JP4391254B2 - Light-scattering thermoplastic resin composition - Google Patents
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- JP4391254B2 JP4391254B2 JP2004016856A JP2004016856A JP4391254B2 JP 4391254 B2 JP4391254 B2 JP 4391254B2 JP 2004016856 A JP2004016856 A JP 2004016856A JP 2004016856 A JP2004016856 A JP 2004016856A JP 4391254 B2 JP4391254 B2 JP 4391254B2
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- 239000011342 resin composition Substances 0.000 title claims description 19
- 238000000149 argon plasma sintering Methods 0.000 title claims description 12
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims description 26
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920001971 elastomer Polymers 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000005060 rubber Substances 0.000 claims description 15
- 239000004417 polycarbonate Substances 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 229920000515 polycarbonate Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000002834 transmittance Methods 0.000 claims description 11
- 238000012662 bulk polymerization Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 28
- 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 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 9
- 229920001893 acrylonitrile styrene Polymers 0.000 description 9
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000010557 suspension polymerization reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 2
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 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 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- -1 aromatic vinyl compound Chemical class 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- STSRVFAXSLNLLI-UHFFFAOYSA-N penta-2,4-dienenitrile Chemical compound C=CC=CC#N STSRVFAXSLNLLI-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Description
本発明は、流動性が良く、光散乱性、耐熱性等が優れた成形体が得られる光散乱性熱可塑性樹脂組成物、及びその成形体に関する。 The present invention relates to a light-scattering thermoplastic resin composition from which a molded article having good fluidity, excellent light scattering properties, heat resistance, and the like is obtained, and the molded article thereof.
芳香族ポリカーボネート樹脂は、良好な耐衝撃性を有する強靭なエンジニアリング熱可塑性樹脂であるが、流動性が低いため加工が難しいことが一般に知られている。芳香族ポリカーボネート樹脂の強靭性と耐衝撃性を保持したまま、その流動性を向上させるため、他のポリマー性改良材をブレンドする様々な試みが従来からなされている。 Aromatic polycarbonate resins are tough engineering thermoplastic resins with good impact resistance, but are generally known to be difficult to process due to their low fluidity. Various attempts have been made in the past to blend other polymeric modifiers in order to improve the fluidity of the aromatic polycarbonate resin while maintaining its toughness and impact resistance.
特許文献１、２、非特許文献１では、ＡＢＡ（アクリロニトリル-ブタジエンースチレ
ン共重合体）を芳香族ポリカーボネートとブレンドすることで低コストの樹脂組成物が提案されている。
Patent Documents 1 and 2 and Non-Patent Document 1 propose low-cost resin compositions by blending ABA (acrylonitrile-butadiene-styrene copolymer) with an aromatic polycarbonate.
特許文献３では、芳香族ポリカーボネートとして、重平均分子量３５，０００以上の芳香族ポリカーボネートを用いることで、芳香族ビニル化合物とからなる組成物から得られる成形体の耐衝撃性を向上させた樹脂組成物が提案されている。 In patent document 3, the resin composition which improved the impact resistance of the molded object obtained from the composition which consists of an aromatic vinyl compound by using an aromatic polycarbonate with a weight average molecular weight of 35,000 or more as an aromatic polycarbonate. Things have been proposed.
特許文献４では、芳香族ポリカーボネートの分子量を一定以上に特定し、分散相を形成する芳香族ビニルーシアン化ビニル系樹脂の分子量を特定範囲に限定することにより、流動性、耐衝撃性を向上させた樹脂組成物が提案されている。 In Patent Document 4, the flowability and impact resistance are improved by specifying the molecular weight of the aromatic polycarbonate above a certain level and limiting the molecular weight of the aromatic vinyl-vinyl cyanide resin forming the dispersed phase to a specific range. Resin compositions have been proposed.
特許文献５では、芳香族ポリカーボネート樹脂、アクリロニトリル-ブタジエン―スチ
レングラフト共重合体、及びアクリロニトリルースチレンオリゴマー含有量の低下したアクリロニトリルースチレン共重合体をブレンドした樹脂組成物により、流動性と延性を向上させることが提案されている。
In Patent Document 5, fluidity and ductility are improved by a resin composition obtained by blending an aromatic polycarbonate resin, an acrylonitrile-butadiene-styrene graft copolymer, and an acrylonitrile-styrene copolymer having a reduced acrylonitrile-styrene oligomer content. It has been proposed to let
さらに、芳香族ポリカーボネートとＡＢＳの樹脂組成物は、ＡＢＳに含まれるゴムのため、組成物が黒いことが一般的に知られている。この場合、芳香族ポリカーボネートとブレンドするＡＢＳとして、ゴム粒径の小さいＡＢＳを用い、添加量を少なくすればほぼ透明となるが、流動性が損なわれる。 Further, it is generally known that the resin composition of aromatic polycarbonate and ABS is black because of the rubber contained in ABS. In this case, as ABS to be blended with the aromatic polycarbonate, ABS having a small rubber particle diameter is used, and if the addition amount is reduced, it becomes almost transparent, but fluidity is impaired.
一方、芳香族ポリカーボネートとアクリロニトリルースチレン共重合体の樹脂組成物の色相については、各々の樹脂の屈折率が違うため不透明になる。透明性を上げるため、添加するアクリロニトリルースチレン共重合体の重量比率を低くすると、成形体の剛性や耐薬品性が損なわれる。 On the other hand, the hue of the resin composition of aromatic polycarbonate and acrylonitrile-styrene copolymer becomes opaque because the refractive index of each resin is different. If the weight ratio of the acrylonitrile-styrene copolymer to be added is lowered in order to increase transparency, the rigidity and chemical resistance of the molded article are impaired.
特許文献５では、芳香族ポリカーボネート及びアクリロニトリルースチレン共重合体として低い重量平均分子量体を用ることにより、流動性を改善しているが、熱変形温度の低下を招いており、樹脂組成物の色相や透明性についてはなにも言及されていない。
本発明は、流動性が良く、耐薬品性、耐熱性、耐衝撃性等をバランスよく保持しつつ、半透明で光を散乱させやすい成形体が得られる光散乱性熱可塑性樹脂組成物、及びその成形体を提供することを課題とする。 The present invention is a light-scattering thermoplastic resin composition that has a good fluidity, can maintain a good balance of chemical resistance, heat resistance, impact resistance, etc., and can obtain a molded article that is translucent and easily scatters light, and It is an object to provide the molded body.
本発明者は、以下のとおり、樹脂組成物の組成を最適なものに選択することで、得られた成形体の全光線透過率を所定範囲に設定することができるようになり、その結果、成形体に半透明で光を散乱させやすい性質を付与できることを見出し、本発明を完成した。 The present inventor can set the total light transmittance of the obtained molded product within a predetermined range by selecting the optimal composition of the resin composition as follows. The present inventors have found that the molded product can be imparted with a translucent property that easily scatters light.
本発明は、課題の解決手段として、（Ａ）芳香族ポリカーボネート７０〜９０重量％、（Ｂ）芳香族ビニル単量体成分及びシアン化ビニル単量体成分を含む共重合体３〜１５重量％、（Ｃ）芳香族ビニル単量体成分、シアン化ビニル単量体成分及びゴム重合体成分を含む共重合体５〜１５重量％を含有する樹脂組成物であり、
樹脂組成物の厚み３ｍｍの成形体における全光線透過率が４５〜７０％の範囲である光散乱性熱可塑性樹脂組成物、並びにその成形体を提供する。
As a means for solving the problems, the present invention provides (A) an aromatic polycarbonate of 70 to 90% by weight, and (B) a copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component of 3 to 15% by weight. (C) a resin composition containing 5 to 15% by weight of a copolymer containing an aromatic vinyl monomer component, a vinyl cyanide monomer component and a rubber polymer component,
Provided are a light-scattering thermoplastic resin composition having a total light transmittance of 45 to 70% in a molded product having a thickness of 3 mm, and a molded product thereof.
本発明の組成物は、流動性が良く、その成形体は、引張強さ、曲げ強さ、曲げ弾性率、衝撃強度等の機械的強度が優れており、耐熱性も優れている。更に、成形体は、光線透過率を低下させずに光散乱性を発現させることができるので、LED（発光ダイオード）など
の光源の光でも全体が光るという性質を付与できる。このため、携帯電話やＰＤＡ（個人携帯端末）のフリップ、アンテナ、カーオーディオのスイッチ、オーナメントなどに適用した場合、暗所での操作を著しく向上させることができる。
The composition of the present invention has good fluidity, and the molded product has excellent mechanical strength such as tensile strength, bending strength, bending elastic modulus, impact strength, and heat resistance. Furthermore, since the molded body can exhibit light scattering properties without lowering the light transmittance, it can be imparted with the property that the entire body can shine even with light from a light source such as an LED (light emitting diode). For this reason, when applied to flips, antennas, car audio switches, ornaments, etc. of cellular phones and PDAs (personal portable terminals), operations in the dark can be remarkably improved.
（Ａ）成分である芳香族ポリカーボネートは、その製造方法は制限されず、各種のものを使用できる。例えば、塩化メチレンなどの溶剤中で公知の酸受容体と二価フェノールなどのカーボネート前駆体とを反応させるホスゲン法、二価フェノールとジフェニルカーボネートとを溶剤を用いない溶融エステル交換法などによって得られる芳香族ポリカーボネート樹脂が挙げられる。
二価フェノールとしてはビスフェノール類が挙げられ、特に、２，２−ビス（４−ヒドロキシフェニル）プロパンが好ましい。
The manufacturing method of the aromatic polycarbonate as the component (A) is not limited, and various types can be used. For example, it can be obtained by a phosgene method in which a known acid acceptor is reacted with a carbonate precursor such as a dihydric phenol in a solvent such as methylene chloride, a melt transesterification method in which a dihydric phenol and diphenyl carbonate are not used. An aromatic polycarbonate resin is mentioned.
Examples of the dihydric phenol include bisphenols, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.
（Ａ）成分の芳香族ポリカーボネートは、機械的強度及び成形性の観点からその重量平均分子量が３８，０００〜５３，０００のものが好ましく、中でも重量平均分子量が４０，０００〜５０，０００の範囲のものがさらに好ましい。なお、本発明において、重量平均分子量は、ゲルパーミエーションクロマトグラフィーを用いて、ＴＨＦを溶媒として標準ポリスチレン換算で求めた値である。 The aromatic polycarbonate as component (A) preferably has a weight average molecular weight of 38,000 to 53,000 from the viewpoint of mechanical strength and moldability, and the weight average molecular weight is preferably in the range of 40,000 to 50,000. Are more preferred. In addition, in this invention, a weight average molecular weight is the value calculated | required by standard polystyrene conversion using THF as a solvent using gel permeation chromatography.
（Ｂ）成分は、芳香族ビニル単量体成分とシアン化ビニル単量体成分を含む共重合体である。 The component (B) is a copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component.
芳香族ビニル単量体成分は、例えば、スチレン、α―メチルスチレン、パラ−メチルスチレン、ビニルキシレン、ジブロモスチレン、フルオロスチレン、エチルスチレン、ビニルナフタレン等を挙げることができ、好ましくはスチレンである。芳香族ビニル単量体成分は、２種以上の混合物でもよい。 Examples of the aromatic vinyl monomer component include styrene, α-methylstyrene, para-methylstyrene, vinylxylene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and preferably styrene. The aromatic vinyl monomer component may be a mixture of two or more.
シアン化ビニル単量体成分は、例えば、アクリロニトリル、メタクリロニトリル等を挙
げることができ、好ましくはアクリロニトリルである。シアン化ビニル単量体成分は、２種以上の混合物でもよい。
Examples of the vinyl cyanide monomer component include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred. The vinyl cyanide monomer component may be a mixture of two or more.
（Ｂ）成分中の芳香族ビニル単量体成分の含有量は、好ましくは６５〜８０重量％、より好ましくは６５〜７７重量％、さらに好ましくは７０〜７５重量％である。 (B) Content of the aromatic vinyl monomer component in a component becomes like this. Preferably it is 65 to 80 weight%, More preferably, it is 65 to 77 weight%, More preferably, it is 70 to 75 weight%.
（Ｂ）成分中のシアン化ビニル単量体成分の含有量は、好ましくは４０〜２０重量％、より好ましくは３５〜２３重量％、さらに好ましくは３０〜２５重量％である。 (B) Content of the vinyl cyanide monomer component in a component becomes like this. Preferably it is 40-20 weight%, More preferably, it is 35-23 weight%, More preferably, it is 30-25 weight%.
（Ｂ）成分中、芳香族ビニル単量体成分とシアン化ビニル単量体成分の含有量が上記範囲内であると、成形体の耐薬品性が向上し、組成物の流動性も向上し、成形体の着色もない。 In the component (B), when the content of the aromatic vinyl monomer component and the vinyl cyanide monomer component is within the above range, the chemical resistance of the molded body is improved and the fluidity of the composition is also improved. There is no coloring of the molded body.
（Ｂ）成分の共重合体は、機械的強度及び耐薬品性の観点から、その重量平均分子量（Ｍｗ）が９０，０００〜１８０，０００の範囲が好ましく、中でも、重量平均分子量が９０，０００〜１７０，０００の範囲がさらに好ましい。 The copolymer of the component (B) preferably has a weight average molecular weight (Mw) in the range of 90,000 to 180,000 from the viewpoint of mechanical strength and chemical resistance, and among them, the weight average molecular weight is 90,000. A range of ˜170,000 is more preferred.
（Ｂ）成分である共重合体の好ましい例としては、アクリロニトリルースチレン共重合体が挙げられる。 Preferable examples of the copolymer as component (B) include acrylonitrile-styrene copolymers.
（Ｂ）成分の共重合体の製造方法としては、塊状重合、溶液重合、塊状懸濁重合、懸濁重合、乳化重合などが用いられるが、残留溶剤、分散剤、乳化剤等の不純物の少ないか又は実質的に含まない塊状重合法のアクリロニトリルースチレン共重合体が好ましい。 As a method for producing the copolymer of component (B), bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, emulsion polymerization, etc. are used, but there are few impurities such as residual solvent, dispersant, emulsifier, etc. Alternatively, an acrylonitrile-styrene copolymer of a bulk polymerization method substantially not containing is preferable.
溶液重合、塊状懸濁重合、懸濁重合、乳化重合などで用いられる溶剤、分散剤、乳化剤等が含まれていると、（Ｂ）成分の共重合体の特性（熱変形温度、弾性率）に悪影響を及ぼすだけでなく、組成物を製造する際にそれらの影響で耐熱安定性が低下し、着色するので好ましくない。 If the solvent, dispersant, emulsifier, etc. used in solution polymerization, bulk suspension polymerization, suspension polymerization, emulsion polymerization, etc. are included, the characteristics of the copolymer of component (B) (heat distortion temperature, elastic modulus) In addition to adversely affecting the heat resistance, when the composition is produced, the heat resistance stability is lowered due to these influences, and coloring is not preferable.
（Ｃ）成分は、芳香族ビニル単量体成分、シアン化ビニル単量体成分及びゴム重合体成分を含む共重合体である。 Component (C) is a copolymer including an aromatic vinyl monomer component, a vinyl cyanide monomer component, and a rubber polymer component.
芳香族ビニル単量体成分は、例えば、スチレン、α―メチルスチレン、パラ−メチルスチレン、ビニルキシレン、ジブロモスチレン、フルオロスチレン、エチルスチレン、ビニルナフタレン等を挙げることができ、好ましくはスチレンである。芳香族ビニル単量体成分は、２種以上の混合物でもよい。 Examples of the aromatic vinyl monomer component include styrene, α-methylstyrene, para-methylstyrene, vinylxylene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, and preferably styrene. The aromatic vinyl monomer component may be a mixture of two or more.
シアン化ビニル単量体成分は、例えば、アクリロニトリル、メタクリロニトリル等を挙げることができ、好ましくはアクリロニトリルである。シアン化ビニル単量体成分は、２種以上の混合物でもよい。 Examples of the vinyl cyanide monomer component include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred. The vinyl cyanide monomer component may be a mixture of two or more.
ゴム状重体成分は、例えば、ポリブタジエン、ブタジエン―スチレン共重合体、ブタジエン―アクリロニトリル共重合体、ポリイソプレンなどを挙げることができ、好ましくはポリブタジエンである。ゴム状重合体は２種以上の混合物でもよい。 Examples of the rubbery heavy component include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polyisoprene, and preferably polybutadiene. The rubbery polymer may be a mixture of two or more.
（Ｃ）成分中のゴム状重合体成分の含有量は、好ましくは３〜３０重量％、より好ましくは８〜２５重量％、さらに好ましくは１０〜２２重量％である。ゴム状重合体成分の含有量が３重量％以上であると、組成物から得られる成形体の耐衝撃性が向上し、３０重量％以下であると組成物の流動性が向上する。 The content of the rubbery polymer component in the component (C) is preferably 3 to 30% by weight, more preferably 8 to 25% by weight, and still more preferably 10 to 22% by weight. When the content of the rubbery polymer component is 3% by weight or more, the impact resistance of the molded product obtained from the composition is improved, and when it is 30% by weight or less, the fluidity of the composition is improved.
（Ｃ）成分の共重合体の製造方法は、例えば、塊状重合法、懸濁重合法、乳化重合法、塊状―懸濁重合法などが用いられるが、分散剤、乳化剤等の不純物の少ないか又は実質的に含まない塊状重合法が最適である。 As the method for producing the copolymer of component (C), for example, bulk polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization, etc. are used. Alternatively, a bulk polymerization process that is substantially free of is optimal.
懸濁重合法、乳化重合法、塊状―懸濁重合法などで用いられる分散剤、乳化剤等が含まれていると、（Ｃ）成分の共重合体の機械的特性（耐衝撃性）に悪影響を及ぼすだけでなく、組成物を製造する際にそれらの影響で耐熱安定性が低下し、焼けが発生する。 If the dispersant, emulsifier, etc. used in suspension polymerization, emulsion polymerization, bulk-suspension polymerization, etc. are included, the mechanical properties (impact resistance) of the copolymer of component (C) will be adversely affected. In addition, when the composition is produced, the heat resistance stability is reduced due to the influence of the effect, and burning occurs.
（Ｃ）成分の共重合体の分散ゴム相の粒子径は、好ましくは１０μｍ以下、より好ましくは１０μｍ〜０．１μｍ、さらに好ましくは５μｍ〜０．１μｍである。粒子径が１０μｍ以下であると、組成物から得られる成形体の透明性が高くなり、所定の全光線透過率を付与できる。 The particle diameter of the dispersed rubber phase of the copolymer (C) is preferably 10 μm or less, more preferably 10 μm to 0.1 μm, and still more preferably 5 μm to 0.1 μm. When the particle diameter is 10 μm or less, the molded product obtained from the composition has high transparency, and can give a predetermined total light transmittance.
（Ｃ）成分の共重合体のグラフト化率は、好ましくは２０〜６６％、より好ましくは２０〜２８％、さらに好ましくは２０〜２５％である。グラフト化率が２０％以上であると、組成物から得られる成形体の耐衝撃性が向上し、６０％以下であると、組成物の流動性が低下する。 The grafting rate of the copolymer of component (C) is preferably 20 to 66%, more preferably 20 to 28%, and still more preferably 20 to 25%. When the grafting rate is 20% or more, the impact resistance of the molded product obtained from the composition is improved, and when it is 60% or less, the fluidity of the composition is lowered.
本発明の組成物には、本発明の課題を解決できる範囲内で、潤滑剤、離型剤、帯電防止剤、難燃剤、着色剤などの各種添加剤を適宜組み合わせて添加することができる。 Various additives such as a lubricant, a release agent, an antistatic agent, a flame retardant, and a colorant can be appropriately combined and added to the composition of the present invention within a range that can solve the problems of the present invention.
本発明の組成物は、厚み３ｍｍの成形体における全光線透過率が、４５〜７０％、好ましくは４８〜６５％、より好ましくは５０〜６３％である。全光線透過率が４５％以上であることにより、組成物から得られる成形体に、適度な透明性と光散乱性を付与できる。 The composition of the present invention has a total light transmittance of 45 to 70%, preferably 48 to 65%, more preferably 50 to 63% in a molded product having a thickness of 3 mm. When the total light transmittance is 45% or more, moderate transparency and light scattering can be imparted to the molded product obtained from the composition.
本発明の組成物は、組成物全体のゴム含有量が、好ましくは０．８〜１．９５重量％、より好ましくは０．８５〜１．９５重量％、さらに好ましくは０．９〜１．９５重量％である。ゴム含有量が０．８重量％以上であると、組成物から得られる成形体の耐衝撃性が向上し、１．９５重量％以下であると、成形体に所定の全光線透過率を付与できる。 In the composition of the present invention, the rubber content of the whole composition is preferably 0.8 to 1.95% by weight, more preferably 0.85 to 1.95% by weight, and still more preferably 0.9 to 1. 95% by weight. When the rubber content is 0.8% by weight or more, the impact resistance of the molded product obtained from the composition is improved, and when it is 1.95% by weight or less, a predetermined total light transmittance is imparted to the molded product. it can.
本発明の組成物は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び他の添加剤を適宜秤量し、混合して得られる。組成物は、ドライブレンドのまま目的の成形体にすることもできるが、溶融混合してペレットなどの粒状物にすることが好ましい。 The composition of the present invention is obtained by appropriately weighing and mixing the components (A), (B), (C) and other additives. The composition can be formed into a desired molded body as it is by dry blending, but is preferably melt-mixed into a granular material such as pellets.
本発明の組成物は、射出成形法、押出成形法、熱成形法などの各種成形法を適用して、例えば、携帯電話やＰＤＡ（個人携帯端末）のフリップ、アンテナ等の各部品、照明カバー、カーオーディオのスイッチ、オーナメント等に成形することができる。 The composition of the present invention is applied to various molding methods such as an injection molding method, an extrusion molding method, a thermoforming method, etc., for example, flips of mobile phones and PDAs (personal portable terminals), parts such as antennas, lighting covers, etc. Can be molded into car audio switches, ornaments, etc.
（１）使用成分
（Ａ）成分
ＰＣ：ポリカーボネート，Ｓ2000Ｆ（重量平均分子量４４，０００，三菱エンジニアリングプラスチック（株）製）
（Ｂ）成分
ＡＳ−１：塊状重合によるアクリロニトリル−スチレン共重合体（重量平均分子量１５０，０００；アクリロニトリル含有量２５重量％，ダイセル化学工業（株）製）
ＡＳ−２：塊状重合によるアクリロニトリル−スチレン共重合体（重量平均分子量１５０，０００；アクリロニトリル含有量３０重量％，ダイセル化学工業（株）製）
（Ｃ）成分
ＡＢＳ−１：乳化重合によるアクリロニトリル−ブタジエン−スチレン共重合体，ＤＰ６１１（テクノポリマー（株）製）
ＡＢＳ−２：塊状重合によるアクリロニトリル−ブタジエン−スチレン共重合体，ＡＴ０５（日本Ａ＆Ｌ（株）製）
その他の成分
耐熱安定剤：ヒンダードフェノール系耐熱安定剤及びリン系耐熱安定剤
（２）測定方法
〔分散ゴム相の粒子径〕
スライスした試験片をエッチング処理して光硬化性エポキシ樹脂で包み、光硬化させた後、クライオミクロトームで超薄切片を作成し、四酸化ルテニウムで染色後、この切片のゴムの粒子径を透過型電子顕微鏡で測定し、３個の平均値を求めた。
(1) Components used (A) Component PC: Polycarbonate, S2000F (weight average molecular weight 44,000, manufactured by Mitsubishi Engineering Plastics)
(B) Component AS-1: Acrylonitrile-styrene copolymer by bulk polymerization (weight average molecular weight 150,000; acrylonitrile content 25% by weight, manufactured by Daicel Chemical Industries, Ltd.)
AS-2: Acrylonitrile-styrene copolymer by bulk polymerization (weight average molecular weight 150,000; acrylonitrile content 30% by weight, manufactured by Daicel Chemical Industries, Ltd.)
(C) Component ABS-1: Acrylonitrile-butadiene-styrene copolymer by emulsion polymerization, DP611 (manufactured by Technopolymer Co., Ltd.)
ABS-2: Acrylonitrile-butadiene-styrene copolymer by bulk polymerization, AT05 (manufactured by Nippon A & L Co., Ltd.)
Other components Heat resistance stabilizer: hindered phenol heat resistance stabilizer and phosphorus heat resistance stabilizer (2) Measuring method [Particle size of dispersed rubber phase]
The sliced specimen is etched and wrapped with a photo-curable epoxy resin. After photo-curing, an ultra-thin section is created with a cryomicrotome, stained with ruthenium tetroxide, and the rubber particle size of this section is transmitted. It measured with the electron microscope and calculated | required three average values.
〔組成物中の全ゴム量〕
ＡＢＳ中のゴム含有量から計算した。
[Total amount of rubber in the composition]
Calculated from the rubber content in the ABS.
〔ＭＦＲ〕
２４０℃、荷重５ｋｇで測定した。
[MFR]
The measurement was performed at 240 ° C. and a load of 5 kg.
〔引張強さ〕
厚み４ｍｍの試験片を用い、ＵＣＴ−１Ｔ（オリエンテック株式会社製）で、ＩＳＯ５２９に準じて測定した。
〔Tensile strength〕
Using a test piece having a thickness of 4 mm, measurement was performed according to ISO 529 using UCT-1T (Orientec Co., Ltd.).
〔曲げ強さ〕
厚み４ｍｍの試験片を用い、ＵＴＭ−５Ｔ（東洋ボールドウィン株式会社製）で、ＩＳＯ１７８に準じて測定した。
[Bending strength]
Using a test piece having a thickness of 4 mm, measurement was performed according to ISO178 with UTM-5T (manufactured by Toyo Baldwin Co., Ltd.).
〔曲げ弾性率〕
厚み４ｍｍの試験片を用い、ＵＴＭ−５Ｔ（東洋ボールドウィン株式会社製）で、ＩＳＯ１７８に準じて測定した。
(Flexural modulus)
Using a test piece having a thickness of 4 mm, measurement was performed according to ISO178 with UTM-5T (manufactured by Toyo Baldwin Co., Ltd.).
〔熱変形温度（ＨＤＴ）〕
厚み４ｍｍの試験片を用い、ＵＴＭ−５Ｔ（東洋ボールドウィン株式会社製）で、ＩＳＯ７５に準じて測定した。
[Heat deformation temperature (HDT)]
Using a test piece having a thickness of 4 mm, measurement was performed according to ISO75 using UTM-5T (manufactured by Toyo Baldwin Co., Ltd.).
〔シャルピー衝撃強度〕
厚み４ｍｍの試験片を用い、シャルピー衝撃試験機（東洋精機株式会社製）で、ＩＳＯ１７９に準じて測定した。
[Charpy impact strength]
Using a test piece having a thickness of 4 mm, measurement was performed according to ISO 179 with a Charpy impact tester (manufactured by Toyo Seiki Co., Ltd.).
〔全光線透過率〕
厚み３ｍｍの試験片を用い、ヘーズメーター ＨＧＭ−２Ｄ（スガ試験機株式会社製）により測定した。
[Total light transmittance]
Using a test piece having a thickness of 3 mm, measurement was performed with a haze meter HGM-2D (manufactured by Suga Test Instruments Co., Ltd.).
実施例１〜４、比較例１、２
表１に示す各成分（数値は重量部表示。但し、耐熱安定剤は（Ａ）、（Ｂ）、（Ｃ）成分の合計１００重量部に対する重量部表示。）をブレンダーで１分間混合した後、二軸押出機（ＴＥＭ３５Ｂ東芝機械株式会社製）のホッパーに加え、２７０℃で押し出し、ペレット化して本発明の組成物を得た。このペレットをＳＨ−１００（住友重機株式会社製）を用いて射出成形し、上記した各測定用の試験片を製造した。
Examples 1 to 4, Comparative Examples 1 and 2
After mixing each component shown in Table 1 (numerical values are expressed in parts by weight. However, the heat stabilizer is expressed in parts by weight with respect to 100 parts by weight of the total of the components (A), (B), and (C)). In addition to the hopper of a twin screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd.), the composition of the present invention was obtained by extrusion at 270 ° C. and pelletizing. This pellet was injection-molded using SH-100 (manufactured by Sumitomo Heavy Industries, Ltd.) to produce the above test pieces for each measurement.
表１から明らかなとおり、流動性が良いので射出成形等の公知の成形法による成形が容易である。また、組成物から得られた成形体は着色もなく、各種機械的性質、耐熱性が優れており、全光線透過率が４５〜７５％の範囲内であるので、適度な透明性と光散乱性を付与できるので、上記したような用途への適用ができる。比較例１、２では、全光線透過率が低いので、透明性及び光散乱性が十分ではない。 As is apparent from Table 1, since the fluidity is good, molding by a known molding method such as injection molding is easy. In addition, the molded product obtained from the composition is not colored, has excellent mechanical properties and heat resistance, and has a total light transmittance in the range of 45 to 75%. Therefore, it can be applied to the use as described above. In Comparative Examples 1 and 2, since the total light transmittance is low, transparency and light scattering are not sufficient.
Claims (4)
（Ｂ）芳香族ビニル単量体成分及びシアン化ビニル単量体成分を含む共重合体であって、分散剤や乳化剤を使用しない塊状重合法で製造された共重合体３〜１５重量％、
（Ｃ）芳香族ビニル単量体成分、シアン化ビニル単量体成分及びゴム重合体成分を含む共重合体であって、分散剤や乳化剤を使用しない塊状重合法で製造された共重合体５〜１５重量％を含有する樹脂組成物であり、
樹脂組成物全体のゴム含有量が０．８〜１．９５重量％であり、
樹脂組成物の厚み３ｍｍの成形体における全光線透過率が４５〜７０％の範囲である光散乱性熱可塑性樹脂組成物。 (A) 70 to 90% by weight of aromatic polycarbonate,
(B) a copolymer comprising an aromatic vinyl monomer component and a vinyl cyanide monomer component, the copolymer being produced by a bulk polymerization method using no dispersant or emulsifier, 3 to 15% by weight,
(C) Copolymer 5 comprising an aromatic vinyl monomer component, a vinyl cyanide monomer component and a rubber polymer component, which is produced by a bulk polymerization method using no dispersant or emulsifier A resin composition containing -15% by weight,
The rubber content of the entire resin composition is 0.8 to 1.95% by weight,
A light-scattering thermoplastic resin composition having a total light transmittance of 45 to 70% in a molded product having a thickness of 3 mm.
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