JPH06271532A - New sulfonium salt compound and polymerization initiator - Google Patents
New sulfonium salt compound and polymerization initiatorInfo
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- JPH06271532A JPH06271532A JP8017393A JP8017393A JPH06271532A JP H06271532 A JPH06271532 A JP H06271532A JP 8017393 A JP8017393 A JP 8017393A JP 8017393 A JP8017393 A JP 8017393A JP H06271532 A JPH06271532 A JP H06271532A
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- Prior art keywords
- sulfonium salt
- salt compound
- compound
- polymerization initiator
- group
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規スルホニウム塩化
合物およびそれを含有するカチオン重合開始剤にに関す
るものである。該重合開始剤を含有するカチオン重合性
組成物は、加熱により短時間で硬化することができ、得
られた硬化物は、優れた物性を有しているため成型樹
脂、注型樹脂、塗料、接着剤、インキ等の材料として好
適に用いられる。FIELD OF THE INVENTION The present invention relates to a novel sulfonium salt compound and a cationic polymerization initiator containing the same. The cationically polymerizable composition containing the polymerization initiator can be cured in a short time by heating, and the obtained cured product has excellent physical properties, and thus has molding resin, casting resin, paint, It is preferably used as a material for adhesives, inks and the like.
【０００２】[0002]
【従来の技術】従来、エポキシ樹脂の硬化剤として、二
液系で広く利用されている活性なアミン含有化合物、カ
ルボン酸無水物やメルカプト化合物がある。一方、エポ
キシ樹脂を一液系として硬化するのには、フッ化ホウ素
−モノエチルアミンがある。また、熱潜在性カチオン重
合開始剤及びその組成物が記載されているものとして、
特開昭５８−３７００３号公報、特開昭６３−２２３０
０２号公報、特開昭５６−１５２８３３号公報、特開平
２−１７８３１９号公報、特開平３−１７１１９号公報
などが知られている。2. Description of the Related Art Conventionally, as curing agents for epoxy resins, active amine-containing compounds, carboxylic acid anhydrides and mercapto compounds, which are widely used in two-part systems, are available. On the other hand, there is boron fluoride-monoethylamine for curing the epoxy resin as a one-component system. Further, as a thermal latent cationic polymerization initiator and its composition are described,
JP-A-58-37003 and JP-A-63-2230
No. 02, JP-A-56-152833, JP-A-2-178319, JP-A-3-17119 and the like are known.
【０００３】活性なアミン含有化合物やカルボン酸無水
物により、エポキシ樹脂を硬化する所謂二液系では、完
全に各成分を混合する必要があり、硬化時間も数時間要
する。また、反応が室温でも逐次的に起こるので、ポッ
トライフが数時間から数日と短く、取り扱い上問題があ
る。In a so-called two-component system in which an epoxy resin is cured with an active amine-containing compound or carboxylic acid anhydride, it is necessary to mix each component completely, and the curing time also takes several hours. In addition, since the reaction occurs sequentially even at room temperature, the pot life is as short as several hours to several days, which is a problem in handling.
【０００４】一方、エポキシ樹脂を一液系として硬化す
ることができるフッ化ホウ素−モノエチルアミン系で
は、取り扱い上が便利ではあるが、硬化温度が１６０℃
以上と高く、しかも完全硬化するのに１〜８時間要する
という問題がある。また、特開昭５８−３７００３号公
報に記載されているスルホニウム塩系の熱潜在性カチオ
ン重合開始剤および、特開平２−１７８３１９号公報に
記載されているピリジニウム塩系の熱潜在性カチオン重
合開始剤では、一液系とすることができ、硬化時間も短
いという特徴を有しているが、硬化温度が高いという問
題点がある。On the other hand, a boron fluoride-monoethylamine system capable of curing an epoxy resin as a one-pack system is convenient in handling, but the curing temperature is 160 ° C.
There is a problem that it is high as above and it takes 1 to 8 hours to completely cure. Further, a sulfonium salt-based thermal latent cationic polymerization initiator described in JP-A-58-37003 and a pyridinium salt-based thermal latent cationic polymerization initiator described in JP-A-2-178319. The agent is characterized in that it can be made into a one-liquid system and the curing time is short, but there is a problem that the curing temperature is high.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、前に述べた
事情からみてなされたもので、カチオン重合性化合物を
加熱により、低温かつ短時間に硬化させることができる
新規なカチオン重合開始剤を提供し、更に該開始剤を含
む貯蔵安定性のある一液型カチオン重合組成物を得ると
共に優れた物性を有する硬化物を提供することを目的と
している。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides a novel cationic polymerization initiator capable of curing a cationically polymerizable compound by heating at a low temperature in a short time. It is also an object of the present invention to provide a storage-stable one-pack type cationic polymerization composition containing the initiator, and to provide a cured product having excellent physical properties.
【０００６】[0006]
【問題を解決するための手段】本発明者らは、前記目的
を達成するため鋭意検討したところ、特定のスルホニウ
ム塩化合物からなる重合開始剤を用いることで、低温か
つ短時間にてカチオン重合性化合物を硬化することがで
き、更にその硬化物特性に優れた性能を与える新規重合
開始剤を見出して本発明を完成するに至った。[Means for Solving the Problem] The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, by using a polymerization initiator composed of a specific sulfonium salt compound, the cationic polymerization property at low temperature and in a short time can be improved. The present invention has been completed by discovering a novel polymerization initiator which can cure a compound and which gives excellent properties to the cured product.
【０００７】以下、本発明を詳細に説明する。本発明の
スルホニウム塩化合物は、下記の化２で表されるが、The present invention will be described in detail below. The sulfonium salt compound of the present invention is represented by the following chemical formula 2,
【０００８】[0008]
【化２】 [Chemical 2]
【０００９】上記一般式（Ｉ）において、Ｒ．、Ｒ
2 は、それぞれ水素原子、メチル基、エチル基、プロピ
ル基、イソプロピル基、ブチル基、ｔ−ブチル基、ヘキ
シル基、ｃ−ヘキシル基等のアルキル基、Ｆ，Ｃｌ，Ｂ
ｒ，Ｉ等のハロゲン原子、ニトロ基、メトキシ基，エト
キシ基、イソプロポキシ基等のアルコキシ基の群より選
ばれた基であり、Ｒ3 、Ｒ4 は、それぞれメチル基、エ
チル基、プロピル基、イソプロピル基、ブチル基、ｔ−
ブチル基、ヘキシル基、ｃ−ヘキシル基等のアルキル基
の群より選ばれた基であり、また、Ｒ3 とＲ4 は一体と
なって結合して、４〜７員環を形成していてもよく、Ｘ
は、ＳｂＦ6 ，ＡｓＦ6 ，ＰＦ6 又はＢＦ4を表す。Ｘ
は、ＳｂＦ6 ，ＡｓＦ6 ，ＰＦ6 又はＢＦ4 であり、こ
の内、ＳｂＦ6 が好んで用いられる。In the above general formula (I), R. , R
2 is a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group or a c-hexyl group, F, Cl, B.
a group selected from the group consisting of a halogen atom such as r and I, a nitro group, a methoxy group, an ethoxy group, an alkoxy group such as an isopropoxy group, and R 3 and R 4 are a methyl group, an ethyl group and a propyl group, respectively. , Isopropyl group, butyl group, t-
A group selected from the group of alkyl groups such as a butyl group, a hexyl group, and a c-hexyl group, and R 3 and R 4 are bonded together to form a 4- to 7-membered ring. Well, X
Represents SbF 6 , AsF 6 , PF 6 or BF 4 . X
Is SbF 6 , AsF 6 , PF 6 or BF 4 , of which SbF 6 is preferably used.
【００１０】該スルホニウム塩化合物は、例えば、次の
方法で得ることができる。９−ブロモフルオレン等の９
−ハロフルオレンとジメチルスルフェド等のジアルキル
スルフェドまたはテトラヒドロチオフェン等の環状スル
フィドとを等モルづつ、必要に応じてメタノール、アセ
トン、アセトニトリル等の不活性溶媒存在下にて室温〜
８０℃で数時間〜６０日間反応させ、次いで、得られた
固形物を水もしくは水−メタノール系等の水−有機溶媒
系に溶解せしめ、六フッ化アンチモン酸ナトリウム等を
加え激しく攪拌し、析出した液状液状または固形物の生
成物を分離後、乾燥して得られる。The sulfonium salt compound can be obtained, for example, by the following method. 9 such as 9-bromofluorene
-Equimolar amounts of halofluorene and dialkylsulfide such as dimethylsulfide or cyclic sulfides such as tetrahydrothiophene, at room temperature in the presence of an inert solvent such as methanol, acetone or acetonitrile, if necessary.
The reaction is carried out at 80 ° C. for several hours to 60 days, and then the obtained solid matter is dissolved in water or a water-organic solvent system such as a water-methanol system, sodium hexafluoroantimonate and the like are added, and the mixture is vigorously stirred to precipitate. The product is obtained by separating the product in the form of a liquid or liquid, and then drying it.
【００１１】本発明の代表的なスルホニウム塩化合物と
して、下記表１に記載の化合物が例示される。但し、式
中のＸはＳｂＦ6 ，ＡｓＦ6 ，ＰＦ6 又はＢＦ4 であ
る。As typical sulfonium salt compounds of the present invention, the compounds shown in Table 1 below are exemplified. However, X in the formula is SbF 6 , AsF 6 , PF 6 or BF 4 .
【００１２】[0012]
【表１】 [Table 1]
【００１３】本発明において、重合開始剤である前記四
級アンモニウム塩化合物は、カチオン重合性化合物と配
合してカチオン重合組成物として用いられる。カチオン
重合性化合物としては、次のような化合物が挙げられ
る。 （ａ）エポキシ基を有する化合物として、１，１，３−
テトラデカジエンジオキサイド、リモネンジオキサイ
ド、４−ビニルシクロヘキセンジオキサイド、（３，４
−エポキシシクロヘキシル）メチル−３，４−エポキシ
シクロヘキシルカルボキシレート、ジ（３，４−エポキ
シシクロヘキシル）アジペート、フェニルグリシジルエ
ーテル、ビスフェノールＡ型エポシキ樹脂、ハロゲン化
ビスフェノールＡ型エポシキ樹脂、ｏ−，ｍ−，ｐ−ク
レゾールノボラック型エポシキ樹脂、フェノールノボラ
ック型エポシキ樹脂、多価アルコールのポリグリシジル
エーテル等のエポシキ化合物In the present invention, the quaternary ammonium salt compound which is a polymerization initiator is blended with a cationically polymerizable compound to be used as a cationically polymerized composition. Examples of the cationically polymerizable compound include the following compounds. (A) As a compound having an epoxy group, 1,1,3-
Tetradecadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, (3,4
-Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, o-, m-, Epoxy compounds such as p-cresol novolac type epoxy resin, phenol novolac type epoxy resin, polyglycidyl ether of polyhydric alcohol, etc.
【００１４】（ｂ）ビニル化合物として、スチレン、α
−メチルスチレン、ｐ−クロロメチルスチレン等のスチ
レン類；ｎ−ブチルビニルエーテル、イソブチルビニル
エーテル、シクロヘキシルビニルエーテル、ヒドロキシ
ブチルビニルエーテル等のアルキルビニルエーテル類；
アリルビニルエーテル、１−オクタヒドロナフチルビニ
ルエーテル等のアルケニルビニルエーテル類；エチニル
ビニルエーテル、１−メチル−２−プロペニルビニルエ
ーテル等のアルキニルビニルエーテル類；フェニルビニ
ルエーテル、ｐ−メトキシフェニルビニルエーテル等の
アリールビニルエーテル類；ブタンジオールジビニルエ
ーテル、トリエチレングリコールビニルエーテル、シク
ロヘキサンジオールジビニルエーテル等のアルキルジビ
ニルエーテル類；１，４−ベンゼンジメタノールジビニ
ルエーテル、Ｎ−ｍ−クロロフェニルジエタノールアミ
ンジビニルエーテル、ｍ−フェニレンビス（エチレング
リコール）ジビニルエーテル等のアラルキルジビニルエ
ーテル類；ハイドロキノンジビニルエーテル、レゾルシ
ノールジビニルエーテル等のアリールジビニルエーテル
類；Ｎ−ビニルカルバゾール、Ｎ−ビニルピロリドン等
のカチオン重合性窒素含有化合物等(B) As vinyl compounds, styrene and α
-Styrenes such as methylstyrene and p-chloromethylstyrene; alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and hydroxybutyl vinyl ether;
Alkenyl vinyl ethers such as allyl vinyl ether and 1-octahydronaphthyl vinyl ether; alkynyl vinyl ethers such as ethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; butanediol divinyl ether , Alkyldivinyl ethers such as triethylene glycol vinyl ether and cyclohexanediol divinyl ether; aralkyl dialkyl ethers such as 1,4-benzenedimethanol divinyl ether, N-m-chlorophenyldiethanolamine divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether. Vinyl ethers; hydroquinone divinyl ether, resorcinol divinyl ether Aryl divinyl ethers such as ether; N- vinylcarbazole, N- vinylpyrrolidone and cationic polymerizable nitrogen-containing compounds such
【００１５】（ｃ）ビシクロオルソエステル化合物とし
て、１−フェニル−４−エチル−２，６，７−トリオキ
サビシクロ〔２，２，２〕オクタン，１−エチル−４−
ヒドロキシメチル−２，６，７−トリオキサビシクロ
〔２，２，２〕オクタン等As the (c) bicycloorthoester compound, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4-
Hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane etc.
【００１６】（ｄ）スピロオルソカーボネート化合物と
して、１，５，７，１１−テトラオキサスピロ〔５，
５〕ウンデカン、３，９−ジベンジル−１，５，７，１
１−テトラオキサスピロ〔５，５〕ウンデカン等や１，
４，６−トリオキサスピロ〔４，４〕ノナン，２−メチ
ル−１，４，６−トリオキサスピロ〔４，４〕ノナン，
１，４，６−トリオキサスピロ〔４，５〕デカン等のス
ピロオルソエステル化合物等である。 これらは、単独若しくは２種以上を併用して用いても差
し支えない。（ａ）〜（ｄ）の内で、殊に（ａ）のエポ
キシ基を有する化合物が好んで使用される。(D) Spiro-orthocarbonate compound, 1,5,7,11-tetraoxaspiro [5,5]
5] Undecane, 3,9-dibenzyl-1,5,7,1
1-tetraoxaspiro [5,5] undecane, etc.
4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,6-trioxaspiro [4,4] nonane,
Examples thereof include spiro orthoester compounds such as 1,4,6-trioxaspiro [4,5] decane. These may be used alone or in combination of two or more. Of the compounds (a) to (d), the compound having an epoxy group (a) is preferably used.
【００１７】本発明において、前記スルホニウム塩化合
物とカチオン重合性化合物との配合割合は、カチオン重
合性化合物１００部に対し、スルホニウム塩化合物０．
０１〜２０部、好ましくは０．１〜１０部の割合で配合
する。このスルホニウム塩化合物量が少いとカチオン重
合性化合物の硬化性が低下し、過剰であると硬化物の特
性が低下する。In the present invention, the compounding ratio of the sulfonium salt compound and the cationically polymerizable compound is such that the sulfonium salt compound is 0.
It is blended at a ratio of 01 to 20 parts, preferably 0.1 to 10 parts. When the amount of this sulfonium salt compound is small, the curability of the cationically polymerizable compound is lowered, and when it is excessive, the properties of the cured product are lowered.
【００１８】本発明のスルホニウム塩化合物を含有する
カチオン重合組成物は、加熱により容易に硬化できる。
熱硬化する場合は、３０〜２００℃、好ましくは、５０
〜１８０℃の範囲で使用される。The cationic polymerization composition containing the sulfonium salt compound of the present invention can be easily cured by heating.
When thermosetting, it is 30 to 200 ° C., preferably 50.
Used in the range of ~ 180 ° C.
【００１９】本発明のスルホニウム塩化合物を含有する
カチオン重合組成物は、α線、β線、γ線、中性子線、
Ｘ線、加速電子線のような電離性放射線によっても容易
に短時間で硬化することができる。電離性放射線による
硬化の場合は、通常０．５〜６０Ｍｒａｄの線量の範囲
が使用でき、１〜５０Ｍｒａｄの範囲が好ましい。ま
た、電離性放射線および熱を併用して硬化させることも
可能である。The cationic polymerization composition containing the sulfonium salt compound of the present invention contains α rays, β rays, γ rays, neutron rays,
It can be easily cured in a short time by ionizing radiation such as X-rays and accelerated electron beams. In the case of curing by ionizing radiation, a dose range of 0.5-60 Mrad can usually be used, with a range of 1-50 Mrad being preferred. It is also possible to use ionizing radiation and heat in combination for curing.
【００２０】本発明のスルホニウム塩化合物を含有する
カチオン重合組成物は、光によっても容易に短時間で硬
化することができる。また、本発明のスルホニウム塩化
合物を含有するカチオン重合組成物にメトキシフェノー
ルやフェノチアジン等の増感剤を併用すると、光硬化を
より加速することができる。The cationic polymerization composition containing the sulfonium salt compound of the present invention can be easily cured by light in a short time. When a sensitizer such as methoxyphenol or phenothiazine is used in combination with the cationic polymerization composition containing the sulfonium salt compound of the present invention, photocuring can be further accelerated.
【００２１】本発明のスルホニウム塩化合物は一般に単
独で使用されるが、他のカチオン重合開始剤と併用して
用いることもできる。また、前記（ａ）のエポキシ基を
有する化合物を用いる場合は、エポキシ樹脂の硬化剤と
して通常用いられている、フェノール系硬化剤、酸無水
物類硬化剤等の硬化剤を性能が損なわない範囲内で併用
して用いてもよい。The sulfonium salt compound of the present invention is generally used alone, but can also be used in combination with other cationic polymerization initiators. When the compound having an epoxy group (a) is used, the performance of a curing agent such as a phenolic curing agent or an acid anhydride curing agent that is usually used as a curing agent for epoxy resins is not impaired. You may use together in the inside.
【００２２】前記のカチオン重合性化合物に本発明の開
始剤を配合して使用する際に、必要に応じて反応性希釈
剤、硬化促進剤、溶剤、顔料、染料、カップリング剤、
無機充填剤、炭素繊維ガラス繊維、界面活性剤等を添加
して使用される。When the initiator of the present invention is blended with the above-mentioned cationically polymerizable compound and used, a reactive diluent, a curing accelerator, a solvent, a pigment, a dye, a coupling agent, if necessary,
It is used by adding an inorganic filler, carbon fiber glass fiber, surfactant and the like.
【００２３】[0023]
【実施例】以下、本発明を実施例、比較例により更に具
体的に説明する。但し、本発明は、これらの実施例に何
等限定されるものではない。 ＜スルホニウム塩化合物の合成＞ 実施例１：９−フルオレニルジメチルスルホニウムヘキ
サフロロアンチモネートの合成 ９−ブロモフルオレン６．１３ｇとジメチルスルフィド
６．２１ｇを混合し、室温で１７時間反応させた。得ら
れた化合物をエーテルで洗浄し、４０℃で減圧乾燥し、
前駆体の９−フルオレニルジメチルスルホニウムブロマ
イドを得た。収率：５７％ ９−フルオレニルジメチルスルホニウムブロマイド３．
０７ｇを蒸留水１０ｇとメチルエチルケトン（以下、Ｍ
ＥＫと言う）５ｇの混合溶液に溶解させ、六フッ化アン
チモン酸カリウム３．３０ｇを加え、よく攪拌した。こ
の溶液に蒸留水４０ｇを加え、よく攪拌して冷却した。
析出した化合物を濾別し、４０℃で減圧乾燥させた。収
率：９９％ このもののＩＲスペクトルデータは以下のとおりであっ
た。 ＩＲ（ＫＢｒ，ｃｍ-1）：１６０６，１４７８，１４５
４，１４２９，１３３６，１０４３，９９９，７９０，
７４０，６５６EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. <Synthesis of sulfonium salt compound> Example 1: Synthesis of 9-fluorenyldimethylsulfonium hexafluoroantimonate 6.13 g of 9-bromofluorene and 6.21 g of dimethyl sulfide were mixed and reacted at room temperature for 17 hours. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C.
The precursor 9-fluorenyldimethylsulfonium bromide was obtained. Yield: 57% 9-fluorenyldimethylsulfonium bromide 3.
07 g of distilled water and 10 g of methyl ethyl ketone (hereinafter referred to as M
It was dissolved in a mixed solution of 5 g (referred to as EK), 3.30 g of potassium hexafluoroantimonate was added, and the mixture was stirred well. 40 g of distilled water was added to this solution, and the mixture was stirred well and cooled.
The precipitated compound was separated by filtration and dried under reduced pressure at 40 ° C. Yield: 99% The IR spectrum data of this product was as follows. IR (KBr, cm -1 ): 1606, 1478, 145
4,1429,1336,1043,999,790,
740,656
【００２４】実施例２：９−フルオレニルテトラメチレ
ンスルホニウムヘキサフロロアンチモネートの合成 ９−ブロモフルオレン７．３５ｇとテトラヒドロチオフ
ェン４．４１ｇを混合し、５０℃で１０日間反応させ
た。得られた化合物をエーテルで洗浄し、４０℃で減圧
乾燥し、前駆体の９−フルオレニルテトラメチレンスル
ホニウムブロマイドを得た。収率：６４％ ９−フルオレニルテトラメチレンスルホニウムブロマイ
ド３．３３ｇを蒸留水１５ｇとに溶解させ、六フッ化ア
ンチモン酸カリウム３．３０ｇを加え、よく攪拌し、冷
却した。析出した化合物を濾別し、４０℃で減圧乾燥さ
せた。収率：９７％ このもののＩＲスペクトルデータは以下のとおりであっ
た。 ＩＲ（ＫＢｒ，ｃｍ-1）：２９４８，１６０７，１４５
５，１４２２，７８４，７４１，６６０Example 2 Synthesis of 9-fluorenyltetramethylenesulfonium hexafluoroantimonate 7.35 g of 9-bromofluorene and 4.41 g of tetrahydrothiophene were mixed and reacted at 50 ° C. for 10 days. The obtained compound was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor 9-fluorenyltetramethylenesulfonium bromide. Yield: 64% 9-fluorenyltetramethylenesulfonium bromide (3.33 g) was dissolved in distilled water (15 g), potassium hexafluoroantimonate (3.30 g) was added, and the mixture was well stirred and cooled. The precipitated compound was separated by filtration and dried under reduced pressure at 40 ° C. Yield: 97% IR spectrum data of this product was as follows. IR (KBr, cm -1 ): 2948, 1607, 145
5,1422,784,741,660
【００２５】＜硬化性テスト＞ （実施例３〜実施例７）実施例１と２で合成した化合物
をプロピレンカーボネートに溶解させ、ＥＲＬ−４２２
１（ＵＣＣ社製脂環型エポキシ）に純分として２．５部
になるように添加し、表２、表３に記載の配合物を調整
した。この配合物についてＤＳＣ及びＵＶ−ＤＳＣ測定
を行い、ＤＳＣ測定では、発熱ピークのトップ温度、Ｕ
Ｖ−ＤＳＣ測定では、光照射から発熱のトップピークま
での時間を求めた。なお、ＤＳＣ測定条件及びＵＶ−Ｄ
ＳＣ測定条件は下記の通りであり、その測定結果を表２
及び表３に示した。<Curing Test> (Examples 3 to 7) The compounds synthesized in Examples 1 and 2 were dissolved in propylene carbonate to prepare ERL-422.
1 (UCC alicyclic epoxy) was added to 2.5 parts as a pure component to prepare the formulations shown in Tables 2 and 3. DSC and UV-DSC measurements were made on this formulation, with the DSC measurement showing the top temperature of the exothermic peak, U
In the V-DSC measurement, the time from light irradiation to the top peak of heat generation was determined. The DSC measurement conditions and UV-D
The SC measurement conditions are as follows, and the measurement results are shown in Table 2.
And shown in Table 3.
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【表３】 [Table 3]
【００２８】ＤＳＣ測定条件 ＤＳＣ測定機器 ： ＤＳＣ２２０Ｃ（セイコー電子工
業社製） 雰囲気 ： 窒素ガス気流中 ３０ｍｌ／分 昇温速度 ： １０℃／分 サンプル量 ： ０．３〜０．８ｍｇ ＵＶ−ＤＳＣ測定条件 ＤＳＣ測定機器 ： ＤＳＣ２２０Ｃ（セイコー電子工
業社製） ＵＶ照射器 ： 超高圧水銀灯 雰囲気 ： 窒素ガス気流中 ３０ｍｌ／分 測定温度 ： ５０℃ サンプル量 ： ０．１〜０．３ｍｇ 膜 厚 ： ２〜１０μｍ 照射時間 ： １５分 照 度 ： １０ｍＷ／ｃｍ2 （３６５ｎ
ｍ）DSC measurement conditions DSC measurement equipment: DSC220C (manufactured by Seiko Denshi Kogyo Co., Ltd.) Atmosphere: Nitrogen gas flow 30 ml / min Temperature rising rate: 10 ° C./min Sample amount: 0.3-0.8 mg UV-DSC measurement conditions DSC measuring instrument: DSC220C (manufactured by Seiko Denshi Kogyo Co., Ltd.) UV irradiator: Ultra high pressure mercury lamp Atmosphere: Nitrogen gas flow 30 ml / min Measuring temperature: 50 ° C. Sample amount: 0.1-0.3 mg Film thickness: 2-10 μm Irradiation Time: 15 minutes Illumination: 10 mW / cm 2 (365n
m)
【００２９】（比較試料１）本発明の対比として、ベン
ジルジメチルスルホニウムヘキサフロロアンチモネート
を重合開始剤として用い、実施例と同様にしてＥＲＬ−
４２２１（ＵＣＣ社製脂環型エポキシ）に添加し、配合
物を調整し（比較例１、２、比較例３、４）、ＤＤＳＣ
及びＵＶ−ＤＳＣ測定を行い、ＤＳＣ測定では発熱ピー
クのトップ温度、ＵＶ−ＤＳＣ測定では光照射から発熱
のトップピークまでの時間を求めた。これらの結果を前
記の表２及び表３に示した。(Comparative Sample 1) As a comparison of the present invention, ERL- was used in the same manner as in Example except that benzyldimethylsulfonium hexafluoroantimonate was used as a polymerization initiator.
4221 (UCC alicyclic epoxy) was added to adjust the composition (Comparative Examples 1 and 2 and Comparative Examples 3 and 4), and DDSC
And UV-DSC measurement was performed, and the top temperature of the exothermic peak was determined by the DSC measurement, and the time from the light irradiation to the exothermic top peak was determined by the UV-DSC measurement. The results are shown in Tables 2 and 3 above.
【００３０】[0030]
【発明の効果】以上説明したように、本発明の新規スル
ホニウム塩化合物は、カチオン重合製化合物の重合開始
剤として有効であり、表２及び表３に見られるように、
加熱処理または光照射することにより、極めて迅速に重
合、硬化させることができる。INDUSTRIAL APPLICABILITY As described above, the novel sulfonium salt compound of the present invention is effective as a polymerization initiator for a compound produced by cationic polymerization, and as shown in Tables 2 and 3,
By heat treatment or light irradiation, polymerization and curing can be carried out extremely rapidly.
Claims (2)
基、ハロゲン原子、ニトロ基又はアルコキシ基を表し、
Ｒ3 、Ｒ4 は、それぞれアルキル基を表し、Ｒ3 とＲ4
は一体となって結合してもよく、Ｘは、ＳｂＦ6 ，Ａｓ
Ｆ6 ，ＰＦ6 又はＢＦ4 を表す〕1. A sulfonium salt compound represented by the following chemical formula 1. [In the formula, R 1 and R 2 each represent a hydrogen atom, an alkyl group, a halogen atom, a nitro group or an alkoxy group,
R 3 and R 4 each represent an alkyl group, and R 3 and R 4
May be combined together, and X is SbF 6 , As
Represents F 6 , PF 6 or BF 4 ]
少なくとも一種を含有することを特徴とするカチオン重
合開始剤2. A cationic polymerization initiator containing at least one kind of the sulfonium salt compound according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08017393A JP3512437B2 (en) | 1993-03-15 | 1993-03-15 | New sulfonium salt compounds and polymerization initiators |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08017393A JP3512437B2 (en) | 1993-03-15 | 1993-03-15 | New sulfonium salt compounds and polymerization initiators |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06271532A true JPH06271532A (en) | 1994-09-27 |
| JP3512437B2 JP3512437B2 (en) | 2004-03-29 |
Family
ID=13710954
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08017393A Expired - Fee Related JP3512437B2 (en) | 1993-03-15 | 1993-03-15 | New sulfonium salt compounds and polymerization initiators |
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| Country | Link |
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| JP (1) | JP3512437B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009020089A1 (en) * | 2007-08-07 | 2009-02-12 | Adeka Corporation | Aromatic sulfonium salt compound |
| US7611817B2 (en) * | 2002-09-25 | 2009-11-03 | Adeka Corporation | Aromatic sulfonium salt compound, photo-acid generator comprising the same and photopolymerizable composition containing the same, resin composition for optical three-dimensional shaping, and method of optically forming three-dimensional shape |
| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
| WO2014136900A1 (en) | 2013-03-08 | 2014-09-12 | 日立化成株式会社 | Ionic-compound-containing treatment solution, organic electronic element, and method for manufacturing organic electronic element |
-
1993
- 1993-03-15 JP JP08017393A patent/JP3512437B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7611817B2 (en) * | 2002-09-25 | 2009-11-03 | Adeka Corporation | Aromatic sulfonium salt compound, photo-acid generator comprising the same and photopolymerizable composition containing the same, resin composition for optical three-dimensional shaping, and method of optically forming three-dimensional shape |
| WO2009020089A1 (en) * | 2007-08-07 | 2009-02-12 | Adeka Corporation | Aromatic sulfonium salt compound |
| US8227624B2 (en) | 2007-08-07 | 2012-07-24 | Adeka Corporation | Aromatic sulfonium salt compound |
| JP5367572B2 (en) * | 2007-08-07 | 2013-12-11 | 株式会社Ａｄｅｋａ | Aromatic sulfonium salt compounds |
| WO2011040531A1 (en) | 2009-10-01 | 2011-04-07 | 日立化成工業株式会社 | Material for organic electronics, organic electronic element, organic electroluminescent element, display element using organic electroluminescent element, illuminating device, and display device |
| WO2011132702A1 (en) | 2010-04-22 | 2011-10-27 | 日立化成工業株式会社 | Organic electronic material, polymerization initiator and thermal polymerization initiator, ink composition, organic thin film and production method for same, organic electronic element, organic electroluminescent element, lighting device, display element, and display device |
| WO2014136900A1 (en) | 2013-03-08 | 2014-09-12 | 日立化成株式会社 | Ionic-compound-containing treatment solution, organic electronic element, and method for manufacturing organic electronic element |
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| Publication number | Publication date |
|---|---|
| JP3512437B2 (en) | 2004-03-29 |
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