JPH02298506A - Monomer for optical resin and optical resin consisting of same monomer - Google Patents
Monomer for optical resin and optical resin consisting of same monomerInfo
- Publication number
- JPH02298506A JPH02298506A JP1042822A JP4282289A JPH02298506A JP H02298506 A JPH02298506 A JP H02298506A JP 1042822 A JP1042822 A JP 1042822A JP 4282289 A JP4282289 A JP 4282289A JP H02298506 A JPH02298506 A JP H02298506A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- monomer
- compound
- resin
- expressed
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 230000003287 optical effect Effects 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 title claims abstract description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 235000001508 sulfur Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 35
- -1 mercaptan compound Chemical class 0.000 abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 239000011521 glass Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 2
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000005498 polishing Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 3
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 150000007970 thio esters Chemical group 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- SPXSEZMVRJLHQG-XMMPIXPASA-N [(2R)-1-[[4-[(3-phenylmethoxyphenoxy)methyl]phenyl]methyl]pyrrolidin-2-yl]methanol Chemical class C(C1=CC=CC=C1)OC=1C=C(OCC2=CC=C(CN3[C@H](CCC3)CO)C=C2)C=CC=1 SPXSEZMVRJLHQG-XMMPIXPASA-N 0.000 description 1
- 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical group ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical class 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
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 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 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、光学樹脂用単量体およびそれよりなる光学用
樹脂に関するものであり、さらに詳しくはチオールエス
テル基を有する光学樹脂用単量体およびそれよりなる光
学用樹脂、チオールウレタン基を有する光学樹脂用単量
体およびそれよりなる光学用樹脂に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a monomer for optical resins and optical resins made from the monomers, and more specifically to monomers for optical resins having a thiol ester group. The present invention also relates to optical resins made from the same, monomers for optical resins having a thiol urethane group, and optical resins made from the same.
［従来技術］
レンズ、プリズム、オプティカルファイバーの様な光学
素子には、その軽量性及び生産性よりポリスチレン樹脂
やポリカーボネート樹脂等の汎用プラスチックが多く用
いられている。しかし、これらの汎用プラスチックは屈
折率が不十分であり、レンズの薄型化、光学機器の小型
化のためにより高い屈折率を有する樹脂の開発が望まれ
ており、これまでに、芳香環が硫黄原子と直接結合した
芳香族チオールエステルを主成分とする光学素子（特開
昭６０−２６００９号公報）や脂肪族チオールエステル
（特開昭６３−１６２６７１号公報や特開昭６３−１８
８６６０号公報）やチオールウレタン樹脂（特開昭６２
−２６７３１６号公報）が提案されている。[Prior Art] General-purpose plastics such as polystyrene resin and polycarbonate resin are often used for optical elements such as lenses, prisms, and optical fibers because of their light weight and productivity. However, these general-purpose plastics have insufficient refractive index, and there is a desire to develop resins with higher refractive index to make lenses thinner and optical equipment more compact. Optical elements whose main components are aromatic thiol esters directly bonded to atoms (Japanese Patent Laid-Open No. 60-26009) and aliphatic thiol esters (Japanese Patent Laid-Open Nos. 63-162671 and 63-18)
No. 8660) and thiol urethane resin (Japanese Unexamined Patent Publication No. 62
-267316) has been proposed.
［本発明が解決しようとする課題］
かかる特開昭６０−２６００９号公報の樹脂は、屈折率
が高いが、熱可塑性であるため、研磨時の加熱で歪が生
じるため、メガネ等の用途には不向きであり、構造内に
含まれる芳香環が硫黄原子と直接結合する構造を有して
いるため、耐光性が低く、太陽光の照射や加熱によって
、変色したり脆くなるという欠点があった。また、切削
・研磨等の加熱を伴う加工時に強い臭気を発生するとい
う欠点があった。[Problems to be Solved by the Present Invention] The resin disclosed in JP-A-60-26009 has a high refractive index, but since it is thermoplastic, distortion occurs when heated during polishing, so it is not suitable for applications such as glasses. It is unsuitable for use because the aromatic ring in its structure is directly bonded to the sulfur atom, so it has low light resistance and has the disadvantage of discoloration and becoming brittle when exposed to sunlight or heating. . Another drawback is that a strong odor is generated during processing that involves heating, such as cutting and polishing.
また、特開昭６３−１６２６７１号公報や特開昭６３−
１８８６６０号公報で提案されている脂肪族チオールエ
ステルより得られる樹脂は、耐光性は高いものの、原子
屈折が高い硫黄原子の含有率が低いため、十分な高屈折
率は得られていない。Also, JP-A-63-162671 and JP-A-63-162671
Although the resin obtained from the aliphatic thiol ester proposed in Publication No. 188660 has high light resistance, it does not have a sufficiently high refractive index because the content of sulfur atoms, which have high atomic refraction, is low.
また、特開昭６３−１６２６７１号公報のチオールエス
テルよりなる樹脂は研磨時に激しいメルカプタン臭を伴
うという欠点があった。Furthermore, the resin made of thiol ester disclosed in JP-A No. 63-162671 has the disadvantage that it is accompanied by a strong mercaptan odor during polishing.
また、特開昭６２−２６７３１６号公報に提案されてい
るチオールウレタン樹脂も、原子屈折が高い硫黄原子の
含有率が低いため、高屈折率の樹脂を得るためには芳香
環を導入する必要があった。しかしながら、このような
芳香族系チオールウレタン樹脂は、光照射によって黄変
するという光学樹脂としては致命的な欠点を有している
。 本発明は、かかる従来技術の欠点を解消しようとす
るものであり、高い屈折率及び耐光性を有し、さらに加
工時の臭気のない光学樹脂用単量体およびそれよりなる
光学用樹脂を提供することを目的とする［課題を解決す
るための手段］
上記目的を達成するために本発明は以下の構成よりなる
。Furthermore, the thiol urethane resin proposed in JP-A No. 62-267316 also has a low content of sulfur atoms with high atomic refraction, so it is necessary to introduce an aromatic ring in order to obtain a resin with a high refractive index. there were. However, such aromatic thiol urethane resins have a fatal drawback as optical resins in that they yellow when irradiated with light. The present invention aims to eliminate the drawbacks of the prior art, and provides a monomer for optical resins that has a high refractive index and light resistance and has no odor during processing, and an optical resin made from the same. [Means for Solving the Problem] In order to achieve the above object, the present invention has the following configuration.
「（１）下記一般式（Ａ）で示されることを特徴とする
光学樹脂用単量体。(1) A monomer for optical resins, characterized by being represented by the following general formula (A).
（式中、Ｒは水素またはメチル基、ｎはＯまたは１の整
数、ｍは１〜３の整数、Ｘは−ＣＨ２−残基、−ＣＨ−
残基、−Ｃ−残基から選ばれる少なくとも１一種類の残
基と、−８−残基とが、炭素数が３〜１０、イオウ数が
２〜９（ただし、イオウ数は炭素数より少ない）となる
範囲で結合してなる基を示す。）
（２）上記（１）項記載の単量体を主成分としてなる重
合体からなることを特徴とする光学用樹脂。」本発明の
一般式（Ａ）に示した化合物は、下記一般式（Ｂ）に示
した多価メルカプタン化合物と（メタ）アクリル酸ハラ
イドとを、金属水酸化物や三級アミン等のアルカリの存
在下で反応させるか、もしくは、下記一般式（Ｂ）に示
した多価メルカプタン化合物と（メタ）アクリロイルイ
ソシアネートとを反応させることによって合成できる。(In the formula, R is hydrogen or a methyl group, n is O or an integer of 1, m is an integer of 1 to 3, X is -CH2- residue, -CH-
At least one type of residue selected from residues, -C- residues, and -8-residues, the number of carbon atoms is 3 to 10, and the number of sulfur is 2 to 9 (however, the number of sulfur is smaller than the number of carbon atoms. Indicates a group formed by bonding within a range such that ) (2) An optical resin comprising a polymer containing the monomer described in item (1) above as a main component. '' The compound represented by the general formula (A) of the present invention is obtained by combining the polyvalent mercaptan compound represented by the following general formula (B) and (meth)acrylic acid halide with an alkali such as a metal hydroxide or a tertiary amine. It can be synthesized by reacting in the presence of the compound, or by reacting a polyvalent mercaptan compound represented by the following general formula (B) with (meth)acryloyl isocyanate.
Ｈ３−Ｘ−（ＳＨ）ｍ （Ｂ）（式中、Ｒ
は水素またはメチル基、ｎはＯまたは１の整数、ｍは１
〜３の整数、Ｘは−ＣＨ２−残基、−ＣＨ−残基、−Ｃ
−残基から選ばれる少なくとも１種類の残基と、−Ｓ−
残基とが、炭素数が３〜１０、イオウ数が２〜９（ただ
し、イオウ数は炭素数より少ない）となる範囲で結合し
てなる基は、Ｘ中に、２つ以上台まれず、さらに、−８
−残基が、２つ以上続けて結合した残基、例えば、−８
−８−などもＸ中には含まれない。）前記一般式（Ｂ）
に示した多価メルカプタン化合物とは、１分子中に一３
Ｈ基を２〜４個有する含硫黄脂肪族化合物であり、例え
ば、下記式（Ｃ）〜（Ｇ）に示される化合物である。H3-X-(SH)m (B) (wherein R
is hydrogen or methyl group, n is O or an integer of 1, m is 1
An integer of ~3, X is -CH2- residue, -CH- residue, -C
- at least one type of residue selected from residues, and -S-
A group formed by bonding with a residue in such a range that the number of carbon atoms is 3 to 10 and the number of sulfur is 2 to 9 (however, the number of sulfur is less than the number of carbon atoms) is not present two or more times in X. , furthermore, -8
- residues in which two or more residues are bonded in succession, e.g. -8
-8- etc. are also not included in X. ) Said general formula (B)
The polyvalent mercaptan compound shown in
It is a sulfur-containing aliphatic compound having 2 to 4 H groups, and is, for example, a compound represented by the following formulas (C) to (G).
Ｈ３−Ｒ，−８−Ｒ２−３−Ｒ３−３Ｈ（Ｃ）Ｈ８−Ｒ
４−８−Ｒ５−８−Ｒ６−３−Ｒ７−８）Ｉ （
Ｄ）Ｈ３−Ｒｓ −３−Ｒ９−３−ＲＩＤ−８−Ｒ１１
−３−Ｒ１２−３Ｈ（Ｅ）Ｓ−Ｒ，−８Ｈ
１（Ｓ−Ｒ，３−３−ＣＩ（−８−Ｒ□、−８）ｌ
（Ｆ ）Ｈ８−Ｒ□６−３
Ｓ−Ｒ，□−８Ｈ／ ＼
（Ｇ）Ｈ８Ｒ１８−３５−Ｒｌ９−３Ｈ
（前記式（Ｃ）〜（Ｇ）中、Ｒ１−Ｒ１，は−ＣＨ２−
または−Ｃ８２ＣＲ２−を示す。）
本発明の光学樹脂用単量体に、過酸化物系あるいはアゾ
系の開始剤を単量体１００重量部に対して０．０１〜５
重量部加えた後、加熱あるいは光照射することによって
重合することにより、透明性に優れた樹脂を製造するこ
とができる。この時、単量体として本発明の前記一般式
（Ａ）で示される単量体に、これ以外の単量体を加えて
共重合させることができる。H3-R, -8-R2-3-R3-3H(C)H8-R
4-8-R5-8-R6-3-R7-8) I (
D) H3-Rs-3-R9-3-RID-8-R11
-3-R12-3H(E)S-R,-8H 1(S-R,3-3-CI(-8-R□,-8)l
(F)H8-R□6-3
S-R, □-8H/ ＼
(G) H8R18-35-Rl9-3H (In the above formulas (C) to (G), R1-R1, is -CH2-
or -C82CR2-. ) A peroxide-based or azo-based initiator is added to the optical resin monomer of the present invention in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the monomer.
After adding part by weight, the resin is polymerized by heating or irradiation with light, thereby producing a resin with excellent transparency. At this time, other monomers can be added to the monomer represented by the general formula (A) of the present invention and copolymerized.
この場合、得られる樹脂の特性上、本発明の単量体を２
０％以上加えることが好ましい。In this case, due to the characteristics of the resulting resin, the monomer of the present invention may be
It is preferable to add 0% or more.
加える単量体としては、オレフィン系化合物であれば特
に限定はせず、好ましくは（メタ）アクリル系化合物や
スチレン系化合物、アリル系化合物、アクリロニトリル
、Ｎ−フェニルマレイミド等があげられる。具体的には
、メチル（メタ）アクリレート、エチル（メタ）アクリ
レート、プロピル（メタ）アクリレート、ベンジル（メ
タ）アクリレート、フェニル（メタ）アクリレート、ベ
ンジル（メタ）アクリレート、シクロヘキシル（メタ）
アクリレート、シクロへキシルメチレン（メタ）アクリ
レート、スチレン、ビニルナフタレン、ハロゲン置換ス
チレン、α−メチルスチレン、ジビニルベンゼン、ジア
リルフタレート、エチレングリコールジ（メタ）アクリ
レート、ジエチレングリコールビスアリルカーボネート
、ペンタエリスリトールテトラキス（メタ）アクリレー
トなどである。The monomer to be added is not particularly limited as long as it is an olefinic compound, and preferred examples include (meth)acrylic compounds, styrene compounds, allyl compounds, acrylonitrile, and N-phenylmaleimide. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and cyclohexyl (meth)acrylate.
Acrylate, cyclohexylmethylene (meth)acrylate, styrene, vinylnaphthalene, halogen-substituted styrene, α-methylstyrene, divinylbenzene, diallyl phthalate, ethylene glycol di(meth)acrylate, diethylene glycol bisallyl carbonate, pentaerythritol tetrakis (meth) Such as acrylate.
また、共重合成分として、前述のオレフィン系化合物以
外に多官能チオール化合物を加えることによって、研磨
等の加工性に優れた樹脂を得ることができる。Moreover, by adding a polyfunctional thiol compound in addition to the above-mentioned olefin compounds as a copolymerization component, a resin having excellent processability such as polishing can be obtained.
多官能チオール化合物としては、前記式（Ｃ）〜（Ｇ）
で示される化合物やペンタエリスリトールテトラキスチ
オグリコレート、トリスメルカプトプロピルイソシアヌ
レート等がある。As the polyfunctional thiol compound, the above formulas (C) to (G) are used.
Examples include compounds represented by , pentaerythritol tetrakisthioglycolate, trismercaptopropyl isocyanurate, and the like.
また、本発明の光学樹脂用単量体においては、イオウ含
有率が３５ｗｔ％以上であるものが、屈折率の点で、特
に好ましい。Further, in the optical resin monomer of the present invention, one having a sulfur content of 35 wt% or more is particularly preferable from the viewpoint of refractive index.
本発明の樹脂は、注型重合法によって成形できる。この
場合の成形方法の好ましい一例としては、本発明の単量
体あるいは前述の共重合成分のうち少なくとも１成分と
本発明の単量体を混合した液体を重合開始剤とともに、
ガラスあるいは金属製のモールドと粘着テープあるいは
塩ビ製のガスケットよりなる型に注入し、３０〜１５０
℃で０゜１〜４０時間加熱、あるいは、紫外線を照射す
ることによって成形できる。The resin of the present invention can be molded by a cast polymerization method. A preferred example of the molding method in this case is to use a liquid mixture of the monomer of the present invention or at least one component of the above-mentioned copolymer components and the monomer of the present invention together with a polymerization initiator.
Pour into a mold made of glass or metal mold and adhesive tape or PVC gasket,
It can be molded by heating at 0°C for 1 to 40 hours or by irradiating it with ultraviolet light.
本発明の光学樹脂用単量体を用いて透明性に優れた樹脂
を製造することができ、得られた樹脂は硫黄含有樹脂で
あるにも関わらず、加工時に臭気はしなかった。Using the optical resin monomer of the present invention, a resin with excellent transparency could be produced, and although the obtained resin was a sulfur-containing resin, it did not emit any odor during processing.
本発明の光学樹脂用単量体あるいは光学用樹脂に紫外線
吸収剤や酸化防止剤を加えてもよい。An ultraviolet absorber or an antioxidant may be added to the optical resin monomer or optical resin of the present invention.
［実施例］ 以下実施例により、本発明を具体的に説明する。[Example] The present invention will be specifically described below with reference to Examples.
９ 一
実施例１〜４及び比較例に示した樹脂の性質を表１に示
した。9 Properties of the resins shown in Examples 1 to 4 and Comparative Examples are shown in Table 1.
屈折率及びアツベ数は、プルフリッヒ屈折計を用いて測
定した。透過率及び耐光性はカラーコンピューターとフ
ェードメーターを用いて測定した。The refractive index and Atsube number were measured using a Pulfrich refractometer. Transmittance and light resistance were measured using a color computer and a fade meter.
耐光性については、フェードメーター１００時間後のΔ
ＹＩ値が、０〜５を○、５〜１０を△、１０以上を×と
した。゛
耐衝撃性はＦＤＡ規格に基づき、厚さ１．３ｍｍの硬化
物の平板に高さ１２７ｃｍより直径１５゜９ｍｍ重さ１
６．２ｇの鋼球を落下し、破損しなかったものを○それ
以外のものを×とした。Regarding light resistance, Δ after 100 hours on a fade meter
YI values of 0 to 5 were rated as ◯, 5 to 10 as △, and 10 or more as ×.゛Impact resistance is based on FDA standards.
A 6.2 g steel ball was dropped, and those that did not break were marked as ○.Others were marked as ×.
耐熱性については、１００°ＣでのシヨアＤ硬度がＯ〜
３０を×、３０〜５０を△、５０〜１００を○とした。Regarding heat resistance, shore D hardness at 100°C is O~
30 was marked as x, 30 to 50 was marked as Δ, and 50 to 100 was marked as ○.
研磨性は眼鏡レンズ用研磨機を用いて研磨し、研磨面が
良好なものを○、それ以外のものを×とした。The polishability was determined by polishing using an eyeglass lens polishing machine, and those with a good polished surface were rated as ○, and the others were rated as ×.
実施例１
１０００ｃｃの三ツロフラスコに下記式（Ｈ）＝ １０
−
に示した化合物１００ ｇ、テトラヒドロフラン３００
ｇ１ナトリウムボロヒドライド１ｇ１ヒドロキノンモノ
メチルエーテル１００ｍｇを仕込み、０℃、窒素下でか
くはんしながら、メタクリル酸クロライド７５ｇをゆっ
くり連子後、トリエチルアミン９０ｇを滴下し、０°Ｃ
で２時間かくはんした。その後、ろ過、溶媒の留去を行
い、下記式（１）の化合物を得た。この化合物９９重量
部にベンゾイルパーオキサイドを１重量部加えた溶液を
ガラスモールドと粘着テープよりなるモールド型に注入
し、５０℃から１２０°Ｃまで１５時間かけて昇温し樹
脂を得た。Example 1 The following formula (H) = 10 was added to a 1000cc Mitsuro flask.
- 100 g of the compound shown in, 300 g of tetrahydrofuran
1 g1 Sodium borohydride 1 g1 100 mg hydroquinone monomethyl ether was charged, and 75 g of methacrylic acid chloride was slowly added to the mixture at 0°C while stirring under nitrogen, and 90 g of triethylamine was added dropwise to the mixture at 0°C.
I stirred it for 2 hours. Thereafter, filtration and distillation of the solvent were performed to obtain a compound of the following formula (1). A solution prepared by adding 1 part by weight of benzoyl peroxide to 99 parts by weight of this compound was poured into a mold made of a glass mold and adhesive tape, and the temperature was raised from 50°C to 120°C over 15 hours to obtain a resin.
Ｈ８ＣＨ２−３ＣＨ，ＣＨ２−−８ＣＨ，ＳＨ（Ｈ）Ｃ
）（３ＣＨ３
Ｃ）１２＝Ｃ−Ｃ−３−Ｃ）ｌ ｙｓｃＨ丁Ｃ）ＩｒＳ
Ｃ１Ｉ ＴＳ−Ｃ−Ｃ＝Ｃ）１２］１１１
０ ０ （Ｉ）実施例２
メタクリル酸クロライドをアクリル酸クロライドに代え
た以外は、実施例１と同様にして、下記式（Ｊ）に示す
化合物を製造・重合した。H8CH2-3CH, CH2--8CH, SH(H)C
)(3CH3C)12=C-C-3-C)lyscHdingC)IrS
C1I TS-C-C=C)12]111 0 0 (I) Example 2 A compound represented by the following formula (J) was prepared in the same manner as in Example 1 except that methacrylic acid chloride was replaced with acrylic acid chloride. Manufactured and polymerized.
ＣＨ２・ＣＨ−ＣＳ ＣＨ２５ＣＨＴＣＨ２ＳＣＨ２
５−Ｃ−Ｃ１（−ＣＩ（□ＩＩ
ＩＩｏ
０ （Ｊ）実施例３
実施例１で得た式（１）の化合物７０重量部とジビニル
ベンゼン３０重量部を混合し、実施例１−と同様にして
重合を行い樹脂を得た。CH2・CH-CS CH25CHTCH2SCH2
5-C-C1(-CI(□II
IIo
0 (J) Example 3 70 parts by weight of the compound of formula (1) obtained in Example 1 and 30 parts by weight of divinylbenzene were mixed and polymerized in the same manner as in Example 1- to obtain a resin.
実施例４
化合物（Ｈ）を化合物（Ｋ）に代えた以外は、実施例１
と同様にして、下記式（Ｉ、）に示す化合物を製造・重
合した。Example 4 Example 1 except that compound (H) was replaced with compound (K)
In the same manner as above, a compound represented by the following formula (I) was produced and polymerized.
１（ＳＣＨ「５ＣＩＩｒＣＨ２−８ＣＩＩ、ＣＨ，Ｖ−
３ＣＩＩ、ＳＨ（Ｋ）ＣＨ３
ＣＨ２＝Ｃ−Ｃ−８−ＣＨ２−５ＣＨ２−ＣＨ「ＳＣＨ
，ＣＨ２−５ＣＨ２ＣＩ（３
■
−５−Ｃ−Ｃ＝ＣＨ２
］）
０ （Ｌ）実施例５
化合物（Ｈ）を化合物（Ｍ）に代えた以外は、実施例１
と同様にして、下記式（Ｎ）に示す化合物を製造・重合
した。1 (SCH "5CIIrCH2-8CII, CH, V-
3CII, SH(K)CH3 CH2=C-C-8-CH2-5CH2-CH "SCH
, CH2-5CH2CI(3 ■ -5-C-C=CH2 ]) 0 (L) Example 5 Example 1 except that compound (H) was replaced with compound (M)
In the same manner as above, a compound represented by the following formula (N) was produced and polymerized.
ｎ５ｃＨ，、−Ｃ）＋２−８Ｃ）Ｉ「ＳＣＨ，ＣＨ２−
３Ｈ（Ｍ）ＣＨ３
ＣＨ２＝Ｃ−Ｃ−８−Ｃ１ｈ ＣＨ２５ＣＩ（２８ＣＨ
２Ｃ１（２３Ｃ−１］１］
ＣＨ３
−Ｃ＝ＣＨ２（Ｎ）
実施例６
化合物（Ｈ）を化合物（０）に代えた以外は、実施例１
と同様にして、下記式（Ｐ）に示す化合物を製造・重合
した。n5cH,, -C)+2-8C)I"SCH,CH2-
3H(M)CH3 CH2=C-C-8-C1h CH25CI(28CH
2C1(23C-1]1] CH3 -C=CH2(N) Example 6 Example 1 except that compound (H) was replaced with compound (0)
A compound represented by the following formula (P) was produced and polymerized in the same manner as above.
５−ＣＨｒＣＨｒ−３Ｈ
）１ｓ−Ｃ）ｌ、ＣＨ２−３−Ｃ）ｌ−３−ＣＩ（ｒｃ
Ｈ，Ｓ）ｌ （０）ＣＨ３
（Ｃ１１２・Ｃ−Ｃ−３−ＣＨｙＣ）Ｉ２−３） ３−
ＣＨ（Ｐ）実施例７
化合物（Ｈ）を化合物（Ｑ）に代えた以外は、実施例１
と同様にして、下記式（Ｓ）に示す化合物を製造し、こ
の化合物５０重量部にペンタエリストールテトラキスチ
オグリコレート２０重量部エチレングリコールジメタク
リレート３０重量部を加えて、実施例１と同様に重合を
行った。5-CHrCHr-3H)1s-C)l, CH2-3-C)l-3-CI(rc
H,S)l (0)CH3 (C112・C-C-3-CHyC)I2-3) 3-
CH(P) Example 7 Example 1 except that compound (H) was replaced with compound (Q)
In the same manner as in Example 1, a compound represented by the following formula (S) was produced, and 20 parts by weight of pentaerythol tetrakisthioglycolate and 30 parts by weight of ethylene glycol dimethacrylate were added to 50 parts by weight of this compound. Polymerization was performed.
Ｈ８ＣＨｒＣ１（、−８Ｓ−ＣＨ２−ＣＨｒＳＨ／ ＼
（Ｑ）
１（ＳＣＨ２ＣＨ２Ｓ Ｓ−ＣＨ２−ＣＬ ５Ｈ
ＣＩ（３
（ＣＨ２・Ｃ−Ｃ−８−０８丁ＣＨ２−８）４−Ｃ（Ｓ
）実施例８
１０００ｃｃの三ツロフラスコに前記式（Ｈ）の化合物
５０ｇ１テトラヒドロフラン３００ ｇｓナナトリウム
ロヒドライド１ｇ１ヒドロキノンモノメチルエーテル１
００ｍｇを仕込み、０℃、窒素下でかくはんしながら、
メタクリロイルイソシアネート７０ｇをゆっくり連子後
、ＯｏＣで２時間かくはんした。その後、ろ過、溶媒の
留去を行い、下記式（Ｔ）の化合物を得た。H8CHrC1(, -8S-CH2-CHrSH/ \
(Q) 1(SCH2CH2S S-CH2-CL 5H
CI(3 (CH2・CC-8-08 CH2-8) 4-C(S
) Example 8 In a 1000 cc three-tube flask, 50 g of the compound of formula (H) 1 300 gs of tetrahydrofuran 1 g of sodium hydride 1 1 hydroquinone monomethyl ether
00mg and stirred at 0℃ under nitrogen.
After slowly adding 70 g of methacryloyl isocyanate, the mixture was stirred at OoC for 2 hours. Thereafter, filtration and distillation of the solvent were performed to obtain a compound of the following formula (T).
この化合物にベンゾイルパーオキサイド１重量部を加え
た液体を実施例１に示した方法で重合し−１Ａ −
樹脂を得た。A liquid obtained by adding 1 part by weight of benzoyl peroxide to this compound was polymerized by the method shown in Example 1 to obtain -1A- resin.
ＣＨ３
ＣＩ（２＝Ｃ−Ｎ−Ｃ−３−、ＣＨ，２−８ＣＨ２−Ｃ
Ｈ２−−３ＣＨ２−８−Ｃ−Ｎ−１ＩＩ
Ｉｆ ＩＨＯＯＨ
−Ｃ＝ＣＩ（２
実施例９
１０００ｃｃの三ツロフラスコに前記式（Ｋ）に示した
化合物１００ ｇ、テトラヒドロフラン３００ｇ１ナト
リウムボロヒドライド１ｇ１ヒドロキノンモノメチルエ
ーテル１００ｍｇを仕込み、０℃、窒素下でかくはんし
ながら、メタクリロイルイソシアネート７５ｇをゆっく
り滴下後、０°Ｃで２時間かくはんした。その後、ろ過
、溶媒の留去を行い、下記式（Ｕ）の化合物を得た。こ
の化合物９９重量部にをベンゾイルパーオキサイドを１
重量部加えた溶液をガラスモールドと粘着テープよりな
るモールド型に注入し、５０℃から１２０℃まで１５時
間かけて昇温し樹脂を得た。CH3 CI (2=C-N-C-3-, CH, 2-8CH2-C
H2--3CH2-8-C-N-1II
If IHOOH -C=CI (2 Example 9 100 g of the compound shown in the formula (K) above, 300 g of tetrahydrofuran, 1 g of sodium borohydride, 100 mg of hydroquinone monomethyl ether were placed in a 1000 cc Mitsulo flask, and the mixture was stirred at 0° C. under nitrogen. After slowly dropping 75 g of methacryloyl isocyanate, the mixture was stirred at 0°C for 2 hours.Then, filtration and distillation of the solvent were performed to obtain a compound of the following formula (U).99 parts by weight of this compound was added with benzoyl peroxide. 1 oxide
The solution added in parts by weight was injected into a mold made of a glass mold and adhesive tape, and the temperature was raised from 50°C to 120°C over 15 hours to obtain a resin.
ＯＨ３
□
１］］
ＯＨ
比較例１
１０００ｃｃの三ツロフラスコに下記式（Ｖ）に示した
化合物ｉ ｏ ｏ ｇ、テトラヒドロフラン３００ｇ、
ナトリウムボロヒドライド１ｇ１ ヒドロキノンモノメ
チルエーテル１００ｍｇを仕込み、０℃、窒素下でかく
はんしながら、メタクリル酸クロライド７５ｇをゆっく
り滴下後、トリエチルアミン９０ｇを滴下し、０℃で２
時間がくはんした。その後、ろ過、溶媒の留去を行い、
下記式（Ｗ）の化合物を得た。この化合物４９重量部を
実施例１に示した方法で重合し樹脂を得た。OH3 □ 1]] OH Comparative Example 1 In a 1000 cc Mitsulo flask, i o o g of the compound shown in the following formula (V), 300 g of tetrahydrofuran,
1 g of sodium borohydride 100 mg of hydroquinone monomethyl ether was charged, and while stirring under nitrogen at 0°C, 75 g of methacrylic acid chloride was slowly added dropwise, and then 90 g of triethylamine was added dropwise, and the mixture was stirred at 0°C for 2 hours.
Time passed. After that, filtration and distillation of the solvent are performed.
A compound of the following formula (W) was obtained. 49 parts by weight of this compound was polymerized by the method shown in Example 1 to obtain a resin.
Ｈ３ＣＨ２ＣＨ２５ＣＨ２ＣＢ２８Ｈ（Ｖ）ＣＨ３ＣＨ
３
比較例２
１００・Ｏｃｃの三ツロフラスコに前記式（Ｙ）に示し
た化合物ｉ ｏ ｏ ｇ、テトラヒドロフラン３００ｇ
１ナトリウムボロヒドライド１ｇ１ヒドロキノンモノメ
チルエーテル１００ｍｇを仕込み、０°Ｃ１窒素下でか
くはんしながら、メタクリロイルイソシアネート７５ｇ
をゆっくり滴下後、トリエチルアミン９０ｇを滴下し、
０℃で２時間がくはんした。その後、ろ過、溶媒の留去
を行い、下記式（Ｚ）の化合物を得た。この化合物４９
重量部を実施例１に示した方法で重合し樹脂を得た。H3CH2CH25CH2CB28H(V)CH3CH
3 Comparative Example 2 I o o g of the compound shown in the above formula (Y) and 300 g of tetrahydrofuran were placed in a 100 Occ Mitsuro flask.
1g of sodium borohydride 100mg of hydroquinone monomethyl ether was charged, and while stirring under nitrogen at 0°C, 75g of methacryloyl isocyanate was added.
After slowly dropping 90 g of triethylamine,
Stirred at 0°C for 2 hours. Thereafter, filtration and distillation of the solvent were performed to obtain a compound of the following formula (Z). This compound 49
Parts by weight were polymerized by the method shown in Example 1 to obtain a resin.
Ｈ３ＣＨ２べΣｈ ＣＨ２−３Ｈ（Ｙ ）［発明の効果
］
本発明の光学用単量体により製造した光学用樹脂は、透
明性に優れ、耐光性が良く、さらに、屈折率が高く、光
学機器用レンズ、眼鏡用レンズやプリズムとして非常に
有効である。H3CH2beΣh CH2-3H(Y) [Effects of the Invention] The optical resin produced using the optical monomer of the present invention has excellent transparency, good light resistance, and has a high refractive index, making it suitable for optical equipment. Very effective as lenses, eyeglass lenses and prisms.
また、加工する際、イオウ特有の臭気がしない。Also, during processing, there is no odor typical of sulfur.
Claims (2)
学樹脂用単量体。 ▲数式、化学式、表等があります▼［Ａ］ （式中、Ｒは水素またはメチル基、ｎは０または１の整
数、ｍは１〜３の整数、Ｘは−ＣＨ＿２−残基、▲数式
、化学式、表等があります▼残基、▲数式、化学式、表
等があります▼残基から選ばれる少なくとも１種類の残
基と、−Ｓ−残基とが、炭素数が３〜１０、イオウ数が
２〜９（ただし、イオウ数は炭素数より少ない）となる
範囲で結合してなる基を示す。）(1) A monomer for optical resins characterized by being represented by the following general formula (A). ▲There are mathematical formulas, chemical formulas, tables, etc.▼[A] (In the formula, R is hydrogen or methyl group, n is an integer of 0 or 1, m is an integer of 1 to 3, X is -CH_2- residue, ▲Mathical formula , chemical formulas, tables, etc. ▼ Residues ▲ Numerical formulas, chemical formulas, tables, etc. Indicates a group formed by bonding within the range of 2 to 9 numbers (however, the number of sulfurs is less than the number of carbons).
合体からなることを特徴とする光学用樹脂。(2) An optical resin comprising a polymer containing the monomer according to claim (1) as a main component.
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1042822A JPH02298506A (en) | 1989-02-07 | 1989-02-22 | Monomer for optical resin and optical resin consisting of same monomer |
| CA002010364A CA2010364C (en) | 1989-02-22 | 1990-02-19 | Thiol methacrylate or acrylate and resin made therefrom |
| AT90301845T ATE99292T1 (en) | 1989-02-22 | 1990-02-21 | THIOL(METH)ACRYLATE AND RESIN MADE THEREOF. |
| DE69005477T DE69005477T2 (en) | 1989-02-22 | 1990-02-21 | Thiol (meth) acrylate and resin made from it. |
| ES90301845T ES2062331T3 (en) | 1989-02-22 | 1990-02-21 | METHACRYLATE OR THYL ACRYLATE AND RESIN FROM THEM. |
| KR1019900002102A KR960015189B1 (en) | 1989-02-22 | 1990-02-21 | Thiol metacrylate or acrylate |
| DK90301845.5T DK0384725T3 (en) | 1989-02-22 | 1990-02-21 | Thiol methacrylate or acrylate and resin made therefrom |
| AU49959/90A AU629301B2 (en) | 1989-02-22 | 1990-02-21 | Thiol methacrylate or acrylate and resin made therefrom |
| EP90301845A EP0384725B1 (en) | 1989-02-22 | 1990-02-21 | Thiol methacrylate or acrylate and resin made therefrom |
| US07/844,477 US5247041A (en) | 1989-02-22 | 1992-03-02 | Thiol methacrylate or acrylate resin obtained by polymerizing a thiol methacrylate or acrylate compound |
| US08/001,075 US5294690A (en) | 1989-02-22 | 1993-01-06 | Thiol methacrylate or acrylate resin |
| US08/169,603 US5399735A (en) | 1989-02-22 | 1993-12-17 | Thiol methacrylate or acrylate, method of making same and a lens made therefrom |
| US08/351,687 US5502141A (en) | 1989-02-22 | 1994-12-08 | Method of making thiol methacrylate or acrylate and a lens made therefrom |
| US08/480,090 US5612390A (en) | 1989-02-22 | 1995-06-07 | Thiol Methacrylate or acrylate resin and a method of making same |
| KR1019960029899A KR970005476B1 (en) | 1989-02-22 | 1996-07-19 | Thiol methacrylate or acrylate and resin made therefrom |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2836689 | 1989-02-07 | ||
| JP1-28366 | 1989-02-07 | ||
| JP1042822A JPH02298506A (en) | 1989-02-07 | 1989-02-22 | Monomer for optical resin and optical resin consisting of same monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02298506A true JPH02298506A (en) | 1990-12-10 |
Family
ID=26366454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1042822A Pending JPH02298506A (en) | 1989-02-07 | 1989-02-22 | Monomer for optical resin and optical resin consisting of same monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02298506A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288844A (en) * | 1991-08-01 | 1994-02-22 | Teruo Sakagami | High-refractive index plastic optical material |
| JP2014019862A (en) * | 2012-07-24 | 2014-02-03 | Mitsui Chemicals Inc | (meth)acrylate compound, and polymerizable composition and resin using the same |
-
1989
- 1989-02-22 JP JP1042822A patent/JPH02298506A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288844A (en) * | 1991-08-01 | 1994-02-22 | Teruo Sakagami | High-refractive index plastic optical material |
| JP2014019862A (en) * | 2012-07-24 | 2014-02-03 | Mitsui Chemicals Inc | (meth)acrylate compound, and polymerizable composition and resin using the same |
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