JP4601757B2 - Adhesive composition for temporary fixing and method of using the same - Google Patents

Description

【００１６】
但し、Ｒ１、Ｒ２、Ｒ３はＨまたはＣＨ_３、ｎは４〜８の整数；及び
３）ラジカル重合開始剤。
【００１７】
本発明組成物により仮固定されたワークは、水、又はアルコール系、ケトン系、多価アルコール系、窒素化合物系、及び硫黄化合物系水溶性有機溶剤から成る群から選択される少なくとも一種類の水溶性有機溶剤と水とを混合した水溶液から成る剥離液に浸漬することで、欠損を生じることなく速やかに剥離することが可能である。
従って、本発明は、上記仮固定用接着剤組成物、剥離液、並びに該接着剤組成物及び該剥離液を含む仮着剤キットにも関する。
【００１８】
【発明の実施の形態】
本発明に使用される仮固定用接着剤組成物の構成成分について以下に詳しく説明する。
本発明組成物に含まれる少なくとも１種類の親水性ビニルモノマーは、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−ビニルカプロラクタム、アクリロイルモルホリン、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、及びグリセロール（メタ）アクリレートから成る群から選択される。
これらのモノマーは仮固定接着剤に良好な接着性を与えると共に水分に対する親和性を示すことで水または水と上記剥離液に浸漬した時に短時間で水分が浸透する性質を付与し剥離時間の促進に役立つ。
【００１９】
本発明の構造式（Ｉ）で示される少なくとも１種のポリアルキレンオキシドモノ（メタ）アクリレートは、ワークの仮固定時においてはワークに対する適度な密着性を示し、上記剥離液に浸漬した際には水和により速やかに剥離するという性質を有するため、仮固定用接着剤の成分として非常に優れた特性を有している。
ポリアルキレンオキシド連鎖の重合度を表す構造式（Ｉ）中のｎは４〜８であり、ｎがこれを下回ると、本発明の剥離液に浸漬した時に剥離し難くい。またｎが本発明の範囲を上回るとワークとの密着性の低下してワークの固定に欠陥が生じたり、常温で固体状となり本発明の前記親水性ビニルモノマーとの仮固定用接着剤組成物が不均質になり性能低下を招いたり、冬季に結晶状態となって使用困難になる等の欠点が発生する他、仮固定用接着剤組成物の粘度が高くなり精密な固定精度を要するワークの仮固定が困難になる等の問題が発生する。
【００２０】
前記構造式（Ｉ）の化合物の使用量は、該化合物の種類、ワークの種類・大きさ等に応じて当業者が適宜選択することが出来るが、通常、５〜７０重量％が好ましく、10〜60重量％が更に好ましい。
上記の好適な組成範囲で用いることで０．３〜５０ｍｍ程度の大きさの一般的な物品の加工において好適な固定強度と剥離時間を有する仮固定用接着剤が得られる。しかしワークの大きさが大きい場合には更に使用量を増大することも可能であり、逆に長時間の加工を要する場合等においては３〜５重量％等の使用量に減じて加工中の剥離欠陥を低減する等の調節が可能である。しかし本発明の構造式（Ｉ）の化合物を用いないと剥離時間が非常に長くなり生産性が著しく低下するという実用上の問題が発生する。
【００２１】
本発明の仮固定用仮着剤組成物に使用するラジカル重合開始剤としては有機過酸物やアゾビスイソブチロニトリル等の公知の熱重合開始剤や紫外線重合開始剤や可視光重合開始剤を用いる。
熱重合開始剤はベンゾイルパーオキサイド、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロドデカン、t-ブチルパーロイルベンゾエイト、n-ブチル-4,4-ビス(t-ブチルパーロイル)バラレイト、2,5-ジメチル-2,5-ジ(t-ブチルパーロイル)ヘキサン等の有機過酸化物、および2,2’-アゾビスイソブチロニトリル、2-(カルバモイルアゾ)-イソブチロニトリル、2,2’-アゾビス(2,4,4-トリメチルペンタン)等のアゾ化合物が挙げられる。
紫外線重合開始剤としてはベンゾイン、ベンゾインメチルエーテル等のベンゾイン系、ベンゾイル安息香酸、4-フェニルベンゾフェノン等のベンゾフェノン系、1-ヒドロキシシクロヘキシルフェニルケトン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン等のアセトフェノン系等が挙げられる。
【００２２】
また可視光重合開始剤としてはベンジル、キノン類、アシルフォスフィンオキサイド、α-アミノケトン、ビスアシルフォスフィンオキサイド、メタロセン、チオキサントン等が挙げられるが、カンファーキノン、アシルフォスフィンオキサイド、α-アミノケトン、ビスアシルフォスフィンオキサイド、及びメタロセンから成る群から選択することが好ましい。
かかる群に属する化合物の具体例としては、カンファーキノン、2, 4, 6-トリメチルベンゾイルジフェニルホスフィンオキサイド、2-メチル-1[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルフォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、ビス(η^５-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム等が挙げられる。
尚、上記可視光重合開始剤を使用した場合にも、紫外光照射による紫外線重合により仮固定を実施することが可能である。
本発明では前記のラジカル重合開始剤を二種類以上混合して用いても差し支えなく、その合計の使用量は通常0.05〜10重量％の範囲で適宜調整される。
【００２３】
また、本発明の仮固定用接着剤組成物には本発明の効果を損なわない限りにおいて、任意成分として疎水性モノマー、ポリマー、無機フィラー等を添加して粘度や力学特性を調整したり、色素等を添加して着色することも可能である。
疎水性モノマーは接着剤組成物に適度な疎水性を付与して、機械加工時の耐水性を向上し、長時間の加工に耐えるようにするに調整することができる。疎水性モノマーの具体例としては、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニルオキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等の単官能(メタ)アクリレートおよび1,6-ヘキサンジオールジ(メタ)アクリレート、トリエチレングリコールジメタクリレート、ポリエチレングリコール#400ジメタクリレート、ポリエチレングリコール#600ジメタクリレート等の多官能(メタ)アクリレートが挙げられる。
ポリマーは接着剤組成物の粘度を高めて、平面度の悪いワークを基板に固定する際に生じる隙間を充填し易くすることができる。但し、本発明の仮固定用接着剤組成物は少量のポリマーの添加によって粘度を高められるため、水等に浸漬して剥離する際に粘着性物質とならず、剥離時間の遅延などの生産性の低下が生じることがない。本発明に好適に用いられるポリマーの具体的としてはポリビニルピロリドンやポリメチルメタクリレート等が挙げられ、その添加量は通常1〜10重量％の範囲である。
【００２４】
更に本発明は、本発明の仮固定用接着剤組成物を用いて被加工部品を仮固定し、所定の機械加工を行った後に、水、又は水とアルコール系、ケトン系、多価アルコール系、窒素化合物系、及び硫黄化合物系の水溶性有機溶剤から成る群から選択される少なくとも一種類の水溶性有機溶剤を混合した水溶液から成る剥離液に浸漬して剥離することを特徴とする部品の加工方法に係る。
本発明の加工方法において、本発明の仮固定用接着剤組成物を用いて仮固定することの出来る被加工部品の材質に特に制限はない。好適な材質として、透明材料としては、例えば、板ガラス、カラーガラス、光学ガラス、レーザーガラス、ＹＡＧ、水晶、ルビー、サファイア、石英等を挙げることが出来る。又、不透明材料としては、例えば、アルミナ、ジルコニア、フェライト、希土類磁性体、強誘電性セラミクス、シリコンウェーハー、チタン、チタン合金、ステンレス、アルミニウム、鉄、真鍮等が挙げられる。
以下、本発明の加工方法について具体的に説明する。
【００２５】
まず、被加工部品を仮固定する為に、接着固定する一方のワーク又は支持基板上に、接着面積に応じて本発明の仮固定接着剤組成物を適量塗布し、続いてもう一方のワークを重ね合わせるという方法を用いたり、また予め仮固定するワークを多数積層しておき、本発明の仮固定用接着剤組成物を隙間に浸透させて塗布する。
本発明の仮固定用接着剤組成物は、ワックスや松ヤニなどのホットメルト接着剤のように粘性変化を伴う加熱条件下での塗布作業を行う必要が無く、室温の安定した粘度で作業者の必要とする任意の時間で操作出来るため、経験の浅い作業者でも容易に正確な位置合わせができ、位置合わせに伴う火傷等の危険性もない。
また、本発明仮固定用接着剤組成物は低粘度であるため、塗布後の接着剤の厚みが薄くなり、ワークの傾きや厚みムラが極めて小さい、高い固定精度が得られるとともに、多数のワークを積層した場合でも接着剤組成物がワークの隙間に速やかに浸透させることができる。尚、仮固定するワークの表面が粗い場合や平面度が悪い場合で、基板とワーク表面に間隙が生じる様な場合は本発明の仮固定用接着剤組成物に前述のポリマーを少量添加して粘度を高めることで隙間無く充填することも可能である。
【００２６】
次に、従来公知の熱重合、紫外線重合、可視光重合を行い、塗布した本発明の仮固定用接着剤組成物を硬化させることにより、被加工部品を仮固定する。
例えば、セラミックスおよびステンレス、アルミニウム、フェライトなどの金属等の不透明なワークを仮固定する場合はラジカル重合開始剤として熱重合開始剤を添加した接着剤組成物とし、塗布工程を終えた後にワークを加熱すれば良い。その際、通常、40℃〜150℃の温度範囲で５分〜５時間、好ましくは50℃〜120℃の温度範囲で10分〜120分の加熱により熱重合を行うことが出来る。尚、当業者であれば、熱重合開始剤の添加量と種類を調整することで、生産工程に都合の良いように重合温度と重合時間を適宜調節することができる。
【００２７】
これに対して、例えば、光学ガラス、水晶等の透明なワークを仮固定する場合は、紫外線重合または可視光重合で仮固定することができる。
紫外線重合をおこなう場合は、ラジカル重合開始剤として紫外線重合開始剤かまたは可視光重合開始剤を添加した接着剤組成物を使用し、塗布工程を終えたワークに光照射を行うことで固定する。紫外線重合を行う際の光源としては高圧水銀灯、水銀キセノンランプ、メタルハライドランプ、紫外線蛍光ランプ等が用いられる。紫外線照射条件は当業者が適宜決めることが出来るが、360nmにおける放射照度が0.5mW/cm^２以上が好ましく、照射時間は放射照度に応じて1０秒〜３０分程度の範囲で実施するのが好ましい。
【００２８】
可視光重合をおこなう場合は、ラジカル重合開始剤として可視光重合開始剤を添加した接着剤組成物としておき、塗布工程を終えたワークへ可視光を照射する。光源は可視専用蛍光ランプ、ハロゲンランプ等を用いる。可視光照射条件は当業者が適宜決めることが出来るが、420nmにおける放射照度が２mW/cm^２以上で照射時間は10秒〜20分間が好ましい。
特に可視光重合開始剤を配合した仮固定用接着剤組成物を用いると、ケミカルランプなどの紫外線光源を用いたときでも、紫外線重合開始剤を用いた場合よりも短時間の光照射で大きな硬化深度が得られる。
更に可視光光源を用いた可視光照射を行うことで、その効果は更に数倍増大して数十ｍｍに及ぶ硬化深度が容易に得られる為、例えば多数のワークを積層して一度に硬化する場合などにおいてワークの深部まで確実に硬化させることができ確実な固定性や硬化時間の短縮効果等の非常に優れた効果をもたらす。
また可視光重合開始剤を添加して可視光硬化型の接着剤組成物として、可視光光源により可視光重合すると、紫外線吸収性を有する光学素子や着色フィルタ等についても、水晶やガラス等と同様に数分程度の光照射による仮固定が可能となり、従来の数十分以上を要した熱重合による方法に比べて生産性を大幅に高めることができる。又、重合を可視光で行うようにすることで、作業者が有害な紫外線に暴露される危険性もなくなり、仮固定工程の安全性の点でも非常に好ましい作業環境を構築することができる。
尚、本発明の仮固定用接着剤組成物は、本発明の構造式（Ｉ）で示されるポリアルキレンオキシド（メタ）アクリレートの作用によって重合温度、重合時間、放射照度等を増大しても剥離困難になる恐れがないため、誤って過剰な光照射を行ったり、加熱時間が長くなる等した場合においても、加工工程や剥離工程でのトラブルを招く恐れがないので、生産工程の安定化にも役立つ。
【００２９】
次に、仮固定したワークには所望の形状に切断、研削、研磨、孔開け等の通常の機械加工が施されるが、更に、半田付けや蝋付け加工等の短時間の接合加工も本発明方法の機械加工に含まれる。その際、本発明の仮固定用接着剤組成物で仮固定されたワークは高い接着強度で接着されているので、機械加工中に脱落したり変形し難く良好な加工耐久性を示す。
機械加工を施されたワークは支持基板やワーク同士から剥離される。剥離方法は該ワークを単に上記剥離液に浸漬することで行うことが出来る。この際、本発明の仮固定用接着剤組成物はワークに直接触れることなく自然に剥離するので、剥離中の破損を防ぐことができる。また、ハロゲン系溶剤または強アルカリ水溶液を使用しないので作業の安全性や環境保護の点で優れている。水で剥離する場合は、通常、室温〜90℃の温度にして行う。水と水溶性有機溶剤を混合した剥離液で剥離する場合は、その共沸温度以下でおこなう。剥離時の温度はワークの耐熱性等に応じて適宜設定されるが、ワークに支障が無い限りに於いて40℃〜80℃で剥離するのが好適である。
本発明の剥離液に使用する水溶性有機溶剤としては，メタノール、エタノール、２−プロパノール、２−ヒドロキシイソ酪酸メチル、N-メチルピロリドン、又はジメチルスルホキシドが特に好ましく、二種以上の溶剤を混合して用いても差し支えない。
【００３０】
本発明の剥離液における水と水溶性有機溶剤の混合比は、本発明の仮固定用接着剤組成物の種類等に応じて、当業者が適宜選択することが可能であるが、重量比で水：水溶性有機溶剤＝３：９７〜８０：２０の範囲にすることが好ましい。特に、水と水溶性有機溶剤を含有する剥離液で剥離すると、水だけで剥離するよりも短時間で剥離することができ、またワークがステンレスおよびアルミナ等の場合や表面が粗面である様な場合では、膨潤した仮固定接着剤の残渣がワーク表面から剥がれ易いなどの効果も得られるため、ワークの洗浄効果においても好適である。
なお、上記水溶性有機溶剤だけで剥離を試みると、剥離時間が大幅に長くなったり剥離できなくなるという問題が発生する。しかし、水溶性有機溶剤に水を少量混合することで剥離時間が著しく短縮され優れた剥離特性を示す。このことは本発明で初めて見いだされた現象であり、本発明の仮固定用接着剤組成物との組合わせることで得られる非常に有用な性質である。
【００３１】
また、本発明の仮固定用接着剤組成物で仮固定された鉄、フェライト、希土類金属等の腐食しやすい材質よりなるワークを剥離する場合には、前記のような水溶性有機溶剤に水を少量混合した水溶液を剥離液として使用すれば、錆の発生を抑制する効果も得られるが、より積極的に錆の発生を防止する方法として、更に剥離液に、脂肪族アミン類、芳香族アミン類、尿素縮合体およびその誘導体、チオ尿素及びその置換体、並びにアルデヒド類等の水溶性吸着型腐食抑制剤を含有させることができる。
水溶性吸着型腐食抑制剤の具体例としては、オクチルアミン、ドデシルアミン、アニリン、チオ尿素、アセトアルデヒド等の他、特開平9-291381号公報, 特開平9-3667号公報等に開示されている高性能な水溶性防錆剤等を適用することができる。これら水溶性吸着型腐食抑制剤の使用量は水に対して、通常1〜１０重量%の範囲であり、水だけで剥離する際に用いる他、水と水溶性有機溶剤を含有する剥離液で用いても良い。特にワークの材質が希土類磁性体等の非常に腐食し易い場合には、水の重量比を３〜２０％程度に低減した剥離液に更に上記水溶性吸着型腐食抑制剤を添加して用いることで非常に優れた防錆効果が得られる。
なお、本発明ではワークを破損しないなど本発明の効果を損なわない限りにおいて、剥離の際にワークに揺動、水流、超音波や温度変化等の物理的刺激を与えて、剥離時間や洗浄に要する時間を更に短縮することも可能である。
【００３２】
尚、本発明の加工方法の対象となる被加工部品の大きさに特に制限はない。従って、例えば、幅１ｍｘ長さ２ｍ程度の板ガラスを仮固定することも可能である。
しかしながら、機械加工後、生産工程として実用的である時間内に剥離が完了するという観点から、機械加工後の被加工部品の大きさとして、本発明の仮固定用接着剤組成物で仮固定されている部分の寸法が、好ましくは０．１mm〜２００mmの範囲にあることが好ましい。更に、機械加工後の被加工部品のかかる寸法が０．３mm〜５０mmの範囲にあるときには、機械加工工程とその後の剥離工程の時間的バランスも良好に保たれ、１日数千〜数万個に及ぶ大量生産も遅滞なく可能ならしめる為、有利である。
【００３３】
又、本発明加工方法における機械加工の中でも、特に、本発明の仮固定用接着剤組成物による仮固定の効果が有効に発揮されるものとして、例えば、機械加工後の厚みが０．１μｍ〜１０μｍの範囲にあるような高度な寸法精度が要求される精密研削及び研磨工程を挙げることが出来る。
即ち、本発明の仮固定用接着剤組成物は大きさ数十mmの被加工部品であっても、仮固定後に平均１０μｍ以下の厚みで仮固定することが可能であり、しかも厚みのムラを１０μｍ以下に低減することも出来、更に、加工圧力や加工時の熱等による寸法変化が極めて小さいという特長を有するものである。従って、本発明の仮固定用接着剤組成物を使用して繰り返し多数の被加工部品を仮固定した場合においても、仮固定後の被加工部品の厚みを常に１０μｍ以下の固定精度に抑制することが出来、且つ、仮固定された被加工部品の傾斜角も極めて小さく（約５０秒以下）出来る。
このような本発明の特長は、例えば、水晶振動子、超音波遅延線ガラス、精密抵抗、精密コンデンサ等の数μｍ以下の高度な厚み精度が要求される部品の加工に特に適した性能である。
尚、本発明の仮固定用接着剤組成物の厚みが数μｍの範囲で変動しても、前記の高精度部品の加工工程では厚みを計測管理しながら加工することが出来るため、実質的な厚み精度は仮固定された被加工部品の傾斜角に支配される。本発明の仮固定用接着剤組成物で仮固定した被加工部品の傾斜は縦横１mm当り０．２μｍ以下にできるので、同程度の厚み精度を要する加工にも本発明方法を適用することが出来る。
【００３４】
本発明仮固定用接着剤組成物を好適に用いることのできるその他の機械加工の具体例としては、例えば、加工後の本発明の仮固定用接着剤組成物で仮固定されている部分の寸法が、０．３mm〜３０mmの範囲にある水晶又はセラミックス製の振動子の切断、研磨加工、同寸法が０．３mm〜５０mmの範囲にある光学プリズム、光学レンズ、光学フィルタ、超音波遅延線ガラス等の切断、研磨、研削加工、同寸法が１mm〜５０mmの範囲にあるステンレス又はアルミニウム等のパッケージ部品の切断、研磨、研削、孔開け加工、同寸法が２mm〜５０mmの範囲にあるマイクロモーター又はリレー用のミニチュア磁石の切断、研削、研磨加工、同寸法が０．２mm〜３０mmの範囲にあるセラミックスコンデンサ又は精密抵抗体の切断、研磨加工、同寸法が０．１mm〜数mmの範囲にあるシリコン、ゲルマニウム、酸化ケイ素等のマイクロマシン又はマイクロコンデンサ等の切断、研磨加工、及び、同寸法が０．３mm〜２０mmの範囲にある超音波遅延線ガラスの切断、研削、精密研磨加工を挙げることが出来る。
【００３５】
【実施例】
次に実施例および比較例により本発明を更に詳しく説明する。これらは単なる例示であって、本発明の技術範囲を何等制限するものではない。
仮固定用接着剤組成物の調製方法：表１および２に記載された組成比で、各成分を秤量し攪拌して溶解させて仮固定用接着剤組成物を得た。紫外線重合開始剤または可視光重合開始剤を使用した場合は遮光容器を使用した。また、表１および２における組成を示す数値の表示は重量部を示す。
紫外光重合方法：ケミカルランプ(東芝ライテック（株）製)を用いて紫外線を照射した。
熱重合方法：80℃の恒温内で30分間加熱した。
可視光重合方法：可視光ランプ（（株）アーデル製 FL-V）を用いて可視光を照射した。
剥離時間測定方法：仮固定されたワークを所定温度の剥離液中に浸漬して、ワークに触れないで自然に剥離した時間を測定した。
【００３６】
【実施例１】
N,N-ジメチルアクリルアミド(DMAA) 30g、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが６であるヘキサプロピレングリコールモノアクリレート(HPGA) 70g、2,2’-アゾビスイソブチロニトリル(AIBN) 0.5gをねじ口ガラス瓶に入れ、攪拌して溶解し仮固定用接着剤組成物を調製した。二枚のスライドガラス(縦76、横26、厚さ1.3mm)を用意し、一方のスライドガラス上に調製された接着剤組成物を塗布し、その上にもう一枚のスライドガラスを、気泡を巻き込まないようにのせた。このとき、接着剤組成物の粘度変化はなく、スライドガラスの重ね合わせは容易にできて操作性は良好であった。熱重合を行うと二枚のスライドガラスは強固に固定されており、手指で剥離しようとするとガラス自身が破損するほどであった。同接着剤組成物で直径６ｍｍ高さ１０ｍｍ、直径２０ｍｍ高さ２５ｍｍのパイレックスガラス同士を同条件にて仮固定し、材料試験機を使用してクロスヘッド速度１ｍｍ／ｍｉｎで圧縮剪断試験を実施したところ、7.0MPaの良好な接着強度を示した。
次に前記の方法で仮固定された二枚のスライドガラスの厚さをマイクロメーターで測定して、硬化した接着剤組成物の厚さのムラを計測したところ、0.010mm以下であり、厚さムラの小さい高い固定精度が得られることが確認された。このスライドガラスをダイヤモンドカッターで幅10mmに切断したところ、切断中にスライドガラスの脱落や欠損は発生せず、良好な切断耐久性を有していた。切断されたスライドガラスを80℃の水に浸漬すると2〜5時間で剥離した。
以上、本実施例の仮固定用接着剤組成物は、良好な操作性と、高い固定精度を有し、加工耐久性も良好であり、短時間で剥離する優れた生産性を有することが確認された。
【００３７】
以下に示す比較例1〜5は、本発明の実施例1に対する比較例であり、本発明の優れた特長をより明確に示したものである。
［比較例１］表２に示された組成比で仮固定用接着剤組成物を調製した。即ち、ポリアルキレンオキシドモノ（メタ）アクリレートを使用しないで、実施例1と同様の操作で二枚のスライドガラスを重ね合わせた。このとき、接着剤組成物の粘度変化はなく、スライドガラスの重ね合わせは容易であり、操作性は良好であった。熱重合で固定した二枚のスライドガラスは強固に固定されていた。
実施例1と同様に接着強度の測定をおこなうと、接着強度は17.2MPa以上の非常に高い接着強度を与えた。実施例1と同様に硬化接着剤組成物の厚さのムラを測定すると0.010mm以下となり、厚さのムラの小さい良好な固定精度が得られた。このスライドガラスをダイヤモンドカッターで幅10mmに切断したところ、切断中にスライドガラスの脱落や欠損は発生せず加工耐久性も良好であった。
しかし、切断されたスライドガラスを80℃の水に浸漬すると、接着剤組成物は粘着物質となり、20時間浸漬してもスライドガラスは剥離せず、仮固定用接着剤組成物として使用できないという問題が生じた。
即ち、本発明に開示した親水性ビニルモノマーのN,N-ジメチルアクリルアミド(DMAA)を単独で用いても、仮固定用接着剤組成物として使用できないことが確認された。
【００３８】
［比較例２］ 表２に示された組成比で仮固定用接着剤組成物を調整した。即ち、親水性ビニルモノマーを使用しないで、実施例1と同様に二枚のスライドガラスを熱重合で仮固定した。実施例1と同様に接着強度を測定すると1.9MPaと非常に小さいことが分かった。仮固定されたスライドガラスをダイヤモンドカッターで幅10ｍｍに切断すると、切断中にスライドガラスが剥がれてしまい、十分な加工耐久性が得られなかった。
即ち、本発明で開示した構造式（Ｉ）の化合物であるヘキサプロピレングリコールモノアクリレートだけを単独で用いたとしても、仮固定用接着剤組成物として使用できないと言うことが明らかになった。
【００３９】
［比較例３］表２に示された組成比で仮固定用接着剤組成物を調製した。即ち、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとして、ｎが２３であるメトキシポリエチレングリコールモノメタクリレート(MPEGMA)を使用した。MPEGMAはN,N-ジメチルアクリルアミドに溶けずに沈殿し、また12℃付近で接着剤組成物は凝固して塗布することが困難であった。
即ち、本発明で開示した構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが本発明の範囲を越えると、均質な接着剤組成物が得られず、また塗布操作も困難になることが確認された。
【００４０】
［比較例４］表２に示された組成比で仮固定用接着剤組成物を調製した。即ち、比較例３と同様に、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとして、ｎが２３であるメトキシポリエチレングリコールモノメタクリレート(MPEGMA)を使用した。しかし、MPEGMAはアクリロイルモルホリンに溶けず沈殿し、また12℃付近で接着剤組成物は凝固して塗布することができなかった。
即ち、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎ数が本発明の範囲以上の場合、親水性モノマーの種類を代えても均質な接着剤組成物を調製することができず、また塗布もできないことが確認された。
【００４１】
［比較例５］表２に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明で開示した構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが２である、ジエチレングリコールモノメタクリレート(DEGMA)を使用して、実施例1と同様の操作で二枚のスライドガラスを重ね合わせた。このとき、実施例1と同様に、操作性は良好であった。熱重合で二枚のスライドガラスは強固に固定された。実施例1と同様に硬化接着剤組成物の厚さのムラを測定すると0.010mm以下で厚さのムラは小さく、高い固定精度が得られた。仮固定されたスライドガラスをダイヤモンドカッターで幅10mmに切断した場合、切断中にスライドガラスの脱落や欠損は発生せず良好な加工耐久性を示した。
しかし、切断されたスライドガラスを80℃の水に浸漬すると、20時間を経過しても剥離しなかった。
即ち、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが本発明の範囲を下回ると部品の剥離時間が極めて長くなり、生産性に著しく低下することが明らかになった。
【００４２】
【実施例２】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明で開示した構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが８である、オクタエチレングリコールモノメタクリレート(OEGMA)を使用して、実施例1と同様の操作で二枚のスライドガラスを重ね合わせたところ、実施例1と同様に良好な操作性を示した。熱重合を行ったところ、二枚のスライドガラスは強固に固定されており、手指で剥離しようとするとガラスが破損するほどであった。実施例1と同様に硬化接着剤組成物の厚さのムラを測定すると0.010mm以下であり、厚さのムラの小さい高い固定精度を有していた。仮固定されたスライドガラスをダイヤモンドカッターで幅10mmに切断すると、切断中にスライドガラスの脱落や欠損は発生せず、良好な加工耐久性を示した。切断されたスライドガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬したところ、2〜5時間の短時間のうちに自然に剥離した。
これらの結果から、実施例1において構造式（Ｉ）のポリアルキレンオキシドモノ(メタ)アクリレートのｎを８とし、親水性モノマーの組成比を代えた場合においても、実施例１と同様に、良好な操作性と、高い固定精度を有し、加工耐久性が良好で、剥離時間も短いという本発明の特長を有する仮固定用接着剤組成物が得られることが確認された。
【００４３】
【実施例３】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明で開示した構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが４である、テトラエチレングリコールモノメタクリレート(TEGMA)を使用して、実施例1と同様の操作で二枚のスライドガラスを重ね合わせた。このとき、接着剤組成物の粘度変化はなく、スライドガラスの重ね合わせは容易にでき、操作性は良好であった。紫外線重合により固定した二枚のスライドガラスは強固に固定されており、手指で剥離しようとするとガラス自身が破損するほどであった。実施例1と同様に硬化接着剤組成物の厚さのムラを測定すると0.010mm以下であって、厚さのムラの小さい高い固定精度を有していた。仮固定されたスライドガラスをダイヤモンドカッターで幅10mmに切断したところ、切断中にスライドガラスの脱落や欠損は発生せず良好な加工耐久性を示した。切断されたスライドガラスを60℃の水とエタノールとの重量比で50対50に混合した水溶液に浸漬すると、2〜5時間の短時間で剥離することが確認された。
本発明で開示した構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが４の場合には、操作性が良好で、高い固定精度を有し、加工耐久性が良好で、剥離時間が短く良好な結果が得られることが確認された。
【００４４】
【実施例４】
表１に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明で開示した構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが４である、メトキシテトラエチレングリコールモノメタクリレート(MTEGMA)を使用して、50枚積層したカバーガラス(24x60x0.15mm)を用意して、積層されたカバーガラスの側面から接着剤組成物を浸透させた。接着剤組成物は速やかに各カバーガラス間の隙間に浸透し、優れた浸透性を示した。積層されたカバーガラスの側面から紫外線を照射して仮固定した。全体が完全に硬化するのに必要な硬化時間は30分間であった。仮固定されたカバーガラスをダイヤモンドカッターで幅5mmに切断した。仮固定されたカバーガラスは切断中に脱落したり欠損が発生することはなく、良好な加工耐久性を示した。切断されたカバーガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると、3〜6時間で全て自然に剥離し、カバーガラス同士が付着していたり、剥離中に破損したりすることはなかった。
以上より、本接着剤組成物は、積層品への浸透性が良く、十分な硬化深度を示すと共に、加工耐久性が良好で加工後の部品の剥離時間も短いなど、優れた性能を示した。
【００４５】
【実施例５】
実施例４と同一の組成比で仮固定用接着剤組成物を調製し、50枚積層したカバーガラスを用意して、積層したカバーガラスの側面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し、優れた浸透性を示した。積層したカバーガラスの側面から可視光を照射して仮固定した。その硬化時間は5分間であり、紫外線重合よりも極めて短時間で内部まで硬化することが確認された。仮固定されたカバーガラスをダイヤモンドカッターで幅5mmに切断した。切断中にカバーガラスは脱落や欠損は発生せず加工耐久性は良好であった。切断されたカバーガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると、3〜6時間で剥離した。
可視光重合開始剤を使用して紫外線重合をおこなった実施例４に比較して、可視光重合をおこなった本実施例では、硬化時間を大幅に短縮すると共に、紫外線重合時と同等の性能を示すことが確認され、生産性を更に高められることが明らかになった。
【００４６】
以下に示す比較例６及び７は、本発明の実施例４及び５に対する比較例であり、本発明の優れた特長をより明確に示したものである。
［比較例６］表２に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明で開示した構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが９である、メトキシノナエチレングリコールモノメタクリレート(MNPGMA)を使用して、実施例４と同様に、50枚積層したカバーガラスを用意して、積層面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し、優れた浸透性を示した。積層したカバーガラスの側面から紫外線を照射して仮固定した。その硬化時間は30分間を要した。仮固定されたカバーガラスをダイヤモンドカッターで幅5mmに切断したところ、切断中にカバーガラスに脱落が発生し、十分な加工耐久性が得られなかった。
このように、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートのｎが本発明の範囲を上回ると、ワークとの密着性が低下して加工耐久性が得られなくなることが明らかとなった。
［比較例７］表２に示された組成比で仮固定用接着剤組成物を調製した。即ち、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートを含有せずに、実施例４と同様に50枚積層したカバーガラスを用意して、積層面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し、浸透性は優れていた。積層側から紫外線を照射した。30分間照射したときの硬化距離は3mmであり、中心部が未硬化のままとなった。
このように、実施例４および５に比較して、構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートを含有せずに、親水性モノマーおよび紫外線重合開始剤のみで構成された接着剤組成物は、積層品を仮着できず接着剤組成物として不適当であることが判明した。
【００４７】
【実施例６】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、ラジカル重合開始剤として、実施例１で使用した(AIBN)の代わりにビス（2,4,6-トリメチルベンゾイル）-フェニルフォスフィンオキシド(BTPO)を使用して、実施例1と同様の操作で二枚のスライドガラスを重ね合わせた。このとき、接着剤組成物の粘度変化はなく、スライドガラスの重ね合わせは容易にでき、操作性は良好であった。可視光重合で二枚のスライドガラスは強固に固定された。実施例1と同様に硬化接着剤組成物の厚さのムラを測定すると0.010mm以下となり、厚さのムラの小さい高い固定精度が得られた。このスライドガラスをダイヤモンドカッターで幅10mmに切断した場合、切断中にスライドガラスの脱落や欠損は発生せず良好な加工耐久性を示した。切断されたスライドガラスを80℃の水に浸漬すると、2〜5時間で剥離した。
【００４８】
【実施例７】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、実施例６でポリアルキレンオキシドモノ(メタ)アクリレートとして使用したHPGAの使用量を70重量部から60重量部に減少させて、実施例１と同様の操作で二枚のスライドガラスを重ね合わせた。このとき、接着剤組成物の粘度変化はなく、スライドガラスの重ね合わせは容易にでき、操作性は良好であった。可視光重合で固定した二枚のスライドガラスは実施例１と同様に強固に固定されていた。実施例1と同様に硬化接着剤組成物の厚さのムラを測定すると0.010mm以下となり、厚さのムラは小さく高い固定精度が得られた。仮固定されたスライドガラスをダイヤモンドカッターで幅10mmに切断した場合、切断中にスライドガラスの脱落や欠損は発生せず良好な加工耐久性を示した。切断されたスライドガラスを80℃の水に浸漬すると、２時間で剥離して実施例６よりも更に短い時間で剥離した。
これらの結果から、実施例６に比較して、ポリアルキレンオキシドモノ(メタ)アクリレートとして使用したHPGAの使用量が70重量部から60重量部に調整することで、剥離時間が更に短くなり、生産性が更に向上することが確認された。
【００４９】
【実施例８】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、実施例４でポリアルキレンオキシドモノ(メタ)アクリレートとして使用したMTEGMAの使用量を70重量部から50重量部に減少させて、実施例4と同様に50枚積層したカバーガラスを用意して、積層されたカバーガラスの側面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し優れた浸透性を示した。積層されたカバーガラスの側面から紫外線を照射して仮固定した。その硬化時間は30分間を要し、内部まで硬化した。このカバーガラスをダイヤモンドカッターで幅5mmに切断した。切断工程でカバーガラスに脱落や欠損は発生せず良好な加工耐久性を示した。切断されたカバーガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると、2〜4時間で剥離して、実施例4よりも更に短い時間で剥離した。
これらの結果から、ポリアルキレンオキシドモノ(メタ)アクリレートとして使用したMTEGMAの使用量が実施例4で70重量部であることに対して、本実施例で50重量部とした結果、剥離時間が短縮され、生産性が高まることが判明した。
【００５０】
【実施例９】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、実施例８と同様にMTEGMAの使用量を50重量部に減少させて、50枚積層したカバーガラスを用意して、積層したカバーガラスの側面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し優れた浸透性を示した。積層したカバーガラスの側面から可視光を照射して仮固定した。その硬化時間は5分間を要し、短時間で内部まで硬化した。このカバーガラスをダイヤモンドカッターで幅5mmに切断した。切断工程でワークに脱落や欠損は発生せず良好な加工耐久性を示した。切断されたカバーガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると、2〜4時間で剥離した。
これらの結果から、紫外線開始剤を使用して紫外線重合をおこなった実施例8に対して、可視光重合開始剤を使用して可視光重合おこなうと、硬化時間が更に短縮されることが判明した。
【００５１】
【実施例１０】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとしてOEGMAの使用量を７重量部として、実施例1と同様の操作で二枚のスライドガラスを重ね合わせた。このとき、接着剤組成物の粘度変化はなく、スライドガラスの重ね合わせは容易にでき、操作性は良好であった。紫外線重合で固定した二枚のスライドガラスは実施例１と同様に強固に固定されていた。実施例1と同様に接着強度の測定をおこなうと、接着強度は11.0MPaであり、優れた接着強度を示した。実施例１と同様に硬化接着剤組成物の厚さのムラを測定すると0.010mm以下となり、厚さのムラは小さく高い固定精度が得られた。このスライドガラスをダイヤモンドカッターで幅10mmに切断した場合、切断中にスライドガラスの脱落や欠損は発生せず良好な加工耐久性を示した。切断されたスライドガラスを80℃の水に浸漬すると、6時間で剥離した。
これらの結果から、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートの使用量が10重量部以下であっても、積層したワークへの良好な浸透性を有し、良好な操作性と高い固定精度を示し、加工耐久性良好で剥離時にも支障のない優れた仮固定用接着剤組成物が得られることが判明した。
【００５２】
【実施例１１】
実施例１０と同一の組成比で調製された接着剤組成物を用いて、実施例１０と同様に５０枚のスライドガラスを仮固定して、切断加工した。切断された幅10ｍｍのスライドガラスを60℃の水とエタノールとを重量比で80対20に混合した水溶液に浸漬すると、3時間で剥離し、剥離時間は実施例10にくらべて短縮された。水に代えて本発明で開示した水とエタノールとを重量比で80対20で混合した水溶液で剥離した場合には、剥離時間が更に短縮されることが確認された。
【００５３】
【実施例１２】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとしてHPGAの使用量を７重量部として、実施例4と同様に50枚積層したカバーガラスを用意して、積層されたカバーガラスの側面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し優れた浸透性を示した。積層されたカバーガラスの側面から紫外光を照射した。その硬化時間は30分間を要した。このカバーガラスをダイヤモンドカッターで幅2mmに切断した。切断工程でカバーガラスに脱落や欠損は発生せず良好な加工耐久性を示した。切断されたカバーガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると、3時間で剥離した。
これらの結果から、ポリアルキレンオキシドモノ(メタ)アクリレートの使用量が少量であっても、優れた浸透性を示し、短い硬化時間であり、良好な加工耐久性を示し、加工された部品は短時間で剥離した。
【００５４】
【実施例１３】
実施例１２と同一の組成比で調製された接着剤組成物を用いて、実施例１２と同様に50枚積層したカバーガラスを用意して、積層されたカバーガラスの側面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し優れた浸透性を示した。積層されたカバーガラスの側面から可視光線を照射した。その硬化時間は5分間を要した。このカバーガラスをダイヤモンドカッターで幅2mmに切断した。切断工程でワークに脱落や欠損は発生せず良好な加工耐久性を示した。切断されたカバーガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると、3時間で剥離した。可視光開始剤を使用して紫外線重合をおこなった実施例12に対して、可視光重合開始剤を使用した上で、更に可視光重合行うことで硬化時間が更に短縮された。
【００５５】
【実施例１４】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとしてTEGMAの使用量を２５重量部として、二枚のアルミナ製試験片(縦25、横25、厚さ2mm)を用意し、一方のアルミナ製試験片上に接着剤組成物を塗布し、その上にもう一枚のアルミナ製試験片をのせた。このとき、接着剤組成物の粘度変化はなく、アルミナ製試験片の重ね合わせは容易にでき、操作性は良好であった。熱重合で二枚のアルミナ製試験片は強固に固定された。このアルミナ製試験片をダイヤモンドカッターで幅5mmに切断した。切断工程でアルミナ製試験片に脱落や欠損は発生せず加工耐久性は良好であった。
切断されたアルミナ製試験片を80℃の水に浸漬すると、4時間で剥離した。剥離されたアルミナ製試験片上には若干の接着剤組成物の残渣が付着していた。追加として１時間の浸漬を行うことでこの付着物は除去された。また追加浸漬の代わりに５０％のアルコール水溶液中で超音波洗浄を行うと１０分間で除去されることが分かった。
また実施例１に準じて別途用意した直径６ｍｍ高さ10mm、直径２０ｍｍ高さ２０ｍｍのアルミナ製試験片を本発明の接着剤組成物を用いて、本実施例と同一の条件で熱重合して接着した。この試験片の圧縮剪断接着強度を材料試験機を用いてクロスヘッド速度１ｍｍ／ｍｉｎで測定したところ、１０ＭＰａの優れた接着強度を示した。
【００５６】
【実施例１５】
実施例１４と同一の組成比で調製された接着剤組成物を用いて、実施例１４と同一条件によりアルミナ製試験片を仮固定して切断した。切断されたアルミナ製試験片を80℃の水と2-ヒドロキシイソ酪酸メチル(HBM)とを重量比で50対50に混合した水溶液に浸漬すると、3時間で剥離し、実施例13よりも短時間に剥離した。また、本実施例では剥離したアルミナ製試験片上に接着剤組成物の残渣は付着していなかった。
即ち、水の代わりに水と2-ヒドロキシイソ酪酸メチル(HBM)とを重量比で50対50に混合した水溶液で剥離すると、剥離時間が短縮され、また部品に剥離した接着剤組成物が付着しないことで、部品の洗浄工程の簡素化ができ生産性が向上することが判明した。
【００５７】
【実施例１６】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとしてHPGAの使用量を２５重量部として、二個のステンレス製試験片を(縦8、横5、厚さ5mm)用意し、一方のステンレス製試験片上に接着剤組成物を塗布し、その上にもう一個のステンレス製試験片をのせた。熱重合により二個のステンレス製試験片を仮固定した。このとき、接着剤組成物の粘度変化はなく、ステンレス製試験片の重ね合わせは容易にでき、操作性は良好であった。熱重合で二個のステンレス製試験片は強固に固定された。実施例１４と同様に、接着試験用のステンレス製試験片を用意して、本実施例の重合条件で仮固定し、その接着強度を測定すると11.0MPaの優れた接着強度を示した。
次に本実施例で仮固定し切断されたステンレス製試験片を60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると、2時間で剥離したが表面に若干の接着剤組成物の残渣が付着していた。その後１時間の追加浸漬を行うとこの付着物はきれいに除去された。また前記の追加の浸漬を行う代わりに、５０％のエタノール水溶液中で超音波洗浄を実施したところ１０分間で除去されることが分かった。
【００５８】
【実施例１７】
実施例１６と同一の組成比で調製された接着剤組成物を用いて、実施例１６で仮固定されたステンレス製試験片を80℃の水/HBM=50/50 wt/wtの水溶液に浸漬すると、2時間で剥離した。また、本実施例では剥離したステンレス製試験片上に接着剤組成物が付着していなかった。
即ち、剥離液を水とエタノールとを重量比で50対50で混合した水溶液の代わりに水と2-ヒドロキシイソ酪酸メチル(HBM)とを重量比で50対50で混合した水溶液として剥離した場合には剥離時間が短縮され、また部品に剥離した接着剤組成物が付着せず、小物品の洗浄工程の簡素化ができ生産性が向上することが判明した。
【００５９】
【実施例１８】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとしてHPGAの使用量を１５重量部として、縦横約50mmの二枚の希土類磁性体製の試験片を用意し、一方の希土類磁性体製の試験片上に接着剤組成物を塗布し、その上にもう一枚の希土類磁性体製の試験片をのせた。このとき、接着剤組成物の粘度変化はなく、希土類磁性体製の試験片の重ね合わせは容易にでき、操作性は良好であった。熱重合で二枚の希土類磁性体製の試験片は強固に固定された。この希土類磁性体製の試験片をダイヤモンドカッターで幅2mmに切断した。切断工程で脱落や欠損は発生せず優れた加工耐久性を示した。切断された希土類磁性体製の試験片を80℃の水と2-ヒドロキシイソ酪酸メチル(HBM)とを重量比で3対97に混合した水溶液に浸漬すると、4時間で剥離した。この試験片は剥離中に錆の発生は見られなかった。しかし剥離液から取り出して剥離液を拭き取り乾燥した室内に３日放置したところ若干の錆の発生の兆候が見られた。
【００６０】
［比較例8］ 実施例１８で幅２mmに切断された希土類磁性体製の試験片を80℃のHBM１００％の溶剤中に浸漬すると、20時間を経過しても剥離しなかった。実施例18と比較して、HBMが100％で水を含まない場合は剥離しないが、、水を3％添加した本発明の水溶液を用いることで剥離時間を著しく短縮できるという本発明の効果が端的に示された。
【００６１】
【実施例１９】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとしてHPGAの使用量を１５重量部として、実施例4と同様に、50枚積層したカバーガラスを用意して、積層されたカバーガラスの側面から接着剤組成物を浸透させた。接着剤組成物は速やかに浸透し、優れた浸透性を示した。積層されたカバーガラスの側面から可視光を照射したところ5分間で全体が完全に重合した。実施例１と同様に接着強度の測定したところ11.0MPa以上の優れた接着強度を示した。仮固定されたカバーガラスをダイヤモンドカッターで幅２mmに切断した。切断中にカバーガラスは脱落や欠損は発生せず加工耐久性は良好であった。切断されたカバーガラスを60℃の水とエタノールとを重量比で50対50に混合した水溶液に浸漬すると2時間で剥離した。
実施例13に対して、ポリアルキレンオキシドモノ(メタ)アクリレートの使用量が増加した場合に、剥離時間が短縮された。
この希土類磁性体製の試験片は剥離液に浸漬中は錆が生じなかった。しかし剥離液から取り出して剥離液を拭き取り、乾燥した室内に放置したところ翌日に錆の発生することが分かった。
【００６２】
【実施例２０】
表1に示された組成比で仮固定用接着剤組成物を調製した。即ち、本発明の構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートとしてOEGMAの使用量を６０重量部として、実施例１８と同様の二枚の希土類磁性体製の試験片を用意し、一方の希土類磁性体製の試験片上に接着剤組成物を塗布し、その上にもう一枚の希土類磁性体製の試験片をのせた。このとき、接着剤組成物の粘度変化はなく、希土類磁性体製の試験片の重ね合わせは容易にでき、操作性は良好であった。熱重合で二枚の希土類磁性体製の試験片を仮固定すると、希土類磁性体製試験片は強固に固定された。この希土類磁性体製の試験片をダイヤモンドカッターで幅5mmに切断した。切断工程で脱落や欠損は発生せず優れた加工耐久性を示した。切断された希土類磁性体製の試験片を80℃の水と2-ヒドロキシイソ酪酸メチル(HBM)とを重量比で10対90に混合した水溶液に浸漬すると、3時間で剥離した。この希土類磁性体製の試験片は剥離中には錆の発生は見られなかったが、剥離液から取り出して剥離液を拭き取り、乾燥した室内に放置したところ２日目に僅かではあるが錆が発生した。
【００６３】
【実施例２１】
実施例20で切断された幅5mmの希土類磁性体を水溶性吸着型腐食抑制剤としてユシロ化学工業（株）製のユシローケンＳＣ２５Ａを水に４重量％添加して、これと2-ヒドロキシイソ酪酸メチル(HBM)とを重量比で10対90に混合した水溶液(60℃)に浸漬して剥離させると剥離時間は4時間と短時間であり良好な剥離性を示した。更に、剥離した希土類磁性製の試験片は剥離中に錆が生じることがなく、更に剥離液から取り出して水滴を拭き取り乾燥した室内に３日間放置しても錆が発生せず優れた防錆効果を示した。
【００６４】
【発明の効果】
本発明の仮固定用接着剤組成物は、ワックスや松ヤニなどのホットメルト接着剤のように粘性変化を伴う加熱条件下での塗布作業を行う必要が無く、室温の安定した粘度で作業者の必要とする任意の時間で操作出来るため、経験の浅い作業者でも容易に正確な位置合わせができ操作性が高く、また高温操作を行わないので位置合わせに伴う火傷の危険もなく安全性が高い。
そして、本仮固定用接着剤組成物は浸透性が優れているため積層したワークの仮固定ができるため、１回の仮固定操作で多数の部品をまとめて加工可能であり高い生産性が得られる。また、仮固定した接着剤組成物の厚さムラも小さいため、機械加工時の加工精度も高い。更に仮固定時の接着強度においても優れているため加工対象物の機械加工における十分な加工耐久性を示し、加工中の部品の脱落や欠損等が防止され、製造歩留まりを向上させる。更にまた、加工された部品を水または水と有機溶剤の混合した水溶液に浸漬することで、速やかに欠損なく剥離することができるため工程時間の短縮と歩留りの向上にも寄与し、良好な生産性を示す。
また、本発明の仮固定用接着剤組成物のラジカル重合開始剤として可視光重合開始剤を用いると、特に多層に積層されたワークや紫外線吸収性の加工対象物に対しても簡便で短時間の光照射によって仮固定することができ、更に生産性を向上することができる。
更に、本発明の仮固定用接着剤組成物において構造式（Ｉ）で示されるポリアルキレンオキシドモノ(メタ)アクリレートの使用量を限定すれば、剥離時間を更に短縮することができ、更に生産性を向上することも可能である。
【００６５】
また、本発明の仮固定用接着剤組成物の剥離に際して、本発明で開示した水と特定の水溶性有機溶剤とを混合した水溶液に浸漬する方法を用いれば、剥離時間を更に短くすることも可能である。更に、剥離液として用いる水に本発明で開示した水溶性吸着型腐食抑制剤を添加することで、錆の発生し易い金属や希土類磁性体等の材質からなる部品に対しても、錆の発生の問題を発生させることをなく本発明の仮固定用接着剤組成物を適用することもでき、従来これらの材質に水や水溶液を剥離液として用いる際にしばしば生じた実用上の問題も解消される。
更に、本発明の加工方法は、本発明の仮固定用接着剤を用いて仮固定した後、水または水と特定の水溶性有機溶剤との混合した水溶液で剥離することを特徴とする方法である為に、有害性や危険性を伴う炭化水素系溶剤やハロゲン溶剤等を使用する必要がなく、部品の加工工程から環境汚染物質が排除され、環境保全と作業の安全性を大幅に改善することが出来る。
本発明のこの様な優れた効果は、水または水と特定の水溶性有機溶剤を剥離液として用いる時に得られる本発明の仮固定用接着剤組成物特有の効果であると共に、本発明で開示した部品の加工方法が本発明の仮固定用接着剤の特長を十分に発揮させることで達成されるものである。
【００６６】
表１及び表２を以下に示す。更に、明細書及びこれら表中で使用される物質の略号の意味を表３及び表４にまとめた。
【００６７】
【表１】

【００６８】
【表２】

【００６９】
【表３】

【００７０】
【表４】

【００７１】
【表５】

[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in workability and processing accuracy, and has a high-performance temporary fixing adhesive composition that uses water or an aqueous solution obtained by mixing water and a water-soluble organic solvent as a peeling solution in the peeling step after machining, and the temporary fixing. The present invention relates to a method for processing a part using an adhesive composition.
More specifically, the present invention eliminates harmful substances accompanied with environmental pollution from the machining process involving temporary fixing of parts, thereby greatly improving environmental conservation and work safety, as well as operability and machining accuracy. Further, the present invention relates to a temporary fixing adhesive composition for improving productivity and the above-described peeling liquid, and a part processing method using the temporary fixing adhesive composition and the peeling liquid.
The present invention also provides the temporary fixing adhesive composition and at least selected from the group consisting of water or alcohol-based, ketone-based, polyhydric alcohol-based, nitrogen compound-based, and sulfur compound-based water-soluble organic solvents. The present invention relates to a temporary adhesive kit including a stripping solution containing an aqueous solution obtained by mixing one kind of water-soluble organic solvent and water.
[0002]
[Prior art]
Temporarily fixing workpieces (workpieces) during cutting and polishing of various precision parts such as crystal, quartz, optical glass, ceramics, stainless steel, ferrite, aluminum, etc., vibrators, lenses, prisms, capacitors, package parts, magnets, etc. Hot melt adhesives such as wax and pine sprout were used for. However, this type of hot melt adhesive requires work at a high temperature of about 150 ° C. during bonding and desorption, and then further cleaning with an alkaline solvent or a halogen-based organic solvent. For this reason, not only is it necessary to be skillful in temporary fixing operations and operations in peeling, but there is also a danger, and the working environment is deteriorated and the environment is contaminated.
[0003]
Various publications have been disclosed to solve the above-mentioned drawbacks.
In JP-A-61-287976, (A) a terminal has a polymerizable ethylenic double bond, and the main chain has? ₂ -CH ₂ -O) n- (where n is an integer from 9 to 25), a prepolymer containing polyethylene oxide, (B) a water-soluble monomer having at least one polymerizable ethylenic double bond, (C ) Including a polymerization initiator. This (A) is a urethane prepolymer having a polymerizable ethylenic double bond at the terminal and containing polyethylene oxide in the main chain. Specifically, the urethane-based prepolymer is a prepolymer obtained by reacting a polyurethane polymer obtained by reacting an organic mono- or polyhydric alcohol having a polyethylene oxide bond and an isocyanate group with a (meth) acrylate monomer having active hydrogen. It is a polymer.
[0004]
Japanese Patent Application Laid-Open No. 2-140279 discloses a temporary fixing adhesive composition comprising a water-absorbing monomer having an ethylenic double bond and a photopolymerization initiator.
In JP-A-2-42874, (A) a water-absorbing monomer having at least one polymerizable ethylenic double bond in the molecule, (B) a water-absorbing or water-soluble polymer substance, and (C) a photopolymerization initiator. An adhesive composition for temporary fixing using the above is disclosed.
[0005]
In JP-A-2-47678, (A) a water-absorbing monomer having at least one polymerizable ethylenic double bond in the molecule, (B) an adhesive composition for temporary fixing using a redox initiator, and this A method of use is disclosed.
[0006]
JP-A-6-116534 discloses an adhesive cured product comprising a resin component of (meth) acrylamide having a water-soluble heterocyclic secondary amine residue, a photopolymerization initiator, and water as required. Discloses an ultraviolet-polymerizable adhesive composition for water-soluble temporary fixing, and JP-A-6-116535 discloses quaternary compounds such as methyl chloride of N, N-dimethylaminoethyl methacrylate. An adhesive composition using an ammonium salt is disclosed.
[0007]
In JP-A-10-245526, one or more compounds selected from (A) N-vinyl-2-pyrrolidone, N, N-dimethylaminoethyl (meth) acrylate, etc., (B) N-vinyl-2- Pyrrolidone homopolymer, N, N-dimethyl (meth) acrylamide homopolymer, water-soluble copolymer selected from N-vinyl-2-pyrrolidone and N, N-dimethyl (meth) acrylamide copolymer Disclosed is a method for processing a small article using a temporary fixing adhesive composition comprising one or a plurality of polymer materials having a water-absorbing property or a water-swelling property and (C) a polymerization initiator.
[0008]
[Problems to be solved by the invention]
The adhesive composition for temporary fixing described in JP-A-61-287976 has a high viscosity of a prepolymer containing a long-chain polyethylene oxide having a polymerization degree of 9 to 25, so that it penetrates into a gap formed by laminating a large number of workpieces. It is difficult to apply, or the applied adhesive becomes thick and the workpiece is lifted up, making it difficult to precisely position it, or the workpiece is inclined and the predetermined processing accuracy cannot be obtained. there were. Moreover, since the prepolymer containing the long-chain polyethylene oxide has a large molecular weight, it is poorly compatible with other components, which may cause problems such as precipitation in the adhesive or solidification in winter. Furthermore, since the processing method disclosed in the publication is immersed in high-temperature boiling water when removing a small article after machining, for example, it has a problem of being easily damaged when a thin article having a small thickness is peeled off. .
[0009]
Since the temporary fixing adhesive composition disclosed in JP-A-2-140279, JP-A-2-47678 and JP-A-6-116534 is composed of only a monomer having a strong hydrophilicity, it has an adhesive force with a workpiece. It takes a very long time to peel off because it becomes too strong, or it becomes a sticky gel when water is absorbed and adheres to the work surface, which requires time and effort for cleaning. It was.
In addition, as a method of reducing the adhesive strength of the temporary fixing adhesive composition, the light irradiation time for curing the adhesive is extremely shortened, or the ultraviolet irradiance is decreased to polymerize the hydrophilic monomer. There is a method to interrupt in the middle, but the characteristics of the polymer interrupted in this way are very unstable, the daily temperature fluctuation of the working environment, the irradiance decrease of the ultraviolet lamp over time, the adhesive Adhesive strength is likely to change due to differences in raw material lots of components and various fluctuation factors that are unavoidable in processes such as moisture absorption. For example, adhesive strength is greatly reduced and drops during processing, or requires adhesive strength as described above. There arises a problem in the process such as higher and more difficult to peel off, resulting in a problem that process management becomes difficult.
[0010]
The adhesive composition for temporary fixing disclosed in JP-A-2-42874 contains a large amount of a water-soluble polymer, so that the viscosity of the adhesive composition increases and the adhesive composition described in JP-A-61-287976 It can not be used for precise temporary fixation like objects, and it becomes a gel that has adhesive properties when immersed in water, making it difficult to wash and adhere to the workpiece, or when peeling small thin parts In addition, there is a drawback that the parts do not peel apart for a long time due to the adhesive force.
[0011]
Since quaternary ammonium salts such as the methyl chloride salt of N, N-dimethylaminoethyl methacrylate disclosed in JP-A-6-116535 are fixed at room temperature, water or 2-hydroxyethyl (meth) acrylate, It is used by blending 2-hydroxypropyl (meth) acrylate, but water-containing ones have poor adhesion at the time of temporary fixing, causing problems such as workpiece dropping or chipping due to processing pressure in the machining process, There was a drawback that the water was evaporated during coating, and the quaternary ammonium salt was precipitated as a solid, causing trouble. In addition, it is possible to increase the adhesive strength by further blending 2-hydroxyethyl (meth) acrylate, etc., but it is unavoidable in the production process such as the change in temperature and humidity of the workplace due to the season and the temperature rise at the time of ultraviolet irradiation. Disturbances change the content of moisture contained in the applied adhesive, making the adhesive properties unstable, causing parts to be dropped or chipped during processing, and making peeling difficult. Such problems are likely to occur.
[0012]
N-vinylpyrrolidone used in the adhesive composition disclosed in JP-A-10-245526 is mutagenic and harmful as disclosed in JP-A-6-116534. The N, N-dimethylacrylamide disclosed in the same report is not harmful, but a large amount of water-soluble polymer is used as an adhesive component, resulting in a very high viscosity, as in JP-A-61-287976. It is difficult to apply the adhesive by penetrating into the gaps in the laminate, and the accuracy of alignment in temporary fixing tends to decrease. In addition, as in JP-A-2-14274, when water is absorbed in the peeling process, it exhibits adhesiveness, and there is also a problem that small thin parts are difficult to peel off.
[0013]
In view of such problems of the prior art, the present invention has excellent permeability and can penetrate and adhere to the gaps between the stacked workpieces, has excellent dimensional accuracy of alignment, and can withstand machining after temporary fixing. An adhesive composition for temporary fixing that has an adhesive force and can be peeled off quickly without causing defects by being immersed in a peeling solution composed of relatively low temperature water or a mixture of water and a water-soluble organic solvent; It was made for the purpose of providing the processing method.
Further, the present invention provides the temporary fixing adhesive composition and the stripping solution, the temporary adhesive kit containing the composition and the stripping solution, and a method for using them, from a machining step involving temporary fixing, It was made for the purpose of eliminating the halogen-based solvents that are harmful and polluting the environment, greatly improving the environmental protection and work safety, and greatly improving the workability and productivity of the processing process.
[0014]
[Means for Solving the Problems]
That is, the present invention relates to a temporary fixing adhesive composition characterized by containing the following 1), 2), and 3):
1) at least one selected from the group consisting of N, N-dimethylacrylamide, N-vinylcaprolactam, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerol (meth) acrylate Kinds of hydrophilic vinyl monomers;
2) At least one polyalkylene oxide mono (meth) acrylate represented by the following structural formula (I)
[0015]
[Chemical 2]

[0016]
However, R1, R2, and R3 are H or CH ₃ , N is an integer from 4 to 8; and
3) Radical polymerization initiator.
[0017]
The work temporarily fixed by the composition of the present invention is water or at least one water-soluble substance selected from the group consisting of alcohol-based, ketone-based, polyhydric alcohol-based, nitrogen compound-based, and sulfur compound-based water-soluble organic solvents. By immersing in a stripping solution made of an aqueous solution obtained by mixing a water-soluble organic solvent and water, it is possible to strip quickly without causing defects.
Therefore, the present invention also relates to the temporary fixing adhesive composition, the release liquid, and the temporary adhesive kit containing the adhesive composition and the release liquid.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The components of the temporary fixing adhesive composition used in the present invention will be described in detail below.
At least one hydrophilic vinyl monomer contained in the composition of the present invention is N, N-dimethylacrylamide, N-vinylcaprolactam, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, And glycerol (meth) acrylate.
These monomers give good adhesiveness to temporary fixing adhesives and show an affinity for moisture, which gives water or water and the property of allowing moisture to penetrate when immersed in the above stripping solution and promotes stripping time. To help.
[0019]
The at least one polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention exhibits appropriate adhesion to the workpiece at the time of temporary fixing of the workpiece, and when immersed in the stripping solution, Since it has the property of being promptly peeled off by hydration, it has very excellent characteristics as a component of the temporary fixing adhesive.
N in the structural formula (I) representing the degree of polymerization of the polyalkylene oxide chain is 4 to 8, and when n is less than this, it is difficult to peel off when immersed in the stripping solution of the present invention. Further, when n exceeds the range of the present invention, the adhesiveness with the workpiece decreases due to a decrease in the adhesion to the workpiece, or the workpiece is fixed at a normal temperature and becomes solid at room temperature. Inhomogeneous, resulting in performance degradation, and in the winter season, it becomes difficult to use due to the crystalline state, and the viscosity of the temporary fixing adhesive composition is increased, and the work requires precise fixing accuracy. Problems such as difficulty in temporary fixing occur.
[0020]
The amount of the compound represented by the structural formula (I) can be appropriately selected by those skilled in the art according to the type of the compound, the type and size of the workpiece, etc., but is usually preferably 5 to 70% by weight. More preferred is ˜60% by weight.
By using it in the above preferred composition range, an adhesive for temporary fixing having a suitable fixing strength and peeling time can be obtained in the processing of general articles having a size of about 0.3 to 50 mm. However, if the workpiece size is large, it is possible to further increase the amount of use. Conversely, when long processing is required, the amount of use is reduced to 3-5% by weight, etc. Adjustments such as reducing defects are possible. However, if the compound of the structural formula (I) of the present invention is not used, a practical problem that the peeling time becomes very long and the productivity is remarkably lowered occurs.
[0021]
The radical polymerization initiator used in the temporary fixing temporary adhesive composition of the present invention includes known thermal polymerization initiators such as organic peroxides and azobisisobutyronitrile, ultraviolet polymerization initiators and visible light polymerization initiators. Is used.
Thermal polymerization initiators are benzoyl peroxide, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoylbenzoate, n-butyl- Organic peroxides such as 4,4-bis (t-butylperloyl) valerate, 2,5-dimethyl-2,5-di (t-butylperloyl) hexane, and 2,2'-azobisisobutyrate Examples include azo compounds such as nitrile, 2- (carbamoylazo) -isobutyronitrile, and 2,2′-azobis (2,4,4-trimethylpentane).
UV polymerization initiators include benzoins such as benzoin and benzoin methyl ether, benzophenones such as benzoylbenzoic acid and 4-phenylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] Examples include acetophenone series such as -2-hydroxy-2-methyl-1-propan-1-one.
[0022]
Examples of visible light polymerization initiators include benzyl, quinones, acylphosphine oxide, α-aminoketone, bisacylphosphine oxide, metallocene, thioxanthone, and the like, but camphorquinone, acylphosphine oxide, α-aminoketone, bis It is preferably selected from the group consisting of acylphosphine oxide and metallocene.
Specific examples of compounds belonging to this group include camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like.
Even when the above visible light polymerization initiator is used, temporary fixation can be carried out by ultraviolet polymerization by ultraviolet light irradiation.
In the present invention, two or more of the above radical polymerization initiators may be mixed and used, and the total amount used is usually adjusted in the range of 0.05 to 10% by weight.
[0023]
Further, as long as the effects of the present invention are not impaired, the adhesive composition for temporary fixing of the present invention may be added with a hydrophobic monomer, polymer, inorganic filler or the like as an optional component to adjust viscosity or mechanical properties, It is also possible to add the color and the like.
Hydrophobic monomers can be adjusted to impart moderate hydrophobicity to the adhesive composition, to improve water resistance during machining and to withstand prolonged processing. Specific examples of hydrophobic monomers include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl Monofunctional (meth) acrylates such as (meth) acrylate and polyfunctional (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, triethylene glycol dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate ) Acrylate.
The polymer can increase the viscosity of the adhesive composition and can easily fill a gap generated when a workpiece having poor flatness is fixed to a substrate. However, because the viscosity of the temporary fixing adhesive composition of the present invention can be increased by adding a small amount of polymer, it does not become a sticky substance when peeled off by being immersed in water or the like, and productivity such as a delay in peeling time There will be no decrease in Specific examples of the polymer suitably used in the present invention include polyvinyl pyrrolidone and polymethyl methacrylate, and the addition amount is usually in the range of 1 to 10% by weight.
[0024]
Furthermore, the present invention provides a temporary fixing of a workpiece using the temporary fixing adhesive composition of the present invention, and after performing predetermined machining, water or water and alcohol, ketone, polyhydric alcohol A part characterized by being immersed in a stripping solution consisting of an aqueous solution mixed with at least one water-soluble organic solvent selected from the group consisting of nitrogen compound-based and sulfur compound-based water-soluble organic solvents. It relates to the processing method.
In the processing method of the present invention, there is no particular limitation on the material of the workpiece that can be temporarily fixed using the temporary fixing adhesive composition of the present invention. Examples of suitable materials include transparent glass, color glass, optical glass, laser glass, YAG, crystal, ruby, sapphire, quartz, and the like. Examples of the opaque material include alumina, zirconia, ferrite, rare earth magnetic material, ferroelectric ceramics, silicon wafer, titanium, titanium alloy, stainless steel, aluminum, iron, and brass.
Hereinafter, the processing method of the present invention will be specifically described.
[0025]
First, in order to temporarily fix a workpiece, an appropriate amount of the temporarily fixing adhesive composition of the present invention is applied on one workpiece or support substrate to be bonded and fixed according to the bonding area, and then the other workpiece is applied. A method of overlapping is used, or a number of workpieces to be temporarily fixed are stacked in advance, and the temporary fixing adhesive composition of the present invention is applied to the gaps.
The temporary fixing adhesive composition of the present invention does not need to be applied under heating conditions with a viscosity change like hot-melt adhesives such as wax and pine yarn, and has a stable viscosity at room temperature. Therefore, even an inexperienced operator can easily perform accurate alignment, and there is no risk of burns or the like associated with alignment.
In addition, since the adhesive composition for temporary fixing of the present invention has a low viscosity, the thickness of the adhesive after application is reduced, the inclination of the workpiece and the thickness unevenness are extremely small, high fixing accuracy is obtained, and a large number of workpieces are obtained. Even when the layers are laminated, the adhesive composition can quickly penetrate into the gaps between the workpieces. When the surface of the workpiece to be temporarily fixed is rough or when the flatness is poor, and there is a gap between the substrate and the workpiece surface, a small amount of the aforementioned polymer is added to the temporary fixing adhesive composition of the present invention. It is also possible to fill without gaps by increasing the viscosity.
[0026]
Next, by performing conventionally known thermal polymerization, ultraviolet polymerization, and visible light polymerization, and curing the applied adhesive composition for temporary fixing of the present invention, the workpiece is temporarily fixed.
For example, when temporarily fixing opaque workpieces such as ceramics and metals such as stainless steel, aluminum, and ferrite, use an adhesive composition to which a thermal polymerization initiator is added as a radical polymerization initiator, and heat the workpiece after finishing the coating process. Just do it. In this case, the thermal polymerization can be usually carried out by heating in a temperature range of 40 ° C. to 150 ° C. for 5 minutes to 5 hours, preferably in a temperature range of 50 ° C. to 120 ° C. for 10 minutes to 120 minutes. A person skilled in the art can appropriately adjust the polymerization temperature and the polymerization time so as to be convenient for the production process by adjusting the addition amount and type of the thermal polymerization initiator.
[0027]
On the other hand, for example, when a transparent workpiece such as optical glass or quartz is temporarily fixed, it can be temporarily fixed by ultraviolet polymerization or visible light polymerization.
When ultraviolet polymerization is performed, an adhesive composition to which an ultraviolet polymerization initiator or a visible light polymerization initiator is added as a radical polymerization initiator is used, and fixing is performed by irradiating the work after the coating process. A high pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, an ultraviolet fluorescent lamp, or the like is used as a light source for the ultraviolet polymerization. Ultraviolet irradiation conditions can be appropriately determined by those skilled in the art, but the irradiance at 360 nm is 0.5 mW / cm. ² The above is preferable, and the irradiation time is preferably in the range of about 10 seconds to 30 minutes depending on the irradiance.
[0028]
When performing visible light polymerization, it is set as the adhesive composition which added the visible light polymerization initiator as a radical polymerization initiator, and visible light is irradiated to the workpiece | work which finished the application | coating process. As the light source, a visible-only fluorescent lamp, a halogen lamp, or the like is used. Visible light irradiation conditions can be appropriately determined by those skilled in the art, but the irradiance at 420 nm is 2 mW / cm. ² The irradiation time is preferably 10 seconds to 20 minutes.
In particular, when a temporary fixing adhesive composition containing a visible light polymerization initiator is used, even when an ultraviolet light source such as a chemical lamp is used, it is hardened by light irradiation in a shorter time than when an ultraviolet polymerization initiator is used. Depth is obtained.
Furthermore, by performing visible light irradiation using a visible light source, the effect is further increased several times and a curing depth of several tens of millimeters can be easily obtained. For example, when a large number of workpieces are laminated and cured at once. Can be reliably cured to the deep part of the workpiece, and brings about very excellent effects such as reliable fixation and shortening effect of the curing time.
In addition, when visible light polymerization is performed with a visible light source as a visible light curable adhesive composition with the addition of a visible light polymerization initiator, the optical elements and colored filters having ultraviolet absorptivity are the same as for quartz and glass. In addition, temporary fixing by light irradiation for about several minutes is possible, and productivity can be significantly increased as compared with a conventional method by thermal polymerization that requires several tens of minutes or more. In addition, by performing the polymerization with visible light, there is no risk of the operator being exposed to harmful ultraviolet rays, and a very favorable working environment can be constructed from the viewpoint of safety of the temporary fixing process.
The temporary fixing adhesive composition of the present invention peels off even when the polymerization temperature, polymerization time, irradiance, etc. are increased by the action of the polyalkylene oxide (meth) acrylate represented by the structural formula (I) of the present invention. Since there is no risk of difficulty, even if excessive light irradiation is mistakenly performed or the heating time is prolonged, there is no risk of causing troubles in the processing process or peeling process, which stabilizes the production process. Also useful.
[0029]
Next, the temporarily fixed workpiece is subjected to normal machining such as cutting, grinding, polishing, drilling, etc. in a desired shape, but it is also possible to perform short-time joining such as soldering and brazing. Included in the machining of the inventive method. In that case, since the workpiece | work temporarily fixed with the adhesive composition for temporary fixing of this invention is adhere | attached with high adhesive strength, it does not fall out or deform | transforms during machining, and shows favorable processing durability.
The machined workpiece is peeled from the support substrate and the workpieces. The peeling method can be performed by simply immersing the workpiece in the above-described peeling solution. Under the present circumstances, since the adhesive composition for temporary fixing of this invention peels naturally, without touching a workpiece | work directly, the damage during peeling can be prevented. Further, since a halogen-based solvent or a strong alkaline aqueous solution is not used, it is excellent in terms of work safety and environmental protection. When peeling with water, it is usually performed at a temperature of room temperature to 90 ° C. When stripping with a stripping solution in which water and a water-soluble organic solvent are mixed, the stripping is performed at or below the azeotropic temperature. The temperature at the time of peeling is appropriately set according to the heat resistance of the workpiece, etc., but it is preferable to peel at 40 ° C. to 80 ° C. as long as there is no problem with the workpiece.
As the water-soluble organic solvent used in the stripping solution of the present invention, methanol, ethanol, 2-propanol, methyl 2-hydroxyisobutyrate, N-methylpyrrolidone, or dimethyl sulfoxide is particularly preferable, and two or more kinds of solvents are mixed. Can be used.
[0030]
The mixing ratio of water and the water-soluble organic solvent in the stripping solution of the present invention can be appropriately selected by those skilled in the art according to the type of the temporary fixing adhesive composition of the present invention, Water: water-soluble organic solvent = preferably in a range of 3:97 to 80:20. In particular, peeling with a stripping solution containing water and a water-soluble organic solvent can peel in a shorter time than peeling with water alone, and the workpiece is made of stainless steel or alumina, or the surface is rough. In such a case, an effect such that the residue of the swollen temporarily fixing adhesive is easily peeled off from the workpiece surface can be obtained.
In addition, when peeling is attempted only with the water-soluble organic solvent, there arises a problem that the peeling time becomes significantly long or cannot be peeled off. However, by mixing a small amount of water with a water-soluble organic solvent, the peeling time is remarkably shortened and excellent peeling characteristics are exhibited. This is a phenomenon found for the first time in the present invention, and is a very useful property obtained by combining with the temporary fixing adhesive composition of the present invention.
[0031]
When peeling a workpiece made of a corrosive material such as iron, ferrite, rare earth metal, etc. temporarily fixed with the temporary fixing adhesive composition of the present invention, water is added to the water-soluble organic solvent as described above. If an aqueous solution mixed in a small amount is used as a stripping solution, the effect of suppressing the generation of rust can also be obtained. However, as a method for more actively preventing the generation of rust, the stripping solution can be further divided into aliphatic amines and aromatic amines. , Urea condensates and derivatives thereof, thiourea and substitutes thereof, and water-soluble adsorption-type corrosion inhibitors such as aldehydes.
Specific examples of the water-soluble adsorption-type corrosion inhibitor are disclosed in JP-A-9-291381, JP-A-9-3667, etc. in addition to octylamine, dodecylamine, aniline, thiourea, acetaldehyde and the like. A high-performance water-soluble rust preventive agent can be applied. The amount of these water-soluble adsorption-type corrosion inhibitors used is usually in the range of 1 to 10% by weight with respect to water. It may be used. In particular, when the workpiece material is very susceptible to corrosion, such as rare earth magnetic materials, the above water-soluble adsorption type corrosion inhibitor should be added to the stripping solution in which the weight ratio of water is reduced to about 3 to 20%. With this, a very excellent rust prevention effect is obtained.
In the present invention, as long as the effect of the present invention is not impaired such as not damaging the workpiece, the workpiece is subjected to physical stimulation such as rocking, water flow, ultrasonic wave, temperature change, etc. at the time of peeling. It is possible to further reduce the time required.
[0032]
In addition, there is no restriction | limiting in particular in the magnitude | size of the workpiece processed by the processing method of this invention. Therefore, for example, it is possible to temporarily fix a plate glass having a width of about 1 mx and a length of about 2 m.
However, from the viewpoint that peeling is completed within a time that is practical as a production process after machining, it is temporarily fixed with the adhesive composition for temporary fixation of the present invention as the size of the processed part after machining. It is preferable that the dimension of the part which exists is in the range of 0.1 mm-200 mm preferably. Furthermore, when the dimension of the processed part after machining is in the range of 0.3 mm to 50 mm, the time balance between the machining process and the subsequent peeling process is maintained well, and several thousand to several tens of thousands a day It is advantageous because it enables mass production of up to 10 to be possible without delay.
[0033]
Further, among the machining in the processing method of the present invention, in particular, the effect of temporary fixing by the temporary fixing adhesive composition of the present invention is effectively exhibited. For example, the thickness after machining is 0.1 μm to Examples thereof include precision grinding and polishing processes that require high dimensional accuracy in the range of 10 μm.
That is, the temporary fixing adhesive composition of the present invention can be temporarily fixed to an average thickness of 10 μm or less after temporary fixing, even if the workpiece is several tens of millimeters in size. It can be reduced to 10 μm or less, and further has a feature that the dimensional change due to processing pressure, heat during processing, etc. is extremely small. Therefore, even when a number of workpieces are repeatedly temporarily fixed using the temporary fixing adhesive composition of the present invention, the thickness of the workpiece after temporary fixing is always suppressed to a fixing accuracy of 10 μm or less. In addition, the inclination angle of the temporarily fixed workpiece can be made extremely small (about 50 seconds or less).
Such a feature of the present invention is, for example, a performance particularly suitable for processing a part requiring a high thickness accuracy of several μm or less, such as a crystal resonator, an ultrasonic delay line glass, a precision resistor, and a precision capacitor. .
In addition, even if the thickness of the adhesive composition for temporary fixing of the present invention fluctuates within a range of several μm, it can be processed while measuring and managing the thickness in the processing step of the high-precision part, The thickness accuracy is governed by the inclination angle of the temporarily fixed workpiece. Since the inclination of the workpiece temporarily fixed with the temporary fixing adhesive composition of the present invention can be 0.2 μm or less per 1 mm in length and width, the method of the present invention can be applied to processing that requires the same level of thickness accuracy. .
[0034]
Specific examples of other machining that can suitably use the temporary fixing adhesive composition of the present invention include, for example, dimensions of a portion temporarily fixed with the temporary fixing adhesive composition of the present invention after processing. Cutting, polishing processing of quartz or ceramic vibrators in the range of 0.3 mm to 30 mm, optical prisms, optical lenses, optical filters, ultrasonic delay line glass having the same dimensions in the range of 0.3 mm to 50 mm Cutting, polishing, grinding, etc., cutting, polishing, grinding, drilling of package parts such as stainless steel or aluminum having the same size in the range of 1 mm to 50 mm, micromotor having the same size in the range of 2 mm to 50 mm, or Cutting, grinding, and polishing of miniature magnets for relays, cutting and polishing of ceramic capacitors or precision resistors with the same dimensions in the range of 0.2 mm to 30 mm, and the same dimensions of 0.1 mm to Cutting, polishing and grinding of micromachines or microcapacitors such as silicon, germanium and silicon oxide in the range of several mm, and cutting, grinding and precision of ultrasonic delay line glass in the same range of 0.3 mm to 20 mm A polishing process can be mentioned.
[0035]
【Example】
Next, the present invention will be described in more detail with reference to examples and comparative examples. These are merely examples and do not limit the technical scope of the present invention.
Preparation method of temporary fixing adhesive composition: Each component was weighed, stirred and dissolved at the composition ratio described in Tables 1 and 2 to obtain a temporary fixing adhesive composition. When an ultraviolet polymerization initiator or a visible light polymerization initiator was used, a light shielding container was used. Moreover, the display of the numerical value which shows a composition in Table 1 and 2 shows a weight part.
Ultraviolet photopolymerization method: UV irradiation was performed using a chemical lamp (manufactured by Toshiba Lighting & Technology Corp.).
Thermal polymerization method: Heated within a constant temperature of 80 ° C. for 30 minutes.
Visible light polymerization method: Visible light was irradiated using a visible light lamp (FL-V manufactured by Adel Co., Ltd.).
Peeling time measuring method: The temporarily fixed work was immersed in a peeling solution at a predetermined temperature, and the time when the work was peeled naturally without touching the work was measured.
[0036]
[Example 1]
30 g of N, N-dimethylacrylamide (DMAA), 70 g of hexapropylene glycol monoacrylate (HPGA) in which n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is 6, 2,2′-azobis 0.5 g of isobutyronitrile (AIBN) was placed in a screw cap glass bottle and dissolved by stirring to prepare an adhesive composition for temporary fixing. Prepare two slide glasses (length 76, width 26, thickness 1.3mm), apply the prepared adhesive composition on one slide glass, and put another slide glass on it, bubbles It was put so that it might not get involved. At this time, there was no change in the viscosity of the adhesive composition, the slide glasses could be easily overlapped, and the operability was good. When the thermal polymerization was performed, the two glass slides were firmly fixed, and the glass itself was damaged when it was peeled off with fingers. Pyrex glass having a diameter of 6 mm and a height of 10 mm and a diameter of 20 mm and a height of 25 mm was temporarily fixed with the same adhesive composition under the same conditions, and a compression shear test was performed at a crosshead speed of 1 mm / min using a material testing machine. However, it showed a good adhesive strength of 7.0 MPa.
Next, the thickness of the two glass slides temporarily fixed by the above method was measured with a micrometer, and when the thickness unevenness of the cured adhesive composition was measured, it was 0.010 mm or less. It was confirmed that high fixing accuracy with little unevenness can be obtained. When this slide glass was cut into a width of 10 mm with a diamond cutter, the slide glass did not fall off or was broken during the cutting, and had good cutting durability. When the cut glass slide was immersed in water at 80 ° C., it peeled off in 2 to 5 hours.
As described above, it is confirmed that the temporary fixing adhesive composition of this example has good operability, high fixing accuracy, good processing durability, and excellent productivity for peeling in a short time. It was done.
[0037]
Comparative Examples 1 to 5 shown below are comparative examples with respect to Example 1 of the present invention, and more clearly show the excellent features of the present invention.
[Comparative Example 1] An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, two slide glasses were overlapped by the same operation as in Example 1 without using polyalkylene oxide mono (meth) acrylate. At this time, there was no change in the viscosity of the adhesive composition, the slide glass was easily superimposed, and the operability was good. The two glass slides fixed by thermal polymerization were firmly fixed.
When the adhesive strength was measured in the same manner as in Example 1, the adhesive strength gave a very high adhesive strength of 17.2 MPa or more. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less, and a good fixing accuracy with a small thickness unevenness was obtained. When this slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not drop or break during the cutting, and the processing durability was good.
However, when the cut glass slide is immersed in water at 80 ° C., the adhesive composition becomes a sticky substance, and the glass slide does not peel even after 20 hours of immersion, and cannot be used as an adhesive composition for temporary fixing. Occurred.
That is, it was confirmed that even if the hydrophilic vinyl monomer N, N-dimethylacrylamide (DMAA) disclosed in the present invention was used alone, it could not be used as an adhesive composition for temporary fixing.
[0038]
[Comparative Example 2] A temporary fixing adhesive composition was prepared at the composition ratio shown in Table 2. That is, two glass slides were temporarily fixed by thermal polymerization in the same manner as in Example 1 without using a hydrophilic vinyl monomer. When the adhesive strength was measured in the same manner as in Example 1, it was found to be as small as 1.9 MPa. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass was peeled off during cutting, and sufficient processing durability could not be obtained.
That is, it has been clarified that even if only hexapropylene glycol monoacrylate, which is a compound of structural formula (I) disclosed in the present invention, is used alone, it cannot be used as an adhesive composition for temporary fixing.
[0039]
[Comparative Example 3] An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, methoxypolyethylene glycol monomethacrylate (MPEGMA) having n of 23 was used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I). MPEGMA precipitated without dissolving in N, N-dimethylacrylamide, and the adhesive composition was difficult to solidify and apply at around 12 ° C.
That is, when n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention exceeds the range of the present invention, a homogeneous adhesive composition cannot be obtained and the coating operation is difficult. It was confirmed that
[0040]
[Comparative Example 4] An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, as in Comparative Example 3, methoxypolyethylene glycol monomethacrylate (MPEGMA) in which n is 23 was used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I). However, MPEGMA did not dissolve in acryloylmorpholine and precipitated, and the adhesive composition solidified at around 12 ° C. and could not be applied.
That is, when the n number of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is more than the range of the present invention, a homogeneous adhesive composition can be prepared even if the kind of the hydrophilic monomer is changed. It was confirmed that it could not be applied or applied.
[0041]
[Comparative Example 5] An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, diethylene glycol monomethacrylate (DEGMA) in which n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention is 2 was prepared in the same manner as in Example 1. Sheet glass slides were stacked. At this time, like in Example 1, the operability was good. The two glass slides were firmly fixed by thermal polymerization. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, the thickness unevenness was small at 0.010 mm or less, and high fixing accuracy was obtained. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or was broken during the cutting, showing good processing durability.
However, when the cut glass slide was immersed in water at 80 ° C., it did not peel even after 20 hours.
That is, it has been clarified that when the n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is below the range of the present invention, the part peeling time becomes extremely long and the productivity is remarkably lowered.
[0042]
[Example 2]
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the same operation as in Example 1 was performed using octaethylene glycol monomethacrylate (OEGMA) in which n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention was 8. When two glass slides were superposed on each other, good operability was exhibited as in Example 1. As a result of thermal polymerization, the two glass slides were firmly fixed, and the glass was broken when it was peeled off with fingers. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less and had high fixing accuracy with a small thickness unevenness. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not drop or break during the cutting, indicating good processing durability. When the cut glass slide was immersed in an aqueous solution in which water at 60 ° C. and ethanol were mixed at a weight ratio of 50:50, the glass slide peeled naturally within a short time of 2 to 5 hours.
From these results, even when n of the polyalkylene oxide mono (meth) acrylate of the structural formula (I) is set to 8 and the composition ratio of the hydrophilic monomer is changed in Example 1, it is good as in Example 1. It has been confirmed that a temporary fixing adhesive composition having the features of the present invention that has excellent operability, high fixing accuracy, good processing durability, and short peeling time can be obtained.
[0043]
[Example 3]
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the same operation as in Example 1 was performed using tetraethylene glycol monomethacrylate (TEGMA) in which n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention was 4. The two glass slides were overlapped. At this time, there was no change in the viscosity of the adhesive composition, the slide glass could be easily overlapped, and the operability was good. The two glass slides fixed by ultraviolet polymerization were firmly fixed, and the glass itself was damaged when it was peeled off with fingers. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less and had a high fixing accuracy with a small thickness unevenness. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or was broken during the cutting, showing good processing durability. It was confirmed that when the cut glass slide was immersed in an aqueous solution mixed in a 50:50 weight ratio of water and ethanol at 60 ° C., it peeled off in a short time of 2 to 5 hours.
When n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention is 4, the operability is good, the fixing accuracy is high, and the processing durability is good. It was confirmed that good results were obtained with a short peeling time.
[0044]
[Example 4]
An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 1. That is, a cover glass formed by laminating 50 sheets of methoxytetraethylene glycol monomethacrylate (MTEGMA) in which n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention is 4. (24 × 60 × 0.15 mm) was prepared, and the adhesive composition was infiltrated from the side surface of the laminated cover glass. The adhesive composition quickly penetrated into the gaps between the cover glasses and showed excellent permeability. It was temporarily fixed by irradiating ultraviolet rays from the side surface of the laminated cover glass. The cure time required for complete cure was 30 minutes. The temporarily fixed cover glass was cut to a width of 5 mm with a diamond cutter. The temporarily fixed cover glass did not drop off during the cutting or no chipping occurred, and showed good working durability. When the cut cover glass is immersed in an aqueous solution in which water and ethanol at 60 ° C. are mixed in a weight ratio of 50:50, the cover glass peels off naturally in 3 to 6 hours. It was never damaged.
From the above, this adhesive composition showed excellent performance such as good permeability to laminated products, sufficient curing depth, good processing durability and short peeling time of parts after processing. .
[0045]
[Example 5]
A temporary fixing adhesive composition was prepared at the same composition ratio as in Example 4, 50 cover glasses were prepared, and the adhesive composition was infiltrated from the side of the laminated cover glass. The adhesive composition penetrated rapidly and showed excellent permeability. Visible light was irradiated from the side surface of the laminated cover glass and temporarily fixed. The curing time was 5 minutes, and it was confirmed that it cured to the inside in a much shorter time than ultraviolet polymerization. The temporarily fixed cover glass was cut to a width of 5 mm with a diamond cutter. During the cutting, the cover glass did not drop off or chipped, and the processing durability was good. When the cut cover glass was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 50:50, the cover glass was peeled off in 3 to 6 hours.
Compared with Example 4 in which UV polymerization was performed using a visible light polymerization initiator, in this example in which visible light polymerization was performed, the curing time was greatly shortened and performance equivalent to that during UV polymerization was achieved. It has been confirmed that the productivity can be further improved.
[0046]
Comparative Examples 6 and 7 shown below are comparative examples with respect to Examples 4 and 5 of the present invention, and more clearly show the excellent features of the present invention.
[Comparative Example 6] An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, in the same manner as in Example 4 using methoxynonaethylene glycol monomethacrylate (MNPGMA) in which n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) disclosed in the present invention is 9, 50 cover glasses were prepared, and the adhesive composition was infiltrated from the laminated surface. The adhesive composition penetrated rapidly and showed excellent permeability. It was temporarily fixed by irradiating ultraviolet rays from the side surface of the laminated cover glass. The curing time required 30 minutes. When the temporarily fixed cover glass was cut to a width of 5 mm with a diamond cutter, the cover glass fell off during the cutting, and sufficient processing durability was not obtained.
Thus, when n of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) exceeds the range of the present invention, it is clear that the adhesion with the workpiece is lowered and the processing durability cannot be obtained. It became.
[Comparative Example 7] An adhesive composition for temporary fixing was prepared at the composition ratio shown in Table 2. That is, a cover glass in which 50 sheets were laminated in the same manner as in Example 4 without containing the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) was prepared, and the adhesive composition penetrated from the laminated surface. I let you. The adhesive composition penetrated rapidly and the permeability was excellent. Ultraviolet rays were irradiated from the lamination side. The curing distance when irradiated for 30 minutes was 3 mm, and the central portion remained uncured.
Thus, as compared with Examples 4 and 5, the adhesive composed only of the hydrophilic monomer and the ultraviolet polymerization initiator without containing the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) The adhesive composition was found to be unsuitable as an adhesive composition because it could not be temporarily attached to the laminate.
[0047]
[Example 6]
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, as radical polymerization initiator, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (BTPO) was used instead of (AIBN) used in Example 1, and the same as in Example 1. Two slide glasses were overlapped by operation. At this time, there was no change in the viscosity of the adhesive composition, the slide glass could be easily overlapped, and the operability was good. Two glass slides were firmly fixed by visible light polymerization. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less, and a high fixing accuracy with a small thickness unevenness was obtained. When this slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or was broken during the cutting, showing good processing durability. When the cut glass slide was immersed in water at 80 ° C., it peeled off in 2 to 5 hours.
[0048]
[Example 7]
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the amount of HPGA used as polyalkylene oxide mono (meth) acrylate in Example 6 was reduced from 70 parts by weight to 60 parts by weight, and two slide glasses were overlapped in the same manner as in Example 1. It was. At this time, there was no change in the viscosity of the adhesive composition, the slide glass could be easily overlapped, and the operability was good. The two glass slides fixed by visible light polymerization were firmly fixed as in Example 1. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less, and the thickness unevenness was small and high fixing accuracy was obtained. When the temporarily fixed slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or was broken during the cutting, showing good processing durability. When the cut glass slide was immersed in water at 80 ° C., it peeled off in 2 hours and peeled off in a shorter time than Example 6.
From these results, the amount of HPGA used as the polyalkylene oxide mono (meth) acrylate was adjusted from 70 parts by weight to 60 parts by weight as compared with Example 6, and the peeling time was further shortened. It was confirmed that the property was further improved.
[0049]
[Example 8]
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, a cover glass in which 50 sheets were laminated in the same manner as in Example 4 was prepared by reducing the amount of MTEGMA used as polyalkylene oxide mono (meth) acrylate in Example 4 from 70 parts by weight to 50 parts by weight. The adhesive composition was infiltrated from the side surface of the laminated cover glass. The adhesive composition penetrated rapidly and showed excellent permeability. It was temporarily fixed by irradiating ultraviolet rays from the side surface of the laminated cover glass. The curing time required 30 minutes and cured to the inside. This cover glass was cut into a width of 5 mm with a diamond cutter. In the cutting process, the cover glass did not drop off or chipped and showed good processing durability. When the cut cover glass was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 50:50, the cover glass was peeled off in 2 to 4 hours and peeled off in a shorter time than Example 4.
From these results, the amount of MTEGMA used as polyalkylene oxide mono (meth) acrylate was 70 parts by weight in Example 4, whereas the result was 50 parts by weight in this example, resulting in a reduction in peeling time. It has been found that productivity is increased.
[0050]
[Example 9]
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the amount of MTEGMA used was reduced to 50 parts by weight in the same manner as in Example 8 to prepare a cover glass in which 50 sheets were laminated, and the adhesive composition was infiltrated from the side surface of the laminated cover glass. The adhesive composition penetrated rapidly and showed excellent permeability. Visible light was irradiated from the side surface of the laminated cover glass and temporarily fixed. The curing time required 5 minutes, and cured to the inside in a short time. This cover glass was cut into a width of 5 mm with a diamond cutter. In the cutting process, the workpiece did not fall off or chipped and showed good machining durability. When the cut cover glass was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 50:50, the cover glass was peeled off in 2 to 4 hours.
From these results, it was found that the curing time was further shortened when visible light polymerization was performed using a visible light polymerization initiator in Example 8 where ultraviolet polymerization was performed using an ultraviolet initiator. .
[0051]
[Example 10]
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, two slide glasses were overlapped in the same manner as in Example 1 with the amount of OEGMA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention being 7 parts by weight. At this time, there was no change in the viscosity of the adhesive composition, the slide glass could be easily overlapped, and the operability was good. The two glass slides fixed by UV polymerization were firmly fixed as in Example 1. When the adhesive strength was measured in the same manner as in Example 1, the adhesive strength was 11.0 MPa, indicating excellent adhesive strength. When the thickness unevenness of the cured adhesive composition was measured in the same manner as in Example 1, it was 0.010 mm or less, and the thickness unevenness was small and high fixing accuracy was obtained. When this slide glass was cut to a width of 10 mm with a diamond cutter, the slide glass did not fall off or was broken during the cutting, showing good processing durability. When the cut glass slide was immersed in water at 80 ° C., it peeled off in 6 hours.
From these results, even when the amount of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention is 10 parts by weight or less, it has good permeability to the laminated workpieces, It has been found that an excellent temporary fixing adhesive composition that exhibits good operability and high fixing accuracy, has excellent processing durability and does not interfere with peeling can be obtained.
[0052]
Example 11
Using the adhesive composition prepared at the same composition ratio as in Example 10, 50 slide glasses were temporarily fixed in the same manner as in Example 10 and cut. When the cut glass slide having a width of 10 mm was immersed in an aqueous solution in which water at 60 ° C. and ethanol were mixed at a weight ratio of 80:20, it was peeled off in 3 hours, and the peeling time was shortened compared to Example 10. It was confirmed that the peeling time was further shortened when peeling with an aqueous solution in which water and ethanol disclosed in the present invention were mixed at a weight ratio of 80:20 instead of water.
[0053]
Example 12
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, a cover glass in which 50 sheets of HPGA were used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention in an amount of 7 parts by weight as in Example 4 was prepared and laminated. The adhesive composition was infiltrated from the side surface of the cover glass. The adhesive composition penetrated rapidly and showed excellent permeability. Ultraviolet light was irradiated from the side surface of the laminated cover glass. The curing time required 30 minutes. This cover glass was cut into a width of 2 mm with a diamond cutter. In the cutting process, the cover glass did not drop off or chipped and showed good processing durability. When the cut cover glass was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 50:50, the cover glass peeled off in 3 hours.
From these results, even if the amount of polyalkylene oxide mono (meth) acrylate used is small, it shows excellent permeability, short curing time, good processing durability, and processed parts are short. It peeled in time.
[0054]
Example 13
Using the adhesive composition prepared at the same composition ratio as in Example 12, a cover glass having 50 laminated layers was prepared in the same manner as in Example 12, and the adhesive composition was applied from the side surface of the laminated cover glass. Infiltrated. The adhesive composition penetrated rapidly and showed excellent permeability. Visible light was irradiated from the side surface of the laminated cover glass. The curing time required 5 minutes. This cover glass was cut into a width of 2 mm with a diamond cutter. In the cutting process, the workpiece did not fall off or chipped and showed good machining durability. When the cut cover glass was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 50:50, the cover glass peeled off in 3 hours. The curing time was further shortened by performing visible light polymerization on Example 12 in which UV polymerization was performed using a visible light initiator and further using visible light polymerization initiator.
[0055]
Example 14
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the amount of TEGMA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention is 25 parts by weight, and two alumina test pieces (length 25, width 25, thickness 2 mm) The adhesive composition was applied onto one alumina test piece, and another alumina test piece was placed thereon. At this time, there was no change in the viscosity of the adhesive composition, the alumina test pieces could be easily overlapped, and the operability was good. The two alumina test pieces were firmly fixed by thermal polymerization. The alumina test piece was cut to a width of 5 mm with a diamond cutter. In the cutting process, the alumina test piece did not drop off or chipped, and the processing durability was good.
When the cut specimen made of alumina was immersed in water at 80 ° C., it peeled off in 4 hours. Some residue of the adhesive composition was adhered on the peeled alumina test piece. This deposit was removed by additional 1 hour immersion. It was also found that ultrasonic cleaning in a 50% alcohol aqueous solution instead of additional dipping removed in 10 minutes.
In addition, an alumina test piece having a diameter of 6 mm, a height of 10 mm, and a diameter of 20 mm and a height of 20 mm separately prepared according to Example 1 was thermally polymerized using the adhesive composition of the present invention under the same conditions as in this example. Glued. When the compression shear adhesive strength of this test piece was measured at a crosshead speed of 1 mm / min using a material testing machine, it showed an excellent adhesive strength of 10 MPa.
[0056]
Example 15
Using an adhesive composition prepared at the same composition ratio as in Example 14, an alumina test piece was temporarily fixed and cut under the same conditions as in Example 14. When the cut specimen made of alumina was immersed in an aqueous solution in which water at 80 ° C. and methyl 2-hydroxyisobutyrate (HBM) were mixed at a weight ratio of 50:50, it peeled in 3 hours and was shorter than that in Example 13. Peeled in time. Moreover, the residue of the adhesive composition did not adhere on the peeled alumina test piece in this example.
That is, when peeling with an aqueous solution in which water and methyl 2-hydroxyisobutyrate (HBM) are mixed at a weight ratio of 50:50 instead of water, the peeling time is shortened and the peeled adhesive composition adheres to the part. By not doing so, it was found that the cleaning process of parts can be simplified and the productivity is improved.
[0057]
Example 16
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the amount of HPGA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention was 25 parts by weight, and two stainless steel test pieces (length 8, width 5, thickness 5 mm). The adhesive composition was coated on one stainless steel test piece, and another stainless steel test piece was placed thereon. Two stainless steel test pieces were temporarily fixed by thermal polymerization. At this time, there was no change in the viscosity of the adhesive composition, and the stainless steel test pieces could be easily overlapped, and the operability was good. Two stainless steel specimens were firmly fixed by thermal polymerization. In the same manner as in Example 14, a stainless steel test piece for adhesion test was prepared, temporarily fixed under the polymerization conditions of this example, and when the adhesive strength was measured, an excellent adhesive strength of 11.0 MPa was shown.
Next, when the stainless steel test piece temporarily fixed and cut in this example was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 50:50, it peeled off in 2 hours, but slightly adhered to the surface. The residue of the agent composition was adhered. Thereafter, this deposit was removed cleanly by additional immersion for 1 hour. Moreover, when performing ultrasonic cleaning in 50% ethanol aqueous solution instead of performing the said additional immersion, it turned out that it removes in 10 minutes.
[0058]
[Example 17]
Using the adhesive composition prepared at the same composition ratio as in Example 16, the stainless steel test piece temporarily fixed in Example 16 was immersed in an aqueous solution of 80 ° C. water / HBM = 50/50 wt / wt. Then, it peeled in 2 hours. In this example, the adhesive composition did not adhere to the peeled stainless steel test piece.
That is, when the stripping solution is stripped as an aqueous solution in which water and methyl 2-hydroxyisobutyrate (HBM) are mixed at a weight ratio of 50:50 instead of an aqueous solution in which water and ethanol are mixed at a weight ratio of 50:50 It has been found that the peeling time is shortened, and the peeled adhesive composition does not adhere to the part, which simplifies the cleaning process of small articles and improves the productivity.
[0059]
Example 18
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the amount of HPGA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention is 15 parts by weight, and two rare earth magnetic specimens having a length and width of about 50 mm are prepared. The adhesive composition was applied on one rare earth magnetic test piece, and another rare earth magnetic test piece was placed thereon. At this time, there was no change in the viscosity of the adhesive composition, the test pieces made of rare earth magnetic material could be easily overlapped, and the operability was good. Two rare earth magnetic specimens were firmly fixed by thermal polymerization. This rare earth magnetic specimen was cut to a width of 2 mm with a diamond cutter. No cutting or chipping occurred in the cutting process and showed excellent processing durability. When the cut specimen made of rare earth magnetic material was immersed in an aqueous solution in which water at 80 ° C. and methyl 2-hydroxyisobutyrate (HBM) were mixed at a weight ratio of 3 to 97, it was peeled off in 4 hours. The test piece did not show rust during peeling. However, it was taken out from the stripping solution, wiped off the stripping solution and allowed to stand in a dry room for 3 days, and some signs of rusting were observed.
[0060]
[Comparative Example 8] When a rare earth magnetic test piece cut to a width of 2 mm in Example 18 was immersed in a 100% HBM solvent at 80 ° C, it did not peel even after 20 hours. Compared with Example 18, when HBM is 100% and does not contain water, it does not exfoliate, but the effect of the present invention is that the exfoliation time can be remarkably shortened by using the aqueous solution of the present invention to which 3% of water is added. It was shown simply.
[0061]
Example 19
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, the amount of HPGA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention is 15 parts by weight, and similarly to Example 4, a cover glass in which 50 sheets are laminated is prepared, The adhesive composition was infiltrated from the side surface of the laminated cover glass. The adhesive composition penetrated rapidly and showed excellent permeability. When visible light was irradiated from the side surface of the laminated cover glass, the whole was completely polymerized in 5 minutes. When the adhesive strength was measured in the same manner as in Example 1, it showed an excellent adhesive strength of 11.0 MPa or more. The temporarily fixed cover glass was cut into a width of 2 mm with a diamond cutter. During the cutting, the cover glass did not drop off or chipped, and the processing durability was good. When the cut cover glass was immersed in an aqueous solution in which water and ethanol at 60 ° C. were mixed at a weight ratio of 50:50, it was peeled off in 2 hours.
Compared to Example 13, when the amount of polyalkylene oxide mono (meth) acrylate used was increased, the peeling time was shortened.
The test piece made of rare earth magnetic material did not rust during immersion in the stripping solution. However, when it was taken out from the stripping solution, wiped off, and left in a dry room, it was found that rust was generated the next day.
[0062]
Example 20
Adhesive compositions for temporary fixing were prepared at the composition ratios shown in Table 1. That is, two rare earth magnetic test pieces similar to Example 18 were prepared with the amount of OEGMA used as the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) of the present invention being 60 parts by weight. Then, the adhesive composition was applied on one rare earth magnetic test piece, and another rare earth magnetic test piece was placed thereon. At this time, there was no change in the viscosity of the adhesive composition, the test pieces made of rare earth magnetic material could be easily overlapped, and the operability was good. When two rare earth magnetic specimens were temporarily fixed by thermal polymerization, the rare earth magnetic specimens were firmly fixed. This rare earth magnetic specimen was cut to a width of 5 mm with a diamond cutter. No cutting or chipping occurred in the cutting process and showed excellent processing durability. When the cut specimen made of rare earth magnetic material was immersed in an aqueous solution in which water at 80 ° C. and methyl 2-hydroxyisobutyrate (HBM) were mixed at a weight ratio of 10:90, it was peeled off in 3 hours. This rare earth magnetic specimen did not show any rust during peeling, but it was removed from the stripping solution, wiped off the stripping solution, and left in a dry room. Occurred.
[0063]
Example 21
4% by weight of Yushiroken SC25A manufactured by Yushiro Chemical Industry Co., Ltd. was added as a water-soluble adsorption-type corrosion inhibitor to the rare earth magnetic material having a width of 5 mm cut in Example 20, and this was added to methyl 2-hydroxyisobutyrate. When exfoliated by dipping in an aqueous solution (60 ° C) mixed with (HBM) at a weight ratio of 10 to 90, the peel time was as short as 4 hours, indicating good peelability. Furthermore, the peeled rare earth magnetic test piece does not cause rust during peeling, and it has excellent rust prevention effect because it does not generate rust even if it is removed from the stripping solution, wiped off water droplets and left in a dry room for 3 days. showed that.
[0064]
【The invention's effect】
The temporary fixing adhesive composition of the present invention does not need to be applied under heating conditions with a viscosity change like hot-melt adhesives such as wax and pine yarn, and has a stable viscosity at room temperature. Therefore, even an inexperienced operator can easily perform accurate alignment and high operability, and since high-temperature operation is not performed, there is no danger of burns associated with alignment and safety is ensured. high.
And since this temporary fixing adhesive composition has excellent permeability, it can temporarily fix stacked workpieces, so a large number of parts can be processed in a single temporary fixing operation, resulting in high productivity. It is done. Moreover, since the thickness unevenness of the temporarily fixed adhesive composition is small, the processing accuracy at the time of machining is also high. Furthermore, since the adhesive strength at the time of temporary fixing is also excellent, it shows sufficient processing durability in the machining of the workpiece, prevents parts from being dropped or lost during processing, and improves the manufacturing yield. In addition, by immersing the processed parts in water or an aqueous solution of water and organic solvent, the parts can be removed quickly without defects, which contributes to shortening the process time and improving the yield. Showing gender.
In addition, when a visible light polymerization initiator is used as the radical polymerization initiator of the adhesive composition for temporary fixing of the present invention, it is simple and short-time particularly for multi-layered workpieces and UV-absorbing workpieces. Can be temporarily fixed by light irradiation, and productivity can be further improved.
Furthermore, if the amount of the polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is limited in the temporary fixing adhesive composition of the present invention, the peeling time can be further shortened, and the productivity is further improved. It is also possible to improve.
[0065]
Further, when the temporary fixing adhesive composition of the present invention is peeled off, if the method disclosed in the present invention is immersed in an aqueous solution in which water and a specific water-soluble organic solvent are mixed, the peeling time can be further shortened. Is possible. Furthermore, by adding the water-soluble adsorptive corrosion inhibitor disclosed in the present invention to the water used as the stripping solution, rust is generated even for parts made of materials such as metals or rare earth magnetic materials that are likely to generate rust. The adhesive composition for temporary fixing of the present invention can be applied without causing the above problem, and the practical problems often caused when water or an aqueous solution is conventionally used as a stripping solution for these materials are also eliminated. The
Furthermore, the processing method of the present invention is a method characterized in that after temporarily fixing using the temporary fixing adhesive of the present invention, peeling is performed with water or a mixed aqueous solution of water and a specific water-soluble organic solvent. Therefore, there is no need to use harmful or dangerous hydrocarbon solvents or halogen solvents, and environmental pollutants are eliminated from the parts processing process, greatly improving environmental protection and work safety. I can do it.
Such an excellent effect of the present invention is an effect peculiar to the adhesive composition for temporary fixing of the present invention obtained when water or water and a specific water-soluble organic solvent are used as a stripping solution, and is disclosed in the present invention. The part processing method thus achieved is achieved by fully exhibiting the features of the temporary fixing adhesive of the present invention.
[0066]
Tables 1 and 2 are shown below. Furthermore, the meanings of the abbreviations of the substances used in the specification and in these tables are summarized in Tables 3 and 4.
[0067]
[Table 1]

[0068]
[Table 2]

[0069]
[Table 3]

[0070]
[Table 4]

[0071]
[Table 5]

Claims (12)

1), 2), and 3) below, an adhesive composition for temporary fixing,
1) at least one selected from the group consisting of N, N-dimethylacrylamide, N-vinylcaprolactam, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and glycerol (meth) acrylate Kinds of hydrophilic vinyl monomers;
2) At least one polyalkylene oxide mono (meth) acrylate represented by the following structural formula (I)

However, R1, R2, R3 is H or _CH 3, n is an integer from 4 to 8; and 3) a radical polymerization initiator. The radical polymerization initiator is at least one visible light polymerization initiator selected from the group consisting of camphorquinone, acylphosphine oxide, α-aminoketone, bisacylphosphine oxide, and metallocene, The adhesive composition for temporary fixing according to claim 1. The temporary fixing adhesive according to claim 1, wherein the amount of the at least one polyalkylene oxide mono (meth) acrylate represented by the structural formula (I) is 10 to 60% by weight. Composition. The radical polymerization initiator is at least one visible light polymerization initiator selected from the group consisting of camphorquinone, acylphosphine oxide, α-aminoketone, bisacylphosphine oxide, and metallocene, and a structural formula ( The adhesive composition for temporary fixing according to claim 1, wherein the amount of the at least one polyalkylene oxide mono (meth) acrylate represented by I) is 10 to 60% by weight. A part to be processed is temporarily fixed using the adhesive composition for temporary fixing according to claim 1 and subjected to predetermined machining, followed by water, alcohol, ketone, polyhydric alcohol, or nitrogen compound. , And a part to be processed is peeled off by immersing the workpiece in a stripping solution composed of an aqueous solution obtained by mixing at least one water-soluble organic solvent selected from the group consisting of sulfur compound-based water-soluble organic solvents and water. How to process parts. 6. The component processing method according to claim 5, wherein the temporary fixing adhesive composition according to claim 2 is used for temporary fixing by irradiation with visible light. 6. The method for processing a part according to claim 5, wherein the adhesive composition for temporary fixing according to claim 3 is used. 6. The component processing method according to claim 5, wherein the temporary fixing adhesive composition according to claim 4 is temporarily fixed by irradiation with visible light. The water-soluble organic solvent is at least one organic solvent selected from the group consisting of methanol, ethanol, 2-propanol, methyl 2-hydroxyisobutyrate, N-methylpyrrolidone, and dimethyl sulfoxide, and the mixing ratio is The method of processing a part according to any one of claims 5 to 8, wherein the ratio of water: water-soluble organic solvent is 3:97 to 80:20. The stripping solution further contains at least one water-soluble adsorptive corrosion inhibitor selected from the group consisting of aliphatic amines, aromatic amines, thiourea and substitution products thereof, and aldehydes. The method of processing a part according to any one of claims 5 to 9. 2. An aqueous solution obtained by mixing at least one water-soluble organic solvent selected from the group consisting of alcohol-based, ketone-based, polyhydric alcohol-based, nitrogen compound-based, and sulfur compound-based water-soluble organic solvents with water. The stripping solution for adhesive composition for temporary fixing as described in any one of 1 thru | or 4. From the adhesive composition for temporary fixing according to any one of claims 1 to 4, and water or an alcohol-based, ketone-based, polyhydric alcohol-based, nitrogen compound-based, and sulfur compound-based water-soluble organic solvent. A temporary adhesive kit comprising a stripping solution comprising an aqueous solution obtained by mixing at least one water-soluble organic solvent selected from the group consisting of water and water.