JP5082262B2 - Manufacturing method of resin film - Google Patents
Manufacturing method of resin film Download PDFInfo
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- JP5082262B2 JP5082262B2 JP2006057468A JP2006057468A JP5082262B2 JP 5082262 B2 JP5082262 B2 JP 5082262B2 JP 2006057468 A JP2006057468 A JP 2006057468A JP 2006057468 A JP2006057468 A JP 2006057468A JP 5082262 B2 JP5082262 B2 JP 5082262B2
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- 239000011347 resin Substances 0.000 title claims abstract description 79
- 229920005989 resin Polymers 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000012790 adhesive layer Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 40
- 230000008569 process Effects 0.000 abstract description 10
- 230000001788 irregular Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 27
- 239000000758 substrate Substances 0.000 description 25
- 239000010410 layer Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000004695 Polyether sulfone Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920006393 polyether sulfone Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Natural products CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001494 step-and-flash imprint lithography Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Abstract
Description
本発明は樹脂膜の製造方法に関し、特に、表面に微細形状を有する大面積の樹脂膜を製造するのに好適な樹脂膜の製造方法に関する。 The present invention relates to a method for producing a resin film , and more particularly to a method for producing a resin film suitable for producing a large-area resin film having a fine shape on the surface.
近年、急速に発展しているディスプレイの分野では、拡散や集光、反射防止などさまざまな機能を持ったシートが使用されている。その一部には、表面にサブミクロンから数十ミクロン程度の微細な凹凸形状を有する樹脂シートが適している。そのような樹脂シートの製造方法としては、あらかじめ微細な凹凸形状に対応する金型（モールド）を作製しておき、そのモールドの形状を転写することによって製造する手法が適している。 In recent years, in the field of displays that are rapidly developing, sheets having various functions such as diffusion, light collection, and antireflection are used. For some of them, a resin sheet having a fine concavo-convex shape of about submicron to several tens of microns on the surface is suitable. As a method for manufacturing such a resin sheet, a method of manufacturing a mold (mold) corresponding to a fine uneven shape in advance and transferring the shape of the mold is suitable.
従来より微細な凹凸を樹脂に転写する手法として、ＵＶ硬化樹脂を用いてモールドに圧力をかけてＵＶ光を照射して形状を転写するＵＶインプリントや熱可塑性樹脂を用いてモールドに熱及び圧力をかけて形状を転写する熱インプリントなどの手法が知られている（例えば、特許文献１〜５、非特許文献１等参照。）。
As a technique for transferring finer irregularities to the resin than before, heat and pressure are applied to the mold using UV imprint or thermoplastic resin that uses UV curable resin to apply pressure to the mold and irradiate UV light to transfer the shape. A method such as thermal imprinting is known in which the shape is transferred by applying (see, for example,
しかしながらそれらの手法では、作製する面積全体にわたり均一な圧力を加える必要があり、装置が大型となり、また大面積化が難しいという課題を抱えていた。 However, these methods have a problem that it is necessary to apply a uniform pressure over the entire area to be manufactured, the apparatus becomes large, and it is difficult to increase the area.
大面積に微細な構造を転写するのに適した手法として、ナノキャスト法と呼ばれる手法が提案されている。微細な凹凸形状が形成されたモールドに、有機溶剤に可溶な有機材料を溶かした液状組成物や液状の有機材料からなる液状組成物を塗布して微細な凹部に液状組成物を充填し、乾燥もしくは重合などにより有機材料を固化した後、モールドから剥離することにより、微細な凹凸形状が表面に形成された有機材料の層を形成する手法の１例が開示されている（非特許文献２参照。）。 As a technique suitable for transferring a fine structure over a large area, a technique called a nanocast method has been proposed. Applying a liquid composition made of an organic material soluble in an organic solvent or a liquid composition made of a liquid organic material to a mold having a fine concavo-convex shape and filling the liquid composition into the fine recesses, An example of a method of forming a layer of an organic material having a fine uneven shape formed on the surface by solidifying the organic material by drying or polymerization and then peeling it from the mold is disclosed (Non-patent Document 2). reference.).
上記の様な種々の方法が開示されているが、何れも転写精度は必ずしも十分ではなく、又、材料の利用効率も低いものであった。
従来の製造方法では、液状組成物をモールド上に塗布する手法として、スピンコートが用いられている。しかしながら、スピンコートによる手法では、塗布時に微細な構造の内部にまで液状組成物を充填することが困難という課題を抱えていた。また、液状組成物のうち、一部しか利用することができず、材料の利用効率が悪いという課題を抱えていた。また、大面積に均一な厚さで塗布することが困難という課題を抱えていた。 In a conventional manufacturing method, spin coating is used as a method for applying a liquid composition onto a mold. However, the spin coating method has a problem that it is difficult to fill the liquid composition into the fine structure at the time of coating. Moreover, only a part of the liquid composition can be used, and there is a problem that the utilization efficiency of the material is poor. In addition, there is a problem that it is difficult to apply a uniform thickness to a large area.
上記課題を解決するために、液状組成物を塗布する際に、インクジェット手法を用いることに到達した。インクジェット手法による塗布を行うことで、従来手法では困難だった微細な構造にまで液状組成物を充填することが可能となり、より微細で高アスペクト比の構造を転写することが可能となる。 In order to solve the above-mentioned problems, the present inventors have reached the use of an inkjet technique when applying a liquid composition. By applying the ink-jet method, the liquid composition can be filled into a fine structure that was difficult with the conventional method, and a finer and higher aspect ratio structure can be transferred.
また、作製する面積に合せてインクジェットヘッドを作製して、滴下量をコントロールすることにより、材料の利用効率を高めることができた。 In addition, the use efficiency of the material could be improved by producing an ink jet head in accordance with the area to be produced and controlling the dropping amount.
また、大面積でも均一な膜厚に液状組成物を塗布することができる。 In addition, the liquid composition can be applied to a uniform film thickness even in a large area.
上記課題は、以下の構成により解決することができた。 The above problem could be solved by the following configuration.
１．液状組成物をインクジェット方式のノズルから液滴として凹凸形状が設けられたモールドに吐出して塗布する工程と、液状組成物を乾燥もしくは重合により硬化して樹脂膜を形成する工程と、該樹脂膜上に接着剤層を形成する工程と、該樹脂膜をモールドから離型する工程とを備えることを特徴とする樹脂膜の製造方法。 1. A step of applying by ejecting into a mold provided with concave convex a liquid composition as a Bruno nozzle or al droplet inkjet type, a step of a liquid composition cures upon drying or polymerization to form a resin film A method for producing a resin film , comprising: forming an adhesive layer on the resin film; and releasing the resin film from a mold.
本発明により、モールドに対する転写精度が高く、大面積で、高アスペクト比の構造を容易に転写することが可能となり、更に材料の利用効率も高めることができた。 According to the present invention, it is possible to easily transfer a structure having a large area and a high aspect ratio with high transfer accuracy with respect to the mold, and further, the utilization efficiency of the material can be improved.
本発明の実施の形態を図をもって説明する。 Embodiments of the present invention will be described with reference to the drawings.
図１は本発明の樹脂膜の製造方法の一実施態様を示す工程図である。 FIG. 1 is a process diagram showing an embodiment of a method for producing a resin film of the present invention.
図１（ａ）では、モールド１を作製し、離型剤を塗布する。
In FIG. 1A, a
次に、図１（ｂ）では、溶媒に溶解した液状組成物２をインクジェット方式によりモールド上に塗布し、乾燥して硬化樹脂層を得る。 Next, in FIG.1 (b), the liquid composition 2 melt | dissolved in the solvent is apply | coated on a mold with an inkjet system, and it dries and obtains a cured resin layer.
図１（ｃ）では、硬化した樹脂層の上にＵＶ硬化性接着剤層３を塗布し、図１（ｄ）では、基材４を接着し、ＵＶ光照射してＵＶ硬化性樹脂を硬化した後、図１（ｅ）では、基材をモールドから離型する。 In FIG. 1 (c), a UV curable adhesive layer 3 is applied on the cured resin layer, and in FIG. 1 (d), the base material 4 is adhered and UV light irradiation is performed to cure the UV curable resin. After that, in FIG. 1E, the substrate is released from the mold.
一方、図２は本発明の樹脂膜の製造方法の他の実施態様を示す工程図である。 On the other hand, FIG. 2 is a process diagram showing another embodiment of the method for producing a resin film of the present invention.
図２（ａ）は、図１（ａ）と同様にモールド１を作製し、離型剤を塗布する。
In FIG. 2A, a
次に、図２（ｂ）、（ｃ）では、ＵＶ硬化性樹脂を用いた液状組成物２をインクジェット方式によりモールド上に塗布する。 Next, in FIGS. 2B and 2C, the liquid composition 2 using a UV curable resin is applied onto the mold by an inkjet method.
次に、図２（ｄ）では、基材４を接着し、ＵＶ光照射してＵＶ硬化性樹脂を硬化した後、図１（ｅ）で、基材をモールドから離型する。 Next, in FIG. 2D, after the base material 4 is adhered and the UV curable resin is cured by UV light irradiation, the base material is released from the mold in FIG.
以下に、本発明に用いられる材料や作製方法について更に詳細に説明する。 Hereinafter, the materials and production methods used in the present invention will be described in more detail.
（モールドの製作）
モールドの素材としては、シリコン、ガラス、ニッケルなどの材料を用いることができる。ここでは、石英ガラスを例に説明する。石英ガラスのモールドを製作するには、石英ガラス基板上に感光性のレジスト材料を均一に塗布し、レーザでパターン露光する。現像後にエッチングを施し、石英ガラス上に凹凸が設けられたモールドが作製される。
(Mold production)
Materials such as silicon, glass and nickel can be used as the mold material. Here, quartz glass will be described as an example. In order to manufacture a quartz glass mold, a photosensitive resist material is uniformly applied on a quartz glass substrate, and pattern exposure is performed with a laser. Etching is performed after development to produce a mold having irregularities on quartz glass.
（離型剤の塗布）
塩素系フッ素樹脂含有シランカップリング剤であるトリデカフルオロ−１，１，２，２−テトラヒドロオクチルトリクロロシラン［ＣＦ3−（ＣＦ2）5−ＣＨ2−ＣＨ2ＳｉＣｌ3］で石英ガラス製のモールドを表面処理し、微細な形状表面へフッ素樹脂の化学吸着膜を生成する。詳細は下記非特許文献３や４に記載されている。
(Application of release agent)
Made of quartz glass with tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane [CF 3- (CF 2 ) 5 —CH 2 —CH 2 SiCl 3 ] which is a chlorine-based fluororesin-containing silane coupling agent The mold is surface treated to produce a fluororesin chemisorbed film on a finely shaped surface. Details are described in Non-Patent Documents 3 and 4 below.
非特許文献３：
Ｍ．Ｃｏｌｂｕｒｎ，Ｓ．Ｊｏｈｎｓｏｎ，Ｍ．Ｓｔｅｗａｒｔ，Ｓ．Ｄａｍｌｅ，Ｔ．Ｂａｉｌｅｙ，Ｂ．Ｃｈｏｉ，Ｍ．Ｗｅｄｌａｋｅ，Ｔ．Ｍｉｃｈａｅｌｓｏｎ，Ｓ．Ｖ．Ｓｒｅｅｎｉｖａｓａｎ，Ｊ．Ｅｋｅｒｄｔ ａｎｄ Ｃ．Ｇ．Ｗｉｌｌｓｏｎ，Ｐｒｏｃ．ｏｆ ＳＰＩＥ ３６７６，（１９９９）３７８
非特許文献４：
Ｔ．Ｂａｉｌｅｙ，Ｂ．Ｊ．Ｃｈｏｉ，Ｍ．Ｃｏｌｂｕｒｎ，Ｍ．Ｍｅｉｓｓｌ，Ｓ．Ｓｈａｙａ，Ｊ．Ｇ．Ｅｋｅｒｄｔ，Ｓ．Ｖ．Ｓｒｅｅｎｉｖａｓａｎ，Ｃ．Ｇ．Ｗｉｌｌｓｏｎ；”Ｓｔｅｐ ａｎｄ Ｆｌａｓｈ Ｉｍｐｒｉｎｔ Ｌｉｔｈｏｇｒａｐｈｙ：Ｔｅｍｐｌａｔｅ Ｓｕｒｆａｃｅ Ｔｒｅａｔｍｅｎｔ ａｎｄ Ｄｅｆｅｃｔ Ａｎａｌｙｓｉｓ．”Ｊ．Ｖａｃ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．Ｂ，１８（６），３５７２−３５７７（２０００）
（樹脂材料と溶媒について）
微細な凹凸形状を形成する樹脂膜に用いる樹脂としては、溶剤に溶ける樹脂を用いて、溶剤に溶解し液状化してインクジェット法により塗布する方法と、もう一方は、液状のＵＶ硬化性樹脂や熱硬化性樹脂を用いインクジェット法により塗布した後硬化する方法とがある。
Non-Patent Document 3:
M.M. Colburn, S.M. Johnson, M.M. Stewart, S.M. Damle, T .; Bailey, B.M. Choi, M .; Wedlake, T .; Michaelson, S.M. V. Srenivasan, J. et al. Ekerdt and C.I. G. Willson, Proc. of SPIE 3676, (1999) 378
Non-patent document 4:
T.A. Bailey, B.M. J. et al. Choi, M .; Colburn, M.M. Meissl, S.M. Shaya, J .; G. Ekerdt, S .; V. Srenivasan, C.I. G. Willson; "Step and Flash Imprint Lithography: Template Surface Treatment Treatment and Defect Analysis." Vac. Sci. Technol. B, 18 (6), 3572-3577 (2000)
(About resin materials and solvents)
The resin used for the resin film that forms a fine uneven shape is a method in which a resin that is soluble in a solvent is used, dissolved in a solvent, liquefied, and applied by an inkjet method, and the other is a liquid UV curable resin or a heat There is a method in which a curable resin is applied by an ink jet method and then cured.
溶剤溶解性樹脂としては、例えばポリメチルメタクリレート、ポリカーボネート、ポリスチレン、ポリエーテルスルホン、ノルボルネン系樹脂、アモルファスポレオレフィンなどが用いられる。 Examples of the solvent-soluble resin include polymethyl methacrylate, polycarbonate, polystyrene, polyethersulfone, norbornene resin, and amorphous polyolefin.
上記の樹脂を溶解する有機溶剤としては、ジオキサン、ジオキソラン、テトラヒドロフラン、ベンゼン、トルエン、メチレンクロライド、クロロフォルム、エチレンクロライド、アノン、アセトン、メチルエチルケトン、ヘキサン、ヘプタン、石油ベンジン、シクロヘキサンなどの脂肪族炭化水素、ベンゼン、キシレン、エチルベンゼンなどの芳香族炭化水素、塩化メチレン、四塩化炭素、トリクロルエタンなどのハロゲン系炭化水素、メタノール、エタノール、ｎ−プロパノールなどのアルコール、エチルエーテル、テトラヒドロフランなどのエーテル、メチルエチルケトン、シクロヘキサンなどのケトン、蟻酸メチル、酢酸−ｎ−プロピルなどのエステル、エチレングリコールモノエチルエーテルなどの多価アルコール誘導体、酢酸などの脂肪酸やフェノール、その他窒素や硫黄を含む化合物が使用される。これらは単独または二種類以上の混合で使用することが出来る。 Examples of organic solvents for dissolving the above resins include dioxane, dioxolane, tetrahydrofuran, benzene, toluene, methylene chloride, chloroform, ethylene chloride, anone, acetone, methyl ethyl ketone, hexane, heptane, petroleum benzine, cyclohexane, and other aliphatic hydrocarbons, Aromatic hydrocarbons such as benzene, xylene and ethylbenzene, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride and trichloroethane, alcohols such as methanol, ethanol and n-propanol, ethers such as ethyl ether and tetrahydrofuran, methyl ethyl ketone and cyclohexane Such as ketones, esters such as methyl formate and acetic acid-n-propyl, polyhydric alcohol derivatives such as ethylene glycol monoethyl ether, acetic acid, etc. Fatty and phenols, compounds containing other nitrogen or sulfur is used. These can be used individually or in mixture of 2 or more types.
好ましい有機溶媒としては、表面張力の低い溶媒、例えばトルエンやトリハロメタンであり、インクジェット方式による液滴吐出が可能な粘度とすることが必要であるが、この時、樹脂材料と溶媒の質量比率は好ましくは１／２０〜１／４０である。 A preferable organic solvent is a solvent having a low surface tension, for example, toluene or trihalomethane, and it is necessary to have a viscosity capable of ejecting droplets by an inkjet method. At this time, the mass ratio of the resin material to the solvent is preferable. Is 1/20 to 1/40.
また、ＵＶ硬化性樹脂としては、アクリル系、エポキシ系、オキセタン系等種々のものを用いることができるが、好ましくは単官能や多官能のアクリル系ＵＶ硬化性樹脂である。 Various UV curable resins such as acrylic, epoxy, oxetane, etc. can be used, and monofunctional or polyfunctional acrylic UV curable resins are preferred.
（インクジェット方式による塗布）
液状組成物をインクジェット方式を用いてモールド上に塗布する。インクジェット方式には、圧電体素子を用いたピエゾ型インクジェット方式、あるいは気泡ジェット方式等が挙げられるが、特にピエゾ型インクジェット方式を用いると数ｃｐ〜１００ｃｐ程度までの幅広い粘度の液状組成物を吐出できるので、より望ましい。
(Application by inkjet method)
A liquid composition is apply | coated on a mold using an inkjet system. Examples of the ink jet method include a piezo type ink jet method using a piezoelectric element, a bubble jet method, and the like. In particular, when a piezo type ink jet method is used, a liquid composition having a wide viscosity of about several cp to 100 cp can be discharged. So more desirable.
液状組成物をインクジェットヘッドに充填し、ノズルから吐出してモールド表面の必要な部分に塗布する。 The liquid composition is filled into an ink jet head, and is discharged from a nozzle and applied to a necessary portion of the mold surface.
（硬化）
液状組成物として溶剤を用いたり、熱硬化性樹脂を用いた場合は、ドライヤー、ホットプレート、オーブンなどの手法で、液状組成物が塗布されたモールドを熱し溶剤の除去あるいは硬化を行う。一方、ＵＶ硬化性樹脂を用いた場合は、ＵＶ光源を用いて光照射して硬化を行う。また、ＵＶ硬化性樹脂や熱硬化性樹脂を用いる場合は、この段階で硬化させても良いが、この段階では硬化せずに、次の接着剤の塗布を省略し、基材を接着した後硬化させる方法であっても良い。
(Curing)
When a solvent is used as the liquid composition or a thermosetting resin is used, the mold to which the liquid composition is applied is heated or removed by a technique such as a dryer, a hot plate, or an oven. On the other hand, when a UV curable resin is used, it is cured by light irradiation using a UV light source. In addition, when using a UV curable resin or a thermosetting resin, it may be cured at this stage, but at this stage, it is not cured and after the application of the next adhesive is omitted and the substrate is adhered. A curing method may be used.
硬化した樹脂層の上に接着剤層を塗布する。 An adhesive layer is applied on the cured resin layer.
硬化後にＵＶ硬化接着剤（例えば、東洋合成 ＰＡＫ−０１）や熱硬化接着剤をインクジェット手法或いはスピンコート法等により塗布する。 After curing, a UV curable adhesive (for example, Toyo Gosei PAK-01) or a thermosetting adhesive is applied by an inkjet method or a spin coat method.
（基材）
基材としては、使用目的に応じて樹脂基板やフィルム、金属、ガラス等種々の材料や厚さのものを選択することができるが、バリア層が形成された樹脂基板（ポリエーテルスルホン、ＰＥＳ）を用いることが好ましい。樹脂基板を接着剤層の上に貼合する。ＵＶ硬化接着剤の場合は、例えば、石英ガラスのモールド側からＵＶ光を照射して、ＵＶ硬化性樹脂を硬化させる。また、熱硬化接着剤の場合には、適切な温度にコントロールされた雰囲気中にデバイスを置き、接着剤を硬化させる。
(Base material)
As the base material, various materials and thicknesses such as a resin substrate, a film, metal, glass and the like can be selected according to the purpose of use, but a resin substrate on which a barrier layer is formed (polyethersulfone, PES) Is preferably used. A resin substrate is bonded on the adhesive layer. In the case of a UV curable adhesive, for example, UV light is irradiated from the mold side of quartz glass to cure the UV curable resin. In the case of a thermosetting adhesive, the device is placed in an atmosphere controlled at an appropriate temperature to cure the adhesive.
基材をモールドから離型することにより、バリア層付き樹脂基板上に、微細凹凸のパターンが形成される。微細凹凸パターンは光の波長程度から数十μｍのピッチで形成される。 By releasing the substrate from the mold, a pattern with fine irregularities is formed on the resin substrate with a barrier layer. The fine concavo-convex pattern is formed with a pitch of about several tens of micrometers from the wavelength of light.
以下に、本発明を実施例により具体的に説明するが、本発明はこれらの記載に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these descriptions.
実施例１
バリア層を有する樹脂基板上に、深さ２００ｎｍ、直径１５０ｎｍのピラーが２次元にピッチ３００ｎｍで配列する微細形状の樹脂層を形成する手段を示す。
Example 1
Means for forming a fine resin layer in which pillars having a depth of 200 nm and a diameter of 150 nm are two-dimensionally arranged at a pitch of 300 nm on a resin substrate having a barrier layer is shown.
（樹脂材料溶液の作製）
樹脂材料としてポリメチルメタクリレート（ＰＭＭＡ）を用い、ＰＭＭＡを表面張力の低いトルエンに溶解し樹脂材料溶液を作製した。この時、ポリマーと溶媒の質量比率を１／２０とした。
(Preparation of resin material solution)
Polymethylmethacrylate (PMMA) was used as a resin material, and PMMA was dissolved in toluene having a low surface tension to prepare a resin material solution. At this time, the mass ratio of the polymer to the solvent was set to 1/20.
（モールドの製作）
モールドの素材として、石英ガラスを用いる。石英ガラスは紫外線を透過する特徴を持つので、後の樹脂基板へのＵＶ硬化性樹脂による接着工程を容易に行うことができる。
(Mold production)
Quartz glass is used as the mold material. Since quartz glass has a characteristic of transmitting ultraviolet rays, it is possible to easily perform a subsequent bonding process using a UV curable resin to a resin substrate.
石英ガラス基板上に感光性のレジスト材料を均一に塗布する。 A photosensitive resist material is uniformly applied on a quartz glass substrate.
レジスト材料にレーザを２光束に分けた後に、適切な角度を持たせてレジスト材料表面を照射して干渉露光することにより、ピッチ３００ｎｍの１次元のストライプ状の潜像が得られる。次に石英ガラス基板を面内に９０度回転させて多重露光し、現像することで、ホールがピッチ３００ｎｍで２次元に配列したレジストパターンが得られる。ホールの直径１５０ｎｍは、露光と現像の条件を適切に設定することで達成できる。これをエッチングすることで、直径１５０ｎｍのホールが２次元に配列した表面構造を持つ石英ガラスのモールドを得ることができる。ホールの深さ２００ｎｍはエッチングスピードとエッチング時間を適切に設定することで容易に達成できる。 After dividing the laser into two light fluxes on the resist material, the resist material surface is irradiated with an appropriate angle and subjected to interference exposure to obtain a one-dimensional striped latent image having a pitch of 300 nm. Next, the quartz glass substrate is rotated 90 degrees in the plane, subjected to multiple exposure, and developed to obtain a resist pattern in which holes are two-dimensionally arranged at a pitch of 300 nm. The hole diameter of 150 nm can be achieved by appropriately setting the exposure and development conditions. By etching this, a quartz glass mold having a surface structure in which holes having a diameter of 150 nm are two-dimensionally arranged can be obtained. The hole depth of 200 nm can be easily achieved by appropriately setting the etching speed and the etching time.
（離型剤の塗布：図１（ａ）参照）
塩素系フッ素樹脂含有シランカップリング剤であるトリデカフルオロ−１，１，２，２−テトラヒドロオクチルトリクロロシラン［ＣＦ3−（ＣＦ2）5−ＣＨ2−ＣＨ2ＳｉＣｌ3］で石英製の金型を表面処理する。
(Application of release agent: see FIG. 1 (a))
Gold made of quartz with tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane [CF 3- (CF 2 ) 5 —CH 2 —CH 2 SiCl 3 ] which is a chlorine-based fluororesin-containing silane coupling agent Surface the mold.
（液状組成物の塗布：図１（ｂ）参照）
ピエゾ方式のインクジェットヘッドを有するインクジェット記録装置を用い、インクカートリッジに上記液状組成物を充填し、モールド上にインクジェット方式により塗布した。
(Application of liquid composition: see FIG. 1 (b))
Using an ink jet recording apparatus having a piezo type ink jet head, the ink composition was filled with the liquid composition and applied onto the mold by the ink jet method.
（乾燥）
オーブンで、樹脂材料溶液が塗布されたモールドを８０℃に加熱して十分に乾燥させる。
(Dry)
In the oven, the mold coated with the resin material solution is heated to 80 ° C. and sufficiently dried.
（ＵＶ硬化性樹脂の塗布：図１（ｃ）参照）
乾燥された樹脂材料の表面にＵＶ硬化性樹脂として、ＰＡＫ−０１（東洋合成社製）をスピンコート法により塗布した。
(Application of UV curable resin: see FIG. 1C)
As a UV curable resin, PAK-01 (manufactured by Toyo Gosei Co., Ltd.) was applied to the surface of the dried resin material by a spin coating method.
（基材の接着：図１（ｄ）参照）
基材としてバリア層が形成された樹脂基板（ＰＥＳ）を用いた。樹脂基板をＵＶ硬化性樹脂層の上に貼合し、石英ガラスのモールド側からＵＶ光を照射して、ＵＶ硬化性樹脂を硬化させた。
(Adhesion of substrate: see FIG. 1 (d))
A resin substrate (PES) on which a barrier layer was formed was used as a base material. The resin substrate was bonded onto the UV curable resin layer, and UV light was irradiated from the quartz glass mold side to cure the UV curable resin.
（離型：図１（ｅ）参照）
基材をモールドから離型する。
(Release: See Fig. 1 (e))
The substrate is released from the mold.
以上のプロセスにより、バリア層付き樹脂基板上に、高さ２００ｎｍのピラーがピッチ３００ｎｍで２次元に配列した微細凹凸パターンが精度良く形成された。 Through the above process, a fine uneven pattern in which pillars having a height of 200 nm were two-dimensionally arranged at a pitch of 300 nm was formed on a resin substrate with a barrier layer with high accuracy.
実施例２
バリア層を有する樹脂基板上に、深さ２００ｎｍ、直径１５０ｎｍのピラーが２次元にピッチ３００ｎｍで配列する微細形状の樹脂層を形成するもう一つの手段を示す。
Example 2
Another means for forming a fine resin layer in which pillars having a depth of 200 nm and a diameter of 150 nm are two-dimensionally arranged at a pitch of 300 nm on a resin substrate having a barrier layer is shown.
なお、モールドは実施例１で作製したモールドを用い、離型剤も同様に塗布した（図２（ａ）参照。）。 In addition, the mold produced in Example 1 was used for the mold, and the release agent was applied in the same manner (see FIG. 2A).
（液状組成物（ＵＶ硬化樹脂）の塗布：図２（ｂ）、（ｃ）参照）
実施例１の液状組成物をＵＶ硬化性樹脂に変え、以下同様にしてモールド上にインクジェット手法で塗布した。
(Application of liquid composition (UV curable resin): see FIGS. 2B and 2C)
The liquid composition of Example 1 was changed to a UV curable resin, and thereafter applied in the same manner on the mold by an inkjet method.
（基材の接着、ＵＶ硬化：図２（ｄ）参照）
基材としてバリア層が形成された樹脂基板（ＰＥＳ）を用い、樹脂基板をＵＶ硬化性樹脂層の上に貼合し、石英ガラスのモールド側からＵＶ光を照射して、ＵＶ硬化性樹脂を硬化させ、樹脂基板と接着させた。
(Adhesion of substrate, UV curing: see FIG. 2 (d))
Using a resin substrate (PES) on which a barrier layer is formed as a base material, the resin substrate is bonded onto the UV curable resin layer, irradiated with UV light from the quartz glass mold side, and the UV curable resin is applied. Cured and adhered to the resin substrate.
（離型：図２（ｅ）参照）
基材をモールドから離型した。
(Release: Refer to FIG. 2 (e))
The substrate was released from the mold.
以上のプロセスにより、バリア層付き樹脂基板上に、高さ２００ｎｍのピラーがピッチ３００ｎｍで２次元に配列した微細凹凸パターンが精度良く形成された。 Through the above process, a fine uneven pattern in which pillars having a height of 200 nm were two-dimensionally arranged at a pitch of 300 nm was formed on a resin substrate with a barrier layer with high accuracy.
１ モールド
２ 樹脂膜
３ 接着剤層
４ 樹脂基板
１０ インクジェットヘッド
1 Mold 2 Resin Film 3 Adhesive Layer 4
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| JP5065101B2 (en) * | 2008-03-05 | 2012-10-31 | 東洋合成工業株式会社 | Pattern formation method |
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| JP5760412B2 (en) * | 2010-12-08 | 2015-08-12 | 大日本印刷株式会社 | Imprint method and imprint apparatus |
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