JP4890961B2 - Optical resin - Google Patents
Optical resin Download PDFInfo
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- JP4890961B2 JP4890961B2 JP2006171471A JP2006171471A JP4890961B2 JP 4890961 B2 JP4890961 B2 JP 4890961B2 JP 2006171471 A JP2006171471 A JP 2006171471A JP 2006171471 A JP2006171471 A JP 2006171471A JP 4890961 B2 JP4890961 B2 JP 4890961B2
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- 230000003287 optical effect Effects 0.000 title claims description 57
- 229920005989 resin Polymers 0.000 title claims description 56
- 239000011347 resin Substances 0.000 title claims description 56
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 72
- 238000000465 moulding Methods 0.000 claims description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 11
- 229920001890 Novodur Polymers 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 239000012788 optical film Substances 0.000 claims description 7
- 230000005693 optoelectronics Effects 0.000 claims description 5
- 238000004455 differential thermal analysis Methods 0.000 claims description 4
- 239000013307 optical fiber Substances 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 6
- 239000002952 polymeric resin Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-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
- -1 alkyl methacrylate Chemical compound 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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
- LUECERFWADIZPD-UHFFFAOYSA-N 1-tert-butyl-2-ethenylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1C=C LUECERFWADIZPD-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-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
- XCKNZURKNJKFPB-UHFFFAOYSA-N CCCOC(=O)C1=CC(=C(C(=C1C2=CC=CC=C2)C(=O)OCCC)C(=O)OCCC)C(=O)OCCC Chemical compound CCCOC(=O)C1=CC(=C(C(=C1C2=CC=CC=C2)C(=O)OCCC)C(=O)OCCC)C(=O)OCCC XCKNZURKNJKFPB-UHFFFAOYSA-N 0.000 description 1
- 101100288971 Mus musculus Lgals3bp gene Proteins 0.000 description 1
- 101001119633 Myxococcus xanthus RNA polymerase sigma factor RpoD Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- BZDKYAZTCWRUDZ-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 BZDKYAZTCWRUDZ-UHFFFAOYSA-N 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- BRDXNBARQIJLOG-UHFFFAOYSA-N diethyl 4-[3,4-bis(ethoxycarbonyl)phenyl]benzene-1,2-dicarboxylate Chemical compound C1=C(C(=O)OCC)C(C(=O)OCC)=CC=C1C1=CC=C(C(=O)OCC)C(C(=O)OCC)=C1 BRDXNBARQIJLOG-UHFFFAOYSA-N 0.000 description 1
- NJIGQKCRWMSZBA-UHFFFAOYSA-N dimethyl 4-[3,4-bis(methoxycarbonyl)phenyl]benzene-1,2-dicarboxylate Chemical compound C1=C(C(=O)OC)C(C(=O)OC)=CC=C1C1=CC=C(C(=O)OC)C(C(=O)OC)=C1 NJIGQKCRWMSZBA-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing 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
- 239000002904 solvent Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、種々の光学要素の材料として用いることのできる複屈折の小さい樹脂であって、かつ透明性に優れ、黄色度と成形加工時の臭気が少なく、実用的な耐熱性を有する光学用樹脂に関する。 The present invention is a resin with low birefringence that can be used as a material for various optical elements, has excellent transparency, has low yellowness and little odor during molding, and has practical heat resistance. It relates to resin.
近年、眼鏡レンズや透明板などの一般光学部品はもとよりオプトエレクトロニクス用の光学部品、例えば音響、映像、文字情報等を記録する光ディスク装置のようなレーザー関連機器に用いる光学部品の材料などとして、従来のガラス系材料に代えて、高分子樹脂を用いる傾向が強まっている。これは、高分子樹脂からなる光学材料が、一般にガラス系光学材料に比べ、射出成形や押出成形のような成形技術を容易に適用でき、また透明性や実用的な耐熱性に優れ、安価に光学部品を生産できるためである。また近年では光学部品の薄型化が求められており、成形加工性の優れた光学用樹脂が求められている。しかしながら、高分子樹脂を射出成形や押出成形を行うと複屈折性を示すため、光学部品としての機能性を損なう場合がある。この問題を解決すべく種々の提案がなされており、例えば、高分子樹脂に光学異方性低分子の添加により複屈折を打ち消す方法（例えば、特許文献１）が提案されている。
本発明の目的は、ビフェニル誘導体を含有することにより複屈折を低減し、成形加工性と透明性に優れ、黄色度が低く、成形加工時の臭気が少なく、実用的な耐熱性を有するスチレン系樹脂組成物を提供するものである。 The object of the present invention is to reduce birefringence by containing a biphenyl derivative, excellent in molding processability and transparency, low yellowness, low odor during molding processing, and practical heat resistance. A resin composition is provided.
本発明は、
（１）スチレン系樹脂が、一般式（１）で表されるビフェニル誘導体を０．１〜２０質量％含有してなるスチレン系樹脂組成物からなることを特徴とする光学用樹脂。
The present invention
(1) styrene-based resin, the general formula (1) contain 0.1 to 20% by weight of biphenyl derivative represented by in such away styrene-based optical resin, characterized in that the resin composition.
（２）スチレン系樹脂が、単一のスチレン系単量体を重合して得られたスチレン系樹脂である（１）の光学用樹脂。
（３）スチレン系樹脂が、スチレン系単量体及びそのスチレン系単量体と共重合可能な単量体とを重合して得られたスチレン系樹脂であって、該共重合可能な単量体が９０質量％以下（但し、０質量％は含まない。）である（１）の光学用樹脂。
（４）ビフェニル誘導体の、空気気流（２００ｍｌ／分）中の示差熱分析（昇温速度１０℃／分）により測定した１０％減量温度が２００℃以上である（１）〜（３）のいずれかの光学用樹脂。
（５）ＪＩＳ Ｋ７２１０に基づき測定されたメルトマスフローレイト（ＭＦＲ）が０．５〜２０ｇ／１０分である（１）〜（４）のいずれかの光学用樹脂。
（６）（１）〜（５）のいずれかに記載の光学用樹脂を成形してなる光学部材。
（７）（１）〜（５）のいずれかに記載の光学用樹脂を成形してなるレンズ。
（８）レンズが、スクリーンレンズ、フレネルレンズ、レンチキュラーレンズ、眼鏡レンズ、光学機器用レンズ、オプトエレクトロニクス用レンズ、レーザー用レンズ、ピックアップ用レンズ、自動車用ランプレンズ又はＯＨＰ用レンズである（７）記載のレンズ。
（９）（１）〜（５）のいずれかに記載の光学用樹脂を成形してなる光ディスク基板。
（１０）（１）〜（５）のいずれかに記載の光学用樹脂を成形してなる光学シート。
（１１）光学シートが、光学用ベースシート、導光板、光拡散板又は集光板である（１０）記載の光学シート。
（１２）（１）〜（５）のいずれかに記載の光学用樹脂を成形してなる光学フィルム。
（１３）光学フィルムが、光学用ベースフィルム、光反射防止フィルム又は光拡散フィルムである（１２）の光学フィルム。
（１４）（１）〜（５）のいずれかに記載の光学用樹脂を成形してなる光ファイバー。
である。
(2) The optical resin according to (1), wherein the styrene resin is a styrene resin obtained by polymerizing a single styrene monomer.
(3) The styrene resin is a styrene resin obtained by polymerizing a styrene monomer and a monomer copolymerizable with the styrene monomer, and the copolymerizable monomer Optical resin of (1) whose body is 90 mass% or less (however, 0 mass% is not included).
(4) Any of (1) to (3), wherein the 10% weight loss temperature of the biphenyl derivative measured by differential thermal analysis (heating rate 10 ° C./min) in an air stream (200 ml / min) is 200 ° C. or higher. Optical resin .
(5) Optical resin in any one of (1)-(4) whose melt mass flow rate (MFR) measured based on JIS K7210 is 0.5-20 g / 10min.
( 6 ) An optical member formed by molding the optical resin according to any one of (1) to (5) .
( 7 ) A lens formed by molding the optical resin according to any one of (1) to (5) .
(8) lenses, screens lenses, Fresnel lenses, lenticular lenses, spectacle lenses, optical instruments lens, a optoelectronic lenses, laser lenses, pickup lenses, lamp lenses or OHP lenses for automobiles (7), wherein Lens.
( 9 ) An optical disk substrate formed by molding the optical resin according to any one of (1) to (5) .
( 10 ) An optical sheet obtained by molding the optical resin according to any one of (1) to (5) .
(11) An optical sheet, optical base sheet, a light guide plate, a light diffusion plate or the condenser plates (10) An optical sheet according.
( 12 ) An optical film formed by molding the optical resin according to any one of (1) to (5) .
(13) light optical film of optical films, a base film for an optical, an antireflection film or light diffusion film (12).
( 14 ) An optical fiber formed by molding the optical resin according to any one of (1) to (5) .
It is.
本発明のスチレン系樹脂組成物は、複屈折が小さく、成形加工性と透明性に優れ、黄色度が低く、成形加工時の臭気が少なく、実用的な耐熱性を有することから、例えば眼鏡レンズや透明板などの一般光学部品、音響、映像、文字情報等を記録する光ディスク、オプトエレクトロニクス用の光学部品、光ファイバー等の用途に適しており有用である。 The styrenic resin composition of the present invention has small birefringence, excellent moldability and transparency, low yellowness, little odor during molding, and practical heat resistance. It is suitable and useful for general optical components such as optical plates and transparent plates, optical discs for recording sound, video, character information, etc., optical components for optoelectronics, and optical fibers.
以下に本発明を詳細に説明する。 The present invention is described in detail below.
スチレン系樹脂は、スチレン系単量体を含む樹脂であれば特に制限されるものではない。中でも、例えば、単一のスチレン系単量体を重合して得られたスチレン系樹脂を重合した樹脂が好ましい。このスチレン系単量体は、スチレン構造を有する単量体であれば特に制限されるものではないが、例えば、スチレン、置換スチレン（ｐ−メチルスチレン、ｍ−メチルスチレン、ｏ−メチルスチレン、ｏ−ｔ−ブチルスチレン、ｍ−ｔ−ブチルスチレン、ｐ−ｔ−ブチルスチレン、α−メチルスチレン等）等があげられる。 The styrene resin is not particularly limited as long as it is a resin containing a styrene monomer. Among these, for example, a resin obtained by polymerizing a styrene resin obtained by polymerizing a single styrene monomer is preferable. The styrene monomer is not particularly limited as long as it is a monomer having a styrene structure. For example, styrene, substituted styrene (p-methylstyrene, m-methylstyrene, o-methylstyrene, o -T-butyl styrene, mt-butyl styrene, pt-butyl styrene, α-methyl styrene, etc.).
スチレン系樹脂は、上記のスチレン系単量体のうち、異なる２種以上を共重合した共重合樹脂でも、上記のスチレン系単量体以外でスチレン系単量体と共重合可能な単量体とスチレン系単量体とを共重合して得られた共重合樹脂でもよい。上記のスチレン系単量体以外の単量体としては、例えば、アクリロニトリル、アルキルアクリレート、アルキルメタクリレート、ブタジエン、無水マレイン酸等があげられる。 The styrene resin is a monomer that can be copolymerized with a styrene monomer other than the above styrene monomers even in a copolymer resin obtained by copolymerizing two or more different styrene monomers. And a copolymer resin obtained by copolymerizing styrene monomer. Examples of the monomer other than the styrene monomer include acrylonitrile, alkyl acrylate, alkyl methacrylate, butadiene, maleic anhydride and the like.
このようにして得られたスチレン系樹脂の具体例として、単一のスチレン系単量体を重合して得られたスチレン系樹脂ではポリスチレン樹脂が、共重合樹脂では、例えば、スチレン−α−メチルスチレン樹脂、アクリロニトリル−スチレン樹脂、メチルメタクリレート−スチレン樹脂、メチルメタクリレート−ブタジエン−スチレン樹脂、メチルメタクリレート−アクリロニトリル−ブタジエン−スチレン樹脂、スチレン−メタクリル酸樹脂、スチレン−無水マレイン酸樹脂、スチレン−ブタジエン−スチレン樹脂等が挙げられる。成形加工性が良好で成形品の吸湿による変形が少なく、比較的安価という観点から、ポリスチレン樹脂、又はメチルメタクリレート−スチレン樹脂が好ましい。 As specific examples of the styrene resin thus obtained, polystyrene resin is used for styrene resin obtained by polymerizing a single styrene monomer, and styrene-α-methyl is used for copolymer resin. Styrene resin, acrylonitrile-styrene resin, methyl methacrylate-styrene resin, methyl methacrylate-butadiene-styrene resin, methyl methacrylate-acrylonitrile-butadiene-styrene resin, styrene-methacrylic acid resin, styrene-maleic anhydride resin, styrene-butadiene-styrene Examples thereof include resins. Polystyrene resin or methyl methacrylate-styrene resin is preferred from the viewpoint of good molding processability, little deformation due to moisture absorption of the molded product, and relatively low cost.
共重合樹脂において、スチレン系単量体と共重合可能な単量体の比率は、０質量％を超え９０質量％以下が好ましい。 In the copolymer resin, the ratio of the monomer copolymerizable with the styrene monomer is preferably more than 0% by mass and 90% by mass or less.
スチレン系樹脂の重合方法は公知の手法が採用できるが、透明性、黄色度の観点から塊状重合あるいは、溶液重合が好ましい。 A known method can be adopted as a method for polymerizing the styrene resin, but bulk polymerization or solution polymerization is preferable from the viewpoint of transparency and yellowness.
ビフェニル誘導体は一般式（１）で示され、スチレン系樹脂が有する配向複屈折性を低減する傾向の配向複屈折性を示すもので、スチレン系樹脂中に０．１〜２０質量％含むことが必要である。その含有率が０．１〜１５質量％であれば好ましく、０．１〜１０質量％であれば、更に好ましい。含有率が０．１質量％を未満の場合は複屈折の低減効果が少なく、２０質量％を超える場合は透明性や耐熱性が大きく低下する。 The biphenyl derivative is represented by the general formula (1) and exhibits an orientation birefringence that tends to reduce the orientation birefringence of the styrene resin, and is contained in the styrene resin in an amount of 0.1 to 20% by mass. is necessary. The content is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass. When the content is less than 0.1% by mass, the birefringence reduction effect is small, and when it exceeds 20% by mass, the transparency and heat resistance are greatly reduced.
ビフェニル誘導体の分子量は好ましくは５０００以下、さらに好ましくは１０００以下である。分子量が５０００を越えたビフェニル誘導体を用いると、透明性が低下したり、複屈折の低減効果が低下したりして好ましくない。 The molecular weight of the biphenyl derivative is preferably 5000 or less, more preferably 1000 or less. Use of a biphenyl derivative having a molecular weight exceeding 5000 is not preferable because transparency is lowered and birefringence reduction effect is lowered.
ビフェニル誘導体は、空気気流（２００ｍｌ／分）中の示差熱分析（昇温速度１０℃／分）により測定した１０％減量温度が２００℃以上であることが好ましい。更に好ましくは２５０℃以上である。１０％減量温度が２００℃未満の場合、黄色度や成形加工時の臭気が強くなり、また実用的な耐熱性が得られない。なお、示差熱分析は、エスアイアイ・ナノテクノロジー株式会社製示差熱熱重量同時測定装置ＴＧ／ＤＴＡ６２００を用いて行った。 The biphenyl derivative preferably has a 10% weight loss temperature of 200 ° C. or higher as measured by differential thermal analysis (temperature increase rate: 10 ° C./min) in an air stream (200 ml / min). More preferably, it is 250 degreeC or more. When the 10% weight loss temperature is less than 200 ° C., the yellowness and odor during molding become strong, and practical heat resistance cannot be obtained. In addition, the differential thermal analysis was performed using the differential thermal thermogravimetric simultaneous measuring apparatus TG / DTA6200 by SII nanotechnology.
このような条件を満足するビフェニル誘導体として例えば、３，３’，４，４’−ビフェニルテトラカルボン酸テトラメチルエステル、３，３’，４，４’−ビフェニルテトラカルボン酸テトラエチルエステル、３，３’，４，４’−ビフェニルテトラカルボン酸テトラプロピルエステルなどがある。 Examples of biphenyl derivatives that satisfy such conditions include 3,3 ′, 4,4′-biphenyltetracarboxylic acid tetramethyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid tetraethyl ester, 3,3 Examples include ', 4,4'-biphenyltetracarboxylic acid tetrapropyl ester.
スチレン系樹脂組成物の製造方法としては特に制限はなく、スチレン系樹脂の重合時にビフェニル誘導体を添加する方法、スチレン系樹脂とビフェニル誘導体を押出機やバンバリーミキサー、ロール等を使用して溶融混練して得る方法等が採用できる。 The method for producing the styrene resin composition is not particularly limited. A method of adding a biphenyl derivative during polymerization of the styrene resin, a styrene resin and a biphenyl derivative are melt-kneaded using an extruder, a Banbury mixer, a roll, or the like. Can be used.
スチレン系樹脂組成物は、ＪＩＳ Ｋ７２１０に基づき測定されたメルトマスフローレイト（ＭＦＲ）が、好ましくは０．５〜２０ｇ／１０分である。より好ましくは、１．０〜１５ｇ／１０分で、特に好ましくは１．５〜１０ｇ／１０分である。なお、測定温度は２００℃、荷重は４９Ｎの条件で、東洋精機製作所社製メルトインデックサ（Ｆ−Ｆ０１）を使用して測定した。ＭＦＲが０．５ｇ／１０分未満であると成形加工性に課題が発生するとともに複屈折が大きくなり、２０ｇ／１０分を越えると耐熱性に劣る等の課題が発生する。ＭＦＲの調整は、スチレン系樹脂の分子量やビフェニル誘導体の添加量等で調整することができる。 The styrene resin composition has a melt mass flow rate (MFR) measured based on JIS K7210 of preferably 0.5 to 20 g / 10 min. More preferably, it is 1.0-15 g / 10min, Most preferably, it is 1.5-10g / 10min. In addition, it measured using the melt indexer (F-F01) by the Toyo Seiki Seisakusho Co., Ltd. on conditions with a measurement temperature of 200 degreeC and a load of 49N. When the MFR is less than 0.5 g / 10 minutes, problems occur in molding processability and birefringence increases, and when it exceeds 20 g / 10 minutes, problems such as poor heat resistance occur. The MFR can be adjusted by adjusting the molecular weight of the styrenic resin, the added amount of the biphenyl derivative, or the like.
スチレン系樹脂組成物には、必要に応じて酸化防止剤、耐候剤、滑剤、可塑剤、着色剤、帯電防止剤、鉱油、難燃剤等の添加剤を添加することができ、製造時任意の段階で配合することができる。 Additives such as antioxidants, weathering agents, lubricants, plasticizers, colorants, antistatic agents, mineral oils, flame retardants and the like can be added to the styrenic resin composition as necessary. Can be blended in stages.
スチレン系樹脂組成物は、射出成形、押出成形、圧縮成形、真空成形等の公知の方法により各種成形体に加工され、レンズ（スクリーンレンズ、眼鏡レンズ、光学機器用レンズ、オプトエレクトロニクス用レンズ、レーザー用レンズ、ピックアップ用レンズ、自動車用ランプレンズ、ＯＨＰ用レンズ等）、光ディスク、光学シート（導光板、光拡散板、集光板等）、光学フィルム（光反射防止フィルム、光拡散フィルム等）、光ファイバー等の用途に好適である。 Styrenic resin compositions are processed into various molded products by known methods such as injection molding, extrusion molding, compression molding, and vacuum molding, and lenses (screen lenses, eyeglass lenses, lenses for optical instruments, lenses for optoelectronics, lasers) Lens, pickup lens, automotive lamp lens, OHP lens, etc.), optical disc, optical sheet (light guide plate, light diffusing plate, condensing plate, etc.), optical film (light antireflection film, light diffusing film, etc.), optical fiber It is suitable for such applications.
次に実施例をもって本発明をさらに説明するが、本発明はこれらの例によって限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further, this invention is not limited by these examples.
実験例１
容積約２０Ｌの完全混合型攪拌槽である第一反応器と容積約４０Ｌの攪拌機付塔式プラグフロー型反応器である第二反応器を直列に接続し、さらに予熱器を付した脱揮槽を２基直列に接続して構成した。スチレン５２質量％、メチルメタクリレート（以下、ＭＭＡと略す。）４８質量％で構成する単量体溶液８５質量部に対し、エチルベンゼン１５質量部、ｔ−ブチルパーオキシイソプロピルモノカーボネート０．０１質量部、ｎ−ドデシルメルカプタン（以下ｎ−ＤＤＭと略す）０．０１質量部、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート０．０５質量部を混合し原料溶液とした。
Experimental example 1
A devolatilizing tank in which a first reactor which is a fully mixed stirring tank having a capacity of about 20 L and a second reactor which is a tower-type plug flow reactor with a stirring capacity of about 40 L are connected in series, and a preheater is further attached. Two units were connected in series. 15 parts by mass of ethylbenzene, 0.01 parts by mass of t-butylperoxyisopropyl monocarbonate with respect to 85 parts by mass of a monomer solution composed of 52% by mass of styrene and 48% by mass of methyl methacrylate (hereinafter abbreviated as MMA), 0.01 parts by mass of n-dodecyl mercaptan (hereinafter abbreviated as n-DDM) and 0.05 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate were mixed with a raw material solution. did.
この原料溶液を毎時６．２ｋｇで１２７℃に制御した第１反応器に連続的に供給し、ついで第一反応器から出た反応液を、入り口から流れの方向に向かって１２７℃から１５５℃の勾配がつくように調整した第二反応器に導入した。第二反応器から出た反応液を予熱器で１６０℃に加温した後、６７ｋＰａに減圧した第一脱揮槽に導入し、さらに予熱器で２３０℃に加温した後、１．３ｋＰａに減圧した第二脱揮槽に導入して単量体と溶剤を除去した。これをダイから溶融状態でストランド状に押し出した後カッティングし、ペレット状の高分子樹脂（以下、ＭＳと略す。）を得た。 This raw material solution was continuously supplied to the first reactor controlled to 127 ° C. at 6.2 kg per hour, and then the reaction solution exiting from the first reactor was 127 ° C. to 155 ° C. from the inlet toward the flow direction. Was introduced into a second reactor adjusted to have a gradient of. The reaction solution from the second reactor was heated to 160 ° C. with a preheater, then introduced into the first devolatilization tank reduced in pressure to 67 kPa, further heated to 230 ° C. with a preheater, and then increased to 1.3 kPa. The monomer and solvent were removed by introducing into a second devolatilized tank. This was extruded from a die in a molten state into a strand shape and then cut to obtain a pellet-shaped polymer resin (hereinafter abbreviated as MS).
実験例２
単量体溶液をスチレン１００質量％で構成した以外は実験例１と同様に行い高分子樹脂（以下、ＰＳと略す。）を得た。
Experimental example 2
A polymer resin (hereinafter abbreviated as PS) was obtained in the same manner as in Experimental Example 1 except that the monomer solution was composed of 100% by mass of styrene.
実施例１〜３、比較例１〜４
表１に示す配合で、スチレン系樹脂とビフェニル誘導体を配合し、東芝機械社製２軸押出機ＴＥＭ−３５Ｂを用いてストランド状に押出し、ペレタイザーにて切断することによりペレット形状のスチレン系樹脂組成物を得た。評価結果を表１に示した。
Examples 1-3, Comparative Examples 1-4
A styrenic resin and a biphenyl derivative are blended as shown in Table 1, and extruded into a strand using a twin-screw extruder TEM-35B manufactured by Toshiba Machine Co., Ltd., and cut with a pelletizer to form a pellet-shaped styrenic resin composition I got a thing. The evaluation results are shown in Table 1.
評価は下記の方法によった。 Evaluation was based on the following method.
（１）透明性
射出成形機（住友重機械社製サイキャップ１６５／７５）を用いて、シリンダー温度２３０℃、金型温度５０℃で縦９０ｍｍ、横９０ｍｍ、厚さ２ｍｍのプレートを成形した。このプレートの中央部を、ＡＳＴＭ Ｄ１００３に基づきヘーズメーター（日本電色工業社製ＮＤＨ−１００１ＤＰ型）を用いてヘーズを測定した（単位：％）。ヘーズが２％以下を合格とした。
(1) Transparency A plate having a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C., a length of 90 mm, a width of 90 mm, and a thickness of 2 mm was formed using an injection molding machine (Sycap 165/75 manufactured by Sumitomo Heavy Industries, Ltd.). The haze of the central part of this plate was measured based on ASTM D1003 using a haze meter (NDH-1001DP type manufactured by Nippon Denshoku Industries Co., Ltd.) (unit:%). A haze of 2% or less was accepted.
（２）黄色度
透明性と同じプレートの中央部を、色差計（日本電色工業社製Σ−８０）を用いて、黄色度の尺度としてｂ値を測定した。ｂ値が１以下を合格とした。
(2) Yellowness The b value was measured as a measure of yellowness using a color difference meter (Σ-80 manufactured by Nippon Denshoku Industries Co., Ltd.) at the center of the same plate as the transparency. A b value of 1 or less was accepted.
（３）複屈折
透明性と同じプレートを用い、プレートの中央部を、位相差測定装置（王子計測社製ＫＯＢＲＡ−ＷＲ）を用いてリタデーションＲｅ1を測定した（単位：ｎｍ）。ビフェニル誘導体を配合していない樹脂のリタデーションＲｅ0を用い、下記式でリタデーション保持率（単位：％）を計算した。リタデーション保持率が９０％以下を合格とした。
リタデーション保持率（％）＝Ｒｅ1／Ｒｅ0×１００
(3) Birefringence Using the same plate as the transparency, retardation Re 1 was measured at the center of the plate using a phase difference measuring device (KOBRA-WR manufactured by Oji Scientific Co., Ltd.) (unit: nm). Retardation retention (unit:%) was calculated by the following formula using retardation Re 0 of a resin not containing a biphenyl derivative. Retardation retention was 90% or less.
Retardation retention ratio (%) = Re 1 / Re 0 × 100
（４）耐熱性
射出成形機（東芝機械社製ＩＳ−５０ＥＰＮ）を用いて、シリンダー温度２２０℃、金型温度５０℃で長さ８０ｍｍ、幅１０ｍｍ、厚さ４ｍｍのバーを成形した。この成形品より１０ｍｍ×１０ｍｍ×４ｍｍの試験片を切り出し、ＪＩＳ Ｋ７２０６に基づき、東洋精機製作所社製ＨＤＴ＆ＶＳＰＴ試験装置を用い、５０法（荷重５０Ｎ、昇温速度５０℃／時間）でビカット軟化温度（以下、ＶＳＴと略す。）を測定した（単位：℃）。ＶＳＴが８０℃以上を合格とした。
(4) Heat resistance Using an injection molding machine (IS-50EPN manufactured by Toshiba Machine Co., Ltd.), a bar having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was formed at a cylinder temperature of 220 ° C and a mold temperature of 50 ° C. A test piece of 10 mm × 10 mm × 4 mm was cut out from this molded product, and the Vicat softening temperature (load 50 N, heating rate 50 ° C./hour) was used according to 50 methods (load 50 N, heating rate 50 ° C./hour) based on JIS K7206. Hereinafter, it was abbreviated as VST) (unit: ° C.). VST set 80 degreeC or more as the pass.
（５）臭気
成形中における臭気を１点（無臭）、２点（僅かに臭う）、３点（臭い）、４点（かなり臭い）、５点（耐えられない）の５段階で評価した。２点以下を合格とした。
(5) Odor The odor during molding was evaluated in five levels: 1 point (no odor), 2 points (slightly odor), 3 points (odor), 4 points (very odor), and 5 points (unbearable). Two points or less were accepted.
実施例１のスチレン系樹脂組成物を用いて、プロジェクター用のレンズを射出成形で作成し、実際に投影してみたところ、投影画面の周囲にも虹色は認められなかった。なお、レンズ成形は、住友重機械社製サイキャップ１６５／７５）を用いて、シリンダー温度２３０℃、金型温度７０℃で行った。 When a lens for a projector was prepared by injection molding using the styrenic resin composition of Example 1 and actually projected, no rainbow color was recognized around the projection screen. In addition, the lens molding was performed at a cylinder temperature of 230 ° C. and a mold temperature of 70 ° C. using a CYCAP 165/75 manufactured by Sumitomo Heavy Industries, Ltd.
本発明のスチレン系樹脂組成物に関わる実施例は、複屈折が小さく、透明性が良好で、黄色度と成形加工時の臭気が少なく、実用的な耐熱性を示した。 Examples relating to the styrenic resin composition of the present invention showed low practical birefringence, good transparency, little yellowness and odor during molding, and practical heat resistance.
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