JPH0430410B2 - - Google Patents
Info
- Publication number
- JPH0430410B2 JPH0430410B2 JP59005669A JP566984A JPH0430410B2 JP H0430410 B2 JPH0430410 B2 JP H0430410B2 JP 59005669 A JP59005669 A JP 59005669A JP 566984 A JP566984 A JP 566984A JP H0430410 B2 JPH0430410 B2 JP H0430410B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- polymerization
- carbon atoms
- present
- optical material
- 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.)
- Expired - Lifetime
Links
- 230000003287 optical effect Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000004641 Diallyl-phthalate Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 methacryloxymethyl Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-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
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-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
- NNWNNQTUZYVQRK-UHFFFAOYSA-N 5-bromo-1h-pyrrolo[2,3-c]pyridine-2-carboxylic acid Chemical compound BrC1=NC=C2NC(C(=O)O)=CC2=C1 NNWNNQTUZYVQRK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002574 CR-39 Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 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
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229940024874 benzophenone Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 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
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は光学材料の製造法に関し、さらに詳し
くは低分散、高屈折率を有し、注型重合時の収縮
が少なく、しかも耐吸湿性に優れた光学材料の製
造法に関する。
プラスチツク光学材料は、ガラス製のものに比
べて、軽い、耐衝撃性が高い、研磨が不要で大量
生産が容易である、非球面レンズが量産できる等
の利点を有している。しかしながら、一方、ガラ
ス製のものに比べ、屈折率の選択の幅が小さい、
吸湿性が大きい等の欠点を有しており、従来これ
らの欠点がプラスチツク光学材料の使用を阻害す
る要因となつていた。特に低分散で、しかも高屈
折率を有するプラスチツク光学材料は従来得られ
ておらず、その開発が要望されていた。
本発明の目的は、上記従来技術の欠点を除去
し、低分散、高屈折率を有し、注型重合時の収縮
が少なく、しかも耐吸湿性に優れた光学材料の製
造法を提供することにある。
本発明者らは、前記目的を達成するため、鋭意
研究の結果、オレフイン性基を含有するアクリレ
ートモノマーとして、後記一般式（）または
（）で表わされる特定の化合物を使用すること
により、注型時の重合収縮性、耐吸湿性、複屈折
性等を改良し、かつメチルメタクリレート程度の
低分散性を有し、しかも高屈折率を有する光学材
料が得られることを見出し、本発明に到達した。
本発明は、一般式（）
（式中、R1は水素原子またはメチル基、R2は炭
素数１〜５のアルキレン基またはアルキレンオキ
サイド基、R3は水素原子または炭素数１〜３の
アルキル基、ｎは１または２の整数を意味する）
で表される化合物および／または一般式（）
（式中、R1、R3およびｎは前記の意味を有する）
で表される化合物を主要モノマー成分としてラジ
カル重合することを特徴とする光学材料の製造法
に関する。
本発明に用いられる主要モノマー成分である前
記一般式（）または（）の化合物は、ジシク
ロペンタジエンまたはトリシクペンタジエンから
誘導されるジオール体を、メタクリル酸またはア
クリル酸でエステル化することにより容易に製造
することができる。
一般式（）の化合物としては、例えば
等があげられる。
また一般式（）の化合物としては、例えば
（ビス（メタクリロキシメチル）トリシクロ
〔５、２、１、02.6〕デカン）
（ビス（アクリロキシメチル）トリシクロ
〔５、２、１、02.6〕デカン）
（ビス（メタクリロキシメチル）ペンタシクロ
〔６、５、12.6、02.7、09.13〕ペンタデカン）
等があげられる。
これらの一般式（）または（）の化合物以
外に、所望により他のモノマーが併用される。こ
れらの併用モノマーとしては、ラジカル重合性を
有し、重合後に透明性を損わないモノマー成分で
あればよく、例えばメチルメタクリレート、シク
ロヘキシルメタクリレート、アダマンチルメタク
リレート等のアクリル酸またはメタクリル酸のエ
ステル類、スチレン、α−メチルスチレン、ｐ−
メチルスチレン、ブロモスチレン、ビニルナフタ
レン等の芳香族ビニル化合物類、エチレングリコ
ール、ジエチレングリコール、ペンタエリスリト
ール等の多価アルコールとメタクリル酸またはア
クリル酸とのエステル類、アリルジグリコールカ
ーボネート等のアルキルアリルエーテル類、フタ
ル酸ジアリル、イソフタル酸ジアリル等が用いら
れる。
これらの併用モノマーの種類および使用量は、
光学材料として要求される屈折率および耐熱性等
により、種々選択することができるが、通常注型
重合時の収縮性の面から、一般式（）または
（）の化合物10重量部に対して、好ましくは100
重量部未満、より好ましくは10重量部未満の量で
用いられる。
本発明において、光学材料は、例えば前記モノ
マー成分を、ラジカル重合開始剤を用いて重合す
る方法または紫外線、放射線を照射して重合する
方法等の公知のラジカル重合法により重合するこ
とにより得られる。
ラジカル重合開始剤としては、特に限定され
ず、公知の化合物を使用することができ、所望の
反応温度に応じて選択される。例えば、ベンゾイ
ルパーオキサイド、ジ−ｔ−ブチルパーオキサイ
ド、ジイソプロピルパーオキシジカーボネート、
メチルエチルケトンパーオキサイド、ラウロイル
パーオキサイド等の過酸化物、アゾビスイソブチ
ロニトリル等のアゾ系化合物等が用いられる。
光または紫外線照射等の手段を用いて硬化する
場合には、必要に応じて開始剤および／または増
感剤を使用することができ、例えばアセトフエノ
ン、ベンゾフエノン、ベンゾイン、ベンゾインメ
チルエーテル、ベンゾインエチルエーテル、ベン
ゾインイソプロピルエーテル等が使用される。
本発明における重合方法は、特に限定されず、
公知の重合方法、例えば注型重合法が用いられ
る。
この方法によれば、例えばガスケツトまたはス
ペーサーで保持されているモールド間に、ラジカ
ル重合開始剤を含む前記モノマー成分を注入して
重合させる。また予め重合開始剤の存在下に、前
記モノマー成分を予備的に重合させた後、注型重
合することもできる。
重合反応に際して、加熱する場合の反応温度は
使用触媒により異なるが、一般に比較的低温下で
重合を開始し、徐々に温度を上昇させていき硬化
させることが好ましい。
重合反応に際して、必要に応じて離型剤、紫外
線吸収剤、酸化防止剤、着色防止剤、帯電防止
剤、螢光染料、各種安定剤等の添加剤を添加使用
してもよい。なお、これらの添加物は重合後に加
えてもよい。
本発明の方法により得られるラジカル重合体か
らなる光学材料は、原料として２個のオレフイン
性基を含有するジアリルモノマーである一般式
（）または（）で表わされる特定の化合物を
用いているため、注型時の重合性および複屈折性
が著しく改良され、しかも例えばジエチレングリ
コールビスアリルカーボネート程度の低分散性お
よび耐衝撃性を有し、また例えばフタル酸ジアリ
ル程度の高屈折率および耐熱性をも有している。
なお、本発明において、光学材料を製造する際に
は一般式（）で表される化合物と一般式（）
で表される化合物を混合して用いてもよい。
このため本発明の光学材料は、例えば眼鏡用、
スチールカメラ用、ビデオカメラ用、望遠鏡用、
太陽光集光用等のレンズ類、プリズム類、光導波
路等の光導性素子類、ビデオデイスク、コンパク
トデイスク、追記可能光デイスクおよび消却再書
込可能光デイスク等のデイスク類等の、光を透過
または反射する機能を要求される材料として好適
に用いられる。
以下、実施例により本発明をさらに詳しく説明
する。
実施例 １
ビス（メタクリロキシメチル）トリシクロ
〔５，２，１，02.6〕デカン20ｇに、イゾビスイソ
ブチロニトリルを0.1ｇの割合で溶解させたモノ
マー溶液を、２枚のガラス板とシリコンラバー製
ガスケツトで組まれたモールド中に注入し、窒素
雰囲気下に、80℃で６時間100℃で２時間加熱硬
化させた後、離型して重合体Ａを得た。
実施例 ２
ビス（メタクリロキシメチル）トリシクロ
〔５，２，１，02.6〕デカンの代わりに、ビス（メ
タクリロキシメチル）ペンタシクロ〔６，５，
１，13.6，02.7，09.13〕ペンタデカンを用い、その
他は実施例１と同様にして重合体Ｂを得た。
実施例 ３
ビス（メタクリロキシメチル）トリシクロ
〔５，２，１，02.6〕デカンの代わりに、
を用い、その他は実施例１と同様にして重合体Ｃ
を得た。
実施例 ４
ビス（メタクリロキシメチル）トリシクロ
〔５，２，１，02.6〕デカン70部およびメチルメタ
クリレート30部を用い、その他は実施例１と同様
にして重合体Ｄを得た。
実施例 ５
ビス（メタクリロキシメチル）トリシクロ
〔５，２，１，02.6〕デカン60部およびスチレン40
部を用い、その他は実施例１と同様にして重合体
Ｅを得た。
実施例１〜５で得られた重合体（Ａ〜Ｅ）につ
て、屈折率、分散性、重合収縮率、表面硬度、吸
水率、複屈折、熱変形温度（耐熱性）および耐衝
撃性について試験した。得られた結果を第１表に
示す。
比較のため、それぞれジエチレングリコールビ
スアリルカーボネート（PPG製品）（比較例１）
フタル酸ジアリル（比較例２）、メチルメタアク
リレート（比較例３）またはスチレン（比較例
４）、を実施例１と同様に重合して得られた化合
物について、試験した結果も第１表に併せて示
す。
The present invention relates to a method for producing an optical material, and more particularly to a method for producing an optical material that has low dispersion, a high refractive index, little shrinkage during cast polymerization, and excellent moisture absorption resistance. Plastic optical materials have advantages over glass materials, such as being lightweight, having high impact resistance, requiring no polishing and being easy to mass produce, and allowing mass production of aspherical lenses. However, on the other hand, the range of refractive index selection is smaller than that of glass ones.
It has drawbacks such as high hygroscopicity, and these drawbacks have hitherto been a factor inhibiting the use of plastic optical materials. In particular, plastic optical materials with low dispersion and high refractive index have not been available so far, and there has been a demand for their development. An object of the present invention is to provide a method for producing an optical material that eliminates the drawbacks of the above-mentioned prior art, has low dispersion, high refractive index, has little shrinkage during cast polymerization, and has excellent moisture absorption resistance. It is in. In order to achieve the above object, the present inventors have conducted intensive research and found that casting molding is possible by using a specific compound represented by the general formula () or () below as an acrylate monomer containing an olefinic group. The present inventors have discovered that it is possible to obtain an optical material that has improved polymerization shrinkage properties, moisture absorption resistance, birefringence, etc., has low dispersion comparable to that of methyl methacrylate, and has a high refractive index, and has arrived at the present invention. . The present invention is based on the general formula () (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is an alkylene group having 1 to 5 carbon atoms or an alkylene oxide group, R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 1 or 2 carbon atoms. (means an integer)
Compound and/or general formula () represented by (wherein R 1 , R 3 and n have the above meanings)
The present invention relates to a method for producing an optical material, which is characterized by carrying out radical polymerization using a compound represented by the following as a main monomer component. The compound of general formula () or (), which is the main monomer component used in the present invention, can be easily obtained by esterifying a diol derivative derived from dicyclopentadiene or tricyclopentadiene with methacrylic acid or acrylic acid. can be manufactured. As a compound of general formula (), for example, etc. can be mentioned. Further, as a compound of the general formula (), for example, (Bis(methacryloxymethyl)tricyclo[5,2,1,0 2.6 ]decane) (Bis(acryloxymethyl)tricyclo[5,2,1,0 2.6 ]decane) ( bis (methacryloxymethyl)pentacyclo[ 6,5,12.6,02.7,09.13 ] pentadecane), etc. In addition to these compounds of general formula () or (), other monomers may be used in combination, if desired. The monomer used in combination with these may be any monomer component that has radical polymerizability and does not impair transparency after polymerization, such as esters of acrylic acid or methacrylic acid such as methyl methacrylate, cyclohexyl methacrylate, and adamantyl methacrylate, and styrene. , α-methylstyrene, p-
Aromatic vinyl compounds such as methylstyrene, bromostyrene, and vinylnaphthalene; esters of polyhydric alcohols such as ethylene glycol, diethylene glycol, and pentaerythritol, and methacrylic acid or acrylic acid; alkyl allyl ethers such as allyl diglycol carbonate; Diallyl phthalate, diallyl isophthalate, etc. are used. The types and amounts of these monomers used are as follows:
Various selections can be made depending on the refractive index and heat resistance required for the optical material, but from the viewpoint of shrinkage during cast polymerization, for 10 parts by weight of the compound of general formula () or (), preferably 100
It is used in an amount of less than 10 parts by weight, more preferably less than 10 parts by weight. In the present invention, the optical material is obtained, for example, by polymerizing the monomer components using a known radical polymerization method, such as a method of polymerizing using a radical polymerization initiator or a method of polymerizing by irradiating ultraviolet rays or radiation. The radical polymerization initiator is not particularly limited, and known compounds can be used, and it is selected depending on the desired reaction temperature. For example, benzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxydicarbonate,
Peroxides such as methyl ethyl ketone peroxide and lauroyl peroxide, azo compounds such as azobisisobutyronitrile, and the like are used. When curing using means such as light or ultraviolet irradiation, an initiator and/or sensitizer may be used as necessary, such as acetophenone, benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether and the like are used. The polymerization method in the present invention is not particularly limited,
Known polymerization methods, such as cast polymerization, are used. According to this method, the monomer component containing a radical polymerization initiator is injected between molds held, for example, by a gasket or a spacer, and polymerized. Alternatively, the monomer components may be preliminarily polymerized in the presence of a polymerization initiator and then cast polymerized. During the polymerization reaction, the reaction temperature when heating varies depending on the catalyst used, but it is generally preferable to start the polymerization at a relatively low temperature and gradually raise the temperature to effect curing. During the polymerization reaction, additives such as a mold release agent, an ultraviolet absorber, an antioxidant, an anti-coloring agent, an antistatic agent, a fluorescent dye, and various stabilizers may be added as necessary. Note that these additives may be added after polymerization. The optical material made of a radical polymer obtained by the method of the present invention uses a specific compound represented by the general formula () or (), which is a diallyl monomer containing two olefinic groups, as a raw material. It has significantly improved polymerizability and birefringence during casting, has low dispersion and impact resistance comparable to diethylene glycol bisallyl carbonate, and also has high refractive index and heat resistance comparable to diallyl phthalate. are doing.
In addition, in the present invention, when producing an optical material, a compound represented by the general formula () and a general formula ()
You may use a mixture of the compounds represented by. Therefore, the optical material of the present invention can be used, for example, for eyeglasses,
For still cameras, video cameras, telescopes,
Transmits light through lenses such as lenses for concentrating sunlight, prisms, light guide elements such as optical waveguides, disks such as video disks, compact disks, write-once optical disks, and erasable and rewritable optical disks. Alternatively, it can be suitably used as a material that requires a reflective function. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 A monomer solution prepared by dissolving 0.1 g of isobisisobutyronitrile in 20 g of bis(methacryloxymethyl)tricyclo[5,2,1,0 2.6 ]decane was placed between two glass plates and silicon. The mixture was poured into a mold equipped with a rubber gasket, heated and cured at 80°C for 6 hours at 100°C for 2 hours under a nitrogen atmosphere, and then released from the mold to obtain Polymer A. Example 2 Bis(methacryloxymethyl)pentacyclo[ 6,5 ,
Polymer B was obtained in the same manner as in Example 1 except that pentadecane was used. Example 3 Instead of bis(methacryloxymethyl)tricyclo[5,2,1,0 2.6 ]decane, Polymer C was prepared in the same manner as in Example 1.
I got it. Example 4 Polymer D was obtained in the same manner as in Example 1 except that 70 parts of bis(methacryloxymethyl)tricyclo[5,2,1,0 2.6 ]decane and 30 parts of methyl methacrylate were used. Example 5 60 parts of bis(methacryloxymethyl)tricyclo[5,2,1,0 2.6 ]decane and 40 parts of styrene
Polymer E was obtained in the same manner as in Example 1 except that the same procedure was used as in Example 1. About the refractive index, dispersibility, polymerization shrinkage rate, surface hardness, water absorption, birefringence, heat distortion temperature (heat resistance) and impact resistance of the polymers (A to E) obtained in Examples 1 to 5. Tested. The results obtained are shown in Table 1. For comparison, diethylene glycol bisallyl carbonate (PPG product) (Comparative Example 1)
Table 1 also shows the test results for compounds obtained by polymerizing diallyl phthalate (Comparative Example 2), methyl methacrylate (Comparative Example 3), or styrene (Comparative Example 4) in the same manner as in Example 1. Shown.
【表】【table】
【表】
第１表の結果から明らかなように、本発明の製
造法により得られた重合体は、低分散、高屈折率
を有し、注型重合時の収縮が少なく、しかも耐吸
湿性に優れたものである。[Table] As is clear from the results in Table 1, the polymer obtained by the production method of the present invention has low dispersion, high refractive index, little shrinkage during cast polymerization, and moisture absorption resistance. It is excellent.
Claims (1)
素数１〜５のアルキレン基またはアルキレンオキ
サイド基、R3は水素原子または炭素数１〜３の
アルキル基、ｎは１または２の整数を意味する）
で表される化合物および／または一般式（） （式中、R1、R3およびｎは前記の意味を有する）
で表される化合物を主要モノマー成分としてラジ
カル重合することを特徴とする光学材料の製造
法。[Claims] 1 General formula () (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is an alkylene group having 1 to 5 carbon atoms or an alkylene oxide group, R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 1 or 2 carbon atoms. (means an integer)
Compound and/or general formula () represented by (wherein R 1 , R 3 and n have the above meanings)
A method for producing an optical material, characterized by carrying out radical polymerization using a compound represented by as a main monomer component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59005669A JPS60152515A (en) | 1984-01-18 | 1984-01-18 | Optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59005669A JPS60152515A (en) | 1984-01-18 | 1984-01-18 | Optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60152515A JPS60152515A (en) | 1985-08-10 |
| JPH0430410B2 true JPH0430410B2 (en) | 1992-05-21 |
Family
ID=11617506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59005669A Granted JPS60152515A (en) | 1984-01-18 | 1984-01-18 | Optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60152515A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0755966B2 (en) * | 1985-12-26 | 1995-06-14 | 日本化薬株式会社 | Resin composition for groove material or protective film of optical disk |
| JPH0745555B2 (en) * | 1986-03-28 | 1995-05-17 | 三菱油化株式会社 | Resin for optical material and manufacturing method thereof |
| JPS63243109A (en) * | 1987-03-31 | 1988-10-11 | Japan Synthetic Rubber Co Ltd | Optical material |
| JPH07103195B2 (en) * | 1987-10-14 | 1995-11-08 | 株式会社日立製作所 | Optical material |
| JP2537644B2 (en) * | 1987-11-05 | 1996-09-25 | 日本化薬株式会社 | Overcoat composition for optical disk |
| JP2002285042A (en) * | 2001-03-27 | 2002-10-03 | Dainippon Ink & Chem Inc | Uv setting composition for optical disc and photo disc |
| KR100398534B1 (en) * | 2001-12-28 | 2003-09-19 | 씨멘스브이디오한라 주식회사 | An unity instructure of temperature and humidity sensor |
| JP2006083225A (en) * | 2004-09-14 | 2006-03-30 | Fuji Photo Film Co Ltd | Functional film |
| JP2010254984A (en) * | 2009-03-31 | 2010-11-11 | Mitsubishi Chemicals Corp | Polymerizable composition and cured material therefrom |
| JP5573804B2 (en) | 2011-09-23 | 2014-08-20 | 株式会社村田製作所 | Band pass filter |
-
1984
- 1984-01-18 JP JP59005669A patent/JPS60152515A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60152515A (en) | 1985-08-10 |
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