JPH10338688A - New sulfonium salt and photosensitive resin composition using the same - Google Patents
New sulfonium salt and photosensitive resin composition using the sameInfo
- Publication number
- JPH10338688A JPH10338688A JP9575298A JP9575298A JPH10338688A JP H10338688 A JPH10338688 A JP H10338688A JP 9575298 A JP9575298 A JP 9575298A JP 9575298 A JP9575298 A JP 9575298A JP H10338688 A JPH10338688 A JP H10338688A
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- Prior art keywords
- sulfonium salt
- curing
- resin composition
- photosensitive resin
- formula
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Resins (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、光カチオン重合開
始剤として、例えばエポキシ樹脂の硬化等に使用し得
る、新規なスルホニウム塩に関するものである。TECHNICAL FIELD The present invention relates to a novel sulfonium salt which can be used as a cationic photopolymerization initiator, for example, for curing an epoxy resin.
【0002】[0002]
【従来の技術】光カチオン重合開始剤は、紫外線エネル
ギー等のエネルギー線を吸収し、カチオン重合を開始さ
せる触媒成分を放出する物質であり、例えばエポキシ樹
脂の硬化や各種環状エーテル、環状エステル、環状有機
ケイ素化合物、多官能ビニルエーテル等の重合反応や硬
化反応に用いられている。2. Description of the Related Art A cationic photopolymerization initiator is a substance that absorbs an energy ray such as ultraviolet energy and releases a catalyst component for initiating cationic polymerization. For example, curing of an epoxy resin, various cyclic ethers, cyclic esters, and cyclic resins. It is used in polymerization and curing reactions of organosilicon compounds and polyfunctional vinyl ethers.
【0003】このような光カチオン重合開始剤の代表的
なものとしては、例えば、米国特許第3,205,15
7号明細書及び同第3,708,296号明細書に記載
のアリールジアゾニウム塩及びハロゲン含有錯アニオン
のアリールジアゾニウム塩や、米国特許第4,231,
951号明細書に記載のトリアリールスルホニウム錯体
塩や、米国特許第4,058,401号明細書及び同第
4,138,255号明細書に記載のVIa族元素の芳
香族オニウム塩や、特開昭59−147001号公報に
記載のジアルキルフェナシルスルホニウム塩等が挙げら
れる。A typical example of such a cationic photopolymerization initiator is disclosed in US Pat. No. 3,205,15.
7 and 3,708,296, and aryldiazonium salts of halogen-containing complex anions, and U.S. Pat.
No. 951, the aromatic onium salts of Group VIa elements described in US Pat. Nos. 4,058,401 and 4,138,255, and the like. And dialkylphenacylsulfonium salts described in JP-A-59-147001.
【0004】しかしながら、これら既知の光カチオン重
合開始剤は、例えばジアゾニウム塩系のものは、樹脂中
での貯蔵安定性が悪い、光照射により窒素が副生するた
めに塗膜に気泡が生じる等の欠点を有し、また、ジアル
キルフェナシルスルホニウム塩の場合には、分子吸光係
数がいずれも比較的小さいという問題がある。また、ト
リアリールスルホニウム塩、ヨードニウム塩等のオニウ
ム塩の場合には、実際にこれを例えばエポキシ樹脂等の
硬化に使用した場合、硬化速度の点で必ずしも十分に満
足し得るものであるとはいえない。However, among these known cationic photopolymerization initiators, for example, those based on diazonium salts have poor storage stability in a resin, and bubbles are generated in the coating film due to by-produced nitrogen by light irradiation. In the case of dialkylphenacylsulfonium salts, there is a problem that the molecular extinction coefficient is relatively small. Further, in the case of an onium salt such as a triarylsulfonium salt or an iodonium salt, when this is actually used for, for example, curing an epoxy resin or the like, it can be said that it is not always satisfactory in terms of curing speed. Absent.
【0005】さらに、これらいずれの光カチオン重合開
始剤も、その極大吸収波長は300nm以下であるた
め、300nm以上の光源を用いる条件下では硬化速度
が低下するという問題がある。このようなことから、よ
り長波長域での感度が高く、より速硬化性に優れ、より
重合活性の高い更に新たな光カチオン重合開始剤の出現
が待ち望まれていた。Furthermore, since the maximum absorption wavelength of any of these photocationic polymerization initiators is 300 nm or less, there is a problem that the curing speed is reduced under the condition of using a light source of 300 nm or more. For this reason, there has been a long-awaited need for a new photocationic polymerization initiator having a higher sensitivity in a longer wavelength region, a faster curing property, and a higher polymerization activity.
【0006】[0006]
【発明が解決しようとする課題】本発明は、上記した如
き現状に鑑みてなされたもので、光カチオン重合開始剤
としての用途が期待でき、しかも300nm以上での分
子吸光係数が大きく、高重合活性を有し、例えばこれを
エポキシ樹脂等の硬化剤として用いた場合には優れた速
硬化性を示すことを見出し、本発明を完成した。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned situation, and is expected to be used as a cationic photopolymerization initiator. The present invention has been found to have an activity and exhibit excellent fast-curing properties when used as a curing agent such as an epoxy resin.
【0007】従って、本発明は、300nm以上での分
子吸光係数が大きく、高重合活性を有し、例えばこれを
エポキシ樹脂等の硬化剤として用いた場合に優れた速硬
化性を示し、光カチオン重合開始剤として有用な新規な
スルホニウム塩及びこれを用いた感光性樹脂組成物を提
供することにある。Accordingly, the present invention has a large molecular extinction coefficient at 300 nm or more, has a high polymerization activity, and exhibits excellent rapid curing properties when this is used as a curing agent such as an epoxy resin. It is to provide a novel sulfonium salt useful as a polymerization initiator and a photosensitive resin composition using the same.
【0008】[0008]
【課題を解決するための手段】すなわち、本発明は、下
記一般式(1)That is, the present invention provides a compound represented by the following general formula (1):
【化2】 (但し、式中、Rは共役五員環、又は、共役五員環と1
個以上のベンゼン環との縮合多環を示し、P及びQはそ
れぞれ独立にアルキルを示すか、又は、PとQとSが連
結して炭素原子数4個又は5個の環を形成し、X- は求
核性の弱いルイス酸残基を示す)で示されるスルホニウ
ム塩である。Embedded image (Wherein, R is a conjugated five-membered ring or a conjugated five-membered ring and 1
A condensed polycyclic ring with two or more benzene rings, wherein P and Q each independently represent alkyl, or P, Q and S are linked to form a ring having 4 or 5 carbon atoms, X - is a sulfonium salt represented by showing a weak Lewis acid residues having nucleophilic).
【0009】また、本発明は、光カチオン重合開始剤と
して少なくとも上記一般式(1)で示されるスルホニウ
ム塩を含有してなる感光性樹脂組成物である。Further, the present invention is a photosensitive resin composition comprising at least a sulfonium salt represented by the above general formula (1) as a cationic photopolymerization initiator.
【0010】上記一般式(1)で示される本発明のスル
ホニウム塩において、X- は求核性の弱いルイス酸残基
であるが、この求核性の弱いルイス酸残基としては、求
核性の弱いルイス酸であって、遊離してブレンステッド
酸となるようなルイス酸の残基であればよく、例えば代
表的なものとしてはBF4 - 、PF6 - 、SbF6 -、
AsF6 - 等を挙げることができる。In the sulfonium salt of the present invention represented by the general formula (1), X - is a Lewis acid residue having a weak nucleophilic property. Any Lewis acid that is a weak Lewis acid and may be a Lewis acid residue that can be liberated to form a Bronsted acid, such as BF 4 − , PF 6 − , SbF 6 − ,
AsF 6- and the like.
【0011】[0011]
【発明の実施の形態】本発明のスルホニウム塩は、例え
ばBull. Chem. Soc. Jpn., 60, 1159 (1987)及びJ. Pol
ym. Sci. Polym. Chem. Ed.,17, 2877 (1979) に記載の
方法に準じて、一般に下記の如くして容易に合成され
る。BEST MODE FOR CARRYING OUT THE INVENTION The sulfonium salt of the present invention is described, for example, in Bull. Chem. Soc. Jpn., 60, 1159 (1987) and J. Pol.
According to the method described in ym. Sci. Polym. Chem. Ed., 17, 2877 (1979), it can be easily synthesized generally as follows.
【0012】即ち、アセチル誘導体を適当な溶媒、例え
ばジクロルメタン、ジクロルエタン、クロロホルム、テ
トラクロルエタン等のハロゲン化炭化水素とメタノール
等のアルコールとの混合溶媒に溶解し、これにテトラブ
チルアンモニウムトリブロマイドを室温で加えて、1時
間撹拌反応させる。反応終了後、溶媒を留去し、沈殿物
をエーテルで抽出する。エーテル層を硫酸マグネシウム
で乾燥し、溶媒を留去して得られる生成物をエタノール
―水の混合溶剤で再結晶させてブロモアセチル誘導体を
得る。That is, the acetyl derivative is dissolved in a suitable solvent, for example, a mixed solvent of a halogenated hydrocarbon such as dichloromethane, dichloroethane, chloroform and tetrachloroethane and an alcohol such as methanol, and tetrabutylammonium tribromide is added thereto at room temperature. And react with stirring for 1 hour. After completion of the reaction, the solvent is distilled off, and the precipitate is extracted with ether. The ether layer is dried over magnesium sulfate, and the product obtained by evaporating the solvent is recrystallized with a mixed solvent of ethanol and water to obtain a bromoacetyl derivative.
【0013】得られたブロモアセチル誘導体とジアルキ
ルスルフィド(一般式(1)においてP及びQがそれぞ
れ独立にアルキルを表す場合)、テトラヒドロチオフェ
ン(一般式(1)においてPとQが連結して隣接する硫
黄原子とともに五員環を形成する場合)、またはテトラ
ヒドロチオピラン(一般式(1)においてPとQが連結
して隣接する硫黄原子とともに六員環を形成する場合)
とをアセトンと水の混合溶媒中、25℃で1.5時間撹
拌し、生成したブロモ塩をジエチルエーテルで数回洗浄
し、濾別して風乾する。ブロモ塩の水溶液に求核性の弱
いルイス酸の銀塩又はアルカリ金属塩の水溶液を加え、
結晶化した塩を濾過して水で洗浄し、更に乾燥した後
に、水又は水―アルコールの混合溶剤で再結晶すれば、
目的とするスルホニウム塩が容易に得られる。The obtained bromoacetyl derivative, dialkyl sulfide (when P and Q each independently represent alkyl in the general formula (1)), and tetrahydrothiophene (P and Q are linked to and adjacent to each other in the general formula (1)) A case where a five-membered ring is formed together with a sulfur atom) or tetrahydrothiopyran (a case where P and Q are linked to form a six-membered ring with an adjacent sulfur atom in the general formula (1))
Is stirred at 25 ° C. for 1.5 hours in a mixed solvent of acetone and water, and the resulting bromo salt is washed several times with diethyl ether, filtered and air-dried. An aqueous solution of a silver salt or an alkali metal salt of a weak nucleophilic Lewis acid is added to an aqueous solution of a bromo salt,
If the crystallized salt is filtered, washed with water, dried and then recrystallized with water or a mixed solvent of water and alcohol,
The desired sulfonium salt is easily obtained.
【0014】本発明のスルホニウム塩又はその溶媒付加
物は、モノマー、オリゴマー、低分子ポリマー等の光カ
チオン重合開始剤としての用途を有する。本発明のスル
ホニウム塩又はその溶媒付加物を光カチオン重合開始剤
として用いる場合、これらはそれぞれ単独で用いること
も、また、その2種以上を組み合わせて用いることも、
更に、他の光カチオン重合開始剤や光増感剤等と適宣組
み合わせて用いることも随意である。The sulfonium salt of the present invention or a solvent adduct thereof has use as a cationic photopolymerization initiator for monomers, oligomers, low molecular weight polymers and the like. When the sulfonium salt of the present invention or a solvent adduct thereof is used as a cationic photopolymerization initiator, these may be used alone or in combination of two or more.
Further, it may be optionally used in combination with other cationic photopolymerization initiators, photosensitizers and the like.
【0015】本発明のスルホニウム塩又はその溶媒付加
物からなる光カチオン重合開始剤は、エポキシ樹脂中で
の貯蔵安定性に優れ、また、光照射により窒素を副生す
ることがないので塗膜に気泡を生じることもなく、しか
も、特に300nm以上での分子吸光係数が大きく硬化
速度も従来の光カチオン重合開始剤と比べて速いという
特長を有する。The cationic photopolymerization initiator of the present invention comprising a sulfonium salt or a solvent adduct thereof has excellent storage stability in an epoxy resin and does not produce nitrogen by light irradiation, so that it can be applied to a coating film. It has the feature that it does not generate bubbles, and has a large molecular extinction coefficient especially at 300 nm or more, and has a higher curing rate than the conventional photocationic polymerization initiator.
【0016】本発明のスルホニウム塩からなる光カチオ
ン重合開始剤は、例えばビスフェノールAジグリシジル
エーテル型エポキシ樹脂(DGEBA)、フェノールノ
ボラック型エポキシ樹脂、オルソクレゾールノボラック
型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、
脂環式エポキシ樹脂、メチル置換型エポキシ樹脂、グリ
シジルエステル型エポキシ樹脂等のエポキシ化合物や、
イソブチレン、スチレン、α−メチルスチレン、ブタジ
エン、ビニルアルキルエーテル等のビニル単量体又はこ
れらのオリゴマー若しくは低分子ポリマー等や、環状有
機エーテル、環状有機エステル、環状有機スルフィド、
環状アミン、環状有機ケイ素化合物、多官能ビニルエー
テル等のカチオン重合性化合物等の光重合性や光硬化性
を有する物質に対して効果的に使用し得る。The cationic photopolymerization initiator comprising the sulfonium salt of the present invention includes, for example, bisphenol A diglycidyl ether type epoxy resin (DGEBA), phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, glycidyl ether type epoxy resin,
Epoxy compounds such as alicyclic epoxy resins, methyl-substituted epoxy resins, glycidyl ester type epoxy resins,
Isobutylene, styrene, α-methylstyrene, butadiene, vinyl monomers such as vinyl alkyl ethers or oligomers or low molecular polymers thereof, cyclic organic ethers, cyclic organic esters, cyclic organic sulfides,
It can be effectively used for a photopolymerizable or photocurable substance such as a cyclic amine, a cyclic organosilicon compound, and a cationically polymerizable compound such as a polyfunctional vinyl ether.
【0017】また、本発明の感光性樹脂組成物は、上述
のカチオン重合性化合物に本発明のスルホニウム塩を必
須成分として配合してなることを特徴としている。スル
ホニウム塩は、カチオン重合性化合物100重量部に対
して0.1〜15重量部、より好ましくは3〜10重量
部配合させることができる。0.1重量部より少ないと
重合反応率が極端に低下し、良好な塗膜を形成しづらく
なり好ましくない。また、15重量部を越えると、光透
過性が低下して重合反応率が低下するとともに、未反応
物の開始剤や分解物が塗膜中に多量に残るため好ましく
ない。Further, the photosensitive resin composition of the present invention is characterized in that the sulfonium salt of the present invention is blended as an essential component with the above-mentioned cationically polymerizable compound. The sulfonium salt can be added in an amount of 0.1 to 15 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. If the amount is less than 0.1 part by weight, the polymerization reaction rate is extremely lowered, and it becomes difficult to form a good coating film, which is not preferable. On the other hand, when the amount exceeds 15 parts by weight, the light transmittance is lowered and the polymerization reaction rate is lowered, and unreacted initiators and decomposed products are left in a large amount in the coating film.
【0018】さらに、本発明の感光性樹脂組成物は、カ
チオン重合性化合物としてエポキシ樹脂を使用した場
合、重合反応率をより高くする目的で、無水フタル酸、
ピロメリット酸、テトラヒドロフタル酸等の酸無水物を
エポキシ樹脂に対して90%当量未満添加することも可
能である。この酸無水物がエポキシ樹脂に対して90%
当量以上となると、未反応の酸無水物が塗膜中に残存
し、塗膜の耐湿性や強度を低下させるため好ましくな
い。Further, when the epoxy resin is used as the cationically polymerizable compound, the photosensitive resin composition of the present invention contains phthalic anhydride,
It is also possible to add an acid anhydride such as pyromellitic acid or tetrahydrophthalic acid in an amount less than 90% equivalent to the epoxy resin. 90% of this acid anhydride based on epoxy resin
If the amount is more than the equivalent, unreacted acid anhydride remains in the coating film, and this is not preferable because the moisture resistance and strength of the coating film are reduced.
【0019】また、本発明の感光性樹脂組成物には粘度
を適正にする目的で、非重合性希釈剤を添加することも
可能である。このような非重合性希釈剤としては、例え
ば酢酸エチル、酢酸ブチル、メチルセルソルブ、エチル
セルソルブ、メチルセルソルブアセテート、エチルセル
ソルブアセテート、イソプロピルアルコール、トルエ
ン、キシレン等が挙げられる。塗料の適正粘度は、塗装
方法、塗料の種類、塗装スピード、膜厚によって大きく
変化するので、希釈剤の使用量は任意の割合にすること
ができる。しかし、これらの非重合性希釈剤は加熱乾燥
過程によって大部分が揮発しなければならない。多量に
残存した場合には塗膜の表面硬度、密着性に重大な欠陥
が生ずることが多い。Further, a non-polymerizable diluent can be added to the photosensitive resin composition of the present invention for the purpose of making the viscosity appropriate. Examples of such a non-polymerizable diluent include ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, isopropyl alcohol, toluene, xylene and the like. Since the appropriate viscosity of the coating material varies greatly depending on the coating method, the type of coating material, the coating speed, and the film thickness, the amount of the diluent used can be any ratio. However, these non-polymerizable diluents must be largely volatilized by the heat drying process. When a large amount remains, serious defects often occur in the surface hardness and adhesion of the coating film.
【0020】更に、本発明の感光性樹脂組成物には、上
記以外にも用途に応じて、他の成分、例えば、着色、隠
蔽効果などを目的とする顔料、充填剤、界面活性剤、分
散剤、可塑剤、酸化防止剤等を加えることも可能であ
る。The photosensitive resin composition of the present invention may further contain other components, for example, a pigment, a filler, a surfactant, a dispersant, and the like for the purpose of coloring, hiding, etc. It is also possible to add agents, plasticizers, antioxidants and the like.
【0021】[0021]
【実施例】以下、実施例及び試験例に基づいて、本発明
のスルホニウム塩を具体的に説明する。但し、本発明は
これらの実施例に限定されるものではない。EXAMPLES The sulfonium salt of the present invention will be specifically described below based on examples and test examples. However, the present invention is not limited to these examples.
【0022】実施例1 6弗化アンチモン酸ジアルキルチエノイルスルホニウム
塩〔一般式(1)においてRがチエニル基、PとQが一
緒になって、隣接する硫黄原子とともにテトラヒドロチ
オフェン環を形成、X- =SbF6 - の物質〕を以下の
ようにして合成した。アセチルチオフェン10gをジク
ロルメタン―メタノール混合溶媒1300mlに溶解
し、室温下にテトラブチルアンモニウムトリブロマイド
42gを加えて攪拌下に1時間反応させた後、溶媒を留
去し、沈殿物をエーテルで抽出した。エーテル層を硫酸
マグネシウムで乾燥して溶媒を留去し、エタノール―水
混合溶剤で再結晶させ、ブロモメチルチエニルケトンを
得た。[0022] R is a thienyl group in Example 1 hexafluoride antimonate dialkyl Chie noil sulfonium salts [general formula (1), P and Q together form a tetrahydrothiophene ring together with the adjacent sulfur atom, X - = SbF 6 - the material] was synthesized as follows. 10 g of acetylthiophene was dissolved in 1300 ml of a mixed solvent of dichloromethane and methanol, 42 g of tetrabutylammonium tribromide was added at room temperature and reacted for 1 hour with stirring, the solvent was distilled off, and the precipitate was extracted with ether. The ether layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was recrystallized with a mixed solvent of ethanol and water to obtain bromomethylthienyl ketone.
【0023】得られたブロモメチルチエニルケトン10
gとテトラヒドロチオフェン4.3gとをアセトン―水
混合溶媒50ml中、25℃で1.5時間撹拌し、生成
したブロモ塩をジエチルエーテルで数回洗浄し、濾別し
て風乾した。得られたブロモ塩10gの水溶液70ml
に等モル量の6弗化アンチモン酸銀水溶液34mlを加
え、結晶化した塩を濾過して水で洗浄し、乾燥した後、
水―アルコール混合溶剤で再結晶し、目的の結晶(6弗
化アンチモン酸ジアルキルチエノイルスルホニウム塩)
15gを得た。The obtained bromomethylthienyl ketone 10
g and 4.3 g of tetrahydrothiophene were stirred in 50 ml of a mixed solvent of acetone and water at 25 ° C. for 1.5 hours, and the resulting bromo salt was washed several times with diethyl ether, filtered and air-dried. 70 ml of an aqueous solution of 10 g of the obtained bromo salt
34 ml of an equimolar amount of an aqueous solution of silver hexafluoride antimonate was added thereto, and the crystallized salt was filtered, washed with water, and dried.
Recrystallize with a water-alcohol mixed solvent to obtain the desired crystal (dialkylthienoylsulfonium hexafluoroantimonate)
15 g were obtained.
【0024】得られた結晶について、融点、元素分析、
UV、IR、及びNMRの測定を行った。結果は次の通
りであった。 融点(mp):152〜154℃ 元素分析値(C10H13OF6 SSb): 計算値(%) C:26.7、H:2.90 実測値(%) C:26.4、H:2.67 UV(λmax ):295nm(ε=8582)、265
nm(ε=9147) IR(cm-1):1660(C=O)、650(SbF
6 - ) NMR(DMSO−d6 ;δppm):7.38(1H,
dd, J=1.5, 4.9Hz)、7.22(1H, dd, J=1.5, 3.5H
z)、6.54(1H, dd, J=3.5, 4.9Hz)、4.39(2
H, s, -CH2-)、2.6〜3.0,1.3〜1.6(8H,
m,テトラヒドロチオフェン)With respect to the obtained crystal, melting point, elemental analysis,
UV, IR, and NMR measurements were made. The results were as follows. Melting point (mp): 152~154 ℃ Elemental analysis (C 10 H 13 OF 6 SSb ): Calculated (%) C: 26.7, H : 2.90 Found (%) C: 26.4, H : 2.67 UV (λ max ): 295 nm (ε = 8582), 265
nm (ε = 9147) IR (cm −1 ): 1660 (C = O), 650 (SbF
6 -) NMR (DMSO-d 6; δppm): 7.38 (1H,
dd, J = 1.5, 4.9Hz), 7.22 (1H, dd, J = 1.5, 3.5H)
z), 6.54 (1H, dd, J = 3.5, 4.9 Hz), 4.39 (2
H, s, -CH 2 -) , 2.6~3.0,1.3~1.6 (8H,
m, tetrahydrothiophene)
【0025】実施例2 6弗化アンチモン酸ジアルキルフルオレノイルスルホニ
ウム塩〔一般式(1)においてRがフルオレニル基、P
とQが一緒になって、隣接する硫黄原子とともにテトラ
ヒドロチオフェン環を形成、X- =SbF6 - の物質〕
を以下のようにして合成した。アセチルフルオレン10
gをジクロルメタン―メタノール混合溶媒1300ml
に溶解し、室温下にテトラブチルアンモニウムトリブロ
マイド42gを加えて攪拌下に1時間反応させた後、溶
媒を留去し、沈殿物をエーテルで抽出した。エーテル層
を硫酸マグネシウムで乾燥して溶媒を留去し、エタノー
ル―水混合溶剤で再結晶させ、ブロモメチルフルオレニ
ルケトンを得た。Example 2 Dialkylfluorenoylsulfonium hexafluoride antimonate [In the formula (1), R is a fluorenyl group,
Q together with, form a tetrahydrothiophene ring together with the adjacent sulfur atom, X - = SbF 6 - substances]
Was synthesized as follows. Acetylfluorene 10
g in dichloromethane-methanol mixed solvent 1300ml
After adding 42 g of tetrabutylammonium tribromide at room temperature and reacting with stirring for 1 hour, the solvent was distilled off and the precipitate was extracted with ether. The ether layer was dried over magnesium sulfate, the solvent was distilled off, and recrystallized with a mixed solvent of ethanol and water to obtain bromomethylfluorenyl ketone.
【0026】得られたブロモメチルフルオレニルケトン
10gとテトラヒドロチオフェン4.3gとをアセトン
―水混合溶媒50ml中、25℃で1.5時間撹拌し、
生成したブロモ塩をジエチルエーテルで数回洗浄し、濾
別して風乾した。得られたブロモ塩10gの水溶液70
mlに等モル量の6弗化アンチモン酸銀水溶液34ml
を加え、結晶化した塩を濾過して水で洗浄し、乾燥した
後、水―アルコール混合溶剤で再結晶し、目的の結晶
(6弗化アンチモン酸ジアルキルフルオレノイルスルホ
ニウム塩)15gを得た。10 g of the obtained bromomethylfluorenyl ketone and 4.3 g of tetrahydrothiophene were stirred in 50 ml of an acetone-water mixed solvent at 25 ° C. for 1.5 hours,
The resulting bromo salt was washed several times with diethyl ether, filtered and air-dried. Aqueous solution 70 of 10 g of the obtained bromo salt
34 ml of an aqueous solution of silver hexafluoride antimonate in an equimolar amount per ml
Was added, and the crystallized salt was filtered, washed with water, dried, and then recrystallized with a water-alcohol mixed solvent to obtain 15 g of the desired crystal (dialkylfluorenoylsulfonium hexafluoroantimonate). .
【0027】得られた結晶について、融点、元素分析、
UV、IR、及びNMRの測定を行った。結果は次の通
りであった。 融点(mp):138〜143℃ 元素分析値(C19H19OSF6 Sb): 計算値(%) C:43.0、H:3.60 実測値(%) C:42.8、H:3.48 UV(λmax ):322nm(ε=24687) IR(cm-1):1670(C=O)、650(SbF
6 - ) NMR(DMSO−d6 ;δppm):7.4〜8.3
(7H, m, Aromatic H)、5.4(2H, s, -CH2-)、
4.1(2H, s,フルオレン)、3.4〜3.7,2.1
〜2.4(8H, m,テトラヒドロチオフェン)The obtained crystals were analyzed for melting point, elemental analysis,
UV, IR, and NMR measurements were made. The results were as follows. Melting point (mp): 138~143 ℃ Elemental analysis (C 19 H 19 OSF 6 Sb ): Calculated (%) C: 43.0, H : 3.60 Found (%) C: 42.8, H : 3.48 UV (λ max ): 322 nm (ε = 24687) IR (cm −1 ): 1670 (C = O), 650 (SbF)
6 -) NMR (DMSO-d 6; δppm): 7.4~8.3
(7H, m, Aromatic H) , 5.4 (2H, s, -CH 2 -),
4.1 (2H, s, fluorene), 3.4 to 3.7, 2.1
~ 2.4 (8H, m, tetrahydrothiophene)
【0028】実施例3 表1に示す市販のエポキシ樹脂〔即ち、ダイセル化学社
製商品名セロキサイド2021P(2021P)、油化
シェル社製商品名エピコート828(#828)、及び
新日鐵化学社製商品名ESF300(F−E)〕に対し
て、実施例1で得られた本発明のスルホニウム塩を3重
量%混和した後、ガラス板上に厚さ約30μmとなるよ
うに塗布し、高圧水銀灯(120W/cm)を備えた紫
外線照射装置を用い、表1に示す照射時間で紫外線照射
して硬化させ、硬化後の表面状態をアセトンラビング法
〔即ち、アセトンに浸した綿布を用いて500g/cm
2程度の圧力で表面をこすり、表面の変化を観察する方
法〕で試験し、◎:極めて良好、○:良好、□:タック
感が残る、△:しわが発生、及び×:べとつく、の5段
階評価で評価した。結果を表1に示す。Example 3 Commercially available epoxy resins shown in Table 1 [namely, celloxide 2021P (2021P) manufactured by Daicel Chemical Industries, Epicoat 828 (# 828) manufactured by Yuka Shell Co., Ltd., and Nippon Steel Chemical Co., Ltd.] After mixing 3% by weight of the sulfonium salt of the present invention obtained in Example 1 with respect to the trade name ESF300 (FE)], the mixture was applied on a glass plate so as to have a thickness of about 30 μm. (120 W / cm), using an ultraviolet irradiation device having an irradiation time shown in Table 1, to cure by irradiation with an ultraviolet ray, and the surface state after the curing was determined by an acetone rubbing method [that is, 500 g / cm 2 using a cotton cloth soaked in acetone. cm
A method of rubbing the surface with a pressure of about 2 and observing a change in the surface], ◎: extremely good, :: good, □: tackiness remains, Δ: wrinkles, and ×: sticky. It was evaluated on a scale. Table 1 shows the results.
【0029】また、同様に、表1に示す市販のエポキシ
樹脂に対して、実施例1で得られたスルホニウム塩を3
重量%混和した後、ガラス板上に厚さ約30μmとなる
ように塗布し、100℃で60分、150℃で30分、
及び200℃で20分の各条件で熱硬化を行い、硬化後
の表面状態をアセトンラビング法で試験して評価した。
結果を表1に示す。Similarly, the sulfonium salt obtained in Example 1 was added to the commercially available epoxy resin shown in Table 1.
Weight%, and then applied on a glass plate to a thickness of about 30 μm, at 100 ° C. for 60 minutes, at 150 ° C. for 30 minutes,
And heat curing at 200 ° C. for 20 minutes, and the surface state after the curing was tested and evaluated by an acetone rubbing method.
Table 1 shows the results.
【0030】更に、表1に示す市販のエポキシ樹脂に実
施例1で得られたスルホニウム塩を3重量%混和した
後、ガラス板上に厚さ約30μmとなるように塗布し、
上記と同様にして表1に示す照射時間で紫外線照射した
後、次いで150℃、30分の条件で熱硬化を行い、硬
化後の表面状態をアセトンラビング法で試験して評価し
た。結果を表1に示す。Further, 3% by weight of the sulfonium salt obtained in Example 1 was mixed with a commercially available epoxy resin shown in Table 1 and applied to a glass plate so as to have a thickness of about 30 μm.
After UV irradiation for the irradiation time shown in Table 1 in the same manner as above, thermal curing was performed at 150 ° C. for 30 minutes, and the surface state after curing was tested and evaluated by an acetone rubbing method. Table 1 shows the results.
【0031】[0031]
【表1】 [Table 1]
【0032】実施例4 表2に示す市販のエポキシ樹脂〔即ち、ダイセル化学社
製商品名セロキサイド2021P(2021P)、油化
シェル社製商品名エピコート828(#828)〕に対
して、実施例2で得られた本発明のスルホニウム塩を3
重量%混和した後、ガラス板上に厚さ約30μmとなる
ように塗布し、高圧水銀灯(120W/cm)を備えた
紫外線照射装置を用い、表2に示す照射時間で紫外線照
射して硬化させ、硬化後の表面状態をアセトンラビング
法で試験し、実施例3と同様に評価した。結果を表2に
示す。Example 4 A commercially available epoxy resin shown in Table 2 [namely, celloxide 2021P (2021P) manufactured by Daicel Chemical Industries, Epicoat 828 (# 828) manufactured by Yuka Shell Co., Ltd.) was used in Example 2. With the sulfonium salt of the present invention obtained in
After mixing, the composition was applied on a glass plate so as to have a thickness of about 30 μm, and was cured by irradiating with ultraviolet light for an irradiation time shown in Table 2 using an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm). The surface condition after curing was tested by the acetone rubbing method, and evaluated in the same manner as in Example 3. Table 2 shows the results.
【0033】また、同様に、表2に示す市販のエポキシ
樹脂に実施例2で得られたスルホニウム塩を3重量%混
和した後、ガラス板上に厚さ約30μmとなるように塗
布し、100℃で60分、150℃で30分、及び20
0℃で30分の各条件で熱硬化を行い、硬化後の表面状
態をアセトンラビング法で試験して評価した。結果を表
2に示す。Similarly, 3% by weight of the sulfonium salt obtained in Example 2 was mixed with a commercially available epoxy resin shown in Table 2 and then applied on a glass plate so as to have a thickness of about 30 μm. 60 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 20
Thermal curing was performed at 0 ° C. for 30 minutes, and the surface state after curing was tested and evaluated by an acetone rubbing method. Table 2 shows the results.
【0034】更に、表2に示す市販のエポキシ樹脂に実
施例2で得られたスルホニウム塩を3重量%混和した
後、ガラス板上に厚さ約30μmとなるように塗布し、
上記と同様にして表2に示す照射時間で紫外線照射した
後、次いで150℃、30分の条件で熱硬化を行い、硬
化後の表面状態をアセトンラビング法で試験して評価し
た。結果を表2に示す。Further, 3% by weight of the sulfonium salt obtained in Example 2 was mixed with a commercially available epoxy resin shown in Table 2 and applied to a glass plate so as to have a thickness of about 30 μm.
After UV irradiation for the irradiation time shown in Table 2 in the same manner as above, heat curing was performed at 150 ° C. for 30 minutes, and the surface state after curing was evaluated by an acetone rubbing method. Table 2 shows the results.
【0035】[0035]
【表2】 [Table 2]
【0036】表1及び表2から明らかなように、本発明
のスルホニウム塩は、いずれのエポキシ樹脂に対しても
紫外線照射による優れた速硬化性を示すと共に、熱硬化
性にも優れている。更に、紫外線照射と熱硬化を併用し
た場合には、いずれのエポキシ樹脂においても、より優
れた硬化性(鉛筆硬度5H)が得られ、ガラスへの密着
性及び耐屈曲性(2mmφ)が共に良好であった。As is evident from Tables 1 and 2, the sulfonium salt of the present invention exhibits excellent quick-curing properties by ultraviolet irradiation to any of the epoxy resins and also has excellent thermosetting properties. Furthermore, when ultraviolet irradiation and heat curing are used in combination, more excellent curability (pencil hardness 5H) can be obtained with any epoxy resin, and both adhesion to glass and bending resistance (2 mmφ) are good. Met.
【0037】ここで、一般式(1)においてPとQが連
結して炭素原子数4個のシクロアルキルを形成するスル
ホニウム塩の合成について述べたが、既に説明したよう
に、テトラヒドロチオフェンに代えてテトラヒドロチオ
ピラン及びジアルキルスルフィドを用いることにより、
同様にして容易に、一般式(1)においてPとQが連結
して炭素原子数5個のシクロアルキルを形成するスルホ
ニウム塩、及び、PとQがそれぞれ独立したアルキルで
あるスルホニウム塩を合成することができる。また、一
般式(1)において、このようにP及びQを代えた異な
るスルホニウム塩の重合活性は、それらが同一のR及び
X- を有する場合にはほとんど等しいことも、フェナシ
ルスルホニウム塩における同様な比較実験の結果(Macr
omolecules, 16,864(1983))から容易に類推される。Here, the synthesis of the sulfonium salt in which P and Q are linked to each other to form a cycloalkyl having 4 carbon atoms in the general formula (1) has been described, but as described above, instead of tetrahydrothiophene, By using tetrahydrothiopyran and dialkyl sulfide,
Similarly, a sulfonium salt in which P and Q are linked to each other to form cycloalkyl having 5 carbon atoms in Formula (1), and a sulfonium salt in which P and Q are each independently alkyl are easily synthesized in the same manner. be able to. Further, in the general formula (1), the polymerization activities of the different sulfonium salts in which P and Q are substituted as described above are almost the same when they have the same R and X − , and the same as in the phenacyl sulfonium salt. Of a comparative experiment (Macr
omolecules, 16,864 (1983)).
【0038】また、ここでは、一般式(1)においてR
がチエニル基及びフルオレニル基であるスルホニウム塩
の合成について述べたが、その他の共役五員環及び縮合
多環化合物のアセチル誘導体を用いることにより、それ
ぞれをRとして有するスルホニウム塩を、既に述べた方
法で同様に合成することができる。Here, in the general formula (1), R
Described the synthesis of sulfonium salts in which is a thienyl group and a fluorenyl group.By using other acetyl derivatives of a conjugated five-membered ring and a condensed polycyclic compound, a sulfonium salt having each as R was prepared by the method already described. Similarly, they can be synthesized.
【0039】[0039]
【発明の効果】本発明は、光カチオン重合開始剤として
の用途を有する新規なスルホニウム塩を提供するもので
あり、特にこれを光カチオン重合開始剤として用いた場
合には、従来より長波長域での重合活性が高く、例えば
エポキシ樹脂の硬化等に用いた場合に優れた速硬化性を
示す等の優れた性能を発揮するものであって、斯業に貢
献するところ大なる発明である。The present invention provides a novel sulfonium salt having a use as a photocationic polymerization initiator. Particularly, when the sulfonium salt is used as a photocationic polymerization initiator, the sulfonium salt has a longer wavelength region than conventional ones. The present invention exhibits excellent performance such as excellent fast curing properties when used for curing epoxy resins, for example, and is a great invention contributing to the industry.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 川里 浩信 神奈川県川崎市中原区井田3丁目35番1 号、新日本製鐵株式会社技術開発本部内 (72)発明者 藤城 光一 神奈川県川崎市中原区井田3丁目35番1 号、新日本製鐵株式会社技術開発本部内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hironobu Kawasato 3-35-1, Ida, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture, within the Technology Development Division of Nippon Steel Corporation (72) Inventor Koichi Fujishiro Nakahara, Kawasaki-shi, Kanagawa 3-35-1, Ida-ku, Nippon Steel Corporation Technology Development Division
Claims (2)
個以上のベンゼン環との縮合多環を示し、P及びQはそ
れぞれ独立にアルキルを示すか、又は、PとQとSが連
結して炭素原子数4個又は5個の環を形成し、X- は求
核性の弱いルイス酸残基を示す)で示されるスルホニウ
ム塩。[Claim 1] The following general formula (1) (Wherein, R is a conjugated five-membered ring or a conjugated five-membered ring and 1
A condensed polycyclic ring with two or more benzene rings, wherein P and Q each independently represent alkyl, or P, Q and S are linked to form a ring having 4 or 5 carbon atoms, X - sulfonium salt represented by displays a weak Lewis acid residues having nucleophilic).
請求項1記載のスルホニウム塩を含有してなる感光性樹
脂組成物。2. A photosensitive resin composition comprising at least the sulfonium salt according to claim 1 as a cationic photopolymerization initiator.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9575298A JPH10338688A (en) | 1997-04-09 | 1998-04-08 | New sulfonium salt and photosensitive resin composition using the same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9-90563 | 1997-04-09 | ||
JP9056397 | 1997-04-09 | ||
JP9575298A JPH10338688A (en) | 1997-04-09 | 1998-04-08 | New sulfonium salt and photosensitive resin composition using the same |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10338688A true JPH10338688A (en) | 1998-12-22 |
Family
ID=26432026
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9575298A Withdrawn JPH10338688A (en) | 1997-04-09 | 1998-04-08 | New sulfonium salt and photosensitive resin composition using the same |
Country Status (1)
Country | Link |
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JP (1) | JPH10338688A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
1998
- 1998-04-08 JP JP9575298A patent/JPH10338688A/en not_active Withdrawn
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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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A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20050705 |