JPH03236386A - Polythiol compound, optical material and optical product obtained by using same compound - Google Patents

Polythiol compound, optical material and optical product obtained by using same compound

Info

Publication number
JPH03236386A
JPH03236386A JP2281089A JP28108990A JPH03236386A JP H03236386 A JPH03236386 A JP H03236386A JP 2281089 A JP2281089 A JP 2281089A JP 28108990 A JP28108990 A JP 28108990A JP H03236386 A JPH03236386 A JP H03236386A
Authority
JP
Japan
Prior art keywords
compound
thio
iso
optical
formula
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
Application number
JP2281089A
Other languages
Japanese (ja)
Other versions
JPH065323B2 (en
Inventor
Takeshi Okubo
毅 大久保
Chiyou Guen
グエン　チョウ
Reisuke Okada
岡田　▲禮▼介
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoya Corp
Original Assignee
Hoya Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoya Corp filed Critical Hoya Corp
Priority to AU68480/90A priority Critical patent/AU637662B2/en
Priority to US07/633,304 priority patent/US5326501A/en
Priority to CA002033239A priority patent/CA2033239C/en
Priority to KR1019900022002A priority patent/KR0133656B1/en
Priority to DE69016186T priority patent/DE69016186T2/en
Priority to EP90125652A priority patent/EP0435306B1/en
Priority to ES90125652T priority patent/ES2066948T3/en
Publication of JPH03236386A publication Critical patent/JPH03236386A/en
Priority to US08/073,663 priority patent/US5403938A/en
Publication of JPH065323B2 publication Critical patent/JPH065323B2/en
Priority to HK143695A priority patent/HK143695A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/52—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Abstract

NEW MATERIAL:A compound shown by formula I [X is-(CH2CH2S)n2-H; Y is H or-(CH2)n3-S-X; n1 is 1-5 ; n2 is 0-2 ; n3 is 1-5]. EXAMPLE:2, 5-Dimercaptomethyl-1, 4-dithian. USE:An optical material having high refractive index and large Abbe's number. Providing a polymer having excellent heat resistance, weather resistance and transparency, which is useful as a lens of eyeglasses, accessory, etc. PREPARATION:For example, diallyl disulfide shown by formula II is reacted with bromine to give a cyclic dimerized bromide shown by formula III. This compound is reacted with thiourea to form isothiuronium salt shown by formula IV. This compound is hydrolyzed with an aqueous solution of sodium hydroxide and made acidic with hydrochloric acid to give a compound shown by formula V wherein group X is H (n2=0), Y is H and n1=1.

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明はポリチオール化合物、それを用いて得られた光
学材料及び光学製品に関する。本発明のポリチオール化
合物は例えば光学材料の有用な原料として用いられる。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polythiol compound, and optical materials and optical products obtained using the same. The polythiol compound of the present invention is used, for example, as a useful raw material for optical materials.

また、上記ポリチオール化合物を用いて得られた本発明
の光学材料は、高屈折率、低分散を示し、光学的特性に
優れており、プラスチックレンズ、プリズム、光フアイ
バー情報記録用基板、着色フィルター、赤外線吸収フィ
ルターなどの光学製品に好ましく用いられる。In addition, the optical material of the present invention obtained using the above polythiol compound exhibits a high refractive index and low dispersion, and has excellent optical properties, and can be used for plastic lenses, prisms, optical fiber information recording substrates, colored filters, etc. Preferably used in optical products such as infrared absorption filters.

さらに、高屈折率の特徴を生かしたグラス、花ビン等の
装飾品等にも用いられる。Furthermore, it is also used in decorative items such as glasses and flower vases that take advantage of its high refractive index.

［従来の技術］ プラスチックはガラスに比べると軽量で割れにくく、染
色が容易なため近年、各種レンズ等の光学用途に使用さ
れている。このためのプラスチック材料としてはポリエ
チレングリコールビスアリルカーボネート（ＣＲ−３９
）やポリメチルメタクリレート（ＰＭＭＡ）が一般に用
いられている。[Prior Art] Plastics have recently been used for optical applications such as various lenses because they are lighter, less likely to break, and easier to dye than glass. The plastic material for this purpose is polyethylene glycol bisallyl carbonate (CR-39
) and polymethyl methacrylate (PMMA) are commonly used.

しかし、これらのプラスチック材料の屈折率は１゜５０
以下であり例えばレンズ材料に用いた場合度数が強くな
るとレンズの肉厚を厚くしなければならなくなり、軽量
といったプラスチックの優位性が失われるばかりでなく
、眼鏡用レンズとした場合は審美性が悪くなるので好ま
しくなかった。また特に、凹レンズの場合はレンズの周
囲の厚さが厚くなり複屈折や色収差が生じ、好ましくな
かった。そのため、比重の低いプラスチックの特徴を生
かしつつ、レンズの厚さを薄くでき、かっ色収差の少な
い高屈折率、低分散プラスチック材料が望まれている。However, the refractive index of these plastic materials is 1°50
For example, when used as a lens material, as the power increases, the lens must be made thicker, which not only loses the advantage of lightweight plastic, but also causes poor aesthetics when used as a lens for eyeglasses. So I didn't like it. Further, in particular, in the case of a concave lens, the thickness around the lens becomes thick, causing birefringence and chromatic aberration, which is not desirable. Therefore, there is a need for a high refractive index, low dispersion plastic material that can reduce the thickness of the lens while taking advantage of the characteristics of plastic having low specific gravity, and has less brown color aberration.

そのための材料としては、テトラクロロメタキシリレン
ジチオールや１．　３．　５−トリメルカプトベンゼン
と、ジイソシアネート化合物との重合体が特開昭６３−
４６２１３号公報に開示されている。また、ペンタエリ
スリトールテトラキスチオプロピオネートとジイソシア
ネートとの重合体が特開昭６４−２６６２２号公報に開
示されている。さらには、ペンタエリスリトールテトラ
キスチオプロピオネートとビニル化合物との重合体が特
開昭６３−３０９５０９号公報に開示されている。Materials for this purpose include tetrachloromethaxylylene dithiol and 1. 3. A polymer of 5-trimercaptobenzene and a diisocyanate compound was disclosed in JP-A-63-
It is disclosed in Japanese Patent No. 46213. Further, a polymer of pentaerythritol tetrakisthiopropionate and diisocyanate is disclosed in JP-A-64-26622. Furthermore, a polymer of pentaerythritol tetrakisthiopropionate and a vinyl compound is disclosed in JP-A-63-309509.

［発明が解決しようとする課題］ しかしながら、前記特開昭６３−４６２１３号公報に記
載のチオール化合物は屈折率が高いもののアツベ数が低
く、またこれを原料とした重合体はアツベ数が低く、ま
た耐候性に劣るといった欠点がある。また、特開昭６４
−２６６２２号公報や特開昭６３−３０９５０９号公報
に記載のチオール化合物はアツベ数が大きいものの屈折
率が低く、またこれを原料とした重合体は屈折率が低く
、また耐熱性に劣るといった欠点がある。[Problems to be Solved by the Invention] However, although the thiol compound described in JP-A-63-46213 has a high refractive index, it has a low Atsube number, and a polymer made from this compound as a raw material has a low Atsube number. It also has the disadvantage of poor weather resistance. Also, JP-A-64
Although the thiol compounds described in JP-A-26622 and JP-A-63-309509 have a large Abbe number, they have a low refractive index, and polymers made from these compounds have low refractive index and poor heat resistance. There is.

従って、本発明の目的は上記欠点を解消した新規なチオ
ール化合物、それを原料とした新規な光学材料及び光学
製品を提供することにある。Therefore, an object of the present invention is to provide a new thiol compound that eliminates the above-mentioned drawbacks, and new optical materials and optical products using the same as a raw material.

［課題を解決するための手段］ 本発明は、上記の目的を達成するためになされたもので
あり、本発明の新規なチオール化合物は一般式［１］で
示されることを特徴とする。[Means for Solving the Problems] The present invention has been made to achieve the above object, and the novel thiol compound of the present invention is characterized by being represented by the general formula [1].

［式中、Ｘは＝（ＣＨ２ＣＨ２５）ｎ２　Ｈであり、Ｙ
は水素原子または−（ＣＨｚ）ｎ３　Ｓ−Ｘであり、ｎ
ｌは１〜５の整数であり、ｎ２はＯ〜２の整数であり、
ｎ３は１〜５の整数である］また本発明の新規な光学材
料は、上記一般式［１コで示されるポリチオール化合物
（ａ１）を少なくとも含む成分（Ａ）と、一分子内に二
つ以上のビニル基を有する化合物（ｂ１）、一分子内に
二つ以上のイソ（チオ）シアネート基を有する化合物（
ｂ２）及び一分子内に一つ以上のビニル基と一つ以上の
イソ（チオ）シアネート基を有する化合物（ｂ３）のう
ちの少なくとも一種を少なくとも含む成分（Ｂ）とを重
合させることにより得られた重合体からなることを特徴
とする。なお、上記イソ（チオ）シアネート基とはイソ
シアネート基とイソチオシアネート基の両者を意味する
。[Wherein, X is =(CH2CH25)n2H, Y
is a hydrogen atom or -(CHz)n3S-X, and n
l is an integer of 1 to 5, n2 is an integer of O to 2,
n3 is an integer of 1 to 5] Furthermore, the novel optical material of the present invention comprises a component (A) containing at least a polythiol compound (a1) represented by the general formula [1], and two or more polythiol compounds in one molecule. A compound (b1) having a vinyl group, a compound (b1) having two or more iso(thio)cyanate groups in one molecule (
b2) and a component (B) containing at least one of the compounds (b3) having one or more vinyl groups and one or more iso(thio)cyanate groups in one molecule. It is characterized by being made of a polymer. In addition, the above-mentioned iso(thio)cyanate group means both an isocyanate group and an isothiocyanate group.

以下、本発明の詳細な説明する。The present invention will be explained in detail below.

本発明の新規ポリチオール化合物は、上記の一般式［１
］で示されるように、脂環式スルフィドである１、４−
ジチアン環を有することを特徴としている。この１，４
−ジチアン環は、ポリチオール化合物自体の屈折率及び
アツベ数を高めるので、このポリチオール化合物を用い
て重合体を製造した場合に、その重合体の屈折率及びア
ツベ数をも高める。またこのポリチオール化合物中の１
゜４−ジチアン環は剛直であるため、このポリチオール
化合物を用いて重合体を製造した場合、その重合体に高
耐熱性、優れた機械的物性を与える。The novel polythiol compound of the present invention has the above general formula [1
], the alicyclic sulfide 1,4-
It is characterized by having a dithian ring. This 1,4
- The dithiane ring increases the refractive index and Abbe's number of the polythiol compound itself, so when a polymer is produced using this polythiol compound, the refractive index and Abbe's number of the polymer are also increased. In addition, 1 in this polythiol compound
Since the 4-dithiane ring is rigid, when a polymer is produced using this polythiol compound, it imparts high heat resistance and excellent mechanical properties to the polymer.

次に一般式［１コにおいてｎ工およびｎ３が１から５、
ｎ２が０から２の整数に限定した理由を述べる。ｎ　１
　、ｎ　３が０では、ポリチオール化合物を用いて得ら
れる重合体がもろくなり、耐衝撃性が低下し、一方ｎｌ
　、ｎ３が６以上となると、ポリチオール化合物の屈折
率が低下し、得られる重合体の屈折率が低下し、耐熱性
も低下する傾向にあり好ましくない。また、ｎ２が３以
上になると、ポリチオール化合物を用いて得られる重合
体の耐熱性が低下するので好ましくない。Next, the general formula [in one piece, n and n3 are from 1 to 5,
The reason why n2 is limited to an integer between 0 and 2 will be explained. n 1
, n 3 is 0, the polymer obtained using the polythiol compound becomes brittle and the impact resistance decreases, while nl
, n3 of 6 or more is not preferable because the refractive index of the polythiol compound tends to decrease, the refractive index of the obtained polymer decreases, and the heat resistance also tends to decrease. Moreover, when n2 is 3 or more, the heat resistance of the polymer obtained using the polythiol compound decreases, which is not preferable.

本発明のポリチオール化合物は一般式［１］において、
例えばＸが水素原子（ｎ２　＝０）　、Ｙが水素原子、
ｎ１＝１の場合、次式に示される方法により合成するこ
とができる。The polythiol compound of the present invention has the general formula [1],
For example, X is a hydrogen atom (n2 = 0), Y is a hydrogen atom,
When n1=1, synthesis can be performed by the method shown in the following equation.

させ、環化三量化した臭素化物にチオ尿素を反応させイ
ソチウロニウム塩を生成させる。このものを水酸化ナト
リウム水溶液で加水分解した後、塩酸酸性にすることに
より目的とするポリチオール化合物を得ることができる
。The cyclized and trimerized bromide is then reacted with thiourea to produce an isothiuronium salt. The target polythiol compound can be obtained by hydrolyzing this product with an aqueous sodium hydroxide solution and then acidifying it with hydrochloric acid.

上記でその合成方法を示した、Ｘが水素原子（ｎ２＝０
）　、Ｙが水素原子、ｎ１＝１のチオール化合物以外の
、一般式［１］のポリチオール化合物として以下のもの
が挙げられる。The synthesis method was shown above, where X is a hydrogen atom (n2=0
), Y is a hydrogen atom, and the following polythiol compounds of general formula [1] other than the thiol compound where n1=1 are mentioned.

すなわち、 ジアリルジスルフィ ドに臭素を反応 次に上記一般式［１］のポリチオール化合物を用いて得
られる本発明の光学材料について述べると、この光学材
料は、上記一般式［１コで示されたポリチオール化合物
（ａ１）を少なくとも含む成分（Ａ）と、一分子内に二
つ以上のビニル基を有する化合物（ｂ１）、一分子内に
二つ以上のイソ（チオ）シアネート基を有する化合物（
ｂ２）及び一分子内に一つ以上のビニル基と一つ以上の
イソ（チオ）シアネート基を有する化合物（ｂ３）のう
ちの少なくとも一種を少なくとも含む成分（Ｂ）とを重
合させることにより得られる重合体を使用する。ここに
成分（Ａ）中の一般式［１］の化合物（ａ１）について
は、既に詳述したので、その説明を省略する。That is, to describe the optical material of the present invention obtained by reacting diallyl disulfide with bromine and then using the polythiol compound of the above general formula [1], this optical material is obtained by reacting bromine with diallyl disulfide. A component (A) containing at least (a1), a compound (b1) having two or more vinyl groups in one molecule, and a compound (b1) having two or more iso(thio)cyanate groups in one molecule (
b2) and a component (B) containing at least one of the compounds (b3) having one or more vinyl groups and one or more iso(thio)cyanate groups in one molecule. Use polymers. Since the compound (a1) of general formula [1] in component (A) has already been described in detail, its explanation will be omitted.

成分（Ａ）中には、重合体の物性等を適宜改良するため
に、一般式［１］で示される化合物（ａ１）以外に、一
分子内にメルカプト基および／またはヒドロキシ基を有
し、かつ一分子内のメルカプト基とヒドロキシ基の総数
が２以上の化合物（ａ２）を一種もしくは二種以上含ん
でいてもよい。この化合物（ａ２）としては、具体的に
はトリメチロールプロパン、１．２−エタンジチオール
、１，３−プロパンジチオール、テトラキスメルカプト
メチルメタン、ペンタエリスリトールテトラキスメルカ
プトプロピオネート、ペンタエリスリトールテトラキス
メルカプトアセテート、２−メルカプトエタノール、２
，３−ジメルカプトプロパノール、１．２−ジヒドロキ
シ−３−メルカプトプロパン、４−メルカプトフェノー
ル、１．２−ベンゼンジチオール、１，３−ベンゼンジ
チオール、１，４−ベンゼンジチオール、１゜３．５−
ベンゼントリチオール、１，２−ジメルカプトメチルベ
ンゼン、１，３−ジメルカプトメチルベンゼン、１，４
−ジメルカプトメチルベンゼン、１．　３．　５−トリ
メルカプトメチルベンゼン、トルエン−３，４−ジチオ
ール、４．４′ジヒドロキシフエニルスルフイド等が挙
げられる。Component (A) contains, in addition to the compound (a1) represented by general formula [1], a mercapto group and/or a hydroxy group in one molecule, in order to appropriately improve the physical properties of the polymer. The compound (a2) may also contain one or more compounds (a2) in which the total number of mercapto groups and hydroxyl groups in one molecule is two or more. Specifically, the compound (a2) includes trimethylolpropane, 1,2-ethanedithiol, 1,3-propanedithiol, tetrakismercaptomethylmethane, pentaerythritol tetrakismercaptopropionate, pentaerythritol tetrakismercaptoacetate, 2 -Mercaptoethanol, 2
, 3-dimercaptopropanol, 1,2-dihydroxy-3-mercaptopropane, 4-mercaptophenol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1°3.5-
Benzene trithiol, 1,2-dimercaptomethylbenzene, 1,3-dimercaptomethylbenzene, 1,4
-dimercaptomethylbenzene, 1. 3. Examples include 5-trimercaptomethylbenzene, toluene-3,4-dithiol, and 4,4' dihydroxyphenyl sulfide.

なお一般式［１コで示される化合物（ａ１）の使用量は
、成分（Ａ）の総量に対して、０．１−１１−１Ｏ０％
であり、好ましくは１０−１０−１Ｏ０％である。The amount of compound (a1) represented by the general formula [1] is 0.1-11-1O0% based on the total amount of component (A).
and preferably 10-10-10%.

成分（Ｂ）に使用されるビニル基含有化合物（ｂ１）と
しては、具体的にはジビニルベンゼン、エチレングリコ
ールジ（メタ）アクリレート、トリメチロールプロパン
トリ（メタ）アクリレート、一分子内に少なくとも二つ
以上の（メタ）アクリロキシ基を含むウレタン変性（メ
タ）アクリレート、エポキシ変性（メタ）アクリレート
、ポリエステル変性（メタ）アクリレート等が挙げられ
る。Examples of the vinyl group-containing compound (b1) used in component (B) include divinylbenzene, ethylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate, at least two or more in one molecule. Examples include urethane-modified (meth)acrylates, epoxy-modified (meth)acrylates, and polyester-modified (meth)acrylates containing (meth)acryloxy groups.

（なお、上記（メタ）アクリレートはアクリレートとメ
タクリレートの両者を意味し、（メタ）アクリロキシ基
は、アクリロキシ基とメタクリロキシ基の両者を意味す
る。） また成分（Ｂ）に使用されるイソ（チオ）シアネート基
含有化合物（ｂ２）としてはキシリレンジイソ（チオ）
シアネート、３，３′　−ジクロロジフェニル−４，４
′−ジイソ（チオ）シアネート、４，４′−ジフェニル
メタンジイソ（チオ）シアネート、ヘキサメチレンジイ
ソ（チオ）シアネート、２．　２’　、　　５．　５’
　−テトラクロロジフェニル−４，４′−ジイソ（チオ
）シアネート、トリレンジイソ（チオ）シアネート等が
挙げられる。さらに、一つ以上のシクロヘキシル環を有
するものとして、ビス（イソ（チオ）シアネートメチル
）シクロヘキサン、ビス（４−イソ（チオ）シアネート
シクロヘキシル）メタン、ビス（４−イソ（チオ）シア
ネートメチルシクロヘキシル）メタン、シクロヘキサン
ジイソ（チオ）シアネート、イソフォロンジイソ（チオ
）シアネート、２゜５−ビス（イソ（チオ）シアネート
メチル）ビシクロ［２，２，２コオクタン、２．５−ビ
ス（イソ（チオ）シアネートメチル）ビシクロ［２，２
゜１］へブタン、２−イソ（チオ）シアネートメチル−
３−（３−イソ（チオ）シアネートプロピル）−５−イ
ソ（チオ）シアネートメチル−ビシクロ［２，２，１コ
ーへブタン、２−イソ（チオ）シアネートメチル−３−
（３−イソ（チオ）シアネートプロピル）−６−イソ（
チオ）シアネートメチル−ビシクロ［２，２，１１へブ
タン、２−イソ（チオ）シアネートメチル−２−［３−
イソ（チオ）シアネートプロピル］−５−イソ（チオ）
シアネートメチル−ビシクロ［２，２，１］−ヘブタン
、２−イソ（チオ）シアネートメチル−２−（３−イソ
（チオ）シアネートプロピル）−６−イソ（チオ）シア
ネートメチル−ビシクロ［２゜２．１コ　−へブタン、
２−イソ（チオ）シアネートメチル−３−（３−イソ（
チオ）シアネートプロピル）−６−（２−イソ（チオ）
シアネートエチル）−ビシクロ［２，２，１］−へブタ
ン、２−イソ（チオ）シアネートメチル−３−（３−イ
ソ（チオ）シアネートプロピル）−６−（２−イソ（チ
オ）シアネートエチル）−ビシクロ［２゜２．１］−へ
ブタン、２−イソ（チオ）シアネートメチル−２−（３
−イソ（チオ）シアネートプロピル）−５−（２−イソ
（チオ）シアネートエチル）−ビシクロ［２，２，１］
−へブタン、２イソ（チオ）シアネートメチル−２−（
３−イソ（チオ）シアネートプロピル）　−６−（２−
イソ（チオ）シアネートエチル）−ビシクロ［２゜２．
１］−へブタン等が挙げられる。(The above (meth)acrylate means both acrylate and methacrylate, and (meth)acryloxy group means both acryloxy group and methacryloxy group.) Also, the iso(thio) used in component (B) The cyanate group-containing compound (b2) is xylylene diiso(thio)
Cyanate, 3,3'-dichlorodiphenyl-4,4
'-diiso(thio)cyanate, 4,4'-diphenylmethane diiso(thio)cyanate, hexamethylene diiso(thio)cyanate, 2. 2', 5. 5'
-tetrachlorodiphenyl-4,4'-diiso(thio)cyanate, tolylene diiso(thio)cyanate, and the like. Furthermore, as having one or more cyclohexyl rings, bis(iso(thio)cyanatomethyl)cyclohexane, bis(4-iso(thio)cyanatocyclohexyl)methane, bis(4-iso(thio)cyanatomethylcyclohexyl)methane , cyclohexane diiso(thio)cyanate, isophorone diiso(thio)cyanate, 2゜5-bis(iso(thio)cyanatomethyl)bicyclo[2,2,2cooctane, 2.5-bis(iso(thio)) cyanate methyl)bicyclo[2,2
゜1] Hebutane, 2-iso(thio)cyanatomethyl-
3-(3-iso(thio)cyanatopropyl)-5-iso(thio)cyanatomethyl-bicyclo[2,2,1-cohebutane, 2-iso(thio)cyanatomethyl-3-
(3-iso(thio)cyanatopropyl)-6-iso(
thio)cyanatomethyl-bicyclo[2,2,11hebutane, 2-iso(thio)cyanatomethyl-2-[3-
iso(thio)cyanatepropyl]-5-iso(thio)
Cyanatemethyl-bicyclo[2,2,1]-hebutane, 2-iso(thio)cyanatomethyl-2-(3-iso(thio)cyanatopropyl)-6-iso(thio)cyanatomethyl-bicyclo[2゜2 .1 Co-hebutane,
2-iso(thio)cyanatomethyl-3-(3-iso(
thio)cyanatepropyl)-6-(2-iso(thio)
cyanatoethyl)-bicyclo[2,2,1]-hebutane, 2-iso(thio)cyanatomethyl-3-(3-iso(thio)cyanatopropyl)-6-(2-iso(thio)cyanatoethyl) -bicyclo[2°2.1]-hebutane, 2-iso(thio)cyanatomethyl-2-(3
-iso(thio)cyanatopropyl)-5-(2-iso(thio)cyanatoethyl)-bicyclo[2,2,1]
-hebutane, 2iso(thio)cyanatomethyl-2-(
3-iso(thio)cyanatepropyl) -6-(2-
iso(thio)cyanatoethyl)-bicyclo[2゜2.
1]-hebutane and the like.

また、成分（Ｂ）に使用されるビニル基およびイソ（チ
オ）シアネート基含有化合物（ｂ３）としては、２−（
メタ）アクリロキシエチルイソ（チオ）シアネート、（
メタ）アクリロイルイソ（チオ）シアネート等が挙げら
れる。In addition, as the vinyl group- and iso(thio)cyanate group-containing compound (b3) used in component (B), 2-(
meth) acryloxyethyl iso(thio)cyanate, (
Examples include meth)acryloyl iso(thio)cyanate.

成分（Ｂ）中にビニル基が混入している場合は成分（Ａ
）の重合官能基が全てメルカプト基であるのが好ましく
、成分（Ａ）中にヒドロキシ基が混入していると重合度
が上がらず、得られた重合体の機械物性の低下を招く場
合がある。If a vinyl group is mixed in component (B), component (A
It is preferable that all polymerizable functional groups in component (A) are mercapto groups; if hydroxy groups are mixed in component (A), the degree of polymerization may not increase and the mechanical properties of the resulting polymer may deteriorate. .

本発明の光学材料を製造するに際して、上記成分（Ａ）
および成分（Ｂ）以外に、他のモノマーも適宜使用する
ことができる。When producing the optical material of the present invention, the above component (A)
In addition to component (B), other monomers can also be used as appropriate.

さらに、耐候性改良のため、紫外線吸収剤、酸化防止剤
、着色防止剤、蛍光染料などの添加剤を適宜加えてもよ
い。また、重合反応性向上のための触媒を適宜使用して
もよく、例えばメルカプト基とビニル基との反応性向上
のためには有機過酸化物、アゾ化合物や塩基性触媒が効
果的であり、メルカプト基やヒドロキシ基と、イソ（チ
オ）シアネート基との反応性向上のためには有機スズ化
合物、アミン化合物などが効果的である。Furthermore, additives such as ultraviolet absorbers, antioxidants, color inhibitors, and fluorescent dyes may be added as appropriate to improve weather resistance. In addition, a catalyst for improving polymerization reactivity may be used as appropriate. For example, organic peroxides, azo compounds, and basic catalysts are effective for improving reactivity between mercapto groups and vinyl groups. Organic tin compounds, amine compounds, and the like are effective for improving the reactivity between mercapto groups, hydroxyl groups, and iso(thio)cyanate groups.

−例として本発明のポリチオール化合物を用いた本発明
の光学材料の製造について述べると以下の通りである。- As an example, the production of the optical material of the present invention using the polythiol compound of the present invention will be described as follows.

上記成分（Ａ）、成分（Ｂ）及び添加剤や触媒の均一混
合物を公知の注型重合法、すなわちガラス製または金属
製のモールドと樹脂製のガスケットを組合せた型の中に
注入し、加熱して硬化させる。この時、成形後の樹脂の
取り出しを容易にするためにあらかじめモールドを離型
処理したり、成分（Ａ）及び成分（Ｂ）の混合物中に離
型剤を混合してもよい。重合温度は、使用する化合物に
より異なるが、一般には一２０〜＋１５０℃で、重合時
間は０．５〜７２時間である。本発明の光学材料は通常
の分散染料を用い、水もしくは有機溶媒中で容易に染色
が可能であり、この際さらに染色を容易にするために、
キャリアーを加えたり加熱しても良い。A homogeneous mixture of the above components (A), component (B), additives and catalysts is poured into a mold using a known cast polymerization method, that is, a mold made of a glass or metal mold and a resin gasket, and heated. and harden. At this time, in order to facilitate the removal of the resin after molding, the mold may be subjected to mold release treatment in advance, or a release agent may be mixed into the mixture of component (A) and component (B). The polymerization temperature varies depending on the compound used, but is generally -20 to +150°C, and the polymerization time is 0.5 to 72 hours. The optical material of the present invention can be easily dyed in water or an organic solvent using a conventional disperse dye.
A carrier may be added or heated.

このようにして得られた光学材料は、これに限定される
ものではないが、プラスチックレンズ等の光学製品とし
て特に好ましく用いられる。The optical material thus obtained is particularly preferably used as optical products such as plastic lenses, although the material is not limited thereto.

［実施例］ 以下、実施例により本発明を具体的に説明するが、本発
明はこれらの実施例に限定されるものではない。[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

（物性の評価） 実施例において得られたポリチオール化合物およびその
重合体並びに比較例で得られた重合体の物性評価は以下
の様にして行なった。(Evaluation of physical properties) The physical properties of the polythiol compounds and their polymers obtained in Examples and the polymers obtained in Comparative Examples were evaluated as follows.

屈折率（ｎＤ）とアツベ数（νＤ） アタゴ社製アツベ屈折率計３Ｔを用いて２０℃にて測定
した。Refractive index (nD) and Atsube number (νD) Measured at 20° C. using Atsube refractometer 3T manufactured by Atago Co., Ltd.

外観 肉眼により観察した。exterior Observation was made with the naked eye.

耐候性 サンシャインカーボンアークランプを装備したウェザ−
メーターにプラスチックレンズをセットし２００時間経
過したところでプラスチックレンズを取り出し、試験前
のプラスチックレンズと色相を比較した。評価基準は変
化なしく○）、わずかに黄変（△）、黄変（×）とした
。Weather equipped with weather resistant sunshine carbon arc lamp
A plastic lens was set in the meter, and after 200 hours had elapsed, the plastic lens was taken out and the hue was compared with the plastic lens before the test. The evaluation criteria were: no change (○), slight yellowing (△), and yellowing (×).

耐熱性 リガク社製ＴＭＡ装置により０．　５ｍｍφのピンを用
いて１０ｇｆの荷重でＴＭＡ測定を行ない、１０℃／ｍ
ｉｎの昇温で得られたチャートのピーク温度により評価
した。0.0 with a heat-resistant Rigaku TMA device. TMA measurement was performed using a 5mmφ pin with a load of 10gf, and the temperature was 10°C/m.
The evaluation was based on the peak temperature of the chart obtained by increasing the temperature in the temperature range.

光学歪 シュリーレン法による目視観察を行なった。optical distortion Visual observation was performed using the Schlieren method.

歪の無いものを○、歪のあるものを×とした。Those with no distortion were marked ○, and those with distortion were marked ×.

（実施例１） ２２、　９ｇ　（０，１５７ｍｏｌ　）　（７）ジアリ
ルジスルフィドを７８０ｍ１のジクロロメタンに溶解し
た溶液に２５．　０ｇ　（０，１５７ｍｏｌ　）の臭素
を一７８℃にて１時間かけて滴下した。そして、２０℃
まで昇温し、その温度にて８時間攪拌した後、減圧下で
ジクロロメタンを除去した。その残渣に１００ｍ１のエ
タノールと２３．　９ｇ　（０゜３１４ｍｏ１）のチオ
尿素を加え、１．５時間還流した。生成した沈殿を濾別
し、エタノールで数回洗浄した後乾燥させた。水７３ｍ
１にこの沈殿を分散させ、窒素雰囲気下で還流させなが
ら６４゜２ｇの１５％水酸化ナトリウム水溶液を１時間
かけて滴下し、その後さらに１時間還流させた。冷却後
、反応混合物を６Ｎ−塩酸で酸性にしベンゼンで抽出し
た。抽出物からベンゼンを減圧下で除き、残渣を２　Ｘ
　１０−２ｍｍＨｇで蒸留し沸点が１２１゜５℃の留分
２２．６ｇ　（収率６８％）を得た。このものの屈折率
は１．６４６、アツベ数は３５゜２であった。以下にこ
の新規ポリチオール化合物の構造決定のための分析結果
を示す。(Example 1) 22.9 g (0,157 mol) (7) 25. 0 g (0,157 mol) of bromine was added dropwise at -78°C over 1 hour. And 20℃
After stirring at that temperature for 8 hours, dichloromethane was removed under reduced pressure. Add 100ml of ethanol to the residue and add 23. 9 g (0°314 mo1) of thiourea was added and the mixture was refluxed for 1.5 hours. The generated precipitate was filtered off, washed several times with ethanol, and then dried. water 73m
This precipitate was dispersed in 1, and while refluxing under a nitrogen atmosphere, 64.2 g of a 15% aqueous sodium hydroxide solution was added dropwise over 1 hour, followed by further refluxing for 1 hour. After cooling, the reaction mixture was acidified with 6N hydrochloric acid and extracted with benzene. Benzene was removed from the extract under reduced pressure and the residue was purified 2X
Distillation was performed at 10-2 mmHg to obtain 22.6 g (yield: 68%) of a fraction with a boiling point of 121.5°C. This material had a refractive index of 1.646 and an Abbe number of 35°2. The analysis results for determining the structure of this new polythiol compound are shown below.

元素分析値 ＢＳ 理論値（％）　　３Ｂ、　９　５．６５　６０．４分析
値（％）　　３３．８　５．８０　６０．０’Ｈ−ＮＭ
Ｒ（溶媒：ＣＤＣｌ３、内部標準物質：ＴＭＳ） δ（ｐｐｍ）　−１，６２（ｔ、　　ＩＨ）２．８８〜
３．１４　（ｍ、５Ｈ） Ｒ ２５４５ｃｍ”（チオールのνｓＨ） なお、この新規ポリチオール化合物のＬＨ−ＮＭＲスペ
クトルを第１図に、ＩＲスペクトルを第２図に示す。Elemental analysis value BS Theoretical value (%) 3B, 9 5.65 60.4 Analysis value (%) 33.8 5.80 60.0'H-NM
R (solvent: CDCl3, internal standard: TMS) δ (ppm) -1,62 (t, IH) 2.88 ~
3.14 (m, 5H) R 2545 cm'' (vsH of thiol) The LH-NMR spectrum of this new polythiol compound is shown in FIG. 1, and the IR spectrum is shown in FIG.

（実施例２） え、室温にて１２時間反応させた。その後Ｏ℃にて濃塩
酸を、水相のｐＨが１になるまで攪拌しながら加え、ベ
ンゼン層を分離、水洗し、減圧下ベンゼンを溜去するこ
とにより目的物である２、５−ビス（２−メルカプトエ
チルチオメチル）−１゜４−ジチアン２４．　６ｇ　（
収率７４％）を得た。(Example 2) The reaction was carried out at room temperature for 12 hours. Thereafter, concentrated hydrochloric acid was added at 0°C with stirring until the pH of the aqueous phase reached 1, the benzene layer was separated, washed with water, and the benzene was distilled off under reduced pressure. 2-Mercaptoethylthiomethyl)-1°4-dithiane24. 6g (
A yield of 74% was obtained.

（実施例３） 造例 実施例１で得られた２、５−ジメルカプトメチル−１，
４−ジチア：／２１．　２ｇ　（０，１ｍｏ１）を１５
％水酸化ナトリウム水溶液５８．７ｇに溶解しベンジル
トリメチルアンモニウムクロライド１００ａ＋ｇの存在
下、１８．０ｇ　（０，３＋ｏｌ　）　０）ｆイランを
２００−のベンゼンに溶解したものを加２２、　９ｇ　
（０，１５７ｍｏ１）のジアリルジスルフィドを７８０
−のジクロロメタンに溶解した溶液に２５．　０ｇ　（
０，１５７ｍｏｌ　）の臭素を一７８℃にて１時間かけ
て滴下した。そして−２０℃まで昇温し、その温度に８
時間攪拌した後、減圧下でジクロロメタンを除去した。(Example 3) 2,5-dimercaptomethyl-1, obtained in Preparation Example 1,
4-Dithia: /21. 2g (0,1mol) to 15
% sodium hydroxide aqueous solution, and in the presence of 100a+g of benzyltrimethylammonium chloride, 18.0g (0,3+ol)0) f ylan dissolved in 200-benzene was added to 22.9g.
(0,157 mo1) of diallyl disulfide to 780
- in dichloromethane solution of 25. 0g (
0,157 mol) of bromine was added dropwise at -78°C over 1 hour. Then, the temperature was raised to -20℃, and at that temperature 8
After stirring for an hour, dichloromethane was removed under reduced pressure.

残留物に乾燥テトラヒドロフラン３００ｍを加え一１０
℃に冷却し、攪拌しながらビニルマグネシウムブロマイ
ドの１．０Ｍ−テトラヒドロフラン溶液を３２９−滴下
し、その後０℃で２時間、室温で１２時間攪拌した。反
応混合物を水中に投入し、ベンゼンで抽出し、抽出液か
ら減圧下ベンゼンを溜去した。Add 300ml of dry tetrahydrofuran to the residue and add 110ml of dry tetrahydrofuran.
The mixture was cooled to 0.degree. C., and 329 mm of a 1.0 M tetrahydrofuran solution of vinylmagnesium bromide was added dropwise with stirring, followed by stirring at 0.degree. C. for 2 hours and at room temperature for 12 hours. The reaction mixture was poured into water, extracted with benzene, and benzene was distilled off from the extract under reduced pressure.

次にこの残留物を２００−のベンゼンに溶解し硫化水素
を吹き込みながら室温にて４時間反応させた。その後、
減圧下にベンゼンを溜去し目的物である２、５−ビス（
３−メルカプトプロピル）−１，４−ジチアン２５．７
ｇ（収率６１％）を得た。Next, this residue was dissolved in 200% benzene and reacted at room temperature for 4 hours while blowing hydrogen sulfide. after that,
Benzene was distilled off under reduced pressure to obtain the target product, 2,5-bis(
3-Mercaptopropyl)-1,4-dithiane 25.7
g (yield 61%).

（実施例４） 本発明の光学材料の製造例 実施例１で得られた２、５−ジメルカプトメチル−１，
４−ジチアン（表１中でＳ−１と表示）０、　１ｍｏｌ
　、ｍ−キシリレンジイソシアネート（表１中でＸＤＩ
と表示）　０．　１ｍｏｌおよびジブチルスズジラウレ
ート（表１中でＤＢＴＤＬと表示）　Ｉ　Ｘ　１０−５
ｍｏｌの混合物を均一に攪拌し、二枚のレンズ成形用ガ
ラス型に注入し、５０℃で１０時間、その後６０℃で５
時間、さらに１２０℃で３時間加熱重合させレンズ形状
の重合体を得た。(Example 4) Example of manufacturing the optical material of the present invention 2,5-dimercaptomethyl-1 obtained in Example 1,
4-dithiane (indicated as S-1 in Table 1) 0, 1 mol
, m-xylylene diisocyanate (XDI in Table 1
) 0. 1 mol and dibutyltin dilaurate (denoted as DBTDL in Table 1) I X 10-5
The mol mixture was stirred uniformly, poured into two lens molds, and heated at 50°C for 10 hours, then at 60°C for 5 hours.
The polymer was further heated and polymerized at 120° C. for 3 hours to obtain a lens-shaped polymer.

得られた重合体の諸物性を表１に示す。表１から、本実
施例４の重合体は無色透明であり、屈折率（ｎｏ　）は
１．６６と非常に高く、アツベ数（νＤ）も３２と高い
（低分散）ものであり、耐候性、耐熱性（９７℃）に優
れ、光学歪の無いものであった。Table 1 shows the physical properties of the obtained polymer. From Table 1, the polymer of Example 4 is colorless and transparent, has a very high refractive index (no) of 1.66, has a high Abbe number (νD) of 32 (low dispersion), and has good weather resistance. It had excellent heat resistance (97° C.) and no optical distortion.

（実施例５〜２５） 本発明の他の光学材料の製造例 表１に示したモノマー組成物を使用し、重合条件を適宜
変更した以外は実施例４と同様の操作を行ない、レンズ
形状の重合体を得た。これらの重合体の諸物性を実施例
４の重合体の諸物性と共に表１に示す。表１から、本実
施例５〜２５の重合体も無色透明であり、屈折率（ｎＤ
）は１．５８〜１．６７と非常に高く、アツベ数（νＤ
）も２９〜４３と高い（低分散）ものであり、耐候性、
耐熱性（９４〜１３８℃）に優れ、光学歪の無いもので
あった。(Examples 5 to 25) Examples of manufacturing other optical materials of the present invention The same operations as in Example 4 were carried out except that the monomer composition shown in Table 1 was used and the polymerization conditions were changed as appropriate. A polymer was obtained. The physical properties of these polymers are shown in Table 1 together with the physical properties of the polymer of Example 4. From Table 1, the polymers of Examples 5 to 25 are also colorless and transparent, and have a refractive index (nD
) is very high at 1.58 to 1.67, and the Atsbe number (νD
) is also high (low dispersion) at 29-43, weather resistance,
It had excellent heat resistance (94 to 138°C) and no optical distortion.

特に、実施例４〜１１及び２３〜２５の重合体は、アツ
ベ数が２９〜３８であり、この範囲のアツベ数を有する
従来の重合体と比べ、屈折率が１゜６２〜１．６７と高
いものであった。In particular, the polymers of Examples 4 to 11 and 23 to 25 have an Abbe number of 29 to 38, and a refractive index of 1°62 to 1.67 compared to conventional polymers having an Abbe number in this range. It was expensive.

また、実施例１２〜２２の重合体は、屈折率が１．５８
〜１．６２であり、この範囲の屈折率を有する従来の重
合体と比ベアッペ数が３８〜４３と高いものであった。Further, the polymers of Examples 12 to 22 had a refractive index of 1.58.
~1.62, and the relative Beappé number was 38 to 43, which was high compared to conventional polymers having a refractive index in this range.

（比較例１） ペンタエリスリトールテトラキスメルカプトプロピオネ
ート（表１中でＰＥＴＭＰと表示）０゜１ｍｏｌ、ｍ−
キシリレンジイソシアネート（表１中でＸＤＩと表示）
　０．　２ｍｏｌおよびジブチルスズジラウレート（表
１中でＤＢＴＤＬと表示）ＩＸ　１０−４ｍｏｌの混合
物を均一に攪拌し、二枚のレンズ成形用ガラス型に注入
し、５０℃で１０時間、その後６０℃で５時間、さらに
１２０℃で３時間加熱重合させレンズ形状の重合体を得
た。得られた重合体の諸物性を表１に示す。表１から、
本比較例の重合体は無色透明で光学歪も観察されなかっ
たが、ｎＤ／ν０が１．５９／３６と低く、耐熱性も８
６℃と劣っていた。(Comparative Example 1) Pentaerythritol tetrakis mercaptopropionate (indicated as PETMP in Table 1) 0° 1 mol, m-
Xylylene diisocyanate (denoted as XDI in Table 1)
0. A mixture of 2 mol of dibutyltin dilaurate (indicated as DBTDL in Table 1) IX and 10-4 mol of dibutyltin dilaurate (indicated as DBTDL in Table 1) was stirred uniformly, poured into two glass molds for lens molding, heated at 50°C for 10 hours, then heated at 60°C for 5 hours. Further, polymerization was carried out by heating at 120° C. for 3 hours to obtain a lens-shaped polymer. Table 1 shows the physical properties of the obtained polymer. From Table 1,
The polymer of this comparative example was colorless and transparent, and no optical distortion was observed, but the nD/ν0 was low at 1.59/36, and the heat resistance was 8.
It was inferior at 6 degrees Celsius.

（比較例２．３） 表１に示したモノマー組成物を使用した以外は比較例１
と同様の操作を行ない、レンズ形状の重合体を得た。こ
れらの重合体の諸物性を実施例４〜２５、比較例１の重
合体の諸物性と共に表１に示した。表１から、本比較例
２の重合体は屈折率が１．６７と高く、耐熱性（９４℃
）にも優れているが、耐候性に劣り、光学歪が観察され
た。また、本比較例３の重合体は、無色透明で光学歪は
観察されず、耐候性は優れていたが、屈折率が１゜５３
と低く、耐熱性が６５℃と劣るものであった。(Comparative Example 2.3) Comparative Example 1 except that the monomer composition shown in Table 1 was used.
A lens-shaped polymer was obtained by performing the same operation as above. The physical properties of these polymers are shown in Table 1 together with the physical properties of the polymers of Examples 4 to 25 and Comparative Example 1. From Table 1, the polymer of Comparative Example 2 has a high refractive index of 1.67 and a high heat resistance (94°C
), but its weather resistance was poor and optical distortion was observed. The polymer of Comparative Example 3 was colorless and transparent, no optical distortion was observed, and had excellent weather resistance, but the refractive index was 1°53.
The temperature was low, and the heat resistance was poor at 65°C.

（以下余白） 表１の略号表 Ｓ−１・ Ｓ−２ニ −３ Ｓ−４： ＸＤＩ：ｍ−キシリレンジイソシアネートＥＤＴ：エタ
ンジチオール ＰＥＴＭＡ：ペンタエリスリトールテトラキスメルカプ
トアセテート ＥＤＭＡ：エチレングリコールジメタクリレートＰＥＴ
ＭＰ：ペンタエリスリトールテトラキスメルカプトプロ
ピオネート ＤＶＢ　ニジビニルベンゼン ４−ＭＰ：４−メルカプトフェノール ＴＭＰＴＭＡ：　トリメチロールプロパントリメタクリ
レート ＴＭＰニトリメチロールプロパン １．２−ＤＨＢ：ｌ、２−ジヒドロキシベンゼンＤＭＢ
：１，３−ジメルカプトベンゼンＴＧ：３−メルカプト
−１，２−ジヒドロキシプロパン ＤＰＭＤＩニジフェニルメタンジイソシアネートＴＭＭ
Ｍ：テトラキスメルカプトメチルメタン１．２−ＢＤＴ
：１，２−ベンゼンジチオールＤＨＰＳ　：４．４’　
−ジヒドロキシフェニルスルフィド ＩＰＤＩ：イソフォロンジイソシアネートＨ６−ＸＤＩ
　：　１，３−ビス（イソシアネートメチル）シクロヘ
キサン Ｈ６−ＭＤＩ・ビス（４−イソシアネートシクロヘキシ
ル）メタン ＭＥＩ：２−メタクリロキシエチルイソシアネート ＴＤ■ニトリレンジイソシアネート ＤＢＴＤＬ　ニジブチルスズジラウレートＤＭＴＤ（Ｊ
　ニジメチルスズジクロライドＤＢＴＤＣｉニジブチル
スズジクロライドＡＤＶＮ　：アゾビスジメチルバレロ
ニトリル１．３．５−ＴＭＢ：１，３．５−トリメルカ
プトベンゼン ＤＡＰＥニジアリリデンペンタエリスリット［発明の効
果］ 本発明の新規ポリチオール化合物は、１，４ジチアン環
を有するので、屈折率及びアツベ数が高く、一分子内に
二つ以上のビニル基を有する化合物、一分子内に二つ以
上のイソ（チオ）シアネート基を有する化合物及び一分
子内に一つ以上のビニル基と一つ以上のイソ（チオ）シ
アネート基を有する化合物のうちの少なくとも一種と容
易に重合反応し重合体を与える。また、この重合体を使
用する本発明の光学材料は、１，４−ジチアン環を主鎖
に含むので、屈折率、アツベ数が高く、耐熱性、耐候性
、透明性に優れているので眼鏡レンズ、カメラレンズ等
のレンズ、プリズムや、光ファイバー、光ディスク、磁
気ディスク等に用いられる記録媒体基板、着色フィルタ
ー、赤外線吸収フィルター等の光学製品に好ましく用い
られる。(Left below) Abbreviations in Table 1 S-1/S-2-3 S-4: XDI: m-xylylene diisocyanate EDT: ethanedithiol PETMA: pentaerythritol tetrakis mercaptoacetate EDMA: ethylene glycol dimethacrylate PET
MP: Pentaerythritol Tetrakis Mercaptopropionate DVB Nidivinylbenzene 4-MP: 4-Mercaptophenol TMPTMA: Trimethylolpropane trimethacrylate TMP Nitrimethylolpropane 1.2-DHB: l,2-dihydroxybenzene DMB
:1,3-dimercaptobenzene TG:3-mercapto-1,2-dihydroxypropane DPMDI diphenylmethane diisocyanate TMM
M: Tetrakismercaptomethylmethane 1,2-BDT
:1,2-benzenedithiol DHPS :4.4'
-Dihydroxyphenyl sulfide IPDI: Isophorone diisocyanate H6-XDI
: 1,3-bis(isocyanatomethyl)cyclohexane H6-MDI/bis(4-isocyanatocyclohexyl)methane MEI: 2-methacryloxyethyl isocyanate TD Nitrilene diisocyanate DBTDL Nidibutyltin dilaurate DMTD (J
Nidimethyltin dichloride DBTDCi Nidibutyltin dichloride ADVN: Azobisdimethylvaleronitrile 1.3.5-TMB: 1,3.5-trimercaptobenzene DAPE Nidiarylidene pentaerythritol [Effects of the invention] New polythiol compound of the present invention has a 1,4 dithian ring, so it has a high refractive index and Atsube number, and is a compound that has two or more vinyl groups in one molecule, and a compound that has two or more iso(thio)cyanate groups in one molecule. It easily undergoes a polymerization reaction with at least one of the compounds having one or more vinyl groups and one or more iso(thio)cyanate groups in one molecule to give a polymer. In addition, the optical material of the present invention using this polymer contains a 1,4-dithiane ring in the main chain, so it has a high refractive index and Atsube's number, and has excellent heat resistance, weather resistance, and transparency, so it can be used for eyeglasses. It is preferably used in optical products such as lenses, prisms such as lenses and camera lenses, recording medium substrates used in optical fibers, optical disks, magnetic disks, etc., colored filters, and infrared absorption filters.

さらに、高屈折率の特徴を生かしたグラス、化ビン等の
装飾品等にも用いられる。Furthermore, it is also used in decorative items such as glasses and bottles that take advantage of its high refractive index.

【図面の簡単な説明】[Brief explanation of drawings]

第１図および第２図は、実施例１で得られたポリチオー
ル化合物のＩＨ−ＮＭＲスペクトルおよびＩＲスペクト
ルをそれぞれ示す図である。FIG. 1 and FIG. 2 are diagrams showing the IH-NMR spectrum and IR spectrum of the polythiol compound obtained in Example 1, respectively.

Claims (6)

【特許請求の範囲】[Claims] （１）一般式［１］ ▲数式、化学式、表等があります▼［１］ ［式中、Ｘは−（ＣＨ＿２ＣＨ＿２Ｓ）ｎ＿２−Ｈであ
り、Ｙは水素原子または−（ＣＨ＿２）ｎ＿３−Ｓ−Ｘ
であり、ｎ＿１は１〜５の整数であり、ｎ＿２は０〜２
の整数であり、ｎ＿３は１〜５の整数である］ で示されることを特徴とするポリチオール化合物。(1) General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] [In the formula, X is -(CH_2CH_2S)n_2-H, and Y is a hydrogen atom or -(CH_2)n_3-S- X
, n_1 is an integer from 1 to 5, and n_2 is 0 to 2.
and n_3 is an integer of 1 to 5.] A polythiol compound characterized by the following. （２）一般式［１］ ▲数式、化学式、表等があります▼［１］ ［式中、Ｘは−（ＣＨ＿２ＣＨ＿２Ｓ）ｎ＿２−Ｈであ
り、Ｙは水素原子または−（ＣＨ＿２）ｎ＿３−Ｓ−Ｘ
であり、ｎ＿１は１〜５の整数であり、ｎ＿２は０〜２
の整数であり、ｎ＿３は１〜５の整数である］ で示されることを特徴とするポリチオール化合物（ａ＿
１）を少なくとも含む成分（Ａ）と、一分子内に二つ以
上のビニル基を有する化合物（ｂ＿１）、一分子内に二
つ以上のイソ（チオ）シアネート基を有する化合物（ｂ
＿２）及び一分子内に一つ以上のビニル基と一つ以上の
イソ（チオ）シアネート基を有する化合物（ｂ＿３）の
うちの少なくとも一種を少なくとも含む 成分（Ｂ）とを重合させることにより得られた重合体を
使用することを特徴とする光学 材料。(2) General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] [In the formula, X is -(CH_2CH_2S)n_2-H, and Y is a hydrogen atom or -(CH_2)n_3-S- X
, n_1 is an integer from 1 to 5, and n_2 is 0 to 2.
and n_3 is an integer of 1 to 5] A polythiol compound (a_3 is an integer of 1 to 5)
Component (A) containing at least 1), a compound (b_1) having two or more vinyl groups in one molecule, and a compound (b_1) having two or more iso(thio)cyanate groups in one molecule.
_2) and a component (B) containing at least one of the compounds (b_3) having one or more vinyl groups and one or more iso(thio)cyanate groups in one molecule. An optical material characterized by using a polymer. （３）成分（Ａ）が、化合物（ａ＿１）とともに、メル
カプト基および／またはヒドロキシ基を有し、一分子内
のメルカプト基とヒドロキシ基の総数が２以上の化合物
（ａ＿２）を含む、請求項（２）に記載の光学材料。(3) A claim in which component (A), together with compound (a_1), contains a compound (a_2) having a mercapto group and/or a hydroxy group, and the total number of mercapto groups and hydroxy groups in one molecule is 2 or more. The optical material according to (2). （４）化合物（ｂ＿２）が一つ以上のシクロヘキシル環
を有する、請求項（２）または（３）に記載の光学材料
。(4) The optical material according to claim (2) or (3), wherein the compound (b_2) has one or more cyclohexyl rings. （５）請求項（２）、（３）および（４）のいずれか一
項に記載の光学材料を使用することを特徴とする光学製
品。(5) An optical product characterized by using the optical material according to any one of claims (2), (3), and (4). （６）光学製品がプラスチックレンズであることを特徴
とする請求項（５）に記載の光学製品。(6) The optical product according to claim (5), wherein the optical product is a plastic lens.
JP2281089A 1989-12-28 1990-10-19 Optical material and optical product obtained by using polythiol compound Expired - Lifetime JPH065323B2 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AU68480/90A AU637662B2 (en) 1989-12-28 1990-12-24 Polythiol compound, and optical material and product produced therefrom
US07/633,304 US5326501A (en) 1989-12-28 1990-12-24 Polythiol compound, and optical material and product produced therefrom
CA002033239A CA2033239C (en) 1989-12-28 1990-12-27 Polythiol compound, and optical material and product produced therefrom
KR1019900022002A KR0133656B1 (en) 1989-12-28 1990-12-27 Polythiol compound and optical material and products
EP90125652A EP0435306B1 (en) 1989-12-28 1990-12-28 Polythiol compound, and optical material and product produced therefrom
DE69016186T DE69016186T2 (en) 1989-12-28 1990-12-28 Polythiol compound and optical material and product made from it.
ES90125652T ES2066948T3 (en) 1989-12-28 1990-12-28 COMPOSITE OF POLYTIOL, AND OPTICAL MATERIAL AND PRODUCT PRODUCED FROM IT.
US08/073,663 US5403938A (en) 1989-12-28 1993-06-08 Polythiol compound, and optical material and product produced therefrom
HK143695A HK143695A (en) 1989-12-28 1995-09-07 Polythiol compound and optical material and product produced therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP34329889 1989-12-28
JP1-343298 1989-12-28

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP5092128A Division JPH075585B2 (en) 1989-12-28 1993-03-25 Polythiol compound

Publications (2)

Publication Number Publication Date
JPH03236386A true JPH03236386A (en) 1991-10-22
JPH065323B2 JPH065323B2 (en) 1994-01-19

Family

ID=18360438

Family Applications (2)

Application Number Title Priority Date Filing Date
JP2281089A Expired - Lifetime JPH065323B2 (en) 1989-12-28 1990-10-19 Optical material and optical product obtained by using polythiol compound
JP5092128A Expired - Fee Related JPH075585B2 (en) 1989-12-28 1993-03-25 Polythiol compound

Family Applications After (1)

Application Number Title Priority Date Filing Date
JP5092128A Expired - Fee Related JPH075585B2 (en) 1989-12-28 1993-03-25 Polythiol compound

Country Status (2)

Country Link
JP (2) JPH065323B2 (en)
KR (1) KR0133656B1 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02153302A (en) * 1988-02-17 1990-06-13 Mitsui Toatsu Chem Inc Resin for high-refractive index plastic lens and lens consisting of this resin and production of lens
WO1996037279A1 (en) * 1995-05-25 1996-11-28 Baker Hughes Incorporated Treatments to reduce aldol condensation and subsequent polymerization in caustic acid gas scrubbers
US6559276B2 (en) 2000-10-26 2003-05-06 Hoya Corporation Asymmetric disulfide compounds, method for producing the same, and optical products
US6696540B2 (en) 2001-11-28 2004-02-24 Hoya Corporation Episulfide compound, method for producing the same and optical product comprising the same
US6706894B2 (en) 2001-11-28 2004-03-16 Hoya Corporation Thiol compound, method for producing the same and optical product made with the same
WO2004108787A1 (en) 2003-06-09 2004-12-16 Hoya Corporation Transparent shaped body
JP2005338109A (en) * 2004-05-24 2005-12-08 Mitsui Chemicals Inc Sulfur-atom-containing resin optical material
JP2005345684A (en) * 2004-06-02 2005-12-15 Mitsui Chemicals Inc Optical material comprising resin containing sulfur atom
JP2006003624A (en) * 2004-06-17 2006-01-05 Mitsui Chemicals Inc Optical material comprising sulfur atom-containing resin
EP1746118A1 (en) * 2004-03-12 2007-01-24 Mitsui Chemicals, Inc. Polyurethane polymerizable composition and method for producing optical resin composed of same
WO2007049658A1 (en) * 2005-10-28 2007-05-03 Ube Industries, Ltd. Dithianedithiol derivative and process for producing the same
WO2008026727A1 (en) 2006-08-31 2008-03-06 Hoya Corporation Method for producing polythiourethane resin
EP1925629A1 (en) * 2005-08-18 2008-05-28 Mitsui Chemicals, Inc. Polythiourethane-based polymerizable composition and optical resin obtained from the same
JP2010229394A (en) * 2009-03-03 2010-10-14 Ube Ind Ltd Ene-thiol cured material and method for producing the same
US7909929B2 (en) 2002-11-13 2011-03-22 Nippon Soda Co., Ltd. Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film
CN102428550A (en) * 2009-05-19 2012-04-25 株式会社村田制作所 Semiconductor switch device and method for manufacturing semiconductor switch device
WO2015046540A1 (en) 2013-09-30 2015-04-02 ホヤ レンズ タイランド リミテッド Transparent plastic substrate and plastic lens
WO2015087822A1 (en) * 2013-12-11 2015-06-18 三菱瓦斯化学株式会社 Novel thiol compound, and composition for optical materials which uses same
WO2020004531A1 (en) * 2018-06-29 2020-01-02 ホヤ レンズ タイランド リミテッド Polymerizable composition for optical member, optical member, and method for producing optical member
WO2020004534A1 (en) * 2018-06-29 2020-01-02 ホヤ レンズ タイランド リミテッド Cured object for optical member and optical member
KR20200004689A (en) 2018-07-04 2020-01-14 에스케이씨 주식회사 Preparation method of thiol compound
KR20210078072A (en) * 2019-12-18 2021-06-28 이근수 Organic compound and method of synthesizing thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4822495B2 (en) * 2004-11-05 2011-11-24 三井化学株式会社 Method for producing polythiol
JP5060036B2 (en) * 2005-09-29 2012-10-31 Ｈｏｙａ株式会社 Method for producing polythiol oligomer
JP5429930B2 (en) * 2008-09-05 2014-02-26 Ｊｓｒ株式会社 High refractive index material with high Abbe number and excellent heat resistance
JP2012177056A (en) * 2011-02-28 2012-09-13 Tokyo Institute Of Technology Polymer having high refractive index
KR102045150B1 (en) 2018-06-21 2019-11-14 에스케이씨 주식회사 Thiol compound and preperation method of the same

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02153302A (en) * 1988-02-17 1990-06-13 Mitsui Toatsu Chem Inc Resin for high-refractive index plastic lens and lens consisting of this resin and production of lens
WO1996037279A1 (en) * 1995-05-25 1996-11-28 Baker Hughes Incorporated Treatments to reduce aldol condensation and subsequent polymerization in caustic acid gas scrubbers
US6559276B2 (en) 2000-10-26 2003-05-06 Hoya Corporation Asymmetric disulfide compounds, method for producing the same, and optical products
US6696540B2 (en) 2001-11-28 2004-02-24 Hoya Corporation Episulfide compound, method for producing the same and optical product comprising the same
US6706894B2 (en) 2001-11-28 2004-03-16 Hoya Corporation Thiol compound, method for producing the same and optical product made with the same
US7909929B2 (en) 2002-11-13 2011-03-22 Nippon Soda Co., Ltd. Dispersoid having metal-oxygen bonds, metal oxide film, and monomolecular film
WO2004108787A1 (en) 2003-06-09 2004-12-16 Hoya Corporation Transparent shaped body
JP4719000B2 (en) * 2003-06-09 2011-07-06 Ｈｏｙａ株式会社 Eyeglass lenses
AU2004245407B2 (en) * 2003-06-09 2008-12-04 Hoya Corporation Transparent molded article
EP1746118A1 (en) * 2004-03-12 2007-01-24 Mitsui Chemicals, Inc. Polyurethane polymerizable composition and method for producing optical resin composed of same
EP1746118A4 (en) * 2004-03-12 2010-08-18 Mitsui Chemicals Inc Polyurethane polymerizable composition and method for producing optical resin composed of same
US8772441B2 (en) 2004-03-12 2014-07-08 Mitsui Chemicals, Inc. Polyurethanes polymerizable composition and method for producing optical resin of the same
JP2005338109A (en) * 2004-05-24 2005-12-08 Mitsui Chemicals Inc Sulfur-atom-containing resin optical material
JP2005345684A (en) * 2004-06-02 2005-12-15 Mitsui Chemicals Inc Optical material comprising resin containing sulfur atom
JP2006003624A (en) * 2004-06-17 2006-01-05 Mitsui Chemicals Inc Optical material comprising sulfur atom-containing resin
EP1925629A4 (en) * 2005-08-18 2008-10-01 Mitsui Chemicals Inc Polythiourethane-based polymerizable composition and optical resin obtained from the same
EP1925629A1 (en) * 2005-08-18 2008-05-28 Mitsui Chemicals, Inc. Polythiourethane-based polymerizable composition and optical resin obtained from the same
AU2006280850B2 (en) * 2005-08-18 2012-05-24 Mitsui Chemicals, Inc. Polythiourethane-based polymerizable composition and optical resin obtained from the same
US8304506B2 (en) 2005-08-18 2012-11-06 Mitsui Chemicals, Inc. Polythiourethane-based polymerizable composition and optical resin obtained from the same
WO2007049658A1 (en) * 2005-10-28 2007-05-03 Ube Industries, Ltd. Dithianedithiol derivative and process for producing the same
US7872093B2 (en) 2006-08-31 2011-01-18 Hoya Corporation Method for producing polythiourethane resin
WO2008026727A1 (en) 2006-08-31 2008-03-06 Hoya Corporation Method for producing polythiourethane resin
JP2010229394A (en) * 2009-03-03 2010-10-14 Ube Ind Ltd Ene-thiol cured material and method for producing the same
CN102428550A (en) * 2009-05-19 2012-04-25 株式会社村田制作所 Semiconductor switch device and method for manufacturing semiconductor switch device
WO2015046540A1 (en) 2013-09-30 2015-04-02 ホヤ レンズ タイランド リミテッド Transparent plastic substrate and plastic lens
EP3936904A1 (en) 2013-09-30 2022-01-12 Hoya Lens Thailand Ltd. Transparent plastic substrate and plastic lens
EP3483220A1 (en) 2013-09-30 2019-05-15 Hoya Lens Thailand Ltd. Transparent plastic substrate and plastic lens
EP3483219A1 (en) 2013-09-30 2019-05-15 Hoya Lens Thailand Ltd. Transparent plastic substrate and plastic lens
EP3936905A1 (en) 2013-09-30 2022-01-12 Hoya Lens Thailand Ltd. Transparent plastic substrate and plastic lens
JP5835526B2 (en) * 2013-12-11 2015-12-24 三菱瓦斯化学株式会社 Novel thiol compound and optical material composition using the same
US9604959B2 (en) 2013-12-11 2017-03-28 Mitsubishi Gas Chemical Company, Inc. Thiol compound and composition for optical materials using the same
TWI619707B (en) * 2013-12-11 2018-04-01 Mitsubishi Gas Chemical Co Novel thiol compound and composition for optical material using the same
WO2015087822A1 (en) * 2013-12-11 2015-06-18 三菱瓦斯化学株式会社 Novel thiol compound, and composition for optical materials which uses same
WO2020004531A1 (en) * 2018-06-29 2020-01-02 ホヤ レンズ タイランド リミテッド Polymerizable composition for optical member, optical member, and method for producing optical member
JPWO2020004534A1 (en) * 2018-06-29 2021-06-24 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ Hardened product for optical member and optical member
JPWO2020004531A1 (en) * 2018-06-29 2021-07-08 ホヤ レンズ タイランド リミテッドＨＯＹＡ Ｌｅｎｓ Ｔｈａｉｌａｎｄ Ｌｔｄ A polymerizable composition for an optical member, an optical member, and a method for manufacturing the optical member.
WO2020004534A1 (en) * 2018-06-29 2020-01-02 ホヤ レンズ タイランド リミテッド Cured object for optical member and optical member
KR20200004689A (en) 2018-07-04 2020-01-14 에스케이씨 주식회사 Preparation method of thiol compound
KR20210078072A (en) * 2019-12-18 2021-06-28 이근수 Organic compound and method of synthesizing thereof

Also Published As

Publication number Publication date
KR0133656B1 (en) 1998-04-23
JPH065323B2 (en) 1994-01-19
JPH06192250A (en) 1994-07-12
KR910011993A (en) 1991-08-07
JPH075585B2 (en) 1995-01-25

Similar Documents

Publication Publication Date Title
JPH03236386A (en) Polythiol compound, optical material and optical product obtained by using same compound
US5326501A (en) Polythiol compound, and optical material and product produced therefrom
US6265510B1 (en) Thiol and sulfur-containing O-(meth)acrylate compounds and use thereof
JPH05148340A (en) Polymer for optical material and its production
AU2002301988B2 (en) Thiol compound, method for producing the same and optical product comprising the same
EP0972772B1 (en) Polyisocyanate compounds, process for producing the same and optical materials using the same
JP2942400B2 (en) Polyisocyanate compound, optical material and optical product obtained using the same
JP2998982B2 (en) Polyisocyanate compound, optical material and optical product obtained using the same
JPH0665193A (en) Polyisocyanate compound and optical material and optical production produced therefrom
JP2896261B2 (en) Vinyl compound, polymer for optical material and optical product obtained using the same
JP3953791B2 (en) Optical products using thiol compounds
JP2004354959A (en) Optical product made of thiol compound
JP2007269649A (en) Organic germanium compound and method for producing the same
US6194603B1 (en) Polyisocyanate compound, process for producing the same and optical materials using the same
JP3029603B2 (en) Optical products
JP3174760B2 (en) Optical products
JP2898119B2 (en) Polyisocyanate compound, optical material and optical product obtained using the same
JP4091227B2 (en) Organic germanium compound and method for producing the same
JP2000044648A (en) Optical product
JP2000044531A (en) Polyisocyanate compound and its production
JP2001172287A (en) Germanium-containing isocyanate compound and method for producing the same
JP2000044530A (en) Polyisocyanate compound and its production
JP2000047002A (en) Optical product

Legal Events

Date Code Title Description
EXPY Cancellation because of completion of term
FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110119

Year of fee payment: 17