JP2008222932A - Thermoplastic resin, thermoplastic resin composition and optical component - Google Patents
Thermoplastic resin, thermoplastic resin composition and optical component Download PDFInfo
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- JP2008222932A JP2008222932A JP2007065514A JP2007065514A JP2008222932A JP 2008222932 A JP2008222932 A JP 2008222932A JP 2007065514 A JP2007065514 A JP 2007065514A JP 2007065514 A JP2007065514 A JP 2007065514A JP 2008222932 A JP2008222932 A JP 2008222932A
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 53
- 230000003287 optical effect Effects 0.000 title claims abstract description 47
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 150000002825 nitriles Chemical group 0.000 claims abstract description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- -1 sebacic acid diester compound Chemical class 0.000 claims description 7
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 238000010521 absorption reaction Methods 0.000 abstract description 28
- 238000012360 testing method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 5
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- JQKBRFGZVVHKPN-UHFFFAOYSA-N 2,2-ditert-butylhexaneperoxoic acid Chemical compound CCCCC(C(C)(C)C)(C(C)(C)C)C(=O)OO JQKBRFGZVVHKPN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- OWQPOVKKUWUEKE-UHFFFAOYSA-N 1,2,3-benzotriazine Chemical compound N1=NN=CC2=CC=CC=C21 OWQPOVKKUWUEKE-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SKMNWICOBCDSSQ-UHFFFAOYSA-N 2-[4-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2,6,6-tetramethylpiperidin-1-yl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCN2C(CC(CC2(C)C)OC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(C)C)=C1 SKMNWICOBCDSSQ-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- RAZWNFJQEZAVOT-UHFFFAOYSA-N 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound O=C1N(CCCCCCCCCCCC)C(=O)NC11CC(C)(C)N(C(C)=O)C(C)(C)C1 RAZWNFJQEZAVOT-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000003825 pressing Methods 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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Abstract
Description
本発明は、透明性、耐光性に優れた光学用部品に適した特定のスチレン系熱可塑性樹脂、スチレン系熱可塑性樹脂組成物、及び、該樹脂あるいは該樹脂組成物を用いた光学部品に関するものである。本願の光学部品とは、シートからなるフレネルレンズ、レンチキユラーレンズ、背面透過型プロジェクションテレビや液晶テレビ等の前面パネル、拡散板等であり、これらに必要な特性は、透明性、剛性、耐久性、低吸水性、良加工性、耐薬品性（二次加工性）、低コストである。本発明は、これらを技術的に満たす特定のスチレン系熱可塑性樹脂、スチレン系熱可塑性樹脂組成物、および該樹脂あるいは該樹脂組成物からなる光学部品を提供するものである。 The present invention relates to a specific styrene-based thermoplastic resin suitable for optical parts having excellent transparency and light resistance, a styrene-based thermoplastic resin composition, and an optical component using the resin or the resin composition. It is. The optical components of the present application are a Fresnel lens made of a sheet, a lenticular lens, a front panel of a rear transmission type projection television or a liquid crystal television, a diffusion plate, and the necessary properties are transparency, rigidity, durability , Low water absorption, good workability, chemical resistance (secondary workability), and low cost. The present invention provides a specific styrenic thermoplastic resin, a styrenic thermoplastic resin composition, and an optical component comprising the resin or the resin composition that technically satisfy these requirements.
近年テレビの大型化に伴い従来の直視型ブラウン管テレビから背面透過型プロジェクションテレビ、ＰＤＰテレビ、液晶テレビの需要が増大している。これらには、光学的に透明な樹脂製のスクリーン、拡散板、導光板等が使われている。例えば、プロジェクションテレビのスクリーンの構成は、一般的にはテレビ内部から順にフレネルレンズ、レンチキュラーレンズのレンズ基板の２枚構成の樹脂製レンズからなり、場合によっては、該スクリーンの前に前面パネルが設けられることもある。 In recent years, the demand for back-transmission projection televisions, PDP televisions, and liquid crystal televisions has increased from conventional direct-view CRT televisions as televisions have become larger. For these, optically transparent resin screens, diffusion plates, light guide plates, and the like are used. For example, the screen of a projection television is generally composed of two resin lenses, a Fresnel lens and a lens substrate of a lenticular lens, in order from the inside of the television. In some cases, a front panel is provided in front of the screen. Sometimes.
一般に、光学部品特にフレネルレンズ、レンチキュラーレンズ等に使用される可能性のある透明樹脂としては、アクリル樹脂、スチレンーアクリル系共重合体、ポリカーボネート、ポリスチレン、スチレン−アクリロニトリル共重合体及び環状オレフィン等があげられる。具体的には、それらの部品には、従来からアクリル樹脂が使用されてきた。しかし、近年のテレビの大型化に伴うスクリーン自体の大型化により、吸水率が大きいアクリル樹脂を使用していることに起因するスクリーンの反りが目立つようになり、結果的に画面が歪む等の問題が発生した。この問題を改善する為に、最近では吸水率の小さいスチレン−アクリル系共重合体が使用されている（例えば、特許文献１参照。）。 In general, transparent resins that may be used for optical components, particularly Fresnel lenses and lenticular lenses, include acrylic resins, styrene-acrylic copolymers, polycarbonate, polystyrene, styrene-acrylonitrile copolymers, and cyclic olefins. can give. Specifically, acrylic resin has been conventionally used for these components. However, due to the enlargement of the screen itself accompanying the recent enlargement of televisions, the warpage of the screen due to the use of acrylic resin with a large water absorption rate becomes conspicuous, resulting in problems such as screen distortion. There has occurred. In order to improve this problem, a styrene-acrylic copolymer having a low water absorption rate has recently been used (see, for example, Patent Document 1).
また、フレネルレンズ、レンチキュラーレンズには、従来はアクリル樹脂が使用されていた。しかし、上記したようにアクリル樹脂は吸水による寸法変化が大きい。テレビの大型化に伴いこれらレンズも大きくなっており、吸水によりレンズの寸法が変化することで、特にレンズの中心部が膨らむように反りが発生する。その結果、焦点ボケ、色再現性の低下、２重像といった現象による映像の画質低下の問題が起こった。これらの現象を解決するために、該レンズの材質としてアクリル樹脂に比べて吸水率の小さいスチレンーアクリル系共重合体が採用され主流となっている。 Conventionally, acrylic resin has been used for Fresnel lenses and lenticular lenses. However, as described above, the acrylic resin has a large dimensional change due to water absorption. As the size of televisions increases, the size of these lenses also increases. When the dimensions of the lenses change due to water absorption, warping occurs particularly as the center of the lens swells. As a result, there has been a problem of image quality deterioration due to phenomena such as defocusing, color reproducibility deterioration, and double image. In order to solve these phenomena, a styrene-acrylic copolymer having a smaller water absorption rate than that of an acrylic resin has been adopted as a material of the lens.
しかしながら、最近は更に大型化の薄型テレビが開発されており、スチレン−アクリル系共重合体でも吸水による寸法変化による反りの発生が問題となり始めている。この問題を解決するために、メタクリル酸メチルの含有量を下げたスチレン−アクリル系共重合体の開発が試みられている。しかし、メタクリル酸メチルの含有量を下げると、吸水による寸法変化は小さくすることはできるが、該樹脂基板を使ってフレネルレンズ等レンズを制作する際に基板の上に塗布される紫外線硬化型樹脂との接着性が不十分となり、フレネルレンズ等を加工できないという問題がある。 Recently, however, larger-sized thin televisions have been developed, and even with styrene-acrylic copolymers, warpage due to dimensional changes due to water absorption has begun to be a problem. In order to solve this problem, an attempt has been made to develop a styrene-acrylic copolymer having a reduced methyl methacrylate content. However, if the content of methyl methacrylate is lowered, the dimensional change due to water absorption can be reduced. However, when producing a lens such as a Fresnel lens using the resin substrate, an ultraviolet curable resin applied on the substrate. Inadequate adhesiveness and inability to process a Fresnel lens or the like.
一方、スチレン−アクリロニトリル共重合体に関しては、従来は、単に共重合体として記載されているのみであり、その具体的な組成等についての検討はなされていない（例えば、特許文献２〜６参照。）。
特許文献７には、スチレン−アクリロニトリル共重合体の具体的な開示があるが、光学学用途への応用に関しては一切記載されていない。
Patent Document 7 has a specific disclosure of a styrene-acrylonitrile copolymer, but does not describe any application to optical applications.
本発明は、上記問題点を鑑みてなされたもので、光学的に透明であり、耐光性に優れ、吸水率および寸法変化率が小さく、なお且つ紫外線硬化型樹脂との接着性に優れる従来のスチレン系樹脂に比較してそれらのバランスに優れた特定のスチレン系熱可塑性樹脂、スチレン系熱可塑性樹脂組成物、および、該樹脂あるいは樹脂組成物製の光学部品を提供することを目的とするものである。また、大型の映像スクリーンの吸水によるスクリーンの寸法変化を改良することを目的とする。 The present invention has been made in view of the above problems, and is optically transparent, excellent in light resistance, small in water absorption and dimensional change, and excellent in adhesiveness with an ultraviolet curable resin. An object of the present invention is to provide a specific styrene-based thermoplastic resin, a styrene-based thermoplastic resin composition, and an optical component made of the resin or the resin composition, which are superior in balance to styrene-based resins. It is. Another object of the present invention is to improve the dimensional change of the screen due to water absorption of a large image screen.
本発明者らは、上記の目的を達成すべく鋭意検討を進めた結果、以下に記す特定のスチレン系熱可塑性樹脂により上記目的を達成できることを見出し、本発明を完成するに至った。また、該樹脂に更に特定のヒンダードアミン系安定剤を組み合わせた樹脂組成物が、更に優れた特性を有することを見出した。 As a result of diligent studies to achieve the above object, the present inventors have found that the above object can be achieved by the specific styrene-based thermoplastic resin described below, and have completed the present invention. Moreover, it discovered that the resin composition which combined specific hindered amine stabilizer with this resin has the further outstanding characteristic.
即ち、本発明においては、光学特性に優れ、且つ、吸水寸法安定性の高い特定組成の樹脂を見出すことで上記目的を達成し、更にその樹脂に耐光性を更に高める為の安定剤を加えた樹脂組成物が、より優れた特性を有することを見出した。
尚、樹脂の耐光（候）性の向上手法としては、トリアジン系、ベンゾトリアジン系、ベンゾフェノン系等の紫外線吸収剤と安定剤との併用が一般的に取られる。しかし、本発明の用途などの様に、紫外線を照射して紫外線硬化型樹脂を硬化させる場合には、紫外線吸収剤が、照射された紫外線を吸収し硬化反応を阻害し、全く硬化しないか、または硬化しても満足する密着性を発揮できない等の問題が生じるため、紫外線吸収剤との併用は好ましくない。この観点から、本発明においては、紫外線吸収剤を併用しないで耐光（候）性を改善し、かつ接着性を阻害しない安定剤についても鋭意研究を行った。
That is, in the present invention, the above object is achieved by finding a resin having a specific composition which is excellent in optical characteristics and has high water absorption dimensional stability, and a stabilizer for further enhancing light resistance is added to the resin. It has been found that the resin composition has more excellent characteristics.
In addition, as a method for improving the light resistance (weather) of the resin, a combination of a triazine-based, benzotriazine-based, benzophenone-based ultraviolet absorber and a stabilizer is generally used. However, when the ultraviolet curable resin is cured by irradiating ultraviolet rays, such as the use of the present invention, the ultraviolet absorber absorbs the irradiated ultraviolet rays and inhibits the curing reaction, does not cure at all, Or, since problems such as inability to exhibit satisfactory adhesion even after curing occur, the combined use with an ultraviolet absorber is not preferred. From this point of view, in the present invention, diligent research was also conducted on a stabilizer that improves light resistance (weather) without using an ultraviolet absorber and does not inhibit adhesiveness.
本発明の目的は、以下の特定のスチレン系熱可塑性樹脂、スチレン系熱可塑性樹脂組成物及び、光学部品により達成された。
１． 芳香族ビニル単位（Ａ）、及び、不飽和ニトリル単位（Ｂ）からなるスチレン系熱可塑性樹脂であり、かつ、樹脂全体に対する成分（Ｂ）の含有量の平均値（Ｘ）が８≦Ｘ≦２７重量％であり、
前記成分（Ｂ）を（Ｘ−５）重量％以下有する共重合体、及び、
前記成分（Ｂ）を（Ｘ＋５）重量％以上有する共重合体が、それぞれ０．５〜５重量％であるスチレン系熱可塑性樹脂。
２. 前記成分（Ａ）と前記成分（Ｂ）の合計量１００重量部に対して、アルキル（メタ）アクリレートからなる群より選ばれる少なくとも１種の成分（Ｃ）を、０〜２０重量部含有する項１に記載のスチレン系熱可塑性樹脂。
３. 前記成分（Ｂ）を（Ｘ−５）重量％以下有する共重合体、及び、前記成分（Ｂ）を（Ｘ＋５）重量％以上有する共重合体の含有量が、それぞれ０．５〜３．５重量％である項１または２に記載のスチレン系熱可塑性樹脂。
４. 項１〜３いずれか一項に記載のスチレン系熱可塑性１００重量部に対して、ヒンダードアミン系安定剤（Ｄ）を０．０５〜２．０重量部含有するスチレン系熱可塑性樹脂組成物。
The object of the present invention has been achieved by the following specific styrenic thermoplastic resin, styrenic thermoplastic resin composition, and optical component.
1. The average value (X) of the content of the component (B) with respect to the whole resin is a styrene-based thermoplastic resin composed of an aromatic vinyl unit (A) and an unsaturated nitrile unit (B), and 8 ≦ X ≦ 27% by weight,
A copolymer having the component (B) not more than (X-5)% by weight, and
Styrenic thermoplastic resins in which the copolymer having the component (B) (X + 5) wt% or more is 0.5 to 5 wt%, respectively.
2. 0 to 20 parts by weight of at least one component (C) selected from the group consisting of alkyl (meth) acrylates with respect to 100 parts by weight of the total amount of the component (A) and the component (B) Item 2. The styrenic thermoplastic resin according to Item 1.
3. The content of the copolymer having (X-5) wt% or less of the component (B) and the copolymer having (X + 5) wt% or more of the component (B) is 0.5 to 3 respectively. Item 3. The styrenic thermoplastic resin according to Item 1 or 2, which is 5% by weight.
4. A styrenic thermoplastic resin composition containing 0.05 to 2.0 parts by weight of a hindered amine stabilizer (D) with respect to 100 parts by weight of the styrenic thermoplastic according to any one of items 1 to 3. .
５. 成分（Ｄ）が、セバシン酸ジエステル化合物である項４に記載のスチレン系熱可塑性樹脂組成物。
６. 成分（Ｄ）が、ビス(２,２,６,６−テトラメチル−４−ピペリジル)セバケートである項４に記載のスチレン系熱可塑性樹脂組成物。
７. 項１〜３のいずれか一項に記載のスチレン系熱可塑性樹脂、あるいは、項４〜６のいずれか一項に記載のスチレン系熱可塑性樹脂組成物からなる光学部品。
８. 光学部品が押出成形シートからなる項７に記載の光学部品。
９. 光学部品が背面透過型プロジェクションテレビ用スクリーンである項７に記載の光学部品。
１０. 光学部品が背面透過型プロジェクションテレビ用スクリーンのフレネルレンズ及びレンチキュラーレンズのレンズ基板である項７に記載の光学部品。
１１. 光学部品が薄型テレビ用前面パネル基板である項７に記載の光学部品。
１２. 光学部品が液晶テレビ用拡散板である項７に記載の光学部品。
5. The styrenic thermoplastic resin composition according to item 4, wherein the component (D) is a sebacic acid diester compound.
6. The styrenic thermoplastic resin composition according to item 4, wherein component (D) is bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
7. An optical component comprising the styrenic thermoplastic resin according to any one of items 1 to 3 or the styrenic thermoplastic resin composition according to any one of items 4 to 6.
8. The optical component according to item 7, wherein the optical component is an extruded sheet.
9. The optical component according to item 7, wherein the optical component is a rear transmission projection television screen.
10. The optical component according to item 7, wherein the optical component is a lens substrate of a Fresnel lens or a lenticular lens of a screen for rear transmission type projection television.
11. The optical component according to item 7, wherein the optical component is a front panel substrate for a flat-screen television.
12. The optical component according to item 7, wherein the optical component is a diffusion plate for a liquid crystal television.
本発明の光学用スチレン系熱可塑性樹脂及びスチレン系熱可塑性樹脂組成物は、優れた光学特性、優れた耐光性、優れた吸水寸法安定性及び紫外線硬化型樹脂との優れた接着性を有しており、家電機器、ＯＡ機器等の光学部品等の用途に使用することが可能となる。 The optical styrene-based thermoplastic resin and the styrene-based thermoplastic resin composition of the present invention have excellent optical properties, excellent light resistance, excellent water absorption dimensional stability, and excellent adhesion to an ultraviolet curable resin. Therefore, it can be used for optical parts such as home appliances and OA devices.
本発明について、以下具体的に説明する。
本発明のスチレン系熱可塑性樹脂は、芳香族ビニル単位（Ａ）、及び、不飽和ニトリル単位（Ｂ）からなり、樹脂成分全体に対する成分（Ｂ）の含有量の平均値（Ｘ）が８≦Ｘ≦２７重量％である。
好ましくは１０≦Ｘ≦２３重量％であり、更に好ましくは１５≦Ｘ≦２２重量％であり、特に好ましくは１６≦Ｘ≦２１重量％である。
The present invention will be specifically described below.
The styrenic thermoplastic resin of the present invention comprises an aromatic vinyl unit (A) and an unsaturated nitrile unit (B), and the average value (X) of the content of the component (B) with respect to the entire resin component is 8 ≦ X ≦ 27% by weight.
Preferably, 10 ≦ X ≦ 23% by weight, more preferably 15 ≦ X ≦ 22% by weight, and particularly preferably 16 ≦ X ≦ 21% by weight.
上記の成分（Ｂ）の含有量は、本発明の樹脂を光学部品用途のレンズ基材に用いる場合の、レンズ基材に接着させる紫外線硬化型樹脂との接着性の観点から８重量％以上であり、飽和吸水時の寸法変化率および黄色度（ＹＩ）の観点から２７重量％以下である。
成分（Ｂ）の平均値（Ｘ）とは、組成分布を持つ成分（Ｂ）の平均値である。測定方法としては、まず、元素分析よりアクリロニトリル含有量（ＡＮ％）が既知の標準アクリロニトリルースチレン共重合体を用いて、液体クロマトグラフを測定し、ピークトップのリテンションタイム（ＲＴ）を求める。各標準ポリマーのＡＮ％とピークトップのＲＴをプロットし、ＡＮ％とＲＴの補正曲線とする。次いでサンプルのクロマトグラフを測定し、ＲＴ(i)とピーク強度（ＰＨ(i)）を読み取り、ピーク強度％比（Ｈｉ）を求め、ＡＮ％補正曲線よりＲＴ(i)に対応したＡＮ％を読み取り、式（１）よりＡＮ比(i)を求める。
（ＡＮ比(i)）＝（ＡＮ％(i)）／１００ ・・・ （１）
次に式（２）よりサンプルのＡＮ％を求める。これを平均値（Ｘ）とする。
（ＡＮ％）＝Σ（Ｈｉ）（ＡＮ比(i)） ・・・ （２）
Content of said component (B) is 8 weight% or more from an adhesive viewpoint with the ultraviolet curable resin made to adhere to a lens base material in the case of using the resin of this invention for the lens base material of an optical component use. Yes, and is 27% by weight or less from the viewpoint of dimensional change at saturated water absorption and yellowness (YI).
The average value (X) of the component (B) is the average value of the component (B) having a composition distribution. As a measuring method, first, a liquid chromatograph is measured using a standard acrylonitrile-styrene copolymer having a known acrylonitrile content (AN%) by elemental analysis, and a peak top retention time (RT) is obtained. Plot the AN% of each standard polymer and the RT of the peak top to obtain a correction curve of AN% and RT. Next, the chromatograph of the sample is measured, RT (i) and peak intensity (PH (i)) are read, the peak intensity% ratio (Hi) is obtained, and AN% corresponding to RT (i) is calculated from the AN% correction curve. Read the AN ratio (i) from the equation (1).
(AN ratio (i)) = (AN% (i)) / 100 (1)
Next, AN% of a sample is calculated | required from Formula (2). This is the average value (X).
(AN%) = Σ (Hi) (AN ratio (i)) (2)
本発明のスチレン系熱可塑性樹脂は、成分（Ｂ）が（Ｘ−５）重量％以下有する共重合体、及び、成分（Ｂ）を（Ｘ＋５）重量％以上有する共重合体が、それぞれ０．５〜５重量％である事が必要である。また、それぞれの共重合体の含有量を０．５〜４．５重量％とすることが好ましく、それぞれの共重合体の含有量を０．５〜３．５重量％とすることが特に好ましい。
本発明のスチレン系熱可塑性樹脂に用いられる芳香族ビニル単位（Ａ）としては、スチレン、α―メチルスチレン、ビニルトルエン、ジメチルスチレン、ｔ−ブチルスチレン、クロルスチレンなどを挙げることができるが、特にスチレンが好ましい。また、不飽和ニトリル単位（Ｂ）としては、アクリロニトリル、メタクリロニトリルなどを挙げることができるが、特にアクリロニトリルが好ましい。
In the styrenic thermoplastic resin of the present invention, the copolymer having component (B) of (X-5) wt% or less and the copolymer having component (B) of (X + 5) wt% or more are each 0.00%. It must be 5 to 5% by weight. Further, the content of each copolymer is preferably 0.5 to 4.5% by weight, and the content of each copolymer is particularly preferably 0.5 to 3.5% by weight. .
Examples of the aromatic vinyl unit (A) used in the styrenic thermoplastic resin of the present invention include styrene, α-methylstyrene, vinyltoluene, dimethylstyrene, t-butylstyrene, and chlorostyrene. Styrene is preferred. Examples of the unsaturated nitrile unit (B) include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred.
また、本発明のスチレン系熱可塑性樹脂は、成分（Ａ）および／または成分（Ｂ）と共重合可能な単量体を含んでも良い。そのような共重合可能な単量体（Ｃ）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチル（メタ）アクリレート、２−エチルヘキシルメタアクリレート等のアルキル（メタ）アクリレート；アクリル酸、メタクリル酸などの（メタ）アクリル酸；無水マレイン酸等のα、β―不飽和カルボン酸；Ｎ−フェニルマレイミド、Ｎ−メチルマレイミド、Ｎ−シクロヘキシルマレイミド等のマレイミド；グリシジルメタクリレート等のグリシジル基含有単量体が挙げられる。これらの単量体は1種あるいは２種以上を組み合わせて用いることが出来る。これらの中でも、アルキル（メタ）アクリレートが好ましく、ブチルアクリレートが更に好ましい。
成分（Ｃ）の含有量は、成分（Ａ）と成分（Ｂ）との合計量１００重量部に対して０〜２０重量部とすることが好ましく、７〜１５重量部とすることが更に好ましい。
Moreover, the styrenic thermoplastic resin of the present invention may contain a monomer copolymerizable with the component (A) and / or the component (B). Examples of such copolymerizable monomer (C) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl methacrylate; (meth) acrylic acid such as acrylic acid and methacrylic acid; α, β-unsaturated carboxylic acid such as maleic anhydride; N-phenylmaleimide, N-methylmaleimide, N- Maleimide such as cyclohexylmaleimide; glycidyl group-containing monomers such as glycidyl methacrylate. These monomers can be used alone or in combination of two or more. Among these, alkyl (meth) acrylate is preferable and butyl acrylate is more preferable.
The content of the component (C) is preferably 0 to 20 parts by weight, more preferably 7 to 15 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). .
本発明のスチレン系熱可塑性樹脂を得る方法としては、例えば、完全攪拌混合槽に、モノマー、開始剤、溶媒等を連続的にフィードし、連続的に反応槽から抜き出し、熱時、脱揮系で揮発分を除去する方法が挙げられる。脱揮系でのポリマー滞留は極力少なくすることが好ましい。
一般に、スチレン−アクリロニトリル共重合体の反応は、アゼオ組成がアクリロニトリル２４〜２５重量％の範囲にあり、それ以外の組成で重合させると組成分布が広くなり、広い組成分布の共重合体は、透明性が大幅に損なわれるために、従来から種々の工夫がされている。工業的に利用されているのはアクリロニトリル成分がアゼオ組成以上の共重合体であり、これらのスチレンーアクリロニトリル共重合体の製造は、一般的に乳化重合方法、懸濁重合方法及び塊状重合方法が用いられている中で、組成分布を狭くする方法としては、塊状重合における完全混合型反応機が用いる製造方法等が挙げられる。完全混合型反応機を用いて、且つ気層部の存在がない満液状態で重合し、重合後の未反応単量体は、速やかに除去することが好ましい。未反応単量体の除去としては、1段または多段の減圧装置等で行なうことができる。
As a method for obtaining the styrenic thermoplastic resin of the present invention, for example, a monomer, an initiator, a solvent, etc. are continuously fed into a complete stirring and mixing tank, and continuously extracted from the reaction tank. The method of removing a volatile matter by is mentioned. It is preferable to minimize polymer retention in the devolatilization system.
In general, the reaction of styrene-acrylonitrile copolymer has an azeo composition in the range of 24 to 25% by weight of acrylonitrile. When polymerized with other compositions, the composition distribution becomes wide, and a copolymer having a wide composition distribution is transparent. In order to greatly impair the performance, various devices have been conventionally devised. Industrially used are copolymers having an acrylonitrile component having an azeo composition or higher, and these styrene-acrylonitrile copolymers are generally produced by emulsion polymerization, suspension polymerization and bulk polymerization methods. Among the methods used, a method for narrowing the composition distribution includes a production method used by a complete mixing reactor in bulk polymerization. It is preferable to perform polymerization in a full liquid state using a fully mixed reactor and without the presence of a gas layer, and to quickly remove unreacted monomers after polymerization. The removal of the unreacted monomer can be performed with a single-stage or multi-stage decompression device.
本発明のスチレン系熱可塑性樹脂の重量平均分子量としては、スチレン換算分子量で１８５,０００〜２５０,０００の範囲が好ましい。重量平均分子量はゲル浸透クロマトグラフィー（東ソー社製 HLC8220GPC）、カラム（東ソー社製 TSK-GEL G6000HXL-G5000HXL-G5000HXL-G4000HXL-G3000HXL 直列）を用いて測定する。試料 ２０ｍｇ±０．５ｍｇをテトラヒドロフラン １０ｍｌに溶解し、０．４５μｍのフィルターで濾過した。この溶液をカラム温度４０℃に１００μｌ注入し、検出器ＲＩ温度 ４０℃で測定しスチレン換算した値を用いる。 The weight average molecular weight of the styrenic thermoplastic resin of the present invention is preferably in the range of 185,000 to 250,000 in terms of styrene equivalent molecular weight. The weight average molecular weight is measured using gel permeation chromatography (HLC8220GPC manufactured by Tosoh Corporation) and column (TSK-GEL G6000HXL-G5000HXL-G5000HXL-G4000HXL-G3000HXL series manufactured by Tosoh Corporation). A sample 20 mg ± 0.5 mg was dissolved in 10 ml of tetrahydrofuran and filtered through a 0.45 μm filter. 100 μl of this solution is injected at a column temperature of 40 ° C., measured at a detector RI temperature of 40 ° C., and converted into styrene.
次に、本発明の光学部品について説明する。 薄型テレビとしては、背面透過型プロジェクションテレビ（又はリアプロジェクションテレビ）、液晶テレビ、ＰＤＰテレビ等が挙げられるが、本発明の光学部品は、背面透過型プロジェクションテレビ、液晶テレビに用いられる。具体的には、背面透過型プロジェクションテレビおよび液晶テレビなどに用いられるスクリーン（フレネルレンズ、レンチキュラーレンズ）、前面パネル、拡散板、導光板等挙げられる。これらの部品においては、部品が吸水して寸法変化が起こり反りが発生した場合、画像が歪む等の不具合が起こる。よって、これらの光学部品には、吸水率及び寸法変化率が低いことが要求されており、本発明の樹脂を用いることでその要求を満たすことができる。 Next, the optical component of the present invention will be described. Examples of thin televisions include rear transmission projection televisions (or rear projection televisions), liquid crystal televisions, PDP televisions, and the like. The optical component of the present invention is used for rear transmission projection televisions and liquid crystal televisions. Specifically, a screen (Fresnel lens, lenticular lens), a front panel, a diffusion plate, a light guide plate and the like used for a rear transmission type projection television and a liquid crystal television can be used. In these parts, when a part absorbs water and a dimensional change occurs to cause warpage, a problem such as distortion of an image occurs. Therefore, these optical components are required to have a low water absorption rate and low dimensional change rate, and the requirements can be satisfied by using the resin of the present invention.
また、光学部品であるスクリーン等は、ＣＲＴ等から照射される光を長時間受けることとなる為に、使用される材質には、耐光性能が高いことが要求される。本発明の樹脂は、優れた耐光性能を有するが、長時間の耐光性を更に高めるために更なる耐光性処方を施すことが好ましい。しかし、該スクリーンのフレネルレンズに塗布される紫外線硬化型樹脂は、紫外線の照射を受けて硬化反応が進行する為、スクリーン用の樹脂に紫外線を吸収する等の硬化反応を阻害するものを添加することは実用的でない。更に、添加したものがスクリーン基材と紫外線硬化型樹脂との接着性を阻害するものであってはならない。また、添加するものが、該スクリーンの透明性を低下させることがあってはならない。 Moreover, since the screen etc. which are optical components will receive the light irradiated from CRT etc. for a long time, it is requested | required that the material used should have high light resistance. The resin of the present invention has excellent light resistance, but it is preferable to apply a further light resistance prescription in order to further improve long-term light resistance. However, the ultraviolet curable resin applied to the Fresnel lens of the screen undergoes a curing reaction upon irradiation with ultraviolet rays, and therefore, a resin that inhibits the curing reaction such as absorbing ultraviolet rays is added to the screen resin. That is not practical. Further, the added material should not inhibit the adhesion between the screen substrate and the ultraviolet curable resin. Also, the additive should not reduce the transparency of the screen.
本発明者らは、耐光性、硬化反応性及び接着性等を満足する耐光剤について鋭意検討した結果、ヒンダードアミン系安定剤が適することを見出した。即ち、本発明のスチレン系熱可塑性樹脂にヒンダードアミン系安定剤を加えることで、長時間の耐光性を更に高めることが可能となる。本発明のヒンダードアミン系安定剤（Ｄ）としては、ビス(２,２,６,６−テトラメチル−４−ピペリジル)セバケート、ビス(１,２,２,６,６−ペンタメチル−４−ピペリジル)セバケート、及びメチル(１,２,２,６,６−ペンタメチル−４−ピペリジル)セバケートなどのセバシン酸ジエステル化合物、１−［２−〔３−（３,５−ジ−t−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕エチル］−４−〔３−（３,５−ジ−t−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕−２,２,６,６−テトラメチルピペリジン、４−ベンゾイルオキシ−２,２,６,６−テトラメチルピペリジン、８−アセチル−３−ドデシル−７,７,９,９−テトラメチル−１,３,８−トリアザスピロ［４,５］デカン−２,４−ジオン、コハク酸ジメチル−１−(２−ヒドロキシエチル)−４−ヒドロキシ−２,２,６,６−テトラメチルピペリジン重縮合物が挙げられ、その１種以上を用いることができる。それらの中でも、ビス(２,２,６,６−テトラメチル−４−ピペリジル)セバケート、ビス(１,２,２,６,６−ペンタメチル−４−ピペリジル)セバケート、メチル(１,２,２,６,６−ペンタメチル−４−ピペリジル)セバケートなどのセバシン酸ジエステル化合物が好ましく、ビス(２,２,６,６−テトラメチル−４−ピペリジル)セバケートが最も好ましい。 As a result of intensive studies on light resistance agents that satisfy light resistance, curing reactivity, adhesion, and the like, the present inventors have found that hindered amine stabilizers are suitable. That is, by adding a hindered amine stabilizer to the styrene thermoplastic resin of the present invention, it is possible to further improve long-term light resistance. Examples of the hindered amine stabilizer (D) of the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). Sebacate and diester compounds such as methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy -2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4- Dione, dimethyl succinate-1- (2- Dorokishiechiru) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and the like, may be used alone or more thereof. Among them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2) Sebacic acid diester compounds such as, 6,6-pentamethyl-4-piperidyl) sebacate are preferred, and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is most preferred.
ヒンダードアミン系安定剤（Ｄ）は、スチレン系熱可塑性樹脂１００重量部に対し、０．０５〜２．０重量部の範囲で添加することが好ましい。ヒンダードアミン系安定剤（Ｄ）の含有量は、好ましくは、樹脂１００重量部に対し、０．１〜１．５重量部の範囲内であり、より好ましくは０．２〜１．０重量部の範囲内である。耐光性向上の観点から、安定剤（Ｄ）の含有量は、０．０５重量部以上であり、紫外線硬化型樹脂との接着性の観点から２．０重量部以下とすることが好ましい。 The hindered amine stabilizer (D) is preferably added in the range of 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the styrene thermoplastic resin. The content of the hindered amine stabilizer (D) is preferably in the range of 0.1 to 1.5 parts by weight, more preferably 0.2 to 1.0 parts by weight with respect to 100 parts by weight of the resin. Within range. From the viewpoint of improving light resistance, the content of the stabilizer (D) is 0.05 parts by weight or more, and preferably 2.0 parts by weight or less from the viewpoint of adhesion to the ultraviolet curable resin.
本発明のヒンダードアミン系安定剤は、スチレン系熱可塑性樹脂の重合時に添加することができる。また、押出機を用いてスチレン系熱可塑性樹脂を溶融する際に、樹脂ペレットと共にホッパー、あるいはサイドフィーダーから添加することもできる。さらにまた、光学部品用として用いる同種のスチレン系熱可塑性樹脂と安定剤とのマスターバッチを事前に準備し、光学部品を押出成形あるいは射出成形する際に、上記マスターバッチを添加する、簡便な方法をとることもできる。 The hindered amine stabilizer of the present invention can be added during polymerization of the styrene thermoplastic resin. Moreover, when melting a styrene-type thermoplastic resin using an extruder, it can also add from a hopper or a side feeder with a resin pellet. Furthermore, a simple method of preparing a masterbatch of the same kind of styrenic thermoplastic resin and stabilizer used for optical parts in advance and adding the masterbatch when the optical part is extruded or injection molded. You can also take
本発明のスチレン系熱可塑性樹脂及びスチレン系熱可塑性樹脂組成物は、光を拡散する目的の拡散材を０．１〜１０重量％含有しても良い。一般的には、拡散材としては架橋させたアクリル樹脂、架橋させたスチレンーアクリル系樹脂、架橋したスチレン樹脂、架橋したシリコン系樹脂等の有機系拡散材や、炭酸カルシューム、タルク、酸化チタン、硫酸バリューム等の無機系拡散材があげられる。 The styrene thermoplastic resin and the styrene thermoplastic resin composition of the present invention may contain 0.1 to 10% by weight of a diffusion material for the purpose of diffusing light. In general, as the diffusing material, a cross-linked acrylic resin, a cross-linked styrene-acrylic resin, a cross-linked styrene resin, a cross-linked silicon-based organic diffusing material, calcium carbonate, talc, titanium oxide, Examples thereof include inorganic diffusing materials such as sulfuric acid valem.
本発明のスチレン系熱可塑性樹脂あるいはスチレン系熱可塑性樹脂組成物を用いて、射出成形あるいは押出成形により所望の成形品を得ることができる。特に大型部品になる程、押出成形のシートから加工するのが好ましい。例えば、本発明のスチレン系熱可塑性樹脂あるいはスチレン系熱可塑性樹脂組成物を設定温度２４０℃の６５ｍｍ単軸押出機（東芝機械（株）製）で溶融し、押出機ヘッドに設けたＴダイから押し出し、ついで３本ロール（温度：上ロール ９８℃、中ロール ９５℃、下ロール ８５℃）を介して厚さ１．８５ｍｍの光学用のスクリーン基板を得ることができる。該基板に、さらに片側に熱硬化性樹脂を所望の形状、例えばフレネルレンズの形状に成形し、規定の紫外線を必要時間、照射し、熱硬化させることで、所望のリアプロジェクションテレビ用のスクリーンを得ることができる。 A desired molded article can be obtained by injection molding or extrusion molding using the styrene thermoplastic resin or styrene thermoplastic resin composition of the present invention. In particular, the larger the part, the more preferably it is processed from an extruded sheet. For example, the styrene thermoplastic resin or styrene thermoplastic resin composition of the present invention is melted by a 65 mm single screw extruder (manufactured by Toshiba Machine Co., Ltd.) having a set temperature of 240 ° C., and from a T die provided on the extruder head. An optical screen substrate having a thickness of 1.85 mm can be obtained through extrusion and then through three rolls (temperature: upper roll 98 ° C., middle roll 95 ° C., lower roll 85 ° C.). A thermosetting resin is further formed on the substrate in a desired shape, for example, in the shape of a Fresnel lens, irradiated with specified ultraviolet rays for a necessary time, and thermally cured to obtain a desired screen for a rear projection television. Obtainable.
以下、本発明の実施の形態を実施例に基づいて詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の表中の各物性は、次に示す方法により評価した。
（１）飽和吸水率
射出成形された１５０ｍｍ×１５０ｍｍ×２．０ｍｍ厚さの平板試験片を、予め８０℃にて３時間乾燥した後に、２３℃のデシケーター中で冷却する。この時の試験片の重量をＷ０とする。次に、この試験片を２３℃の水中に浸漬し、重量増加が平衡に達した時の重量（Ｗ１）を測定して、次式から飽和吸水率（重量％）を求める。
飽和吸水率＝（Ｗ１―Ｗ０）／Ｗ０×１００
Hereinafter, although an embodiment of the invention is described in detail based on an example, the present invention is not limited to these examples. In addition, each physical property in the following table | surfaces was evaluated by the method shown next.
(1) Saturated water absorption rate The injection-molded flat plate test piece of 150 mm × 150 mm × 2.0 mm thickness is dried in advance at 80 ° C. for 3 hours, and then cooled in a desiccator at 23 ° C. The weight of this time of the test piece and W 0. Next, this test piece is immersed in water at 23 ° C., the weight (W 1 ) when the weight increase reaches equilibrium is measured, and the saturated water absorption (wt%) is obtained from the following formula.
Saturated water absorption rate = (W 1 −W 0 ) / W 0 × 100
（２）飽和吸水時の寸法変化
上記で飽和吸水率に達した後に、試験片を取出し、布で表面を拭く。平板の樹脂の流れ方向について、吸水前（Ｌ０）と後（Ｌ１）の寸法をノギスで測定し、吸水前後の寸法変化量を求め、その値を吸水前の寸法（Ｌ０）で除して求める。
寸法変化率（％）＝（Ｌ１−Ｌ０）／Ｌ０×１００
(2) Dimensional change during saturated water absorption After reaching the saturated water absorption rate as described above, the test piece is taken out and the surface is wiped with a cloth. For the flow direction of the resin on the flat plate, measure the dimensions before (L 0 ) and after (L 1 ) water absorption with calipers, determine the dimensional change before and after water absorption, and divide that value by the dimension before water absorption (L 0 ). And ask.
Dimensional change rate (%) = (L 1 −L 0 ) / L 0 × 100
（３）全光線透過率
５０ｍｍ×９０ｍｍ×２．５ｍｍ厚さの試験片を４枚重ねて、ＪＩＳ Ｋ７１０５に準じて測定する。 但し、比較例４は、１２.７ｍｍ×１２.７ｍｍ×１２７ｍｍの短冊試験片を、実施例２と比較例１に関しては両方の試験片を用いた。
(3) Total light transmittance Four test pieces having a thickness of 50 mm × 90 mm × 2.5 mm are stacked and measured according to JIS K7105. However, in Comparative Example 4, a 12.7 mm × 12.7 mm × 127 mm strip test piece was used, and in both Example 2 and Comparative Example 1, both test pieces were used.
（４）曇り度
５０ｍｍ×９０ｍｍ×２．５ｍｍ厚さの試験片を４枚重ねて、ＪＩＳ Ｋ７１０５に準じて測定する。但し、比較例４は、１２.７ｍｍ×１２.７ｍｍ×１２７ｍｍの短冊試験片を、実施例２と比較例１に関しては両方の試験片を用いた。
(4) Haze degree Four test pieces having a thickness of 50 mm × 90 mm × 2.5 mm are stacked and measured according to JIS K7105. However, in Comparative Example 4, a 12.7 mm × 12.7 mm × 127 mm strip test piece was used, and in both Example 2 and Comparative Example 1, both test pieces were used.
（５）耐光性試験
スガ試験機(株)製サンシャインウエザーメータ−を用いて、５０ｍｍ×９０ｍｍ×２．５ｍｍ厚さの試験片を下記の条件にて測定する。
ＢＰ温度６３℃
降雨なし
５００時間暴露
(5) Light resistance test
Using a sunshine weather meter manufactured by Suga Test Instruments Co., Ltd., a test piece having a thickness of 50 mm × 90 mm × 2.5 mm is measured under the following conditions.
BP temperature 63 ℃
No rain
500 hours exposure
（６）黄変指数変化（△ＹＩ）
耐光性試験５００時間後の試料をスガ試験機(株)製多光源分光測色計ＭＳＣ−５Ｎにて黄変指数（ＹＩ５００）を測定し、下式のように、未暴露の試料の黄変指数（ＹＩ０）との差で表す。
△ＹＩ＝ＹＩ５００−ＹＩ０
(6) Yellowing index change (△ YI)
The yellowing index (YI 500 ) of a sample after 500 hours of light resistance test was measured with a multi-light source spectrocolorimeter MSC-5N manufactured by Suga Test Instruments Co., Ltd. Expressed as the difference from the variable index (YI 0 ).
ΔYI = YI 500 −YI 0
（７）接着性試験
紫外線硬化型樹脂として、ウレタンーアクリレート（共栄社化学株式会社製
ＵＡ−３０６Ｈ）を使用する。硬化剤として、イルガキュア９０７（日本バガルギー（株）製）を使用し、硬化型樹脂９０％に対し、１０％の割合で添加する。硬化剤を含んだ硬化型樹脂を試験片（寸法５０ｍｍ×９０ｍｍ×２．５ｍｍ）上に塗布した後、試験片側から光照射を行い、硬化型樹脂を硬化させる。硬化には高圧水銀灯（波長３６５ｎｍにおける光強度１５０ｍｗ／ｃｍ２）を用い、３０秒照射とする。硬化させた面にナイフで１ｍｍの碁盤目１００個を作り、ニチバン製のセロハンテープを圧着した後に、４５度の角度で速やかにセロテープを剥がし、硬化樹脂の接着状態を観察する。
尚、表２では、接着性が十分である場合を“Ａ”、若干剥がれる部分がある場合を“Ｂ”、硬化樹脂の大半が剥がれる場合を“Ｃ”とした。また、表中の“−”印は、未含有または未測定を示す。
(7) Adhesion test As UV curable resin, urethane acrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
UA-306H). As a curing agent, Irgacure 907 (manufactured by Japan Bagalgie Co., Ltd.) is used, and is added at a ratio of 10% with respect to 90% of the curable resin. After a curable resin containing a curing agent is applied on a test piece (dimensions 50 mm × 90 mm × 2.5 mm), light irradiation is performed from the test piece side to cure the curable resin. For curing, a high-pressure mercury lamp (light intensity of 150 mw / cm 2 at a wavelength of 365 nm) is used, and irradiation is performed for 30 seconds. After making 100 1 mm grids with a knife on the cured surface and pressing the cellophane tape made by Nichiban, the cellophane tape is quickly peeled off at an angle of 45 degrees, and the adhesive state of the cured resin is observed.
In Table 2, “A” indicates that the adhesiveness is sufficient, “B” indicates that there is a portion that is slightly peeled off, and “C” indicates that most of the cured resin is peeled off. In addition, “-” mark in the table indicates no inclusion or no measurement.
（８）樹脂組成分布の測定
試料０．０５ｇを４０ｍｌのＴＨＦ（テトラヒドロフラン）に溶解し、高速液体クロマトグラフＷａｔｅｒｓ ＴＭ６００（Ｗａｔｅｒｓ社製）を用い、カラムはμ ＢＯＮＤＡＳＰＨＥＲＥ ３．９ｍｍφ×１５０ｍｍ、カラムオーブン ３５℃、キャリアはヘキサン／クロロホルム １ｍＬ／ｍｉｎ、グラジエント条件は下記の条件、検出器は、Ｍａｓｓ Ｄｅｔｅｃｔｏｒ ＥＬＳＤ−１０００（Ｐｏｌｙｍｅｒ Ｌａｂｏｒａｔｏｒｉｅｓ社製）で、Ｎｅｂ．温度 ４０℃、Ｅｖａ．温度 ７０℃、キャリア液ガス流量 １．０Ｌ／ｍｉｎで共重合体中のアクリロニトリル組成分布を測定した。
グラジエント条件
ＴＩＭＥ ヘキサン％ クロロホルム％
０ ５０ ５０
１５ ０ １００
２０ ０ １００
(8) Measurement of resin composition distribution 0.05 g of a sample was dissolved in 40 ml of THF (tetrahydrofuran), and a high-performance liquid chromatograph Waters TM600 (manufactured by Waters) was used. The column was μ BONDASPHERE 3.9 mmφ × 150 mm, column oven 35 ℃, carrier is hexane / chloroform 1 mL / min, gradient conditions are the following conditions, detector is Mass Detector ELSD-1000 (manufactured by Polymer Laboratories), Neb. Temperature 40 ° C., Eva. The acrylonitrile composition distribution in the copolymer was measured at a temperature of 70 ° C. and a carrier liquid gas flow rate of 1.0 L / min.
Gradient condition TIME Hexane% Chloroform%
0 50 50
15 0 100
20 0 100
［実施例１〜３（製造例１〜３）］
６０リットルの完全混合攪拌槽に下記に示す添加量のスチレン、アクリロニトリル、エチルベンゼンからなる単量体混合物、または、更にブチルアクリレートンからなる単量体混合物を連続的に供給し、開始剤として、ｔ−ブチル−ペロキシ−イソプロピル−モノカーボネイトの存在下で下記条件で重合反応を行った。この際に、反応槽内は満液状態とした。重合率４０％で反応生成物を定常的に取り出して、予熱器で２５５℃に加熱した後、脱揮槽に入れ、２２５℃、真空度２０トールで未反応単量体等の揮発分を速やかに除去し、次いでベント付押出機で減圧下でペレットを得た。詳細条件と得られた樹脂の組成、分子量を表１に示す。
得られた各々の樹脂を東芝機械（株）製ＩＳ−５５ＥＰＮを用いて、温度２４０℃、金型温度６０℃の条件で射出成形し評価用試験片を作成した。評価結果を表２に示す。
[Examples 1 to 3 (Production Examples 1 to 3)]
A monomer mixture consisting of styrene, acrylonitrile, and ethylbenzene in the following addition amounts or a monomer mixture consisting of butyl acrylate are continuously fed to a 60 liter complete mixing and stirring tank, and t is used as an initiator. The polymerization reaction was carried out under the following conditions in the presence of -butyl-peroxy-isopropyl-monocarbonate. At this time, the reaction tank was filled with liquid. The reaction product is constantly taken out at a polymerization rate of 40%, heated to 255 ° C. with a preheater, put into a devolatilization tank, and quickly volatile components such as unreacted monomers at 225 ° C. and a vacuum of 20 Torr. And then pellets were obtained under reduced pressure in a vented extruder. Detailed conditions, the composition of the obtained resin, and the molecular weight are shown in Table 1.
Each obtained resin was injection-molded under the conditions of a temperature of 240 ° C. and a mold temperature of 60 ° C. using IS-55EPN manufactured by Toshiba Machine Co., Ltd., to produce test pieces for evaluation. The evaluation results are shown in Table 2.
［比較例１］
攪拌機付きの反応槽６０リットルに２５ｋｇの蒸留水を仕込み、懸濁安定剤として部分懸化ポリビニルアルコール１２５ｇ、更にラウリル硫酸ナトリウム０．７ｇを加えて溶解させる。その後スチレン８．３ｋｇ、アクリロニトリル３．７ｋｇ、ジ−ｔ−ブチルパーオキシヘキサノエート２２ｇ、オクチルメルカブタン１９ｇを次々と投入し、回転数８０ｒｐｍで攪拌しながら８０℃で７.５時間重合反応をさせた。更に、９５℃に上げて２時間反応させた。得られた共重合体は、洗浄し、脱水し、乾燥させた。乾燥後のスチレン系樹脂の重量平均分子量は、198,000であった。評価結果を表２に示す。
[Comparative Example 1]
25 kg of distilled water is charged into a 60 liter reaction tank equipped with a stirrer, and 125 g of partially suspended polyvinyl alcohol and 0.7 g of sodium lauryl sulfate are added and dissolved as a suspension stabilizer. Thereafter, 8.3 kg of styrene, 3.7 kg of acrylonitrile, 22 g of di-t-butylperoxyhexanoate, and 19 g of octyl mercaptan are successively added, and the polymerization reaction is carried out at 80 ° C. for 7.5 hours while stirring at a rotational speed of 80 rpm. I let you. Further, the temperature was raised to 95 ° C. and reacted for 2 hours. The resulting copolymer was washed, dehydrated and dried. The weight average molecular weight of the styrene resin after drying was 198,000. The evaluation results are shown in Table 2.
［比較例２］
アクリロニトリル成分等を含有しないポリスチレンが、スチレン系熱可塑性樹脂の中で最も吸水率の低い樹脂であり、その代表としてＰＳＪポリスチレンＨＦ７７（ＰＳジャパン(株)製）を用いた。評価結果を表２に示す。
[Comparative Example 2]
Polystyrene that does not contain an acrylonitrile component or the like is the resin having the lowest water absorption among styrene-based thermoplastic resins, and PSJ polystyrene HF77 (manufactured by PS Japan Co., Ltd.) was used as a representative thereof. The evaluation results are shown in Table 2.
［実施例４〜７および比較例３］
実施例４は実施例1の樹脂を用い、実施例５〜７と比較例３は実施例２の樹脂を用いて、表２に示した量の安定剤を配合し、３０ｍｍベント式単軸押出機（（株）石中鉄工所製 ＨＳ−Ｂ）を用いて、２２０℃で混練りし、目的の樹脂組成物を得た。安定剤としては、ＪＦ９０（城北化学工業(株)製）を用いた。評価結果を表２に示す。
[Examples 4 to 7 and Comparative Example 3]
Example 4 uses the resin of Example 1, Examples 5 to 7 and Comparative Example 3 use the resin of Example 2, and blends the amount of stabilizer shown in Table 2 and 30 mm vent type single screw extrusion. Using a machine (HS-B manufactured by Ishinaka Iron Works Co., Ltd.), the mixture was kneaded at 220 ° C. to obtain the desired resin composition. As a stabilizer, JF90 (manufactured by Johoku Chemical Industry Co., Ltd.) was used. The evaluation results are shown in Table 2.
［比較例４］
部分懸化ポリビニルアルコール１２０ｇ、更にラウリル硫酸ナトリウム０．６ｇを加えて溶解させる。その後スチレン９．７ｋｇ、アクリロニトリル２．５ｋｇ、ジ−ｔ−ブチルパーオキシヘキサノエート２４ｇ、オクチルメルカブタン２０ｇを次々と投入し、回転数８０ｒｐｍで攪拌しながら８０℃で８時間重合反応をさせた他は、比較例―１と同じように行った。乾燥後のスチレン系樹脂の重量平均分子量は、191,000であった。評価結果を表２に示す。
[Comparative Example 4]
120 g of partially suspended polyvinyl alcohol and 0.6 g of sodium lauryl sulfate are added and dissolved. Thereafter, 9.7 kg of styrene, 2.5 kg of acrylonitrile, 24 g of di-t-butylperoxyhexanoate, and 20 g of octyl mercabtan were successively added, and the polymerization reaction was allowed to proceed at 80 ° C. for 8 hours while stirring at a rotational speed of 80 rpm. Others were the same as in Comparative Example-1. The weight average molecular weight of the styrene resin after drying was 191,000. The evaluation results are shown in Table 2.
表２に示す通り、実施例１〜７は飽和吸水率が小さく、且つ寸法変化率も小さく、紫外線硬化型樹脂との接着性に優れている。
比較例１のようにアクリロニトリル含有量が高くなると、飽和吸水率は大きく、寸法変化率も大きくなる。比較例２のようにアクリロニトリルを含まないと吸水率は小さく、吸水寸法変化率も小さくなるが、紫外線硬化樹脂との接着性が得られなくなる。また、比較例３のように、実施例２の共重合体を用いても、安定剤の量が多くなると紫外線硬化樹脂との接着性が得られない。また比較例４のようにアクリロニトリルの組成分布が広くなると、光学特性が低下し、寸法変化が大きくなり好ましくない。
As shown in Table 2, Examples 1 to 7 have a low saturated water absorption rate and a small dimensional change rate, and are excellent in adhesiveness with an ultraviolet curable resin.
When the acrylonitrile content is high as in Comparative Example 1, the saturated water absorption is large and the dimensional change rate is also large. If acrylonitrile is not included as in Comparative Example 2, the water absorption is small and the water absorption dimensional change rate is small, but the adhesiveness with the ultraviolet curable resin cannot be obtained. Moreover, even if the copolymer of Example 2 is used like the comparative example 3, if the amount of a stabilizer increases, adhesiveness with an ultraviolet curable resin cannot be obtained. Further, when the composition distribution of acrylonitrile is wide as in Comparative Example 4, the optical characteristics are lowered and the dimensional change is increased, which is not preferable.
光学的に透明な樹脂製の大型スクリーン（フレネルレンズ、レンチキュラーレンズ）、前面パネル、拡散板、導光板等などに使用することが可能である。 It can be used for an optically transparent resin large screen (Fresnel lens, lenticular lens), front panel, diffusion plate, light guide plate, and the like.
Claims (12)
前記成分（Ｂ）を（Ｘ−５）重量％以下有する共重合体、及び、
前記成分（Ｂ）を（Ｘ＋５）重量％以上有する共重合体の含有量が、それぞれ０．５〜５重量％であるスチレン系熱可塑性樹脂。 The average value (X) of the content of the component (B) with respect to the whole resin is a styrene-based thermoplastic resin composed of an aromatic vinyl unit (A) and an unsaturated nitrile unit (B), and 8 ≦ X ≦ 27% by weight,
A copolymer having the component (B) not more than (X-5)% by weight, and
A styrene-based thermoplastic resin in which the content of the copolymer having the component (B) is (X + 5) wt% or more is 0.5 to 5 wt%, respectively.
前記成分（Ｂ）を（Ｘ＋５）重量％以上有する共重合体の含有量が、それぞれ０．５〜３．５重量％である請求項１または２に記載のスチレン系熱可塑性樹脂。 A copolymer having the component (B) not more than (X-5)% by weight, and
The styrenic thermoplastic resin according to claim 1 or 2, wherein the content of the copolymer having (X + 5) wt% or more of the component (B) is 0.5 to 3.5 wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222462A (en) * | 2009-03-23 | 2010-10-07 | Ps Japan Corp | Styrene-based resin composition excellent in chemical resistance and molded article formed using this |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01170631A (en) * | 1987-12-25 | 1989-07-05 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JPH03269006A (en) * | 1990-03-19 | 1991-11-29 | Asahi Chem Ind Co Ltd | New copolymer resin having excellent transparency |
| JPH0411660A (en) * | 1990-04-27 | 1992-01-16 | Kyodo Yakuhin Kk | Synthetic resin composition |
| JP2004262987A (en) * | 2003-02-28 | 2004-09-24 | Asahi Kasei Chemicals Corp | Production process for acrylonitrile-containing copolymer, and resin composition |
| JP2007106991A (en) * | 2005-09-15 | 2007-04-26 | Asahi Kasei Chemicals Corp | Styrenic thermoplastic resin for optical component and thermoplastic resin composition |
| JP4986215B2 (en) * | 2005-09-15 | 2012-07-25 | 旭化成ケミカルズ株式会社 | Optical components |
-
2007
- 2007-03-14 JP JP2007065514A patent/JP2008222932A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01170631A (en) * | 1987-12-25 | 1989-07-05 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
| JPH03269006A (en) * | 1990-03-19 | 1991-11-29 | Asahi Chem Ind Co Ltd | New copolymer resin having excellent transparency |
| JPH0411660A (en) * | 1990-04-27 | 1992-01-16 | Kyodo Yakuhin Kk | Synthetic resin composition |
| JP2004262987A (en) * | 2003-02-28 | 2004-09-24 | Asahi Kasei Chemicals Corp | Production process for acrylonitrile-containing copolymer, and resin composition |
| JP2007106991A (en) * | 2005-09-15 | 2007-04-26 | Asahi Kasei Chemicals Corp | Styrenic thermoplastic resin for optical component and thermoplastic resin composition |
| JP4986215B2 (en) * | 2005-09-15 | 2012-07-25 | 旭化成ケミカルズ株式会社 | Optical components |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222462A (en) * | 2009-03-23 | 2010-10-07 | Ps Japan Corp | Styrene-based resin composition excellent in chemical resistance and molded article formed using this |
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