JPH0534642B2 - - Google Patents
Info
- Publication number
- JPH0534642B2 JPH0534642B2 JP59155502A JP15550284A JPH0534642B2 JP H0534642 B2 JPH0534642 B2 JP H0534642B2 JP 59155502 A JP59155502 A JP 59155502A JP 15550284 A JP15550284 A JP 15550284A JP H0534642 B2 JPH0534642 B2 JP H0534642B2
- Authority
- JP
- Japan
- Prior art keywords
- fumarate
- plastic lens
- diester
- dicarboxylic acid
- polymerization
- 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 - Fee Related
Links
- 239000004033 plastic Substances 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 14
- 150000005690 diesters Chemical class 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- -1 cyclohexyl phenyl Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- WTIFDVLCDRBEJK-VAWYXSNFSA-N diphenyl (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1OC(=O)/C=C/C(=O)OC1=CC=CC=C1 WTIFDVLCDRBEJK-VAWYXSNFSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- CPZVJYPXOWWFSW-VAWYXSNFSA-N dibenzyl (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1COC(=O)/C=C/C(=O)OCC1=CC=CC=C1 CPZVJYPXOWWFSW-VAWYXSNFSA-N 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- QAOSKUKLWLPBLU-MDZDMXLPSA-N bis(2-chlorophenyl) (e)-but-2-enedioate Chemical compound ClC1=CC=CC=C1OC(=O)\C=C\C(=O)OC1=CC=CC=C1Cl QAOSKUKLWLPBLU-MDZDMXLPSA-N 0.000 claims description 2
- IFQDRRWLSXCVTR-BQYQJAHWSA-N CC(C)C1=CC=CC=C1OC(=O)\C=C\C(O)=O Chemical compound CC(C)C1=CC=CC=C1OC(=O)\C=C\C(O)=O IFQDRRWLSXCVTR-BQYQJAHWSA-N 0.000 claims 1
- LKRQOCKTKSEEMX-CMDGGOBGSA-N OC(=O)/C=C/C(=O)OC(C(C)C)C1=CC=CC=C1 Chemical compound OC(=O)/C=C/C(=O)OC(C(C)C)C1=CC=CC=C1 LKRQOCKTKSEEMX-CMDGGOBGSA-N 0.000 claims 1
- IOKVRLROGHEDFO-MDZDMXLPSA-N bis(2-bromophenyl) (e)-but-2-enedioate Chemical compound BrC1=CC=CC=C1OC(=O)\C=C\C(=O)OC1=CC=CC=C1Br IOKVRLROGHEDFO-MDZDMXLPSA-N 0.000 claims 1
- 239000003505 polymerization initiator Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OQHBIGTXRDOUOP-CMDGGOBGSA-N 1-o-benzyl 4-o-propan-2-yl (e)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C\C(=O)OCC1=CC=CC=C1 OQHBIGTXRDOUOP-CMDGGOBGSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- QKUGKZFASYQCGO-SREVYHEPSA-N (z)-4-oxo-4-phenylmethoxybut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1=CC=CC=C1 QKUGKZFASYQCGO-SREVYHEPSA-N 0.000 description 1
- 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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 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 1
- 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 1
- REHPGLORUKBHEM-VAWYXSNFSA-N bis[bromo(phenyl)methyl] (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1C(Br)OC(=O)\C=C\C(=O)OC(Br)C1=CC=CC=C1 REHPGLORUKBHEM-VAWYXSNFSA-N 0.000 description 1
- UPJCTQLDYABBHJ-VAWYXSNFSA-N bis[chloro(phenyl)methyl] (e)-but-2-enedioate Chemical compound C=1C=CC=CC=1C(Cl)OC(=O)\C=C\C(=O)OC(Cl)C1=CC=CC=C1 UPJCTQLDYABBHJ-VAWYXSNFSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002776 polycyclohexyl methacrylate Polymers 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、特殊なジカルボン酸のジエステルの
重合物あるいは当該共重合体からなるプラスチツ
クレンズに関し、さらに詳しくは、耐熱性、高屈
折率、低収縮性、耐候性、離型性等に優れたプラ
スチツクレンズに関する。
従来より、プラスチツク素材は、その有する透
明性、軽量性、安全性、加工性等の優れた特性を
生かし無機ガラスの代替品として使われてきてい
る。
その代表的なものとして、ポリメチルメタクリ
レート、ポリクロヘキシルメタクリレート、ポリ
ジエチレングリコールビスアリルカーボネート、
ポリスチレン等が挙げられる。
これらプラスチツク素材は、無機ガラスに比し
て耐傷性、屈折率、耐熱性等において劣つている
点もあるが、前述の優れた特性を生かし広く光学
分野で使用されている。しかし、例えばポリメチ
ルメタクリレート、ポリシクロヘキシルメタクリ
レートおよびポリジエチレングリコールビスアリ
ルカーボネートでは、屈折率がnD＝1.49〜1.50程
度と低いため、レンズに成型した場合無機ガラス
に比してかなり厚いものが要求され、注型成型に
おいてはその熱硬化時の収縮率が10〜20％と著し
く大きいため成型にかなり高度な技術が必要であ
る他、耐熱性に劣るなどの欠点があつた。
また、ポリスチレン、ポリカーボネートでは屈
折率に関してはnD＝1.59程度と高いものの、耐候
性、耐薬品性、耐熱性に欠点を有しており、成型
法については射出成型等の溶融成型によるものが
多く、他種品目生産に有利な注型成型法に適さな
いなどの欠点があつた。
本発明者らは、これら従来の欠点を改良すべく
鋭意検討を重ねた結果、ジカルボン酸のジエステ
ルの重合物あるいは当該共重合体からなるプラス
チツクレンズが、耐熱性、高屈折率、低収縮性、
離型性等に優れていることを見い出し本発明を完
成させた。
本発明は、一般式が
で表わされるR1およびR2の少なくとも一つが芳
香族環を有するエステル残基であるジカルボン酸
のジエステルを重合あるいは主成分として共重合
させてなる重合体からなるプラスチツクレンズを
提供するものである。
本発明に用いるジカルボン酸のジエステルとし
ては、例えばジフエニルフマレート、ジベンジル
フマレート、ジフエネチルフマレート、ジ（クロ
ルフエニル）フマレート、ジ（ブロムフエニル）
フマレート、ジ（クロルベンジル）フマレート、
ジ（ブロムベンジル）フマレート、イソプロピル
ーフエニルフマレート、イソプロピルーベンジル
フマレート、シクロヘキシルーフエニルフマレー
ト、シクロヘキシルーベンジルフマレート、アリ
ルーフエニルフマレート、アリルーベンジルフマ
レート、ジフエニルマレート、ジベンジルマレー
ト、アリルーフエニルマレート、アリルーベンジ
ルマレート等が挙げられる。上記のフマレートお
よびマレートともエステル残基の少なくとも１つ
が芳香族環を有することが特徴であり、当該芳香
族環が、アルキル基やハロゲン基等の該置換体で
あつてもよいが、トランス体であるフマレートの
方がシス体であるマレートよりも好ましい。
本発明のプラスチツクレンズは、上記ジカルボ
ン酸のジエステルの１種あるいは２種以上を重合
させて得ることができる。また上記ジカルボン酸
のジエステルとラジカル重合性二重結合を有する
モノマーを１種あるいは２種以上とをラジカル共
重合させて得ることも可能である。
ラジカル重合性二重結合を有するモノマーとし
ては、例えばスチレン、０−メタルスチレン、０
−クロルスチレン、ジビニルベンゼン等の芳香族
ビニル化合物、メチルメタクリレート、ブチルメ
タクリレート等のメタクリル酸エステル、メチル
アクリレート、エチルアクリレート等のアクリル
酸エステル、酢酸ビニル、プロピオン酸ビニル等
のカルボン酸ビニル、ジアリルフマレート、ジア
リルマレート、ジアリルフタレート、ジエチレン
グリコールビスアリルカーボネート等のアリル化
合物が挙げられる。この場合、前記ジカルボン酸
のジエステルに対するラジカル重合性二重結合を
有するモノマーの共重合組成比としては、前記ジ
カルボン酸のジエステルが主成分となつておれば
任意である。
本発明にかかる重合体あるいは共重合体を重合
させる際に用いられる重合開始剤としては、選定
10時間半減期温度が100℃以下の有機過酸化物な
いしアゾ化合物の１種ないし２種以上が使用され
る。その例として、過酸化ベンゾイル、ジイソプ
ロピルオキシジカーボネート、ターシヤリーブチ
ルペルオキシピバレート、ターシヤリーブチルペ
ルオキシネオデカノエート、ターシヤリーブチル
ペルオキシジイソブチレート、アゾビスイソブチ
ルニトリル等が挙げられる。重合開始剤の使用量
としては原料モノマー総重量に対して10重量％以
下が好ましく、さらに好ましくは５重量％以下で
ある。本発明で前記重合あるいは共重合によりプ
ラスチツクレンズを得るには、当該モノマー原料
に重合開始剤を加えた配合物を直接所望の型内に
仕込み、系を加熱硬化させる方法が好ましく、重
合あるいは共重合させた後の溶融成型は適さな
い。この場合、適時、重合系を不活性ガス例え
ば、窒素、二酸化炭素、ヘリウム等で置換ない
し、雰囲気下にすることが望ましい。また、原料
モノマーに重合開始剤を添加後、所定の温度下で
前もつて若干重合あるいは共重合させておいた
後、所望の型内に仕込み、加熱硬化させて重合を
完結させる方法を取ることも可能である。
なお、前記、加熱硬化させる場合の温度として
は、使用する重合開始剤により異なるが30〜100
℃の範囲が好ましいが、使用する重合開始剤の10
時間半減期温度程度がさらに好ましい。また、硬
化時間の短縮および未反応モノマーや重合開始剤
の残存量を減らす目的で適時、硬化温度を昇温さ
せることも可能である。この場合、硬化に要する
全時間としては10〜60時間程度である。
このようにして得られた本発明のプラスチツク
レンズは、従来のプラスチツクレンズに比して、
耐熱性、耐候性に優れ、屈折率も大巾に改善さ
れ、さらに加工時の低収縮性、型との離型性にも
優れている。
以下、本発明を実施例により詳細に説明するが
実施例によつて本発明が制限さるものでない。
実施例 １
40℃に保温したアリル−ベンジルフマレート
100重量部に重合開始剤としてジイソプロピルペ
ルオキシジカーボネート３重量部を仕込み、この
混合液を、２枚の20cm×20cm硬質ガラス板とシリ
コンゴムパツキンで構成された型内に流し込み、
窒素雰囲気下40℃のオーブン中に24時間保持し
た。その後100℃で24時間保持し硬化を完了させ
た。得られたプラスチツクレンズの特性を表１に
示した。
なお、硬化後の収縮率は、ガラス板に指標され
た目盛りより、重合前と重合後の線収縮の変化よ
り次式に従つて算出した。
（重合前の長さ）−（重合後の長さ）／重合前の長さ
屈折率はアツベ屈折計により測定し、耐熱性
は、前記プラスチツクレンズと同様に作製した20
×20×２mmのテストピースを、150℃の恒温相に
１時間保持し、全く変形及び変色しなかつた場合
を合格、少しでも変形及び変色したものを不合格
とした。離型性は硬化後重合物が無理なくガラス
面より離型するものを合格とした。
実施例 ２
60℃に保温したジフエニルフマレート90重量部
およびジアリルフマレート10重量部に、重合開始
剤として過酸化ベンゾイル３重量部を用い80℃で
24時間重合硬化させた以外は実施例１と全く同様
に行なつた。
実施例 ３
70℃に保温したジベンジルフマレート90重量部
およびイソフタル酸ジアリル10重量部に重合開始
剤として過酸化ベンゾイル３重量部を用いた以外
The present invention relates to a plastic lens made of a polymer or copolymer of a special diester of a dicarboxylic acid, and more specifically to a plastic lens that has excellent heat resistance, high refractive index, low shrinkage, weather resistance, mold release properties, etc. Regarding lenses. Plastic materials have traditionally been used as a substitute for inorganic glass, taking advantage of their excellent properties such as transparency, lightness, safety, and workability. Typical examples include polymethyl methacrylate, polychlorohexyl methacrylate, polydiethylene glycol bisallyl carbonate,
Examples include polystyrene. Although these plastic materials are inferior to inorganic glasses in terms of scratch resistance, refractive index, heat resistance, etc., they are widely used in the optical field, taking advantage of the above-mentioned excellent properties. However, for example, polymethyl methacrylate, polycyclohexyl methacrylate, and polydiethylene glycol bisallyl carbonate have a low refractive index of about n D = 1.49 to 1.50, so when molded into a lens, they are required to be considerably thicker than inorganic glass. In cast molding, the shrinkage rate during heat curing is extremely high, at 10 to 20%, so a fairly sophisticated technique is required for molding, and it also has drawbacks such as poor heat resistance. In addition, although polystyrene and polycarbonate have a high refractive index of about n D = 1.59, they have shortcomings in weather resistance, chemical resistance, and heat resistance, and the molding method is often melt molding such as injection molding. However, it had drawbacks such as being unsuitable for the cast molding method, which is advantageous for producing other types of products. As a result of intensive studies to improve these conventional drawbacks, the present inventors have found that a plastic lens made of a polymer of diester of dicarboxylic acid or a copolymer thereof has high heat resistance, high refractive index, low shrinkage,
The present invention was completed by discovering that it has excellent mold releasability. In the present invention, the general formula is The present invention provides a plastic lens made of a polymer obtained by polymerizing or copolymerizing as a main component a diester of a dicarboxylic acid in which at least one of R 1 and R 2 is an ester residue having an aromatic ring. Examples of diesters of dicarboxylic acids used in the present invention include diphenyl fumarate, dibenzyl fumarate, diphenethyl fumarate, di(chlorophenyl) fumarate, and di(bromphenyl).
fumarate, di(chlorobenzyl) fumarate,
Di(bromobenzyl) fumarate, isopropyl benzyl fumarate, isopropyl benzyl fumarate, cyclohexyl benzyl fumarate, cyclohexyl benzyl fumarate, aryl phenyl fumarate, aryl benzyl fumarate, diphenyl maleate, di Examples include benzyl maleate, allylbenzyl maleate, allyl benzyl maleate, and the like. Both fumarate and maleate are characterized in that at least one of the ester residues has an aromatic ring, and the aromatic ring may be a substituent such as an alkyl group or a halogen group, but it may be a trans form. Some fumarates are preferred over the cis form of malate. The plastic lens of the present invention can be obtained by polymerizing one or more diesters of dicarboxylic acids. Moreover, it is also possible to obtain it by radical copolymerization of the diester of the above dicarboxylic acid and one or more monomers having a radically polymerizable double bond. Examples of monomers having radically polymerizable double bonds include styrene, 0-metal styrene, 0
- Aromatic vinyl compounds such as chlorostyrene and divinylbenzene, methacrylic esters such as methyl methacrylate and butyl methacrylate, acrylic esters such as methyl acrylate and ethyl acrylate, vinyl carboxylates such as vinyl acetate and vinyl propionate, diallyl fumarate , diallyl maleate, diallyl phthalate, diethylene glycol bisallyl carbonate, and other allyl compounds. In this case, the copolymerization ratio of the monomer having a radically polymerizable double bond to the diester of the dicarboxylic acid is arbitrary as long as the diester of the dicarboxylic acid is the main component. The polymerization initiator used when polymerizing the polymer or copolymer according to the present invention is selected from
One or more organic peroxides or azo compounds having a 10-hour half-life temperature of 100° C. or lower are used. Examples thereof include benzoyl peroxide, diisopropyloxydicarbonate, tertiary-butyl peroxypivalate, tertiary-butylperoxyneodecanoate, tertiary-butylperoxydiisobutyrate, azobisisobutylnitrile, and the like. The amount of the polymerization initiator used is preferably 10% by weight or less, more preferably 5% by weight or less based on the total weight of the raw material monomers. In order to obtain a plastic lens by the polymerization or copolymerization in the present invention, it is preferable to directly charge a mixture of the monomer raw materials and a polymerization initiator into a desired mold and heat and harden the system. Melt molding after this process is not suitable. In this case, it is desirable to replace the polymerization system with an inert gas, such as nitrogen, carbon dioxide, helium, etc., or to put it under an atmosphere. Alternatively, after adding a polymerization initiator to the raw material monomer, it may be slightly polymerized or copolymerized at a predetermined temperature, and then placed in a desired mold and heated to harden to complete the polymerization. is also possible. In addition, as for the temperature in the case of heat curing as mentioned above, it varies depending on the polymerization initiator used, but it is 30 to 100℃.
The temperature range of the polymerization initiator used is preferably 10 °C.
More preferably, the temperature is around the time half-life temperature. Furthermore, it is also possible to raise the curing temperature at an appropriate time for the purpose of shortening the curing time and reducing the remaining amount of unreacted monomers and polymerization initiators. In this case, the total time required for curing is about 10 to 60 hours. The plastic lens of the present invention thus obtained has the following features compared to conventional plastic lenses:
It has excellent heat resistance and weather resistance, has a greatly improved refractive index, and also has low shrinkage during processing and excellent mold release properties. EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the Examples. Example 1 Allyl-benzyl fumarate kept at 40°C
3 parts by weight of diisopropyl peroxydicarbonate as a polymerization initiator was added to 100 parts by weight, and this mixed solution was poured into a mold consisting of two 20 cm x 20 cm hard glass plates and a silicone rubber gasket.
It was kept in an oven at 40°C under nitrogen atmosphere for 24 hours. Thereafter, it was held at 100°C for 24 hours to complete curing. Table 1 shows the properties of the obtained plastic lens. The shrinkage rate after curing was calculated from the scale marked on the glass plate from the change in linear shrinkage before and after polymerization according to the following formula. (Length before polymerization) - (Length after polymerization) / Length before polymerization The refractive index was measured with an Atsube refractometer, and the heat resistance was determined using
A test piece measuring 20 mm x 2 mm was held in a constant temperature phase at 150° C. for 1 hour, and a test piece with no deformation or discoloration was considered to be a pass, and a test piece with even the slightest deformation or discoloration was judged to be a fail. Regarding mold releasability, a product that could easily release the polymer from the glass surface after curing was considered acceptable. Example 2 90 parts by weight of diphenyl fumarate and 10 parts by weight of diallyl fumarate kept at 60°C were heated at 80°C using 3 parts by weight of benzoyl peroxide as a polymerization initiator.
The same procedure as in Example 1 was carried out except that polymerization and curing were carried out for 24 hours. Example 3 Except for using 3 parts by weight of benzoyl peroxide as a polymerization initiator in 90 parts by weight of dibenzyl fumarate and 10 parts by weight of diallyl isophthalate kept at 70°C.
【表】
表１から明らかなように、実施例のものはすべ
て屈折率が1.55以上と高く、収縮率が小さく、耐
熱性および離型性も良好なので、光学用樹脂とし
て比較例のものより著しく優れていることがわか
る。[Table] As is clear from Table 1, all of the examples have a high refractive index of 1.55 or more, have a small shrinkage rate, and have good heat resistance and mold release properties, so they are significantly better than the comparative examples as optical resins. It turns out that it is excellent.
Claims (1)
香族環を有するエステル残基であるジカルボン酸
のジエステルを重合あるいは主成分として共重合
させてなる重合体からなるプラスチツクレンズ。 ２ ジカルボン酸のジエステルがジフエニルフマ
レート、ジベンジルフマレート、ジフエネチルフ
マレート、ジ（クロルフエニル）フマレート、ジ
（ブロムフエニル）フマレート、イソプロピルー
フエニルフマレート、イソプロピルーベンジルフ
マレート、シクロヘキシル−フエニルフマレー
ト、アリル−フエニルフマレート又はアリル−ベ
ンジルフマレートである特許請求の範囲第１項記
載のプラスチツクレンズ。 ３ 共重合成分がラジカル重合性二重結合を有す
るモノマーである特許請求の範囲第１項または第
２項記載のプラスチツクレンズ。[Claims] 1 General formula () A plastic lens made of a polymer obtained by polymerizing or copolymerizing as a main component a diester of a dicarboxylic acid in which at least one of R 1 and R 2 is an ester residue having an aromatic ring. 2 The diester of dicarboxylic acid is diphenyl fumarate, dibenzyl fumarate, diphenethyl fumarate, di(chlorophenyl) fumarate, di(bromphenyl) fumarate, isopropylphenyl fumarate, isopropylbenzyl fumarate, cyclohexyl phenyl The plastic lens according to claim 1, which is fumarate, allyl-phenyl fumarate or allyl-benzyl fumarate. 3. The plastic lens according to claim 1 or 2, wherein the copolymerization component is a monomer having a radically polymerizable double bond.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15550284A JPS6134007A (en) | 1984-07-27 | 1984-07-27 | Optical resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15550284A JPS6134007A (en) | 1984-07-27 | 1984-07-27 | Optical resin and its production |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10301092A Division JPH05112614A (en) | 1992-04-22 | 1992-04-22 | Production of optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6134007A JPS6134007A (en) | 1986-02-18 |
| JPH0534642B2 true JPH0534642B2 (en) | 1993-05-24 |
Family
ID=15607446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15550284A Granted JPS6134007A (en) | 1984-07-27 | 1984-07-27 | Optical resin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6134007A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62235901A (en) * | 1986-04-07 | 1987-10-16 | Nippon Oil & Fats Co Ltd | Composition for synthetic resin lens and its production |
| JP2004051851A (en) * | 2002-07-22 | 2004-02-19 | Nof Corp | Monomer composition for optical material and cured product of the same |
| JP4725046B2 (en) | 2003-08-20 | 2011-07-13 | 東ソー株式会社 | Plastic substrate for display and display element |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5698210A (en) * | 1979-12-21 | 1981-08-07 | Ici Ltd | Manufacture of polymer particle and coating composition containing said particle |
-
1984
- 1984-07-27 JP JP15550284A patent/JPS6134007A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5698210A (en) * | 1979-12-21 | 1981-08-07 | Ici Ltd | Manufacture of polymer particle and coating composition containing said particle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6134007A (en) | 1986-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2592010B2 (en) | Allyl ester oligomer composition and organic glass for optical material using the same | |
| EP0142118B1 (en) | Monomeric mixture of cured polymeric material used in organic glass | |
| EP0233299B1 (en) | Optical resin and process for preparing the same | |
| EP0242618B1 (en) | Transparent optical article and process for preparing same | |
| JPH0534642B2 (en) | ||
| JPS6128513A (en) | Optical resin and its production | |
| JPS6225162B2 (en) | ||
| JPH0478644B2 (en) | ||
| JPH05112614A (en) | Production of optical material | |
| JPH05132522A (en) | Production of optical material | |
| JPH02145610A (en) | Resin for plastic lens | |
| JPH0644081B2 (en) | Optical lens and manufacturing method thereof | |
| JPH0128054B2 (en) | ||
| JPS6343908A (en) | Optical resin and its production | |
| JPH0784507B2 (en) | Resin for plastic lens | |
| JPH01118802A (en) | Optical resin | |
| JPS6343909A (en) | Optical resin and its production | |
| JP2597640B2 (en) | Resin manufacturing method | |
| JPS62222201A (en) | Optical resin and its production | |
| JPS62116615A (en) | Production of transparent resin molding | |
| JPH051116A (en) | Resin for optics | |
| JPH0493306A (en) | Optical resin | |
| JPH04296307A (en) | Resin for optical use | |
| JPS60179406A (en) | Resin for high-refractive index lens | |
| SU732281A1 (en) | Brominated aryloxysubstituted benzyl alcohol metha-crylate (co) polymers for making organic glass and their preparing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |