used as a storage container for recording media, such as a storage container for audio tapes, video tapes, audio cassettes, video cassette tapes, audio discs, video discs, floppy discs, etc.
【００６３】又、薄肉製品、例えば、ビデオカセットテ
ープ、オーディオテープ等のハウジング等にも用いるこ
とができる。なお、本発明では重合度の尺度である１０
重量％トルエン溶液の粘度はオストワルドキャノンフェ
ンスケ粘度管♯３５０を用いて２５℃の恒温槽で測定す
る。分散粒子の粒子径は樹脂の超薄切片法による透過型
電子顕微鏡写真拡大倍率１０，０００を撮影し、写真中
の分散粒子約１０００〜２０００個の粒子数を測定し、
次式により求めたものである。[0063] It can also be used for thin-walled products, such as housings for video cassette tapes, audio tapes, etc. In addition, in the present invention, 10 is a measure of the degree of polymerization.
The viscosity of the wt% toluene solution is measured using an Ostwald Cannon-Fenske viscosity tube #350 in a constant temperature bath at 25°C. The particle size of the dispersed particles is determined by taking a transmission electron micrograph of the resin at a magnification of 10,000 using an ultra-thin section method, and measuring the number of dispersed particles of about 1000 to 2000 in the photo.
It was calculated using the following formula.
【００６４】
分散粒子の粒子径＝ΣＤｉ／ｎ Ｄｉ＝ｉ番
目の粒子径
ｎ ＝測定した粒子の
数なお、電子顕微鏡写真に映った分散粒子は完全な円形
ではないので、粒子径の測定は粒子の長軸（ａ）と短軸
（ｂ）の長さの測定値を用いて次式により算出する。Particle diameter of dispersed particles=ΣDi/n Di=i-th particle diameter
n = Number of measured particles Note that the dispersed particles shown in the electron micrograph are not perfectly circular, so when measuring the particle diameter, the measured value of the length of the long axis (a) and short axis (b) of the particle is used. Calculated using the following formula.
【００６５】[0065]
【数１】[Math 1]
【００６６】スチレン系樹脂中のゴム状弾性体の量は、
ゴム補強ポリスチレンで一般的に用いられている赤外吸
収スペクトル法で測定される。構成単位（Ａ）、（Ｂ）
、（Ｃ）は以下の方法で測定する。スチレン系樹脂をト
ルエンに溶解後、遠心分離機で２０，０００ｒｐｍで３
０分間処理した後、上澄液を分離し、上澄液に多量のメ
タノールを加え、スチレン系重合体を沈澱させる。この
沈澱物を５０℃、１０ｍｍＨｇの減圧下で乾燥する。こ
のサンプルを用いて、日本分光（株）ＪＮＭ−Ｇ４００
ＦＴ−ＮＭＲを用いて、以下に記す測定条件で １
Ｈを測定する。
（ １Ｈの測定条件）
パルス幅＝８．４μｓ
デーダーポイント＝１６３８４
繰り返し時間＝７．５５９秒
ＡＤコンバーター＝１６ビット
積算回数＝１０００
サンプル濃度＝１０ｗｔ％
溶媒＝１，１，２，２−テトラクロロエタンー（ｄ２
）サンプル管＝５ｍｍ
測定温度＝１２０℃
構成単位（Ａ）のフェニル基の水素に由来するピークが
６．２〜７．４ｐｐｍに現れる。構成単位（Ｂ）の水素
に由来するピークが３．４〜３．８ｐｐｍに現れる。
又、構成単位（Ｂ）、（Ｃ）、のメチル基の水素に由来
するピークが０．２〜１．１ｐｐｍに現れる。ピーク分
離操作を行ってピーク面積比より構成単位（Ａ）、（Ｂ
）、（Ｃ）の重量％を求める。[0066] The amount of rubbery elastic material in the styrene resin is
Measured using infrared absorption spectroscopy, which is commonly used for rubber-reinforced polystyrene. Constituent units (A), (B)
, (C) are measured by the following method. After dissolving the styrene resin in toluene, use a centrifuge at 20,000 rpm for 3
After treating for 0 minutes, the supernatant is separated, and a large amount of methanol is added to the supernatant to precipitate the styrenic polymer. This precipitate is dried at 50° C. under reduced pressure of 10 mmHg. Using this sample, JASCO Corporation JNM-G400
Using FT-NMR, under the measurement conditions described below: 1
Measure H. (Measurement conditions for 1H) Pulse width = 8.4 μs Dader points = 16384 Repetition time = 7.559 seconds AD converter = 16 bits Number of integration = 1000 Sample concentration = 10 wt% Solvent = 1,1,2,2-tetrachloroethane (d2
) Sample tube = 5 mm Measurement temperature = 120°C A peak derived from the hydrogen of the phenyl group of the structural unit (A) appears at 6.2 to 7.4 ppm. A peak derived from hydrogen in the structural unit (B) appears at 3.4 to 3.8 ppm. Moreover, a peak derived from hydrogen of the methyl group of the structural units (B) and (C) appears at 0.2 to 1.1 ppm. Performing a peak separation operation, the structural units (A) and (B) were determined from the peak area ratio.
), determine the weight percent of (C).
【００６７】[0067]
【実施例】実施例における物性試験法を以下に記す。
メルトフローレート（ＭＦＲ）：ＩＳＯ Ｒ１１３３
に準ずる。
ビカット軟化点（ＶＩＣＡＴ）：ＡＳＴＭ Ｄ１５２
５に準ずる
アイゾット衝撃強度：ＡＳＴＭ Ｄ２５６に準ずる。[Example] The physical property test method in the example is described below. Melt flow rate (MFR): ISO R1133
According to. Vicat Softening Point (VICAT): ASTM D152
Izod impact strength according to 5: according to ASTM D256.
【００６８】一撃衝撃強度：成形温度＝２４０℃、成形
圧力＝ＳＳＰ＋５ｋｇ／ｃｍ２ 、金型温度＝６０℃の
条件で５ｃｍ×８．８ｃｍ×２ｍｍの試験片を射出成形
し、東洋精機製作所の「落錘型グラフィックインパクト
テスター」を用いて、高さ２０ｃｍより質量６．５ｋｇ
のミサイルを自然落下させて破壊の最大荷重を求める。
シートの場合は、シートより５ｃｍ×８．８ｃｍのサン
プルを切出し上記の方法に準じて測定する。One-shot impact strength: A test piece of 5 cm x 8.8 cm x 2 mm was injection molded under the conditions of molding temperature = 240°C, molding pressure = SSP + 5 kg/cm2, and mold temperature = 60°C. Using a weight-shaped graphic impact tester, the mass is 6.5 kg from a height of 20 cm.
Let the missile fall naturally and find the maximum load for destruction. In the case of a sheet, a 5 cm x 8.8 cm sample is cut out from the sheet and measured according to the above method.
【００６９】（スチレン系樹脂−１）攪拌機を備えた反
応機２基を直列連結し、その後に二段ベント付き二軸押
出機を配置した重合装置を用いてスチレン系樹脂を製造
する。(Styrenic Resin-1) A styrene resin is produced using a polymerization apparatus in which two reactors equipped with a stirrer are connected in series, followed by a twin-screw extruder with a two-stage vent.
【００７０】スチレン４７．５重量部、ブチルアクリレ
ート１０．０重量部、メチルメタクリレート３３．２部
、ゴム状弾性体としてＢ−Ｓタイプ（Ｂ：ブタジエンブ
ロック、Ｓ：スチレンブロック）で、スチレン含有量が
３８重量％であるゴム状弾性体６．５重量部、エチルベ
ンゼン２．８重量部、１，１ビス（ｔ−ブチルパーオキ
シ）シクロヘキサン０．０１重量部からなる原料溶液を
反応機に供給し重合を行う。得られたゴム変性スチレン
系樹脂１００重量部とポリジメチルシロキサン０．０５
重量部をブレンドし、単軸押出機で造粒する。得られた
スチレン系樹脂の物性を表１に示す。
（スチレン系樹脂−２、−３、−４、−５）反応機の攪
拌数を変化させた以外、スチレン系樹脂−１と同様に操
作する。得られたスチレン系樹脂の物性を表１に示す。
（スチレン系樹脂−６）スチレン４４．８重量部、ブチ
ルアクリレート９．４重量部、メチルメタクリレート３
１．２部、ゴム状弾性体としてＢ−Ｓタイプ（Ｂ：ブタ
ジエンブロックＳ：スチレンブロック）で、スチレン含
有量が３８重量％であるゴム状弾性体１２．０重量％、
エチルベンゼン２．６重量部、１，１ビス（ｔ−ブチル
パーオキシ）シクロヘキサン０．０１重量部からなる原
料溶液を反応機に供給する以外スチレン系樹脂−１と同
様に操作する。得られたスチレン系樹脂の物性を表１に
示す。
（スチレン系樹脂−７）ゴム状弾性体としてポリブタジ
エンを使用し、攪拌数が異なる以外スチレン系樹脂−１
と同様に操作する。得られたスチレン系樹脂の物性値を
表１に示す。
（スチレン系樹脂−８）ゴム状弾性体としてＢ−Ｓタイ
プでスチレン含有量が６０重量％であるゴム状弾性体を
使用し、攪拌数が異なる以外スチレン系樹脂−１と同様
に操作する。得られたスチレン系樹脂の物性を表１に示
す。
（スチレン系樹脂−９）スチレン５０．８重量部、ブチ
ルアクリレート１０．７重量部、メチルメタアクリレー
ト３５．５重量部、エチルベン３．０重量部、１，１ビ
ス（ｔ−ブチルパーオキシ）シクロヘキサン０．０１重
量部である以外、スチレン系樹脂−１と同様に操作する
。得られたスチレン系樹脂の物性を表１に示す。
（スチレン系樹脂−１０）スチレン７５．３重量部、ブ
チルアクリレート１２．６重量部、スチレン系樹脂−１
で用いたゴム状弾性体６．５重量部、エチルベンゼン５
．６重量部、１，１ビス（ｔ−ブチルパーオキシ）シク
ロヘキサン０．０１重量部である以外、スチレン系樹脂
−１と同様に操作する。得られたスチレン系樹脂の物性
を表１に示す。47.5 parts by weight of styrene, 10.0 parts by weight of butyl acrylate, 33.2 parts by weight of methyl methacrylate, B-S type (B: butadiene block, S: styrene block) as a rubber-like elastic body, styrene content A raw material solution consisting of 6.5 parts by weight of a rubber-like elastic material of 38% by weight, 2.8 parts by weight of ethylbenzene, and 0.01 parts by weight of 1,1 bis(t-butylperoxy)cyclohexane was supplied to the reactor. Carry out polymerization. 100 parts by weight of the obtained rubber-modified styrenic resin and 0.05 parts by weight of polydimethylsiloxane
The parts by weight are blended and granulated using a single screw extruder. Table 1 shows the physical properties of the obtained styrenic resin. (Styrenic resin-2, -3, -4, -5) The same procedure as for styrene resin-1 was performed except that the stirring number of the reactor was changed. Table 1 shows the physical properties of the obtained styrenic resin. (Styrenic resin-6) 44.8 parts by weight of styrene, 9.4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate
1.2 parts, 12.0% by weight of a rubbery elastic body of B-S type (B: butadiene block S: styrene block) with a styrene content of 38% by weight, as a rubbery elastic body;
The procedure was the same as for styrenic resin-1 except that a raw material solution consisting of 2.6 parts by weight of ethylbenzene and 0.01 parts by weight of 1,1 bis(t-butylperoxy)cyclohexane was supplied to the reactor. Table 1 shows the physical properties of the obtained styrenic resin. (Styrene resin-7) Styrene resin-1 except that polybutadiene is used as the rubber-like elastic body and the stirring number is different.
Operate in the same way. Table 1 shows the physical properties of the obtained styrene resin. (Styrenic Resin-8) A B-S type rubber-like elastic material having a styrene content of 60% by weight was used as the rubber-like elastic material, and the procedure was the same as for Styrene-based Resin-1 except that the stirring number was different. Table 1 shows the physical properties of the obtained styrenic resin. (Styrenic resin-9) 50.8 parts by weight of styrene, 10.7 parts by weight of butyl acrylate, 35.5 parts by weight of methyl methacrylate, 3.0 parts by weight of ethylben, 1,1 bis(t-butylperoxy)cyclohexane The procedure is the same as for styrene resin-1 except that the amount is 0.01 part by weight. Table 1 shows the physical properties of the obtained styrenic resin. (Styrene resin-10) 75.3 parts by weight of styrene, 12.6 parts by weight of butyl acrylate, styrene resin-1
6.5 parts by weight of the rubber-like elastic material used in , 5 parts by weight of ethylbenzene
．． 6 parts by weight, and 0.01 part by weight of 1,1 bis(t-butylperoxy)cyclohexane, the same procedure as for styrene resin-1 was performed. Table 1 shows the physical properties of the obtained styrenic resin.
【００７１】（スチレン系樹脂−１１）スチレン５３．
３重量部、ブチルアクリレート７．０重量部、メチルメ
タアクリレート３０．４重量部である以外、スチレン系
樹脂−１と同処方、同操作を行い、スチレン系樹脂を得
る。物性を表１に示す。
（スチレン系樹脂−１２）スチレン５６．１重量部、ブ
チルアクリレート１．９重量部、メチルメタアクリレー
ト３２．７重量部である以外、スチレン系樹脂−１と同
処方、同操作を行い、スチレン系樹脂を得る。物性を表
１に示す。
（スチレン系樹脂−１３）スチレン５３．３重量部、ブ
チルアクリレート０．０重量部、メチルメタアクリレー
ト３７．４重量部である以外、スチレン系樹脂−１と同
処方、同操作を行い、スチレン系樹脂を得る。物性を表
１に示す。(Styrenic resin-11) Styrene 53.
A styrene resin is obtained using the same formulation and same operation as in styrenic resin-1, except that 3 parts by weight, butyl acrylate 7.0 parts by weight, and methyl methacrylate 30.4 parts by weight. The physical properties are shown in Table 1. (Styrenic Resin-12) The same formulation and operation as in Styrene Resin-1 were carried out, except that styrene was 56.1 parts by weight, butyl acrylate was 1.9 parts by weight, and methyl methacrylate was 32.7 parts by weight. Get resin. The physical properties are shown in Table 1. (Styrenic resin-13) The same recipe and operation as for styrene resin-1 were carried out, except that 53.3 parts by weight of styrene, 0.0 parts by weight of butyl acrylate, and 37.4 parts by weight of methyl methacrylate were used. Get resin. The physical properties are shown in Table 1.
【００７２】[0072]
【実施例１】スチレン系樹脂−１を用いて物性を測定し
た。結果を表２に示す。[Example 1] Physical properties were measured using styrene resin-1. The results are shown in Table 2.
【００７３】[0073]
【実施例２】スチレン系樹脂−２を用いて物性を測定し
た。結果を表２に示す。[Example 2] Physical properties were measured using styrene resin-2. The results are shown in Table 2.
【００７４】[0074]
【実施例３】スチレン系樹脂−３を用いて物性を測定し
た。結果を表２に示す。Example 3 Physical properties were measured using styrene resin-3. The results are shown in Table 2.
【００７５】[0075]
【実施例４】スチレン系樹脂−１とスチレン系樹脂−３
を５０／５０（重量％）でブレンドし、単軸押出機でペ
レット化し、物性を測定した。測定結果を表２に示す。[Example 4] Styrene resin-1 and styrene resin-3
were blended at a ratio of 50/50 (wt%), pelletized using a single screw extruder, and the physical properties were measured. The measurement results are shown in Table 2.
【００７６】[0076]
【実施例５、６、７、８】スチレン系樹脂−６とスチレ
ン系樹脂−９を２０／８０、４０／６０、５５／４５、
７０／３０（重量％）でブレンドし、単軸押出機でペレ
ット化し、物性を測定した。実施例−５のゴム状弾性体
含有量は３．１重量％、実施例６のゴム状弾性体含有量
は６．１重量％、実施例７のゴム状重合体含有量は８．
４重量％、実施例８のゴム状弾性体含有量は１０．７重
量％である。測定結果を表２に示す。[Examples 5, 6, 7, 8] Styrene resin-6 and styrene resin-9 were mixed at 20/80, 40/60, 55/45,
The mixture was blended at a ratio of 70/30 (wt%), pelletized using a single screw extruder, and the physical properties were measured. The rubbery elastic material content of Example-5 was 3.1% by weight, the rubbery elastic material content of Example 6 was 6.1% by weight, and the rubbery polymer content of Example 7 was 8.1% by weight.
4% by weight, and the rubbery elastomer content of Example 8 is 10.7% by weight. The measurement results are shown in Table 2.
【００７７】[0077]
【実施例９】ポリジメチルシロキサン０．００５重量部
をブレンドする以外スチレン系樹脂−１と同様に操作し
て得たゴム変性スチレン系樹脂を用いて物性を測定した
。測定結果を表２に示す。Example 9 Physical properties were measured using a rubber-modified styrenic resin obtained in the same manner as styrenic resin-1 except that 0.005 parts by weight of polydimethylsiloxane was blended. The measurement results are shown in Table 2.
【００７８】[0078]
【比較例１】スチレン系樹脂−４を用いて物性を測定し
た。結果を表２に示す。[Comparative Example 1] Physical properties were measured using styrene resin-4. The results are shown in Table 2.
【００７９】[0079]
【比較例２】スチレン系樹脂−５を用いて物性を測定し
た。結果を表２に示す。[Comparative Example 2] Physical properties were measured using styrene resin-5. The results are shown in Table 2.
【００８０】[0080]
【比較例３】スチレン系樹脂−７を用いて物性を測定し
た。結果を表２に示す。[Comparative Example 3] Physical properties were measured using styrene resin-7. The results are shown in Table 2.
【００８１】[0081]
【比較例４】スチレン系樹脂−８を用いて物性を測定し
た。結果を表２に示す。[Comparative Example 4] Physical properties were measured using styrene resin-8. The results are shown in Table 2.
【００８２】[0082]
【比較例５】スチレン系樹脂−１０を用いて物性を測定
した。結果を表２に示す。[Comparative Example 5] Physical properties were measured using styrene resin-10. The results are shown in Table 2.
【００８３】[0083]
【比較例６】旭化成工業（株）のポリスチレン Ｇ８
１０２とスチレン−ブタジエンブロック共重合体 ア
サフレックス８１０を９０／１０（重量％）の割合でブ
レンドし、単軸押出機でペレット化し、物性を測定する
。測定結果を表２に示す。[Comparative Example 6] Polystyrene G8 manufactured by Asahi Kasei Industries, Ltd.
102 and the styrene-butadiene block copolymer Asaflex 810 were blended in a ratio of 90/10 (wt%), pelletized using a single screw extruder, and the physical properties were measured. The measurement results are shown in Table 2.
【００８４】[0084]
【比較例７】旭化成工業（株）のポリスチレン Ｇ８
１０２とスチレン−ブタジエンブロック共重合体 ア
サフレックス８１０を８０／２０（重量％）の割合でブ
レンドし、単軸押出機でペレット化し、物性を測定する
。測定結果を表２に示す。[Comparative Example 7] Polystyrene G8 manufactured by Asahi Kasei Industries, Ltd.
102 and the styrene-butadiene block copolymer Asaflex 810 were blended in a ratio of 80/20 (wt%), pelletized using a single screw extruder, and the physical properties were measured. The measurement results are shown in Table 2.
【００８５】[0085]
【比較例８】スチレン系樹脂−１において、ポリジメチ
ルシロキサンをブレンドする前のゴム変性スチレン系樹
脂を用いてブツ物性を測定する。測定結果を表２に示す
。[Comparative Example 8] Regarding styrene resin-1, physical properties are measured using a rubber-modified styrenic resin before blending with polydimethylsiloxane. The measurement results are shown in Table 2.
【００８６】[0086]
【比較例９】スチレン系樹脂−１において、ポリジメチ
ルシロキサンをブレンドする前のゴム変性スチレン系樹
脂を用いてブツ物性を測定する。測定結果を表２に示す
。[Comparative Example 9] Regarding styrene resin-1, physical properties are measured using a rubber-modified styrene resin before blending with polydimethylsiloxane. The measurement results are shown in Table 2.
【００８７】[0087]
【比較例１０】ポリジメチルシロキサン０．４０重量部
をブレンドする以外スチレン系樹脂−１と同様に操作し
て得たゴム変性スチレン系樹脂を用いて物性を測定した
。測定結果を表２に示す。本発明のスチレン系樹脂は、
強度、透明性に優れていることが理解できる。分散粒子
径が０．１μ〜１．２μの範囲から外れると、強度、又
は透明性が悪化し、使用出来なくなる。又、分散粒子を
形成するゴム状弾性体のブタジエン含有量が本発明の構
成要件から外れた場合も、強度、又は透明性が実用に向
かないレベルになる。Comparative Example 10 Physical properties were measured using a rubber-modified styrenic resin obtained in the same manner as styrenic resin-1 except that 0.40 parts by weight of polydimethylsiloxane was blended. The measurement results are shown in Table 2. The styrenic resin of the present invention is
It can be seen that it has excellent strength and transparency. When the dispersed particle size is outside the range of 0.1 μm to 1.2 μm, the strength or transparency deteriorates and the product becomes unusable. Furthermore, if the butadiene content of the rubber-like elastic body forming the dispersed particles deviates from the constituent requirements of the present invention, the strength or transparency will be at a level that is not suitable for practical use.
【００８８】有機ポリシロキサンを含まないゴム変性ス
チレン系樹脂は強度補強効果が発現しない。特に、分散
相の粒子系が小さくなるほど有機ポリシロキサンの補強
効果は顕著になる。従来、多用されていたポリスチレン
／スチレン−ブタジエンブロック共重合体混合樹脂の透
明性、強度よりも本発明のスチレン系樹脂の強度、透明
性は著しく向上していることが理解できる。又、強度、
透明性が著しく向上しているうえに成形性（流動性）も
改良されている。Rubber-modified styrenic resins that do not contain organic polysiloxane do not exhibit strength reinforcing effects. In particular, the reinforcing effect of the organic polysiloxane becomes more pronounced as the particle size of the dispersed phase becomes smaller. It can be seen that the strength and transparency of the styrenic resin of the present invention are significantly improved compared to the transparency and strength of the polystyrene/styrene-butadiene block copolymer mixed resin that has been widely used in the past. Also, strength,
Not only is transparency significantly improved, but moldability (flowability) is also improved.
【００８９】＜スチレン系樹脂シート＞<Styrenic resin sheet>
【００９０】[0090]
【実施例１０】スチレン系樹脂−１２を用いて、３０ｍ
ｍ押出機で厚み０．６５ｍｍのシートを作成した。この
シートを熱板圧空成形機を用いて熱成形を行った。加熱
圧力１．０ｋｇ／ｃｍ２ でシートを加熱し、成形圧力
２．５ｋｇ／ｃｍ２ 、成形時間２秒、金型温度６０℃
の条件下で成形し、金型（フードパック）のヒンジ３Ｒ
が金型通り再現出来る熱板温度１１５℃、１３０℃での
加熱時間を求めた。[Example 10] Using styrene resin-12, 30 m
A sheet with a thickness of 0.65 mm was produced using an extruder. This sheet was thermoformed using a hot plate air pressure forming machine. The sheet was heated at a heating pressure of 1.0 kg/cm2, a molding pressure of 2.5 kg/cm2, a molding time of 2 seconds, and a mold temperature of 60°C.
Molding under the following conditions, the hinge 3R of the mold (food pack)
The heating time at a hot plate temperature of 115° C. and 130° C., which can be reproduced according to the mold, was determined.
【００９１】又、シートの一撃衝撃試験、透明性の評価
を行った。結果を表３に示す。In addition, the sheet was subjected to a single impact impact test and its transparency was evaluated. The results are shown in Table 3.
【００９２】[0092]
【実施例１１】スチレン系樹脂−１１を用いて、実施例
１０と同様の評価を行った。結果を表３に示す。Example 11 The same evaluation as in Example 10 was conducted using styrene resin-11. The results are shown in Table 3.
【００９３】[0093]
【実施例１２】スチレン系樹脂−１を用いて、実施例１
０と同様の評価を行った。結果を表３に示す。[Example 12] Using styrene resin-1, Example 1
The same evaluation as 0 was performed. The results are shown in Table 3.
【００９４】[0094]
【比較例１１】スチレン系樹脂−１３を用いて、実施例
１０と同様の評価を行った。結果を表３に示す。Comparative Example 11 The same evaluation as in Example 10 was conducted using styrene resin-13. The results are shown in Table 3.
【００９５】[0095]
【比較例１２】スチレン系樹脂−７を用いて、実施例１
０と同様の評価を行った。結果を表３に示す。[Comparative Example 12] Using styrene resin-7, Example 1
The same evaluation as 0 was performed. The results are shown in Table 3.
【００９６】[0096]
【比較例１３】スチレン系樹脂−８を用いて、実施例１
０と同様の評価を行った。結果を表３に示す。[Comparative Example 13] Using styrene resin-8, Example 1
The same evaluation as 0 was performed. The results are shown in Table 3.
【００９７】[0097]
【比較例１４】旭化成工業（株）のポリスチレン Ｇ
８１０２とスチレン−ブタジエンブロック共重合体
アサフレックス８１０を５０／５０（重量％）の割合で
ブレンドし、単軸押出機でペレット化し、このスチレン
系樹脂を用いて、実施例１０と同様の評価を行った。結
果を表３に示す。[Comparative Example 14] Polystyrene G from Asahi Kasei Industries, Ltd.
8102 and styrene-butadiene block copolymer
Asaflex 810 was blended at a ratio of 50/50 (wt%), pelletized using a single screw extruder, and the same evaluation as in Example 10 was conducted using this styrene resin. The results are shown in Table 3.
【００９８】[0098]
【比較例１５】旭化成工業（株）のポリスチレン Ｇ
８１０２ １００重量部当り白色鉱油２．５重量部を
混合し、二軸押出機で造粒したスチレン系樹脂を用いて
、実施例１０と同様の評価を行った。結果を表３に示す
。[Comparative Example 15] Polystyrene G from Asahi Kasei Industries, Ltd.
The same evaluation as in Example 10 was conducted using a styrenic resin mixed with 2.5 parts by weight of white mineral oil per 100 parts by weight of 8102 and granulated using a twin-screw extruder. The results are shown in Table 3.
【００９９】0099
【比較例１６】比較例８で用いたゴム変性スチレン系樹
脂を用いて、実施例１０と同様の評価を行った。結果を
表３に示す。本発明のスチレン系樹脂シートは従来使用
されていたポリスチレン系樹脂シートよりも加熱時間が
大幅に短縮できる。即ち、成形サイクル短縮が可能とな
る。又、本発明の構成単位（Ｂ）の含有量を増やしてい
くことにより、低温で成形ができるようになり、塩化ビ
ニル樹脂シートと同等に近い条件で成形できる。[Comparative Example 16] Using the rubber-modified styrene resin used in Comparative Example 8, the same evaluation as in Example 10 was conducted. The results are shown in Table 3. The styrene resin sheet of the present invention can significantly shorten the heating time compared to conventionally used polystyrene resin sheets. That is, it becomes possible to shorten the molding cycle. Furthermore, by increasing the content of the structural unit (B) of the present invention, it becomes possible to mold at low temperatures, and it can be molded under conditions close to those of vinyl chloride resin sheets.
【０１００】更に、本発明のスチレン系樹脂シートは、
従来多用されているポリスチレン／スチレン−ブタジエ
ンブロック共重合体混合樹脂シートより、透明性、強度
が著しく向上している。又、有機ポリシロキサンの含有
の効果も認められる。
＜スチレン系樹脂成形体＞Furthermore, the styrenic resin sheet of the present invention is
The transparency and strength are significantly improved compared to the polystyrene/styrene-butadiene block copolymer mixed resin sheet that has been widely used in the past. Moreover, the effect of containing organic polysiloxane is also recognized. <Styrenic resin molded body>
【０１０１】[0101]
【実施例１３】スチレン系樹脂−１２を用いて、射出成
形機ＩＳ８００Ｂ−７５（東芝機械（株）製）を用いて
、射出圧力１００ｋｇ／ｃｍ２ 、金型温度６０℃の条
件下で、図１に示すトレーを成形した。この時、成形温
度を変えて、トレーが成形できる最低温度を求めた。[Example 13] Using styrene resin-12, an injection molding machine IS800B-75 (manufactured by Toshiba Machinery Co., Ltd.) was used under conditions of an injection pressure of 100 kg/cm2 and a mold temperature of 60°C. The tray shown in is molded. At this time, the molding temperature was varied to find the lowest temperature at which the tray could be molded.
【０１０２】次にこのトレーの中心部に４０ｇの鋼球を
落下させ、割れが生じる高さを検討し、破壊エネルギー
を求めた。又、得られた成形品を目視で透明性を評価し
た。又、成形温度２５０℃である以外、同じ成形条件で
トレーを成形し、成形品表面にスエッティング物質が転
写する迄の射出回数を求めた。結果を表４に示す。Next, a 40 g steel ball was dropped onto the center of this tray, the height at which cracking occurred was examined, and the fracture energy was determined. Further, the transparency of the obtained molded product was visually evaluated. Further, trays were molded under the same molding conditions except that the molding temperature was 250° C., and the number of injections until the sweating substance was transferred to the surface of the molded product was determined. The results are shown in Table 4.
【０１０３】[0103]
【実施例１４】スチレン系樹脂−１１を用いて、実施例
１３と同様の検討を行った。結果を表４に示す。Example 14 The same study as in Example 13 was conducted using styrene resin-11. The results are shown in Table 4.
【０１０４】[0104]
【実施例１５】スチレン系樹脂−１を用いて、実施例１
３と同様の検討を行った。結果を表４に示す。[Example 15] Using styrene resin-1, Example 1
The same study as in 3 was conducted. The results are shown in Table 4.
【０１０５】[0105]
【比較例１７】比較例１２で用いたスチレン系樹脂を用
いて、実施例１３と同様の検討を行う。結果を表４に示
す。[Comparative Example 17] Using the styrene resin used in Comparative Example 12, the same study as in Example 13 was conducted. The results are shown in Table 4.
【０１０６】[0106]
【比較例１８】旭化成工業（株）のポリスチレン Ｇ
８１０２とスチレン−ブタジエンブロック共重合体
アサフレックス８１０を７０／３０（重量％）の割合で
ブレンドし、単軸押出機で造粒し、ペレットを得る。こ
のスチレン系樹脂を用いて、実施例１３と同様の検討を
行う。結果を表４に示す。[Comparative Example 18] Polystyrene G from Asahi Kasei Industries, Ltd.
8102 and styrene-butadiene block copolymer
Asaflex 810 is blended at a ratio of 70/30 (wt%) and granulated using a single screw extruder to obtain pellets. The same study as in Example 13 is conducted using this styrene resin. The results are shown in Table 4.
【０１０７】[0107]
【比較例１９】スチレン系樹脂−７を用いて、実施例１
３と同様の検討を行う。結果を表４に示す。[Comparative Example 19] Using styrene resin-7, Example 1
Perform the same study as in 3. The results are shown in Table 4.
【０１０８】[0108]
【比較例２０】スチレン系樹脂−４を用いて、実施例１
３と同様の検討を行う。結果を表４に示す。[Comparative Example 20] Using styrene resin-4, Example 1
Perform the same study as in 3. The results are shown in Table 4.
【０１０９】[0109]
【比較例２１】スチレン系樹脂−５を用いて、実施例１
３と同様の検討を行う。結果を表４に示す。本発明のス
チレン系樹脂は従来のポリスチレンに可塑剤（白色鉱油
）を添加した樹脂よりも低温で成形でき、かつ、モール
ドスエッティング現象による不良率が低減することが理
解できる。[Comparative Example 21] Using styrene resin-5, Example 1
Perform the same study as in 3. The results are shown in Table 4. It can be seen that the styrenic resin of the present invention can be molded at a lower temperature than the conventional resin made by adding a plasticizer (white mineral oil) to polystyrene, and the defect rate due to the mold sweating phenomenon is reduced.
【０１１０】本発明のスチレン系樹脂成形体は透明性、
強度が優れていることが理解できる。
＜スチレン系樹脂発泡体＞[0110] The styrenic resin molded article of the present invention has transparency,
It can be seen that the strength is excellent. <Styrenic resin foam>
【０１１１】[0111]
【実施例１６】スチレン系樹脂−１とスチレン系樹脂−
９を５０／５０（重量％）の割合でブレンドし、この樹
脂を用いて、フレオン−１２を発泡剤として押出発泡し
、厚さ１．２ｍｍ、密度０．１０ｇ／ｃｃのシート状の
スチレン系樹脂発泡体を得た。得られたスチレン系樹脂
発泡体を１ケ月間養生し、赤外線加熱炉を用いて種々の
温度で１０秒間加熱し、二次発泡させ、図２に示す弁当
箱の成形品を得た。[Example 16] Styrene resin-1 and styrene resin-
9 in a ratio of 50/50 (wt%), and using this resin, extrusion foaming was performed using Freon-12 as a foaming agent to form a sheet-like styrene-based material with a thickness of 1.2 mm and a density of 0.10 g/cc. A resin foam was obtained. The obtained styrenic resin foam was cured for one month and heated for 10 seconds at various temperatures using an infrared heating furnace to cause secondary foaming, thereby obtaining a bento box molded product shown in FIG. 2.
【０１１２】次に、１１０℃で加熱時間を変化させて同
様の二次発泡を行い成形品を得た。その発泡成形品の評
価結果を表５に示す。Next, similar secondary foaming was performed at 110° C. while changing the heating time to obtain a molded product. Table 5 shows the evaluation results of the foamed molded product.
【０１１３】[0113]
【実施例１７】スチレン系樹脂−１２とスチレン系樹脂
−９を５０／５０（重量％）の割合でブレンドし、この
スチレン系樹脂を用い、実施例１６と同様の検討を行っ
た。評価結果を表５に示す。[Example 17] Styrenic resin-12 and styrene-based resin-9 were blended in a ratio of 50/50 (wt%), and the same study as in Example 16 was conducted using this styrene-based resin. The evaluation results are shown in Table 5.
【０１１４】[0114]
【比較例２２】旭化成工業（株）のポリスチレン Ｇ
８１０２とスチレン−ブタジエンブロック共重合体
アサフレックス８１０を９５／５（重量％）の割合でブ
レンドし、このスチレン系樹脂を用い、実施例１６と同
様の検討を行った。評価結果を表５に示す。[Comparative Example 22] Polystyrene G from Asahi Kasei Industries, Ltd.
8102 and styrene-butadiene block copolymer
Asaflex 810 was blended at a ratio of 95/5 (wt%), and the same study as in Example 16 was conducted using this styrene resin. The evaluation results are shown in Table 5.
【０１１５】[0115]
【比較例２３】旭化成工業（株）のポリスチレン Ｇ
８１０２を用い、実施例１６と同様の検討を行った。評
価結果を表５に示す。[Comparative Example 23] Polystyrene G from Asahi Kasei Industries, Ltd.
The same study as in Example 16 was conducted using 8102. The evaluation results are shown in Table 5.
【０１１６】[0116]
【比較例２４】旭化成工業（株）のポリスチレン Ｇ
８１０２ １００重量部当たり白色鉱油２．５重量部
を混合し、二軸押出機で造粒したスチレン系樹脂を用い
て、実施例１６と同様の検討を行った。評価結果を表５
に示す。本発明のスチレン系樹脂発泡体は強度に優れ、
低温で成形でき、たつ、型決まり性が良く、ケロイドの
発生も無い。二次発泡成形性が良好であることが理解で
きる。[Comparative Example 24] Polystyrene G from Asahi Kasei Industries, Ltd.
The same study as in Example 16 was conducted using a styrenic resin mixed with 2.5 parts by weight of white mineral oil per 100 parts by weight of 8102 and granulated using a twin-screw extruder. Table 5 shows the evaluation results.
Shown below. The styrenic resin foam of the present invention has excellent strength,
It can be molded at low temperatures, has good shapeability, and does not cause keloids. It can be seen that the secondary foaming moldability is good.
【０１１７】[0117]
【表１】[Table 1]
【０１１８】[0118]
【表２】[Table 2]
【０１１９】[0119]
【表３】[Table 3]
【０１２０】[0120]
【表４】[Table 4]
【０１２１】[0121]
【表５】[Table 5]
【０１２２】[0122]
【発明の効果】本発明においては、スチレン系単量体と
共重合可能な第二、第三の単量体として、アクリル酸エ
ステル（メタクリル酸エステル）、メチルメタクリレー
トを導入したスチレン系重合体を連続相とし、ゴム状弾
性体を分散相とするゴム変性スチレン系樹脂に有機ポリ
シロキサンを含有させることにより、■ 強度、透明
性、低温成形性（成形サイクル短縮）に優れたスチレン
系樹脂が得られること、■ スチレン系樹脂を成形し
たシートは低温で二次成形でき、かつ成形サイクル短縮
が可能であり、成形体の強度の優れたスチレン系樹脂シ
ートを与えること■ スチレン系樹脂を成形してなる
強度、透明性に優れたスチレン系樹脂成形体を与えるこ
と、■ スチレン系樹脂を成形した発泡体は、加熱二
次発泡成形性に優れ、発泡成形品の強度に優れたスチレ
ン系樹脂発泡体を与える。[Effects of the Invention] In the present invention, a styrene polymer into which acrylic acid ester (methacrylic acid ester) and methyl methacrylate are introduced as second and third monomers copolymerizable with the styrene monomer is used. By incorporating organic polysiloxane into a rubber-modified styrenic resin that has a continuous phase and a rubber-like elastomer as a dispersed phase, a styrenic resin with excellent strength, transparency, and low-temperature moldability (shortened molding cycle) can be obtained. ■ Sheets molded from styrene resin can be secondary-formed at low temperatures, the molding cycle can be shortened, and a styrenic resin sheet with excellent strength can be obtained. ■ Sheets molded from styrene resin To provide a styrene-based resin molded product with excellent strength and transparency; ■ A styrene-based resin foam molded with styrene-based resin has excellent secondary foaming moldability by heating, and has excellent strength as a foamed molded product. give.
Claims (1)
るゴム変性スチレン系樹脂に於いて （ア）連続相が 下記化学式（Ａ）； 【化１】 下記化学式（Ｂ）； 【化２】 下記化学式（Ｃ）； 【化３】 で示される構成単位からなり、構成単位（Ａ）、（Ｂ）
、（Ｃ）の割合が （Ａ）：２０〜７０ 重量％ （Ｂ）：０．５〜２０ 重量％ （Ｃ）：２９．５〜７９．５ 重量％（但し、（Ａ）
＋（Ｂ）＋（Ｃ）＝１００重量％）であり、（イ）分散
相の分散粒子径が０．１〜１．２μｍ、ゴム状弾性体の
含有量が１〜２０重量％であり、（ウ）ゴム変性スチレ
ン系樹脂１００重量部当たり０．００２〜３重量部の有
機ポリシロキサンを含有することを特徴とする強度、透
明性、低温成形性に優れたゴム変性スチレン系樹脂[Claim 1] In a rubber-modified styrenic resin containing a rubber-like elastic body as dispersed particles, (a) the continuous phase has the following chemical formula (A); [Chemical formula 1] the following chemical formula (B); [Chemical formula 2] the following Chemical formula (C); Consisting of structural units represented by [Chemical formula 3], structural units (A) and (B)
, the proportion of (C) is (A): 20 to 70% by weight (B): 0.5 to 20% by weight (C): 29.5 to 79.5% by weight (However, (A)
+ (B) + (C) = 100% by weight), (a) the dispersed particle diameter of the dispersed phase is 0.1 to 1.2 μm, and the content of the rubbery elastic body is 1 to 20% by weight, (c) A rubber-modified styrenic resin with excellent strength, transparency, and low-temperature moldability, characterized by containing 0.002 to 3 parts by weight of organic polysiloxane per 100 parts by weight of the rubber-modified styrenic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3861991A JP2533977B2 (en) | 1991-03-05 | 1991-03-05 | Rubber-modified styrene resin composition with excellent low-temperature moldability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3861991A JP2533977B2 (en) | 1991-03-05 | 1991-03-05 | Rubber-modified styrene resin composition with excellent low-temperature moldability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04277549A true JPH04277549A (en) | 1992-10-02 |
| JP2533977B2 JP2533977B2 (en) | 1996-09-11 |
Family
ID=12530260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3861991A Expired - Lifetime JP2533977B2 (en) | 1991-03-05 | 1991-03-05 | Rubber-modified styrene resin composition with excellent low-temperature moldability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2533977B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002243917A (en) * | 2001-02-19 | 2002-08-28 | Asahi Kasei Corp | Negative sheet for fresnel lens |
-
1991
- 1991-03-05 JP JP3861991A patent/JP2533977B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002243917A (en) * | 2001-02-19 | 2002-08-28 | Asahi Kasei Corp | Negative sheet for fresnel lens |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2533977B2 (en) | 1996-09-11 |
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