JP2011020287A - Resin structure and method for manufacturing the same - Google Patents
Resin structure and method for manufacturing the same Download PDFInfo
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本発明は、各種電子デバイスなどに用いられる、撥水層を有する樹脂構造体及びその製造方法に関する。 The present invention relates to a resin structure having a water-repellent layer used for various electronic devices and a method for producing the same.
近年、有機ＥＬ、液晶、トランジスター製造など、各種電子デバイス分野において部材の一部に撥水性を付与することが求められている。例えば、インクジェット記録ヘッドは、インクの吐出方向や吐出量などの安定した吐出性を得るため、インク吐出穴の周辺に撥水層を設けている。この際、クリーニング時や印刷物への耐擦傷性が要求され、強固な撥水層の形成が必要とされている。
こうした撥水性を付与する際、一般的にシリコーン系やフッ素系の撥水塗料を用いて、電子デバイスの部材上に撥水塗料を塗布して撥水層を作製している。
さらに、作製した撥水層を含めた部材に加工を要することもある。例えば、前述のインクジェット記録ヘッドは、インクの吐出穴の周辺ではなく壁面に撥水性を付与した場合、逆に不安定な吐出性になることもあるため、撥水塗料の塗布には工夫が必要である。
In recent years, it has been required to impart water repellency to some members in various electronic device fields such as organic EL, liquid crystal, and transistor manufacturing. For example, an ink jet recording head is provided with a water-repellent layer around the ink discharge hole in order to obtain stable discharge properties such as the ink discharge direction and discharge amount. At this time, scratch resistance to printed matter is required, and a strong water-repellent layer needs to be formed.
When such water repellency is imparted, a water-repellent layer is generally prepared by applying a water-repellent paint on a member of an electronic device using a silicone-based or fluorine-based water-repellent paint.
Furthermore, the member including the produced water repellent layer may require processing. For example, the ink jet recording head described above may have unstable ejection properties when water repellency is imparted to the wall surface rather than around the ink ejection holes. It is.
特許文献１では簡便に撥水層を作製できる感光性の撥水組成物が開示されているが、撥水層の密着性の問題がある。また、特許文献２では基材上に撥水層を形成した後、その基材にレーザー照射によるインクの吐出穴の加工を行うことが開示されている。
しかし、インクジェット記録ヘッドのインク吐出穴の作製には、基板上に撥水層を作製する工程とインク吐出穴を開ける工程とを必要とする。後からインク吐出穴を開けるため、穴部周辺の処理も必要であることから、非常に時間とコストがかかるという問題がある。
Patent Document 1 discloses a photosensitive water-repellent composition that can easily form a water-repellent layer, but has a problem of adhesion of the water-repellent layer. Patent Document 2 discloses that after forming a water-repellent layer on a substrate, the substrate is subjected to processing of ink ejection holes by laser irradiation.
However, the production of the ink ejection holes of the ink jet recording head requires a process of producing a water repellent layer on the substrate and a process of opening the ink ejection holes. Since an ink discharge hole is opened later, processing around the hole portion is also necessary, and there is a problem that it takes much time and cost.
本発明の目的は、各種電子デバイスに用いる、パターニングされた強固な撥水層を有する樹脂構造体と、その構造体を簡便に製造するための製造方法を提供することである。 An object of the present invention is to provide a resin structure having a strong patterned water-repellent layer used for various electronic devices, and a production method for simply producing the structure.
本発明者等は鋭意研究した結果、第１の塗膜としてカチオン硬化型フォトリソグラフィーにてパターニング可能な組成物を塗布、乾燥させて、その上に第２の塗膜としてカチオン開始剤である酸発生剤を含まないカチオン重合可能な変性シリコーンを塗布し、この２層を一括露光、または一括露光と現像処理を行い、２層を同時に硬化させるという簡便な方法によって、パターニングされた強固な撥水層を有する樹脂構造体を得られることを見出した。 As a result of intensive studies, the present inventors applied a composition that can be patterned by cation curable photolithography as the first coating, dried, and then formed an acid that is a cation initiator as the second coating. Applying a cationically-modified modified silicone that does not contain a generator, and patterning strong water repellency by a simple method of curing the two layers by batch exposure, or batch exposure and development, and simultaneously curing the two layers It has been found that a resin structure having a layer can be obtained.
一般にカチオン重合させるには、エポキシやオキセタンなどのカチオン重合可能な物質と光や熱により酸を発生する酸発生剤が組成物中に含まれていることが必須である。
しかしながら、強い撥水特性を持ったシリコーンなどは酸発生剤との相溶が悪いため、そのままでは混合できず、他の樹脂にシリコーンと酸発生剤を分散させる必要があった。この状態ではシリコーンの濃度が薄まるため、期待通りの撥水性が得られず、他の密着性等の特性については、分散した樹脂に依存してしまっていた。
In general, for cationic polymerization, it is essential that the composition contains a cationically polymerizable substance such as epoxy or oxetane and an acid generator that generates an acid by light or heat.
However, since silicone having strong water repellency is not compatible with the acid generator, it cannot be mixed as it is, and it is necessary to disperse the silicone and the acid generator in another resin. In this state, the concentration of silicone is reduced, so that the expected water repellency cannot be obtained, and other properties such as adhesion depend on the dispersed resin.
そこで、本発明ではカチオン硬化型フォトリソグラフィーにてパターニング可能な組成物を塗布、乾燥させ、その上にカチオン重合可能な変性シリコーンを塗布することとした。この状態で本来の工程である露光、現像を行うと、驚くことに、２層が一括で露光・硬化し、密着性と撥水性に優れたパターニングされた強固な撥水層を有する樹脂構造体が得られることがわかった。 Therefore, in the present invention, a composition that can be patterned by cation curable photolithography is applied and dried, and then a cation polymerizable modified silicone is applied thereon. Surprisingly, when exposure and development, which are the original steps, are performed in this state, two layers are exposed and cured at once, and a resin structure having a strong patterned water-repellent layer excellent in adhesion and water repellency. Was found to be obtained.
これは第１の塗膜用組成物に含有される光酸発生剤が露光時に発した酸が、表層のカチオン重合可能な変性シリコーンに達し、拡散されたと考えられる。つまり、酸発生剤そのものはシリコーンに相溶しないが、発生した酸は充分に拡散されると考えられる。
さらに、本発明により得られた硬化物は、撥水性だけでなく汚れやキズ防止の効果も持ち、硬化物としての密着性及び耐久性にも優れている。また、撥水層を形成した後、レーザー照射等で加工する必要がなく、電子デバイス部材としての構造を製造すると同時に撥水層も作製するという効率的な製造が可能である。
This is presumably because the acid generated during exposure by the photoacid generator contained in the first coating film composition reached the surface-modified cationically polymerizable silicone and was diffused. That is, it is considered that the acid generator itself is not compatible with silicone, but the generated acid is sufficiently diffused.
Furthermore, the cured product obtained by the present invention has not only water repellency but also an effect of preventing dirt and scratches, and is excellent in adhesion and durability as a cured product. In addition, after forming the water repellent layer, it is not necessary to perform processing by laser irradiation or the like, and it is possible to efficiently manufacture the structure as an electronic device member and at the same time the water repellent layer.
すなわち、本発明は常温で固体のエポキシ樹脂及び／又はオキセタン樹脂、光酸発生剤及び有機溶剤を含む樹脂組成物からなる基材上に形成された第１の塗膜と、
カチオン重合可能な変性シリコーンを含有する樹脂組成物によって前記第１の塗膜上に形成された第２の塗膜とを一括露光又は、一括露光と現像して形成した樹脂層を有することを特徴とする樹脂構造体が提供できる。
That is, the present invention is a first coating film formed on a substrate composed of a resin composition containing an epoxy resin and / or oxetane resin, a photoacid generator and an organic solvent that is solid at room temperature;
It has a resin layer formed by batch exposure or batch exposure and development of the second coating film formed on the first coating film by a resin composition containing a cationically polymerizable silicone. A resin structure can be provided.
さらに、常温で固体のエポキシ樹脂及び／又はオキセタン樹脂、光酸発生剤及び有機溶剤を含む樹脂組成物を基材上に塗布・乾燥して第１の塗膜を形成する工程、
カチオン重合可能な変性シリコーンを含有する樹脂組成物を前記第１の塗膜上に第２の塗膜を形成する工程、
前記第１の塗膜と第２の塗膜を一括露光して、前記第１の塗膜中の光酸発生剤から発生した酸により前記第１の塗膜と前記第２の塗膜を同時に硬化させる工程、
露光、又は露光後、現像によってパターニングする工程とを含むことを特徴とする樹脂構造体の製造方法が提供される。
Furthermore, a step of forming a first coating film by applying and drying a resin composition containing an epoxy resin and / or an oxetane resin, a photoacid generator and an organic solvent, which is solid at room temperature, on a substrate,
Forming a second coating film on the first coating film of a resin composition containing a cationically polymerizable silicone;
The first coating film and the second coating film are collectively exposed, and the first coating film and the second coating film are simultaneously exposed to the acid generated from the photoacid generator in the first coating film. Curing,
And a step of patterning by development after exposure or exposure. A method for producing a resin structure is provided.
本発明によれば、電子デバイス等に用いるパターニングされた強固な撥水層を有する樹脂構造体、及びその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the resin structure which has the pattern strong water-repellent layer used for an electronic device etc., and its manufacturing method can be provided.
以下、本発明をさらに詳しく説明する。
本発明の硬化性組成物は、第１の塗膜と第２の塗膜からなる２層コートによって表面に撥水層が形成され、カチオン硬化型フォトリソグラフィーにてパターニング可能な組成物であって、該組成物の第１の塗膜用組成物が常温で固体のエポキシ樹脂及び／またはオキセタン樹脂、光酸発生剤、有機溶剤を含み、第２の塗膜用組成物が酸発生剤を含まず、カチオン重合可能な変性シリコーンを含む。
Hereinafter, the present invention will be described in more detail.
The curable composition of the present invention is a composition in which a water-repellent layer is formed on the surface by a two-layer coat comprising a first coating film and a second coating film, and can be patterned by cation-curable photolithography. The first coating composition of the composition contains an epoxy resin and / or oxetane resin that is solid at room temperature, a photoacid generator, an organic solvent, and the second coating composition contains an acid generator. First, it contains a modified silicone capable of cationic polymerization.
第１の塗膜用組成物に含有される、常温で固体のエポキシ樹脂及び／またはオキセタン樹脂は、従来公知の化合物を用いることができるが、これらに限られるものではない。これらの化合物は単独で又は２種以上を組み合わせて用いることができる。 As the epoxy resin and / or oxetane resin that is solid at room temperature and contained in the first coating film composition, conventionally known compounds can be used, but are not limited thereto. These compounds can be used alone or in combination of two or more.
前記常温で固体のエポキシ樹脂には、１分子中に２個以上のエポキシ基を有する多官能エポキシ樹脂が主に使用可能である。多官能エポキシ樹脂の具体例としては、ジャパンエポキシレジン（株）製のｊＥＲ１００１、ｊＥＲ１００４、大日本インキ化学工業（株）製のエピクロン１０５０、エピクロン１０５５、エピクロン２０５０、エピクロン３０５０、エピクロン４０５０、東都化成（株）製のエポトートＹＤ−０１１、ＹＤ−０１３、ＹＤ−０１７、ＹＤ−９０１、等のビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン製ｊＥＲ４００４Ｐ、ｊＥＲ４００５Ｐ、ｊＥＲ４００７Ｐ、ｊＥＲ４０１０Ｐ、東都化成（株）製のエポトートＹＤＦ−２００１、エポトートＹＤＦ−２００４、エポトートＹＤＦ−２００５ＲＬ等のビスフェノールＦ型エポキシ樹脂；大日本インキ化学工業（株）製のＥＸＡ−１５１４等のビスフェノールＳ型エポキシ樹脂；ジャパンエポキシレジン（株）製のｊＥＲ１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；ジャパンエポキシレジン（株）製のｊＥＲ１５４、ｊＥＲ１５７Ｓ７０、ダウケミカル（株）製のＤＥＮ４３８、大日本インキ化学工業（株）製のエピクロンＮ−７７０、エピクロンＮ−７７５、エピクロンＮ−８６５、東都化成（株）製のエポトートＹＤＣＮ−７００−２、ＹＤＣＮ−７００−３、ＹＤＣＮ−７００−５、ＹＤＣＮ−７００−７、ＹＤＣＮ−７０４、日本化薬（株）製のＥＰＰＮ−５０１Ｈ、ＥＰＰＮ−５０２Ｈ、ＥＯＣＮ−１０２５、ＲＥ−３０６等のノボラック型エポキシ樹脂；東都化成（株）製のエポトートＳＴ−４０００Ｄ等の水添ビスフェノールＡ型エポキシ樹脂；ダイセル化学工業（株）製のＥＨＰＥ３１５０等の脂環式エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＬ−９３３、日本化薬（株）製のＥＰＰＮ−５０１、ＥＰＰＮ−５０２等のトリヒドロキシフェニルメタン型エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＸ−４０００、ＹＬ−６１２１Ｈ、ＹＬ−６６４０、ＹＬ−６６７７等のビキシレノール型もしくはビフェノール型エポキシ樹脂；日産化学（株）製のＴＥＰＩＣ等の複素環式エポキシ樹脂；大日本インキ化学工業（株）製のＨＰ−４７００、ＨＰ−４７７０等のナフタレン基含有エポキシ樹脂；大日本インキ化学工業（株）製のＨＰ−７２００、ＨＰ−７２００Ｈ、ＨＰ−７２００ＨＨ等のジシクロペンタジエン骨格を有するエポキシ樹脂；さらに、ブロム化エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、テトラフェノールエタン型エポキシ樹脂、ジグリシジルフタレート樹脂、グリシジルメタアクリレート共重合系エポキシ樹脂、テトラグリシジルキシレノイルエタン樹脂、ヒダントイン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、スチルベン型エポキシ樹脂、シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂等が挙げられる。これら常温で固体のエポキシ樹脂の中でも、硬化物の物性の観点から、ビスフェノールＡ型エポキシ樹脂が好ましい。 As the epoxy resin that is solid at room temperature, a polyfunctional epoxy resin having two or more epoxy groups in one molecule can be mainly used. Specific examples of the polyfunctional epoxy resin include jER1001 and jER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epicron 1050, Epicron 1055, Epicron 2050, Epicron 3050, Epicron 4050, Tohto Kasei Co., Ltd. EPOTOTO YD-011, YD-013, YD-017, YD-901, etc. manufactured by Etototo Co., Ltd .; Japan Epoxy Resin jER4004P, jER4005P, jER4007P, jER4010P, Etototo YDF manufactured by Toto Kasei Co., Ltd. -2001, Epototo YDF-2004, Epototo YDF-2005RL and other bisphenol F-type epoxy resins; Dainippon Ink and Chemicals Co., Ltd. EXA-1514 and other bisphenol S-type epoxy resins Bisphenol A novolak epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd .; jER154, jER157S70 manufactured by Japan Epoxy Resin Co., Ltd., DEN438 manufactured by Dow Chemical Co., Ltd. ) Epicron N-770, Epicron N-775, Epicron N-865, Etototo YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, manufactured by Tohto Kasei Co., Ltd. YDCN-704, novolak type epoxy resins such as EPPN-501H, EPPN-502H, EOCN-1025, RE-306 manufactured by Nippon Kayaku Co., Ltd .; hydrogenated bisphenols such as Epototo ST-4000D manufactured by Toto Kasei Co., Ltd. Type A epoxy resin; manufactured by Daicel Chemical Industries, Ltd. Cycloaliphatic epoxy resins such as HPE3150; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. Trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 manufactured by Nippon Kayaku Co., Ltd .; Japan Epoxy Resin ( YX-4000, YL-6121H, YL-6640, YL-6777, and other bixylenol-type epoxy resins manufactured by Nippon Kayaku Co., Ltd .; heterocyclic epoxy resins such as TEPIC manufactured by Nissan Chemical Co., Ltd .; Naphthalene group-containing epoxy resins such as HP-4700 and HP-4770 manufactured by Kogyo Co., Ltd .; having a dicyclopentadiene skeleton such as HP-7200, HP-7200H and HP-7200HH manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; further brominated epoxy resin, triphenolmethane Type epoxy resin, tetraphenol ethane type epoxy resin, diglycidyl phthalate resin, glycidyl methacrylate copolymer epoxy resin, tetraglycidyl xylenoyl ethane resin, hydantoin type epoxy resin, triazine nucleus-containing epoxy resin, stilbene type epoxy resin, cyclohexyl Examples thereof include a copolymer epoxy resin of maleimide and glycidyl methacrylate. Among these epoxy resins that are solid at room temperature, bisphenol A type epoxy resins are preferred from the viewpoint of the physical properties of the cured product.
前記常温で固体のオキセタン樹脂には、ノボラック型オキセタン樹脂が主に使用可能であり、例えば東亜合成（株）製のＰＮＯＸ−１００９が好適に使用される。また、常温で固体のオキセタン樹脂であれば、これに限定されるものではない。 As the oxetane resin that is solid at room temperature, a novolak oxetane resin can be mainly used. For example, PNOX-1009 manufactured by Toa Gosei Co., Ltd. is preferably used. Moreover, if it is oxetane resin solid at normal temperature, it will not be limited to this.
また、オキセタン樹脂は、最終的にカチオン硬化度が高い硬化物が得られるが、エポキシ樹脂やビニルエーテル樹脂などを適切な量で添加することにより、反応初期の硬化速度を向上させることができる。この場合の添加量は、オキセタン樹脂に対して５質量％から９５質量％とすることが望ましい。 In addition, the oxetane resin can finally obtain a cured product having a high degree of cationic curing, but the addition of an appropriate amount of an epoxy resin, a vinyl ether resin, or the like can improve the curing rate at the initial stage of the reaction. In this case, the addition amount is desirably 5% by mass to 95% by mass with respect to the oxetane resin.
また、オキセタン樹脂を用いて硬化物を形成する場合には、上述したオキセタン樹脂の他に光酸発生剤が用いられる。紫外線等の活性エネルギー線を照射してパターニングする場合には、光酸発生剤が用いられ、単独で又は２種類以上を組み合わせて用いることができる。 Moreover, when forming hardened | cured material using an oxetane resin, a photo-acid generator other than the oxetane resin mentioned above is used. When patterning is performed by irradiating active energy rays such as ultraviolet rays, a photoacid generator is used, which can be used alone or in combination of two or more.
第１の塗膜用組成物が含有する光酸発生剤として市販されているものは、例えばユニオン・カーバイト社製のＣＹＲＡＣＵＲＥ ＵＶＩ−６９５０、ＵＶＩ−６９７０、旭電化工業社製のオプトマーＳＰ−１５０、ＳＰ−１５１、ＳＰ−１５２、ＳＰ−１７０、ＳＰ−１７１、日本曹達社製のＣＩ−２８５５、デグサ社製のＤｅｇａｃｅｒｅ ＫＩ８５Ｂ等のトリアリールスルホニウム塩や非置換又は置換されたアリールジアゾニウム塩、ジアリールヨードニウム塩が挙げられる。また、スルホン酸誘導体としては、みどり化学社製のＰＡＩ−１０１等が挙げられる。 Commercially available photoacid generators contained in the first coating composition include, for example, CYRACURE UVI-6950 and UVI-6970 manufactured by Union Carbide, and Optomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd. , SP-151, SP-152, SP-170, SP-171, CI-2855 manufactured by Nippon Soda Co., Ltd., Dearyla KI85B manufactured by Degussa, triarylsulfonium salts, unsubstituted or substituted aryldiazonium salts, diaryls An iodonium salt is mentioned. Examples of the sulfonic acid derivative include PAI-101 manufactured by Midori Chemical.
これらの光酸発生剤の配合割合は、上述したオキセタン樹脂１００質量部当たり、２〜４０質量部が適当である。２質量部よりも少ない場合には、活性エネルギー線の照射により生成する酸が少なく、パターン形成が困難になるとともに、撥水性材料の硬化性が著しく悪化する。一方、４０質量部よりも多い場合には、光酸発生剤自身の光吸収により感度が低下し易くなるので好ましくない。また、より硬化度を向上させたい場合には、熱重合カチオン開始剤や光カチオン増感剤を併用してもよい。 The mixing ratio of these photoacid generators is suitably 2 to 40 parts by mass per 100 parts by mass of the oxetane resin described above. When the amount is less than 2 parts by mass, less acid is generated by irradiation with active energy rays, and pattern formation becomes difficult and curability of the water-repellent material is significantly deteriorated. On the other hand, when the amount is more than 40 parts by mass, the sensitivity tends to decrease due to light absorption of the photoacid generator itself, which is not preferable. Moreover, when it is desired to further improve the degree of curing, a thermal polymerization cation initiator or a photocation sensitizer may be used in combination.
有機溶剤は、オキセタン樹脂やその他の添加物を溶解させることができるものであればよい。例えば、メチルエチルケトンやシクロヘキサノン等のケトン類、トルエンやキシレン、テトラメチルベンゼン等の芳香族炭化水素類、セロソルブやメチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトー ル、ブチルカルビトール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類、酢酸エチルや酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等の酢酸エステル類、エタノールやプロパノール、エチレングリコール、プロピレングリコール等のアルコール類、オクタンやデカン等の脂肪族炭化水素類、石油エーテルや石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤類、リモネン等のテルペン類などが挙げられる。特にソルベントナフサ等の石油系溶剤類が好適に使用でき、これを用いることにより、オキセタン樹脂に対しての良好な溶解性が得られる。これらの有機溶剤は、単独で又は２種類以上の混合物として使用することができる。また、有機溶剤の配合量は、用途等に応じた任意の量とすることができる。 The organic solvent should just be what can dissolve oxetane resin and other additives. For example, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol ethers such as glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate and butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, Acetic esters such as dipropylene glycol monomethyl ether acetate, ethanol Alcohols such as propanol, ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane and decane, petroleum solvents such as petroleum ether and petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, and terpenes such as limonene Is mentioned. In particular, petroleum-based solvents such as solvent naphtha can be suitably used, and by using this, good solubility in oxetane resin can be obtained. These organic solvents can be used alone or as a mixture of two or more. Moreover, the compounding quantity of the organic solvent can be made into arbitrary quantity according to a use etc.
カチオン重合可能な変性シリコーンとしては、特に以下のものが好適に使用でき、メタクリル変性シリコーン、脂環式エポキシ変性シリコーン、エポキシ系シリコーン等がある。特に脂環式エポキシ変性シリコーン、エポキシ系シリコーンが好適に使用でき、例えば、信越化学工業社製のＸ−２２−２０４６、ＫＦ−１０２、Ｘ−２２−１６９ＡＳ、Ｘ−２２−１６９Ｂ、Ｘ−２２−３４３、ＫＦ−１０１、ＫＦ−１００１、Ｘ−２２−１６３、ＫＦ−１０５、Ｘ−２２−１６３Ａ、Ｘ−２２−１６３Ｂ、Ｘ−２２−１６３Ｃ、Ｘ−２２−１７３ＤＸ、Ｘ−２２−９００２、Ｘ−４１−１０５３、Ｘ−４１−１０５９Ａ、Ｘ−４１−１０５６；東レ・ダウコーニング社製のＢＹ１６−８３９、ＢＹ−１６−８５５、ＳＦ８４１１、ＳＦ８４１３；チッソ社製のＥＭＳ−２３２、ＥＭＳ−２３４、ＤＭＳ−Ｅ０１、ＤＭＳ−Ｅ１２、ＤＭＳ−Ｅ２１、ＭＣＲ−Ｅ１１、ＭＣＲ−Ｅ２１；モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製のＸＳ６９−Ａ５１９９などが挙げられる。これらを用いることにより、第１の塗膜用組成物中に含まれる光酸発生剤の露光時に発した酸が、第２の塗膜用組成物中に含まれるカチオン重合可能な変性シリコーンに達し、拡散された後、硬化する効果が得られる。 As the modified silicone capable of cationic polymerization, the following can be preferably used, and examples thereof include methacryl-modified silicone, alicyclic epoxy-modified silicone, and epoxy-based silicone. In particular, alicyclic epoxy-modified silicones and epoxy-based silicones can be suitably used. For example, X-22-2046, KF-102, X-22-169AS, X-22-169B, X-22 manufactured by Shin-Etsu Chemical Co., Ltd. -343, KF-101, KF-1001, X-22-163, KF-105, X-22-163A, X-22-163B, X-22-163C, X-22-173DX, X-22-9002 X-41-1053, X-41-1059A, X-41-1056; BY16-839, BY-16-855, SF8411, SF8413 manufactured by Toray Dow Corning; EMS-232, EMS- manufactured by Chisso 234, DMS-E01, DMS-E12, DMS-E21, MCR-E11, MCR-E21; Momentive Performance Ma Such as Riaruzu Japan Co., Ltd. of the XS69-A5199 and the like. By using these, the acid generated upon exposure of the photoacid generator contained in the first coating composition reaches the cationically polymerizable modified silicone contained in the second coating composition. After being diffused, the effect of curing is obtained.
また、上述したオキセタン樹脂及び光酸発生剤などから構成される組成物の他に、必要に応じて各種添加剤等を適宜添加することが可能であり、例えば、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等の公知慣用の着色剤、ハイドロキノン、ハイドロキノンモノメチルエーテル、ｔ−ブチルカテコール、ピロガロール、フェノチアジン等の公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイト等の公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び／又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤などの密着性付与剤、酸化防止剤、防錆剤などの公知慣用の添加剤類を配合することができる。 Further, in addition to the composition composed of the oxetane resin and the photoacid generator described above, various additives and the like can be appropriately added as necessary. For example, phthalocyanine blue, phthalocyanine green, Known conventional colorants such as Iodine Green, Disazo Yellow, Crystal Violet, Titanium Oxide, Carbon Black, Naphthalene Black, etc., Known Conventional Thermal Polymerization Inhibitors such as Hydroquinone, Hydroquinone Monomethyl Ether, t-Butylcatechol, Pyrogallol, Phenothiazine, Known and commonly used thickeners such as finely divided silica, organic bentonite and montmorillonite, defoamers and / or leveling agents such as silicones, fluorines and polymers, silane coupling agents such as imidazole, thiazole and triazole Adhesion such as Azukazai, antioxidants, can be blended a known conventional additives such as corrosion inhibitors.
本発明の硬化性組成物は、必要に応じて希釈して塗布方法に適した粘度に調整し、これを例えば、基板上にカーテンコート法、スプレーコート法、ロールコート法、スピンコート法等の方法により塗布することができる。 The curable composition of the present invention is diluted as necessary and adjusted to a viscosity suitable for the coating method. For example, this is applied to a substrate by a curtain coating method, a spray coating method, a roll coating method, a spin coating method or the like. It can apply | coat by the method.
本発明の硬化性組成物を２層コートによって表面に撥水層が形成され、カチオン硬化型フォトリソグラフィーにてパターン形成する例としては、まず、シリコンウエハ等の基板上に第１の塗膜用組成物を前記の方法にて塗布し、約７０〜９０℃の温度で組成物中に含まれる有機溶剤を揮発乾燥させ、第１の塗膜を形成する。 As an example in which a water-repellent layer is formed on the surface of the curable composition of the present invention by a two-layer coating and pattern formation is performed by cation curable photolithography, first, the first coating film is formed on a substrate such as a silicon wafer. A composition is apply | coated by the said method, the organic solvent contained in a composition is volatilized and dried at the temperature of about 70-90 degreeC, and a 1st coating film is formed.
その後、第１の塗膜の上から第２の塗膜用組成物を塗布し、レーザー光等の活性エネルギー線をパターン通りに直接照射するか、又はパターンを形成したフォトマスクを通して選択的に活性エネルギー線により露光する。 Then, a second coating composition is applied on the first coating, and an active energy ray such as a laser beam is directly irradiated according to the pattern, or selectively activated through a photomask having a pattern formed thereon. Exposure with energy rays.
露光後の塗膜を、約７０〜９０℃の温度で加熱する。これは、第１の塗膜の露光後加熱処理（ＰＥＢ）及び、第１の塗膜用組成物中に含まれる光酸発生剤の露光時に発した酸が、第２の塗膜に達し、拡散され硬化を促進する効果及び、第２の塗膜用組成物中の有機溶剤を揮発乾燥させる効果がある。 The coated film after exposure is heated at a temperature of about 70 to 90 ° C. This is the heat treatment after exposure of the first coating film (PEB) and the acid generated during the exposure of the photoacid generator contained in the first coating composition reaches the second coating film, It has the effect of diffusing and accelerating curing and the effect of evaporating and drying the organic solvent in the second coating film composition.
露光後の塗膜の加熱後、未露光部は有機溶剤系の現像液により現像され、レジストパターンを形成することができる。 After heating of the coated film after exposure, the unexposed portion can be developed with an organic solvent developer to form a resist pattern.
その後さらに、加熱硬化のみ、又は活性エネルギー線の照射後加熱硬化もしくは加熱硬化後活性エネルギー線の照射で硬化させることにより、密着性、パターニング性、撥水性などの諸特性に優れた２層の硬化物が形成される。また、パターンが必要なく、全面に撥水層を形成する場合は、露光はマスクレスで全面に行い、現像は省略できる。 After that, two-layer curing with excellent properties such as adhesion, patternability, and water repellency by curing only by heat curing, or by heat curing after irradiation with active energy rays or irradiation with active energy rays after heat curing. Things are formed. When a pattern is not required and a water repellent layer is formed on the entire surface, exposure is performed on the entire surface without a mask, and development can be omitted.
前記にある活性エネルギー線硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプなどが適当である。その他、レーザー光線なども活性エネルギー線として利用できる。 As the irradiation light source for curing the active energy ray as described above, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like are suitable. In addition, laser beams and the like can also be used as active energy rays.
前記使用の基板としては、シリコンウエハやガラス等の基板があるが、必ずしもこれに限定されるものではない。 Examples of the substrate used include a silicon wafer and a glass substrate, but are not necessarily limited thereto.
以下の実施例により、本発明をさらに具体的に説明するが、本発明はこれに限定されるものではない。 The following examples further illustrate the present invention, but the present invention is not limited thereto.
本発明を適用した樹脂構造体及び樹脂構造体の製造方法について、以下の通り材料物性の検討を行った。また、この材料を硬化させた硬化物のパターニング性、撥水性、及び撥水性の耐久性の評価を行った。 Regarding the resin structure to which the present invention is applied and the method for producing the resin structure, the material properties were examined as follows. Further, the patterning property, water repellency, and water repellency durability of the cured product obtained by curing this material were evaluated.
＜実施例１〜４及び、比較例１〜５＞
以下の表１に示す、第１の塗膜用組成物である硬化性材料を６インチシリコンウエハにスピンコート法により約２０μｍになるよう塗布し、系中の溶剤を除去するためにホットプレートで９０℃、５分間乾燥させた。この乾燥塗膜に対し、表２及び表３に示す第２の塗膜用組成物である撥水性硬化性材料をスピンコート法により約５μｍになるよう塗布し、２層の状態とした。この後、パターンとして残存させたい部分をプリント配線板用露光機にて６００ｍＪ／ｃｍ２の露光を行った。２層の塗膜の露光された部分は硬化し、現像液に不溶となり、露光されなかった部分は、現像液に可溶となる。次に、ホットプレートで９０℃、１０分間加熱させて硬化を促進させた。加熱後、露光されていない部分をジプロピレングリコールモノメチルエーテルによりパドル現像することにより、露光されていない部分の層を除去した。ついで、１５０℃、１時間の加熱硬化を行い、パターンが形成された撥水性硬化物を得た。
<Examples 1-4 and Comparative Examples 1-5>
A curable material, which is the first coating film composition shown in Table 1 below, was applied to a 6-inch silicon wafer to a thickness of about 20 μm by a spin coating method, and then a hot plate was used to remove the solvent in the system. It was dried at 90 ° C. for 5 minutes. A water repellent curable material, which is the second coating film composition shown in Tables 2 and 3, was applied to the dried coating film so as to have a thickness of about 5 μm by a spin coating method to form two layers. Thereafter, the portion desired to remain as a pattern was exposed at 600 mJ / cm 2 with a printed wiring board exposure machine. The exposed portion of the two-layer coating is cured and becomes insoluble in the developer, and the unexposed portion is soluble in the developer. Next, curing was promoted by heating at 90 ° C. for 10 minutes on a hot plate. After heating, the unexposed portion was paddle developed with dipropylene glycol monomethyl ether to remove the unexposed portion of the layer. Subsequently, heat curing was performed at 150 ° C. for 1 hour to obtain a water-repellent cured product having a pattern formed thereon.
＊１：東亞合成（株）製 ＰＮＯＸ−１００９のイプゾール１５０
（テトラメチルベンゼン主体の石油系溶剤）カットワニス（ＮＶ＝８０％）
＊２：ジャパンエポキシレジン（株）製 ｊＥＲ８３４
＊３：ＡＤＥＫＡ（株）製 ＳＰ−１５２
＊４：ビックケミー・ジャパン（株）製 ＢＹＫ−３６１Ｎ
* 1: PNOX-1009 ipsol 150 manufactured by Toagosei Co., Ltd.
(Tetramethylbenzene-based petroleum solvent) Cut varnish (NV = 80%)
* 2: jER834 manufactured by Japan Epoxy Resin Co., Ltd.
* 3: ADEKA Corporation SP-152
* 4: BYK-361N manufactured by Big Chemie Japan Co., Ltd.
＜比較例６〜１１＞
以下の表４に示す組成物は、硬化性材料と撥水性硬化性材料を混合したものであり、
単独の塗膜を形成するものである。硬化物の作製は、前記＜実施例１〜４及び、比較例１〜５＞では塗布工程が２回あったが、本比較例においては単独の組成物であるため塗布工程は１回のみであった。また、硬化物作製における工程は、前記と同様であった。
<Comparative Examples 6-11>
The composition shown in Table 4 below is a mixture of a curable material and a water repellent curable material,
A single coating film is formed. In the preparation of the cured product, there were two coating steps in the above <Examples 1 to 4 and Comparative Examples 1 to 5>. However, in this comparative example, the coating step is only once because it is a single composition. there were. Moreover, the steps in producing the cured product were the same as described above.
＊５：信越化学工業（株）製 Ｘ−２２−１６３
＊６：信越化学工業（株）製 Ｘ−２２−１６９Ｂ
＊７：東レ・ダウコーニング（株）製 ＢＹ１６−８３９
＊８：信越化学工業（株）製 ＫＦ−９６
＊９：信越化学工業（株）製 ＫＢＥ−４０２
＊１０：共栄社化学（株）製 Ｍ−３Ｆ
＊１１：ｎ−ドデカン
* 5: X-22-163, manufactured by Shin-Etsu Chemical Co., Ltd.
* 6: X-22-169B manufactured by Shin-Etsu Chemical Co., Ltd.
* 7: BY16-839 manufactured by Toray Dow Corning Co., Ltd.
* 8: Shin-Etsu Chemical Co., Ltd. KF-96
* 9: Shin-Etsu Chemical Co., Ltd. KBE-402
* 10: M-3F manufactured by Kyoeisha Chemical Co., Ltd.
* 11: n-dodecane
＜塗工性＞
実施例１〜４、比較例１〜１１について、塗工性を確認するため、露光前の塗膜について、目視にて評価を行った。
○：外観が良好である
×：はじきによる外観不良が顕著である
<Coating property>
About Examples 1-4 and Comparative Examples 1-11, in order to confirm coating property, the coating film before exposure was evaluated visually.
○: Appearance is good ×: Appearance failure due to repelling is remarkable
＜パターニング性＞
塗工性が良好であった実施例１〜４、比較例１〜５、７、９、１１について、現像工程後の状態を観察することで評価を行った。
○：現像残渣がなく、パターニング可能なもの
×：現像残渣のあるもの
××：現像できず、塗膜が流されているもの
<Patternability>
For Examples 1 to 4 and Comparative Examples 1 to 5, 7, 9, and 11, which had good coatability, evaluation was performed by observing the state after the development step.
○: There is no development residue and can be patterned. ×: There is a development residue. XX: The image cannot be developed and the coating film is washed away.
＜接触角と撥水性＞
パターニング性が良好であった実施例１〜４、比較例１、３、９、１１について、超純水での接触角を自動接触角計（協和界面科学社製ＤＭ３００）にて測定した。塗膜表面の水滴の接触角θが撥水性の指標になっており、一般にはθが９０°以上の場合を撥水性（疎水性）を有するとしている。
撥水性 ○：θ≧９０°
×：θ＜９０°
<Contact angle and water repellency>
For Examples 1 to 4 and Comparative Examples 1, 3, 9, and 11, which had good patterning properties, the contact angle with ultrapure water was measured with an automatic contact angle meter (DM300 manufactured by Kyowa Interface Science Co., Ltd.). The contact angle θ of water droplets on the surface of the coating film is an indicator of water repellency. Generally, when θ is 90 ° or more, water repellency (hydrophobicity) is assumed.
Water repellent ○: θ ≧ 90 °
×: θ <90 °
＜撥水性の耐久性＞
パターニング性が良好であった実施例１〜４、比較例１、３、９について、有機溶剤であるトルエンを含んだ布で３０回こすった後、前記と同様に撥水性を評価した。
○：θ≧９０°
×：θ＜９０°
<Durable water repellency>
For Examples 1 to 4 and Comparative Examples 1, 3, and 9, which had good patterning properties, water repellency was evaluated in the same manner as described above after rubbing 30 times with a cloth containing toluene as an organic solvent.
○: θ ≧ 90 °
×: θ <90 °
前記各試験の結果を表５〜表７に示す。 The results of each test are shown in Tables 5-7.
上記表５〜表７に示される結果から明らかなように、本発明に従って、２層コートによって形成された組成物を用いて得られた塗膜は、実施例１〜４にあるように、カチオン硬化型フォトリソグラフィーにて現像残渣がなく、パターニング性に優れており、また、組成物表面に撥水層が形成されているため、接触角が大きく撥水性に優れ、さらに、撥水性の耐久性にも優れていることがわかる。 As is clear from the results shown in Tables 5 to 7 above, the coating films obtained using the composition formed by the two-layer coating according to the present invention are cation as in Examples 1-4. There is no development residue in curable photolithography, it has excellent patterning properties, and a water-repellent layer is formed on the surface of the composition, so it has a large contact angle and excellent water repellency. It turns out that it is also excellent.
これに対して単独組成物の場合では、強く撥水特性を持ったシリコーンやフッ素系化合物などは光酸発生剤との相溶が悪いために、塗膜の外観不良等の問題が起こることがわかる。また、塗工性が良かったとしても、第２の塗膜用の組成物によって第１の塗膜を溶解させてしまうため、現像によるパターニング性が劣ることや、現像液により撥水性を有する組成物が流されてしまうために、撥水性が劣ることがわかる。 On the other hand, in the case of a single composition, silicone and fluorine compounds having strong water repellency are not compatible with the photoacid generator, which may cause problems such as poor appearance of the coating film. Recognize. Even if the coating property is good, the first coating film is dissolved by the composition for the second coating film, so that the patterning property by development is inferior or the composition has water repellency by the developer. It can be seen that the water repellency is inferior because the object is washed away.
以上の通り、本発明によれば、カチオン硬化型フォトリソグラフィーにてパターニング可能な組成物を塗布、乾燥させて、その上にカチオン開始剤である酸発生剤を含まない、カチオン重合可能な変性シリコーンを塗布し、一括露光、又は一括露光と現像処理を行うことにより、パターニングされた強固な撥水層を有する樹脂組成物を得ることができ、インクジェット記録ヘッドや電子デバイスに用いる強固にパターニングされた撥水層を容易に製造することが可能である。 As described above, according to the present invention, a cationically polymerizable modified silicone that does not contain an acid generator that is a cation initiator on a composition that can be patterned by cation curable photolithography and is dried. The resin composition having a strong patterned water-repellent layer can be obtained by performing batch exposure or batch exposure and development processing, and is strongly patterned for use in an inkjet recording head or an electronic device. It is possible to easily produce a water repellent layer.
Claims (4)
カチオン重合可能な変性シリコーンを含有する樹脂組成物によって前記第１の塗膜上に形成された第２の塗膜とを一括露光して形成した樹脂層を有することを特徴とする樹脂構造体。 A first coating film formed on a substrate composed of a resin composition containing an epoxy resin and / or an oxetane resin, a photoacid generator and an organic solvent that is solid at room temperature;
A resin structure comprising a resin layer formed by collectively exposing a second coating film formed on the first coating film with a resin composition containing a cationically polymerizable silicone.
カチオン重合可能な変性シリコーンを含有する樹脂組成物によって前記第１の塗膜上に形成された第２の塗膜とを一括露光・現像して形成した樹脂層を有することを特徴とする樹脂構造体。 A first coating film formed on a substrate composed of a resin composition containing an epoxy resin and / or an oxetane resin, a photoacid generator and an organic solvent that is solid at room temperature;
A resin structure comprising a resin layer formed by collectively exposing and developing a second coating film formed on the first coating film with a resin composition containing a modified silicone capable of cationic polymerization body.
カチオン重合可能な変性シリコーンを含有する樹脂組成物を前記第１の塗膜上に第２の塗膜を形成する工程、
前記第１の塗膜と第２の塗膜を一括露光して、前記第１の塗膜中の光酸発生剤から発生した酸により前記第１の塗膜と前記第２の塗膜を同時に硬化させる工程とを含むことを特徴とする樹脂構造体の製造方法。 Applying a resin composition containing an epoxy resin and / or an oxetane resin, a photoacid generator and an organic solvent, which is solid at room temperature, onto a substrate to form a first coating film;
Forming a second coating film on the first coating film of a resin composition containing a cationically polymerizable silicone;
The first coating film and the second coating film are collectively exposed, and the first coating film and the second coating film are simultaneously exposed to the acid generated from the photoacid generator in the first coating film. And a step of curing the resin structure.
カチオン重合可能な変性シリコーンを含有する樹脂組成物を前記第１の塗膜上に第２の塗膜を形成する工程、
前記第１の塗膜と第２の塗膜を一括露光して、前記第１の塗膜中の光酸発生剤から発生した酸により前記第１の塗膜と前記第２の塗膜を同時に硬化させる工程、
露光後、現像によってパターニングする工程とを含むことを特徴とする樹脂構造体の製造方法。 Applying a resin composition containing an epoxy resin and / or an oxetane resin, a photoacid generator and an organic solvent, which is solid at room temperature, onto a substrate to form a first coating film;
Forming a second coating film on the first coating film of a resin composition containing a cationically polymerizable silicone;
The first coating film and the second coating film are collectively exposed, and the first coating film and the second coating film are simultaneously exposed to the acid generated from the photoacid generator in the first coating film. Curing,
And a step of patterning by development after exposure, and a method for producing a resin structure.
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| JPH05318668A (en) * | 1992-05-20 | 1993-12-03 | Three Bond Co Ltd | Sheet material for preventing sticker |
| JP2005283905A (en) * | 2004-03-29 | 2005-10-13 | Osaka Gas Co Ltd | Photopolymerizable resin composition, its cured material and manufacturing method |
| JP2007044926A (en) * | 2005-08-08 | 2007-02-22 | Sony Corp | Passage constituting material of liquid delivering type recording head |
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| JPH05318668A (en) * | 1992-05-20 | 1993-12-03 | Three Bond Co Ltd | Sheet material for preventing sticker |
| JP2005283905A (en) * | 2004-03-29 | 2005-10-13 | Osaka Gas Co Ltd | Photopolymerizable resin composition, its cured material and manufacturing method |
| JP2007044926A (en) * | 2005-08-08 | 2007-02-22 | Sony Corp | Passage constituting material of liquid delivering type recording head |
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| CN103192572A (en) * | 2013-04-01 | 2013-07-10 | 广州市宝励贸易有限公司 | Heat-resisting coverage film, metal matrix heating panel made by using heat-resisting coverage film and preparation method of metal matrix heating panel |
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