JPH0229408A - Lowly water-absorbing and transparent plastic - Google Patents
Lowly water-absorbing and transparent plasticInfo
- Publication number
- JPH0229408A JPH0229408A JP63179014A JP17901488A JPH0229408A JP H0229408 A JPH0229408 A JP H0229408A JP 63179014 A JP63179014 A JP 63179014A JP 17901488 A JP17901488 A JP 17901488A JP H0229408 A JPH0229408 A JP H0229408A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylate
- water absorption
- transparent plastic
- low water
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003023 plastic Polymers 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000010521 absorption reaction Methods 0.000 claims abstract description 52
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract 4
- RSVZYSKAPMBSMY-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)F RSVZYSKAPMBSMY-UHFFFAOYSA-N 0.000 claims abstract 2
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- HBZFBSFGXQBQTB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HBZFBSFGXQBQTB-UHFFFAOYSA-N 0.000 claims 2
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 claims 1
- JXVINEGBEPHVPO-UHFFFAOYSA-N [1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C(F)(F)F)(C(F)(F)F)C(F)(F)F JXVINEGBEPHVPO-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 8
- 125000002723 alicyclic group Chemical group 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 230000003287 optical effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 238000012662 bulk polymerization Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- -1 dimethacrylate Chemical compound 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- GCNKJQRMNYNDBI-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(2-methylprop-2-enoyloxymethyl)butyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CC)COC(=O)C(C)=C GCNKJQRMNYNDBI-UHFFFAOYSA-N 0.000 description 1
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- QZYRMODBFHTNHF-UHFFFAOYSA-N ditert-butyl benzene-1,2-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)OOC(C)(C)C QZYRMODBFHTNHF-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は透明プラスチック、及び、その製造方法に係り
、特に吸水が少なく、しかも耐熱性2機械的強度に優れ
た特性をもつ低吸水性透明プラスチックに関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a transparent plastic and a method for manufacturing the same, and particularly relates to a transparent plastic with low water absorption and excellent heat resistance and mechanical strength. Regarding plastic.
従来、光学部品には種々のガラスが使用されてきたが、
最近はプラスチックがその軽量性、耐衝撃性、生産加工
性等の特徴を生かしてレンズ、光ディスク、光ファイバ
等多くの製品に応用されつつある。それらプラスチック
材料の中で、ポリメチルメタクリレ−1・(以下P M
M Aと略)を主成分とするアクリル樹脂が光学特性
に優れ、且つ、耐熱性2機械的強度にバランスのとられ
たものとなっており、各分野では広く用いられている。Traditionally, various types of glass have been used for optical components, but
Recently, plastics are being applied to many products such as lenses, optical disks, and optical fibers, taking advantage of their characteristics such as light weight, impact resistance, and ease of production. Among these plastic materials, polymethyl methacrylate-1 (hereinafter referred to as P M
Acrylic resin whose main component is M (abbreviated as "A") has excellent optical properties and is well-balanced in heat resistance and mechanical strength, and is widely used in various fields.
しかし、アクリル樹脂はポリスチレン樹脂、ポリカーボ
ネート樹脂に比べ吸水率が大きいという欠点があった。However, acrylic resins have a drawback in that they have a higher water absorption rate than polystyrene resins and polycarbonate resins.
この吸水の影響は成形品の形状によるが、0.2 %
吸水すると成形品に寸法変化や反り、歪が生じたり白濁
したりする。また、環境の変化により、吸水、乾燥を繰
り返すとクラックが生じる場合もある。このように吸水
による成形品の経時変化が大きくなる。すなわち、プラ
スチック成形品に変形を生じさせないためには吸水率の
低い材料が必要である。The effect of this water absorption depends on the shape of the molded product, but it is 0.2%
When water is absorbed, the molded product may change dimensions, warp, become distorted, or become cloudy. Furthermore, due to changes in the environment, repeated water absorption and drying may cause cracks. In this way, the molded product changes significantly over time due to water absorption. That is, in order to prevent plastic molded products from deforming, materials with low water absorption are required.
一方、ポリスチレン樹脂、ポリカーボネート樹脂は吸水
の点では問題ないが、レンズや光ディスク等の分野で重
要視される光学特性の−っである複屈折が大きいという
問題があった。On the other hand, polystyrene resins and polycarbonate resins have no problem in terms of water absorption, but they have a problem in that they have high birefringence, which is an important optical property in the fields of lenses, optical disks, and the like.
ところで、アクリル樹脂で低吸水性の透明プラスチック
材料は特開昭58−13652号公報と特開昭61−7
3705号公報等に開示がある。前者は吸水を少なくす
るための成分量としてシクロへキシルメタクリレートを
使用し、これとメチルメタクリレート(以下MMA)の
共重合を行なったものである。しかし、シクロへキシル
メタクリレートを比較的多く必要とするため、この共重
合体の耐熱温度及び機械的強度を低下させるという問題
があった。後者は吸水を少なくするための成分量として
トリシクロI:5.2.1.02”’)−デシル−メタ
クリレートを用いるため、低吸水性、及び、耐熱性は向
上するがこのトリシクロ〔5.2,1,0”G)−デシ
ル基はシクロヘキシル基より分子容が大きく、更に、剛
直であるため、機械的強度を大きく低下させる。By the way, transparent plastic materials made of acrylic resin and having low water absorption are disclosed in JP-A-58-13652 and JP-A-61-7.
This is disclosed in Publication No. 3705, etc. The former uses cyclohexyl methacrylate as a component to reduce water absorption, and copolymerizes cyclohexyl methacrylate with methyl methacrylate (hereinafter referred to as MMA). However, since a relatively large amount of cyclohexyl methacrylate is required, there is a problem in that the heat resistance and mechanical strength of this copolymer are reduced. The latter uses tricyclo I:5.2.1.02'')-decyl-methacrylate as the component amount to reduce water absorption, so low water absorption and heat resistance are improved. , 1,0''G)-decyl group has a larger molecular volume than a cyclohexyl group and is also more rigid, so it greatly reduces mechanical strength.
本発明者らは、現状を改善するためプラスチックを分子
構造上から検討した結果から、本発明に至った。本発明
の目的は、低吸水性で、耐熱性。The present inventors have arrived at the present invention based on the results of studying plastics from the viewpoint of their molecular structure in order to improve the current situation. The purpose of the present invention is to have low water absorption and heat resistance.
機械的強度に優れた、新しい低吸水性透明プラスチック
を提供することにある。Our objective is to provide a new low water absorption transparent plastic with excellent mechanical strength.
低吸水性透明プラスチックを得るのに次の方法が周知と
なっている。それは疎水基を持つ化合物の導入である。The following method is well known for obtaining transparent plastics with low water absorption. This is the introduction of a compound with a hydrophobic group.
例えば、PMMAを主成分とするアクリル樹脂の場合、
疎水基をカルボキシル基に導入した化合物と共重合する
とMMAの構造単位の中で弱親水性のカルボキシル基の
割合が少なくなるので吸水率は低くなる。一方、吸水率
と共に耐熱性を向上させるには分子容の大きな、剛直な
基を導入する。しかし、炭素数が5以上の脂環式炭化水
素基のように、分子容の大きな疎水基は吸水性、耐熱性
は向上するが、脆くなりやすく機械的強度は低下する。For example, in the case of acrylic resin whose main component is PMMA,
When copolymerized with a compound in which a hydrophobic group is introduced into a carboxyl group, the proportion of weakly hydrophilic carboxyl groups in the structural units of MMA decreases, resulting in a lower water absorption rate. On the other hand, in order to improve the water absorption rate and heat resistance, a rigid group with a large molecular volume is introduced. However, a hydrophobic group with a large molecular volume, such as an alicyclic hydrocarbon group having 5 or more carbon atoms, improves water absorption and heat resistance, but tends to become brittle and decreases mechanical strength.
機械的強度、とりわけ、衝撃強度を向上させるには次の
二つの方法が周知になっている。■ゴム成分の添加、■
高分子量化である。■はアクリル樹脂の場合、PMMA
にブチルアクリレート等ゴム成分を添加する。しかし、
この方法ではゴム成分が島状にミクロ相分離した構造で
あり、分散ゴム成分の大きさが1〜10μm程度でない
と?#撃強度は向上しない。すなわち、可視光の波長よ
り大きな粒子が分散しているため、透明性という点で問
題があった。又、ゴム成分を添加するため耐熱温度も低
下するという傾向しこあった。■については、分子量と
衝撃強度は、はぼ、比例関係にあるため高分子量化と共
に、衝撃強度は向上する。しかし、高分子量化により加
熱溶融時に、粘度が高くなるため、成形性が問題となっ
た。このように従来の技術では機械的強度、耐熱性、成
形性にバランスのとれた低吸水性透明プラスチックをつ
くるのは不可能であった。Two methods are well known for improving mechanical strength, particularly impact strength. ■ Addition of rubber components, ■
This is due to high molecular weight. ■In the case of acrylic resin, PMMA
Rubber components such as butyl acrylate are added to. but,
In this method, the rubber component has a microphase-separated structure in the form of islands, and the size of the dispersed rubber component must be about 1 to 10 μm. #The impact strength does not improve. That is, since particles larger than the wavelength of visible light are dispersed, there is a problem in terms of transparency. Furthermore, since the rubber component was added, the heat resistance temperature also tended to decrease. Regarding (2), since molecular weight and impact strength are in a highly proportional relationship, impact strength improves as the molecular weight increases. However, due to the high molecular weight, the viscosity increases when heated and melted, resulting in moldability problems. As described above, with conventional techniques, it has been impossible to create low water absorption transparent plastics with a good balance of mechanical strength, heat resistance, and moldability.
本発明はこれら問題点を新規な低吸水性透明プラスチッ
クを提供することにより解決しようとするものである。The present invention attempts to solve these problems by providing a new low water absorption transparent plastic.
すなわち、本発明の低吸水性透明プラスチックの構成は
、一般式(I)で表わされる化合物、(式中5Aは一部
、又は、全ての水素原子が弗素原子に置換された炭素数
3〜20のアルキル基を示す)、及び、一般式(II)
で表わされる化合物(式中、2は炭素数10の脂環式炭
化水素基を示す)、及び、メチルメタクリレートの三成
分を必須成分とする共重合体である。That is, the structure of the low water absorbency transparent plastic of the present invention is a compound represented by the general formula (I), (wherein 5A is a compound having 3 to 20 carbon atoms in which some or all of the hydrogen atoms have been replaced with fluorine atoms. ), and general formula (II)
It is a copolymer containing three essential components: a compound represented by (in the formula, 2 represents an alicyclic hydrocarbon group having 10 carbon atoms) and methyl methacrylate.
本発明の低吸水性透明プラスチックは一般式(I)が5
〜70 w t%、一般式(If)が5〜60wt%、
メチルメタクリレートが20〜70wし%を含む構成か
ら成る共重合体である。又、プラスチックは飽和吸水率
が0.7 %以下で、かつ、耐熱性2機械的強度に優れ
た特性を示す。The low water absorption transparent plastic of the present invention has general formula (I) of 5
~70 wt%, general formula (If) is 5 to 60 wt%,
It is a copolymer containing 20 to 70% by weight of methyl methacrylate. In addition, plastic has a saturated water absorption rate of 0.7% or less and exhibits excellent heat resistance and mechanical strength.
本発明の低吸水性透明プラスチックにおいて、優れた低
吸水性、透明性、耐熱性2機械的強度を保持するため共
重合組成の範囲は式(I)の弗素化した化合物は5〜7
0wt%、好ましくは、10〜60wt%、式(II)
の脂環式炭化水素基を含む化合物は5〜60wt%、好
ましくは、7〜50wt%である。メチルメタクリレー
トは20〜70 w t%好ましくは25〜6 ’Ow
t%である。共重合体中弗素化した化合物の単位量が
70wt%を越えると耐熱温度の低下が大きくなり5w
t%以下では機械的強度の向上や実質的な吸水率の低下
に貢献しない。一方、脂環式炭化水素基を含む化合物は
単位量が60wt%を越えると機械的強度の維持が難し
く、又、7wt%未満では吸水率の低下効果と耐熱温度
の上昇効果は得られない。In order to maintain excellent low water absorption, transparency, and heat resistance 2 and mechanical strength in the low water absorption transparent plastic of the present invention, the range of the copolymerization composition is 5 to 7.
0 wt%, preferably 10 to 60 wt%, formula (II)
The amount of the compound containing an alicyclic hydrocarbon group is 5 to 60 wt%, preferably 7 to 50 wt%. Methyl methacrylate is 20-70 wt% preferably 25-6'Ow
t%. If the unit amount of the fluorinated compound in the copolymer exceeds 70 wt%, the heat resistance temperature will decrease significantly.
If it is less than t%, it will not contribute to improving mechanical strength or substantially reducing water absorption. On the other hand, if the unit amount of a compound containing an alicyclic hydrocarbon group exceeds 60 wt%, it is difficult to maintain mechanical strength, and if it is less than 7 wt%, the effect of lowering the water absorption rate and increasing the heat resistance temperature cannot be obtained.
本発明の低吸水性透明プラスチック材料の製造方法は塊
状重合、溶液重合、懸濁重合、乳化重合など周知の方法
で可能である。フィルムやシート材料を得るには注型法
による塊状重合が、又射出成形可能材料は懸濁重合、乳
化重合が作業効率の面で好ましい。いずれも、共重合体
に異物などが混入していないことが好ましいので濾過や
蒸留などにより異物を除いたあと共重合する。The low water absorption transparent plastic material of the present invention can be produced by known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Bulk polymerization by casting is preferred for obtaining film or sheet materials, and suspension polymerization and emulsion polymerization for injection moldable materials are preferred from the viewpoint of work efficiency. In either case, it is preferable that the copolymer is free of foreign substances, so copolymerization is carried out after removing foreign substances by filtration, distillation, etc.
懸濁重合や乳化重合の場合、懸濁分散剤、又、乳化剤を
溶解した水中に、重合開始剤と分子量調整のための連鎖
移動剤を加えて単量体の混合物を分散させた後、重合を
行なうのが周知となっている。注型法により塊状重合法
の場合、任意の単量体混合物から、まず、ある程度共重
合した重合体、又は、未重合の単量体混合物を、ガラス
、金属。In the case of suspension polymerization or emulsion polymerization, a polymerization initiator and a chain transfer agent for molecular weight adjustment are added to water in which a suspension dispersant or emulsifier is dissolved, and the monomer mixture is dispersed, and then polymerization is carried out. It is well known to do this. In the case of bulk polymerization using the casting method, first, a polymer that has been copolymerized to some extent or an unpolymerized monomer mixture is prepared from an arbitrary monomer mixture to form glass or metal.
プラスチック等から成る用途に応じて設計された型枠等
に注入した後、熱重合を行なう。After pouring into a mold made of plastic or the like designed according to the intended use, thermal polymerization is performed.
注入法による塊状重合の場合、共重合を三次元架橋する
ため架橋剤を配合する場合がある。三次元架橋した共重
合体は、耐溶剤性2表面強度生産加工性がよくなるため
、現在ではメガネレンズの生産に用いられている。架橋
剤は、多官能メタクリレート、多官能アクリレート、芳
香族ジビニル化合物がある。しかし、芳香族ジビニル化
合物は二重結合を多く持つため耐光性に問題があり好ま
しくない。多官能メタクリレート、及び、多官能アクリ
レートが好ましい。In the case of bulk polymerization by injection method, a crosslinking agent may be added to three-dimensionally crosslink the copolymer. Three-dimensionally crosslinked copolymers are currently used in the production of eyeglass lenses because of their improved solvent resistance, two-surface strength, and production processability. Examples of crosslinking agents include polyfunctional methacrylates, polyfunctional acrylates, and aromatic divinyl compounds. However, aromatic divinyl compounds have a large number of double bonds and therefore have a problem with light resistance, which is not preferable. Polyfunctional methacrylates and polyfunctional acrylates are preferred.
具体例として、エチレングレコール、ジエチレングリコ
ール、ジアクリレート、ジメタクリレート、プロピレン
グリコールジアクリレート、プロピレングリコールジメ
タクリレート、トリメチロールプロパンジメタクリレー
ト、トリメチロールプロパンジアクリレート、トリメチ
ロールプロパントリアクリレート、トリメチロールプロ
パントリメタクリレート等がある。Specific examples include ethylene glycol, diethylene glycol, diacrylate, dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, etc. There is.
一方、重合開始剤は、2,2′−アゾビス(イソブチロ
ニトリル)、1.1’−アゾビス(シクロヘキサンカル
ボニトリル)、2.2′−アゾビス(2,4−ジメチル
ヴアレロニトリル)、アゾビスイソブタノールアセテー
ト等のアゾ化合物そして、ラウロイルパーオキサイド、
ジーtert−ブチルパーオキサイド、メチルエチルケ
トンパーオキサイド、ジーtert−ブチルパーフタレ
ート、ジtert−ブチルパーアセテート、ジーter
t−アミルパーオキサイド、シミリスチルパーオキシジ
カーボネート等の有機過酸化物等がある。On the other hand, the polymerization initiators include 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and azobis(isobutyronitrile). Azo compounds such as bisisobutanol acetate and lauroyl peroxide,
Di-tert-butyl peroxide, Methyl ethyl ketone peroxide, Di-tert-butyl perphthalate, Di-tert-butyl peracetate, Di-tert
Examples include organic peroxides such as t-amyl peroxide and similystyl peroxydicarbonate.
これら、重合開始剤の配合量は各種配合した化合物の総
量に対し0.05〜2.5 w t%である。The blending amount of these polymerization initiators is 0.05 to 2.5 wt% based on the total amount of various compounds blended.
又、共重合体の分子量を調整する働きのある連鎖移動剤
はtert−ブタンチオール、n−ブタンチオール、
tart−オクタンチオール、n−オクタンチオール、
n−ドデカンチオール、tert−ドデカンチオール等
がある。これら鎖移動剤の配合量は。In addition, chain transfer agents that have the function of adjusting the molecular weight of the copolymer include tert-butanethiol, n-butanethiol,
tart-octanethiol, n-octanethiol,
Examples include n-dodecanethiol and tert-dodecanethiol. What are the amounts of these chain transfer agents?
各種配合した化合物の総量に対し1.0 wt%以下
である。It is 1.0 wt% or less based on the total amount of various compounds blended.
生成した共重合体の用途に応じて帯電防止剤。Antistatic agent depending on the use of the produced copolymer.
着色剤、充填剤、紫外線吸収剤、熱安定剤、酸化防止剤
等を添加してもよい。得られた共重合体は共重合時、あ
るいは、成形時に内包された歪を除去するため、アニー
リングを行なうなどの後処理を行なうことができる。Colorants, fillers, ultraviolet absorbers, heat stabilizers, antioxidants, etc. may be added. The obtained copolymer can be subjected to post-treatment such as annealing in order to remove distortions incorporated during copolymerization or molding.
〔実施例〕
次に、本発明を実施例によって更に詳細に説明する。し
かし、本発明はこれによって何に限定されるものではな
い。[Example] Next, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited thereto.
なお、以下の実施例中の物性測定はノズル温度230℃
の射出成形機で成形したそれぞれの形状の試片を用いて
行なった。全光線透過率はJIS−に6717に準じて
、熱変形温度はJIS−に7207のA法に、機械的強
度の因子である衝撃強度はJIS−に7110 (ただ
し、差を明らかにするために試片にノツチを入れずに測
定した)に従って測定した。The physical properties in the following examples were measured at a nozzle temperature of 230°C.
The tests were carried out using specimens of each shape molded using an injection molding machine. The total light transmittance was determined according to JIS-6717, the heat distortion temperature was determined according to A method of JIS-7207, and the impact strength, which is a factor of mechanical strength, was determined according to JIS-7110 (However, in order to clarify the difference, (Measurement was made without making a notch in the specimen).
飽和吸水率は、まず、試片を70℃/ 0 、1 rt
mHg以下で10時間以上乾燥して初期重量を測定し、
次いで、試片を70℃水中に20日間放置した後の重量
を測定しJIS−に7209の計算式(試験片のもとの
重さと吸水後の重さの増加分の比から求める場合)のA
法から求めた。To determine the saturated water absorption rate, first, test the specimen at 70°C/0, 1 rt.
Dry for 10 hours or more at mHg or less and measure the initial weight,
Next, the weight of the test piece after being left in water at 70°C for 20 days was measured, and the weight was calculated according to the JIS-7209 calculation formula (when calculated from the ratio of the original weight of the test piece to the increase in weight after water absorption). A
I asked for it from the law.
寸法変化率は射出成形で得た50X30X5t(単位:
1)の試片を40℃/95%RH中に放置し、長さの変
化をマイクロメータで測定して次式から求めた。The dimensional change rate is 50X30X5t obtained by injection molding (unit:
The sample obtained in 1) was left in a temperature of 40° C./95% RH, and the change in length was measured using a micrometer and calculated from the following equation.
寸法変化率=((吸湿後の長さ一初期長さ)/初期長さ
)X100 (%)
初期長さは試片を70℃/ 0 、1 mm Hg以下
の雰囲気に10時間以上放置した後の長さであり、吸湿
後の長さは40℃/95%RH中に放置した後の長さで
ある。Dimensional change rate = ((Length after moisture absorption - Initial length) / Initial length) The length after moisture absorption is the length after being left in 40° C./95% RH.
反り試験は、ノズル温度250℃で射出成形を行ない片
面に情報標識の入った300na+φ、厚さ1.2 t
yaの光デイスク基盤を得る。更に、これを蒸着装置で
10−’mHgの真空下にアルミニウム蒸着を行なった
。その後、常法によりSiNの保護膜を被覆し、二枚の
基盤を接着剤により貼り合わせた。これを60℃/95
%RHの雰囲気に二週間放置し光デイスク基盤の反り試
験を行なった。The warpage test was performed by injection molding at a nozzle temperature of 250°C and using a 300na+φ, 1.2t thick product with information markings on one side.
Obtain ya optical disk base. Furthermore, aluminum was vapor-deposited using a vapor deposition apparatus under a vacuum of 10 mHg. Thereafter, a SiN protective film was coated using a conventional method, and the two substrates were bonded together using an adhesive. This is 60℃/95
%RH atmosphere for two weeks, and a warping test of the optical disk substrate was conducted.
反りの測定は光デイスク基盤の中心がディスク基盤の外
周上のある少なくとも二点を通る平面から隔たる距離を
三次元測定器(AF−121,三層製作所II)で測定
し、その反り量を反りとして示した。To measure warpage, measure the distance between the center of the optical disk substrate and a plane passing through at least two points on the outer periphery of the disk substrate using a three-dimensional measuring device (AF-121, Sankai Seisakusho II), and calculate the amount of warpage. Shown as warpage.
〈実施例1〉
攪拌機及び冷却器の付いた4Qのフラスコに分散剤とし
て塩基性燐酸カルシウム10wt%水溶液40g、ドデ
シルベンゼンスルホン酸ナトリウム0.002 g及
び硫酸ナトリウム0.5 gをイオン交換水2200g
と共に加え、攪拌回転数25Orpmに保つ。これに下
記の組成物を加え。<Example 1> In a 4Q flask equipped with a stirrer and a condenser, 40 g of a 10 wt% aqueous solution of basic calcium phosphate, 0.002 g of sodium dodecylbenzenesulfonate, and 0.5 g of sodium sulfate were added as a dispersant to 2200 g of ion-exchanged water.
and keep the stirring speed at 25 rpm. Add the following composition to this.
窒素雰囲気下で65℃で工時間、続いて97℃で二時間
重合させた。Polymerization was carried out at 65° C. for an incubation time under a nitrogen atmosphere, followed by 2 hours at 97° C.
メチルメタクリレート 480gトリシク
ロ〔5.2,1,0”6) 380g−デシルメタ
クリレート
2.2,3.3−テトラフルオロプロ 340gピル
メタクリレート
ラウロイルパーオキサイド 4.2 gl−オ
クタンチオール 1.44gn−オクタデ
シル−3−(4’
ヒドロキシ−3’ 、5’ −ジーtert−ブチルフ
ェニル)プロピオネート 4gステアリルアルコー
ル 2g生成した共重合体粒子を水洗
、脱水の後、乾燥して低吸水性透明プラスチックを得た
。その特性を第1表に示す。Methyl methacrylate 480g tricyclo[5.2,1,0”6) 380g-decyl methacrylate 2.2,3.3-tetrafluoropro 340g pyrumethacrylate lauroyl peroxide 4.2 gl-octanethiol 1.44gn-octadecyl-3 -(4'Hydroxy-3',5'-di-tert-butylphenyl)propionate 4g Stearyl alcohol 2g The produced copolymer particles were washed with water, dehydrated, and then dried to obtain a low water absorption transparent plastic. Its properties are shown in Table 1.
第 表 〔実施例2〜9及び比較例1.〜3〕 共重合体組成を第2表に示す。No. table [Examples 2 to 9 and Comparative Example 1. ~3] The copolymer composition is shown in Table 2.
重合条件を65℃で3〜6時間、97℃で2〜6時間に
した以外は実施例1に準じて低吸水性透明プラスチック
を得た。それらの特性を第1表に併記した。A low water absorption transparent plastic was obtained in the same manner as in Example 1, except that the polymerization conditions were 65°C for 3 to 6 hours and 97°C for 2 to 6 hours. Their properties are also listed in Table 1.
第2表の実施例1〜9及び比較例1〜3で得られた低吸
水性透明プラスチックを40℃/95%RHの雰囲気下
における寸法変化率を測定した。The dimensional change rate of the low water absorption transparent plastics obtained in Examples 1 to 9 and Comparative Examples 1 to 3 in Table 2 was measured in an atmosphere of 40° C./95% RH.
その中で代表として、実施例1.比較例1〜2の測定結
果を第1図に示す。次に実施例1〜3.実施例5.比較
例1〜2の低吸水性透明プラスチックから得られた光デ
イスク基盤の反りを測定した。As a representative example, Example 1. The measurement results of Comparative Examples 1 and 2 are shown in FIG. Next, Examples 1 to 3. Example 5. Warpage of optical disk substrates obtained from the low water absorption transparent plastics of Comparative Examples 1 and 2 was measured.
その測定結果を第3表に示す。The measurement results are shown in Table 3.
第 3 表
尚、表中には反りと密接な関係にある飽和吸水率も併記
した。Table 3 In addition, the saturated water absorption rate, which is closely related to warpage, is also listed in the table.
以上の実施例、比較例から明らかなように、アクリル樹
脂の場合、比較例1のPMMA (ポリメチルメタクリ
レート)の飽和吸水率が2.2 %であるのに対し、い
ずれの実施例も0.7 %以下と低い。熱変形温度も
実施例は比較例に比べて高い。As is clear from the above Examples and Comparative Examples, in the case of acrylic resin, the saturated water absorption rate of PMMA (polymethyl methacrylate) of Comparative Example 1 is 2.2%, while in all Examples the saturated water absorption rate is 0. It is low at less than 7%. The heat distortion temperature of the example is also higher than that of the comparative example.
全光線透過率もいずれの実施例共、最も優れているPM
MAと同等の高い値を示す。すなわち、いずれの実施例
も低吸水率で、透明性、及び、耐熱性2機械的強度にバ
ランスのとれた値を示すことが明らかである。また、第
1図、第3表から明らかなように、光デイスク基盤など
の用途にも、本発明に係る低吸水性透明プラスチックは
吸水に対して安定であることが分る。PM has the best total light transmittance in all examples.
Shows a high value equivalent to MA. That is, it is clear that all of the examples have low water absorption, and exhibit well-balanced values for transparency, heat resistance, and mechanical strength. Furthermore, as is clear from FIG. 1 and Table 3, the low water absorption transparent plastic according to the present invention is stable against water absorption even in applications such as optical disk substrates.
本発明の低吸水透明プラスチックは、耐吸水性。 The low water absorption transparent plastic of the present invention is resistant to water absorption.
耐熱性2機械的強度、透明性に優れている。Heat resistance 2: Excellent mechanical strength and transparency.
第1図は本発明の一実施例の吸水による寸法変化率の経
時変化図である。FIG. 1 is a graph of the dimensional change rate due to water absorption of one embodiment of the present invention over time.
Claims (1)
された炭素数3〜20のアルキル基を示す)及び、一般
式(II)で表わせられる化合物 ▲数式、化学式、表等があります▼……(II) (式中、Zは炭素数10の脂環式炭化水素基を示す)及
び、メチルメタクリレートの三成分を必須成分としたこ
とを特徴とする低吸水性透明プラスチック。 2、前記一般式( I )で表わされる化合物が5〜70
wt%及び、前記一般式(II)で表わされる化合物が5
〜60wt%及びメチルメタクリレートが20〜70w
t%の配合量である共重合体の特許請求の範囲第1項記
載の低吸水性透明プラスチック。 3、飽和吸水率の0.7%以下であることを特徴とする
特許請求の範囲第1項または第2項記載の低吸水性透明
プラスチック。 4、前記一般式( I )において、弗素化置換され炭素
数3〜20のアルキル基を含有する化合物が2,2,3
,3−テトラフルオロプロピルメタクリレート、1H,
1H,5H−オクタフルオロペンチルメタクリレート、
1H,1H,2H,2H−ヘプタデカフルオロデシルメ
タクリレート、1H−ヘキサフルオロイソプロピルメタ
クリレート、パーフルオロ−tert−ブチルメタクリ
レート、1H,1H,2H,2H−ヘプタデカフルオロ
デシルメタクリレート、1H,1H,2H,2H−トリ
デカフルオロオクタメタクリレート、1H,1H,2H
,2H−ヘンエイコサフロオロドデシルメタクリレート
、1H,1H,2H,2H−ペンタコサフルオロテトラ
デシルメタクリレート、のいずれかであることを特徴と
する特許請求の範囲第1項、第2項または第3項記載の
低吸水性透明プラスチック。 5、前記一般式(II)において示される化合物ガトリシ
クロ〔5.2.1.0^2^、^6〕−デシルメタクリ
レート、トリシクロ〔3.3.1.1^3^、^7〕−
デシルメタクリレートであることを特徴とする特許請求
の範囲第1項、第2項または第3項記載の低吸水性透明
プラスチック。[Claims] 1. A compound represented by the general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. (represents an alkyl group having 3 to 20 carbon atoms) and compounds represented by the general formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. A low water absorption transparent plastic characterized by having three essential components: cyclic hydrocarbon group) and methyl methacrylate. 2. The compound represented by the general formula (I) is 5 to 70
wt% and the compound represented by the general formula (II) is 5
~60wt% and 20~70w methyl methacrylate
The low water absorption transparent plastic according to claim 1, wherein the copolymer has a blending amount of t%. 3. The low water absorption transparent plastic according to claim 1 or 2, which has a saturated water absorption of 0.7% or less. 4. In the general formula (I), the compound containing a fluorinated substituted alkyl group having 3 to 20 carbon atoms is 2,2,3
, 3-tetrafluoropropyl methacrylate, 1H,
1H,5H-octafluoropentyl methacrylate,
1H,1H,2H,2H-heptadecafluorodecyl methacrylate, 1H-hexafluoroisopropyl methacrylate, perfluoro-tert-butyl methacrylate, 1H,1H,2H,2H-heptadecafluorodecyl methacrylate, 1H,1H,2H,2H -tridecafluorooctamethacrylate, 1H, 1H, 2H
, 2H-heneicosafluorododecyl methacrylate, and 1H, 1H, 2H, 2H-pentacosafluorotetradecyl methacrylate. Low water absorption transparent plastic as described. 5. Compound represented by general formula (II) Gatricyclo[5.2.1.0^2^,^6]-decyl methacrylate, tricyclo[3.3.1.1^3^,^7]-
The low water absorption transparent plastic according to claim 1, 2 or 3, which is decyl methacrylate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63179014A JPH0229408A (en) | 1988-07-20 | 1988-07-20 | Lowly water-absorbing and transparent plastic |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63179014A JPH0229408A (en) | 1988-07-20 | 1988-07-20 | Lowly water-absorbing and transparent plastic |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0229408A true JPH0229408A (en) | 1990-01-31 |
Family
ID=16058609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63179014A Pending JPH0229408A (en) | 1988-07-20 | 1988-07-20 | Lowly water-absorbing and transparent plastic |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0229408A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001048538A1 (en) * | 1999-12-27 | 2001-07-05 | Mitsubishi Rayon Co., Ltd. | Plastic optical fibers, plastic optical fiber cables, optical fiber cables with plugs and copolymer |
WO2009116492A1 (en) * | 2008-03-21 | 2009-09-24 | コニカミノルタオプト株式会社 | Imaging lens, imaging device, digital instrument, and manufacturing method of the imaging lens |
JP2013107936A (en) * | 2011-11-17 | 2013-06-06 | Asahi Kasei Chemicals Corp | Methacrylic resin and melt molded article thereof |
US8648160B2 (en) | 2004-11-09 | 2014-02-11 | Idemitsu Kosan Co., Ltd. | Optical semiconductor sealing material |
-
1988
- 1988-07-20 JP JP63179014A patent/JPH0229408A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001048538A1 (en) * | 1999-12-27 | 2001-07-05 | Mitsubishi Rayon Co., Ltd. | Plastic optical fibers, plastic optical fiber cables, optical fiber cables with plugs and copolymer |
US7142754B2 (en) | 1999-12-27 | 2006-11-28 | Mitsubishi Rayon Co., Ltd. | Plastic optical fiber, plastic optical fiber cables, optical fiber cables with plugs with copolymer |
US8648160B2 (en) | 2004-11-09 | 2014-02-11 | Idemitsu Kosan Co., Ltd. | Optical semiconductor sealing material |
WO2009116492A1 (en) * | 2008-03-21 | 2009-09-24 | コニカミノルタオプト株式会社 | Imaging lens, imaging device, digital instrument, and manufacturing method of the imaging lens |
US8368786B2 (en) | 2008-03-21 | 2013-02-05 | Konica Minolta Opto, Inc. | Image pickup lens including at least one lens block wherein a lens portion or lens portions are formed on a lens substrate, image pickup device, digital apparatus and manufacturing method of image pickup lens |
JP5267825B2 (en) * | 2008-03-21 | 2013-08-21 | コニカミノルタアドバンストレイヤー株式会社 | IMAGING LENS, IMAGING DEVICE, DIGITAL DEVICE, AND IMAGING LENS MANUFACTURING METHOD |
JP2013107936A (en) * | 2011-11-17 | 2013-06-06 | Asahi Kasei Chemicals Corp | Methacrylic resin and melt molded article thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0109073B1 (en) | Polymerizable compositions | |
JPS633011A (en) | Transparent copolymer having low water-absorption | |
JPS5936111A (en) | Copolymer for optical fiber | |
US4578445A (en) | Halogen-containing lens material | |
JPH0229408A (en) | Lowly water-absorbing and transparent plastic | |
JP3870670B2 (en) | Non-birefringent pickup lens resin composition and pickup lens using the same | |
JPS5986615A (en) | Polymerizable composition | |
KR920002310B1 (en) | Plastic lens and method of manufacturing thereof | |
JPS62109811A (en) | Production of highly heat-resistant methyl methacrylate resin | |
JPS6173705A (en) | Optical resin material | |
JPH0578570B2 (en) | ||
JP2707653B2 (en) | High Abbe number lens | |
JP3870715B2 (en) | Non-birefringent pickup lens resin composition and pickup lens using the same | |
JPS61159408A (en) | Production of polymer | |
JPH0445401A (en) | Lens having high abbe's number | |
JPS60115605A (en) | Lowly moisture-absorptive methacrylate resin | |
JPS61152708A (en) | Production of polymer | |
JP2564273B2 (en) | Casting optical resin material | |
JPS63243109A (en) | Optical material | |
JP2983226B2 (en) | Transparent resin material | |
JPS63138301A (en) | Heat-resistant optical plastic | |
JPS59197412A (en) | Optical material | |
JPH0386712A (en) | Methacrylic resin with low birefringence and low hygroscopicity | |
JPS60200223A (en) | Oxygen permeable hard contact lens | |
JPS63243114A (en) | Optical material |