JP6785054B2 - Styrene-based resin composition - Google Patents
Styrene-based resin composition Download PDFInfo
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- JP6785054B2 JP6785054B2 JP2016075855A JP2016075855A JP6785054B2 JP 6785054 B2 JP6785054 B2 JP 6785054B2 JP 2016075855 A JP2016075855 A JP 2016075855A JP 2016075855 A JP2016075855 A JP 2016075855A JP 6785054 B2 JP6785054 B2 JP 6785054B2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 130
- 239000011342 resin composition Substances 0.000 title claims description 39
- 239000000463 material Substances 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 30
- 238000009826 distribution Methods 0.000 claims description 24
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 18
- 239000003063 flame retardant Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000007561 laser diffraction method Methods 0.000 claims description 3
- -1 aromatic vinyl compound Chemical class 0.000 description 21
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 229920006328 Styrofoam Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000008261 styrofoam Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Description
本発明は、スチレン系樹脂組成物、及び該樹脂組成物からなる成形体に関するものである。 The present invention relates to a styrene-based resin composition and a molded product made of the resin composition.
近年、環境問題に対する意識が高まり、家電やＯＡ機器のプラスチック部品にリサイクル材料を利用する動きが広がってきている。しかし、リサイクル材は劣化や汚れにより物性が低下していたり、廃棄機器の種類や回収量が一定でなかったりするため、プラスチック部品の強度や難燃性を安定させることが難しかった。ポリスチレン系リサイクル材の利用に関する技術として下記が挙げられる。 In recent years, awareness of environmental issues has increased, and the movement to use recycled materials for plastic parts of home appliances and OA equipment is spreading. However, it has been difficult to stabilize the strength and flame retardancy of plastic parts because the physical properties of recycled materials have deteriorated due to deterioration and dirt, and the types of waste equipment and the amount collected are not constant. The following are examples of technologies related to the use of polystyrene-based recycled materials.
本発明は、リサイクル材含有率が高く、未使用のスチレン系樹脂組成物と同等の強度と難燃性を有するスチレン系樹脂組成物およびそれからなる成形体を提供することである。 The present invention provides a styrene resin composition having a high content of recycled material and having strength and flame retardancy equivalent to those of an unused styrene resin composition, and a molded product made of the same.
１. Ｎ，Ｎ−ジメチルホルムアミドに溶解分散させた後、レーザー回折法によって粒径分布曲線を測定した時に、下式［１］で計算される粒径分布の標準偏差が２．０〜３．５μｍであるスチレン系リサイクル材を２０〜７０質量％含有するスチレン系樹脂組成物。
粒径分布の標準偏差＝（ｄ８４％−ｄ１６％）／２ ［１］
（ここで、ｄ８４％、ｄ１６％はそれぞれ、累積頻度が８４％、１６％を示す粒径（μｍ）である。）
２．スチレン系リサイクル材のゴム状重合物含有量が、４〜２０質量％である上記１に記載のスチレン系樹脂組成物。
３. スチレン系リサイクル材がポストコンシューマー材である上記１または２に記載のスチレン系樹脂組成物。
４．リン系難燃剤を含有し、Ｖ−２レベルの燃焼性を有する上記１乃至３のいずれかに記載のスチレン系樹脂組成物。
1. After dissolving and dispersing in N, N-dimethylformamide, when the particle size distribution curve is measured by the laser diffraction method, the standard deviation of the particle size distribution calculated by the following formula [1] is 2.0 to 3. A styrene-based resin composition containing 20 to 70% by mass of a styrene-based recycled material having a size of 5 μm.
Standard deviation of particle size distribution = (d84% -d16%) / 2 [1]
(Here, d84% and d16% are particle sizes (μm) showing cumulative frequencies of 84% and 16%, respectively.)
2. The styrene-based resin composition according to 1 above, wherein the rubber-like polymer content of the styrene-based recycled material is 4 to 20% by mass.
3. The styrene-based resin composition according to 1 or 2 above, wherein the styrene-based recycled material is a post-consumer material.
4. The styrene-based resin composition according to any one of 1 to 3 above, which contains a phosphorus-based flame retardant and has V-2 level flammability.
本発明で得られる樹脂組成物は、リサイクル材含有率が高いため、再資源化率の向上に貢献することができる。また、耐衝撃性に優れるため、家電やＯＡ機器のプラスチック部品に使用可能である。 Since the resin composition obtained in the present invention has a high content of recycled materials, it can contribute to an improvement in the recycling rate. Moreover, since it has excellent impact resistance, it can be used for plastic parts of home appliances and OA equipment.
本発明において使用するスチレン系リサイクル材とは、スチレン系樹脂を含む再生材のことであり、プレコンシューマー材及びポストコンシューマー材のどちらを用いても構わない。プレコンシューマー材とは、スチレン系樹脂製品の生産工程で発生した端材や不良品、及び売れ残ったり品質保証期間を過ぎたりして出荷前に廃棄されたスチレン系樹脂製品を回収して再利用する材料である。ポストコンシューマー材とは、一度市場に出荷され、消費者の使用が終了した後で回収して再利用する材料である。本発明では、環境負荷の小さな製品を製造し、グリーン購入や再資源化率の向上を推進する観点から、スチレン系樹脂組成物中のスチレン系リサイクル材は、ポストコンシューマー材であることが好ましい。ポストコンシューマー材として好適なスチレン系樹脂の具体例としては、発泡スチロール、押出加工したシート、容器、包装材、ＣＤ・ＭＤなどの記録媒体のケース、ボビン、ハンガーなどの雑貨、電気機器及びＯＡ機器のプラスチック部品などが挙げられる。 The styrene-based recycled material used in the present invention is a recycled material containing a styrene-based resin, and either a pre-consumer material or a post-consumer material may be used. Pre-consumer materials are scraps and defective products generated in the production process of styrene resin products, and styrene resin products that are left unsold or have passed the quality guarantee period and are discarded before shipment and reused. It is a material. Post-consumer materials are materials that are once shipped to the market and then collected and reused after they have been used by consumers. In the present invention, the styrene-based recycled material in the styrene-based resin composition is preferably a post-consumer material from the viewpoint of producing a product having a small environmental load and promoting green purchasing and improvement of the recycling rate. Specific examples of styrene-based resins suitable as post-consumer materials include styrofoam, extruded sheets, containers, packaging materials, cases for recording media such as CDs and MDs, miscellaneous goods such as bobbins and hangers, electrical equipment, and OA equipment. Examples include plastic parts.
リサイクル材に含まれるスチレン系樹脂とは、芳香族ビニル化合物を重合して得られるものであり、必要に応じて共役ジエン系ゴム状重合体を加えてゴム変性を行ったものでもよい。重合方法としては、塊状重合法、塊状・懸濁二段重合法、溶液重合法等が公知であり、いずれの方法で製造されたものでも使用可能である。芳香族ビニル化合物系単量体としては、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン等の公知のものが挙げられるが、好ましくはスチレンである。また、これらの芳香族ビニル化合物系単量体と共重合可能なアクリロニトリル、（メタ）アクリル酸、（メタ）アクリル酸エステル等と、スチレン系単量体の共重合体であっても良い。さらにジビニルベンゼン等の架橋剤をスチレン系単量体に対し添加して重合したものも含まれる。 The styrene-based resin contained in the recycled material is obtained by polymerizing an aromatic vinyl compound, and may be rubber-modified by adding a conjugated diene-based rubber-like polymer, if necessary. As the polymerization method, a lumpy polymerization method, a lumpy / suspension two-stage polymerization method, a solution polymerization method and the like are known, and any of the methods produced can be used. Examples of the aromatic vinyl compound-based monomer include known ones such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene, and styrene is preferable. Further, it may be a copolymer of acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, etc., which can be copolymerized with these aromatic vinyl compound-based monomers, and a styrene-based monomer. Further, a cross-linking agent such as divinylbenzene is added to a styrene-based monomer and polymerized.
スチレン系樹脂のゴム変性に用いる共役ジエン系ゴム状重合体としては、ポリブタジエン、スチレン−ブタジエンのランダムまたはブロック共重合体、ポリイソプレン、ポリクロロプレン、スチレン−イソプレンのランダム、ブロック又はグラフト共重合体、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴムなどが挙げられるが、特にポリブタジエン、スチレン−ブタジエンのランダム、ブロック又はグラフト共重合体が好ましい。また、これらは一部水素添加されていても差し支えない。 As the conjugated diene rubber-like polymer used for rubber modification of styrene resin, polybutadiene, styrene-butadiene random or block copolymer, polyisoprene, polychloroprene, styrene-isoprene random, block or graft copolymer, etc. Examples thereof include ethylene-propylene rubber and ethylene-propylene-diene rubber, but polybutadiene and styrene-butadiene random, block or graft copolymers are particularly preferable. In addition, these may be partially hydrogenated.
このようなスチレン系樹脂の例として、ポリスチレン（ＧＰＰＳ）、ゴム変性ポリスチレン（ＨＩＰＳ）、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン共重合体）、ＡＳ樹脂（アクリロニトリル−スチレン共重合体）、ＭＳ樹脂（メチルメタクリレート−スチレン共重合体）、ＡＡＳ樹脂（アクリロニトリル−アクリルゴム−スチレン共重合体）、ＡＥＳ樹脂（アクリロニトリル−エチレンプロピレン−スチレン共重合体）等が挙げられる。この中では、テレビ・エアコン等の家電のプラスチック部品、またはコピー機等のＯＡ機器のプラスチック部品等から回収されるゴム変性ポリスチレンが、樹脂組成物の耐衝撃性を高くすることができるため、特に好ましい。 Examples of such styrene-based resins include polystyrene (GPPS), rubber-modified polystyrene (HIPS), ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), and MS resin (methyl). Memethacrylate-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylenepropylene-styrene copolymer) and the like. Among these, rubber-modified polystyrene recovered from plastic parts of home appliances such as televisions and air conditioners, or plastic parts of OA equipment such as copiers can improve the impact resistance of the resin composition, and thus in particular. preferable.
本発明におけるスチレン系リサイクル材は、スチレン系樹脂以外の添加物、例えば難燃剤、染顔料、着色防止剤、滑剤、酸化防止剤、老化防止剤、光安定剤、帯電防止剤、充填剤、結晶化核剤、相溶化剤、酸化チタンやカーボンブラック等の着色剤などを含んでいても良い。 The styrene-based recycled material in the present invention includes additives other than styrene-based resins, such as flame retardants, dyes and pigments, colorants, lubricants, antioxidants, antioxidants, light stabilizers, antistatic agents, fillers, and crystals. It may contain a crystallization agent, a compatibilizer, a colorant such as titanium oxide or carbon black.
本発明では、スチレン系樹脂組成物の耐衝撃性と難燃性を安定させる目的から、樹脂組成物の原料となるスチレン系リサイクル材のゴム状重合体及び不純物粒子の粒径分布を管理する。スチレン系リサイクル材は、未使用のスチレン系樹脂とは異なり、配合剤や汚れに由来する不純物粒子を含んでいたり、ゴム状重合体の粒子径が異なる複数の材料が混合されていたりするため、未使用のスチレン系樹脂よりも、有機溶媒に溶解分散させた時の粒子径分布が広い。 In the present invention, for the purpose of stabilizing the impact resistance and flame retardancy of the styrene-based resin composition, the particle size distribution of the rubber-like polymer and the impurity particles of the styrene-based recycled material which is the raw material of the resin composition is controlled. Unlike unused styrene-based resins, styrene-based recycled materials contain impurity particles derived from compounding agents and stains, and multiple materials with different particle sizes of rubber-like polymers are mixed. The particle size distribution when dissolved and dispersed in an organic solvent is wider than that of an unused styrene resin.
スチレン系リサイクル材の粒径分布（粒径の頻度分布曲線）は、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）２０ｇに対して、リサイクル材のペレットまたは粉砕品８０〜１２０ｍｇを加え、超音波振動を１５分間以上与えて、超音波で振動させた状態で白濁溶液をサンプリングを行い、スターラーを用いてセル内で撹拌しながらレーザーを照射させて、レーザー回折・散乱法によって測定する。分布曲線は、複数のピークを有していても構わない。 For the particle size distribution (particle size frequency distribution curve) of the styrene-based recycled material, 80 to 120 mg of pellets or crushed product of the recycled material was added to 20 g of N, N-dimethylformamide (DMF), and ultrasonic vibration was applied to 15 g. The cloudy solution is sampled in a state where it is given for a minute or more and vibrated by ultrasonic waves, and a laser is irradiated while stirring in the cell using a stirrer, and the measurement is performed by a laser diffraction / scattering method. The distribution curve may have a plurality of peaks.
本発明で使用するスチレン系リサイクル材は、粒径分布の広さの指標となる、下式［２］で計算される粒径分布の標準偏差が２．０〜３．５μｍである。
粒径分布の標準偏差＝（ｄ８４％−ｄ１６％）／２ ［２］
ここで、ｄ８４％、ｄ１６％はそれぞれ、累積頻度が８４％、１６％を示す粒径（μｍ）を表す。粒径分布の標準偏差が、２．０μｍ未満であると耐衝撃性が不十分となる。一方、粒径分布の標準偏差が、３．５μｍを超えると、スチレン系リサイクル材中に異物や汚れが多く混入している可能性があり、樹脂組成物の耐衝撃性や難燃性が低下する可能性がある。
The styrene-based recycled material used in the present invention has a standard deviation of the particle size distribution calculated by the following formula [2], which is an index of the width of the particle size distribution, of 2.0 to 3.5 μm.
Standard deviation of particle size distribution = (d84% -d16%) / 2 [2]
Here, d84% and d16% represent particle sizes (μm) showing cumulative frequencies of 84% and 16%, respectively. If the standard deviation of the particle size distribution is less than 2.0 μm, the impact resistance becomes insufficient. On the other hand, if the standard deviation of the particle size distribution exceeds 3.5 μm, there is a possibility that a large amount of foreign matter and dirt are mixed in the styrene-based recycled material, and the impact resistance and flame retardancy of the resin composition are lowered. there's a possibility that.
スチレン系リサイクル材のゴム状重合体含有量は、サンプルをクロロホルムに溶解させ、一定量の一塩化ヨウ素／四塩化炭素溶液を加え暗所に約１時間放置した後、１５質量％のヨウ化カリウム溶液と純水５０ｍｌを加え、過剰の一塩化ヨウ素を０．１Ｎチオ硫酸ナトリウム／エタノール水溶液で滴定し、付加した一塩化ヨウ素量から算出する。スチレン系リサイクル材のゴム状重合体含有量は、４〜２０質量％が好ましく、４〜８質量％が更に好ましい。ゴム状重合体含有量が４質量％未満であると、樹脂組成物の耐衝撃性が不十分となり、２０質量％を超えると、樹脂組成物の難燃性が低下するため好ましくない。 The rubbery polymer content of the styrene-based recycled material is 15% by mass of potassium iodide after dissolving the sample in chloroform, adding a certain amount of iodine monochloride / carbon tetrachloride solution and leaving it in the dark for about 1 hour. The solution and 50 ml of pure water are added, and excess iodine monochloride is titrated with a 0.1 N sodium thiosulfate / ethanol aqueous solution, and the amount is calculated from the added iodine monochloride amount. The rubber-like polymer content of the styrene-based recycled material is preferably 4 to 20% by mass, more preferably 4 to 8% by mass. If the content of the rubber-like polymer is less than 4% by mass, the impact resistance of the resin composition becomes insufficient, and if it exceeds 20% by mass, the flame retardancy of the resin composition decreases, which is not preferable.
本発明のスチレン系樹脂組成物は、スチレン系リサイクル材に、難燃剤、染顔料、着色防止剤、滑剤、酸化防止剤、老化防止剤、光安定剤、帯電防止剤、充填剤、結晶化核剤、相溶化剤、酸化チタンやカーボンブラック等の着色剤などの添加剤を、用途と要求性能に応じて配合することによって得られる。これらの添加方法は、特に限定されず、公知の方法で添加すれば良い。例えば、スチレン系リサイクル材のペレット加工時に添加する方法や、押出機や成形機を用いて樹脂組成物を混合する工程で添加する方法を適用することができる。 The styrene-based resin composition of the present invention is a styrene-based recycled material, which is a flame retardant, a dye pigment, an antioxidant, a lubricant, an antioxidant, an antioxidant, a light stabilizer, an antistatic agent, a filler, and a crystallization nucleus. It can be obtained by blending additives such as agents, compatibilizers, and colorants such as titanium oxide and carbon black, according to the application and required performance. These addition methods are not particularly limited, and may be added by a known method. For example, a method of adding the styrene-based recycled material at the time of pellet processing or a method of adding the resin composition in a step of mixing the resin composition using an extruder or a molding machine can be applied.
本発明の樹脂組成物は、難燃性が要求される用途で使用できるようにするため、難燃剤を含有することが好ましい。難燃剤としては、臭素系難燃剤、リン系難燃剤、塩素系難燃剤等が挙げられるが、環境配慮の観点から、燃焼時にハロゲン類が発生しないリン系難燃剤を使用することが好ましい。 The resin composition of the present invention preferably contains a flame retardant so that it can be used in applications requiring flame retardancy. Examples of the flame retardant include a brominated flame retardant, a phosphorus flame retardant, a chlorine flame retardant, and the like, but from the viewpoint of environmental consideration, it is preferable to use a phosphorus flame retardant that does not generate halogens during combustion.
臭素系難燃剤としては、トリス（ポリブロモフェノキシ）トリアジン化合物、臭素化ジフェニルアルカン化合物、臭素化フタルイミド化合物、臭素化ポリスチレン、臭素化ポリアクリレート、臭素化ポリフェニレンエーテル、臭素化ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂の分子鎖末端のグリシジル基の一部又は全部を封止した変性物等が挙げられ、トリス（ポリブロモフェノキシ）トリアジン化合物、臭素化ジフェニルアルカン化合物、臭素化フタルイミド化合物が好適に使用される。 As bromine-based flame retardant, tris (polybromophenoxy) triazine compound, brominated diphenylalkane compound, brominated phthalimide compound, brominated polystyrene, brominated polyacrylate, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, bromine Examples thereof include a modified product in which a part or all of the glycidyl group at the end of the molecular chain of the bisphenol A type epoxy resin is sealed, and a tris (polybromophenoxy) triazine compound, a brominated diphenylalkane compound, and a brominated phthalimide compound are preferable. Used for.
リン系難燃剤としては、赤リン、有機リン酸エステル化合物、ホスファゼン化合物、ホスフィン酸塩類、ホスフォン酸塩類、ホスホルアミド化合物等が挙げられ、特に下記化１で表される芳香族ジオールビス（ジアリールホスフェート）化合物が好適に使用される。 Examples of the phosphorus-based flame retardant include red phosphorus, organic phosphate compounds, phosphazene compounds, phosphinates, phosphonates, phosphoramide compounds and the like, and in particular, aromatic diol bis (diaryl phosphate) compounds represented by the following formula 1. Is preferably used.
芳香族ジオールビス（ジアリールホスフェート）化合物としては、特にビスフェノールＡビス（ジアリールホスフェート）化合物、ベンゼンジオールビス（ジアリールホスフェート）化合物から選択された少なくとも一種の縮合リン酸エステルが好ましく用いられる。 As the aromatic diol bis (diaryl phosphate) compound, at least one condensed phosphate ester selected from a bisphenol A bis (diaryl phosphate) compound and a benzenediol bis (diaryl phosphate) compound is preferably used.
本発明で使用するビスフェノールＡビス（ジアリールホスフェート）化合物は、上記化２の（Ｘ５）で表される化合物である。 The bisphenol A bis (diaryl phosphate) compound used in the present invention is the compound represented by (X5) of Chemical formula 2 above.
ビスフェノールＡビス（ジアリールホスフェート）化合物として具体的には、ビスフェノールＡのビス（ジフェニルホスフェート）、ビス（ジトリルホスフェート）、（ジキシレニルホスフェート）化合物等が挙げられるが、好ましくは、ビスフェノールＡビス（ジフェニルホスフェート）化合物である。 Specific examples of the bisphenol A bis (diaryl phosphate) compound include bis (diphenyl phosphate), bis (ditril phosphate), and (dixylenyl phosphate) compounds of bisphenol A, and bisphenol A bis (diphenyl phosphate) is preferable. It is a diphenyl phosphate) compound.
本発明で使用するベンゼンジオールビス（ジアリールホスフェート）化合物は、上記化２の（Ｘ１）、（Ｘ２）、又は（Ｘ３）から選ばれる化合物である。 The benzenediol bis (diaryl phosphate) compound used in the present invention is a compound selected from (X1), (X2), or (X3) of Chemical formula 2 above.
ベンゼンジオールビス（ジアリールホスフェート）化合物として具体的には、ヒドロキノン、レゾルシノール、カテコール等のビス（ジフェニルホスフェート）、ビス（ジトリルホスフェート）、（ジキシレニルホスフェート）化合物等が挙げられるが、好ましくはレゾルシノールビス（ジフェニルホスフェート）である。 Specific examples of the benzenediol bis (diaryl phosphate) compound include bis (diphenyl phosphate) such as hydroquinone, resorcinol and catechol, bis (ditril phosphate) and (dixylenyl phosphate) compounds, and resorcinol is preferable. Bis (diphenyl phosphate).
難燃剤の添加量について特に制限はないが、スチレン系樹脂組成物中に３〜３０質量％の範囲で用いることが好ましい。難燃剤が３質量％未満では十分な難燃性を確保できず、３０質量％より多いと耐熱性が低下する。 The amount of the flame retardant added is not particularly limited, but it is preferably used in the range of 3 to 30% by mass in the styrene resin composition. If the amount of the flame retardant is less than 3% by mass, sufficient flame retardancy cannot be ensured, and if it is more than 30% by mass, the heat resistance is lowered.
本発明のスチレン系樹脂組成物の混合方法は、特に限定されず、公知の混合技術を適用することができる。例えば、ミキサー型混合機、Ｖ型他ブレンダー、及びタンブラー型混合機等の混合装置を用いて、各種原料を予め混合しておき、その混合物を溶融混練することによって、均一な樹脂組成物を製造することができる。溶融混練装置も、特に限定されないが、例えばバンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等が挙げられる。更に、押出機等の溶融混練装置の途中から難燃剤等の添加剤を別途添加する方法もある。 The method for mixing the styrene-based resin composition of the present invention is not particularly limited, and a known mixing technique can be applied. For example, a uniform resin composition is produced by mixing various raw materials in advance using a mixing device such as a mixer-type mixer, a V-type other blender, and a tumbler-type mixer, and melt-kneading the mixture. can do. The melt-kneading apparatus is also not particularly limited, and examples thereof include a Banbury type mixer, a kneader, a roll, a single-screw extruder, a special single-screw extruder, and a twin-screw extruder. Further, there is also a method of separately adding an additive such as a flame retardant from the middle of a melt kneading device such as an extruder.
本発明のスチレン系樹脂組成物には、スチレン系リサイクル材だけでなく、未使用のスチレン系樹脂を配合しても良い。ただし、スチレン系樹脂組成物中のスチレン系リサイクル材の含有量は２０〜７０質量％である。リサイクル材の含有量が２０質量％未満であると、樹脂組成物が環境対応製品の認定基準を満たさない場合がある。また、リサイクル材の含有量が７０質量％よりも多いと、難燃剤等の添加剤の配合量が制限されるため、樹脂組成物の難燃性が不十分になる。 The styrene-based resin composition of the present invention may contain not only a styrene-based recycled material but also an unused styrene-based resin. However, the content of the styrene-based recycled material in the styrene-based resin composition is 20 to 70% by mass. If the content of the recycled material is less than 20% by mass, the resin composition may not meet the certification criteria for environmentally friendly products. On the other hand, if the content of the recycled material is more than 70% by mass, the amount of the additive such as the flame retardant is limited, so that the flame retardancy of the resin composition becomes insufficient.
本発明のスチレン系樹脂組成物は、米国認証機関アンダーライターズ・ラボラトリーズ・インク（ＵＬ）が定めているＵＬ９４試験において、Ｖ−２レベル以上の難燃性を有することが好ましい。Ｖ−２レベル以上の難燃性を有すると、電気機器やＯＡ機器等の様々なプラスチック部品に使用できるため好ましい。 The styrene resin composition of the present invention preferably has a flame retardancy of V-2 level or higher in the UL94 test defined by the US certification body Underwriters Laboratories, Inc. (UL). It is preferable that it has a flame retardancy of V-2 level or higher because it can be used for various plastic parts such as electrical equipment and OA equipment.
以下に本発明を実施例及び比較例によって詳しく説明するが、本発明はこれらに限定されるものではない。 The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
＜スチレン系リサイクル材＞
（Ａ−１）；家電から回収されたポリスチレン
ポストコンシューマー材含有率１００質量％、粒径分布の標準偏差２．４μｍ、ゴム状重合体含有量６．９質量％
（Ａ−２）；雑貨及び発泡スチロールから回収されたポリスチレン
ポストコンシューマー材含有率１００質量％、粒径分布の標準偏差２．７μｍ、ゴム状重合体含有量４．６質量％
（Ａ−３）；ＯＡ機器から回収されたポリスチレン
ポストコンシューマー材含有率１００％、粒径分布の標準偏差３．７μｍ、ゴム状重合体含有量７．０質量％
（Ａ−４）；リール及び容器から回収されたポリスチレン
ポストコンシューマー材含有率１００％、粒径分布の標準偏差１．７μｍ、ゴム状重合体含有量５．６質量％
＜ポリフェニレンエーテル樹脂＞
（Ｂ）；三菱エンジニアリングプラスチックス株式会社製、商品名「ＰＸ１００Ｆ」、極限粘度０．３８ｄｌ／ｇ
＜難燃剤＞
（Ｃ）；ビスフェノールＡビス−ジフェニルホスフェート、大八化学工業株式会社製、商品名「ＣＲ−７４１」、リン含有量８．９質量％
<Styrene-based recycled material>
(A-1); Polystyrene post-consumer material content recovered from home appliances 100% by mass, standard deviation of particle size distribution 2.4 μm, rubber-like polymer content 6.9% by mass
(A-2); Polystyrene post-consumer material content recovered from miscellaneous goods and Styrofoam 100% by mass, standard deviation of particle size distribution 2.7 μm, rubber-like polymer content 4.6% by mass
(A-3); Polystyrene post-consumer material content recovered from OA equipment 100%, standard deviation of particle size distribution 3.7 μm, rubber-like polymer content 7.0% by mass
(A-4); Polystyrene post-consumer material content recovered from reels and containers 100%, standard deviation of particle size distribution 1.7 μm, rubber-like polymer content 5.6% by mass
<Polyphenylene ether resin>
(B); manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name "PX100F", ultimate viscosity 0.38 dl / g
<Flame retardant>
(C); Bisphenol A bis-diphenyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd., trade name "CR-741", phosphorus content 8.9% by mass
［スチレン系樹脂組成物の調製］
表１及び表２に配合処方を示す。難燃剤以外の試薬を、ヘンシェルミキサー（日本コークス工業株式会社製、ＦＭ２０Ｂ）にて予備混合した後、二軸押出機（東芝機械株式会社製、ＴＥＭ２６ＳＳ）に供給した。更に、難燃剤を、押出機の中間部から供給し、押出機の先端ノズルから排出されたストランドを、水冷してからペレタイザーへ導き、ペレットを作製した。押出機のシリンダー温度は２００（搬送部位）〜３００℃（混練部位）であり、スクリュー回転数は９００ｒｐｍであり、押出速度は５０ｋｇ／ｈである。
[Preparation of styrene resin composition]
Tables 1 and 2 show the formulation. Reagents other than the flame retardant were premixed with a Henschel mixer (manufactured by Nippon Coke Industries, Ltd., FM20B) and then supplied to a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM26SS). Further, the flame retardant was supplied from the middle part of the extruder, and the strands discharged from the tip nozzle of the extruder were water-cooled and then guided to a pelletizer to prepare pellets. The cylinder temperature of the extruder is 200 (conveyed portion) to 300 ° C. (kneaded portion), the screw rotation speed is 900 rpm, and the extrusion speed is 50 kg / h.
［ゴム状重合体含有量］
スチレン系リサイクル材のサンプルをクロロホルムに溶解させ、一定量の一塩化ヨウ素／四塩化炭素溶液を加え暗所に約１時間放置後、１５質量％のヨウ化カリウム溶液と純水５０ｍｌを加え、過剰の一塩化ヨウ素を０．１Ｎチオ硫酸ナトリウム／エタノール水溶液で滴定し、付加した一塩化ヨウ素量から算出した。
[Rubber-like polymer content]
A sample of styrene-based recycled material is dissolved in chloroform, a certain amount of iodine monochloride / carbon tetrachloride solution is added, and the mixture is left in a dark place for about 1 hour, then 15% by mass of potassium iodide solution and 50 ml of pure water are added, and excess is added. Iodine monochloride was titrated with a 0.1 N sodium thiosulfate / ethanol aqueous solution and calculated from the amount of added iodine monochloride.
［粒径分布の標準偏差］
ポリプロピレン製ディスポーサルカップに、スチレン系リサイクル材のサンプル２０ｍｇと、Ｎ，Ｎ−ジメチルホルムアミド２０ｍＬを入れて、超音波振動を１５分間かけて溶解・分散させた。振動させた状態で、サンプルの白濁液の一部を採取し、測定用セルに入れ、回転子で撹拌させながら、レーザー回折式粒径測定装置（（株）堀場製作所製、ＬＡ−９１０）を用いて粒径の頻度分布曲線を測定し、下式［３］により、粒径分布の標準偏差を計算した。
粒径分布の標準偏差＝（ｄ８４％−ｄ１６％）／２ ［１］
（ここで、ｄ８４％、ｄ１６％はそれぞれ、累積頻度が８４％、１６％を示す粒径（μｍ）である。）
[Standard deviation of particle size distribution]
A sample of styrene-based recycled material (20 mg) and N, N-dimethylformamide (20 mL) were placed in a polypropylene disposable cup, and ultrasonic vibration was dissolved and dispersed over 15 minutes. In a vibrated state, a part of the cloudy liquid of the sample was collected, placed in a measuring cell, and while being stirred with a rotor, a laser diffraction type particle size measuring device (LA-910 manufactured by Horiba Seisakusho Co., Ltd.) was used. The frequency distribution curve of the particle size was measured using the above formula, and the standard deviation of the particle size distribution was calculated by the following equation [3].
Standard deviation of particle size distribution = (d84% -d16%) / 2 [1]
(Here, d84% and d16% are particle sizes (μm) showing cumulative frequencies of 84% and 16%, respectively.)
［シャルピー衝撃強さ］
本発明におけるスチレン系樹脂組成物の耐衝撃性はシャルピー衝撃値によりで評価した。
スチレン系樹脂組成物のペレットを温度７０℃×３時間で加熱乾燥後、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）を用いて、シリンダー温度２２０℃、金型温度４５℃にて、ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）を成形した。上記ダンベル片の中央部より切り出し、切削でノッチ（タイプＡ、ｒ＝０．２５ｍｍ）を入れた試験片を用いて、ＪＩＳ Ｋ ７１１１−１に準拠して行った。
[Charpy impact strength]
The impact resistance of the styrene resin composition in the present invention was evaluated by the Charpy impact value.
After heating and drying the pellets of the styrene resin composition at a temperature of 70 ° C. for 3 hours, the cylinder temperature is 220 ° C. and the mold temperature is 45 ° C. using an injection molding machine (J100EP manufactured by Japan Steel Works, Ltd.). Then, the type A test piece (dumbbell) described in JIS K 7139 was molded. A test piece cut out from the center of the dumbbell piece and cut with a notch (type A, r = 0.25 mm) was used in accordance with JIS K 711-1.
［難燃性］
射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）を用いて、長さ１２７ｍｍ×幅１２．７ｍｍ×厚さ２．５ｍｍの燃焼用試験片を成形した。米国アンダーライターズ・ラボラトリーズ社のサブジェクト９４号の垂直燃焼試験方法（ＵＬ９４）に基づき、燃焼試験を行った。この試験方法でＶ−２に満たなかった場合は不合格とした。
[Flame retardance]
A combustion test piece having a length of 127 mm, a width of 12.7 mm and a thickness of 2.5 mm was molded using an injection molding machine (J100E-P, manufactured by Japan Steel Works, Ltd.). A combustion test was conducted based on the vertical combustion test method (UL94) of Subject 94 of Underwriters Laboratories, USA. If this test method did not meet V-2, it was rejected.
下記表１に結果を示した。 The results are shown in Table 1 below.
表１より、本発明のスチレン系樹脂組成物は、Ｖ−２レベル以上の難燃性を有しており、粒径分布が２．０μｍより小さいスチレン系リサイクル材、または３．５μｍを超えるスチレン系リサイクル材を含有する樹脂組成物よりも、耐衝撃性に優れていることがわかる。 From Table 1, the styrene-based resin composition of the present invention has a flame retardancy of V-2 level or higher, and is a styrene-based recycled material having a particle size distribution smaller than 2.0 μm, or styrene having a particle size distribution of more than 3.5 μm. It can be seen that the impact resistance is superior to that of the resin composition containing the recycled material.
本発明のスチレン系樹脂組成物は、リサイクル材を利用しているため環境負荷が低く、耐衝撃性に優れているため、ＯＡ機器や家電部品等の家電分野での利用が可能である。
Since the styrene-based resin composition of the present invention uses a recycled material, it has a low environmental load and is excellent in impact resistance, so that it can be used in the field of home appliances such as OA equipment and home appliance parts.
Claims (4)
The styrene-based resin composition according to any one of claims 1 to 3, which contains a phosphorus-based flame retardant and has a flammability of V-2 level or higher.
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| JP3652438B2 (en) * | 1996-05-09 | 2005-05-25 | 新日鐵化学株式会社 | Rubber-modified styrenic resin composition |
| JPH11166088A (en) * | 1997-09-30 | 1999-06-22 | Mitsui Chem Inc | Production of rubber-modified styrene-based resin composition |
| JP2007162028A (en) * | 1999-03-10 | 2007-06-28 | Suzuka Fuji Xerox Co Ltd | Method for recycling resin-molded product |
| JP3514188B2 (en) * | 1999-09-28 | 2004-03-31 | 旭化成ケミカルズ株式会社 | Injection molded container with excellent sealing strength |
| JP4558123B2 (en) * | 2000-02-10 | 2010-10-06 | 電気化学工業株式会社 | Rubber-modified styrenic resin composition and injection-molded product thereof |
| JP4663092B2 (en) * | 2000-10-12 | 2011-03-30 | 電気化学工業株式会社 | Molded products for insulated containers |
| JP2005225960A (en) * | 2004-02-12 | 2005-08-25 | Nippon Polystyrene Kk | Rubber-modified styrenic resin composition and molded article obtained by using the same |
| JP4556503B2 (en) * | 2004-06-09 | 2010-10-06 | ユーエムジー・エービーエス株式会社 | Recycled styrene resin composition and molded product |
| JP2006137808A (en) * | 2004-11-10 | 2006-06-01 | Asahi Kasei Chemicals Corp | Recovered styrenic resin-containing polyphenylene ether resin composition |
| JP2006307022A (en) * | 2005-04-28 | 2006-11-09 | Nippon Polystyrene Kk | Thermoplastic resin sheet and film |
| JP5448325B2 (en) * | 2006-11-14 | 2014-03-19 | 旭化成ケミカルズ株式会社 | Styrenic resin sheet |
| JP5529572B2 (en) * | 2010-02-09 | 2014-06-25 | 東洋スチレン株式会社 | Rubber-modified styrenic resin composition and sheet and container using the same |
| JP2015000892A (en) * | 2013-06-13 | 2015-01-05 | 株式会社リコー | Regenerated resin composition |
| JP2015016630A (en) * | 2013-07-11 | 2015-01-29 | パナソニック株式会社 | Thermoplastic recycled resin and compact using thermoplastic recycled resin |
| JP2016030807A (en) * | 2014-07-30 | 2016-03-07 | 東洋スチレン株式会社 | Styrenic flame-retardant resin composition and molding comprising the same |
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