JP5005149B2 - Photobase generator, curable composition and curing method - Google Patents
Photobase generator, curable composition and curing method Download PDFInfo
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- JP5005149B2 JP5005149B2 JP2002088776A JP2002088776A JP5005149B2 JP 5005149 B2 JP5005149 B2 JP 5005149B2 JP 2002088776 A JP2002088776 A JP 2002088776A JP 2002088776 A JP2002088776 A JP 2002088776A JP 5005149 B2 JP5005149 B2 JP 5005149B2
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- carbon atoms
- electron
- light irradiation
- phenyl
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- 238000001723 curing Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title abstract description 34
- -1 imidazolium salt compound Chemical class 0.000 claims abstract description 103
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- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 83
- 150000001875 compounds Chemical class 0.000 claims description 46
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
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- 239000011737 fluorine Substances 0.000 claims description 15
- 125000000524 functional group Chemical group 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
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- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
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- 229910052801 chlorine Inorganic materials 0.000 claims description 11
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
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- 125000004663 dialkyl amino group Chemical group 0.000 claims description 6
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- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 4
- 125000005359 phenoxyalkyl group Chemical group 0.000 claims description 4
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 125000006698 (C1-C3) dialkylamino group Chemical group 0.000 claims 1
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001207 fluorophenyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
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- 238000004519 manufacturing process Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- VWUCIBOKNZGWLX-UHFFFAOYSA-N 1h-imidazol-1-ium;bromide Chemical compound [Br-].C1=C[NH+]=CN1 VWUCIBOKNZGWLX-UHFFFAOYSA-N 0.000 description 8
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- 239000013034 phenoxy resin Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical group C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
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- 125000004429 atom Chemical group 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
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- 150000007514 bases Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
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- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 2
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、１５０〜７５０ｎｍの光照射によって塩基を発生する光塩基発生剤およびこれを用いた硬化性組成物、硬化方法に関する。
【０００２】
【従来の技術】
光硬化技術は、従来の熱硬化技術と比較して低温硬化、プロセスの短縮化、短時間硬化、微細加工等の特徴を活かし、コーティング、レジスト等に応用が図られている。光硬化で主に用いられている硬化システムとしては、ラジカル硬化とカチオン硬化に大別される。ラジカル硬化の場合、光ラジカル発生剤と（メタ）アクリレート樹脂が主成分であり、光照射の際に光ラジカル発生剤が開裂や水素引抜き等の過程を経てラジカルを発生し、（メタ）アクリレート樹脂の硬化を行うシステムであり、速硬化が可能であることが特徴である。カチオン硬化の場合、光酸発生剤とカチオン重合性を有するエポキシ樹脂、オキセタン樹脂、ビニルエーテル樹脂等からなり、光照射の際に光酸発生剤が酸を発生してカチオン重合性樹脂の硬化を行うシステムであり、硬化時の硬化収縮が低い特徴を持つ。また、これらの光硬化系は遮光することによりポットライフに優れるという特徴をもつ。しかしながら、ラジカル硬化系の場合には低接着力、カチオン硬化系の場合には強酸が系内に残存するため金属や無機材質の被着体を使用すると腐食を引き起こす問題がある。
従来から接着剤等の用途に対してはイミダゾールやジシアンジアミド等の塩基性基を持つ熱潜在性触媒とエポキシ樹脂、またはエポキシ樹脂と反応性を持つカルボキシル基、メルカプト基、アミノ基、フェノール性水酸基等を組み合わせた熱硬化システムが用いられている。本システムは、無機材質、金属材質、有機材質等の被着体に対して高い接着性を持ち、また耐湿性、耐候性、耐熱性にも優れるため、建築材料から電気・電子材料、半導体材料に至る広範な用途で用いられている。しかしながら、前記潜在性硬化剤を用いた場合、一般に１７０℃以上の硬化温度が必要となり、１７０℃以下の温度で硬化する場合、ポットライフを兼備えた硬化システムの構築が難しい。
ポットライフと低温硬化性を考慮し、光照射によって塩基性化合物を発生する光塩基発生剤の研究が近年行われている。このような光塩基発生剤としては、例えばＣｈｅｍｉｓｔｒｙ ＆ Ｔｅｃｈｎｏｌｏｇｙ ｏｆ ＵＶ ＆ ＥＢ Ｆｏｒｍｕｌａｔｉｏｎ ｆｏｒ Ｃｏａｔｉｎｇｓ， Ｉｎｋｓ ＆ Ｐａｉｎｔｓ，Ｅｄ．ｂｙ Ｇ． Ｂｒａｄｌｅｙ，Ｊｏｈｎ Ｗｉｌｅｙ ａｎｄ Ｓｏｎｓ Ｌｔｄ．（１９９８年）、ｐ４７９〜ｐ５４５に記載されているカルバメート誘導体やオキシムエステル誘導体が一般的に知られている。しかしながら、これらのほとんどの化合物は発生効率が低く、また光照射によって発生する塩基性化合物が１級または２級アミンであるため塩基性が低く、エポキシ樹脂を十分に硬化するための触媒活性を持たない問題がある。
光照射によって強塩基を発生する化合物はいくつか報告されており、例えば特開昭５５-２２６６９号公報に記載されているカルボン酸アンモニウム塩や特開平１１-７１４５０号に記載されているα-アミノアセトフェノン誘導体が挙げられる。
【０００３】
【発明が解決しようとする課題】
しかしながら、カルボン酸アンモニウム塩の場合、カルボン酸と３級アミンとの結合がイオン結合であるため、エポキシ硬化性組成物中に溶解すると、解離が進行してポットライフに劣る欠点がある。また、α-アミノアセトフェノン誘導体の場合、分子内の立体障害によって触媒を不活性化しているものの、エポキシ硬化性組成物中に溶解した場合、分子内の自由回転が可能となるため、ポットライフに劣ることが分かっている。
【０００４】
本発明は、従来の光硬化技術の特徴を維持し、触媒発生効率が高く、触媒活性を有し、ポットライフにも優れた光塩基発生剤、硬化性組成物及び硬化方法を提供する。
【０００５】
【課題を解決するための手段】
本発明者等は、上記事情に鑑みて鋭意検討した結果、イミダゾリウム塩化合物がポットライフに優れ、かつ光照射によって強塩基であるイミダゾールを発生して１７０℃以下の低温でエポキシ樹脂を硬化できることを見出した。
本発明は１５０〜７５０ｎｍの光照射によって塩基を発生することを特徴とする一般式(１)または(２)で示されるイミダゾリウム塩化合物に関するものである。
【０００６】
【化５】
【０００７】
また、Ａｒ１ は一般式（Ｉ）〜（ＸＩＶ）で表される芳香族基であり、
【化６】
【０００８】
【化７】
【化８】
【０００９】
炭素数１〜８のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、iso-プロピル基、ｎ−ブチル基、sec-ブチル基、tert−ブチル基、ペンチル基、iso-ペンチル基、neo-ペンチル基、ヘキシル基、ヘプチル基、オクチル基が挙げられる。炭素数１〜８のアルコキシ基としては、メトシキ基、エトキシ基、ｎ−プロポキシ基、iso−プロポキシ基、n-ブトキシ基、sec-ブトキシ基、ペンチルオキシ基、iso-ペンチルオキシ基、neo-ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基が挙げられる。炭素数１〜８のアルキリデン基としては、例えば、メチリデン基、エチリデン基、ｎ−プロピリデン基、iso-プロピリデン基、n-ブチリデン基、sec-ブチリデン基、tert−ブチリデン基、ペンチリデン基、iso-ペンチリデン基、neo-ペンチリデン基、ヘキシリデン基、ヘプチリデン基、オクチリデン基が挙げられる。炭素数４〜８のシクロアルキル基としては、例えば、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基が挙げられる。炭素数４〜８のシクロアルケニル基としては、例えば、シクロブテニル基、シクロペンテニル基、シクロヘキセニル基、シクロヘプチニル基、シクロオクテニル基が挙げられる。炭素数１〜６のフェノキシアルキル基としては、例えば、フェノキシメチル基、フェノキシエチル基、フェノキシ‐n-プロピル基、フェノキシ‐iso-プロピル基、フェノキシ‐n-ブチル基、フェノキシ‐sec-ブチル基、フェノキシ‐tert-ブチル基、フェノキシペンチル基、フェノキシ‐iso-ペンチル基、フェノキシ‐neo-ペンチル基、フェノキシヘキシル基が挙げられる。炭素数１〜６のフェニルアルキル基としては、例えば、フェニルメチル基、フェニルエチル基、フェニル‐n-プロピル基、フェニル‐iso-プロピル基、フェニル‐n-ブチル基、フェニル‐sec-ブチル基、フェニル‐tert-ブチル基、フェニルペンチル基、フェニル−iso-ペンチル基、フェニル‐neo-ペンチル基、フェニルヘキシル基が挙げられる。炭素数１〜６のシアノアルキル基としては、例えば、シアノメチル基、シアノエチル基、シアノ‐n-プロピル基、シアノ‐iso-プロピル基、シアノ‐ｎ−ブチル基、シアノ‐sec-ブチル基、シアノ‐tert−ブチル基、シアノペンチル基、シアノ‐iso-ペンチル基、シアノ‐neo-ペンチル基、シアノヘキシル基が挙げられる。炭素数１〜６のヒドロキシアルキル基としては、例えば、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシ‐n-プロピル基、ヒドロキシ‐iso-プロピル基、ヒドロキシ‐n-ブチル基、ヒドロキシ‐sec-ブチル基、ヒドロキシ‐tert-ブチル基、ヒドロキシペンチル基、ヒドロキシ‐iso-ペンチル基、ヒドロキシ‐neo-ペンチル基、ヒドロキシヘキシル基が挙げられる。炭素数１〜８のアルキルチオ基としては、例えば、メチルチオ基、エチルチオ基、n-プロピルチオ基、iso-プロピルチオ基、n-ブチルチオ基、sec-ブチルチオ基、tert-ブチルチオ基、ペンチルチオ基、iso-ペンチルチオ基、neo-ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基、オクチルチオ基が挙げられる。炭素数１〜６のアルキルアミノ基としては、例えば、アミノメチル基、アミノエチル基、アミノ‐n-プロピル基、アミノ‐iso-プロピル基、アミノ‐n-ブチル基、アミノ‐sec-ブチル基、アミノ‐tert-ブチル基、アミノ‐ペンチル基、アミノ‐iso-ペンチル基、アミノ‐neo-ペンチル基が挙げられる。炭素数１〜３のジアルキルアミノ基としては、例えば、ジメチルアミノ基、ジエチルアミノ基、ジ-n-プロピルアミノ基、ジ-iso-プロピルアミノ基が挙げられる。電子供与性基としては、例えば、アミノ基、水酸基、ハロゲン（塩素、臭素、ヨウ素など）、アルキル基等が挙げられる。電子吸引性基としては、例えば、ニトロ基、カルボニル基、カルボキシル基、ニトリル基等が挙げられる。
【００１０】
また、本発明はエポキシ樹脂及び上記一般式(１)または(２)で示されるイミダゾリウム塩化合物を少なくとも含む硬化性組成物である。
また、本発明はエポキシ樹脂、上記一般式(１)または(２)で示されるイミダゾリウム塩化合物、エポキシ樹脂と反応性を有する官能基を分子内に二つ以上有する化合物を有する硬化性組成物である。
また、本発明はエポキシ樹脂と反応性を有する官能基が、カルボキシル基、メルカプト基、フェノール性水酸基、１級又２級の芳香族アミノ基である上記の硬化性組成物である。
また、本発明は分子内に二つ以上のイソシアナート基を持つ化合物、上記一般式(１)または(２)で示されるイミダゾリウム塩化合物、分子内に二つ以上の水酸基を持つ化合物を含む硬化性組成物である。
また、本発明は前記硬化性組成物の硬化に際し、光照射のみ、または光照射と加熱を同時または光照射後に加熱を行うことよって硬化物を得る硬化方法である。
【００１１】
【発明の実施の形態】
本発明において用いるイミダゾリウム塩化合物は、上記一般式（１）または（２）で表され、式中Ｒ１、Ｒ２、Ｒ３、Ｒ４は独立に水素、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキリデン基、炭素数４〜８のシクロアルキル基、炭素数４〜８のシクロアルケニル基、炭素数１〜６のフェノキシアルキル基、炭素数１〜６のフェニルアルキル基、炭素数１〜６のシアノアルキル基、炭素数１〜６のヒドロキシアルキル基、フェニル基、電子供与性基および/または電子吸引性基が置換したフェニル基、ベンジル基、電子供与性基および/または電子吸引性基が置換したベンジル基、ニトロ基、シアノ基、メルカプト基、メチルチオ基、フッ素、臭素、塩素、ヨウ素を示す。上記一般式（１）中のＡｒ１は一般式（Ｉ）〜（ＸＩＶ）で表される芳香族基であり、
【化９】
【化１０】
【化１１】
【００１２】
イミダゾリウム塩化合物の合成は、公知の方法を用いることができる。合成の簡便性、安全性を考慮すると、下式に示すように、ハロゲン化アルキルケトン誘導体とイミダゾール誘導体とで、イミダゾリウム・ハロゲン塩を合成した後、アニオン交換反応によって、イミダゾリウム塩を合成する方法が好ましい。
【化１２】
【００１３】
本発明において用いる分子内に少なくとも２個以上のエポキシ基を有する化合物（エポキシ樹脂）としては、分子内に２個以上のエポキシ基を有するものであれば特に制限なく、公知のものを使用しうる。
本発明で使用されるエポキシ基を有する化合物のうち、１分子中に２つのエポキシ基を有する化合物としては、以下に示す化合物が挙げられる（Ｍｅはメチル基、折れ線は場合によりメチレン基を示す）。
【００１４】
【化１３】
【化１４】
また、本発明で使用されるエポキシ基を有する化合物のうち、１分子中に三つのエポキシ基を有する化合物としては、以下に示す化合物が挙げられる(Meは、メチル基、Etはエチル基、折れ線は場合によりメチレン基を示す)。
【００１７】
【化１５】
さらに、本発明で使用されるエポキシ基を有する化合物のうち、１分子中に四つのエポキシ基を有する化合物としては、以下に示す化合物が挙げられる
【化１６】
本発明で用いられるエポキシ基を有する化合物として、一般式（３）で表される化合物も用いることができる。
【化１７】
【００２０】
また、本発明におけるエポキシ基を有する化合物として、エポキシ当量４３から１００００程度のエポキシ基を有する化合物を用いてもよい。エポキシ当量が４３以下では架橋密度が低下し、また１００００より大きい場合は反応速度が低下する傾向がある。また、この際単一分子だけでなく、以下に示すような、繰り返し単位数（ｚ）に分布を持つオリゴマーを用いると、組成物の結晶性が低下し、保存安定性に優れる。したがって、０＜ｚが好ましく、０．５≦ｚがさらに好ましく、１≦ｚが最も好ましい。
【００２１】
【化１８】
このような分子内に少なくとも２個以上のエポキシ基を有する化合物としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、脂肪族鎖状エポキシ樹脂等があり、これらのエポキシ樹脂はハロゲン化されていてもよく、水素添加されていてもよい。これらのエポキシ樹脂は、２種以上を併用してもよい。これらの中で、他の各種のエポキシ化合物と比較すると分子量の異なるグレードが広く入手可能で、接着性や反応性等を任意に設定できる点から、ビスフェノール型エポキシ樹脂が好ましい。
【００２３】
前記イミダゾリウム塩化合物は、一般的にはエポキシ樹脂の硬化触媒として用いることができ、その使用量は、エポキシ樹脂の１００重量部に対して０．０１〜５０重量部とすることが好ましく、０．１〜３０重量部とすることがより好ましい。この量が、０．０１重量部未満では、硬化促進効果が不十分となる傾向があり、５０重量部を超えると、相溶性が低下する傾向がある。
【００２４】
本発明は、前記エポキシ樹脂とイミダゾリウム塩化合物に、さらエポキシ樹脂と反応性を有する官能基を分子内に二つ以上有する化合物を併用することができる。ここでエポキシ樹脂と反応性を有する官能基とは、エポキシ樹脂と反応することが知られているカルボキシル基、メルカプト基、フェノール性水酸基、１級又は２級の芳香族アミノ基を用いることができる。これらの官能基は、３次元硬化性を考慮した場合、一分子中に２つ以上有することが必須である。また、重量平均分子量１０,０００以上のポリマ側鎖に官能基を導入したものを用いても良い。
【００２５】
エポキシ樹脂と反応性を有する官能基を分子内に二つ以上有する化合物の使用量は、前記エポキシ樹脂に対して、官能基の総量／エポキシ基の総量（当量比）で０．５／１．５〜１．５／０．５の比率となるようにすることが好ましく、０．８／１．２〜１．２／０．８の比率となるようにすることがより好ましい。この比率が、０．５／１．５未満の場合及び１．５／０．５を超える場合には未反応のエポキシ基や官能基が硬化物中に多量に残存することとなり、硬化物の機械特性を低下させる傾向がある。
【００２６】
本発明は、イソシアナート基を持つ化合物、水酸基を持つ化合物及び前記イミダゾリウム塩化合物から構成される硬化性組成物としての応用も可能である。
本発明において用いるイソシアナート基をもつ化合物（以後、イソソアネート樹脂とする）としては、分子内に２個以上のイソシアナート基を有するものであれば特に制限なく、公知のものを使用しうる。このような化合物としては、ｐ−フェニレンジイソシアネート、２,４−トルエンジイソシアネート、２，６−トルエンジイソシアネート、１，５−ナフタレンジイソシアネート、ヘキサメチレンジイソシアネート等に代表される低分子化合物の他に、重量平均分子分子量３,０００以上のポリマの側鎖あるいは末端にイソシアネート基が存在するものを用いてもよい。
【００２７】
前記イソシアネート基を持つ化合物は、通常分子内に水酸基を持つ化合物と組み合わせて用いられる。このようなイソシアネート樹脂としては、分子内に２個以上の水酸基を有するものであれば特に制限なく、公知のものを使用しうる。このような化合物としては、エチレングリコール、プロピレングリコール、グリセリン、ジグリセリン、ペンタエリスリトール等の低分子化合物の他に、重量平均分子量３,０００以上のポリマの側鎖あるいは末端に水酸基が存在するものを用いてもよい。
【００２８】
分子内に二つ以上の水酸基を有する化合物の使用量は、前記イソシアネート樹脂に対して、水酸基の総量／イソシアネート基の総量（当量比）で０．５／１．５〜１．５／０．５の比率となるようにすることが好ましく、０．８／１．２〜１．２／０．８の比率となるようにすることがより好ましい。この比率が、０．５／１．５未満の場合及び１．５／０．５を超える場合には未反応のエポキシ基や官能基が硬化物中に多量に残存することとなり、硬化物の機械特性を低下させる傾向がある。
【００２９】
イソシアネート樹脂と水酸基を持つ化合物の硬化触媒として用いるイミダゾリウム塩化合物の使用量は、イソシアネート基を持つ化合物と水酸基を持つ化合物の総量１００重量部に対して０．０１〜５０重量部とすることが好ましく、０．１〜３０重量部とすることがより好ましい。この量が、０．０１重量部未満では、硬化促進効果が不十分となる傾向があり、５０重量部を超えると、相溶性が低下する傾向がある。
【００３０】
本発明の硬化性組成物は、照射光の高吸収化、高感度化を目的に、増感剤を併用してもよい。使用する増感剤としては、硬化性組成物に悪影響を及ぼさない限り、公知の一重項増感剤、三重項増感剤を用いることができる。例えば、ナフタレン、アントラセン、ピレン等の芳香族化合物誘導体、カルバゾール誘導体、ベンゾフェノン誘導体、チオキサントン誘導体、クマリン誘導体等が好適に用いられる。増感剤の使用量は、増感剤の吸収波長及びモル吸光係数を参考にする必要があるが、一般的にイミダゾリウム塩化合物１部に対して０．０１〜５部であり、０.１〜２部が特に好ましい。増感剤が０.０１部以下になると光吸収の効率が低くなり、５部以上では硬化性組成物全体に光が届かない恐れがある。
【００３１】
本発明の硬化性組成物は、必要に応じてカップリング剤等の密着向上剤、レベリング剤、有機または無機充填材などの添加剤を適宜添加してもよい。
【００３２】
本発明の硬化性組成物は、増粘化やフィルム化を目的として、種々のポリマを適宜添加してもよい。使用するポリマは特に制限を受けないが、硬化性に悪影響を及ぼさないことが必須である。このようなポリマとしては、ポリイミド、ポリアミド、ビスフェノールＡ型フェノキシ樹脂やビスフェノールＦ型フェノキシ樹脂、ビスフェノールＡ・ビスフェノールＦ共重合型フェノキシ樹脂等の汎用フェノキシ樹脂類、ポリメタクリレート類、ポリアクリレート類、ポリイミド類、ポリウレタン類、ポリエステル類、ポリビニルブチラール、ＳＢＳ及びそのエポキシ変性体、ＳＥＢＳ及びその変性体などを用いることができる。これらは単独あるいは２種類以上を混合して用いることができる。さらに、これらポリマ中にはシロキサン結合やフッ素置換基が含まれていても良い。これらは、混合する樹脂同士が完全に相溶するか、もしくはミクロ相分離が生じて白濁する状態であれば好適に用いることができる。分子量は特に制限を受けるものではないが、一般的な重量平均分子量としては５，０００〜１５０，０００が好ましく、１０，０００〜８０，０００が特に好ましい。この値が、５，０００未満ではフィルム形成性が劣る傾向があり、また１５０，０００を超えると他の成分との相溶性が悪くなる傾向がある。使用量としてはエポキシ樹脂またはイソシアネート樹脂１００重量部に対して２０〜３２０重量部とすることが好ましい。
【００３３】
本発明の硬化性組成物は、常温（２５℃）で液状である場合にはペースト状で使用することができる。室温で固体の場合には、加熱して使用する他、溶剤を使用してペースト化してもよい。使用できる溶剤としては、硬化性に悪影響を及ぼさず、かつ十分な溶解性を示すものであれば、特に制限は受けないが、常圧での沸点が５０〜１５０℃であるものが好ましい。沸点が５０℃以下の場合、室温で放置すると揮発する恐れがあり、開放系での使用が制限される。また、沸点が１５０℃以上だと、溶剤の除去が難しくなる恐れがある。
【００３４】
本発明の硬化性組成物はフィルム状にして用いることもできる。硬化性組成物に必要により溶剤等を加えるなどした溶液を、フッ素樹脂フィルム、ポリエチレンテレフタレートフィルム、離形紙等の剥離性基材上に塗布し、あるいは不織布等の基材に前記溶液を含浸させて剥離性基材上に載置し、溶剤等を除去してフィルムとして使用することができる。フィルムの形状で使用すると取扱性等の点から一層便利である。
【００３５】
本発明の硬化性組成物は、光照射のみ、または光照射と加熱を同時、または光照射後に加熱を行うことで硬化させることができる。光照射は、１５０〜７５０ｎｍの波長域の照射光が好ましく、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプを使用して０.１〜１００Ｊ／ｃｍ２の照射量で硬化することができる。加熱温度は、使用するエポキシ樹脂及びエポキシ樹脂と反応性を持つ官能基を有する化合物の分解点以下であれば特に制限は受けないが、３０〜２００℃の温度が好ましく、５０〜１７０℃がさらに好ましい。また、加熱時間は、硬化を十分に行うために１秒〜３時間、好ましくは３０秒〜１時間である。
【００３６】
本発明の硬化性組成物は、塗料、接着剤、インク、フォトレジスト、コーティング材、各種自動車部品、電気・電子材料、半導体材料、光学材料、光ファイバー、光ファイバー用接着剤、光導波路材等、多種多様な用途に応用することができる。
特に接着剤に関しては、木材、建材、プラスチック、皮革等の接着の他に、異方導電接着剤、銀ペースト、銀フィルム等に代表される回路接続材料、フリップチップ等の半導体素子とプリント配線板との接続を行うフリップチップ用異方導電材等の半導体素子接着材料として使用することができる。
【００３７】
【実施例】
以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに制限されるものではない。
【００３８】
（実施例１） イミダゾリウム塩１の合成
フェナシルブロマイド (２.００ｇ、１０．５ｍｍｏｌ)をアセトン(２０g)に溶解させ、これにアセトン(５ｇ)に溶解させた１−ベンジル―２−メチルイミダゾール(１．７３ｇ、１０．５ｍｍｏｌ)の溶液をゆっくり添加し、この後、室温（２５℃）で２時間かくはんしたところ、白色結晶が析出した。これをろ過し、アセトンで２度洗浄を行った後、真空下６０℃で５時間乾燥して、イミダゾリウム・ブロマイド塩１を得た（収量３.５４ｇ）。
上記イミダゾール・ブロマイド塩１（２．００ｇ、５．４ｍｍｏｌ）を、メタノール/水（１５ｇ/１５ｇ）溶液に溶解させ、これに水（５．０ｇ）に溶解させたテトラフェニルほう酸ナトリウム（１．８４ｇ、５．４ｍｍｏｌ）の溶液をゆっくり添加した。添加とともに、白色スラリー状の析出が認められ、添加後、さらに室温で５時間かくはんした。この析出物をろ過し、アセトン（２０ｇ）に溶解させて再結晶を行い、目的のイミダゾリウム・テトラフェニルほう酸塩（イミダゾリウム塩１）を得た（収量２．８６ｇ）。
この化合物の１Ｈ-ＮＭＲを図１に示した。また、酸素雰囲気下での融点及び熱分解開始温度をＴＧ-ＤＴＡで測定したところ、融点１８７℃、分解開始温度２２４℃であった。
【００３９】
（実施例２） イミダゾリウム塩２の合成
ｐ−ニトロフェナシルブロマイド (２.００ｇ、８．２ｍｍｏｌ)をアセトン(２０g)に溶解させ、これにアセトン(５ｇ)に溶解させた１，２−ジメチルイミダゾール(０．７９ｇ、８．２ｍｍｏｌ)の溶液をゆっくり添加し、この後、室温で２時間かくはんしたところ、白色結晶が析出した。これをろ過し、アセトンで２度洗浄を行った後、真空下６０℃で５時間乾燥して、イミダゾリウム・ブロマイド塩２を得た（収量２．６２ｇ）。
上記イミダゾール・ブロマイド塩２（２．００ｇ、５．８ｍｍｏｌ）を、メタノール/水（１５ｇ/１５ｇ）溶液に溶解させ、これに水（５．０ｇ）に溶解させたテトラフェニルほう酸ナトリウム塩（２．０１ｇ、５．８ｍｍｏｌ）の溶液をゆっくり添加した。添加とともに、白色スラリー状の析出が認められ、添加後、さらに室温で５時間かくはんした。これをろ過し、アセトン（２０ｇ）に溶解させて再結晶を行い、目的のイミダゾリウム・テトラフェニルほう酸塩（イミダゾリウム塩２）を得た（収量２．８３ｇ）。
この化合物の１Ｈ-ＮＭＲを図２に示した。また、酸素雰囲気下での融点及び熱分解開始温度をＴＧ-ＤＴＡで測定したところ、融点１６５℃、分解開始温度１９５℃であった。
【００４０】
（実施例３）
エポキシ樹脂にＤＥＲ７３６（ダウ・ケミカル社製商品名、エポキシ当量１７２）：１.００ｇ、メルカプト化合物としてペンタエリスリトールテトラ(メルカプトアセテート)（東京化成工業株式会社製、ＳＨ基当量１０８）：０.６１４ｇ、実施例１のイミダゾリウム塩１：０.０１６gを室温で混合し、均一な溶液とした。これをＤＳＣのサンプルパンに３ｍｇとなるようにサンプリングし、光照射を行った後、ＤＳＣを測定した。
光照射は、フュージョン社製紫外線照射装置ＡＥＬ １Ｂ／Ｍ(３６５ｎｍ照度：２１.５ｍＷ/ｃｍ２)を用いて、３Ｊ/ｃｍ2照射した。
【００４１】
（実施例４）
イミダゾリウム塩化合物を実施例２のイミダゾリウム塩２に代えた以外は実施例３と同様にＤＳＣ測定を行った。
【００４２】
（比較例１）
光照射を行わなかった以外は、実施例３と同様にＤＳＣ測定を行った。
【００４３】
（比較例２）
光照射を行わなかった以外は、実施例４と同様にＤＳＣ測定を行った。
【００４４】
実施例３、４及び比較例１、２の結果を表１に示した。なお、表中の反応開始温度は、発熱開始温度を示すＯｎｓｅｔ温度とした。
【００４５】
実施例３、４の硬化性組成物は、比較例１、２と比較して硬化反応が３０℃以上低温で進行することを示しており、光照射によりイミダゾリウム塩化合物が塩基性化合物を発生し低温硬化が可能になったことを示している。
【００４６】
【表１】
（実施例５） イミダゾリウム塩３の合成
フェナシルブロマイド (２.００ｇ、１０．５ｍｍｏｌ)をアセトン(２０g)に溶解させ、これにアセトン(５ｇ)に溶解させた１−ベンジル―２−メチルイミダゾール(１．７３ｇ、１０．５ｍｍｏｌ)の溶液をゆっくり添加し、この後、室温で２時間かくはんしたところ、白色結晶が析出した。これをろ過し、アセトンで２度洗浄を行った後、真空下６０℃で５時間乾燥して、イミダゾリウム・ブロマイド塩３を得た（収量３.５４ｇ）。
上記イミダゾール・ブロマイド塩３（２．００ｇ、５．４ｍｍｏｌ）を、エタノール（５０ｇ）に溶解させ、これにエタノール（２０ｇ）に溶解させたジチオカルバミン酸ナトリウム塩・２水和物（１．３３ｇ、５．４ｍｍｏｌ）の溶液をゆっくり添加した。添加後、２０分間還流させて反応させ、溶媒を留去したところ、黄色粉末が析出した。これを、エタノール（２０ｇ）で３度再結晶を行い、目的のイミダゾリウム・ジチオカルバメート塩（イミダゾリウム塩３）を得た（収量１．８０ｇ）。
この化合物の１Ｈ-ＮＭＲを図３に示した。また、酸素雰囲気下での融点及び熱分解開始温度をＴＧ-ＤＴＡで測定したところ、融点１８１℃、分解開始温度１６８℃であった。
【００４８】
（実施例６）
実施例５で得られたイミダゾリウム塩３を０．１４ｇ、ポリグリシジルメタクリレート（Ｍｎ：１３８，０００、Ｍｗ/Ｍｎ：１．４９）を１．００ｇ秤量し、重量比でシクロヘキサノン／アセトニトリル：５／２となるように調整した混合溶媒２１．７ｇに溶解させた。上記溶液をシリコンウェハ上に膜厚１μｍとなるようにスピンコートした後、高圧水銀灯を用いて全面にＵＶ照射を行った。この後、ＴＨＦ中に室温で３分間浸漬し、シリコンウェハ上の残存膜厚を測定した。
【００４９】
実施例６の結果を表２に示した。なお、表中の残膜率は、現像後膜厚×１００／スピンコート後の膜厚（１μｍ）とした。
【００５０】
ＵＶ照射量の増加と共に、残膜率が上昇していることから、ＵＶ照射によってイミダゾリウム塩３が塩基を発生し、ポリグリシジルメタクリレートの架橋を促進していることが示された。
【００５１】
【表２】
（実施例７） イミダゾリウム塩４の合成
フェナシルブロマイド (２.００ｇ、１０．５ｍｍｏｌ)をアセトン(２０g)に溶解させ、これにアセトン(５ｇ)に溶解させた１−メチルイミダゾール(０．８２ｇ、１０．５ｍｍｏｌ)の溶液をゆっくり添加し、この後、室温で２時間かくはんしたところ、白色結晶が析出した。これをろ過し、アセトンで２度洗浄を行った後、真空下６０℃で５時間乾燥して、イミダゾリウム・ブロマイド塩４を得た（収量２.７６ｇ）。
上記イミダゾール・ブロマイド塩４（２．７６ｇ、９.８ｍｍｏｌ）を、エタノール（２０ｇ）に溶解させ、これにチオシアン酸ナトリウム（０．８８ｇ、９．９ｍｍｏｌ）をゆっくり添加した。添加後、６０分室温で反応させ、溶媒を留去したところ、白色粉末が析出した。これを、エタノール（２０ｇ）で３度再結晶を行い、目的のイミダゾリウム・チオシアナート塩（イミダゾリウム塩４）を得た（収量１．７１ｇ）。
この化合物の１Ｈ-ＮＭＲを図４に示した。また、酸素雰囲気下での融点を測定したところ、融点７４-７６℃であった。
【００５３】
（実施例８）
実施例７で得られたイミダゾリウム塩４を０．１３ｇ、ポリグリシジルメタクリレート（Ｍｎ：１３８，０００、Ｍｗ/Ｍｎ：１．４９）を１．００ｇ秤量し、重量比でシクロヘキサノン／アセトニトリル：５／２となるように調整した混合溶媒２１．７ｇに溶解させた。上記溶液をシリコンウェハ上に膜厚１μｍとなるようにスピンコートした後、高圧水銀灯を用いて全面にＵＶ照射を行い、さらにホットプレート上６０℃、１０分間加熱した。この後、ＴＨＦ中に室温で３分間浸漬し、シリコンウェハ上の残存膜厚を測定した。
【００５４】
実施例８の結果を表３に示した。なお、表中の残膜率は、現像後膜厚×１００／スピンコート後の膜厚（１μｍ）とした。
【００５５】
【表３】
ＵＶ照射量の増加と共に、残膜率が上昇していることから、ＵＶ照射によってイミダゾリウム塩４が塩基を発生し、６０℃/１０分間の加熱でポリグリシジルメタクリレートの架橋を促進していることが示された。
【００５７】
（実施例９）
エポキシ樹脂として、ビスフェノールＡ型エポキシ樹脂（油化シェルエポキシ株式会社製、商品名エピコート８２８、エポキシ当量１８４）５０ｇを、重量比でメチルエチルケトンに溶解して、固形分４０重量％の溶液としこれを用いた。ポリチオールとして、ペンタエリスリチオール（ＳＨ当量５０）を１３．５ｇ用いた。イミダゾリウム塩として、実施例２のイミダゾリウム塩２を２．０ｇ用いた。また、シランカップリング剤として、エポキシシラン化合物(日本ユニカー株式会社製、商品名Ａ１８７)を１.５ｇ用いた。
【００５８】
フェノキシ樹脂として、ビスフェノールＡ、ビスフェノールＦ（１／１）とエピクロロヒドリンから、ビスフェノールＡ、Ｆ共重合型フェノキシ樹脂（平均分子量２０，０００）５０ｇを一般的方法により作製し、これを重量比でメチルエチルケトンに溶解して、固形分４０重量％の溶液とし、これを用いた。導電粒子としては、ポリスチレンを核とする粒子の表面に、厚み０．２μｍのニッケル層を設け、このニッケル層の外側に、厚み０．０２μｍの金属を設け、平均粒径１０μｍ、比重２．０の導電粒子を作製しこれを用いた。
【００５９】
導電粒子を除いて上記成分を配合した溶液（固形分でエポキシ樹脂５０ｇ、ポリチオール１３．５ｇ、イミダゾリウム塩２を２．０ｇ、エポキシシラン化合物１.５ｇ、フェノキシ樹脂５０ｇ）に、導電粒子を３体積％配合分散させ、厚み８０μｍのフッ素樹脂フィルムに塗工装置を用いて塗布し、７０℃、１０分の熱風乾燥によりフッ素樹脂フィルム上に厚みが２５μｍの回路接続用組成物からなるフィルムを形成した。
【００６０】
上記製法によって得たフィルム状接着剤を用いて、ライン幅５０μｍ、ピッチ１００μｍ、厚み１８μｍの銅回路を５００本有するフレキシブル回路板（ＦＰＣ）と、０．２μｍの酸化インジウム（ＩＴＯ）の薄層を形成したガラス（厚み１．１ｍｍ、表面抵抗２０Ω／□）とを、１７０℃、４ＭＰａで６０秒間加熱加圧して幅２ｍｍにわたり接続した。この時、あらかじめＩＴＯガラス上に、フィルム状回路接続材料の接着面を７０℃、０．５ＭＰａで５秒間加熱加圧して仮接続した後、フッ素樹脂フィルムを剥離し、回路接続用組成物からなるフィルム面に、高圧水銀ランプを有する紫外線照射装置（ウシオ電機株式会社製）を用いて３．０Ｊ／ｃｍ２の紫外線を照射した。その後、もう一方の被着体であるＦＰＣと接続し接続体を得た。
この接続体の隣接回路間の抵抗値を測定したところ、隣接回路間の抵抗１５０点の平均（ｘ＋３σ；σは標準偏差）は２.７Ωであり、良好な接続特性を示した。
【００６１】
また、この接続体の接着強度をＪＩＳ−Ｚ０２３７に準じて９０度剥離法で測定し、評価した。ここで、接着強度の測定装置は東洋ボールドウィン株式会社製テンシロンＵＴＭ−４（剥離速度５０ｍｍ／ｍｉｎ、２５℃）を使用した。以上のようにして行った接続体の接着強度は、６００Ｎ／ｍであり、十分な接着強度を示した。
【００６２】
（実施例１０）
イソシアネート樹脂として、ヘキサメチレンジイソシアネート（関東化学株式会社製）０.６７２ｇ、水酸基を持つ樹脂としてポリテトラヒドロフラン（ＢＡＳＦジャパン社製、商品名ポリテトラヒドロフラン２５０）１．００ｇ、実施例１のイミダゾリウム塩１を０.０１６ｇからなる均一なワニスを調整した。これをＤＳＣのサンプルパンに３ｍｇとなるようにサンプリングし、１０分間光照射を行いながら、ＤＳＣを測定した(温度は４０℃で一定とした)。光照射は、ウシオ電機株式会社製スポットキュアを用いた(３６５ｎｍ、５３ｍＷ/ｃｍ２)。この結果、９２.４Ｊ／ｇのイソシアネートと水酸基を有する化合物との反応による発熱が得られ、光照射によって反応が起こっていることが確認された。
【００６３】
本発明によれば、光照射を行うことにより低温で（ａ）エポキシ樹脂とイミダゾリウム塩化合物、（ｂ）エポキシ樹脂、イミダゾリウム塩化合物、エポキシ樹脂と反応性を有する官能基を分子内に二つ以上有する化合物、（ｃ）分子内に二つ以上のイソシアナート基を有する化合物、イミダゾリウム塩化合物、分子内に二つ以上の水酸基を有する化合物の低温硬化が可能な硬化性組成物を提供することができる。
【図面の簡単な説明】
【図１】 イミダゾリウム塩１の１Ｈ-ＮＭＲスペクトル図(溶媒：ＣＤ３ＣＮ、標準物質：ＴＭＳ、図中＊は不純物)
【図２】 イミダゾリウム塩２の１Ｈ-ＮＭＲスペクトル図(溶媒：ＣＤ３ＣＮ、標準物質：ＴＭＳ、図中＊は不純物)
【図３】イミダゾリウム塩３の１Ｈ-ＮＭＲスペクトル図(溶媒：ＣＤＣｌ３、標準物質：ＴＭＳ、図中＊は不純物)
【図４】イミダゾリウム塩４の１Ｈ-ＮＭＲスペクトル図(溶媒：Ｄ２Ｏ)[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photobase generator that generates a base upon irradiation with light of 150 to 750 nm, a curable composition using the photobase generator, and a curing method.
[0002]
[Prior art]
The photo-curing technology has been applied to coatings, resists, and the like by making use of features such as low-temperature curing, process shortening, short-time curing, and microfabrication as compared with conventional thermosetting technologies. Curing systems mainly used in photocuring are roughly classified into radical curing and cationic curing. In the case of radical curing, the photo radical generator and (meth) acrylate resin are the main components. Upon photoirradiation, the photo radical generator generates radicals through processes such as cleavage and hydrogen abstraction, and the (meth) acrylate resin It is a system that cures and is characterized by being capable of rapid curing. In the case of cationic curing, it consists of a photoacid generator and a cationic polymerizable epoxy resin, oxetane resin, vinyl ether resin, etc., and the photoacid generator generates an acid upon light irradiation to cure the cationic polymerizable resin. This system is characterized by low cure shrinkage during curing. In addition, these photocuring systems are characterized by being excellent in pot life by shielding light. However, in the case of a radical curing system, a low adhesive force is used, and in the case of a cationic curing system, a strong acid remains in the system.
Conventionally, for applications such as adhesives, heat latent catalysts with basic groups such as imidazole and dicyandiamide and epoxy resins, or carboxyl groups, mercapto groups, amino groups, phenolic hydroxyl groups reactive with epoxy resins, etc. The thermosetting system which combined is used. This system has high adhesion to adherends such as inorganic materials, metal materials, and organic materials, and also has excellent moisture resistance, weather resistance, and heat resistance. Is used in a wide range of applications. However, when the latent curing agent is used, a curing temperature of 170 ° C. or higher is generally required, and when curing at a temperature of 170 ° C. or lower, it is difficult to construct a curing system having pot life.
Considering pot life and low-temperature curability, researches on photobase generators that generate basic compounds by light irradiation have been conducted in recent years. Examples of such photobase generators include Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Ed. by G. Bradley, John Wiley and Sons Ltd. (1998), carbamate derivatives and oxime ester derivatives described in p479 to p545 are generally known. However, most of these compounds have low generation efficiency, and since the basic compound generated by light irradiation is a primary or secondary amine, it is low in basicity and has a catalytic activity for sufficiently curing an epoxy resin. There is no problem.
Several compounds that generate a strong base by light irradiation have been reported. For example, carboxylic acid ammonium salts described in JP-A No. 55-22669 and α-amino acids described in JP-A No. 11-71450 are disclosed. Examples include acetophenone derivatives.
[0003]
[Problems to be solved by the invention]
However, in the case of the carboxylic acid ammonium salt, the bond between the carboxylic acid and the tertiary amine is an ionic bond, and therefore, when dissolved in the epoxy curable composition, there is a disadvantage that dissociation proceeds and the pot life is inferior. In the case of an α-aminoacetophenone derivative, the catalyst is inactivated by steric hindrance in the molecule, but when dissolved in an epoxy curable composition, free rotation in the molecule is possible, so pot life is reduced. I know it ’s inferior.
[0004]
The present invention provides a photobase generator, a curable composition, and a curing method that maintain the characteristics of conventional photocuring technology, have high catalyst generation efficiency, have catalytic activity, and have excellent pot life.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of the above circumstances, the present inventors have found that an imidazolium salt compound is excellent in pot life and can generate imidazole which is a strong base by light irradiation to cure an epoxy resin at a low temperature of 170 ° C. or lower. I found.
The present invention relates to an imidazolium salt compound represented by the general formula (1) or (2), wherein a base is generated by irradiation with light of 150 to 750 nm.
[0006]
[Chemical formula 5]
[0007]
Ar1 IsAn aromatic group represented by general formulas (I) to (XIV),
[Chemical 6]
[0008]
[Chemical 7]
[Chemical 8]
[0009]
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and iso-pentyl. Group, neo-pentyl group, hexyl group, heptyl group and octyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, pentyloxy group, iso-pentyloxy group, and neo-pentyl. Examples thereof include an oxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. Examples of the alkylidene group having 1 to 8 carbon atoms include methylidene group, ethylidene group, n-propylidene group, iso-propylidene group, n-butylidene group, sec-butylidene group, tert-butylidene group, pentylidene group, and iso-pentylidene group. Group, neo-pentylidene group, hexylidene group, heptylidene group and octylidene group. Examples of the cycloalkyl group having 4 to 8 carbon atoms include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the C 4-8 cycloalkenyl group include a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptynyl group, and a cyclooctenyl group. Examples of the phenoxyalkyl group having 1 to 6 carbon atoms include phenoxymethyl group, phenoxyethyl group, phenoxy-n-propyl group, phenoxy-iso-propyl group, phenoxy-n-butyl group, phenoxy-sec-butyl group, Examples include phenoxy-tert-butyl group, phenoxypentyl group, phenoxy-iso-pentyl group, phenoxy-neo-pentyl group and phenoxyhexyl group. Examples of the phenylalkyl group having 1 to 6 carbon atoms include a phenylmethyl group, a phenylethyl group, a phenyl-n-propyl group, a phenyl-iso-propyl group, a phenyl-n-butyl group, a phenyl-sec-butyl group, Examples include phenyl-tert-butyl group, phenylpentyl group, phenyl-iso-pentyl group, phenyl-neo-pentyl group, and phenylhexyl group. Examples of the cyanoalkyl group having 1 to 6 carbon atoms include cyanomethyl group, cyanoethyl group, cyano-n-propyl group, cyano-iso-propyl group, cyano-n-butyl group, cyano-sec-butyl group, cyano- Examples include tert-butyl group, cyanopentyl group, cyano-iso-pentyl group, cyano-neo-pentyl group, and cyanohexyl group. Examples of the hydroxyalkyl group having 1 to 6 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxy-n-propyl group, a hydroxy-iso-propyl group, a hydroxy-n-butyl group, a hydroxy-sec-butyl group, Examples thereof include a hydroxy-tert-butyl group, a hydroxypentyl group, a hydroxy-iso-pentyl group, a hydroxy-neo-pentyl group, and a hydroxyhexyl group. Examples of the alkylthio group having 1 to 8 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, and iso-pentylthio group. Group, neo-pentylthio group, hexylthio group, heptylthio group and octylthio group. Examples of the alkylamino group having 1 to 6 carbon atoms include aminomethyl group, aminoethyl group, amino-n-propyl group, amino-iso-propyl group, amino-n-butyl group, amino-sec-butyl group, Examples thereof include amino-tert-butyl group, amino-pentyl group, amino-iso-pentyl group, and amino-neo-pentyl group. Examples of the dialkylamino group having 1 to 3 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, and a di-iso-propylamino group. Examples of the electron donating group include an amino group, a hydroxyl group, a halogen (such as chlorine, bromine and iodine), and an alkyl group. Examples of the electron withdrawing group include a nitro group, a carbonyl group, a carboxyl group, and a nitrile group.
[0010]
The present invention is also a curable composition comprising at least an epoxy resin and an imidazolium salt compound represented by the above general formula (1) or (2).
The present invention also relates to a curable composition comprising an epoxy resin, an imidazolium salt compound represented by the above general formula (1) or (2), and a compound having two or more functional groups having reactivity with the epoxy resin in the molecule. It is.
Moreover, this invention is said curable composition whose functional group reactive with an epoxy resin is a carboxyl group, a mercapto group, a phenolic hydroxyl group, a primary or secondary aromatic amino group.
The present invention also includes a compound having two or more isocyanate groups in the molecule, an imidazolium salt compound represented by the above general formula (1) or (2), and a compound having two or more hydroxyl groups in the molecule. It is a curable composition.
Moreover, this invention is a hardening method which obtains hardened | cured material by heating only the light irradiation or light irradiation and a heating simultaneously or after light irradiation in the case of hardening of the said curable composition.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The imidazolium salt compound used in the present invention is represented by the above general formula (1) or (2), wherein R1, R2, R3, R4Is independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylidene group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, or a cycloalkenyl having 4 to 8 carbon atoms. A phenoxyalkyl group having 1 to 6 carbon atoms, a phenylalkyl group having 1 to 6 carbon atoms, a cyanoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a phenyl group, an electron donating group, and / Or phenyl group substituted with an electron withdrawing group, benzyl group, electron donating group and / or benzyl group substituted with electron withdrawing group, nitro group, cyano group, mercapto group,MethylthioGroup, fluorine, bromine, chlorine, iodine. Ar in the general formula (1)1Is an aromatic group represented by general formulas (I) to (XIV),
[Chemical 9]
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[0012]
A known method can be used for the synthesis of the imidazolium salt compound. Considering the simplicity and safety of the synthesis, as shown in the following formula, after synthesizing an imidazolium / halogen salt with a halogenated alkyl ketone derivative and an imidazole derivative, the imidazolium salt is synthesized by anion exchange reaction. The method is preferred.
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[0013]
The compound having at least two epoxy groups in the molecule (epoxy resin) used in the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule, and known compounds can be used. .
Among the compounds having an epoxy group used in the present invention, examples of the compound having two epoxy groups in one molecule include the following compounds (Me represents a methyl group, and a broken line optionally represents a methylene group). .
[0014]
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In addition, among the compounds having an epoxy group used in the present invention, examples of the compound having three epoxy groups in one molecule include the following compounds (Me is a methyl group, Et is an ethyl group, broken line) Optionally represents a methylene group).
[0017]
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Furthermore, among the compounds having an epoxy group used in the present invention, examples of the compound having four epoxy groups in one molecule include the compounds shown below.
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As the compound having an epoxy group used in the present invention, a compound represented by the general formula (3) can also be used.
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[0020]
In addition, as the compound having an epoxy group in the present invention, a compound having an epoxy group with an epoxy equivalent of about 43 to 10,000 may be used. When the epoxy equivalent is 43 or less, the crosslinking density decreases, and when it is greater than 10,000, the reaction rate tends to decrease. In this case, not only a single molecule but also an oligomer having a distribution in the number of repeating units (z) as shown below is used, the crystallinity of the composition is lowered and the storage stability is excellent. Therefore, 0 <z is preferable, 0.5 ≦ z is more preferable, and 1 ≦ z is most preferable.
[0021]
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Examples of the compound having at least two epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol. A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. Yes, these epoxy resins may be halogenated or hydrogenated. Two or more of these epoxy resins may be used in combination. Among these, bisphenol-type epoxy resins are preferable because grades having different molecular weights are widely available as compared with other various epoxy compounds, and adhesiveness and reactivity can be arbitrarily set.
[0023]
The imidazolium salt compound can be generally used as a curing catalyst for an epoxy resin, and the amount used is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin. More preferably, the content is 1 to 30 parts by weight. If this amount is less than 0.01 parts by weight, the curing accelerating effect tends to be insufficient, and if it exceeds 50 parts by weight, the compatibility tends to decrease.
[0024]
In the present invention, the epoxy resin and the imidazolium salt compound can be used in combination with a compound having two or more functional groups having reactivity with the epoxy resin. Here, the functional group having reactivity with the epoxy resin may be a carboxyl group, mercapto group, phenolic hydroxyl group, primary or secondary aromatic amino group known to react with the epoxy resin. . In consideration of three-dimensional curability, it is essential to have two or more of these functional groups in one molecule. Moreover, you may use what introduce | transduced the functional group into the polymer side chain of weight average molecular weight 10,000 or more.
[0025]
The amount of the compound having two or more functional groups reactive with the epoxy resin in the molecule is 0.5 / 1. In terms of the total amount of functional groups / total amount of epoxy groups (equivalent ratio) with respect to the epoxy resin. The ratio is preferably 5 to 1.5 / 0.5, and more preferably 0.8 to 1.2 to 1.2 / 0.8. When this ratio is less than 0.5 / 1.5 and exceeds 1.5 / 0.5, a large amount of unreacted epoxy groups and functional groups remain in the cured product, and There is a tendency to reduce mechanical properties.
[0026]
The present invention can also be applied as a curable composition composed of a compound having an isocyanate group, a compound having a hydroxyl group, and the imidazolium salt compound.
The compound having an isocyanate group used in the present invention (hereinafter referred to as an isocyanate resin) is not particularly limited as long as it has two or more isocyanate groups in the molecule, and known compounds can be used. As such a compound, in addition to low molecular weight compounds represented by p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate and the like, a weight average A polymer having an isocyanate group in the side chain or terminal of a polymer having a molecular weight of 3,000 or more may be used.
[0027]
The compound having an isocyanate group is usually used in combination with a compound having a hydroxyl group in the molecule. Such an isocyanate resin is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and known resins can be used. Examples of such compounds include those having a hydroxyl group in the side chain or terminal of a polymer having a weight average molecular weight of 3,000 or more, in addition to low molecular weight compounds such as ethylene glycol, propylene glycol, glycerin, diglycerin, and pentaerythritol. It may be used.
[0028]
The amount of the compound having two or more hydroxyl groups in the molecule is 0.5 / 1.5 to 1.5 / 0.5 in terms of the total amount of hydroxyl groups / total amount of isocyanate groups (equivalent ratio) with respect to the isocyanate resin. The ratio is preferably 5 and more preferably 0.8 / 1.2 to 1.2 / 0.8. When this ratio is less than 0.5 / 1.5 and exceeds 1.5 / 0.5, a large amount of unreacted epoxy groups and functional groups remain in the cured product, and There is a tendency to reduce mechanical properties.
[0029]
The amount of the imidazolium salt compound used as a curing catalyst for the isocyanate resin and the compound having a hydroxyl group may be 0.01 to 50 parts by weight based on 100 parts by weight of the total amount of the compound having an isocyanate group and the compound having a hydroxyl group. Preferably, it is 0.1 to 30 parts by weight. If this amount is less than 0.01 parts by weight, the curing accelerating effect tends to be insufficient, and if it exceeds 50 parts by weight, the compatibility tends to decrease.
[0030]
The curable composition of the present invention may be used in combination with a sensitizer for the purpose of increasing the absorption and sensitivity of irradiated light. As a sensitizer to be used, a known singlet sensitizer and triplet sensitizer can be used as long as they do not adversely affect the curable composition. For example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used. The amount of the sensitizer used should be referred to the absorption wavelength and molar extinction coefficient of the sensitizer, but is generally 0.01 to 5 parts with respect to 1 part of the imidazolium salt compound. 1-2 parts are particularly preferred. If the sensitizer is 0.01 parts or less, the light absorption efficiency is low, and if it is 5 parts or more, the light may not reach the entire curable composition.
[0031]
The curable composition of the present invention may optionally contain additives such as an adhesion improver such as a coupling agent, a leveling agent, an organic or inorganic filler, as necessary.
[0032]
Various polymers may be appropriately added to the curable composition of the present invention for the purpose of thickening or forming a film. The polymer to be used is not particularly limited, but it is essential that the curability is not adversely affected. Examples of such polymers include polyimide, polyamide, bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A / bisphenol F copolymer type phenoxy resin, and other general-purpose phenoxy resins, polymethacrylates, polyacrylates, and polyimides. Polyurethanes, polyesters, polyvinyl butyral, SBS and its epoxy modified products, SEBS and its modified products, and the like can be used. These can be used alone or in admixture of two or more. Furthermore, these polymers may contain siloxane bonds and fluorine substituents. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy. The molecular weight is not particularly limited, but a general weight average molecular weight is preferably from 5,000 to 150,000, particularly preferably from 10,000 to 80,000. If this value is less than 5,000, the film formability tends to be inferior, and if it exceeds 150,000, the compatibility with other components tends to deteriorate. The amount used is preferably 20 to 320 parts by weight with respect to 100 parts by weight of the epoxy resin or isocyanate resin.
[0033]
The curable composition of the present invention can be used in the form of a paste when it is liquid at normal temperature (25 ° C.). In the case of a solid at room temperature, it may be heated and used, or may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the curability and exhibits sufficient solubility, but a solvent having a boiling point of 50 to 150 ° C. at normal pressure is preferable. When the boiling point is 50 ° C. or lower, there is a risk of volatilization if left at room temperature, which restricts use in an open system. If the boiling point is 150 ° C. or higher, it may be difficult to remove the solvent.
[0034]
The curable composition of the present invention can also be used in the form of a film. A solution prepared by adding a solvent or the like to the curable composition as necessary is applied to a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or a substrate such as a nonwoven fabric is impregnated with the solution. Can be used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.
[0035]
The curable composition of the present invention can be cured only by light irradiation, or simultaneously with light irradiation and heating, or by heating after light irradiation. The light irradiation is preferably an irradiation light in a wavelength range of 150 to 750 nm, and 0.1 to 100 J / cm using a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or a metal halide lamp.2It can be cured with a dose of. The heating temperature is not particularly limited as long as it is below the decomposition point of the epoxy resin to be used and the compound having a functional group reactive with the epoxy resin, but a temperature of 30 to 200 ° C is preferable, and 50 to 170 ° C is more preferable. preferable. The heating time is 1 second to 3 hours, preferably 30 seconds to 1 hour, in order to sufficiently perform curing.
[0036]
The curable composition of the present invention includes a variety of paints, adhesives, inks, photoresists, coating materials, various automobile parts, electrical / electronic materials, semiconductor materials, optical materials, optical fibers, optical fiber adhesives, optical waveguide materials, and the like. It can be applied to various uses.
Especially for adhesives, in addition to adhesion of wood, building materials, plastics, leather, etc., anisotropic conductive adhesives, circuit pastes such as silver paste and silver film, semiconductor elements such as flip chips, and printed wiring boards It can be used as a semiconductor element adhesive material such as an anisotropic conductive material for flip chip that is connected to.
[0037]
【Example】
Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
[0038]
Example 1 Synthesis of imidazolium salt 1
A solution of 1-benzyl-2-methylimidazole (1.73 g, 10.5 mmol) dissolved in acetone (20 g) in which phenacyl bromide (2.00 g, 10.5 mmol) was dissolved. Was added slowly, followed by stirring at room temperature (25 ° C.) for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain imidazolium bromide salt 1 (yield 3.54 g).
The above-mentioned imidazole bromide salt 1 (2.00 g, 5.4 mmol) was dissolved in a methanol / water (15 g / 15 g) solution, and sodium tetraphenylborate (1.84 g) dissolved in water (5.0 g). 5.4 mmol) was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This precipitate was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired imidazolium tetraphenylborate (imidazolium salt 1) (yield 2.86 g).
Of this compound11 H-NMR is shown in FIG. Moreover, when the melting point and thermal decomposition start temperature in an oxygen atmosphere were measured by TG-DTA, the melting point was 187 ° C. and the decomposition start temperature was 224 ° C.
[0039]
Example 2 Synthesis of
p-Nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g) and 1,2-dimethylimidazole (0.79 g, 8.2 mmol) dissolved in acetone (5 g) was dissolved therein. The solution was slowly added, and then stirred at room temperature for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain imidazolium bromide salt 2 (yield 2.62 g).
The above-mentioned imidazole bromide salt 2 (2.00 g, 5.8 mmol) was dissolved in a methanol / water (15 g / 15 g) solution, and this was dissolved in water (5.0 g) and sodium tetraphenylborate (2. A solution of 01 g, 5.8 mmol) was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired imidazolium tetraphenylborate (imidazolium salt 2) (yield 2.83 g).
Of this compound1H-NMR is shown in FIG. Moreover, when the melting point and thermal decomposition start temperature in an oxygen atmosphere were measured by TG-DTA, the melting point was 165 ° C. and the decomposition start temperature was 195 ° C.
[0040]
(Example 3)
DER736 (trade name, epoxy equivalent 172, manufactured by Dow Chemical Co., Ltd.): 1.00 g as an epoxy resin, pentaerythritol tetra (mercaptoacetate) as a mercapto compound (manufactured by Tokyo Chemical Industry Co., Ltd., SH group equivalent 108): 0.614 g, The imidazolium salt 1: 0.016 g of Example 1 was mixed at room temperature to obtain a uniform solution. This was sampled to 3 mg in a DSC sample pan, irradiated with light, and then DSC was measured.
The light irradiation was performed by Fusion UV irradiation device AEL 1B / M (365 nm illuminance: 21.5 mW / cm).2), 3J / cm2Irradiated.
[0041]
Example 4
DSC measurement was performed in the same manner as in Example 3 except that the imidazolium salt compound was replaced with the
[0042]
(Comparative Example 1)
DSC measurement was performed in the same manner as in Example 3 except that no light irradiation was performed.
[0043]
(Comparative Example 2)
DSC measurement was performed in the same manner as in Example 4 except that light irradiation was not performed.
[0044]
The results of Examples 3 and 4 and Comparative Examples 1 and 2 are shown in Table 1. In addition, the reaction start temperature in a table | surface was taken as Onset temperature which shows heat generation start temperature.
[0045]
The curable compositions of Examples 3 and 4 show that the curing reaction proceeds at a low temperature of 30 ° C. or more as compared with Comparative Examples 1 and 2, and the imidazolium salt compound generates a basic compound by light irradiation. This shows that low-temperature curing has become possible.
[0046]
[Table 1]
Example 5 Synthesis of imidazolium salt 3
A solution of 1-benzyl-2-methylimidazole (1.73 g, 10.5 mmol) dissolved in acetone (20 g) in which phenacyl bromide (2.00 g, 10.5 mmol) was dissolved. Was added slowly, followed by stirring at room temperature for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain imidazolium bromide salt 3 (yield 3.54 g).
The above-mentioned imidazole bromide salt 3 (2.00 g, 5.4 mmol) was dissolved in ethanol (50 g) and dithiocarbamic acid sodium salt dihydrate (1.33 g, 5 g) dissolved in ethanol (20 g). .4 mmol) solution was added slowly. After the addition, the mixture was reacted for 20 minutes under reflux, and when the solvent was distilled off, a yellow powder was precipitated. This was recrystallized three times with ethanol (20 g) to obtain the desired imidazolium dithiocarbamate salt (imidazolium salt 3) (yield 1.80 g).
Of this compound1H-NMR is shown in FIG. Moreover, when the melting point and thermal decomposition start temperature in an oxygen atmosphere were measured by TG-DTA, the melting point was 181 ° C. and the decomposition start temperature was 168 ° C.
[0048]
(Example 6)
0.14 g of imidazolium salt 3 obtained in Example 5 and 1.00 g of polyglycidyl methacrylate (Mn: 138,000, Mw / Mn: 1.49) were weighed and cyclohexanone / acetonitrile: 5 / It was dissolved in 21.7 g of a mixed solvent adjusted to be 2. The solution was spin-coated on a silicon wafer to a film thickness of 1 μm, and then UV irradiation was performed on the entire surface using a high-pressure mercury lamp. Then, it was immersed in THF at room temperature for 3 minutes, and the remaining film thickness on the silicon wafer was measured.
[0049]
The results of Example 6 are shown in Table 2. The remaining film ratio in the table was film thickness after development × 100 / film thickness after spin coating (1 μm).
[0050]
Since the residual film ratio increased with the increase in the UV irradiation amount, it was shown that the imidazolium salt 3 generated a base by UV irradiation and promoted the crosslinking of polyglycidyl methacrylate.
[0051]
[Table 2]
Example 7 Synthesis of
Phenacyl bromide (2.00 g, 10.5 mmol) was dissolved in acetone (20 g), and a solution of 1-methylimidazole (0.82 g, 10.5 mmol) dissolved in acetone (5 g) was slowly added thereto. Thereafter, the mixture was stirred at room temperature for 2 hours, and white crystals were precipitated. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain imidazolium bromide salt 4 (yield 2.76 g).
The imidazole bromide salt 4 (2.76 g, 9.8 mmol) was dissolved in ethanol (20 g), and sodium thiocyanate (0.88 g, 9.9 mmol) was slowly added thereto. After the addition, the mixture was reacted at room temperature for 60 minutes, and when the solvent was distilled off, a white powder was precipitated. This was recrystallized three times with ethanol (20 g) to obtain the desired imidazolium thiocyanate salt (imidazolium salt 4) (yield 1.71 g).
Of this compound1H-NMR is shown in FIG. Further, the melting point under an oxygen atmosphere was measured and found to be 74-76 ° C.
[0053]
(Example 8)
0.13 g of
[0054]
The results of Example 8 are shown in Table 3. The remaining film ratio in the table was film thickness after development × 100 / film thickness after spin coating (1 μm).
[0055]
[Table 3]
Since the remaining film rate increases with the increase in UV irradiation amount, the
[0057]
Example 9
As an epoxy resin, 50 g of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name Epicoat 828, epoxy equivalent 184) is dissolved in methyl ethyl ketone in a weight ratio to obtain a solution having a solid content of 40% by weight. It was. As the polythiol, 13.5 g of pentaerythritol (SH equivalent 50) was used. As an imidazolium salt, 2.0 g of the
[0058]
As a phenoxy resin, 50 g of bisphenol A, F copolymerization type phenoxy resin (average molecular weight 20,000) is prepared by a general method from bisphenol A, bisphenol F (1/1) and epichlorohydrin, and this is weight ratio. Was dissolved in methyl ethyl ketone to obtain a 40% by weight solid solution, which was used. As the conductive particles, a nickel layer having a thickness of 0.2 μm is provided on the surface of a particle having polystyrene as a core, and a metal having a thickness of 0.02 μm is provided outside the nickel layer, and an average particle size of 10 μm and a specific gravity of 2.0. The conductive particles were prepared and used.
[0059]
In a solution containing the above components except for the conductive particles (50 g of epoxy resin, 13.5 g of polythiol, 2.0 g of
[0060]
Using the film-like adhesive obtained by the above manufacturing method, a flexible circuit board (FPC) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm and a thin layer of 0.2 μm of indium oxide (ITO) The formed glass (thickness 1.1 mm, surface resistance 20Ω / □) was heated and pressurized at 170 ° C. and 4 MPa for 60 seconds to be connected over a width of 2 mm. At this time, the adhesive surface of the film-like circuit connecting material is preliminarily connected to the ITO glass by heating and pressurizing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is peeled off to form the circuit connecting composition. Using an ultraviolet irradiation device (USHIO INC.) Having a high-pressure mercury lamp on the film surface, 3.0 J / cm2The ultraviolet rays were irradiated. Then, it connected with FPC which is another to-be-adhered body, and obtained the connection body.
When the resistance value between adjacent circuits of this connection body was measured, the average of 150 resistances between adjacent circuits (x + 3σ; σ is a standard deviation) was 2.7Ω, indicating a good connection characteristic.
[0061]
Moreover, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength. The connection strength of the connected body as described above was 600 N / m, indicating a sufficient adhesion strength.
[0062]
(Example 10)
As the isocyanate resin, 0.672 g of hexamethylene diisocyanate (manufactured by Kanto Chemical Co., Ltd.), 1.00 g of polytetrahydrofuran (trade name: polytetrahydrofuran 250, manufactured by BASF Japan Ltd.) as the resin having a hydroxyl group, and the imidazolium salt 1 of Example 1 were used. A uniform varnish consisting of 0.016 g was prepared. This was sampled to 3 mg in a DSC sample pan, and DSC was measured while irradiating with light for 10 minutes (temperature was constant at 40 ° C.). For light irradiation, a spot cure manufactured by Ushio Electric Co., Ltd. was used (365 nm, 53 mW / cm2). As a result, heat generation due to the reaction between 92.4 J / g isocyanate and the compound having a hydroxyl group was obtained, and it was confirmed that the reaction occurred by light irradiation.
[0063]
According to the present invention, two functional groups having reactivity with (a) an epoxy resin and an imidazolium salt compound, (b) an epoxy resin, an imidazolium salt compound, and an epoxy resin are formed in the molecule at a low temperature by light irradiation. Provided is a curable composition capable of low-temperature curing of a compound having two or more, (c) a compound having two or more isocyanate groups in the molecule, an imidazolium salt compound, or a compound having two or more hydroxyl groups in the molecule can do.
[Brief description of the drawings]
FIG. 1 of imidazolium salt 11H-NMR spectrum (solvent: CD3CN, reference material: TMS, * in the figure is an impurity)
[Fig. 2] Imidazolium salt 21H-NMR spectrum (solvent: CD3CN, reference material: TMS, * in the figure is an impurity)
[Fig. 3] Imidazolium salt 31H-NMR spectrum (solvent: CDCl3Standard substance: TMS, * in the figure is an impurity)
FIG. 4: Imidazolium salt 41H-NMR spectrum (solvent: D2O)
Claims (4)
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| KR100641358B1 (en) | 2004-09-23 | 2006-11-01 | 삼성전자주식회사 | method of fabricating ink-jet print head using photocurable resin composition |
| EP2000299A4 (en) | 2006-03-24 | 2009-08-05 | Konica Minolta Med & Graphic | Transparent barrier sheet and method for producing transparent barrier sheet |
| JP5356828B2 (en) | 2006-12-14 | 2013-12-04 | 旭化成ケミカルズ株式会社 | Photobase generator and photocurable resin composition |
| WO2008152005A1 (en) * | 2007-06-12 | 2008-12-18 | Basf Se | Catalyst for curing epoxides |
| WO2009123122A1 (en) | 2008-03-31 | 2009-10-08 | 大日本印刷株式会社 | Base-generating agent, photosensitive resin composition, pattern-forming material comprising the photosensitive resin composition, pattern formation method using the photosensitive resin composition, and article |
| WO2010064631A1 (en) | 2008-12-02 | 2010-06-10 | 和光純薬工業株式会社 | Photobase generator |
| WO2010113813A1 (en) | 2009-03-31 | 2010-10-07 | 大日本印刷株式会社 | Base-generating agent, photosensitive resin composition, patterning material comprising the photosensitive resin composition, patterning method and article using the photosensitive resin composition |
| JP2012025710A (en) * | 2010-07-27 | 2012-02-09 | Wako Pure Chem Ind Ltd | Photobase generator |
| KR101958343B1 (en) * | 2011-12-16 | 2019-03-15 | 쓰리본드 화인 케미칼 가부시키가이샤 | Curable resin composition |
| JP5912946B2 (en) * | 2012-01-11 | 2016-04-27 | 株式会社Adeka | Photosensitive resin composition |
| JP5949123B2 (en) * | 2012-05-11 | 2016-07-06 | 住友化学株式会社 | Polarizer |
| JP5997041B2 (en) * | 2012-12-26 | 2016-09-21 | 東京応化工業株式会社 | Photosensitive resin composition |
| US10100070B2 (en) | 2014-01-24 | 2018-10-16 | Fujifilm Wako Pure Chemical Corporation | Borate-based base generator, and base-reactive composition comprising such base generator |
| JP7277226B2 (en) * | 2018-04-16 | 2023-05-18 | 株式会社Adeka | Compound, polymerization initiator, polymerizable resin composition and photosensitive resin composition |
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2002
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