JP2015143290A - Photocationic-curable resin composition - Google Patents
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本発明は，紫外線を照射することにより硬化する光カチオン硬化型樹脂組成物に関し、特には増感剤無しで且つ少量の重合開始剤により、さらには少ない照射線量にて、十分な硬化反応を行わせることができる光カチオン硬化型樹脂組成物に関する。 The present invention relates to a photocationically curable resin composition that is cured by irradiating ultraviolet rays, and in particular, a sufficient curing reaction is carried out with a small amount of polymerization initiator without a sensitizer and with a small amount of irradiation. The present invention relates to a photocationically curable resin composition that can be applied.
従来、光に暴露されて硬化可能な光カチオン硬化型接着剤及び加熱されて硬化可能な熱カチオン硬化型接着剤として、脂肪族エポキシと、脂環式エポキシ及び／又はオキセタンと、光重合開始剤とを含む光カチオン硬化型接着剤、並びに脂肪族エポキシと、脂環式エポキシ及び／又はオキセタンと、熱重合開始剤とを含む熱カチオン硬化型接着剤が提案されている（特許文献１）。 Conventionally, as a photocation curable adhesive that can be cured by exposure to light and a heat cation curable adhesive that can be cured by heating, aliphatic epoxy, alicyclic epoxy and / or oxetane, and photopolymerization initiator And a photocationic curable adhesive, and a thermal cation curable adhesive containing an aliphatic epoxy, an alicyclic epoxy and / or oxetane, and a thermal polymerization initiator have been proposed (Patent Document 1).
しかしながら、特許文献１に示されるカチオン硬化型樹脂組成物は、高価な光増感剤を必要とし、且つ重合開始剤の配合量も比較的多く、さらには硬化には３６５ｎｍの紫外線で積算光量１５００〜３０００ｍＪ／ｃｍ２を必要とし、さらには室温で一晩または４０〜１００℃で１〜１０分間熱養生する等の後養生を行なって確実に硬化させる必要があるという課題があった。 However, the cationic curable resin composition disclosed in Patent Document 1 requires an expensive photosensitizer and has a relatively large amount of polymerization initiator. Further, the cured product has an integrated light quantity of 1500 nm with ultraviolet light of 365 nm. There is a problem in that it requires ˜3000 mJ / cm 2 , and further it needs to be cured by post-curing such as heat curing at room temperature overnight or at 40-100 ° C. for 1-10 minutes.
本発明が解決しようとする課題は、光増感剤を不要とし、高価な重合開始剤の配合量が少なく、また硬化に必要とする紫外線の積算光量が少なく、さらには紫外線を照射した後に室温や熱養生を行なう必要のない光カチオン硬化型樹脂組成物を提供することにある。 The problem to be solved by the present invention is that a photosensitizer is not required, the amount of an expensive polymerization initiator is small, the cumulative amount of ultraviolet light necessary for curing is small, and further, room temperature after irradiation with ultraviolet light. Another object of the present invention is to provide a photocationically curable resin composition that does not require heat curing.
請求項１記載の発明は、脂環構造の両側にグリシジルエーテル基を有するジグリシジルエーテル化合物と、スルホニウム系光重合開始剤とを含むことを特徴とする光カチオン硬化型樹脂組成物である。 The invention according to claim 1 is a photocationically curable resin composition comprising a diglycidyl ether compound having a glycidyl ether group on both sides of an alicyclic structure, and a sulfonium photopolymerization initiator.
請求項２記載の発明は、スルホニウム系光重合開始剤は脂環構造の両側にグリシジルエーテル基を有するジグリシジルエーテル化合物１００重量部に対し０．５〜１０重量部であることを特徴とする請求項１記載の光カチオン硬化型樹脂組成物である。 The invention according to claim 2 is characterized in that the sulfonium-based photopolymerization initiator is 0.5 to 10 parts by weight with respect to 100 parts by weight of the diglycidyl ether compound having glycidyl ether groups on both sides of the alicyclic structure. Item 2. A photocationically curable resin composition according to Item 1.
請求項３記載の発明は、さらにシランカップリング剤を含むことを特徴とする請求項１または請求項２記載の光カチオン硬化型樹脂組成物である。 The invention according to claim 3 is the photocationically curable resin composition according to claim 1 or 2, further comprising a silane coupling agent.
請求項４記載の発明は、シランカップリング剤がエポキシシランであることを特徴とする請求項３記載の光カチオン硬化型樹脂組成物である。 The invention according to claim 4 is the photocationically curable resin composition according to claim 3, wherein the silane coupling agent is epoxy silane.
本発明に係る光カチオン硬化型樹脂組成物は、光増感剤を使用せずとも紫外線を照射するだけで十分に実用に供する程に硬化するという効果がある。また、一般的に高価な重合開始剤の硬化に必要な配合量は少量でよいという効果がある。さらには硬化に必要とする紫外線の積算光量が従来より少量で良く、また紫外線を照射した後に室温や熱養生を行なう必要がないという効果がある。 The photocationically curable resin composition according to the present invention has an effect that it is cured to such a degree that it can be sufficiently put into practical use by irradiating ultraviolet rays without using a photosensitizer. Further, there is an effect that a small amount is generally required for curing an expensive polymerization initiator. Further, the cumulative amount of ultraviolet light necessary for curing may be smaller than in the past, and there is an effect that it is not necessary to perform room temperature or heat curing after irradiation with ultraviolet light.
以下本発明について詳細に説明する。 The present invention will be described in detail below.
本発明の光カチオン硬化型樹脂組成物は、脂環構造の両側にグリシジルエーテル基を有するジグリシジルエーテル化合物と、スルホニウム系光重合開始剤とを含むことを特徴とする光カチオン硬化型樹脂組成物であり、必要により、消泡剤、レベリング剤、チクソ付与剤、希釈剤、接着付与剤、難燃剤等が配合される。 The photocationically curable resin composition of the present invention comprises a diglycidyl ether compound having a glycidyl ether group on both sides of an alicyclic structure, and a sulfonium-based photopolymerization initiator. If necessary, an antifoaming agent, a leveling agent, a thixotropic agent, a diluent, an adhesion-imparting agent, a flame retardant, and the like are blended.
脂環構造の両側にグリシジルエーテル基を有するジグリシジルエーテル化合物
本発明に使用される脂環構造の両側にグリシジルエーテル基を有するジグリシジルエーテル化合物は、脂環構造の両側にグリシジルエーテル基を有するエポキシ樹脂であって、例えば水素化ビスフェノールＡエポキシ樹脂や、水素化ビスフェノールＦエポキシ樹脂、ジシクロペンタジエンジメタノールとエピクロルヒドリンを反応させたジシクロペンタジエン型エポキシ樹脂、シクロヘキサンジメタノールとエピクロルヒドリンを反応させたシクロヘキサン型エポキシ樹脂等、より成るジグリシジルエーテル化合物を使用することが出来る。特に分子量は、１００〜２０００程度、より好ましくは２００〜１０００のものが適している。分子量が１００未満では、揮発しやすい状態となり、分子量が２０００超ではハンドリング困難となる。分子量が２００未満ではアウトガス発生の傾向があり、分子量が１０００超ではハンドリング困難の傾向がある。
Diglycidyl ether compounds having glycidyl ether groups on both sides of the alicyclic structure
The diglycidyl ether compound having glycidyl ether groups on both sides of the alicyclic structure used in the present invention is an epoxy resin having glycidyl ether groups on both sides of the alicyclic structure, such as hydrogenated bisphenol A epoxy resin, hydrogen Diglycidyl ether compounds comprising bisphenol F epoxy resin, dicyclopentadiene type epoxy resin obtained by reacting dicyclopentadiene dimethanol and epichlorohydrin, cyclohexane type epoxy resin obtained by reacting cyclohexanedimethanol and epichlorohydrin, etc. I can do it. In particular, a molecular weight of about 100 to 2000, more preferably 200 to 1000 is suitable. If the molecular weight is less than 100, it tends to volatilize, and if the molecular weight exceeds 2000, handling becomes difficult. If the molecular weight is less than 200, outgassing tends to occur, and if the molecular weight exceeds 1000, handling tends to be difficult.
スルホニウム系光重合開始剤
本発明に使用されるスルホニウム系光重合開始剤は、例えば、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、４,４´−ビス（ジフェニルスルホニオ）ジフェニルスルフィドビスヘキサフルオロホスフェート、４，４´−ビス[ジ（β−ヒドロキシエトキシ）フェニルスルホニオ]ジフェニルスルフィドビスヘキサフルオロアンチモネート、４，４´−ビス[（ジ（β−ヒドロキシエトキシ）フェニルスルホニオ]ジフェニルスルフィドビスヘキサフルオロホスフェート、７−[ジ（ｐ−トルイル）スルホニオ]−２−イソプロピルチオキサントンヘキサフルオロアンチモネート、７−[（ジ（ｐ−トルイル）スルホニオ]−２−イソプロピルチオキサントンテトラキス（ペンタフルオロフェニル）ボレート、４−フェニルカルボニル−４´−ジフェニルスルホニオ−ジフェニルスルフィドハキサフルオロホスフェート、などを使用することが出来る。
Sulfonium photopolymerization initiator The sulfonium photopolymerization initiator used in the present invention is, for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4, 4′-bis (diphenylsulfonio) diphenylsulfide bishexafluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide bishexafluoroantimonate, 4,4′-bis [( Di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate , 7-[(di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide haxafluorophosphate, etc. I can do it.
スルホニウム系光重合開始剤は、上記脂環構造の両側にグリシジルエーテル基を有するジグリシジルエーテル化合物１００重量部に対して、０．５〜１０重量部が好ましく、より好ましくは１〜８重量部である。０．５重量部未満では硬化不足となり、１０重量部超では溶解しにくくなる。１重量部未満では硬化不足となる傾向があり、８重量部超では溶解しにくい傾向がある。市販スルホニウム系光重合開始剤としては、ＣＰＩ−２１０Ｓ（商品名、サンアプロ社製、化学名：ジフェニル（４−（フェニルチオ）フェニル）スルホニウムトリフェルオロトリスペンタフルオロエチルホスファート）、Ｉｒｇａｃｕｒｅ ＰＡＧ−２７０（商品名、ＢＡＳＦ社製、化学名：トリアリールスルフォニウムヘキサフルオロフォスフィン）などがある。 The sulfonium-based photopolymerization initiator is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight with respect to 100 parts by weight of the diglycidyl ether compound having glycidyl ether groups on both sides of the alicyclic structure. is there. If it is less than 0.5 part by weight, curing is insufficient, and if it exceeds 10 parts by weight, it is difficult to dissolve. If it is less than 1 part by weight, it tends to be insufficiently cured, and if it exceeds 8 parts by weight, it tends to be difficult to dissolve. Commercially available sulfonium photopolymerization initiators include CPI-210S (trade name, manufactured by San Apro, chemical name: diphenyl (4- (phenylthio) phenyl) sulfonium triferrotrispentafluoroethyl phosphate), Irgacure PAG-270 ( Trade name, manufactured by BASF, chemical name: triarylsulfonium hexafluorophosphine).
本発明には特に接着付与剤としてシランカップリング剤を使用することができ、シランカップリング剤はエポキシシランが好ましい。エポキシシランとしては、β―（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ―グリシドキシプロピルトリメトキシシラン、γ―グリシドキシプロピルメチルジメトキシシラン、γ―グリシドキシプロピルメチルジエトキシシラン等を使用することができる。エポキシシランの配合量は、上記脂環構造の両側にグリシジルエーテル基を有するジグリシジルエーテル化合物１００重量部に対して、０．１〜１０重量部が好ましく、より好ましくは０．５〜８重量部である。０．１重量部未満では接着性が不十分となり、１０重量部超では硬化性低下となる。０．５重量部未満では接着性不十分となる傾向があり、８重量部超では硬化性低下となる傾向がある。市販のエポキシシランとしては、ＳＩＬＱＵＥＳＴ Ａ‐１８７（Ｍｏｍｅｎｔｉｖｅ社製、化学名：γ―グリシドキシプロピルトリメトキシシラン）、ＤＹＮＡＳＩＬＡＮＥ ＧＬＹＭＯ（ＥＶＯＮＩＣ社製、化学名：γ―グリシドキシプロピルトリメトキシシラン）などがある。 In the present invention, a silane coupling agent can be used as an adhesion-imparting agent, and epoxy silane is preferable as the silane coupling agent. Epoxy silanes include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Etc. can be used. The compounding amount of the epoxy silane is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the diglycidyl ether compound having glycidyl ether groups on both sides of the alicyclic structure. It is. If it is less than 0.1 part by weight, the adhesiveness is insufficient, and if it exceeds 10 parts by weight, the curability is lowered. If it is less than 0.5 part by weight, the adhesiveness tends to be insufficient, and if it exceeds 8 parts by weight, the curability tends to be lowered. As commercially available epoxy silanes, SILQUEST A-187 (manufactured by Momentive, chemical name: γ-glycidoxypropyltrimethoxysilane), DYNASILANE GLYMO (manufactured by EVONIC, chemical name: γ-glycidoxypropyltrimethoxysilane) and so on.
以下，実施例及び比較例にて本出願に係る光カチオン硬化型樹脂組成物について具体的に説明する。 Hereinafter, the photocation curable resin composition according to the present application will be specifically described with reference to Examples and Comparative Examples.
実施例１乃至実施例３
脂環構造の両側にグリシジルエーテル基を有するグリシジルエーテル化合物として、シクロヘキサンジメタノールとエピクロルヒドリンを反応させたシクロヘキサン型エポキシ樹脂であるＥＸ−２１６Ｌ（商品名、分子量；３００、ナガセケミテックス社製）、ジシクロペンタジエンジメタノールとエピクロルヒドリンを反応させたジシクロペンタジエン型エポキシ樹脂であるＥＰ−４０８８Ｓ（商品名、分子量；３４０、ＡＤＥＫＡ社製）、水素化ビスフェノールＡエポキシ樹脂であるＹＸ−８０００（商品名、分子量；４１０（代表値）、三菱化学社製）を使用し、スルホニウム系光重合開始剤としてＣＰＩ−２１０Ｓ（商品名、サンアプロ社製）を使用し、接着性付与剤としてＤＹＮＡＳＩＬＡＮＥ ＧＬＹＭＯ（ＥＶＯＮＩＣ社製）を使用し、表１に示す配合にて十分に攪拌し、混合溶解して実施例１乃至実施例３の光カチオン硬化型樹脂組成物を得た。
Example 1 to Example 3
As a glycidyl ether compound having a glycidyl ether group on both sides of the alicyclic structure, EX-216L (trade name, molecular weight; 300, manufactured by Nagase ChemteX), which is a cyclohexane type epoxy resin obtained by reacting cyclohexanedimethanol and epichlorohydrin, di EP-4088S (trade name, molecular weight; 340, manufactured by ADEKA), a dicyclopentadiene type epoxy resin obtained by reacting cyclopentadiene dimethanol and epichlorohydrin, YX-8000 (trade name, molecular weight), a hydrogenated bisphenol A epoxy resin. 410 (typical value, manufactured by Mitsubishi Chemical Corporation), CPI-210S (trade name, manufactured by San Apro) as a sulfonium photopolymerization initiator, and DYNASILANE GLYMO (manufactured by EVONIC) as an adhesion promoter. The The photocationic curable resin compositions of Examples 1 to 3 were obtained by stirring and mixing sufficiently with the formulation shown in Table 1, and mixing and dissolving.
比較例１乃至比較例７
ビスフェノールＡ型エポキシ樹脂としてＥＰ−８２８（商品名、三菱化学社製）を、ビスフェノールＦ型エポキシ樹脂としてＥＰ−８０７（商品名、三菱化学社製）を、フェノールノボラック型エポキシ樹脂としてＮ−７３０Ａ（商品名、ＤＩＣ社製）を、脂環式エポキシ樹脂としてセロキサイド２０２１Ｐ（商品名、ダイセル社製）を、ビフェニル型オキセタンとしてＥＴＥＲＮＡＣＯＬＬ ＯＸＢＰ（商品名、宇部興産社製）を、キシリレンビスオキセタンとしてアロンオキセタンＯＸＴ−１２１（商品名、東亞合成社製）を、脂肪族エポキシ樹脂（ポリエーテルエポキシ樹脂）としてＹＬ−７４１０（商品名、三菱化学社製）を使用し、接着付与剤とスルホニウム系光重合開始剤は実施例と同じにし、また該スルホニウム系光重合開始剤の他にヨードニウム塩系光重合開始剤としてＩｒｇａｃｕｒｅ ２５０（商品名、ＢＡＳＦ社製）を使用し、さらには光増感剤としてカヤキュアＤＥＴＸ−Ｓ（商品名、日本化薬社製）を使用して、表１に示す配合にて十分に攪拌し混合溶解して、比較例１乃至比較例７の光カチオン硬化型樹脂組成物を得た。
Comparative Examples 1 to 7
EP-828 (trade name, manufactured by Mitsubishi Chemical Corporation) as a bisphenol A type epoxy resin, EP-807 (trade name, manufactured by Mitsubishi Chemical Corporation) as a bisphenol F type epoxy resin, and N-730A (trade name, manufactured by Mitsubishi Chemical Corporation) (Trade name, manufactured by DIC Corporation), Celoxide 2021P (trade name, manufactured by Daicel Corp.) as an alicyclic epoxy resin, ETERNACOLL OXBP (trade name, manufactured by Ube Industries) as biphenyl type oxetane, and Aaron as xylylene bis oxetane Using Oxetane OXT-121 (trade name, manufactured by Toagosei Co., Ltd.) and YL-7410 (trade name, manufactured by Mitsubishi Chemical Corporation) as an aliphatic epoxy resin (polyether epoxy resin), an adhesion promoter and a sulfonium-based photopolymerization The initiator is the same as in the examples, and the sulfonium photopolymerization initiator In addition, Irgacure 250 (trade name, manufactured by BASF) is used as an iodonium salt photopolymerization initiator, and Kayacure DETX-S (trade name, manufactured by Nippon Kayaku Co., Ltd.) is used as a photosensitizer. The composition shown in Table 1 was sufficiently stirred, mixed and dissolved to obtain the photocationically curable resin compositions of Comparative Examples 1 to 7.
評価項目及び評価方法Evaluation items and evaluation methods
反応率
実施例１乃至実施例３又は比較例１乃至比較例９の光カチオン硬化型樹脂組成物を離型紙上に厚み１００μｍ程度に塗布し、浜松ホトニクス社製スポット光源ＬＣ８ ＬＩＧＨＴＣＵＲＥ Ｌ９５６６（紫外線照射強度：４５００ｍＷ／ｃｍ２：３６５ｎｍ）にて、１００ｍＷ、１０秒（３６５ｎｍ、積算光量１０００ｍＪ／ｃｍ２）を照射する。未照射のものと、照射して硬化した硬化物についてフーリエ変換赤外分光光度計 ＦＴＩＲ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）にて、赤外吸収スペクトルを取得し、メチレン鎖とエポキシ基のピーク強度比を比較して反応率を算出した。
Reaction rate The photocationically curable resin compositions of Examples 1 to 3 or Comparative Examples 1 to 9 were applied to a release paper to a thickness of about 100 μm, and spot light source LC8 LIGHTCURE L9566 (ultraviolet irradiation intensity) manufactured by Hamamatsu Photonics Co., Ltd. : 4500 mW / cm 2 : 365 nm), 100 mW for 10 seconds (365 nm, integrated light quantity 1000 mJ / cm 2 ) is irradiated. Infrared absorption spectra are obtained for unirradiated and cured products cured by irradiation using a Fourier transform infrared spectrophotometer FTIR (manufactured by Perkin Elmer), and the peak intensity ratios of methylene chains and epoxy groups are compared. The reaction rate was calculated.
初期せん断強度
６０ｍｍ×２０ｍｍ×２ｍｍ厚みの青板ガラスの長手方向の端部から２５ｍｍに実施例１乃至実施例３又は比較例１乃至比較例９の光カチオン硬化型樹脂組成物をそれぞれ１００μｍ厚みに塗布する。塗布後直ちに同形状の青板ガラスを長手方向の端部２５ｍｍのみがオーバーラップするように貼り付け、全体として９５ｍｍ×２０ｍｍの試験片を作成する。該試験片の光カチオン硬化型樹脂組成物を塗布した部分に、浜松ホトニクス社製スポット光源ＬＣ８ ＬＩＧＨＴＣＵＲＥ Ｌ９５６６（紫外線照射強度：４５００ｍＷ／ｃｍ２：３６５ｎｍ）にて、１００ｍＷ、１０秒（３６５ｎｍ、積算光量１０００ｍＪ／ｃｍ２）を照射し、光カチオン硬化型樹脂組成物を硬化させる。その後、２３℃下にて引張試験機ＴＧＩ−１ｋＮ（ミネベア社製）にて試験片を長手方向に５ｍｍ／分で引張り、せん断強度（ＭＰａ）を測定し、初期せん断強度とした。
The photocationic curable resin composition of Example 1 to Example 3 or Comparative Example 1 to Comparative Example 9 was applied to a thickness of 100 μm to 25 mm from the end in the longitudinal direction of blue glass having an initial shear strength of 60 mm × 20 mm × 2 mm. To do. Immediately after application, the same shape of blue plate glass is pasted so that only the end portion 25 mm in the longitudinal direction overlaps, and a test piece of 95 mm × 20 mm is created as a whole. 100 mW for 10 seconds (365 nm, integrated light intensity) on a spot light source LC8 LIGHTCURE L9566 (UV irradiation intensity: 4500 mW / cm 2 : 365 nm) manufactured by Hamamatsu Photonics Co., Ltd. 1000 mJ / cm 2 ) is irradiated to cure the photocationically curable resin composition. Thereafter, the test piece was pulled in the longitudinal direction at 5 mm / min with a tensile tester TGI-1kN (manufactured by Minebea) at 23 ° C., and the shear strength (MPa) was measured to obtain the initial shear strength.
加熱後せん断強度
６０ｍｍ×２０ｍｍ×２ｍｍ厚みの青板ガラスの長手方向の端部から２５ｍｍに実施例１乃至実施例３又は比較例１乃至比較例９の光カチオン硬化型樹脂組成物をそれぞれ１００μｍ厚みに塗布する。塗布後直ちに同形状の青板ガラスを長手方向の端部２５ｍｍのみがオーバーラップするように貼り付け、全体として９５ｍｍ×２０ｍｍの試験片を作成する。該試験片の光カチオン硬化型樹脂組成物を塗布した部分に、浜松ホトニクス社製スポット光源ＬＣ８ ＬＩＧＨＴＣＵＲＥ Ｌ９５６６にて（紫外線照射強度：３５００ｍＷ／ｃｍ２：３６５ｎｍ）１００ｍＷ、１０秒（１０００ｍＪ／ｃｍ２）を照射し、光カチオン硬化型樹脂組成物を硬化させる。さらに１００℃のオーブンに１００時間放置する。その後２３℃にて除冷し、引張試験機ＴＧＩ−１ｋＮ（ミネベア社製）にて試験片を長手方向に５ｍｍ／分で引張り、せん断強度（ＭＰａ）を測定し、加熱後せん断強度とした。
After heating, the photocationically curable resin compositions of Example 1 to Example 3 or Comparative Example 1 to Comparative Example 9 are each 100 μm in thickness from 25 mm from the end in the longitudinal direction of a blue sheet glass having a shear strength of 60 mm × 20 mm × 2 mm. Apply. Immediately after application, the same shape of blue plate glass is pasted so that only the end portion 25 mm in the longitudinal direction overlaps, and a test piece of 95 mm × 20 mm is created as a whole. On the portion of the test piece to which the photocationic curable resin composition was applied, spot light source LC8 LIGHTCURE L9566 manufactured by Hamamatsu Photonics Co., Ltd. (UV irradiation intensity: 3500 mW / cm 2 : 365 nm) 100 mW, 10 seconds (1000 mJ / cm 2 ) To cure the photocationically curable resin composition. Further, it is left in an oven at 100 ° C. for 100 hours. Thereafter, the sample was cooled at 23 ° C., the test piece was pulled in the longitudinal direction at 5 mm / min with a tensile tester TGI-1kN (manufactured by Minebea Co., Ltd.), the shear strength (MPa) was measured, and the post-heating shear strength was obtained.
評価結果
評価結果を表２に示す。
Evaluation results The evaluation results are shown in Table 2.
まとめ
実施例１乃至実施例３は１０００ｍＪ／ｃｍ２の積算光量で８３％以上の反応率を有し、光増感剤が無く、重合開始剤の配合量が少量であっても、その後の熱養生が不要であり、且つ初期せん断強度は８．２ＭＰａ以上、加熱後せん断強度は１０．７ＭＰａ以上であり、少ない紫外線照射量（積算光量）であっても十分な硬化を示した。
Summary Examples 1 to 3 have a reaction rate of 83% or more with an integrated light amount of 1000 mJ / cm 2 , no photosensitizer, and a small amount of polymerization initiator, Curing was unnecessary, the initial shear strength was 8.2 MPa or more, the post-heating shear strength was 10.7 MPa or more, and sufficient curing was exhibited even with a small amount of ultraviolet irradiation (integrated light amount).
Claims (4)
4. The photocationically curable resin composition according to claim 3, wherein the silane coupling agent is epoxy silane.
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