JPS63268707A - Resin having high refractive index - Google Patents
Resin having high refractive indexInfo
- Publication number
- JPS63268707A JPS63268707A JP10301987A JP10301987A JPS63268707A JP S63268707 A JPS63268707 A JP S63268707A JP 10301987 A JP10301987 A JP 10301987A JP 10301987 A JP10301987 A JP 10301987A JP S63268707 A JPS63268707 A JP S63268707A
- Authority
- JP
- Japan
- Prior art keywords
- refractive index
- polymerizable monomer
- resin
- high refractive
- polymerizable
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 27
- 239000011347 resin Substances 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229920001519 homopolymer Polymers 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 3
- LYJHVEDILOKZCG-UHFFFAOYSA-N Allyl benzoate Chemical compound C=CCOC(=O)C1=CC=CC=C1 LYJHVEDILOKZCG-UHFFFAOYSA-N 0.000 abstract description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 2
- 150000004662 dithiols Chemical class 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- JLOIRPJHPDQHHN-UHFFFAOYSA-N (2,3,4-trichlorophenyl) prop-2-enoate Chemical compound ClC1=CC=C(OC(=O)C=C)C(Cl)=C1Cl JLOIRPJHPDQHHN-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- ZSVFYHKZQNDJEV-UHFFFAOYSA-N (2,3,4-tribromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(Br)C(Br)=C1Br ZSVFYHKZQNDJEV-UHFFFAOYSA-N 0.000 description 1
- IGWMFERXHIUPRD-UHFFFAOYSA-N (2,3,4-trichlorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(Cl)C(Cl)=C1Cl IGWMFERXHIUPRD-UHFFFAOYSA-N 0.000 description 1
- OEZWIIUNRMEKGW-UHFFFAOYSA-N (2-bromophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1Br OEZWIIUNRMEKGW-UHFFFAOYSA-N 0.000 description 1
- VNYTWDAWZSFABS-UHFFFAOYSA-N (2-bromophenyl) prop-2-enoate Chemical compound BrC1=CC=CC=C1OC(=O)C=C VNYTWDAWZSFABS-UHFFFAOYSA-N 0.000 description 1
- YKZMWXJHPKWFLS-UHFFFAOYSA-N (2-chlorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1Cl YKZMWXJHPKWFLS-UHFFFAOYSA-N 0.000 description 1
- GOUZWCLULXUQSR-UHFFFAOYSA-N (2-chlorophenyl) prop-2-enoate Chemical compound ClC1=CC=CC=C1OC(=O)C=C GOUZWCLULXUQSR-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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- JZOBIVDRMAPQDS-UHFFFAOYSA-N 2-[2,6-dibromo-4-[2-[3,5-dibromo-4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=C(Br)C(OCCOC(=O)C(=C)C)=C(Br)C=C1C(C)(C)C1=CC(Br)=C(OCCOC(=O)C(C)=C)C(Br)=C1 JZOBIVDRMAPQDS-UHFFFAOYSA-N 0.000 description 1
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-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
- OIWXLVBZDMAARO-UHFFFAOYSA-N 2-decylsulfanylethanamine Chemical compound CCCCCCCCCCSCCN OIWXLVBZDMAARO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002216 antistatic agent 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
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-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
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- HVYCQBKSRWZZGX-UHFFFAOYSA-N naphthalen-1-yl 2-methylprop-2-enoate Chemical compound C1=CC=C2C(OC(=O)C(=C)C)=CC=CC2=C1 HVYCQBKSRWZZGX-UHFFFAOYSA-N 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/38—Esters containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は無色透明性に優れた高屈折率樹脂に関する。[Detailed description of the invention] <Industrial application field> The present invention relates to a high refractive index resin that is colorless and transparent.
〈従来の技術〉
無機光学レンズに替る素材として透明性合成樹脂よりな
る高屈折率レンズ用樹脂は、その軽量性や耐衝撃性、成
型加工性、染色性が良好なことから、プラスチックレン
ズ材料として適用分野を拡大しつつある。<Prior art> Resin for high refractive index lenses made of transparent synthetic resin is used as a material to replace inorganic optical lenses because of its light weight, impact resistance, moldability, and dyeability. The field of application is expanding.
従来、プラスチックレンズ材料として用いられているジ
エチレングリコールビスアリルカーボネート樹脂は、屈
折率が１．４９〜１．５０と低いため、これから得られ
る樹脂を矯正用眼鏡レンズにすると無機光学ガラスレン
ズに比較して中心厚、コバ厚が大きくなる欠点があった
。又、ナフチルメタクリレートやビスフェノール人ジメ
タクリレートは高屈折率な樹脂を与えるが、これらの単
量体は室温で固体であるため、注型重合時には他の液状
単量体に溶解したシ、加熱し融点以上の温度で操作をし
なければならない等の制約があった。一方ビニルナフタ
レンやビニルカルバゾール４高屈Ｆｒ率な樹脂を与える
が、得られる樹脂は着色が著しく分散が大きい等眼鏡用
プラスチックレンズ用樹脂として満足できるものではな
かった。Diethylene glycol bisallyl carbonate resin, which has been conventionally used as a plastic lens material, has a low refractive index of 1.49 to 1.50, so if the resin obtained from this resin is used as a corrective eyeglass lens, it will have a lower refractive index than an inorganic optical glass lens. There was a drawback that the center thickness and edge thickness became large. In addition, naphthyl methacrylate and bisphenol dimethacrylate give resins with high refractive index, but since these monomers are solid at room temperature, they are dissolved in other liquid monomers during cast polymerization and heated to lower the melting point. There were restrictions such as having to operate at a temperature higher than that. On the other hand, vinylnaphthalene and vinylcarbazole 4 resins with a high refractive index were obtained, but the resulting resins were not satisfactory as resins for plastic lenses for eyeglasses, as they were extremely colored and had large dispersion.
〈発明が解決しようとする問題点〉
本発明の目的は、製造時においては煩雑な操作を必要と
せず、しかも無色透明性に優れ友高屈折率樹脂を提供す
るととＫある。<Problems to be Solved by the Invention> An object of the present invention is to provide a Tomotaka refractive index resin that does not require complicated operations during production and is colorless and transparent.
く問題点を解決するための手段および作用〉本発明者ら
は、このような現状Ｋかんがみ鋭意決し、高屈折率で無
色透明性に優れたものであることを見い出し、本発明を
完成するに至ったものである。In view of the current situation, the present inventors have determined that the present invention has a high refractive index and is excellent in colorless transparency, and has completed the present invention. This is what we have come to.
即ち、本発明は
一般式（１）
（但し、ＸはＨｌＣＨ，基またはＣ）を示し、ｎはＯ〜
４の整数を示し、Ｙ、Ｙ、はそれぞれ独立にＨｌＣＪＩ
、Ｂｒまたは工を示す。）で表わされる重合性単量体（
１）の１種または２種以上を必須成分とし、必要によシ
その単独重合体の屈折率が１．４８以上の他の重合性単
量体（［１）を含む重合性単量体成分から得られる重合
体からなることを特徴とする屈折率が１．５５以上の高
屈折率樹脂に関するものである。That is, the present invention represents the general formula (1) (wherein, X is HlCH, a group, or C), and n is O-
Indicates an integer of 4, Y, Y, each independently HlCJI
, Br or engineering. ) is a polymerizable monomer (
A polymerizable monomer component containing one or more of 1) as an essential component and optionally another polymerizable monomer ([1) whose homopolymer has a refractive index of 1.48 or more] The present invention relates to a high refractive index resin having a refractive index of 1.55 or more, which is made of a polymer obtained from.
本発明に用いる一般式（１）で示される重合性単量体（
１）は下記一般式（２）で示されるジチオールを通常の
方法で（メタ）アクリル酸エステルとすることによ）得
られ
ＨＳ ＋ ＣＨｔ ＣＨｔＸ ）−ＣＨｔ ＣＨｔ Ｓ
Ｈ（２）（但し、Ｘは０またはＳを示し、ｎは０〜３
の整数である。）るものである。すなわち、一般式（２
）で示されるジチオールと（メタ）アクリル酸ハライド
とを有機塩基や無機塩基性物質の存在下に反応させて得
る方法を挙げることができる。The polymerizable monomer represented by the general formula (1) used in the present invention (
1) is obtained by converting a dithiol represented by the following general formula (2) into a (meth)acrylic ester in a conventional manner, and is obtained as HS + CHt CHtX ) -CHt CHt S
H(2) (where, X represents 0 or S, and n is 0 to 3
is an integer. ). That is, the general formula (2
) and (meth)acrylic halide in the presence of an organic base or an inorganic basic substance.
本発明の高屈折率樹脂は、重合性単量体（１）の１種ま
たは２種以上のみを用いて得られる重合体からなるもの
であってもよいが、必要にょシ他の重合性単量体（ＩＩ
）を得られる高屈折率樹脂の屈折率が１．５５未満とな
らないように、共重合成分に用いた重合体からなるもの
であってもよい。使用できる他の重合性単量体（ＩＩ）
としてはその単独重合体の屈折率が１．４８以上でかつ
重合性単量体（１）と共重合しうるものであれば特に制
限されず、例えばメチルメタクリレート、フェニルアク
リレート、フェニルメタクリレート、ベンジルアクリレ
ート、ペンシルメタクリレート、クロロフェニルアクリ
レート、クロロフェニルメタクリレート、ブロモフェニ
ルアクリレート、ブロモフェニルメタクリレート、トリ
クロロフェニルアクリレート、トリクロロフェニルメタ
クリレート、トリクロロフェニルアクリレート、トリブ
ロモフェニルメタクリレ−）、２．２−ビス−（４−ア
クリロイルオキシフェニル）プロパン、２，２−ビス−
（４−メタクリロイルオキシフェニル）プロパン、２．
２−ビス−（４−アクリロイルオキシエトキシフェニル
）プロパン、２，２−ビス−（４−メタクリロイルオキ
シエトキシフェニル）プロパン、２，２−ビス−（４−
メタクリロイルオキシエトキシ−３，５−ジブロモフェ
ニル）プロパン等の（メタ）アクリル酸ニスデル類、安
息香酸アリル、フタル酸ジアリル、ジエチレングリコー
ルビスアリルカーボネート等のアリルエステル及びアリ
ルカーボネート類、スチレン、クロルスチレン、ジビニ
ルベンゼン等のビニル芳香族類等を挙げることができ、
これらの１種または２種以上を好適に用いることができ
る。重合性単量体（１ｍ）は得られる高屈折率樹脂の屈
折率が１．５５未満とならないようＫその種類と使用量
を適宜選択して用いるものであるが、高屈折率でしかも
無色透明性にも著しく優れた樹脂を得る上で、好ましく
はその使用量を重合性単量体成分中８００重量部満、よ
シ好ましくは７００重量部満とするのが好適である。The high refractive index resin of the present invention may be made of a polymer obtained using only one or more polymerizable monomers (1), but if necessary, other polymerizable monomers may also be used. mass (II
) may be made of a polymer used as a copolymer component so that the refractive index of the high refractive index resin obtained is not less than 1.55. Other polymerizable monomers (II) that can be used
The homopolymer is not particularly limited as long as it has a refractive index of 1.48 or more and can be copolymerized with the polymerizable monomer (1), such as methyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate. , pencil methacrylate, chlorophenyl acrylate, chlorophenyl methacrylate, bromophenyl acrylate, bromophenyl methacrylate, trichlorophenyl acrylate, trichlorophenyl methacrylate, trichlorophenyl acrylate, tribromophenyl methacrylate), 2,2-bis-(4-acryloyloxyphenyl) ) propane, 2,2-bis-
(4-methacryloyloxyphenyl)propane, 2.
2-bis-(4-acryloyloxyethoxyphenyl)propane, 2,2-bis-(4-methacryloyloxyethoxyphenyl)propane, 2,2-bis-(4-
Nisder (meth)acrylates such as methacryloyloxyethoxy-3,5-dibromophenyl)propane, allyl esters and allyl carbonates such as allyl benzoate, diallyl phthalate, diethylene glycol bisallyl carbonate, styrene, chlorstyrene, divinylbenzene Examples include vinyl aromatics such as
One or more of these can be suitably used. The polymerizable monomer (1m) is used by selecting the type and amount of K appropriately so that the refractive index of the resulting high refractive index resin does not become less than 1.55. In order to obtain a resin with excellent properties, it is preferable that the amount used be less than 800 parts by weight, more preferably less than 700 parts by weight, in the polymerizable monomer component.
本発明に用いる重合性単量体（１）は、室温で液状であ
るため注型重合時の型への注入や重合性単量体（ＩＩ）
と混合する場合に煩雑な操作が必要で危くなるほか低温
から重合を始められるので成型体に歪が生じにくい等の
利点がある。Since the polymerizable monomer (1) used in the present invention is liquid at room temperature, it can be injected into a mold during cast polymerization, and the polymerizable monomer (II)
In addition to requiring complicated operations and being dangerous when mixed with other materials, polymerization can be started at low temperatures, which has the advantage that distortion is less likely to occur in the molded product.
本発明の高屈折率樹脂は、重合性単量体（１）を必須成
分とし、必要によシ重合性単量体ＣＩりを共重合成分に
用いて得られる重合体からなるものである。該重合体を
得るための重合方法は％に制限されず従来から公知の方
法、例えば塊状重合、溶液重合、懸濁重合、乳化重合等
の方法を挙げることができるが、本発明においては、注
型重合によυ重合時に所望の形状に影付できるために、
塊状重合によるのが好ましく、例えばラジカル重合開始
剤を加えた重合性単量体成分をガラス製のモールドに注
入して、３０〜６０℃から次第に昇温して重合させる方
法がその具体例である。重合に際し、使用できるラジカ
ル重合開始剤としては、例えばベンゾイルパーオキサイ
ド、アセチルパーオキサイド、ジ−ｔ−ブチルパーオキ
サイド、ジイソプロピルパーオキシジカーボネート等の
過酸化物や２，２−アゾビスイソブチロニトリル、２．
２’−アゾビス−２，４−ジメチルバレロニトリル等の
アゾ系化合物等を挙げることができ、これらの１種また
は２８！以上を通常重合性単量体成分に対し、０．０５
〜１０重ｆ％、好ましくは０．１〜５重量係の範囲で必
要によシ促進剤と併用して用いることができる。The high refractive index resin of the present invention is composed of a polymer obtained by using the polymerizable monomer (1) as an essential component and optionally using the polymerizable monomer CI as a copolymerization component. The polymerization method for obtaining the polymer is not limited to % and may include conventionally known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Because it is possible to shade the desired shape during υ polymerization by type polymerization,
Bulk polymerization is preferred, and a specific example is a method in which a polymerizable monomer component to which a radical polymerization initiator has been added is injected into a glass mold and polymerized by gradually raising the temperature from 30 to 60°C. . Examples of radical polymerization initiators that can be used during polymerization include peroxides such as benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, and diisopropyl peroxydicarbonate, and 2,2-azobisisobutyronitrile. , 2.
Examples include azo compounds such as 2'-azobis-2,4-dimethylvaleronitrile, and one of these or 28! The above amount is usually 0.05 to the polymerizable monomer component.
It can be used in a range of 10 to 10% by weight, preferably 0.1 to 5% by weight, in combination with a percolation accelerator if necessary.
本発明の高屈折率樹脂は、上記の重合体以外に、公知の
添加剤、例えば紫外線吸収剤、帯電防止剤、魁
防滴剤、着色尋等を適宜含んでいてもよい。The high refractive index resin of the present invention may appropriately contain known additives such as ultraviolet absorbers, antistatic agents, drip-proofing agents, coloring agents, etc. in addition to the above-mentioned polymers.
〈発明の効果〉
本発明の高屈折率樹脂は重合性単量体（Ｉ）を必須成分
に用いて得られる重合体からなるために、高屈折率でし
かも無色透明性に優れている。また、本発明に用いる重
合性単量体（１）は室温で無色透明な液状であるため、
注型重合によシ重合体を得る場合の型への注入や重合性
単量体（Ｉ［）と混合のための煩雑々操作が必要でまく
なる他、低温から重合を始められるので得られる重合体
の成型物に歪が生じにくい等の優れた利点があシ、光学
材料用樹脂として特に有用であり、例えばレンズ、光フ
ァイバー、光ディスク、フィルム、光学素子の封止剤等
の部材として、更に顔料、着色剤、充填剤等を配合して
装飾用、建材用成型物にも使用できる。<Effects of the Invention> Since the high refractive index resin of the present invention is composed of a polymer obtained by using the polymerizable monomer (I) as an essential component, it has a high refractive index and is excellent in colorless transparency. In addition, since the polymerizable monomer (1) used in the present invention is a colorless and transparent liquid at room temperature,
When obtaining a polymer by cast polymerization, complicated operations for injection into a mold and mixing with the polymerizable monomer (I[) are not required, and the polymerization can be started at a low temperature. It has excellent advantages such as less distortion in polymer molded products, and is particularly useful as a resin for optical materials. It can also be used in decorative and building material moldings by adding pigments, colorants, fillers, etc.
〈実施例〉 以下、実施例によシ具体的に説明する。<Example> The present invention will be specifically explained below using examples.
実施例１
２−（トリシクロ（５，２，１，０）−３，４−ジブロ
モデシルチオ）エチルメタクリレート７０重量部、エチ
レングリコールジメタクリレート３０重ｆ部ト２．２’
−アゾビス−２，４−ジメチルバレロニトリル０．５重
量部との混合物を２枚のガラス板とシリコンラバー製ガ
スケットよりなるモールド中に注入し、５０℃で６時間
、６０℃で１６時間、９０℃で１時間加熱し重合させた
。得られた高屈折率樹脂〔１〕は無色透明であった。こ
の高屈折率樹脂の諸物性を表−１に示す。Example 1 70 parts by weight of 2-(tricyclo(5,2,1,0)-3,4-dibromodecylthio)ethyl methacrylate, 30 parts by weight of ethylene glycol dimethacrylate, 2.2'
- A mixture with 0.5 parts by weight of azobis-2,4-dimethylvaleronitrile was poured into a mold made of two glass plates and a silicone rubber gasket, and the mixture was heated at 50°C for 6 hours and at 60°C for 16 hours for 90 hours. The mixture was heated at ℃ for 1 hour to polymerize. The obtained high refractive index resin [1] was colorless and transparent. Table 1 shows the physical properties of this high refractive index resin.
実施例２〜７
実施例１と同様にして組成を変えて高屈折率樹脂〔２〕
〜〔７〕を得た。それらの諸物性を表−１に併せて示す
。Examples 2 to 7 High refractive index resin [2] with different composition in the same manner as in Example 1
~ [7] was obtained. Their physical properties are also shown in Table 1.
表 −１
１Ｂｒ２ＤＴＢ仏／ＥＧＤＭＡ−９１１，５８０３７，
７２ Ｂｒｔ ＤＴＢＭＡ／Ｓ ｔ ／ＢＧＤＭＡ
９０ １．５．８７ ３５．４３ Ｂｒ２Ｄ
ＴＨＭＡ／’ＢｚＭＡ／ＥＧＤＭＡ ９１ １．
５８２ ３６．６４ Ｂｒｔ ＤＴＢＭＡ／Ｂｒ４
ＢＭＥＰＰ ９０ １．６０８ ３０．４５
Ｂｒ２ＤＴＥＡ／Ｓｔ／ＥＧＤＭＡ ９０
１．５８１ ３５．８６ Ｂｒ、ＤＴＥＡ７４３ｚＭ
Ａ／ＢＧＤＭＡ ９１ １．５７２ ３８．１７
Ｂｒ２ＤＴＥＡ／Ｂｒ４ＢＭＥＰＰ ９０
１．６０４ ３１．２Ｂｒ、ＤＴＥＭＡ ： ２−
（）リシツク（５，２，１，０”）−３，４−ジブロモ
デシルチオ）エ
チルメタクリレート
Ｂｒ、ＤＴＥＡ ： ２− （）リシツク（５，２，
１，０）−３，４−ジブロモデシルチオ）エ
チルアクリレート
ＥＧＤＭＡ ：エチレングリコールジメタクリレー
ト
Ｓｔ：スチレン
Ｂ ｚ ＭＡ ＊ベンジルメタクリレートＢｒ４
ＢＭＥＰＰ ： ２，２−ビス（４−メタクリロイルオ
キシエトキシ−３，５−ジブロモ
フェニル）プロパン
特許出願人 日本触媒化学工業株式会社手 続
補 正 書 （自発）昭和６２年 １月２２日Table-1 1Br2DTB France/EGDMA-911,58037,
72 Brt DTBMA/S t /BGDMA
90 1.5.87 35.43 Br2D
THMA/'BzMA/EGDMA 91 1.
582 36.64 Brt DTBMA/Br4
BMEPP 90 1.608 30.45
Br2DTEA/St/EGDMA 90
1.581 35.86 Br, DTEA743zM
A/BGDMA 91 1.572 38.17
Br2DTEA/Br4BMEPP 90
1.604 31.2Br, DTEMA: 2-
() Lissik (5,2,1,0”)-3,4-dibromodecylthio)ethyl methacrylate Br, DTEA: 2- () Lissik (5,2,
1,0)-3,4-dibromodecylthio)ethyl acrylate EGDMA: Ethylene glycol dimethacrylate St: Styrene Bz MA *Benzyl methacrylate Br4
BMEPP: 2,2-bis(4-methacryloyloxyethoxy-3,5-dibromophenyl)propane Patent applicant Nippon Shokubai Chemical Co., Ltd. Procedures
Amendment (voluntary) January 22, 1986
Claims (1)
〜４の整数を示し、Ｙ＿１、Ｙ＿２はそれぞれ独立にＨ
、Ｃｌ、ＢｒまたはＩを示す。）で表わされる重合性単
量体〔 I 〕の１種または２種以上を必須成分とし、必
要によりその単独重合体の屈折率が１．４８以上の他の
重合性単量体〔II〕を含む重合性単量体成分から得られ
る重合体からなることを特徴とする屈折率が１．５５以
上の高屈折率樹脂。 ２、重合性単量体〔 I 〕を重合性単量体成分中２０重
量％以上の量で用いる特許請求の範囲第１項記載の高屈
折率樹脂。[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (However, X represents H, CH_3 group or Cl, and n is 0
Indicates an integer of ~4, Y_1 and Y_2 are each independently H
, Cl, Br or I. ) is an essential component of one or more polymerizable monomers [I], and if necessary, other polymerizable monomers [II] whose homopolymer has a refractive index of 1.48 or more. A high refractive index resin having a refractive index of 1.55 or more, characterized in that it is made of a polymer obtained from a polymerizable monomer component. 2. The high refractive index resin according to claim 1, wherein the polymerizable monomer [I] is used in an amount of 20% by weight or more in the polymerizable monomer component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10301987A JPS63268707A (en) | 1987-04-28 | 1987-04-28 | Resin having high refractive index |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10301987A JPS63268707A (en) | 1987-04-28 | 1987-04-28 | Resin having high refractive index |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63268707A true JPS63268707A (en) | 1988-11-07 |
| JPH0474364B2 JPH0474364B2 (en) | 1992-11-26 |
Family
ID=14342936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10301987A Granted JPS63268707A (en) | 1987-04-28 | 1987-04-28 | Resin having high refractive index |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63268707A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5274044A (en) * | 1992-07-28 | 1993-12-28 | General Electric Company | Graft copolymers containing (thioaromatic) alkyl acrylate rubber substrates |
-
1987
- 1987-04-28 JP JP10301987A patent/JPS63268707A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5274044A (en) * | 1992-07-28 | 1993-12-28 | General Electric Company | Graft copolymers containing (thioaromatic) alkyl acrylate rubber substrates |
| US5512631A (en) * | 1992-07-28 | 1996-04-30 | General Electric Company | Transparent blend compositions containing graft copolymers of (thioaromatic) alkylate rubber substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0474364B2 (en) | 1992-11-26 |
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