JPH0224308A - Resin for optical material - Google Patents
Resin for optical materialInfo
- Publication number
- JPH0224308A JPH0224308A JP17353388A JP17353388A JPH0224308A JP H0224308 A JPH0224308 A JP H0224308A JP 17353388 A JP17353388 A JP 17353388A JP 17353388 A JP17353388 A JP 17353388A JP H0224308 A JPH0224308 A JP H0224308A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- mixture
- parts
- acrylate
- resin
- 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
- 239000011347 resin Substances 0.000 title claims abstract description 20
- 229920005989 resin Polymers 0.000 title claims abstract description 20
- 230000003287 optical effect Effects 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 claims abstract description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 5
- QYFACSDTKGXDDM-UHFFFAOYSA-N OC.OC.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1 Chemical compound OC.OC.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1.C1CCCCCCCCCCCCCC1 QYFACSDTKGXDDM-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- -1 diene compound Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- ZFOJJQNPKAVYPM-UHFFFAOYSA-N CO.CO.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1 Chemical compound CO.CO.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1 ZFOJJQNPKAVYPM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- OKQAAFJXUODTHO-UHFFFAOYSA-N decane;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCCCCCCC OKQAAFJXUODTHO-UHFFFAOYSA-N 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-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
- MVWPVABZQQJTPL-UHFFFAOYSA-N 2,3-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVWPVABZQQJTPL-UHFFFAOYSA-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
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical compound CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 1
- CJTKLGXZALTIEI-UHFFFAOYSA-N 3-butoxy-2,2-dimethylpropanoic acid Chemical group CCCCOCC(C)(C)C(O)=O CJTKLGXZALTIEI-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001417527 Pempheridae Species 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AFVYWKMVEGBLGD-UHFFFAOYSA-N hectane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC AFVYWKMVEGBLGD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- BHFJQXAFTZBCCB-UHFFFAOYSA-N n-[2-[(2-amino-2-oxoethyl)-(3,3-diphenylpropyl)amino]-2-oxoethyl]-n-(3,3-diphenylpropyl)-2-(oxolan-2-ylmethylamino)acetamide Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)CCN(C(=O)CNCC1OCCC1)CC(=O)N(CC(=O)N)CCC(C=1C=CC=CC=1)C1=CC=CC=C1 BHFJQXAFTZBCCB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- LTBKJTHWKYUMTA-UHFFFAOYSA-N pentadeca-3,10-diene Chemical compound CCCCC=CCCCCCC=CCC LTBKJTHWKYUMTA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920002776 polycyclohexyl methacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、エチレン性不飽和単量体のラジカル重合体か
らなる光学材料用樹脂に関する。詳しくは、重合させて
樹脂とすべきエチレン性不飽和単量体に主要な特徴を有
する光学材料用樹脂に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin for optical materials comprising a radical polymer of ethylenically unsaturated monomers. Specifically, the present invention relates to a resin for optical materials that has the main characteristics of an ethylenically unsaturated monomer that is to be polymerized to form a resin.
近年、レンズあるいは元ディスク基也に代表されるプラ
スチック光学用素子の要求が急増し、各種の樹脂が市場
に提供されつつある。In recent years, the demand for plastic optical elements such as lenses and original disk Motoya has rapidly increased, and various resins are being offered on the market.
中でも、ポリメチルメタクリレート樹脂（ＰＭＭＡ樹脂
）は、その優れた光学特性、即ち良透明性。Among them, polymethyl methacrylate resin (PMMA resin) has excellent optical properties, that is, good transparency.
低複屈折により広汎な用途で使用されている。しかし一
方では、用途分野が拡がるにつれて、原料樹脂に対する
要求性能が高くなｐｌその性能の改良が要望されている
。例えば、吸湿性をとシあげろとメタクリル系の樹脂は
、ポリオレフィン系樹脂や、ポリカーゲネイト系樹脂に
比べ比較的吸湿性が高く、吸湿による寸法変化を生じ、
光学的に不安定である。またこの様な問題を解決すべく
種々の改良技術が公開されている。It is used in a wide range of applications due to its low birefringence. On the other hand, however, as the field of application expands, the performance required for the raw material resin is high, and improvements in the performance of plastic resins are desired. For example, methacrylic resin has relatively high hygroscopicity compared to polyolefin resins and polycargenate resins, and dimensional changes occur due to moisture absorption.
Optically unstable. In addition, various improved techniques have been disclosed to solve such problems.
例えばメタクリル酸エステルのアルコール残基金高級化
（炭素数増大〕することによる低吸水化を試みたものと
して、ポリシクロへキシルメタクリレート及びそのコポ
リマー等があるが、耐熱性及び低吸水性を同時に向上さ
せることは困難である（％開昭５８−１２５７４２．同
１６２６１４号公報他）。また耐熱性を向上させる手法
の一つとして、メチルメタクリレートと架橋性モノマー
を使用した注型重合による技術が開示されている（％開
昭６１−８３２１３、同４１７１６号公報他）。しかし
、いずれの技術も熱的性能及び吸水性が改良される場合
もあるものの大きな改善は期待できない。For example, polycyclohexyl methacrylate and its copolymers are examples of attempts to lower water absorption by upgrading the alcohol residue of methacrylic acid ester (increasing the number of carbon atoms), but it is difficult to improve heat resistance and low water absorption at the same time. It is difficult to do so. (% JP-A-61-83213, JP-A No. 41716, etc.) However, although either technique may improve thermal performance and water absorption, no major improvement can be expected.
一方、ポリカーボネイト樹脂の場合、ＰＭＭＡ樹脂に比
べ、耐熱性が高く吸湿性が低いが、光学的等方性が劣り
、複屈折が生じ易いという欠点があり、光学素子の高精
度化に対応するには、克服すべき課題が多い。On the other hand, polycarbonate resin has higher heat resistance and lower moisture absorption than PMMA resin, but it has disadvantages such as poor optical isotropy and easy birefringence, making it difficult to respond to higher precision optical elements. There are many challenges to overcome.
上記の様にいずれの場合も光学的特性、吸湿性。 As mentioned above, in both cases, optical properties and hygroscopicity.
耐熱性のいずれかに問題を残している。とシわけ、書き
換え一消去可能型（Ｅ−ＤＲＡＷ型）光デイスク基板等
の低複屈折、高耐熱性、低吸湿性を要求される用途に使
用する為には更に性能を向上させることが必要である。There remains a problem with either heat resistance. However, in order to use it in applications that require low birefringence, high heat resistance, and low moisture absorption, such as rewritable and erasable (E-DRAW type) optical disk substrates, it is necessary to further improve performance. It is.
本発明は、上記の問題点を解決し、優れた光学特性、耐
熱性に加え低吸湿性を有する光学用樹脂を提供せんとす
るものである。The present invention aims to solve the above-mentioned problems and provide an optical resin having excellent optical properties, heat resistance, and low hygroscopicity.
本発Ｆ！Ａは、エチレン性不飽和単量体のラジカル重合
体からなる光学材料用樹脂において、該単量体がペンタ
シクロデカンジメタノール１モルをアクリル酸及びメタ
クリル酸２モルの混合物でエステル化して得られるジ（
メタ）アクリレート混合光学材料用樹脂を提供するもの
である。Original F! A is a resin for optical materials consisting of a radical polymer of ethylenically unsaturated monomers, which is obtained by esterifying 1 mole of pentacyclodecane dimethanol with a mixture of 2 moles of acrylic acid and methacrylic acid. Ji(
The present invention provides a resin for a meth)acrylate mixed optical material.
ペンタシクロデカンジメタノール（以下、 ＰＣＰＤ・
ＤＭと略す）の多脂環構造は、シクロペンタジェントリ
マーより構成される。このトリマーは、ジシクロペンタ
ジェンをオートクレーブ中で加熱することにより容易に
合成されることが矧られている（特開昭４９−９９７８
２号、特開昭４９−１０００６７号公報等）。得られる
トリマーは、ペンタシクロ（９，Ｊ１１１′ＢｔＯ”７
９０”１３］ペンタデカン−４，１１−ジエン（トリマ
ーＩ）とペンタシクロ（９，２，１，１’°７０２−１
０ 、０３°８〕ペンタデカン−５，１２−ジエン（ト
リマーＵ）の混合物である。Pentacyclodecane dimethanol (hereinafter referred to as PCPD)
The polyalicyclic structure of DM (abbreviated as DM) is composed of a cyclopentadiene trimer. It is believed that this trimer can be easily synthesized by heating dicyclopentadiene in an autoclave (Japanese Patent Laid-Open No. 49-9978
No. 2, JP-A-49-100067, etc.). The resulting trimer is pentacyclo(9,J111′BtO”7
90"13]pentadecane-4,11-diene (trimer I) and pentacyclo(9,2,1,1'°702-1
0,03°8] pentadecane-5,12-diene (trimer U).
上記のジエン化合物を原料としてオキソ合成によシ本発
明に用いるジメタツール体を製造することができる。即
ち、シクロペンタジェントリマー−酸化炭素および水素
を用いてコバルト錯体等を触媒として、加熱／加圧下で
反応させ蒸留単離することに２．９ ＰＣＰＤ−ＤＭｔ
−容易に得ることができる（４ｅｊ開昭５６−１４０９
４０号公報等）。The dimethazole compound used in the present invention can be produced by oxo synthesis using the above diene compound as a raw material. That is, 2.9 PCPD-DMt is obtained by reacting the cyclopentadiene trimer with carbon oxide and hydrogen using a cobalt complex or the like as a catalyst under heat/pressure, and then isolating it by distillation.
-Easy to obtain (4ej Kaisho 56-1409
40, etc.).
本発明に用いられるジ（メタ）アクリレート混合物（以
下、ＰＣＰＤ−ＤＭ−ＭＡと略す。）は、上記側・ＤＭ
１モルをメタクリル酸とアクリル酸との混合物２モル
でエステル化して得られる化合物である。The di(meth)acrylate mixture (hereinafter abbreviated as PCPD-DM-MA) used in the present invention is
This is a compound obtained by esterifying 1 mole of methacrylic acid with 2 moles of a mixture of methacrylic acid and acrylic acid.
ここでＰＣＰＤ−ＤＭ １モルをメタクリル酸とアクリ
ル酸トの混合物２モルでエステル化するということは、
先ずエステル化反応の一方の反応体であるメタクリル酸
とアクリル酸との混合物の化学量論的な量が２モルであ
ることを意味するだけであって、化学反応の常法通シ一
方の反応体（通常は安価または除去容易な方の単量体で
あって、本件ではメタクリル酸とアクリル酸との混合物
）を過剰に使用する場合、あるいは反応を二段階の反応
操作で行なう場合、たとえば先ずジメタツール化合物と
メタクリル酸とを反応させ、次いでアクリル酸混合物え
てさらに反応させる等の操作を行なう場合、をも包含す
るものであシ、そしてエステル化が必ずしも両反応体を
アルコールおよびカル？ン酸の形態として使用する脱水
反応に限定されることを意味するものではなくて、一方
または両者をその機能的誘導体の形・たとえば低級アル
コールエステルの形態で使用してエステル交換によって
エステルを生成させる場合をも包含するものである。Here, esterifying 1 mole of PCPD-DM with 2 moles of a mixture of methacrylic acid and acrylic acid means that
First of all, it only means that the stoichiometric amount of the mixture of methacrylic acid and acrylic acid, which is one of the reactants in the esterification reaction, is 2 moles, and one of the reactants is normally used in a chemical reaction. (usually the cheaper or easier to remove monomer, in this case a mixture of methacrylic acid and acrylic acid) or when the reaction is carried out in two steps, e.g. This also includes operations such as reacting a dimethacrylic acid with a dimethacrylic acid mixture, followed by further reaction with an acrylic acid mixture; The present invention is not meant to be limited to dehydration reactions in which one or both of the acids are used in the form of their functional derivatives, such as lower alcohol esters, to produce esters by transesterification. It also includes cases.
従って、ジメタツール化合物１モルと（メタ）アクリル
酸混合物２．０〜２．６モル程度とをエステル化反応に
付す。（メタ）アクリル酸混合物中のメタクリル酸／ア
クリル酸モル比は、０．２５〜４程度、好筐しくに０．
５〜２．５程度、が過当である。Therefore, 1 mol of the dimethadol compound and about 2.0 to 2.6 mol of the (meth)acrylic acid mixture are subjected to an esterification reaction. The molar ratio of methacrylic acid/acrylic acid in the (meth)acrylic acid mixture is approximately 0.25 to 4, preferably 0.25 to 4.
About 5 to 2.5 is appropriate.
エステル化は、これらの使用原料を反応容器内に同時に
仕込み、脱水剤をかねた反応溶媒及びエステル化触媒、
必要に応じて重合糸止剤を加えて、反応温度５０〜２０
０℃、好ましくは８０〜１５０℃、で空気または不活性
ガス中でエステル化反応を行う。In esterification, these raw materials are placed in a reaction vessel at the same time, and a reaction solvent that also serves as a dehydrating agent, an esterification catalyst,
Add a polymerization stopper if necessary, and adjust the reaction temperature to 50-20℃.
The esterification reaction is carried out at 0°C, preferably from 80 to 150°C, in air or inert gas.
このときの重合禁止剤としては、例えば、ラジカル重合
防止として用いられるハイドロキノン、ハイドロキノン
モノメチルエーテルなどフェノール類、ベンゾキノン、
ジフェニルベンゾキノンなどのキノン類、フェノチアジ
ン、銅塩などが挙げられる。これら重合禁止剤の使用ｔ
はメタクリル酸とアクリル酸との混合物１００重量部に
対して０．００１〜１０重量部、好ましくは０．１〜５
重量部、である。脱水共沸剤としてはｎ−ヘキサン、ｎ
−ペンタン、シクロヘキサン、メチルシクロヘキサン、
ベンゼン、トルエン、キシレン、トリクロルエチレン、
テトラクロルエチレン、メチルクロロホルム、ジイソプ
ロピルエーテルなどが好ましく用いられる。Examples of the polymerization inhibitor at this time include phenols such as hydroquinone and hydroquinone monomethyl ether, which are used to prevent radical polymerization, benzoquinone,
Examples include quinones such as diphenylbenzoquinone, phenothiazine, and copper salts. Use of these polymerization inhibitors
is 0.001 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the mixture of methacrylic acid and acrylic acid.
Parts by weight. As a dehydration entrainer, n-hexane, n
-pentane, cyclohexane, methylcyclohexane,
benzene, toluene, xylene, trichlorethylene,
Tetrachloroethylene, methyl chloroform, diisopropyl ether and the like are preferably used.
エステル化触媒としては、硫酸、塩酸、リン酸、フッ化
ホウ素、ｐ−トルエンスルホン酸、ベンゼンスルホン酸
、カチオン型交換樹脂など通常のエステル化触媒が適宜
用いられる。As the esterification catalyst, common esterification catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, p-toluenesulfonic acid, benzenesulfonic acid, and cationic exchange resins are used as appropriate.
エステル化反応終了後、反応液はアルカリ水浴液及び水
で洗浄し、水層を分離し、有機層を減圧下で脱水共沸剤
を除去する。After the esterification reaction is completed, the reaction solution is washed with an alkaline bath solution and water, the aqueous layer is separated, and the organic layer is dehydrated under reduced pressure to remove the entrainer.
本発明に用いられる単官能（メタ）アクリレートは、脂
肪族及び／又は芳香族の単官能アクリレート及びメタク
リレートであシ、具体的には、メチルメタクリレートエ
チルメタクリレート、シクロヘキシルメタクリレート、
ベンジルメタクリレート、イソゲニルメタクリレート、
トリシクロ（５，２，１，０”５）デカンメタクリレー
ト、ペンタシクロ［９，２，１，１’参８．０２，７．
０？、１３ ）インタデカンメタクリレート、アダマン
チルメタクリレート、アダｉンチルメチルメタクリレー
ト、ビシクロ（２，２，１）ヘクタンメタクリレート、
ビシクロ［２，２，１］へブチルメチルメタクリレート
、及びそれらのアクリレート、があげられるが、耐熱性
を維持しつつ吸湿性を下げるには、上記のモノマーのう
ち、炭素数１０以上の脂環系（メタ）アクリレートが特
に好ましい。The monofunctional (meth)acrylates used in the present invention are aliphatic and/or aromatic monofunctional acrylates and methacrylates, specifically, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate,
benzyl methacrylate, isogenyl methacrylate,
Tricyclo(5,2,1,0''5)decane methacrylate, pentacyclo[9,2,1,1'See 8.02,7.
0? , 13) interdecane methacrylate, adamantyl methacrylate, adainthyl methyl methacrylate, bicyclo(2,2,1)hectane methacrylate,
Examples include bicyclo[2,2,1]hebutyl methyl methacrylate and their acrylates, but in order to reduce hygroscopicity while maintaining heat resistance, among the above monomers, alicyclic monomers with a carbon number of 10 or more (Meth)acrylates are particularly preferred.
本発明の光学材料用樹脂は、 ＰＣＰＤ−ＤＭ−ＭＡ
ｔ−５０〜９５重量％、好ましくは６０〜９０重量−と
、単官能モノマーを５〜５０重量％、好ましくは１０〜
４０重量％の範囲で用いられる。この場合、単官能モノ
マーが５重量慢以下であると吸湿性の改善がみられず、
５０重量−以上であると、耐熱性に劣る。The resin for optical materials of the present invention is PCPD-DM-MA
t-50 to 95% by weight, preferably 60 to 90% by weight, and 5 to 50% by weight of monofunctional monomer, preferably 10 to
It is used in a range of 40% by weight. In this case, if the monofunctional monomer is less than 5% by weight, no improvement in hygroscopicity is observed;
If it is more than 50% by weight, the heat resistance will be poor.
ラジカル重合の手法は周知であって、例えば重合性組成
物に有機過酸化物、アゾ化合物等のラジカル開始剤を配
合し、加熱する方法及び光増感剤を配合して、紫外線、
電子線、放射線等を照射する方法等によジラジカル共重
合することができる。Radical polymerization techniques are well known, such as a method in which a radical initiator such as an organic peroxide or an azo compound is blended into a polymerizable composition and heated;
Diradical copolymerization can be carried out by irradiation with electron beams, radiation, etc.
その際に使用されるラジカル開始剤としては、例えば過
酸化ベンゾイル、ジイソプロピルパーオキサイド、ター
シャリープチルノや−オキシピバレート、ラウロイルノ
４−オキティド等の有機過酸化物、アゾイソブチ四ニト
リル等の７ノ化合物、ベンゾフェノン、ベンゾインエチ
ルエーテル、ベンジル、アセトフェノン、アントラキノ
ｙ等の光増感剤、ジフェニルスルフィード、チオカーバ
メート等硫黄化合物などのラジカル開始剤が使用できる
。ラジカル開始剤の使用量は、前記−形式で表わされる
アクリル系化合物１００部に対して０，０１〜２０部、
更に好ましくは０．０１〜１０部、の範囲である。Examples of radical initiators used in this case include organic peroxides such as benzoyl peroxide, diisopropyl peroxide, tertiary butyl-oxypivalate, and lauroyl-4-oxtide, seven compounds such as azoisobutytetranitrile, and benzophenone. Radical initiators such as photosensitizers such as , benzoin ethyl ether, benzyl, acetophenone, and anthraquinol, and sulfur compounds such as diphenyl sulfide and thiocarbamate can be used. The amount of the radical initiator used is 0.01 to 20 parts per 100 parts of the acrylic compound represented by the above-mentioned formula.
More preferably, it is in the range of 0.01 to 10 parts.
本発明の重合性組成物のラジカル共重合方法は、大気中
もしくは不活性ガス中で、１０〜１５０℃の温度で行う
のが好ましい。The method for radical copolymerization of the polymerizable composition of the present invention is preferably carried out at a temperature of 10 to 150°C in the atmosphere or an inert gas.
本発明の特色をなす単量体はジエチレン性不飽和単量体
５０〜９５重量−を含むものであるから、生成重合体は
架橋していて、融解を伴う手段によって成形することは
できない。従って、重合は所謂「注型重合」によって行
なって、生成重合体を板状あるいは塊状で得ることが好
ましいといえる。Since the monomers that characterize the present invention contain 50-95% by weight of diethylenically unsaturated monomer, the resulting polymer is crosslinked and cannot be shaped by means involving melting. Therefore, it is preferable to carry out the polymerization by so-called "cast polymerization" to obtain the resulting polymer in the form of plates or blocks.
以下に実験例を示して本発明をよシ具体的に説明する。 The present invention will be explained in more detail below with reference to experimental examples.
以下の実験例中の部は重量部チはＮ量基準である。また
実施例において得られた樹脂の諸物性は、下記の試験法
によシ測定した。In the following experimental examples, parts are by weight and are based on the amount of N. Further, various physical properties of the resins obtained in the Examples were measured by the following test methods.
（１）光透過率二分光光度計にて、５００ ｎｍの光透
過率を測定
（２） 複屈折 二個光顕微鏡にて測定（３） 飽
和吸水率：６０℃で水中に浸漬した時の飽和吸水率
（４）弾性率 ：ダイナミックメカニカルアナリシス（
ＤＭＡ ）によって測定
（５０℃における貯蔵弾性率）
（５） 耐熱性 二同上、損失弾性率のピーク温度製
造例
攪拌装置、温度計、窒素導入管、水分離器を取り付けた
１リツトル四つロフラスコ内に、前記の合成例で得られ
たＰＣＰＤ−ＤＭ １モル（２６５部）に対してメタア
クリル酸とアクリル酸との混合物２．４モル（メタアク
リル酸とアクリル酸のモル比が１ｏ５：以下Ｍ ／ Ａ
比＝１．５と称す）１９３部とトルエン２００部、ｐ−
）ルエンスルホンｆｆ５０部、銅粉０．３部を同時に仕
込み、窒素ガスをオーツ４−フローさせながら反応温度
９０〜１２０℃で３時間反応させた。反応終了後、冷却
し、過剰の酸を炭酸ソーダ水で中和し、さらに有機層を
純水で３回況浄し、トルエンをエバポレータを用いて留
去して、目的物であるＭ／Ａ比＝１．５の重合性組成物
３８０部を得た。(1) Light transmittance: Measure the light transmittance at 500 nm using a dual spectrophotometer (2) Birefringence: Measure using a dual light microscope (3) Saturation water absorption: Saturation when immersed in water at 60°C Water absorption rate (4) Elastic modulus: Dynamic mechanical analysis (
Measured by DMA) (storage modulus at 50°C) (5) Heat resistance 2 Same as above, peak temperature of loss modulus Production example In a 1 liter four-bottle flask equipped with a stirrer, thermometer, nitrogen inlet tube, and water separator. In addition, 2.4 mol of a mixture of methacrylic acid and acrylic acid (the molar ratio of methacrylic acid and acrylic acid is 105: or less M /A
Ratio = 1.5) 193 parts and 200 parts of toluene, p-
) 50 parts of luenesulfone ff and 0.3 parts of copper powder were charged at the same time, and the mixture was reacted at a reaction temperature of 90 to 120° C. for 3 hours while nitrogen gas was allowed to flow. After the reaction is completed, it is cooled, the excess acid is neutralized with sodium carbonate water, the organic layer is purified three times with pure water, and the toluene is distilled off using an evaporator to obtain the target product, M/A. 380 parts of a polymerizable composition having a ratio of 1.5 was obtained.
実施例１
製造例で得たＰＣＰＤ−ＤＭ−ＭＡ ８０部に対してシ
クロヘキシルメタクリレート２０部、光増感剤（イルガ
キュアー１８４：チバガイギー社製）０．３部、ジクミ
ルノ４−オΦサイド１，２部を加え均一に加熱攪拌混合
し、ガラス板とシリコンプムのスイーサーで構成された
型の中に注入した後、８０ Ｗ／ｌ：ｍのＵＶランデを
用いて紫外線を照射したプレキーアーを行り九後、１６
０℃のオープン内で２時間保持してポストキュアーを行
い、型よシ取出して硬化物を得た。硬化物の物性測定結
果を表−１に示す。Example 1 To 80 parts of PCPD-DM-MA obtained in Production Example, 20 parts of cyclohexyl methacrylate, 0.3 parts of photosensitizer (Irgacure 184: manufactured by Ciba Geigy), and 1,2 parts of dicumyl-4-OΦside The mixture was heated and mixed uniformly, poured into a mold made up of a glass plate and a silicone pump sweeper, and then pre-keyed by irradiating ultraviolet light using an 80 W/l:m UV rande. , 16
Post-curing was performed by holding in an open room at 0° C. for 2 hours, and the mold was removed to obtain a cured product. Table 1 shows the physical property measurement results of the cured product.
実施例２
製造例で得たＰＣＰＤ−ＤＭ−ＭＡ ６０部とシクロヘ
キシルメタクリレート４０部を用い念以外は実施例１と
全く同様にして硬化物を得た。硬化物の物性測定結果を
表−１に示す。Example 2 A cured product was obtained in the same manner as in Example 1 except for using 60 parts of PCPD-DM-MA obtained in Production Example and 40 parts of cyclohexyl methacrylate. Table 1 shows the physical property measurement results of the cured product.
実施例３〜５
シクロヘキシルメタクリレ、−ト２０部の代りに、各々
、ペン外ルメタクリレート２０部（実施例３）テトラシ
クロ（５，２，１，０”５）デカンメタクリレ−）２０
部（実施例４）、イソがニルアクリレート２０部（実施
例５）を用いた以外は実施例１と全く同様にして硬化物
を得た。硬化物の物性測定結果を表−１に示す。Examples 3 to 5 20 parts of cyclohexyl methacrylate (Example 3) 20 parts of tetracyclo(5,2,1,0''5)decane methacrylate in place of 20 parts of cyclohexyl methacrylate, respectively
A cured product was obtained in exactly the same manner as in Example 1, except that 20 parts of iso(Example 4) and 20 parts of iso-nylacrylate (Example 5) were used. Table 1 shows the physical property measurement results of the cured product.
実施例６〜７
実施例２においてシクロヘキシルメタクリレ−）４０部
の代シに、各々テトラシクロ（５，２，１，０２−５〕
デカンメタクリレ−）４０部（実施例６）イソがニルア
クリレート４０部（実施例７）を用いた以外は実施例２
と全く同様にして硬化物を得た。硬化物の物性測定結果
を表−１に示す。Examples 6 to 7 In Example 2, in place of 40 parts of cyclohexyl methacrylate, tetracyclo(5,2,1,02-5) was added, respectively.
Example 2 except that 40 parts of decane methacrylate (Example 6) was used.
A cured product was obtained in exactly the same manner. Table 1 shows the physical property measurement results of the cured product.
比較例１
実施例１においてＰＣＰＤ−ＤＭ−ＭＡ ８０部のかわ
りに、トリシクロデカンゾメタノールｌモ／Ｉ／ｌ−ア
クリル酸及びメタフリルミ１！混合物ＣＭ／Ａ比＝１．
５）２モルでエステル化して得られる（メタ）アクリレ
ート混合物（以下ＴＣＤ−ＤＭ−凧と略す）８０部を用
いた以外は全く同様にして硬化物を得た。硬化物の物性
を表−１に示す。Comparative Example 1 In Example 1, instead of 80 parts of PCPD-DM-MA, tricyclodecanezomethanol lmo/I/l-acrylic acid and methafurylumi 1! Mixture CM/A ratio=1.
5) A cured product was obtained in exactly the same manner except that 80 parts of a (meth)acrylate mixture (hereinafter abbreviated as TCD-DM-Kite) obtained by esterification with 2 moles was used. Table 1 shows the physical properties of the cured product.
Claims (1)
る光学材料用樹脂において、該単量体がペンタシクロペ
ンタデカンジメタノール１モルをアクリル酸及びメタク
リル酸２モルの混合物でエステル化して得られるジ（メ
タ）アクリレート混合物５０〜９５重量％、単官能（メ
タ）アクリレート５〜５０重量部からなるものである光
学材料用樹脂(1) In a resin for optical materials consisting of a radical polymer of ethylenically unsaturated monomer, the monomer is obtained by esterifying 1 mole of pentacyclopentadecane dimethanol with a mixture of 2 moles of acrylic acid and methacrylic acid. A resin for optical materials comprising 50 to 95% by weight of a di(meth)acrylate mixture and 5 to 50 parts by weight of a monofunctional (meth)acrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17353388A JPH0224308A (en) | 1988-07-12 | 1988-07-12 | Resin for optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17353388A JPH0224308A (en) | 1988-07-12 | 1988-07-12 | Resin for optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0224308A true JPH0224308A (en) | 1990-01-26 |
Family
ID=15962298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17353388A Pending JPH0224308A (en) | 1988-07-12 | 1988-07-12 | Resin for optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0224308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1065231A3 (en) * | 1999-07-02 | 2001-10-04 | Mitsubishi Gas Chemical Company, Inc. | Cycloaliphatic copolycarbonates, their production and use |
| EP1018528A3 (en) * | 1999-01-08 | 2001-10-04 | Mitsubishi Gas Chemical Company, Inc. | Polycarbonate resin and process for producing the same |
-
1988
- 1988-07-12 JP JP17353388A patent/JPH0224308A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1018528A3 (en) * | 1999-01-08 | 2001-10-04 | Mitsubishi Gas Chemical Company, Inc. | Polycarbonate resin and process for producing the same |
| EP1065231A3 (en) * | 1999-07-02 | 2001-10-04 | Mitsubishi Gas Chemical Company, Inc. | Cycloaliphatic copolycarbonates, their production and use |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5466863B2 (en) | Polymerizable compound, polymerizable composition containing the same, and polymer thereof | |
| US20020123590A1 (en) | Brominated materials | |
| JP4803331B2 (en) | (Meth) acrylate resin, production method thereof, curable resin composition, cured product thereof, and plastic lens | |
| EP0240260B1 (en) | Optical resin materials | |
| JPH01294718A (en) | Novel transparent resin, transparent resin having high refractive index for optics, coating resin and monomer | |
| JP3454544B2 (en) | (Meth) acrylic acid ester, method for producing the same, curable resin composition using the same, and cured product thereof | |
| JP4054967B2 (en) | Vinyl polymerizable monomer having tertiary hydroxyl group and polymer thereof | |
| JPH0224308A (en) | Resin for optical material | |
| JPH0267248A (en) | Novel (meth)acrylic ester | |
| JPH02258819A (en) | New polymerizable monomer | |
| JP2801494B2 (en) | Diallyl compound and method for producing crosslinked polymer using said compound | |
| JP2735789B2 (en) | Synthetic resin lens | |
| JPH01168712A (en) | Resin for optical material | |
| JPH01261408A (en) | Resin for optical material | |
| JPS62101620A (en) | Resin composition and coating agent | |
| JP3543359B2 (en) | Thioacetal compound, monomer composition and optical material | |
| JP5509719B2 (en) | Curable resin composition, cured product thereof, and plastic lens | |
| JPH02115205A (en) | Resin composition for optical material | |
| JPH04356443A (en) | Fluorine-containing (meth)acrylate ester, its production and cured cured product therefrom | |
| JPH0240345A (en) | Biphenyl compound and production thereof | |
| JP3981602B2 (en) | Radical polymerizable sulfur-containing adamantane compound and cured product | |
| JP2000281627A (en) | Acrylic acid ester derivative and its use | |
| JPS63175010A (en) | Resin for optical material | |
| JP2764450B2 (en) | Curable composition and plastic lens comprising the cured product | |
| JPH10182770A (en) | Photopolymerization composition and transparent cured product |