JPH01300201A - High-refractive index plastic lens - Google Patents
High-refractive index plastic lensInfo
- Publication number
- JPH01300201A JPH01300201A JP63130084A JP13008488A JPH01300201A JP H01300201 A JPH01300201 A JP H01300201A JP 63130084 A JP63130084 A JP 63130084A JP 13008488 A JP13008488 A JP 13008488A JP H01300201 A JPH01300201 A JP H01300201A
- Authority
- JP
- Japan
- Prior art keywords
- refractive index
- plastic lens
- high refractive
- parts
- thiol
- 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.)
- Granted
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 13
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 13
- 150000001491 aromatic compounds Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims 3
- 238000006116 polymerization reaction Methods 0.000 description 14
- -1 Poly(diethylene glycol bisallyl carbonate) Polymers 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000003573 thiols Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003440 styrenes Chemical group 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
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 2
- 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
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 2
- AHWAAQOJHMFNIV-UHFFFAOYSA-N 2-tert-butylperoxy-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C AHWAAQOJHMFNIV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 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
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920006295 polythiol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- AFSSYGZIYMAAOC-UHFFFAOYSA-N 2-butylperoxy-2-ethylhexanoic acid Chemical group CCCCOOC(CC)(C(O)=O)CCCC AFSSYGZIYMAAOC-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
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 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
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 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
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 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 description 1
- CPZVJYPXOWWFSW-QXMHVHEDSA-N dibenzyl (z)-but-2-enedioate Chemical compound C=1C=CC=CC=1COC(=O)\C=C/C(=O)OCC1=CC=CC=C1 CPZVJYPXOWWFSW-QXMHVHEDSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は光学用材料、特に眼鏡用レンズとじて好適な高
屈折率プラスチックレンズに関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to optical materials, particularly to high refractive index plastic lenses suitable as eyeglass lenses.
（従来の技術とその問題点）
プラスチックレンズ用として実用化されている硬化型樹
脂の代表はポリ（ジエチレングリコールビスアリルカー
ボネート）であり、耐衝撃性が良く軽量かつ染色性に優
れているため視力矯正用眼鏡用レンズとして良く使われ
ている。(Conventional technology and its problems) Poly(diethylene glycol bisallyl carbonate) is a typical curable resin that has been put into practical use for plastic lenses, and it is suitable for vision correction because it has good impact resistance, is lightweight, and has excellent dyeability. It is often used as a lens for eyeglasses.
しかしポリ（ジエチレングリコールビスアリルカーボネ
ート）は屈折率が１．５０と低いため、レンズの縁の厚
みが大きくなりファツション性に乏しい欠点を有してい
る。However, since poly(diethylene glycol bisallyl carbonate) has a low refractive index of 1.50, it has the disadvantage that the edge of the lens becomes thick, making it less fashionable.
そのため屈折率がポリ（ジエチレングリコールビスアリ
ルカーボネート）よりも充分に高いプラスチックレンズ
が望まれている。Therefore, a plastic lens with a refractive index sufficiently higher than that of poly(diethylene glycol bisallyl carbonate) is desired.
高屈折率プラスチックレンズ用樹脂としてブロム原子を
含むヒドロキシ化合物とイソシアネートとの反応により
得られる樹脂（特開昭５８−１６４６１５号公報）や硫
黄原子を含むポリオール化合物とポリイソシアネートと
の反応により得られる樹脂（特開昭６０−２１７２２９
号公報）ブロム原子を含む芳香族アクリル化合物からな
る樹脂（特開昭５７−１０４９０１号公報）等、数多く
の樹脂が提案されている。As resins for high refractive index plastic lenses, resins obtained by the reaction of a hydroxy compound containing a bromine atom with an isocyanate (JP-A-58-164615) and a resin obtained by a reaction of a polyol compound containing a sulfur atom with a polyisocyanate. (Unexamined Japanese Patent Publication No. 60-217229
A number of resins have been proposed, such as a resin made of an aromatic acrylic compound containing a bromine atom (Japanese Patent Application Laid-open No. 104901/1983).
しかしながら、ブロム原子を含む芳香族アクリル化合物
を用いた場合は比重が大きくなる欠点があり、又ポリオ
ール化合物とポリイソシアネートを用いた場合は耐熱性
が悪い欠点がある。However, when an aromatic acrylic compound containing a bromine atom is used, the specific gravity becomes large, and when a polyol compound and a polyisocyanate are used, the heat resistance is poor.
また特開昭５９−１６４５０１号公報には−Ｓ−あるい
は−ＣＩＩｚＳＣＩｈ−等のポリチオエーテル基で結合
したビス（スチレン）化合物の重合体が提案されている
。しかし、−８−基で結合したビス（スチレン）系は原
料上ツマ−の製法が複雑の上、耐候性が極度に悪い。ま
た、ポリチオエーテル基で結合したビス（スチレン）化
合物系は重合体の着色が著しく、原料モノマーの悪臭、
重合体を研磨する際の硫黄臭等の欠点があり、実用的と
は言いがたい。Further, JP-A-59-164501 proposes a polymer of bis(styrene) compounds bonded with polythioether groups such as -S- or -CIIzSCIh-. However, the -8-group-bonded bis(styrene) type is not only a raw material but also requires a complicated manufacturing process and has extremely poor weather resistance. In addition, bis(styrene) compounds bonded with polythioether groups cause significant coloring of the polymer, bad odor of raw material monomers,
It has disadvantages such as sulfur odor when polishing the polymer, and is hardly practical.
（問題点を解決するための手段）
本発明者等は高屈折率かつ比重が小さい実用的な高屈折
率プラスチックレンズについて検討した結果、本発明に
到達した。(Means for Solving the Problems) The present inventors have arrived at the present invention as a result of studying practical high refractive index plastic lenses that have a high refractive index and a low specific gravity.
すなわち、本発明は一般式〔１〕で表される芳香族化合
物６０〜９９重量％、−形式〔■］で表される３〜４価
チオール１〜４０重債％から成る組成物を硬化して得た
高屈折率プラスチックレンズである。That is, the present invention cures a composition consisting of 60 to 99% by weight of an aromatic compound represented by the general formula [1] and 1 to 40% by weight of a trivalent to tetravalent thiol represented by the -form [■]. This is a high refractive index plastic lens obtained by
（Ｘは−ＣＯＯＣＨ２ＣＩｈ００Ｃ−、−Ｃ１１ｚＣ０
０Ｃ１ｌｚＣｔｂＯＣＯＣＩＩｚ−１−ＣＩＩｚＯＣＨ
ｚ−、−Ｃ１（ｚＯｃＨｚＯｃｌｌｇ−又は−ＣＩＩ２
０ＣＩＩ□ＣＬＯＣＩ＋□−を示す）
（ＩＩｓＲｃＯＯｃＩＩ□）Ｒ（ＣＨ３）４□Ｃ（Ｉｌ
ｌ（Ｒは−ｃＨｚｃ＋＋ｚ−又は−Ｃ＋＋Ｚ−を、ｎは
３又は４を示す）。(X is -COOCH2CIh00C-, -C11zC0
0C1lzCtbOCOCIIz-1-CIIzOCH
z-, -C1 (zOcHzOcllg- or -CII2
0CII□CLOCI+□-) (IIsRcOOcII□)R(CH3)4□C(Il
l (R represents -cHzc++z- or -C++Z-, n represents 3 or 4).
上記−形式（１）で表される芳香族化合物の具体例とし
ては、
及び上記化合物のメタ異性体、メタとパラの混合異性体
、及びそれらの混合物を挙げることができる。Specific examples of the aromatic compound represented by the above-format (1) include: and meta isomers of the above compounds, mixed meta and para isomers, and mixtures thereof.
上記一般式〔ＩＩ〕で表される３〜４価チオールの具体
例としては、トリメチロールプロパントリス（チオグリ
コレート）、トリメチロールプロパントリス（β−チオ
プロピオネート）、ペンタエリスリトールテトラキス（
チオグリコレート）、ペンタエリスリトールテトラキス
（β−チオプロピオネート）等である。Specific examples of tri- to tetravalent thiols represented by the above general formula [II] include trimethylolpropane tris (thioglycolate), trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (
thioglycolate), pentaerythritol tetrakis (β-thiopropionate), and the like.
−ｉ式（１）で表される芳香族化合物は適当なラジカル
重合開始剤によって単独で硬化することが可能だが、重
合歪み委生じ易く、面精度が不〜ト分で、硬化物が着色
し易い欠点を有する。-i The aromatic compound represented by formula (1) can be cured alone with a suitable radical polymerization initiator, but it tends to cause polymerization distortion, the surface accuracy is poor, and the cured product may be colored. It has some disadvantages.
一般式〔ＩＩ〕で表される３〜４価チオールは単独で重
合硬化物を与えないが、−形式［１）で表される芳香族
化合物と共重合し、重合歪みを低下し、面精度を上げ、
着色を抑制する。同時に力学強度を向上させ、表面のコ
ーティング処理を施し易くする。The trivalent to tetravalent thiol represented by the general formula [II] does not give a polymerized cured product by itself, but it copolymerizes with the aromatic compound represented by the -format [1] to reduce the polymerization distortion and improve the surface precision. Raise the
Suppresses coloration. At the same time, it improves mechanical strength and makes surface coating easier.
一般式〔Ｉ〕で表される芳香族化合物と一般式（ＩＩ）
で表される３〜４価チオールの使用量は、前者６０〜９
９重量％、後者１〜４０重量％の範囲が適し、より好ま
しくは、前者７０〜９８重量％、後者２〜３０重量％の
範囲である。Aromatic compound represented by general formula [I] and general formula (II)
The amount of trivalent to tetravalent thiol used is 60 to 9 for the former
A suitable range is 9% by weight for the former and 1 to 40% by weight for the latter, more preferably a range of 70 to 98% by weight for the former and 2 to 30% by weight for the latter.
この使用範囲以外では得られる硬化物の重合歪み、面精
度、着色、力学強度あるいは表面コーティング処理性等
が不足する。Outside this range of use, the cured product obtained will be insufficient in polymerization distortion, surface precision, coloring, mechanical strength, surface coating processability, etc.
硬化触媒としては公知のラジカル重合開始剤が使用され
る。例えば過酸化ベンゾイル、ジイソプロピルパーオキ
シカーボネート、ターシャリ−ブチルパーオキシ（２−
エチル）ヘキサノエート、アゾビスイソブチロニトリル
等の熱重合開始剤、ベンゾフェノン、ベンゾイン、ベン
ゾインメチルエーテル等の光重合開始剤が挙げられる。A known radical polymerization initiator is used as the curing catalyst. For example, benzoyl peroxide, diisopropyl peroxycarbonate, tert-butyl peroxy (2-
Examples include thermal polymerization initiators such as ethyl)hexanoate and azobisisobutyronitrile, and photopolymerization initiators such as benzophenone, benzoin, and benzoin methyl ether.
ラジカル重合開始剤の配合量は通常、重合部組成物総量
の０．００５重量％〜５重量％、好ましくは０．０５重
量％〜５重量％の範囲である。The amount of the radical polymerization initiator is usually in the range of 0.005% to 5% by weight, preferably 0.05% to 5% by weight, based on the total amount of the polymerization part composition.
かくて−形式ＣＩ）で表される芳香族化合物、−ＩＩＩ
Ｑ式（ＩＩ）で表される３〜４価チオール及びラジカル
重合開始剤を混合して本発明の硬化物を与える重合部組
成物が得られる。Thus, an aromatic compound of the form CI), -III
A polymerization part composition that provides the cured product of the present invention is obtained by mixing a trivalent to tetravalent thiol represented by formula (II) and a radical polymerization initiator.
この重合部組成物には、公知のラジカル反応性化合物や
イソシアネート化合物を希釈剤として１〜５０重景％加
え、粘度を調整したり、硬化後の硬度、耐熱性や屈折率
等の物性を調整することができる。このような希釈剤と
しては、例えば、スチレン、クロロスチレン、ジビニル
ベンゼン等のスチレン系化合物、トリメチロールプロパ
ントリス（アクリレート）、ビスフェノールＡジアクリ
レート、ビスフェノールＡジメタクリレート、ビスフェ
ノールＡエチレンオキシド付加体のジアクリレート、テ
トラブロムビスフェノールＡエチレンオキシド付加体の
ジアクリレート等のアクリル系化合物、ジアリルフタレ
ート、トリアリルイソシアヌレート等のアリル系化合物
、ジベンジルマレート等のマレイン酸エステル、ジベン
ジルフマレート等のフマール酸エステル、トルイレンジ
イソシアネート、キシリレンジイソシアネート、ヘキサ
メチレンジイソシアネート等のイソシアネート化合物が
挙げられる。To this polymerization part composition, 1 to 50% of known radically reactive compounds and isocyanate compounds are added as diluents to adjust the viscosity and physical properties such as hardness, heat resistance, and refractive index after curing. can do. Examples of such diluents include styrene compounds such as styrene, chlorostyrene, and divinylbenzene, trimethylolpropane tris(acrylate), bisphenol A diacrylate, bisphenol A dimethacrylate, diacrylate of bisphenol A ethylene oxide adduct, Acrylic compounds such as diacrylate of tetrabromobisphenol A ethylene oxide adduct; allyl compounds such as diallyl phthalate and triallyl isocyanurate; maleic esters such as dibenzyl maleate; fumaric esters such as dibenzyl fumarate; Examples include isocyanate compounds such as diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
また重合部組成物には、公知のラジカル禁止剤、紫外線
吸収剤、トリアルキルホスフィンや次亜燐酸またはその
エステル等の酸化防止剤を加えて、組成物の取扱性や得
られるレンズの実用性をより向上させることができる。In addition, known radical inhibitors, ultraviolet absorbers, trialkylphosphines, hypophosphorous acid or esters thereof, and other antioxidants are added to the polymerization composition to improve the handleability of the composition and the practicality of the resulting lenses. It can be further improved.
本発明の重合部組成物は通常ガラスや金属製の型に注入
し、加熱あるいは紫外線や電子線照射によって重合硬化
反応を進め、０．１〜２４時間後に型から取り外す。更
に必要に応じてハードコート、反射防止、防曇性付与等
の表面処理を行い高屈折率プラスチックレンズとする。The polymerization part composition of the present invention is usually poured into a mold made of glass or metal, the polymerization and curing reaction is advanced by heating or irradiation with ultraviolet rays or electron beams, and the composition is removed from the mold after 0.1 to 24 hours. Furthermore, if necessary, surface treatments such as hard coating, antireflection, and antifogging properties are performed to obtain a high refractive index plastic lens.
（発明の効果）
本発明で得られるレンズは無色透明、屈折率が高く、ア
ツベ数の値が良好である。特に、比重が小さく軽量であ
る特徴を有する。又、耐候性、重合歪み、面精度、表面
のコーティング処理性に優れる。それゆえ、光学用高屈
折率レンズとして各種用途に使用でき、特に眼鏡用プラ
スチックレンズとして好適である。(Effects of the Invention) The lens obtained by the present invention is colorless and transparent, has a high refractive index, and has a good Abbe number value. In particular, it has the characteristics of low specific gravity and light weight. It also has excellent weather resistance, polymerization distortion, surface precision, and surface coating processability. Therefore, it can be used for various purposes as an optical high refractive index lens, and is particularly suitable as a plastic lens for eyeglasses.
（実施例）
以下、参考例、実施例及び比較例で本発明を更に詳しく
説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference examples, examples, and comparative examples.
なお、硬化物の耐熱性、耐衝撃性と耐候性は次の方法に
て評価を行った。The heat resistance, impact resistance, and weather resistance of the cured product were evaluated using the following methods.
耐熱性 ：硬化物のビカット熱軟化温度（荷重ＩＫｇ）
が１２０°Ｃ以上の場合を良好とする。Heat resistance: Vicat heat softening temperature of cured product (load IKg)
A case where the temperature is 120°C or higher is considered good.
耐衝撃性：硬化物（６０ｍ＋φＸ２． ５ｔｔｔｍ厚み
）に１．２７ｍの高さから１６ｇの鉄球を落とし割れな
い場合を良好とする。Impact resistance: A 16 g iron ball is dropped onto a cured product (60 m + φ x 2.5 tttm thickness) from a height of 1.27 m, and a case where no cracking occurs is considered good.
耐候性：アルゴンランプウェザ−試験で２００時間後の
黄色度変化がΔＹ値で＋１以下の場合を良好とする。Weather resistance: A case where the change in yellowness after 200 hours in the argon lamp weather test is +1 or less in ΔY value is considered good.
参考例
３Ｌの攪拌機付き反応フラスコに４−クロロメチルスチ
レン２２９ｇ （１，５０モル）、炭酸カリウム２９０
ｇ （２，１モル）及びメチルエチルケトン１．５Ｌを
混合し、７０°Ｃで攪拌しながらエチレングリコールジ
チオグリコレート１８９ｇ（０，９０モル）を３０分か
けて滴下した。更に７５°Ｃリフラックス下で１時間撹
拌を続は反応を終了した。Reference Example 229 g (1,50 mol) of 4-chloromethylstyrene and 290 g of potassium carbonate were placed in a 3L reaction flask equipped with a stirrer.
g (2.1 mol) and 1.5 L of methyl ethyl ketone were mixed, and 189 g (0.90 mol) of ethylene glycol dithioglycolate was added dropwise over 30 minutes while stirring at 70°C. The reaction was further stirred for 1 hour under reflux at 75°C to complete the reaction.
反応終了液を冷却し、濾過後に安定剤としてＢＩＴｌｏ
ｏｐｐｍを加え、５０°Ｃで減圧蒸留しメチルエチルケ
トンを留去した。続いて、濃縮液をＩＮ水酸化ナトリウ
ム２して３回、水２して２回洗浄した。After cooling the reaction solution and filtering, add BITlo as a stabilizer.
oppm was added and distilled under reduced pressure at 50°C to remove methyl ethyl ketone. Subsequently, the concentrated solution was washed three times with two portions of IN sodium hydroxide and two times with two portions of water.
更に、濃縮液をヘキサン３Ｌで、再結晶し、無色固体結
晶２４３ｇを得た。Furthermore, the concentrated solution was recrystallized with 3 L of hexane to obtain 243 g of colorless solid crystals.
この固体結晶はｒＲ及びＮＭＲ分析の結果、次式（Ａ）
で示す化合物であった。As a result of rR and NMR analysis, this solid crystal has the following formula (A)
It was a compound shown in
また４−クロロメチルスチレンに代えて３−及び４−ク
ロロメチルスチレンのｌ：ｌ混合物を用い、同上の方法
でｍ−１ｐ−混合体ＣＢ）を得た。Further, m-1p-mixture CB) was obtained in the same manner as above using a 1:1 mixture of 3- and 4-chloromethylstyrene in place of 4-chloromethylstyrene.
更に、エチレングリコールジチオグリコレートに代えて
エチレングリコールジ（β−チオプロピオネート）及び
１．２−ビス（２−メルカプトエチルオキシ）エタンを
用いてそれぞれ式（Ｃ）及びＣＤ）で示す化合物を得た
。Furthermore, compounds represented by formulas (C) and CD), respectively, were prepared by using ethylene glycol di(β-thiopropionate) and 1,2-bis(2-mercaptoethyloxy)ethane in place of ethylene glycol dithioglycolate. Obtained.
実施例 ｌ
参考例で得た化合物（Ａ３９５部、ペンタエリスリトー
ルテトラキス（β−チオプロピオネート）５部、及びタ
ーシャリ−ブチルパーオキシ（２−エチル）ヘキサノエ
ート ０．５部を混合し、時計皿とゴム製パツキンから
成る型に入れ、５０°Ｃから９０°Ｃまで２０時間かけ
て昇温し、重合硬化した。Example 1 The compound obtained in Reference Example (395 parts of A, 5 parts of pentaerythritol tetrakis (β-thiopropionate), and 0.5 parts of tertiary-butylperoxy(2-ethyl)hexanoate were mixed and mixed with a watch glass. The mixture was placed in a mold made of rubber packing and heated from 50°C to 90°C over 20 hours to polymerize and harden.
得られたレンズ状硬化物は、無色透明で屈折率ＮＦ＝１
．６１２、アツベ数＝３２であり、屈折率が高くしかも
高アツベ数という良好な光学的性質を有していた。又、
外見の重合歪みが無く、面精度も優れ、耐熱性、耐衝撃
性及び耐候性も良好であった。特に比重は１．２３と軽
量で、高屈折率プラスチックレンズとして適したもので
あった。The obtained lens-shaped cured product is colorless and transparent and has a refractive index NF = 1.
．． 612, Abbe number = 32, and had good optical properties such as a high refractive index and a high Abbe number. or,
There was no apparent polymerization distortion, the surface precision was excellent, and the heat resistance, impact resistance, and weather resistance were also good. In particular, it was lightweight with a specific gravity of 1.23, making it suitable as a high refractive index plastic lens.
実施例 ２
参考例で得た化合物ＣＢ）９５部、ペンタエリスリトー
ルテトラキス（チオグリコレート）５部及びターシャリ
−ブチルパーオキシ（２−エチル）ヘキサノエート ０
．５部を混合し、実施例１と同様の方法で重合硬化した
。Example 2 Compound CB obtained in Reference Example 95 parts, pentaerythritol tetrakis(thioglycolate) 5 parts and tert-butylperoxy(2-ethyl)hexanoate 0
．． 5 parts were mixed and polymerized and cured in the same manner as in Example 1.
得られたレンズ状硬化物は 無色透明、ＮＦ−１，６１
５、アツベ数＝３２、重合歪み無く、面精度、耐熱性、
耐衝撃性及び耐候性も良好であった。又、比重は１．２
４と軽量であった。The obtained lens-shaped cured product is colorless and transparent, NF-1,61
5. Atsube number = 32, no polymerization distortion, surface accuracy, heat resistance,
Impact resistance and weather resistance were also good. Also, the specific gravity is 1.2
It was lightweight at 4.
実施例 ３
参考例で得た化合物（Ｃ）８５部、ペンタエリスリトー
ルテトラキス（β−チオプロピオネート）５部、スチレ
ン１０部及びターシャリ−ブチルパーオキシ（２−エチ
ル）ヘキサノエート ０． ５部を混合し、実施例１と
同様の方法で重合硬化した。Example 3 85 parts of the compound (C) obtained in Reference Example, 5 parts of pentaerythritol tetrakis (β-thiopropionate), 10 parts of styrene, and 0.0 parts of tert-butylperoxy(2-ethyl)hexanoate. 5 parts were mixed and polymerized and cured in the same manner as in Example 1.
得られたレンズ状硬化物は 無色透明、Ｎ Ｆ＝１．６
０６、アツベ数＝３３、重合歪みが無く、面精度、耐熱
性、耐衝撃性及び耐候性も良好であり、比重＝１．２１
と軽量であった。The obtained lens-shaped cured product is colorless and transparent, N F = 1.6
06, Atsube number = 33, no polymerization distortion, good surface accuracy, heat resistance, impact resistance and weather resistance, specific gravity = 1.21
It was lightweight.
実施例 ４
参考例で得た化合物ＣＤ）８０部、ペンタエリスリトー
ルテトラキス（β−チオプロピオネート）５部、ｍ−ジ
ビニルベンゼン５部、スチレン１０部及びターシャリ−
ブチルパーオキシ（２−エチル）ヘキサノエート ０．
５部を混合し、実施例１と同様の方法で重合硬化した。Example 4 80 parts of the compound CD obtained in Reference Example, 5 parts of pentaerythritol tetrakis (β-thiopropionate), 5 parts of m-divinylbenzene, 10 parts of styrene, and tertiary
Butylperoxy(2-ethyl)hexanoate 0.
5 parts were mixed and polymerized and cured in the same manner as in Example 1.
得られたレンズ状硬化物は 無色透明、Ｎ Ｆ −１，
６１５、アツベ数−３３、重合歪みが無く、面精度、耐
熱性、耐衝撃性及び耐候性も良好であった。又、比重は
１．１９と軽量であった。The obtained lens-shaped cured product is colorless and transparent, NF -1,
615, Atsube's number -33, no polymerization distortion, and good surface precision, heat resistance, impact resistance, and weather resistance. In addition, it was lightweight with a specific gravity of 1.19.
比較例 １〜４
参考例で得た化合物（Ａ）、ＣＢ）、（Ｃ）及びＣＤ）
のそれぞれ１００部にターシャリ−ブチルパーオキシ（
２−エチル）ヘキサノエート０．５部を混合し、実施例
１と同様の方法で重合硬化した。得られたレンズ状硬化
物はいずれも黄色に着色し、耐衝撃性が不十分であった
。Comparative Examples 1 to 4 Compounds (A), CB), (C) and CD) obtained in Reference Examples
100 parts each of tert-butyl peroxy (
0.5 part of 2-ethyl)hexanoate was mixed and polymerized and cured in the same manner as in Example 1. All of the obtained lens-shaped cured products were colored yellow and had insufficient impact resistance.
Claims (1)
９重量％、一般式〔II〕で表される３〜４価チオール１
〜４０重量％から成る組成物を硬化して得たプラスチッ
クレンズ ▲数式、化学式、表等があります▼〔 I 〕 （Ｘは▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼又は▲数式、化学式、表等があります
▼ を示す） （ＨＳＲＣＯＯＣＨ＿２）＿ｎ（ＣＨ＿３）＿４＿−＿
ｎＣ〔II〕（Ｒは−ＣＨ＿２ＣＨ＿２−又は−ＣＨ＿２
−を、ｎは３又は４を示す）。(1) Aromatic compounds 60 to 9 represented by general formula [I]
9% by weight, trivalent to tetravalent thiol 1 represented by general formula [II]
A plastic lens obtained by curing a composition consisting of ~40% by weight▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
(HSRCOOCH_2)_n(CH_3)_4_-_
nC[II] (R is -CH_2CH_2- or -CH_2
-, n indicates 3 or 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63130084A JP2661142B2 (en) | 1988-05-30 | 1988-05-30 | High refractive index plastic lens |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63130084A JP2661142B2 (en) | 1988-05-30 | 1988-05-30 | High refractive index plastic lens |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01300201A true JPH01300201A (en) | 1989-12-04 |
| JP2661142B2 JP2661142B2 (en) | 1997-10-08 |
Family
ID=15025595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63130084A Expired - Lifetime JP2661142B2 (en) | 1988-05-30 | 1988-05-30 | High refractive index plastic lens |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2661142B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5475074A (en) * | 1993-01-29 | 1995-12-12 | Tokuyama Corporation | Polymerizable composition, organic glass and ophthalmic lens |
-
1988
- 1988-05-30 JP JP63130084A patent/JP2661142B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5475074A (en) * | 1993-01-29 | 1995-12-12 | Tokuyama Corporation | Polymerizable composition, organic glass and ophthalmic lens |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2661142B2 (en) | 1997-10-08 |
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