JP2007093856A - Photosensitive epoxy resin adhesive film - Google Patents
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Abstract
Description
本発明は、感光性エポキシ樹脂接着性フィルムに関し、詳しくは、被着体上に転写し、フォトマスクを介して露光させ、現像処理することによってパターン形成することができ、更に、このようにして、パターン形成した後においても、加熱すれば、そのパターンを維持したまま、そのパターン上に第２の被着体を加圧接着することができ、しかも、フィルム厚みが大きい場合であっても、上述したように、上記パターン上に第２の被着体を加圧接着する際の変形、即ち、膜厚の減少を抑えた感光性エポキシ樹脂接着性フィルムに関する。 The present invention relates to a photosensitive epoxy resin adhesive film, and more specifically, a pattern can be formed by transferring onto an adherend, exposing through a photomask, and developing, and in this way. Further, even after the pattern is formed, if the heating is performed, the second adherend can be pressure-bonded on the pattern while maintaining the pattern, and even if the film thickness is large, As described above, the present invention relates to a photosensitive epoxy resin adhesive film that suppresses deformation when a second adherend is pressure-bonded onto the pattern, that is, a reduction in film thickness.
近年、情報通信機器の小型化や高集積化に伴い、内部の実装部品も、これまでのリードフレームパッケージからＢＧＡ、ＣＳＰ等のような新しい高密度半導体パッケージに移行しつつあり、そこで、例えば、半導体素子と回路板との接合や複数の回路板相互の接合のために、パターン形成した接着剤を用いることが提案されている（例えば、特許文献１参照）。 In recent years, with the miniaturization and high integration of information communication equipment, internal mounting components are also shifting from the conventional lead frame package to new high-density semiconductor packages such as BGA, CSP, etc. It has been proposed to use a patterned adhesive for joining a semiconductor element and a circuit board or joining a plurality of circuit boards (for example, see Patent Document 1).
しかし、一般に、従来より知られている感光性接着剤組成物は、これを露光させ、現像して、パターン形成する際に、それに用いられている樹脂が架橋し、硬化するので、このようにパターン形成した後の接着剤組成物層に被着体を接着するには、高い温度で被着体を熱圧着せざるを得ない。また、従来の感光性接着剤組成物は、上述したように、パターン形成の際に、架橋、硬化しているので、このように高い温度で熱圧着しても、その際、幾らかは軟化するものの、十分な流動性を有するには至らず、その結果として、接着剤と被着体との間の接着界面に部分的な空隙が生じるので、通常、接着剤と被着体との間に十分な接着力を得ることが困難である。勿論、このような接着剤によって接着させる半導体素子や回路板には、加熱によって損傷を受けるものもあるので、上述したように、高い温度での接着は、本来、避けるべきものである。 However, in general, conventionally known photosensitive adhesive compositions are exposed to light, developed, and formed into a pattern, because the resin used in the composition is crosslinked and cured. In order to adhere the adherend to the adhesive composition layer after pattern formation, the adherend must be thermocompression bonded at a high temperature. In addition, since the conventional photosensitive adhesive composition is crosslinked and cured during pattern formation as described above, even if thermocompression bonding is performed at such a high temperature, some softening occurs at that time. However, it does not have sufficient fluidity, and as a result, a partial gap is formed at the adhesive interface between the adhesive and the adherend, and thus usually between the adhesive and the adherend. It is difficult to obtain a sufficient adhesive strength. Of course, some semiconductor elements and circuit boards to be bonded by such an adhesive are damaged by heating, and as described above, bonding at high temperatures should be avoided originally.
更に、従来は、被着体上に感光性接着剤組成物にて厚み５０μｍ以上の塗膜を形成した後、露光させ、現像して、パターンを形成した後、又は厚み５０μｍ以上の感光性接着性フィルムを被着体上に転写し、これを露光させ、現像して、パターンを形成した後、このパターン上に第２の被着体を加熱下に加圧接着するときに、上記パターンの変化、即ち、主として、膜厚の減少が生じる問題があった。このように、第１の被着体上に形成したパターン上に第２の被着体を加圧接着するときにパターンの膜厚が減少すれば、例えば、第１と第２の被着体の間にそのパターンをスペーサとして空隙を形成する際に、スペーサとしての精度に劣ることとなる。
本発明は、従来の感光性接着性フィルムにおける上述したような問題を解決するためになされたものであって、被着体上に転写し、フォトマスクを介して露光させ、現像処理することによってパターン形成することができ、更に、このようにして、パターン形成した後においても、加熱すれば、そのパターンを維持したまま、高い接着性を有し、従って、そのパターン上に第２の被着体を容易に加圧接着することができ、しかも、フィルム厚みが、例えば、５０μｍ以上というように、大きい場合であっても、上述したように、上記パターン上に加熱下に第２の第２の被着体を加圧接着する際に、パターンの変化、即ち、主として、膜厚の減少の少ない感光性エポキシ樹脂接着性フィルムを提供することを目的とする。 The present invention has been made to solve the above-mentioned problems in conventional photosensitive adhesive films, and is transferred onto an adherend, exposed through a photomask, and developed. Further, after the pattern is formed in this way, if it is heated, it has high adhesiveness while maintaining the pattern, so that the second deposition is applied on the pattern. Even if the body can be pressure-bonded easily and the film thickness is large, for example, 50 μm or more, as described above, the second second layer is heated on the pattern as described above. It is an object of the present invention to provide a photosensitive epoxy resin adhesive film in which a change in pattern, that is, a reduction in film thickness is mainly small when the adherend is pressure-bonded.
本発明によれば、中間層とこれを挟む一対の表面層とからなる感光性エポキシ樹脂接着性フィルムにおいて、上記中間層と上記一対の表面層のいずれもがエポキシ当量１００〜３００ｇ／当量のグリシジル基を有する多官能エポキシ樹脂とエポキシ当量４５０〜１００００ｇ／当量のグリシジル基を有する多官能エポキシ樹脂とからなる低反応性エポキシ樹脂と光酸発生剤とを有し、上記中間層が更に脂環式エポキシ樹脂及びオキセタン樹脂から選ばれる少なくとも１種の高反応性樹脂を含有することを特徴とする感光性エポキシ樹脂接着性フィルムが提供される。 According to the present invention, in the photosensitive epoxy resin adhesive film comprising an intermediate layer and a pair of surface layers sandwiching the intermediate layer, each of the intermediate layer and the pair of surface layers has an epoxy equivalent of 100 to 300 g / equivalent glycidyl. A low-reactivity epoxy resin comprising a polyfunctional epoxy resin having a group and a polyfunctional epoxy resin having an epoxy equivalent of 450 to 10,000 g / equivalent glycidyl group, and a photoacid generator, wherein the intermediate layer is further alicyclic There is provided a photosensitive epoxy resin adhesive film comprising at least one highly reactive resin selected from an epoxy resin and an oxetane resin.
本発明によれば、このような感光性エポキシ樹脂接着性フィルムにおいて、上記一対の表面層がそれぞれ、低反応性エポキシ樹脂として、エポキシ当量１００〜３００ｇ／当量の多官能エポキシ樹脂５〜９０重量％とエポキシ当量４５０〜１００００ｇ／当量の多官能エポキシ樹脂１０〜９５重量％とを含有することが好ましい。また、上記中間層は、エポキシ当量１００〜３００ｇ／当量の多官能エポキシ樹脂４〜６０重量％とエポキシ当量４５０〜１００００ｇ／当量の多官能エポキシ樹脂１０〜９５重量％と高反応性樹脂１〜３０重量％とを含有することが好ましい。 According to the present invention, in such a photosensitive epoxy resin adhesive film, each of the pair of surface layers is a low-reactivity epoxy resin, and an epoxy equivalent of 100 to 300 g / equivalent polyfunctional epoxy resin of 5 to 90% by weight. And 10 to 95% by weight of a polyfunctional epoxy resin having an epoxy equivalent of 450 to 10,000 g / equivalent. The intermediate layer is composed of 4 to 60% by weight of a polyfunctional epoxy resin having an epoxy equivalent of 100 to 300 g / equivalent, 10 to 95% by weight of a polyfunctional epoxy resin having an epoxy equivalent of 450 to 10,000 g / equivalent and 1 to 30 highly reactive resins. It is preferable to contain the weight%.
更に、本発明によれば、感光性エポキシ樹脂接着性フィルムは、５０〜２００μｍの範囲の厚みを有し、この厚みのうち、中間層が３０〜９０％を占めることが好ましい。また、上記中間層と一対の表面層のうち、少なくとも一対の表面層は、いずれか又は両方がエポキシ変性シリコーンを含有することが好ましい。 Furthermore, according to the present invention, the photosensitive epoxy resin adhesive film has a thickness in the range of 50 to 200 μm, and the intermediate layer preferably accounts for 30 to 90% of this thickness. In addition, it is preferable that at least one of the intermediate layer and the pair of surface layers includes at least one epoxy-modified silicone.
本発明の感光性エポキシ樹脂接着性フィルムは、中間層とこれを挟む一対の表面層とからなる３層構造を有し、上記中間層と上記表面層のいずれもがエポキシ当量１００〜３００ｇ／当量のグリシジル基を有する多官能エポキシ樹脂とエポキシ当量４５０〜１００００ｇ／当量のグリシジル基を有する多官能エポキシ樹脂とからなる低反応性エポキシ樹脂と光酸発生剤を含むので、露光と現像処理によってパターン形成することができ、しかも、パターン形成した後においても、加熱すれば、そのパターンを維持したまま、耐湿信頼性や耐薬品性にすぐれる高い接着性を発現することができ、従って、そのパターン上に第２の被着体を容易に加圧接着することができる。 The photosensitive epoxy resin adhesive film of the present invention has a three-layer structure comprising an intermediate layer and a pair of surface layers sandwiching the intermediate layer, and both the intermediate layer and the surface layer have an epoxy equivalent of 100 to 300 g / equivalent. A pattern is formed by exposure and development processing because it contains a low-reactivity epoxy resin comprising a polyfunctional epoxy resin having a glycidyl group and a polyfunctional epoxy resin having an epoxy equivalent of 450 to 10,000 g / equivalent glycidyl group and a photoacid generator. Furthermore, even after pattern formation, if the pattern is heated, high adhesiveness with excellent moisture resistance reliability and chemical resistance can be expressed while maintaining the pattern. In addition, the second adherend can be easily pressure-bonded.
ここに、本発明によれば、上記中間層は、上記低反応性エポキシ樹脂に加えて、更に、脂環式エポキシ樹脂とオキセタン樹脂から選ばれる少なくとも１種の高反応性樹脂を含有するので、露光、現像後、表面層に比べて、架橋密度がより高く、従って、より硬い樹脂層を形成し、かくして、このような中間層を含む架橋したエポキシ樹脂からなるパターン上に第２の被着体を加圧接着しても、パターンの膜厚の変化が小さく、従って、第１と第２の被着体の間にそのパターンをスペーサとして精度高く空隙を形成しつつ、第１と第２の被着体をそのパターンにて相互に接着することができる。 Here, according to the present invention, the intermediate layer further contains at least one highly reactive resin selected from an alicyclic epoxy resin and an oxetane resin in addition to the low reactivity epoxy resin. After exposure and development, the cross-linking density is higher than the surface layer, thus forming a harder resin layer, and thus a second deposition on a pattern of cross-linked epoxy resin containing such an intermediate layer. Even if the body is pressure-bonded, the change in the film thickness of the pattern is small. Therefore, the first and second are formed with high accuracy using the pattern as a spacer between the first and second adherends. The adherends can be bonded to each other in the pattern.
かくして、本発明の感光性エポキシ樹脂接着性フィルムによれば、厚みが大きい場合であっても、被着体への密着性にすぐれる微細なパターンを形成することができ、しかも、このように、パターンを形成した後、このパターンの変形を抑えつつ、維持したまま、このパターン上に第２の被着体を熱圧着して、容易に速やかに被着体間に所要の空隙を形成することができる。 Thus, according to the photosensitive epoxy resin adhesive film of the present invention, it is possible to form a fine pattern with excellent adhesion to an adherend even when the thickness is large, and in this way After the pattern is formed, the second adherend is thermocompression-bonded on the pattern while suppressing and maintaining the deformation of the pattern, and a required gap is easily formed between the adherends. be able to.
更に、本発明に従って、感光性接着性フィルムを被着体に転写したとき、外部に露出している外側層をなす表面層に比べて、被着体への転写面をなす表面層、即ち、内側層において、光酸発生剤をより多く配合することによって、接着性フィルムの厚みが５０μｍ以上のように大きい場合であっても、露光に際して、被着体上の上記フィルムの底部近傍において、ここに到達する活性光線量が外側層に比べて少ない場合であっても、光酸発生剤が十分な量の酸を発生して、エポキシ樹脂の架橋、硬化反応を引き起こすので、かくして、得られるパターンは断面が矩形状であって、被着体に対して高い密着力を有する。 Furthermore, when the photosensitive adhesive film is transferred to the adherend according to the present invention, the surface layer forming the transfer surface to the adherend is compared with the surface layer forming the outer layer exposed to the outside, that is, In the inner layer, by adding more photoacid generator, even when the thickness of the adhesive film is as large as 50 μm or more, in the vicinity of the bottom of the film on the adherend, Even when the amount of actinic rays reaching the surface is smaller than that of the outer layer, the photoacid generator generates a sufficient amount of acid to cause crosslinking and curing reaction of the epoxy resin. Has a rectangular cross section and has high adhesion to the adherend.
更に、本発明の感光性エポキシ樹脂接着性フィルムにおいては、少なくとも一方の表面層が上記エポキシ樹脂と共に、エポキシ変性シリコーンを含有していてもよい。このように、エポキシ樹脂と共にエポキシ変性シリコーンを含有する表面層は、露光後の現像処理において、未露光部が現像液によって速やかに溶解されるので、エポキシ変性シリコーンを含んでいない場合に比べて、現像時間が短縮される。従って、本発明の感光性エポキシ樹脂接着性フィルムは、厚みが５０μｍ以上のように大きい場合であっても、これを被着体上に転写し、露光させ、現像する際に、現像時間を短縮して、速やかに所要のパターンを形成することができる。 Furthermore, in the photosensitive epoxy resin adhesive film of this invention, at least one surface layer may contain the epoxy-modified silicone with the said epoxy resin. Thus, the surface layer containing the epoxy-modified silicone together with the epoxy resin, in the development processing after the exposure, the unexposed portion is quickly dissolved by the developer, compared with the case where the epoxy-modified silicone is not included, Development time is shortened. Therefore, the photosensitive epoxy resin adhesive film of the present invention shortens the development time when the film is transferred onto the adherend, exposed and developed even when the thickness is as large as 50 μm or more. Thus, a required pattern can be formed promptly.
本発明の感光性エポキシ樹脂接着性フィルムは、中間層とこれを挟む一対の表面層とからなる３層構造を有し、表面層の一方は、この接着性フィルムを被着体上に転写するに際して、被着体と対面し、接触する層、即ち、内側層を形成し、表面層の他方は、外部に露出する外側層を形成し、この接着性フィルムを被着体上に転写し、露光させ、現像して、所要のパターンを形成した後、このパターンを加熱することによって接着性を有せしめて、別の被着体と接着することとなる層である。 The photosensitive epoxy resin adhesive film of the present invention has a three-layer structure comprising an intermediate layer and a pair of surface layers sandwiching the intermediate layer, and one of the surface layers transfers the adhesive film onto an adherend. At this time, the layer facing the adherend is formed, that is, an inner layer is formed, and the other surface layer is formed as an outer layer exposed to the outside, and the adhesive film is transferred onto the adherend. It is a layer that is exposed to light and developed to form a desired pattern, and then this pattern is heated to give adhesiveness and adhere to another adherend.
本発明の接着性フィルムにおいては、上記中間層と表面層のいずれも、エポキシ当量１００〜３００ｇ／当量のグリシジル基を有する多官能エポキシ樹脂（低エポキシ当量エポキシ樹脂）とエポキシ当量４５０〜１００００ｇ／当量のグリシジル基を有する多官能エポキシ樹脂（高エポキシ当量エポキシ樹脂）との組合わせからなる低反応性エポキシ樹脂を含有している。 In the adhesive film of the present invention, both the intermediate layer and the surface layer are a polyfunctional epoxy resin having a glycidyl group having an epoxy equivalent of 100 to 300 g / equivalent (low epoxy equivalent epoxy resin) and an epoxy equivalent of 450 to 10,000 g / equivalent. A low-reactivity epoxy resin comprising a combination with a polyfunctional epoxy resin having a glycidyl group (high epoxy equivalent epoxy resin).
本発明による接着性フィルムにおいて、上記低反応性エポキシ樹脂のうち、低エポキシ当量エポキシ樹脂は、溶融粘度が低いので、被着体への転写に際して、被着体への濡れ性にすぐれており、また、露光と現像によって、高い解像度のパターン形成を可能とする。このような低エポキシ当量エポキシ樹脂としては、グリシジルエーテル型エポキシ樹脂が好ましく、なかでも、ビスフェノールＡ型、ビスフェノールＦ型、ビフェニル型、ノボラック型又はフルオレン型のグリシジルエーテル型エポキシ樹脂が好ましく用いられる。 In the adhesive film according to the present invention, among the low-reactivity epoxy resins, the low epoxy equivalent epoxy resin has a low melt viscosity, and therefore has excellent wettability to the adherend when transferred to the adherend. In addition, a pattern with high resolution can be formed by exposure and development. As such a low epoxy equivalent epoxy resin, a glycidyl ether type epoxy resin is preferable, and among them, a bisphenol A type, bisphenol F type, biphenyl type, novolak type or fluorene type glycidyl ether type epoxy resin is preferably used.
他方、高エポキシ当量エポキシ樹脂は、それ自体で可撓性を有するので、一つには、上記低エポキシ当量エポキシ樹脂と光酸発生剤と、場合によっては、エポキシ変性シリコーンとをまとめて、フィルムとすることができる役割を担っている。このような高エポキシ当量エポキシ樹脂としては、例えば、ビスフェノールＡ型フェノキシ樹脂やビスフェノールＦ型フェノキシ樹脂等が好ましく用いられる。ここに、フェノキシ樹脂とは、ビスフェノールＡやビスフェノールＦとエピクロルヒドリンとを反応させ、分子量を格段に大きくしたエポキシ樹脂をいう。 On the other hand, since the high epoxy equivalent epoxy resin itself has flexibility, the low epoxy equivalent epoxy resin, the photoacid generator, and, in some cases, the epoxy-modified silicone may be combined into a film. Has a role that can be. As such a high epoxy equivalent epoxy resin, for example, a bisphenol A type phenoxy resin, a bisphenol F type phenoxy resin, or the like is preferably used. Here, the phenoxy resin refers to an epoxy resin having a molecular weight significantly increased by reacting bisphenol A or bisphenol F with epichlorohydrin.
本発明によれば、このように、光酸発生剤と共に高エポキシ当量エポキシ樹脂を上記低エポキシ当量エポキシ樹脂と組合わせて用いて、表面層を形成することによって、被着体への転写に際して、被着体への濡れ性にすぐれ、更に、露光と現像処理によって微細なパターン形成が可能であると共に、このようなパターン形成の後においても、そのパターンを維持したまま、高い接着性を有する感光性エポキシ樹脂接着性フィルムを得ることができる。 According to the present invention, as described above, when a high epoxy equivalent epoxy resin is used in combination with the low epoxy equivalent epoxy resin together with a photoacid generator to form a surface layer, It has excellent wettability to the adherend, and furthermore, it is possible to form fine patterns by exposure and development processing, and even after such pattern formation, it has high adhesion while maintaining the pattern. An epoxy resin adhesive film can be obtained.
本発明による感光性エポキシ樹脂接着性フィルムにおいては、表面層は、低反応性エポキシ樹脂として、このような低エポキシ当量エポキシ樹脂５〜９０重量％と高エポキシ当量エポキシ樹脂１０〜９５重量％とからなる組合わせ、好ましくは、低エポキシ当量エポキシ樹脂１０〜５０重量％と高エポキシ当量エポキシ樹脂５０〜９０重量％との組合わせが好ましく用いられる。低エポキシ当量エポキシ樹脂の割合が高すぎるときは、上記高エポキシ当量エポキシ樹脂と組合わせて用いても、これらをフィルム化することができず、他方、高エポキシ当量エポキシ樹脂の割合が高すぎるときは、上記低エポキシ当量エポキシ樹脂と組合わせて用いても、得られる接着性フィルムは、露光、現像によって微細なパターン形成が困難であり、また、被着体との間に耐湿信頼性や耐薬品性にすぐれた接着を形成することができない。 In the photosensitive epoxy resin adhesive film according to the present invention, the surface layer is composed of 5 to 90% by weight of such low epoxy equivalent epoxy resin and 10 to 95% by weight of high epoxy equivalent epoxy resin as low reactivity epoxy resin. A combination of 10 to 50% by weight of a low epoxy equivalent epoxy resin and 50 to 90% by weight of a high epoxy equivalent epoxy resin is preferably used. When the proportion of low epoxy equivalent epoxy resin is too high, even if used in combination with the above high epoxy equivalent epoxy resin, these cannot be filmed, while the proportion of high epoxy equivalent epoxy resin is too high However, even when used in combination with the above low epoxy equivalent epoxy resin, it is difficult to form a fine pattern by exposure and development of the resulting adhesive film. Bonds with excellent chemical properties cannot be formed.
本発明によれば、中間層は、上記低反応性エポキシ樹脂に加えて、更に、脂環式エポキシ樹脂及びオキセタン樹脂から選ばれる少なくとも１種の高反応性樹脂を含有する。ここに、脂環式エポキシ樹脂は分子中に１つのエポキシ基（オキシラン環）を有する化合物を含むものとし、オキセタン樹脂は分子中に１つのオキセタニル基（オキセタン環）を有する化合物を含むものとする。 According to the present invention, the intermediate layer further contains at least one highly reactive resin selected from an alicyclic epoxy resin and an oxetane resin in addition to the low-reactivity epoxy resin. Here, the alicyclic epoxy resin includes a compound having one epoxy group (oxirane ring) in the molecule, and the oxetane resin includes a compound having one oxetanyl group (oxetane ring) in the molecule.
従って、本発明においては、上記脂環式エポキシ樹脂として、例えば、３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート、１，２−エポキシ−４−ビニルシクロヘキサン、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、１−エポキシエチル−３，４−エポキシシクロヘキサン、リモネンジエポキシド、３，４−エポキシシクロヘキシルメタノール、ジシクロペンタジエンジオキシド、 Accordingly, in the present invention, as the alicyclic epoxy resin, for example, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, bis (3 , 4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl-3,4-epoxycyclohexane, limonene diepoxide, 3,4-epoxycyclohexylmethanol, dicyclopentadiene dioxide,
等が好ましく用いられる。 Etc. are preferably used.
また、オキセタン樹脂としては、例えば、３−エチル−３−ヒドロキシメチルオキセタン、次式 Examples of the oxetane resin include 3-ethyl-3-hydroxymethyloxetane,
で表される１，４−ビス｛〔（３−エチル−３−オキセタニル）メトキシ〕メチル｝ベンゼン、 1,4-bis {[((3-ethyl-3-oxetanyl) methoxy] methyl} benzene represented by
等が好ましく用いられる。 Etc. are preferably used.
本発明によれば、中間層は、エポキシ当量１００〜３００ｇ／当量の多官能エポキシ樹脂４〜６０重量％とエポキシ当量４５０〜１００００ｇ／当量の多官能エポキシ樹脂１０〜９５重量％と高反応性樹脂１〜３０重量％とを含有し、好ましくは、エポキシ当量１００〜３００ｇ／当量の多官能エポキシ樹脂５〜６０重量％とエポキシ当量４５０〜１００００ｇ／当量の多官能エポキシ樹脂２５〜９０重量％と高反応性樹脂５〜１５重量％とを含有する。 According to the present invention, the intermediate layer comprises 4 to 60% by weight of an epoxy equivalent of 100 to 300 g / equivalent polyfunctional epoxy resin and 10 to 95% by weight of an epoxy equivalent of 450 to 10,000 g / equivalent polyfunctional epoxy resin and a highly reactive resin. 1 to 30% by weight, preferably 5 to 60% by weight of polyfunctional epoxy resin having an epoxy equivalent of 100 to 300 g / equivalent and 25 to 90% by weight of polyfunctional epoxy resin having an epoxy equivalent of 450 to 10,000 g / equivalent 5 to 15% by weight of reactive resin.
中間層において、高反応性樹脂の割合が１重量％よりも少ないときは、得られる感光性エポキシ樹脂接着性フィルムがそのような中間層を有しても、露光、現像して得られたパターン上に第２の被着体を熱圧着するとき、そのパターンは依然として変形する。しかし、中間層において、高反応性樹脂の割合が３０重量％よりも多いときは、露光、現像後に中間層が硬く、脆い層を形成するので、得られるパターンが容易に割れたり、また、硬化収縮によってパターンにひび割れが生じたりする問題がある。また、中間層の反応性が高すぎるために、露光時、マスクの外へも反応が広がって、パターンが太くなる問題もある。 In the intermediate layer, when the proportion of the highly reactive resin is less than 1% by weight, the pattern obtained by exposure and development even if the resulting photosensitive epoxy resin adhesive film has such an intermediate layer. When the second adherend is thermocompression bonded on top, the pattern is still deformed. However, when the proportion of the highly reactive resin in the intermediate layer is more than 30% by weight, the intermediate layer is hard and fragile after exposure and development, so that the resulting pattern can be easily cracked or cured. There is a problem that the pattern is cracked by the shrinkage. Further, since the reactivity of the intermediate layer is too high, there is a problem that the reaction spreads out of the mask during exposure and the pattern becomes thick.
更に、本発明による感光性エポキシ樹脂接着性フィルムは、少なくとも、表面層の一方又は両方が前記低反応性エポキシ樹脂と共に、例えば、一般式（Ｉ） Furthermore, the photosensitive epoxy resin adhesive film according to the present invention has at least one or both of the surface layers together with the low-reactivity epoxy resin, for example, the general formula (I)
（式中、ｎは０〜８の範囲の数である。）
で表されるエポキシ変性シリコーンを前記低反応性エポキシ樹脂１００重量部に対して、１〜１０重量部の範囲で含有していてもよい。
(In the formula, n is a number in the range of 0 to 8.)
The epoxy-modified silicone represented by the formula (1) may be contained in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the low-reactivity epoxy resin.
本発明による接着性フィルムにおいては、少なくとも表面層がこのように前記低反応性エポキシ樹脂と共に、このようなエポキシ変性シリコーンを含有しているとき、この接着性フィルムの厚みが大きい場合であっても、これを被着体上に転写し、これを露光させ、現像処理するときに、現像液によって少なくとも表面層の未露光部を速やかに溶解させることができる。即ち、現像時間を短縮することができる。勿論、中間層にも上記エポキシ変性シリコーンを含有させることによって、接着性フィルムの厚みが大きい場合であっても、これを被着体上に転写し、これを露光させ、現像処理するときに、現像液によって、フィルムの未露光部を速やかに溶解させることができる。 In the adhesive film according to the present invention, when at least the surface layer contains such an epoxy-modified silicone together with the low-reactivity epoxy resin, even if the thickness of the adhesive film is large. When this is transferred onto the adherend, exposed, and developed, at least the unexposed portion of the surface layer can be quickly dissolved by the developer. That is, the development time can be shortened. Of course, by including the epoxy-modified silicone in the intermediate layer, even when the thickness of the adhesive film is large, it is transferred onto the adherend, exposed to light, and developed. The unexposed part of the film can be quickly dissolved by the developer.
本発明による接着性フィルムにおいて、表面層や中間層のいずれについても、エポキシ樹脂１００重量部に対して、エポキシ変性シリコーンの含有量が１重量部よりも少ないときは、現像時間の短縮に効果がなく、他方、エポキシ樹脂１００重量部に対して、エポキシ変性シリコーンの含有量が１０重量部を超えるときは、エポキシ変性シリコーンを含有する層の硬度が低いので、接着性フィルムが圧力を加えられたとき、厚みが減少したり、また、現像処理時に露光部も溶出して、鮮明な露光パターンを得ることができないおそれがある。 In the adhesive film according to the present invention, when the content of the epoxy-modified silicone is less than 1 part by weight with respect to 100 parts by weight of the epoxy resin in any of the surface layer and the intermediate layer, it is effective for shortening the development time. On the other hand, when the content of the epoxy-modified silicone exceeds 10 parts by weight with respect to 100 parts by weight of the epoxy resin, the adhesive film was pressed because the hardness of the layer containing the epoxy-modified silicone was low. In some cases, the thickness decreases or the exposed part is eluted during the development process, and a clear exposure pattern cannot be obtained.
本発明による接着性フィルムにおいては、表面層は、前記低反応性エポキシ樹脂と共に光酸発生剤を含有しており、また、中間層は、前記低反応性エポキシ樹脂と高反応性樹脂と共に光酸発生剤を含有しており、この光酸発生剤によって、フィルムが感光性を有する。即ち、光酸発生剤は、上記接着性フィルムの露光時に酸を発生し、この酸によって上記低反応性エポキシ樹脂や高反応性樹脂を架橋、硬化させる。中間層や表面層が前記エポキシ変性シリコーンを含有しているときは、このエポキシ変性シリコーンも同様に、架橋、硬化する。 In the adhesive film according to the present invention, the surface layer contains a photoacid generator together with the low-reactivity epoxy resin, and the intermediate layer contains a photoacid together with the low-reactivity epoxy resin and the high-reactivity resin. It contains a generator, and the film has photosensitivity by this photoacid generator. That is, the photoacid generator generates an acid when the adhesive film is exposed, and the acid reacts to crosslink and cure the low-reactivity epoxy resin or high-reactivity resin. When the intermediate layer or the surface layer contains the epoxy-modified silicone, the epoxy-modified silicone is similarly crosslinked and cured.
このような光酸発生剤としては、種々のオニウム塩、特に、ＢＦ4、ＰＦ6、ＡｓＦ6、ＳｂＦ6 等を対アニオンとするトリアリルスルホニウム塩、ジアリルヨウドニウム塩等、従来より知られているものが適宜に用いられる。これらは市販品として入手することができる。 As such a photoacid generator, various onium salts, in particular, triallylsulfonium salts and diallylodonium salts having BF 4 , PF 6 , AsF 6 , SbF 6, etc. as a counter anion have been conventionally known. Are used as appropriate. These can be obtained as commercial products.
本発明において、このような光酸発生剤は、低反応性エポキシ樹脂と高反応性樹脂との合計量１００重量部に対して、通常、１〜２０重量部の範囲で用いられ、好ましくは、５〜１５重量部の範囲で用いられる。 In the present invention, such a photoacid generator is usually used in a range of 1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the low-reactivity epoxy resin and the high-reactivity resin, It is used in the range of 5 to 15 parts by weight.
本発明によれば、中間層とそれぞれ表面層中の光酸発生剤量はすべて同じでもよいが、特に、フィルムの厚みを大きくする場合には、フィルムを被着体に転写する際の内側層をなす表面層における光酸発生剤量を外側層における光酸発生剤量よりも多くしてもよい。例えば、接着性フィルムを被着体に転写する際に外側層をなす表面層は、光酸発生剤を低反応性エポキシ樹脂１００重量部に対して１〜５重量部の範囲で含有し、接着性フィルムを被着体に転写する際に内側層をなす表面層は、光酸発生剤を低反応性エポキシ樹脂１００重量部に対して５〜１５重量部の範囲で、且つ、前記外側層におけるよりも多く含有するようにしてもよい。 According to the present invention, the amount of the photoacid generator in each of the intermediate layer and the surface layer may be the same. In particular, when increasing the thickness of the film, the inner layer when transferring the film to the adherend. The amount of the photoacid generator in the surface layer forming the above may be larger than the amount of the photoacid generator in the outer layer. For example, the surface layer that forms the outer layer when the adhesive film is transferred to the adherend contains a photoacid generator in an amount of 1 to 5 parts by weight with respect to 100 parts by weight of the low-reactivity epoxy resin. The surface layer that forms the inner layer when transferring the conductive film to the adherend is in the range of 5 to 15 parts by weight of the photoacid generator with respect to 100 parts by weight of the low-reactivity epoxy resin, and in the outer layer. You may make it contain more.
このように、接着性フィルムにおいて、内側層をなす表面層における光酸発生剤量を外側層における光酸発生剤量よりも多くすることによって、フィルムの厚みが５０μｍ以上のように大きい場合であっても、この接着性フィルムを被着体上に転写し、露光させ、現像して、パターンを形成する場合において、露光に際して、被着体上の上記フィルムの底部近傍においては、光酸発生剤を高濃度で含有しているので、被着体上の上記フィルムの底部近傍に到達する活性光線量が外側層よりも少ない場合であっても、光酸発生剤が十分な量の酸を発生して、エポキシ樹脂の架橋、硬化反応を引き起こす。かくして、得られるパターンは、断面が逆台形状となることはなく、矩形状であって、被着体に対して高い密着力を有する。 Thus, in the adhesive film, the amount of the photoacid generator in the surface layer constituting the inner layer is larger than the amount of the photoacid generator in the outer layer, so that the film thickness is as large as 50 μm or more. However, when this adhesive film is transferred onto an adherend, exposed and developed to form a pattern, a photoacid generator is formed in the vicinity of the bottom of the film on the adherend upon exposure. The photoacid generator generates a sufficient amount of acid even when the amount of actinic rays reaching the bottom of the film on the adherend is less than that of the outer layer. As a result, crosslinking and curing reaction of the epoxy resin is caused. Thus, the pattern obtained does not have an inverted trapezoidal cross section, is rectangular, and has a high adhesion to the adherend.
本発明による感光性エポキシ樹脂接着性フィルムは、中間層、表面層のいずれも、上述したエポキシ樹脂と（エポキシ変性シリコーンと）光酸発生剤に加えて、必要に応じて、難燃剤、離型剤、レベリング剤等、従来より感光性接着剤組成物に用いられる適宜の添加剤を含んでいてもよい。 In the photosensitive epoxy resin adhesive film according to the present invention, both of the intermediate layer and the surface layer, in addition to the above-described epoxy resin and (epoxy-modified silicone) photoacid generator, if necessary, flame retardant, mold release An appropriate additive conventionally used for a photosensitive adhesive composition, such as an agent and a leveling agent, may be included.
本発明による感光性エポキシ樹脂接着性フィルムは、上述した中間層とこれを挟む一対の表面層とからなる３層構造を有すれば、その製造方法は特に限定されるものではなく、種々の方法によって得ることができる。例えば、一つの方法として、低エポキシ当量エポキシ樹脂と高エポキシ当量エポキシ樹脂とからるな低反応性エポキシ樹脂とこれに対して所定の割合の光酸発生剤と、必要に応じて、エポキシ変性シリコーンとを適宜の有機溶剤、例えば、ジオキサン、シクロヘキサン等に溶解させて、製膜溶液（ワニス）を調製し、次いで、この製膜溶液を適宜の基材上にコーティングした後、上記有機溶剤を揮散させることによって、表面層のためのフィルムを調製する。別に、低反応性エポキシ樹脂と高反応性樹脂とこれらのエポキシ樹脂に対して所定の割合の光酸発生剤と、必要に応じて、エポキシ変性シリコーンとを適宜の有機溶剤、例えば、ジオキサン、シクロヘキサン等に溶解させて、製膜溶液（ワニス）を調製し、次いで、この製膜溶液を適宜の基材上にコーティングした後、上記有機溶剤を揮散させることによって、中間層のためのフィルムを調製する。次いで、これら表面層のためのフィルムと中間層のためのフィルムを表面層／中間層／表面層の３層構造を有するようにラミネート（貼り合わせ）することによって得ることができる。 As long as the photosensitive epoxy resin adhesive film according to the present invention has a three-layer structure comprising the above-described intermediate layer and a pair of surface layers sandwiching the intermediate layer, the manufacturing method is not particularly limited, and various methods are possible. Can be obtained by: For example, as one method, a low-reactivity epoxy resin consisting of a low epoxy equivalent epoxy resin and a high epoxy equivalent epoxy resin, a predetermined ratio of a photoacid generator, and, if necessary, an epoxy-modified silicone Is dissolved in an appropriate organic solvent such as dioxane or cyclohexane to prepare a film-forming solution (varnish), and after coating the film-forming solution on an appropriate substrate, the organic solvent is volatilized. To prepare a film for the surface layer. Separately, a low-reactivity epoxy resin, a high-reactivity resin, a photoacid generator in a predetermined ratio with respect to these epoxy resins, and, if necessary, an epoxy-modified silicone and an appropriate organic solvent such as dioxane, cyclohexane Prepare a film for an intermediate layer by coating the film-forming solution on an appropriate substrate and then stripping off the organic solvent. To do. Then, the film for the surface layer and the film for the intermediate layer can be obtained by laminating (bonding) so as to have a three-layer structure of surface layer / intermediate layer / surface layer.
また、別の方法として、上述したようにして、中間層と表面層のための製膜溶液を調製し、適宜の基材上に、例えば、内側層をなす表面層のための製膜溶液をコーティングし、乾燥させて、内側層のための表面層を形成し、次いで、この内側層のための表面層の上に中間層のための製膜溶液をコーティングし、乾燥させて、中間層を形成し、更に、この中間層の上に外側層をなす表面層のための製膜溶液をコーティングし、乾燥させて、表面層を形成し、かくして、中間層とこれを挟む一対の表面層とからなる３層構造を有する接着性フィルムを得ることもできる。 As another method, a film forming solution for the intermediate layer and the surface layer is prepared as described above, and the film forming solution for the surface layer forming the inner layer is formed on an appropriate base material. Coating and drying to form a surface layer for the inner layer, then coating the film forming solution for the intermediate layer on the surface layer for the inner layer and drying to form the intermediate layer Further, a film forming solution for a surface layer forming an outer layer is coated on the intermediate layer and dried to form a surface layer, and thus the intermediate layer and a pair of surface layers sandwiching the intermediate layer. It is also possible to obtain an adhesive film having a three-layer structure.
本発明による感光性エポキシ樹脂接着性フィルムを適宜の基板、例えば、ガラス基板、有機基板、シリコン基板等の表面に熱転写し、これにフォトマスクを介して紫外線、電子線、マイクロ波等の適宜の活性光線を露光させ、前述したように、光酸発生剤の作用によってエポキシ樹脂とエポキシ変性シリコーンを架橋、硬化させた後、現像処理し、即ち、未露光部を現像剤を用いて溶解、除去し、次いで、必要に応じて、露光後加熱することによって、第１の被着体上に所要のパターンを有する接着性フィルムを得ることができる。上記現像剤としては、例えば、Ｎ−メチル−２−ピロリドン、メチルエチルケトン等の有機溶剤が用いられる。このような現像剤を用いる現像には、例えば、浸漬法やスプレー法等が用いられる。 The photosensitive epoxy resin adhesive film according to the present invention is thermally transferred onto the surface of an appropriate substrate, for example, a glass substrate, an organic substrate, a silicon substrate, etc., and an ultraviolet ray, an electron beam, a microwave, etc. Actinic rays are exposed to light, and as described above, the epoxy resin and the epoxy-modified silicone are crosslinked and cured by the action of a photoacid generator, and then developed, that is, the unexposed areas are dissolved and removed using a developer. Then, if necessary, an adhesive film having a required pattern on the first adherend can be obtained by heating after exposure. As the developer, for example, an organic solvent such as N-methyl-2-pyrrolidone or methyl ethyl ketone is used. For the development using such a developer, for example, an immersion method or a spray method is used.
次いで、このような第１の被着体上に形成した所要のパターンからなる接着性フィルム上に第２の被着体を重ねて、通常、９０〜２００℃、好ましくは、１００〜１６０℃の温度にて加熱加圧することによって、上記接着性フィルムにそのパターンを維持させたまま、第１と第２の被着体とを上記パターン化した接着性フィルムにて接着することができる。 Next, the second adherend is stacked on the adhesive film having the required pattern formed on the first adherend, and usually 90 to 200 ° C., preferably 100 to 160 ° C. By heating and pressurizing at a temperature, the first and second adherends can be bonded with the patterned adhesive film while maintaining the pattern on the adhesive film.
従って、本発明による感光性エポキシ樹脂接着性フィルムは、これを第１の被着体上に熱転写した後、感光させ、現像して、空間を有するように適宜にパターン形成した後、その上に第２の被着体を熱圧着することによって、第１と第２の被着体との間に信頼性の高い接着を形成しつつ、その間に上記空間に対応して、所要の空隙を形成することができる。 Therefore, the photosensitive epoxy resin adhesive film according to the present invention is thermally transferred onto the first adherend, exposed to light, developed, and appropriately patterned so as to have a space, and then formed thereon. By thermocompression bonding the second adherend, a highly reliable bond is formed between the first and second adherends, and a required gap is formed between the spaces corresponding to the space. can do.
しかも、本発明による感光性エポキシ樹脂接着性フィルムを用いれば、接着性フィルムの厚みが５０μｍ以上のように大きい場合であっても、露光、現像して得られたパターン上に第２の被着体を熱圧着するに際して、そのパターンは、架橋密度が高く、硬い樹脂層からなる中間層が表面層に挟まれている３層構造を有するので、変形が少なく、かくして、精度高く、所要の空隙を形成しつつ、第１と第２の被着体をこのパターンにて相互に接着することができる。 In addition, if the photosensitive epoxy resin adhesive film according to the present invention is used, even if the thickness of the adhesive film is as large as 50 μm or more, the second deposition is applied on the pattern obtained by exposure and development. When the body is subjected to thermocompression bonding, the pattern has a three-layer structure in which an intermediate layer made of a hard resin layer is sandwiched between surface layers with a high crosslink density, so that there is little deformation, and thus the required gap is high. The first and second adherends can be bonded to each other in this pattern.
更に、本発明に従って、感光性接着性フィルムを被着体に転写したとき、外側層をなす表面層に比べて、内側層に光酸発生剤をより多く配合することによって、接着性フィルムの厚みが５０μｍ以上のように大きい場合であっても、被着体上の上記フィルムの底部近傍において、光酸発生剤が十分な量の酸を発生して、エポキシ樹脂の架橋、硬化反応を引き起こすので、得られるパターンは断面が矩形状であって、被着体に対して高い密着力を有する。 Furthermore, according to the present invention, when the photosensitive adhesive film is transferred to the adherend, the thickness of the adhesive film can be increased by adding more photoacid generator to the inner layer than the surface layer forming the outer layer. Even when the thickness is as large as 50 μm or more, the photoacid generator generates a sufficient amount of acid in the vicinity of the bottom of the film on the adherend to cause crosslinking and curing reaction of the epoxy resin. The obtained pattern has a rectangular cross section and has high adhesion to the adherend.
また、表面層や中間層に上記エポキシ樹脂と共にエポキシ変性シリコーンを含有させることによって、露光後の現像処理において、未露光部が現像液によって速やかに溶解されるので、現像時間を短縮することができる。 In addition, by including an epoxy-modified silicone together with the above epoxy resin in the surface layer or the intermediate layer, the unexposed portion is rapidly dissolved by the developer in the development processing after exposure, so the development time can be shortened. .
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
低エポキシ当量エポキシ樹脂としてエポキシ当量２５０ｇ／当量のビスフェノールＡ型エポキシ樹脂１０重量部と高エポキシ当量エポキシ樹脂としてエポキシ当量８６９０ｇ／当量のビスフェノールＦ型フェノキシ樹脂９０重量部と前記一般式（Ｉ）で表されるエポキシ変性シリコーン（エポキシ当量１９２ｇ／当量、以下、同じ。）３重量部と光酸発生剤として４，４−ビス〔ジ（β−ヒドロキシエトキシ）フェニルスルフィニオ〕フェニルスルフィドビス（ヘキサフルオロアンチモネート）（以下、同じ。）８重量部をジオキサンに溶解させ、感光性エポキシ樹脂接着剤組成物を固形分濃度４５重量％のワニスとして得た。このワニスをポリエステルフィルム上に塗布し、８０℃に加熱し、乾燥させて、上記感光性エポキシ樹脂接着剤組成物よりなる厚み３０μｍの表面層のための感光性フィルムを調製した。
Example 1
10 parts by weight of bisphenol A type epoxy resin with an epoxy equivalent of 250 g / equivalent as a low epoxy equivalent epoxy resin, 90 parts by weight of bisphenol F type phenoxy resin with an epoxy equivalent of 8690 g / equivalent as a high epoxy equivalent epoxy resin, and represented by the above general formula (I) 3 parts by weight of epoxy-modified silicone (epoxy equivalent 192 g / equivalent, hereinafter the same) and 4,4-bis [di (β-hydroxyethoxy) phenylsulfinio] phenyl sulfide bis (hexafluoro as a photoacid generator 8 parts by weight of antimonate (hereinafter the same) was dissolved in dioxane to obtain a photosensitive epoxy resin adhesive composition as a varnish having a solid content concentration of 45% by weight. This varnish was applied onto a polyester film, heated to 80 ° C., and dried to prepare a photosensitive film for a surface layer having a thickness of 30 μm and comprising the photosensitive epoxy resin adhesive composition.
別に、低エポキシ当量エポキシ樹脂としてエポキシ当量２５０ｇ／当量のビスフェノールＡ型エポキシ樹脂１０重量部と高エポキシ当量エポキシ樹脂としてエポキシ当量８６９０ｇ／当量のビスフェノールＦ型フェノキシ樹脂８０重量部と、高反応性樹脂として、脂環式エポキシ樹脂である３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート１０重量部とエポキシ変性シリコーン３重量部と光酸発生剤８重量部をジオキサンに溶解させ、感光性エポキシ樹脂接着剤組成物を固形分濃度４５重量％のワニスとして得た。このワニスをポリエステルフィルム上に塗布し、８０℃に加熱し、乾燥させて、上記感光性エポキシ樹脂接着剤組成物よりなる厚み４０μｍの中間層のための感光性フィルムを調製した。 Separately, 10 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of 250 g / equivalent as a low epoxy equivalent epoxy resin, 80 parts by weight of a bisphenol F type phenoxy resin having an epoxy equivalent of 8690 g / equivalent as a high epoxy equivalent epoxy resin, , 10 parts by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, which is an alicyclic epoxy resin, 3 parts by weight of epoxy-modified silicone, and 8 parts by weight of a photoacid generator are dissolved in dioxane, A photosensitive epoxy resin adhesive composition was obtained as a varnish having a solid concentration of 45% by weight. This varnish was applied on a polyester film, heated to 80 ° C., and dried to prepare a photosensitive film for an intermediate layer having a thickness of 40 μm made of the photosensitive epoxy resin adhesive composition.
次いで、上記表面層のための感光性フィルムと中間層のための感光性フィルムを表面層／中間層／表面層の３層構造を有するようにラミネータを用いて貼り合わせて、本発明による厚み１００μｍの感光性エポキシ樹脂接着性フィルムを得た。 Next, the photosensitive film for the surface layer and the photosensitive film for the intermediate layer are laminated using a laminator so as to have a three-layer structure of surface layer / intermediate layer / surface layer, and the thickness of the present invention is 100 μm. A photosensitive epoxy resin adhesive film was obtained.
この感光性接着性フィルムをその内側層がガラス板の表面に対面するように１００℃で転写した。高圧水銀灯を用いて、このガラス板表面の感光性接着性フィルムをフォトマスクを介して１０００Ｊ／ｃｍ2 の露光量にて露光させ、９０℃で１０分間、露光後加熱した後、Ｎ−メチル−２−ピロリドンを現像液として現像して、５０μｍ幅の線が１００μｍ間隔で平行して並ぶパターンを形成することができた。 This photosensitive adhesive film was transferred at 100 ° C. so that the inner layer faced the surface of the glass plate. Using a high-pressure mercury lamp, the photosensitive adhesive film on the surface of the glass plate was exposed through a photomask at an exposure amount of 1000 J / cm 2 and heated after exposure at 90 ° C. for 10 minutes, and then N-methyl- 2-Pyrrolidone was developed as a developer to form a pattern in which 50 μm-wide lines were arranged in parallel at intervals of 100 μm.
次いで、このパターン上にラミネータを用いて１５０℃の温度にてガラス板を貼り合わせて、ガラス板の間に上記感光性接着性フィルムから得られたパターンによって間隔９９μｍの空隙を有せしめつつ、上記一対のガラス板を相互に接着することができた。 Next, a glass plate is laminated on the pattern at a temperature of 150 ° C. using a laminator, and the gap between the glass plates is 99 μm with the pattern obtained from the photosensitive adhesive film, and the pair of pairs. Glass plates could be bonded to each other.
同様にして、ウェハー上に上記感光性接着性フィルムを転写し、全面露光させ、９０℃で１０分間、露光後加熱し、次いで、Ｎ−メチル−２−ピロリドンを現像液として現像した。これを３ｍｍ四方の小片に裁断し、スライドガラス上に温度１５０℃、圧力５ｋｇ／ｃｍ2 の条件下に１０秒間熱圧着し、更に、温度１５０℃で１時間加熱して、後硬化させた後、剪断接着力を測定したところ、５ＭＰａ以上であった。また、この小片を温度６０℃、相対湿度９０％の条件下に２００時間放置する吸湿試験の後においても、剪断接着力は５ＭＰａ以上であった。 Similarly, the photosensitive adhesive film was transferred onto a wafer, exposed on the entire surface, heated after exposure at 90 ° C. for 10 minutes, and then developed using N-methyl-2-pyrrolidone as a developer. This is cut into 3 mm square pieces, thermocompression bonded on a slide glass at a temperature of 150 ° C. and a pressure of 5 kg / cm 2 for 10 seconds, and further heated at 150 ° C. for 1 hour to be post-cured. When the shear adhesive force was measured, it was 5 MPa or more. Further, even after the moisture absorption test in which the small piece was allowed to stand for 200 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, the shear adhesive strength was 5 MPa or more.
別に、得られた感光性フィルムを加熱加圧したときの膜厚の変化を次のようにして調べた。即ち、得られた感光性フィルムの膜厚を２５℃にて測定し、次に、温度１５０℃において、このフィルムに４９ＭＰａの圧力を３分間加えた後、フィルムへの加圧を止め、フィルムを室温まで放冷して、膜厚を再度、測定した。当初の膜厚をｔ0、加熱下に加圧した後の膜厚をｔとして、膜厚変化量Δｔ＝（（ｔ0−ｔ）／ｔ0）×１００（％）を求めたところ、２．５％であった。 Separately, the change in film thickness when the obtained photosensitive film was heated and pressurized was examined as follows. That is, the film thickness of the obtained photosensitive film was measured at 25 ° C., and then at a temperature of 150 ° C., a pressure of 49 MPa was applied to the film for 3 minutes, and then the pressurization to the film was stopped. After cooling to room temperature, the film thickness was measured again. The film thickness change amount Δt = ((t 0 −t) / t 0 ) × 100 (%) was obtained with the initial film thickness being t 0 and the film thickness after being pressurized under heating being t. .5%.
実施例２
低エポキシ当量エポキシ樹脂としてエポキシ当量１８６ｇ／当量のビフェニルＡ型エポキシ樹脂５０重量部と高エポキシ当量エポキシ樹脂としてエポキシ当量４４００ｇ／当量のビスフェノールＦ型エポキシ樹脂５０重量部とエポキシ変性シリコーン３重量部と光酸発生剤５重量部をジオキサンに溶解させ、感光性エポキシ樹脂接着剤組成物を固形分濃度４５重量％のワニスとして得た。このワニスをポリエステルフィルム上に塗布し、８０℃に加熱し、乾燥させて、上記感光性エポキシ樹脂接着剤組成物よりなる厚み２０μｍの内側層のための表面層としての感光性フィルムを調製した。
Example 2
50 parts by weight of biphenyl A type epoxy resin having an epoxy equivalent of 186 g / equivalent as a low epoxy equivalent epoxy resin, 50 parts by weight of bisphenol F type epoxy resin having an epoxy equivalent of 4400 g / equivalent as a high epoxy equivalent epoxy resin, and 3 parts by weight of epoxy-modified silicone 5 parts by weight of an acid generator was dissolved in dioxane to obtain a photosensitive epoxy resin adhesive composition as a varnish having a solid content concentration of 45% by weight. This varnish was applied on a polyester film, heated to 80 ° C., and dried to prepare a photosensitive film as a surface layer for an inner layer having a thickness of 20 μm, composed of the photosensitive epoxy resin adhesive composition.
次いで、低エポキシ当量エポキシ樹脂としてエポキシ当量２５０ｇ／当量のビスフェノールＡ型エポキシ樹脂４０重量部と高エポキシ当量エポキシ樹脂としてエポキシ当量４４００ｇ／当量のビスフェノールＦ型エポキシ樹脂５０重量部と、高反応性樹脂であるオキセタン樹脂として１，４−ビス｛〔（３−エチル−３−オキセタニル）メトキシ〕メチル｝ベンゼン（前記式（４）において、ｎ＝１であるもの８０〜８５％、ｎ＝２であるもの１０〜１５％、ｎ＝３であるもの５％未満の混合物、融点４１〜４４℃）１０重量部と光酸発生剤５重量部をジオキサンに溶解させ、感光性エポキシ樹脂接着剤組成物を固形分濃度４５重量％のワニスとして得た。このワニスを上記表面層のための感光性フィルム上に塗布し、８０℃に加熱し、乾燥させて、上記表面層（内側層）としての感光性フィルム上に厚み６０μｍの中間層を形成した。 Next, 40 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of 250 g / equivalent as a low epoxy equivalent epoxy resin, 50 parts by weight of a bisphenol F type epoxy resin having an epoxy equivalent of 4400 g / equivalent as a high epoxy equivalent epoxy resin, As an oxetane resin, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (in the above formula (4), n = 1 is 80 to 85%, n = 2 10 to 15%, n = 3, less than 5% mixture, melting point 41 to 44 ° C.) 10 parts by weight and photoacid generator 5 parts by weight are dissolved in dioxane, and the photosensitive epoxy resin adhesive composition is solidified A varnish with a partial concentration of 45% by weight was obtained. This varnish was applied on the photosensitive film for the surface layer, heated to 80 ° C., and dried to form an intermediate layer having a thickness of 60 μm on the photosensitive film as the surface layer (inner layer).
次いで、低エポキシ当量エポキシ樹脂としてエポキシ当量１７７ｇ／当量のノボラック型エポキシ樹脂４０重量部と高エポキシ当量エポキシ樹脂としてエポキシ当量４４００ｇ／当量のビスフェノールＦ型エポキシ樹脂６０重量部とエポキシ変性シリコーン３重量部と光酸発生剤１５重量部をジオキサンに溶解させ、感光性エポキシ樹脂接着剤組成物を固形分濃度４５重量％のワニスとして得た。このワニスを上記中間層上に塗布し、８０℃に加熱し、乾燥させて、上記中間層上に厚み２０μｍの表面層（外側層）を形成し、かくして、本発明による厚み１００μｍの感光性エポキシ樹脂接着性フィルムを得た。 Next, 40 parts by weight of a novolak type epoxy resin having an epoxy equivalent of 177 g / equivalent as a low epoxy equivalent epoxy resin, 60 parts by weight of a bisphenol F type epoxy resin having an epoxy equivalent of 4400 g / equivalent as an epoxy equivalent, and 3 parts by weight of an epoxy-modified silicone 15 parts by weight of a photoacid generator was dissolved in dioxane to obtain a photosensitive epoxy resin adhesive composition as a varnish having a solid content concentration of 45% by weight. The varnish is applied on the intermediate layer, heated to 80 ° C. and dried to form a surface layer (outer layer) having a thickness of 20 μm on the intermediate layer, and thus a photosensitive epoxy having a thickness of 100 μm according to the present invention. A resin adhesive film was obtained.
この感光性接着性フィルムをその内側層がガラス板の表面に対面するように１００℃で転写した。高圧水銀灯を用いて、このガラス板表面の感光性接着性フィルムをフォトマスクを介して１０００Ｊ／ｃｍ2 の露光量にて露光させ、９０℃で１０分間、露光後加熱した後、Ｎ−メチル−２−ピロリドンを現像液として現像して、５０μｍ幅の線が１００μｍ間隔で平行して並ぶパターンを形成することができた。 This photosensitive adhesive film was transferred at 100 ° C. so that the inner layer faced the surface of the glass plate. Using a high-pressure mercury lamp, the photosensitive adhesive film on the surface of the glass plate was exposed through a photomask at an exposure amount of 1000 J / cm 2 , heated after exposure at 90 ° C. for 10 minutes, and then N-methyl- 2-Pyrrolidone was developed as a developing solution to form a pattern in which lines having a width of 50 μm were arranged in parallel at intervals of 100 μm.
次いで、このパターン上にラミネータを用いて１５０℃の温度にてガラス板を貼り合わせて、ガラス板の間に上記感光性接着性フィルムから得られたパターンによって間隔９９μｍの空隙を有せしめつつ、上記一対のガラス板を相互に接着することができた。 Next, a glass plate is laminated on the pattern at a temperature of 150 ° C. using a laminator, and the gap between the glass plates is 99 μm with the pattern obtained from the photosensitive adhesive film, and the pair of pairs. Glass plates could be bonded to each other .
同様にして、ウェハー上に上記感光性接着性フィルムを転写し、全面露光させ、９０℃で１０分間、露光後加熱し、次いで、Ｎ−メチル−２−ピロリドンを現像液として現像した。これを３ｍｍ四方の小片に裁断し、スライドガラス上に温度１５０℃、圧力５ｋｇ／ｃｍ2 の条件下に１０秒間熱圧着し、更に、温度１５０℃で１時間加熱して、後硬化させた後、剪断接着力を測定したところ、５ＭＰａ以上であった。また、この小片を温度６０℃、相対湿度９０％の条件下に２００時間放置する吸湿試験の後においても、剪断接着力は５ＭＰａ以上であった。また、実施例１と同様にして調べた膜厚変化量は１．２％であった。 Similarly, the photosensitive adhesive film was transferred onto a wafer, exposed on the entire surface, heated after exposure at 90 ° C. for 10 minutes, and then developed using N-methyl-2-pyrrolidone as a developer. This is cut into 3 mm square pieces, thermocompression bonded on a slide glass at a temperature of 150 ° C. and a pressure of 5 kg / cm 2 for 10 seconds, and further heated at 150 ° C. for 1 hour to be post-cured. When the shear adhesive force was measured, it was 5 MPa or more. Further, even after the moisture absorption test in which the small piece was allowed to stand for 200 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, the shear adhesive strength was 5 MPa or more. Further, the amount of change in film thickness examined in the same manner as in Example 1 was 1.2%.
比較例１
低エポキシ当量エポキシ樹脂としてエポキシ当量１７７ｇ／当量のノボラック型エポキシ樹脂４０重量部と高エポキシ当量エポキシ樹脂としてエポキシ当量４４００ｇ／当量のビスフェノールＦ型エポキシ樹脂６０重量部とエポキシ変性シリコーン３重量部と光酸発生剤８重量部をジオキサンに溶解させ、感光性エポキシ樹脂接着剤組成物を固形分濃度４５重量％のワニスとして得た。このワニスをポリエステルフィルム上に塗布し、８０℃に加熱し、乾燥させて、上記感光性エポキシ樹脂接着剤組成物よりなる厚み５０μｍの感光性フィルムを調製した。次に、この感光性フィルムの２枚をラミネータを用いて貼り合わせて、比較例としての厚み１００μｍの感光性エポキシ樹脂接着性フィルムを得た。
Comparative Example 1
40 parts by weight of a novolac type epoxy resin having an epoxy equivalent of 177 g / equivalent as a low epoxy equivalent epoxy resin, 60 parts by weight of a bisphenol F type epoxy resin having an epoxy equivalent of 4400 g / equivalent as a high epoxy equivalent epoxy resin, and 3 parts by weight of an epoxy-modified silicone 8 parts by weight of the generator was dissolved in dioxane to obtain a photosensitive epoxy resin adhesive composition as a varnish having a solid content concentration of 45% by weight. This varnish was applied on a polyester film, heated to 80 ° C., and dried to prepare a photosensitive film having a thickness of 50 μm made of the photosensitive epoxy resin adhesive composition. Next, two of the photosensitive films were bonded together using a laminator to obtain a photosensitive epoxy resin adhesive film having a thickness of 100 μm as a comparative example.
この感光性接着性フィルムをその内側層がガラス板の表面に対面するように１００℃で転写した。高圧水銀灯を用いて、このガラス板表面の感光性接着性フィルムをフォトマスクを介して１０００Ｊ／ｃｍ2 の露光量にて露光させ、９０℃で１０分間、露光後加熱した後、Ｎ−メチル−２−ピロリドンを現像液として現像したところ、５０μｍ幅のパターンは形成されていたが、表面の幅５０μｍに対して、底部の幅は３０μｍであった。 This photosensitive adhesive film was transferred at 100 ° C. so that the inner layer faced the surface of the glass plate. Using a high-pressure mercury lamp, the photosensitive adhesive film on the surface of the glass plate was exposed through a photomask at an exposure amount of 1000 J / cm 2 and heated after exposure at 90 ° C. for 10 minutes, and then N-methyl- When developed using 2-pyrrolidone as a developer, a pattern having a width of 50 μm was formed, but the width of the bottom was 30 μm with respect to the width of 50 μm of the surface.
次いで、このパターン上にラミネータを用いて１５０℃の温度にてガラス板を貼り合わせて、ガラス板の間に上記感光性接着性フィルムから得られたパターンによって間隔９７μｍの空隙を有せしめつつ、上記一対のガラス板を相互に接着することができた。 Next, a glass plate is laminated on the pattern using a laminator at a temperature of 150 ° C., and a gap of 97 μm is provided between the glass plates by the pattern obtained from the photosensitive adhesive film. Glass plates could be bonded to each other.
同様にして、ウェハー上に上記感光性接着性フィルムを転写し、全面露光させ、９０℃で１０分間、露光後加熱し、次いで、Ｎ−メチル−２−ピロリドンを現像液として現像した。これを３ｍｍ四方の小片に裁断し、スライドガラス上に温度１５０℃、圧力５ｋｇ／ｃｍ2 の条件下に１０秒間熱圧着し、更に、温度１５０℃で１時間加熱して、後硬化させた後、剪断接着力を測定したところ、５ＭＰａ以上であった。また、この小片を温度６０℃、相対湿度９０％の条件下に２００時間放置する吸湿試験の後においても、剪断接着力は５ＭＰａ以上であった。また、実施例１と同様にして調べた膜厚変化量は５％であった。
Similarly, the photosensitive adhesive film was transferred onto a wafer, exposed on the entire surface, heated after exposure at 90 ° C. for 10 minutes, and then developed using N-methyl-2-pyrrolidone as a developer. This is cut into 3 mm square pieces, thermocompression bonded on a slide glass at a temperature of 150 ° C. and a pressure of 5 kg / cm 2 for 10 seconds, and further heated at 150 ° C. for 1 hour to be post-cured. When the shear adhesive force was measured, it was 5 MPa or more. Further, even after the moisture absorption test in which the small piece was allowed to stand for 200 hours under conditions of a temperature of 60 ° C. and a relative humidity of 90%, the shear adhesive strength was 5 MPa or more. Further, the amount of change in film thickness examined in the same manner as in Example 1 was 5%.
Claims (6)
The photosensitive epoxy resin adhesive film according to claim 1, wherein at least one surface layer contains an epoxy-modified silicone.
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| JPWO2008149625A1 (en) * | 2007-06-06 | 2010-08-19 | 日立化成工業株式会社 | Photosensitive adhesive composition, film adhesive, adhesive sheet, method for forming adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device, and method for manufacturing semiconductor device |
| JP2011039297A (en) * | 2009-08-11 | 2011-02-24 | Taiyo Holdings Co Ltd | Laminated structure and method for producing the same |
| US20130236149A1 (en) * | 2012-03-12 | 2013-09-12 | Nitto Denko Corporation | Optical waveguide forming epoxy resin composition, curable film formed from the epoxy resin composition for formation of optical waveguide, and light transmission flexible printed board |
| JP2015168757A (en) * | 2014-03-07 | 2015-09-28 | 東洋インキＳｃホールディングス株式会社 | active energy ray-polymerizable resin composition and laminate |
| JP7507635B2 (en) | 2020-08-26 | 2024-06-28 | 東京応化工業株式会社 | Negative photosensitive composition, laminated film, and pattern forming method |
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| US9075303B2 (en) * | 2012-03-12 | 2015-07-07 | Nitto Denko Corporation | Optical waveguide forming epoxy resin composition, curable film formed from the epoxy resin composition for formation of optical waveguide, and light transmission flexible printed board |
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| JP7507635B2 (en) | 2020-08-26 | 2024-06-28 | 東京応化工業株式会社 | Negative photosensitive composition, laminated film, and pattern forming method |
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