JPH01185501A - Production of high-refractive index resin for lens having large central thickness - Google Patents
Production of high-refractive index resin for lens having large central thicknessInfo
- Publication number
- JPH01185501A JPH01185501A JP63008623A JP862388A JPH01185501A JP H01185501 A JPH01185501 A JP H01185501A JP 63008623 A JP63008623 A JP 63008623A JP 862388 A JP862388 A JP 862388A JP H01185501 A JPH01185501 A JP H01185501A
- Authority
- JP
- Japan
- Prior art keywords
- tri
- refractive index
- mono
- polymn
- producing
- 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 description 21
- 239000011347 resin Substances 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- -1 mercaptoalkyl ester Chemical class 0.000 claims description 17
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical group NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- OOQZNLPSEKLHJX-UHFFFAOYSA-N 3,3,3-tris(sulfanyl)propanoic acid Chemical compound OC(=O)CC(S)(S)S OOQZNLPSEKLHJX-UHFFFAOYSA-N 0.000 claims description 2
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 2
- JQFBSWMHURZKOM-UHFFFAOYSA-N CC(S)(S)C(S)(S)C(O)=O Chemical compound CC(S)(S)C(S)(S)C(O)=O JQFBSWMHURZKOM-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 claims description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- PYXMAQOBQCYFNS-UHFFFAOYSA-N 2,2,2-tris(sulfanyl)acetic acid Chemical compound OC(=O)C(S)(S)S PYXMAQOBQCYFNS-UHFFFAOYSA-N 0.000 claims 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 claims 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 claims 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 125000005358 mercaptoalkyl group Chemical group 0.000 abstract 2
- 238000000034 method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002440 hydroxy compounds Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- QQCHYQXRQHGKEX-UHFFFAOYSA-N 2,2,3,3-tetrakis(sulfanyl)propanoic acid Chemical compound OC(=O)C(S)(S)C(S)S QQCHYQXRQHGKEX-UHFFFAOYSA-N 0.000 description 1
- GVPODVKBTHCGFU-UHFFFAOYSA-N 2,4,6-tribromoaniline Chemical compound NC1=C(Br)C=C(Br)C=C1Br GVPODVKBTHCGFU-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[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
- ACHVQPPJRVUUSV-UHFFFAOYSA-N 4,4,4-tris(sulfanyl)butanoic acid Chemical compound OC(=O)CCC(S)(S)S ACHVQPPJRVUUSV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- GPDWNEFHGANACG-UHFFFAOYSA-L [dibutyl(2-ethylhexanoyloxy)stannyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CC)CCCC GPDWNEFHGANACG-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229940071127 thioglycolate Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
「利用分野」
本発明は、高屈折率で、切削や研磨等の加工性に優れた
透明なポリウレタン樹脂の製造方法に関し、更に詳しく
は中心厚の厚い各種のレンズや光学素子として好適なポ
リウレタン樹脂の製造方法に関する。Detailed Description of the Invention "Field of Application" The present invention relates to a method for manufacturing transparent polyurethane resin that has a high refractive index and is excellent in processability such as cutting and polishing. The present invention relates to a method for producing a polyurethane resin suitable for use as an optical element.
「従来技術及びその問題点」
プラスチックレンズは、無機ガラスレンズに比べて軽量
で、割れ難（、また染色性が良いため、メガネ用やカメ
ラ用のレンズとして近年繁用されている。``Prior Art and its Problems'' Plastic lenses are lighter and more difficult to break than inorganic glass lenses (and have good stainability), so they have been frequently used as lenses for glasses and cameras in recent years.
レンズ用樹脂としては、従来、ジエチレングリコールビ
スアリルカーボネートをラジカル重合させたものが知ら
れている。この樹脂は、軽量で、耐衝撃性、染色性、加
工性等において優れているが、屈折率が低いという欠点
があった。As resin for lenses, resins obtained by radical polymerization of diethylene glycol bisallyl carbonate are conventionally known. This resin is lightweight and has excellent impact resistance, dyeability, processability, etc., but has the drawback of a low refractive index.
屈折率を向上させたレンズ用樹脂として、イソシアネー
ト化合物とジエチレングリコール等のヒドロキシ化合物
との反応により得られるウレタン樹脂（特開昭５７−１
３６６０１号公報、特開昭５７−１３６６０２号公報）
及びイソシアネート化合物とテトラブロモビスフェノー
ルＡ等のハロゲン原子含有ヒドロキシ化合物との反応に
より得られるウレタン樹脂（特開昭５８−１６４６１５
号公報）が知られている。しかしながら、これらの樹脂
の屈折率も充分に高くはない。As a lens resin with improved refractive index, a urethane resin obtained by the reaction of an isocyanate compound with a hydroxy compound such as diethylene glycol (Japanese Patent Laid-Open No. 57-1
36601, JP-A-57-136602)
and urethane resins obtained by the reaction of isocyanate compounds with halogen atom-containing hydroxy compounds such as tetrabromobisphenol A (JP-A-58-164615).
No. 2) is known. However, the refractive index of these resins is also not high enough.
特開昭６０−２１７２２９号公報には、高屈折率の樹脂
としてジイソシアネートとジ（２−ヒドロキシエチル）
スルフィドのような、硫黄原子を有するジオールとを反
応させて得られる硫黄原子含有ポリウレタン系レンズ用
樹脂が記載されている。しかしながら、この樹脂を用い
てレンズを製造する場合には、重合歪あるいは成形歪を
生じやすく、特に中心厚の厚いレンズを製造することは
困難であった。JP-A-60-217229 discloses diisocyanate and di(2-hydroxyethyl) as high refractive index resins.
A sulfur atom-containing polyurethane lens resin obtained by reacting with a diol having a sulfur atom, such as sulfide, is described. However, when manufacturing lenses using this resin, polymerization distortion or molding distortion tends to occur, making it particularly difficult to manufacture lenses with a thick center thickness.
「発明の目的」
従って、本発明は、重合歪あるいは成形歪を生じること
なく中心厚が６〜１８閣の各種のレンズや光学素子を製
造しうる高屈折率樹脂の製造方法を提供することを目的
とするものである。``Object of the Invention'' Therefore, the present invention aims to provide a method for producing a high refractive index resin that can produce various lenses and optical elements having a center thickness of 6 to 18 mm without causing polymerization distortion or molding distortion. This is the purpose.
「発明の構成」
本発明の中心厚の厚いレンズ用の高屈折率樹脂の１遣方
法は、ジイソシアネートと、３価以上のポリオールのメ
ルカプトアルキルエステルとを開始剤の存在で、−ＮＣ
Ｏ基／−ＯＨ基及び−ＳＨ基の和−０，５〜１．５の比
率で反応させてポリウレタン樹脂を製造する際に、初期
重合を一２０″Ｃ〜＋１０℃で行い、その後さらに３０
〜ｌ ２０ ’Ｃで重合を行うことを特徴とする。"Structure of the Invention" One method of producing a high refractive index resin for a lens with a thick center thickness according to the present invention is to combine a diisocyanate and a mercaptoalkyl ester of a trivalent or higher polyol in the presence of an initiator to form -NC.
When producing a polyurethane resin by reacting the sum of O groups/-OH groups and -SH groups at a ratio of -0.5 to 1.5, initial polymerization is carried out at -20"C to +10"C, and then further polymerization is carried out at 30"C to +10"C.
It is characterized in that the polymerization is carried out at ~120'C.
本発明方法において原料として使用するジイソシアネー
トは、芳香族系、脂肪族系のいずれでもよく、例えばｍ
−キシリレンジイソシアネート、ｐ−キシリレンジイソ
シアネート、テトラクロル−ｍ−キシリレンジイソシア
ネート、テトラクロル−ｐ−キシリレンジイソシアネー
ト、イソホロンジイソシアネート、ヘキサメチレンジイ
ソシアネート、ジシクロヘキシルメタンジイソシアネー
ト、ビス（イソシアナトメチル）シクロヘキサン、４．
４゛−ジフェニルメタンジイソシアネート、トリレンジ
イソシアネート等がある。ジイソシアネートとして、上
記のようなジイソシアネートを単独で又は２種以上混合
して使用することもできる。また、上記のジイソシアネ
ートのうち、ｍ −キシリレンジイソシアネートが特に
好ましい。The diisocyanate used as a raw material in the method of the present invention may be either aromatic or aliphatic, for example m
-xylylene diisocyanate, p-xylylene diisocyanate, tetrachlor-m-xylylene diisocyanate, tetrachlor-p-xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, bis(isocyanatomethyl)cyclohexane, 4.
Examples include 4'-diphenylmethane diisocyanate and tolylene diisocyanate. As the diisocyanate, the above diisocyanates can be used alone or in combination of two or more. Furthermore, among the above diisocyanates, m-xylylene diisocyanate is particularly preferred.
本発明方法においては、ポリオール成分として３価以上
のポリオールのメルカプトアルキルエステルを使用する
。この具体例としては、トリメチロールプロパンのモノ
−、ジ−若しくはトリ−メルカプトアセテート、モノ−
、ジ−若しくはトリ−メルカプトプロピオネート又はモ
ノ−、ジ−若しくはトリ−メルカプトブチレート；ペン
タエリトリットのモノ−、ジ−、トリ−若しくはテトラ
キズ−メルカプトアセテート、モノ＝、ジ−、トリ−若
しくはテトラキス−メルカプトプロピオネート又はモノ
−、ジ−、トリ−若しくはテトラキス−メルカプトブチ
レートが挙げられる。これらのうち、ペンタエリトリッ
トテトラキス（３−メルカプトプロピオネート）が好ま
しい。In the method of the present invention, a mercaptoalkyl ester of a trivalent or higher polyol is used as the polyol component. Examples of this include mono-, di- or trimercaptoacetate of trimethylolpropane, mono-
, di- or tri-mercaptopropionate or mono-, di- or tri-mercaptobutyrate; mono-, di-, tri- or tetrakid-mercaptoacetate, mono-, di-, tri- or Mention may be made of tetrakis-mercaptopropionate or mono-, di-, tri- or tetrakis-mercaptobutyrate. Among these, pentaerythritoltetrakis (3-mercaptopropionate) is preferred.
本発明においては、上記のようなジイソシアネ−トと、
ポリオールのメルカプトアルキルエステルとを、−ＮＣ
Ｏ基／−ＯＨ基及び−ＳＨ基の和＝０．５〜１．５の比
率、好ましくは１．０の比率となるように混合する。こ
の範囲を外れると、屈折率や加工性等、レンズとして望
ましい物性が悪化する。In the present invention, the above-mentioned diisocyanate and
mercaptoalkyl ester of polyol, -NC
They are mixed so that the ratio of O group/total of -OH group and -SH group = 0.5 to 1.5, preferably 1.0. Outside this range, physical properties desirable for a lens, such as refractive index and workability, deteriorate.
上記成分の重合は、本発明においては重合開始剤の存在
で行う。開始剤としては、例えばジブチル錫ジアセテー
ト、ジブチル錫ジ−２−エチルヘキソエート、ジブチル
錫ジマレエート、ジブチル錫ジラウレート等の有機錫化
合物、メチルアミン、エチルアミン、ｔ−ブチルアミン
、メチルエチルアミン、Ｎ、Ｎ−ジエタノール−ｐ−）
ルイジン、ジメチル−ｐ−トルイジン、Ｐ−）ルイジン
、ジフェニルアミン、０−ニトロアニリン、ｐ−ブロモ
アニリン、２，４．６−トリブロモアニリン等のアミン
化合物等を使用することができる。開始剤の使用量は、
用いるモノマーの種類や他の状況にも左右されるが、一
般には七ツマー混合物中０．０３〜０．３重量％、好ま
しくは０．０５〜０．１５重量％とする。In the present invention, the above-mentioned components are polymerized in the presence of a polymerization initiator. Examples of initiators include organotin compounds such as dibutyltin diacetate, dibutyltin di-2-ethylhexoate, dibutyltin dimaleate, dibutyltin dilaurate, methylamine, ethylamine, t-butylamine, methylethylamine, N,N -diethanol-p-)
Amine compounds such as luidine, dimethyl-p-toluidine, P-)luidine, diphenylamine, 0-nitroaniline, p-bromoaniline, and 2,4.6-tribromoaniline can be used. The amount of initiator used is
Although it depends on the type of monomer used and other circumstances, the amount is generally 0.03 to 0.3% by weight, preferably 0.05 to 0.15% by weight in the seven-mer mixture.
上記のような成分の他、原料混合物に紫外線吸収剤、酸
化防止剤等を添加してもよい。In addition to the above components, ultraviolet absorbers, antioxidants, etc. may be added to the raw material mixture.
重合方法としては、通常、注型重合法が用いられ、上記
のような各種成分を均一に混合し、脱気した後、ガラス
製又は金属製の鋳型中に注入し、重合反応を適切な温度
で行う０本発明方法においては、まず、初期重合を−２
０℃〜＋１０℃１好ましくは一１０℃〜０℃の低温で行
う、このような低温での初期重合は、通常１５〜７２時
間、好ましくは４８時間行う、中心厚の厚いレンズを製
造する場合には、厚い部分における熱の発散が悪く、歪
の原因となるので、本発明においては、上記のように低
温に冷却しながら重合を行い、歪の発生を防止する。そ
の後、３０℃〜１２０℃で更に重合を続ける。この時の
重合温度及び重合時間は、使用するモノマーの組み合わ
せや開始剤及び他の状況によって適宜決定することがで
き、通常、
段階的に温度を上昇して重合を行う。Cast polymerization is usually used as a polymerization method, in which the various components listed above are mixed uniformly, degassed, and then poured into a glass or metal mold to allow the polymerization reaction to occur at an appropriate temperature. In the method of the present invention, the initial polymerization is carried out at -2
The initial polymerization at such a low temperature, carried out at a low temperature of 0°C to +10°C, preferably between -10°C and 0°C, is usually carried out for 15 to 72 hours, preferably 48 hours, when producing lenses with a thick center thickness. Since heat dissipates poorly in thick portions and causes distortion, in the present invention, the polymerization is carried out while cooling to a low temperature as described above to prevent the occurrence of distortion. Thereafter, polymerization is further continued at 30°C to 120°C. The polymerization temperature and polymerization time at this time can be appropriately determined depending on the combination of monomers used, the initiator, and other circumstances, and the polymerization is usually carried out by increasing the temperature stepwise.
このようにして得られる樹脂は、公知のレンズ用樹脂に
比べて高い屈折率を有し、しかも重合歪あるいは成形歪
を有しない、中心厚６〜１８ｍのレンズの製造に好適で
ある。The resin thus obtained has a higher refractive index than known resins for lenses, has no polymerization strain or molding strain, and is suitable for manufacturing lenses with a center thickness of 6 to 18 m.
「実施例」
次に、実施例及び比較例により本発明を更に詳しく説明
するが、本発明はこれに限定されるものではない。"Example" Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例１
ｍ−キシリレンジイソシアネート８０ｇ、ペンタエリト
リットテトラキス（３−メルカプトプロピオネート）１
０４ｇ及びジブチル錫ジラウレート（開始剤）０．２ｇ
を混合し、室温付近で撹拌し、均一にした後、冷却しな
がら脱気した。次いで、中心厚１２ａＩ１１、コバ厚２
０１、半径８０！ｌＸ１１のレンズ成形用のガラス製鋳
型中に注入し、−５℃で４８時間、４０”Ｃで１０時間
、６０℃で１時間、１１０℃で３時間かけて重合反応を
行った。Example 1 m-xylylene diisocyanate 80 g, pentaerythritol tetrakis (3-mercaptopropionate) 1
04g and dibutyltin dilaurate (initiator) 0.2g
The mixture was mixed, stirred at around room temperature, made homogeneous, and then degassed while cooling. Next, center thickness 12aI11, edge thickness 2
01, radius 80! The mixture was poured into a glass mold for molding a 1X11 lens, and a polymerization reaction was carried out at -5°C for 48 hours, at 40''C for 10 hours, at 60°C for 1 hour, and at 110°C for 3 hours.
得られたレンズ成形品は、無色透明であり、屈折率は１
．５９９と高く、比重は１．３４であり、歪がなく、強
靭で耐衝撃性、切削性及び研磨性に優れていた。The obtained lens molded product is colorless and transparent, and has a refractive index of 1.
．． It had a high specific gravity of 599 and 1.34, was free from distortion, was strong, and had excellent impact resistance, machinability, and polishability.
比較例１
ペンタエリトリットテトラキス（３−メルカプトプロピ
オネート）１０４ｇの代わりにペンタエリドリフトテト
ラキス（チオグリコレート）１０４ｇを用い、重合を５
５゛Ｃの温度で８時間、７０゛Ｃで４時間、１１０℃で
９時間実施した以外は、実施例１と同様にしてレンズ成
形品を製造した。Comparative Example 1 104 g of pentaerythrift tetrakis (thioglycolate) was used instead of 104 g of pentaerythritol tetrakis (3-mercaptopropionate), and the polymerization was carried out for 5
A lens molded product was produced in the same manner as in Example 1, except that the tests were conducted at a temperature of 5°C for 8 hours, at 70°C for 4 hours, and at 110°C for 9 hours.
得られた成形品は、１．５９５の屈折率を有していたが
、歪を示した。The resulting molded article had a refractive index of 1.595 but exhibited distortion.
「発明の効果」
本発明によりポリウレタン系樹脂のモノマー成分として
ジイソシアネートと、３価以上のポリオールのメルカプ
トアルキルエステルとの組み合わせを用いることにより
、高屈折率で無色透明であり、染色性、耐衝撃性、切削
性及び研磨性に優れた樹脂が得られる。"Effects of the Invention" According to the present invention, by using a combination of diisocyanate and a mercaptoalkyl ester of a trivalent or higher polyol as a monomer component of a polyurethane resin, it is colorless and transparent with a high refractive index, and has good dyeability and impact resistance. , a resin with excellent machinability and polishability can be obtained.
更に、本発明方法によれば、低温重合が可能であるので
、中心厚が６〜１８ｍｍと、著しく厚いレンズを重合歪
あるいは成形歪を生じることなく製造できる。また、３
価以上のポリオールのメルカプトアルキルエステルとい
う多官能性化合物を一方の成分として用いるので、網状
構造を有する樹脂が得られ、硬度の高い樹脂が得られる
。Furthermore, according to the method of the present invention, since low temperature polymerization is possible, extremely thick lenses with a center thickness of 6 to 18 mm can be manufactured without causing polymerization distortion or molding distortion. Also, 3
Since a polyfunctional compound called a mercaptoalkyl ester of a polyol having a polyol or higher is used as one component, a resin having a network structure and a high hardness can be obtained.
従って、本発明方法は、中心厚の厚いメガネレンズ、カ
メラレンズ等の各種レンズや光学素子の製造に有効に利
用される。Therefore, the method of the present invention can be effectively used for manufacturing various lenses and optical elements such as eyeglass lenses and camera lenses having a thick center thickness.
特許出願人 旭光学工業株式会社Patent applicant: Asahi Optical Industry Co., Ltd.
Claims (1)
カプトアルキルエステルとを開始剤の存在で、−ＮＣＯ
基／−ＯＨ基及び−ＳＨ基の和＝０．５〜１．５の比率
で反応させてポリウレタン樹脂を製造する際に、初期重
合を−２０℃〜＋１０℃で行い、その後さらに３０〜１
２０℃で重合を行うことを特徴とする中心厚の厚いレン
ズ用の高屈折率樹脂の製造方法。 ２、３価以上のポリオールのメルカプトアルキルエステ
ルがトリメチロールプロパンのモノ−、ジ−若しくはト
リ−メルカプトアセテート、モノ−、ジ−若しくはトリ
−メルカプトプロピオネート又はモノ−、ジ−若しくは
トリ−メルカプトブチレート；ペンタエリトリットのモ
ノ−、ジ−、トリ−若しくはテトラキズ−メルカプトア
セテート、モノ−、ジ−、トリ−若しくはテトラキス−
メルカプトプロピオネート又はモノ−、ジ−、トリ−若
しくはテトラキス−メルカプトブチレートである請求項
１記載の高屈折率樹脂の製造方法。 ３、ジイソシアネートとしてｍ−キシリレンジイソシア
ネート、ポリオールのメルカプトアルキルエステルとし
てペンタエリトリットテトラキス（３−メルカプトプロ
ピオネート）を使用する請求項１記載の高屈折率樹脂の
製造方法。 ４、開始剤がジブチル錫ジアセテート、ジブチル錫ジ−
２−エチルヘキソエート、ジブチル錫ジマレエート、ジ
ブチル錫ジラウレート等の有機錫化合物、メチルアミン
、エチルアミン、ｔ−ブチルアミン、メチルエチルアミ
ン、Ｎ，Ｎ−ジエタノール−ｐ−トルイジン、ジメチル
−ｐ−トルイジン、ｐ−トルイジン、ジフェニルアミン
、ｏ−ニトロアニリン、ｐ−ブロモアニリン、２，４，
６−トリブロモアニリン等のアミン化合物である請求項
１、２又は３記載の高屈折率樹脂の製造方法。[Claims] 1. In the presence of an initiator, a diisocyanate and a mercaptoalkyl ester of a polyol having a valence of 3 or more are combined into -NCO
When producing a polyurethane resin by reacting at a ratio of groups/sum of -OH and -SH groups = 0.5 to 1.5, initial polymerization is carried out at -20°C to +10°C, and then further polymerization of 30 to 1.
A method for producing a high refractive index resin for lenses with a thick center, characterized by polymerizing at 20°C. The mercaptoalkyl ester of di-, tri- or higher-valent polyol is mono-, di-, or tri-mercaptoacetate of trimethylolpropane, mono-, di-, or tri-mercaptopropionate, or mono-, di-, or tri-mercaptobutylene. Mono-, di-, tri- or tetrakis-mercaptoacetate, mono-, di-, tri- or tetrakis-mercaptoacetate of pentaerythritol;
2. The method for producing a high refractive index resin according to claim 1, wherein the resin is mercaptopropionate or mono-, di-, tri- or tetrakis-mercaptobutyrate. 3. The method for producing a high refractive index resin according to claim 1, wherein m-xylylene diisocyanate is used as the diisocyanate and pentaerythritoltetrakis (3-mercaptopropionate) is used as the mercaptoalkyl ester of the polyol. 4. Initiator is dibutyltin diacetate, dibutyltin diacetate
Organotin compounds such as 2-ethylhexoate, dibutyltin dimaleate, dibutyltin dilaurate, methylamine, ethylamine, t-butylamine, methylethylamine, N,N-diethanol-p-toluidine, dimethyl-p-toluidine, p- Toluidine, diphenylamine, o-nitroaniline, p-bromoaniline, 2,4,
The method for producing a high refractive index resin according to claim 1, 2 or 3, wherein the resin is an amine compound such as 6-tribromoaniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63008623A JPH01185501A (en) | 1988-01-19 | 1988-01-19 | Production of high-refractive index resin for lens having large central thickness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63008623A JPH01185501A (en) | 1988-01-19 | 1988-01-19 | Production of high-refractive index resin for lens having large central thickness |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01185501A true JPH01185501A (en) | 1989-07-25 |
Family
ID=11698072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63008623A Pending JPH01185501A (en) | 1988-01-19 | 1988-01-19 | Production of high-refractive index resin for lens having large central thickness |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01185501A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01295202A (en) * | 1988-02-18 | 1989-11-28 | Mitsui Toatsu Chem Inc | Resin for material of lens comprising s-alkyl ester of thiocarmabic acid, plastic lens comprising the resin and production of the lens |
-
1988
- 1988-01-19 JP JP63008623A patent/JPH01185501A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01295202A (en) * | 1988-02-18 | 1989-11-28 | Mitsui Toatsu Chem Inc | Resin for material of lens comprising s-alkyl ester of thiocarmabic acid, plastic lens comprising the resin and production of the lens |
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