JPH02110112A - Plastic optical material - Google Patents
Plastic optical materialInfo
- Publication number
- JPH02110112A JPH02110112A JP63264735A JP26473588A JPH02110112A JP H02110112 A JPH02110112 A JP H02110112A JP 63264735 A JP63264735 A JP 63264735A JP 26473588 A JP26473588 A JP 26473588A JP H02110112 A JPH02110112 A JP H02110112A
- Authority
- JP
- Japan
- Prior art keywords
- birefringence
- plastic optical
- optical
- optical material
- methacrylate
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000004033 plastic Substances 0.000 title claims abstract description 22
- 229920003023 plastic Polymers 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 2
- -1 acrylic ester Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- HGNRHPWYXDRKEA-UHFFFAOYSA-N [1,1,3,3,3-pentafluoro-2-(fluoromethyl)-2-methylpropyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(C)(CF)C(F)(F)F HGNRHPWYXDRKEA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GWYSWOQRJGLJPA-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(C)(F)F GWYSWOQRJGLJPA-UHFFFAOYSA-N 0.000 description 1
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- 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、複屈折の少ないプラスチック光学月料に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a plastic optical material with low birefringence.
なお、本発明にいうガラス転移点（Ｔｇ）は、″高分子
測定法：構造と物性” （培風館）、上巻第１８１〜１
８２頁に記載された方法により測定した値を意味する。The glass transition point (Tg) referred to in the present invention is described in "Polymer Measurement Method: Structure and Physical Properties" (Baifukan), Vol. 1, No. 181-1.
It means the value measured by the method described on page 82.
即ち、ＤＳＣ（示差走査熱口計）を用いて、昇温速度２
０°Ｃ／分で得られる吸熱曲線の中間点をＴｇとした。That is, using a DSC (differential scanning calorimeter), the heating rate was 2.
The midpoint of the endothermic curve obtained at 0°C/min was defined as Tg.
また、複屈折は、“合成樹脂″第３２巻、Ｎ０８９．５
８〜６３頁（１９８６）に記載の方法で決定した。即ち
、エリプソメーターにより位相差を測定し、測定光の波
長および試料の厚さから複屈折を算出した。In addition, birefringence is “Synthetic Resin” Volume 32, No. 089.5
It was determined by the method described on pages 8-63 (1986). That is, the phase difference was measured using an ellipsometer, and the birefringence was calculated from the wavelength of the measurement light and the thickness of the sample.
従来技術とその問題点
レンズ、プリズム、光学用窓材、光記録ディスクなどの
材料としては、各種の光学用プラスチックが使用されて
いる。これら光学用プラスチックは、経世で、ガラスに
近い透明性を有するという利点の他に、ガラスでは製造
困難な非球面レンズの製造が容易であり、大口生産が可
能であるという際立った特質を備えている。Prior Art and its Problems Various optical plastics are used as materials for lenses, prisms, optical window materials, optical recording disks, etc. Over the years, these optical plastics have had the distinct advantage of having transparency close to that of glass, as well as the ability to easily manufacture aspherical lenses, which are difficult to manufacture with glass, and the ability to produce them in large quantities. There is.
この様な光学用プラスチックとしては、通常ポリスチレ
ン樹脂、ポリカーボネート樹脂、ポリメチルメタクリレ
ート樹脂などが用いられている。As such optical plastics, polystyrene resin, polycarbonate resin, polymethyl methacrylate resin, etc. are usually used.
しかしながら、これらのプラスチックは、成形時に歪み
が残留し易く、大きな複屈折を生じ易い。However, these plastics tend to remain distorted during molding and tend to produce large birefringence.
複屈折が大きいと、レンズにおいては、結像光路の精度
が低くなるのみならず、屈折率分布が生じて、光学系と
しての信頼性が低下する。また、光ディスクでは、レー
ザー光の反射を利用して読取りを行なうので、ディスク
基板の複屈折が大きい場合には、読取りエラーの原因と
もなる。If the birefringence is large, the precision of the imaging optical path in the lens will not only decrease, but also a refractive index distribution will occur, reducing the reliability of the optical system. Furthermore, since optical discs are read using reflection of laser light, if the disc substrate has large birefringence, this may cause reading errors.
従って、複屈折のより小さいプラスチック光学材料の出
現が望まれている。Therefore, the emergence of plastic optical materials with lower birefringence is desired.
問題点を解決するための手段
本発明者は、この様な技術の現状に鑑みて研究を進めた
結果、特定の単量体を含む重合体もしくは共重合体の複
屈折が極めて小さく、プラスチック光学材料として優れ
た性質を発揮することを見出した。Means for Solving the Problems As a result of conducting research in view of the current state of technology, the present inventor found that the birefringence of polymers or copolymers containing specific monomers is extremely small, and that plastic optical It was discovered that it exhibits excellent properties as a material.
すなわち、本発明は、下記のプラスチック光学材料およ
びその用途を提供するものである：■以下の要件を充足
するプラスチック光学材料：（ａ）下記一般式（１）で
示される単量体成分を１重量％以上含む重合体または共
重合体により構成されていること。That is, the present invention provides the following plastic optical material and its uses: ■ A plastic optical material that satisfies the following requirements: (a) A monomer component represented by the following general formula (1) is It must be composed of a polymer or copolymer containing at least % by weight.
０ ０Ｆ３
（式中Ｘは、水素またはメチル基を表イっす；Ｙは、水
素またはメチル基を表わす）
（ｂ）ガラス転移点（Ｔｇ）が、８０℃以上であること
。0 0F3 (In the formula, X represents hydrogen or a methyl group; Y represents hydrogen or a methyl group) (b) The glass transition point (Tg) is 80°C or higher.
（ｃ）Ｔｇよりも１５°Ｃ高い温度で５％延伸した後急
冷し、室温で測定した複屈折（Δｎ）が、±２００Ｘ１
０’の範囲内にあること。(c) The birefringence (Δn) measured at room temperature after being stretched 5% at a temperature 15°C higher than Tg and then rapidly cooled is ±200X1.
Must be within the range of 0'.
■上記第１項に記載されたプラスチック光学材料により
形成されたレンズ、プリズム、光学用窓材または光記録
ディスク。(2) Lenses, prisms, optical window materials, or optical recording disks made of the plastic optical material described in item 1 above.
本発明に係るプラスチック光学材料は、一般式（１）で
示される単量体成分を１重量％以上含んでいることを第
一の要件とする。The first requirement of the plastic optical material according to the present invention is that it contains 1% by weight or more of the monomer component represented by general formula (1).
（式中Ｘは、水素またはメチル基を表わす：Ｙは、水素
またはメチル基を表わす）
即ち、本発明に係るプラスチック光学材料は、一般式（
１）で示される単量体のみからなる単独重合体であって
もよく、或いは他の単量体との共重合体であっても良い
。(In the formula, X represents hydrogen or a methyl group; Y represents hydrogen or a methyl group.) That is, the plastic optical material according to the present invention has the general formula (
It may be a homopolymer consisting only of the monomer shown in 1), or it may be a copolymer with other monomers.
この様な単量体（１）と共重合すべき単量体としては、
プラスチック光学材料の所望の特性を損なわない限り特
に限定されず、スチレンおよびそのアルキル置換体（ア
ルキルとしては、炭素数１〜８程度）；アクリロニトリ
ル；炭素数１〜１５のアルキル基を有する（メタ）アク
リレート；炭素数１〜１５のアルキル基を有する含フッ
素（メタ）アクリレートなどが例示される。炭素数１〜
１５のアルキル基を有する（メタ）アクリレートの具体
例としては、メチルメタクリレート、メチルアクリレー
ト、エチルメタクリレート、シクロへキシルメタクリレ
ート、トリシクロデシルメタクリレートなどが挙げられ
る。また、炭素数１〜１５のアルキル基を有する含フッ
素（メタ）アクリレートの具体例としては、トリフルオ
ロエチルメタクリレート、テトラフルオロプロピルメタ
クリレートなどが挙げられる。Monomers to be copolymerized with such monomer (1) include:
There are no particular limitations as long as the desired properties of the plastic optical material are not impaired; styrene and its alkyl substituted products (alkyl has about 1 to 8 carbon atoms); acrylonitrile; having an alkyl group of 1 to 15 carbon atoms (meth) Acrylate: Examples include fluorine-containing (meth)acrylates having an alkyl group having 1 to 15 carbon atoms. Carbon number 1~
Specific examples of (meth)acrylates having 15 alkyl groups include methyl methacrylate, methyl acrylate, ethyl methacrylate, cyclohexyl methacrylate, tricyclodecyl methacrylate, and the like. Further, specific examples of the fluorine-containing (meth)acrylate having an alkyl group having 1 to 15 carbon atoms include trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, and the like.
本発明プラスチック光学材料が具備すべき［ガラス転移
点（Ｔ ｇ）が、８０℃以上である」という第二の要件
は、Ｔｇがこの値未満である場合には、プラスチック光
学材料がその使用条件下に変形し易く、光学精度が著る
しく低下して、実用上重大な欠点となる為、必要とされ
るものである。The second requirement that the plastic optical material of the present invention should have is that the glass transition point (T g ) is 80°C or higher. This is necessary because it is easily deformed downward and the optical precision is significantly reduced, resulting in a serious drawback in practice.
さらに、本発明プラスチック光学材料は、ｒＴｇよりも
１５℃高い温度で５％延伸した後急冷し、室温で測定し
た場合の複屈折（Δｎ）が、±２００Ｘ１０’の範囲内
にある」という第三の要件を具備することが重要である
。光学材料としてのプラスチック材料に関して問題とな
るのは、配向複屈折である。即ち、これは、プリズム、
光記録ディスクなどの光学製品の成形加工時の分子配向
が凍結されるために生ずる複屈折であるため、成形条件
（金型温度、樹脂の加熱温度など）によって配向度が変
化し、複屈折も変化する。従って、一定の配向条件の下
で加工した成形品についての複屈折の値でプラスチック
利料としての特性を比較する必要がある。この本発明の
第三の要件は、充分にアニールした成形品を溶融加工が
可能な温度Ｔｇ＋１５℃において、５％変型を加えて配
向させた成形品の複屈折が±２００Ｘ１０−６の範囲内
にあることにより特徴付けられる。Furthermore, the plastic optical material of the present invention has a birefringence (Δn) within the range of ±200X10' when measured at room temperature after being stretched 5% at a temperature 15°C higher than rTg and then rapidly cooled. It is important to meet the following requirements. A problem with plastic materials as optical materials is orientational birefringence. That is, this is a prism,
Birefringence occurs when the molecular orientation of optical products such as optical recording disks is frozen during the molding process, so the degree of orientation changes depending on the molding conditions (mold temperature, resin heating temperature, etc.), and birefringence also occurs. Change. Therefore, it is necessary to compare the properties of plastic materials based on the birefringence values of molded products processed under certain orientation conditions. The third requirement of the present invention is that at a temperature Tg + 15°C at which a sufficiently annealed molded product can be melt-processed, the birefringence of the oriented molded product after 5% deformation is within the range of ±200X10-6. characterized by something.
本発明プラスチック光学材料は、複屈折が小さいので、
レンズ、プリズム、光記録ディスクなどの光学製品の性
能を著るしく改善することが出来る。The plastic optical material of the present invention has small birefringence, so
The performance of optical products such as lenses, prisms, and optical recording disks can be significantly improved.
実施例
以下に参考例、実施例および比較例を示し、本発明の特
徴とするところをより一層明確にする。EXAMPLES Below, reference examples, working examples, and comparative examples will be shown to further clarify the features of the present invention.
参考例１
減圧蒸溜により精製したヘキサフルオロネオペンチルメ
タクリレート１００部、ｎ−ドデシルメルカプタン０．
０５部および重合開始剤として２゜２′−アゾイソブチ
ロニトリル０．０２５部を５００ｍ１のガラス製フラス
コ内で溶解混合し、脱気および窒素置換を繰返し、密封
した後、７０℃で１６時間重合させた。Reference Example 1 100 parts of hexafluoroneopentyl methacrylate purified by vacuum distillation, 0.0 parts of n-dodecyl mercaptan.
0.05 parts of 0.05 parts and 0.025 parts of 2゜2'-azoisobutyronitrile as a polymerization initiator were dissolved and mixed in a 500 ml glass flask, and the mixture was repeatedly degassed and replaced with nitrogen, sealed, and then heated at 70°C for 16 hours. Polymerized.
重合終了後、生成物にアセトン３００ｇを加えて溶解さ
せ、得られた溶液をメタノール５１に注ぎ込んだ。沈澱
した重合物を液体から分離し、１００℃の温度で１０時
間減圧乾燥し、固形の重合体９６．２ｇ （収率９６％
）を得た。After the polymerization was completed, 300 g of acetone was added to the product to dissolve it, and the resulting solution was poured into 51 g of methanol. The precipitated polymer was separated from the liquid and dried under reduced pressure at a temperature of 100°C for 10 hours to obtain 96.2 g of solid polymer (96% yield).
) was obtained.
得られた重合体の分子ｍは、３５℃、溶媒メチルエチル
ケトンでの極限粘度［η＝０．５９６］であった。また
、重合体の同定を核磁気共鳴スペクトルで行なったとこ
ろ、下記の構造単位からなっていることが確認された。The molecule m of the obtained polymer had an intrinsic viscosity [η=0.596] at 35° C. and in the solvent methyl ethyl ketone. Furthermore, when the polymer was identified by nuclear magnetic resonance spectroscopy, it was confirmed that it consisted of the following structural units.
ＯＣＦ３
参考例２
ヘキサフルオロネオペンチルメタクリレート単量体とメ
チルメタクリレートとの等重量を使用し、参考例１と同
様にして、共重合体を得た。OCF3 Reference Example 2 A copolymer was obtained in the same manner as in Reference Example 1 using equal weights of hexafluoroneopentyl methacrylate monomer and methyl methacrylate.
実施例１
参考例１で得られたヘキサフルオロネオペンチルメタク
リレート重合体（Ｔｇ＝１０８°Ｃ）粉末を２００℃に
加熱したプレスで加圧し、厚さ０．４ｍｍの透明シート
を成型した後、８ｍｍＸ４０關の試験片を切り出した。Example 1 The hexafluoroneopentyl methacrylate polymer (Tg=108°C) powder obtained in Reference Example 1 was pressed with a press heated to 200°C to form a transparent sheet with a thickness of 0.4 mm, and then an 8 mm x 40 A test piece was cut out.
得られた試験片を延伸治具に固定し、１２３℃の電気炉
中で１０分間アニーリングし、さらに同温度で５％の延
伸を行なった後、直ちに氷水中に投入して、配向を凍結
した。The obtained test piece was fixed in a stretching jig, annealed for 10 minutes in an electric furnace at 123°C, further stretched by 5% at the same temperature, and then immediately placed in ice water to freeze the orientation. .
得られた配向試験片の位相差をエリプソメーター（光源
Ｈｅ−Ｎｅレーザー、波長６３２．８ｎｍ）により測定
し、複屈折を算出したところ、−１，０８Ｘ１０”””
であった。The phase difference of the obtained oriented test piece was measured with an ellipsometer (light source: He-Ne laser, wavelength 632.8 nm), and the birefringence was calculated.
Met.
実施例２
参考例２で得られたヘキサフルオロネオペンチルメタク
リレート／メチルメタクリレート共重合体（Ｔｇ＝１０
６°Ｃ）粉末を使用し且つアニールおよび延伸の温度を
１２１°Ｃとする以外は実施例１と同様にして処理し、
配向試験片を得た。その複屈折は、−３，０２Ｘ１０’
であった。Example 2 Hexafluoroneopentyl methacrylate/methyl methacrylate copolymer obtained in Reference Example 2 (Tg=10
6°C) powder and the annealing and stretching temperature was 121°C,
An oriented test piece was obtained. Its birefringence is -3,02X10'
Met.
比較例１
メチルメタクリレート重合体（商標“アクリペットＶＨ
−００１”、三菱レーヨン（株）製、Ｔｇ＝１０５’Ｃ
）粉末を使用し且つアニールおよび延伸の温度を１２０
℃とする以外は実施例１と同様にして処理し、配向試験
片を得た。その複屈折は、−２，５７ｘｌＯ−４であっ
た。Comparative Example 1 Methyl methacrylate polymer (trademark “Acripet VH”)
-001", manufactured by Mitsubishi Rayon Co., Ltd., Tg=105'C
) powder and annealing and stretching temperature 120
The treatment was carried out in the same manner as in Example 1 except that the temperature was changed to 0.degree. C. to obtain an oriented test piece. Its birefringence was -2,57xlO-4.
比較例２
下記の割合で各単量体を使用して、共重合体を製造した
。Comparative Example 2 A copolymer was produced using each monomer in the following proportions.
ＩＨ，ＩＨ−テトラフルオロプロピルメタクリレート
３０重量部メチルメタクリ
レート ５０重量部シクロへキシルメタクリ
レート １７重量部エチルアクリレート
３重量部即ち、各重合体の混合物１００重量部を
懸濁安定剤としてのリン酸カルシウム１重量部およびド
デシルベンゼンスルホン酸ナトリウム０．０１重量部の
存在下に水２００重量部に加え、分散させた後、７０℃
で６時間重合反応させ、次いで９０°Ｃで２時間重合反
応させた。IH, IH-tetrafluoropropyl methacrylate
30 parts by weight methyl methacrylate 50 parts by weight cyclohexyl methacrylate 17 parts by weight ethyl acrylate
After adding 3 parts by weight, i.e. 100 parts by weight of each polymer mixture, to 200 parts by weight of water in the presence of 1 part by weight of calcium phosphate and 0.01 part by weight of sodium dodecylbenzenesulfonate as suspension stabilizers and dispersing the mixture. ,70℃
The polymerization reaction was carried out at 90°C for 6 hours, and then at 90°C for 2 hours.
重合終了後、反応生成物を冷塩酸で処理し、水洗し、乾
燥することにより、固形の重合体（Ｔｇ＝７５°Ｃ）を
得た。After the polymerization was completed, the reaction product was treated with cold hydrochloric acid, washed with water, and dried to obtain a solid polymer (Tg=75°C).
得られた重合体を使用し且つアニールおよび延伸の温度
を９０°Ｃとする以外は実施例１と同様にして処理し、
配向試験片を得た。その複屈折は、十５．５Ｘ１０’で
あった。The obtained polymer was treated in the same manner as in Example 1 except that the annealing and stretching temperature was 90°C,
An oriented test piece was obtained. Its birefringence was 15.5×10'.
（以 上）(that's all)
Claims (2)
ａ）下記一般式（１）で示される単量体成分を１重量％
以上含む重合体または共重合体により構成されているこ
と。 ▲数式、化学式、表等があります▼（１） （式中Ｘは、水素またはメチル基を表わす；Ｙは、水素
またはメチル基を表わす） （ｂ）ガラス転移点（Ｔｇ）が、８０℃以上であること
。 （ｃ）Ｔｇよりも１５℃高い温度で５％延伸した後急冷
し、室温で測定した複屈折（Δｎ）が、±２００×１０
＾−＾６の範囲内にあること。(1) Plastic optical materials that meet the following requirements: (
a) 1% by weight of the monomer component represented by the following general formula (1)
It must be composed of a polymer or copolymer containing the above. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, X represents hydrogen or a methyl group; Y represents hydrogen or a methyl group) (b) Glass transition point (Tg) is 80°C or higher To be. (c) Birefringence (Δn) measured at room temperature after being stretched 5% at a temperature 15°C higher than Tg and then rapidly cooled is ±200×10
Must be within the range of ＾-＾6.
により形成されたレンズ、プリズム、光学用窓材または
光記録ディスク。(2) A lens, prism, optical window material, or optical recording disk formed from the plastic optical material according to claim (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63264735A JPH02110112A (en) | 1988-10-19 | 1988-10-19 | Plastic optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63264735A JPH02110112A (en) | 1988-10-19 | 1988-10-19 | Plastic optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02110112A true JPH02110112A (en) | 1990-04-23 |
Family
ID=17407442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63264735A Pending JPH02110112A (en) | 1988-10-19 | 1988-10-19 | Plastic optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02110112A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998004601A1 (en) * | 1996-07-30 | 1998-02-05 | Hitachi Chemical Co., Ltd. | Process for the preparation of non-birefringent optical resin and optical elements made by using the resin prepared by the process |
| WO2004055554A1 (en) * | 2002-12-13 | 2004-07-01 | Daikin Industries, Ltd. | Fluorine-containing optical material and fluorine-containing copolymer |
| WO2004104058A1 (en) * | 2003-05-23 | 2004-12-02 | Daikin Industries, Ltd. | Heat-resistant, fluorine-containing optical material and optical transmission medium using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5936111A (en) * | 1982-08-24 | 1984-02-28 | Daikin Ind Ltd | Copolymer for optical fiber |
| JPS63159820A (en) * | 1986-12-24 | 1988-07-02 | Hoya Corp | Hard contact lens having oxygen permeability |
-
1988
- 1988-10-19 JP JP63264735A patent/JPH02110112A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5936111A (en) * | 1982-08-24 | 1984-02-28 | Daikin Ind Ltd | Copolymer for optical fiber |
| JPS63159820A (en) * | 1986-12-24 | 1988-07-02 | Hoya Corp | Hard contact lens having oxygen permeability |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998004601A1 (en) * | 1996-07-30 | 1998-02-05 | Hitachi Chemical Co., Ltd. | Process for the preparation of non-birefringent optical resin and optical elements made by using the resin prepared by the process |
| WO2004055554A1 (en) * | 2002-12-13 | 2004-07-01 | Daikin Industries, Ltd. | Fluorine-containing optical material and fluorine-containing copolymer |
| WO2004104058A1 (en) * | 2003-05-23 | 2004-12-02 | Daikin Industries, Ltd. | Heat-resistant, fluorine-containing optical material and optical transmission medium using same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6195011A (en) | Optical disk substrate | |
| JPH02110112A (en) | Plastic optical material | |
| CN101432325A (en) | Novel copolymer of methacrylic ester, composition, optical element and electric member | |
| US5138001A (en) | Vinylphenyl compound, process for the production thereof, polymerizable composition containing same, and crosslinked polymer formed therefrom | |
| WO1992017529A1 (en) | Thermoplastic saturated norbornene resin sheet and production thereof | |
| JPS62112612A (en) | Acrylic resin | |
| JPH03195710A (en) | Molded polymer having essentially low birefringence | |
| Nagase et al. | Control of thermal, mechanical, and optical properties of three‐component maleimide copolymers by steric bulkiness and hydrogen bonding | |
| JPS60233106A (en) | Optical disk material | |
| JPH01102502A (en) | Optical molding | |
| JPS61278509A (en) | Optical disc base | |
| JPS63264613A (en) | Optical element substrate | |
| JP4187504B2 (en) | Copolymer | |
| JPS6241210A (en) | Heat-resistant methyl methacrylate resin | |
| JPS61152708A (en) | Production of polymer | |
| JPH02233710A (en) | Methacrylic resin having low moisture absorption | |
| WO1989006248A1 (en) | Lowly hygroscopic methacrylate polymer | |
| JPS63234009A (en) | Methacrylic resin composition | |
| JP6015838B2 (en) | Alkoxycinnamic acid ester polymer and retardation film using the same | |
| JP6557985B2 (en) | Alkoxycinnamic ester copolymer and process for producing the same | |
| JP2016098371A (en) | Fumaric diester-alkoxy cinnamic acid ester copolymer and phase difference film prepared therewith | |
| JPS6321186A (en) | Optical disk material | |
| JPS60147416A (en) | Low moisture absorbing methacrylic resin | |
| JPS63241011A (en) | Optical resin material | |
| JPS63213506A (en) | Material for optical use |