WO2012157636A1 - ナノインプリント用モールドおよび曲面体 - Google Patents
ナノインプリント用モールドおよび曲面体 Download PDFInfo
- Publication number
- WO2012157636A1 WO2012157636A1 PCT/JP2012/062391 JP2012062391W WO2012157636A1 WO 2012157636 A1 WO2012157636 A1 WO 2012157636A1 JP 2012062391 W JP2012062391 W JP 2012062391W WO 2012157636 A1 WO2012157636 A1 WO 2012157636A1
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- WIPO (PCT)
- Prior art keywords
- mold
- silicone rubber
- curved
- curved surface
- nanoimprint mold
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
- B29C33/424—Moulding surfaces provided with means for marking or patterning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/40—Plastics, e.g. foam or rubber
- B29C33/405—Elastomers, e.g. rubber
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2883/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as mould material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
Definitions
- the present invention relates to a mold for forming irregularities on the order of nanometers and a curved body using the mold.
- a demultiplexing spectrometer is used for optical communication.
- a wavelength spectroscopic device is used in order to disperse a necessary wavelength.
- the demultiplexing spectrometer is formed on the surface of the transparent support on a flat surface.
- the demultiplexing spectrometer formed on the plane forms a hard mother mold, transfers the surface shape of the mother mold to a resin, and forms the demultiplexing spectrometer using the resin mold.
- a resin mold formed from a flat mother mold is not particularly limited as long as it is transparent and has a certain level of strength, and a normal resin is used.
- a mother mold having the same shape as the curved surface must be manufactured. Don't be.
- Some curved molds have various curvatures or various shapes. If a mother mold is formed according to the curvature or shape, the mother mold becomes very expensive, and the curved surface nanoprint formed into a curved shape. Become very expensive.
- Patent Document 1 a resin mold for nanoimprinting is known in which an acrylic resin or the like is laminated on a PET (polyethylene terephthalate) substrate (Patent Document 1).
- Patent Document 1 since the mold described in Patent Document 1 requires a hard layer formed of a material having high hardness, the mold has almost no elasticity and can be imprinted only on a planar shape. For this reason, it is necessary to prepare a mold corresponding to a form in which a concave and convex shape of a nanometer level is provided on a curved surface such as a lens.
- Patent Document 2 discloses an invention of a “curved member characterized in that a resin film having a concavo-convex pattern formed on a curved surface”. Yes. Patent Document 2 discloses a curved body in which a surface material made of a thermoplastic resin having fine irregularities on its surface is attached on a curved surface.
- the curved body described in Patent Document 2 has a large curvature radius because a thermoplastic resin having an uneven shape on the surface is attached to the surface of a lens or the like, and the thermoplastic resin is relatively hard. There is a problem that it cannot be applied to members (such as lenses).
- An object of the present invention is to provide a resin mold for imprinting capable of imprinting even on a curved surface shape, and a curved surface body using the same.
- the mold for nanoimprinting of the present invention is characterized by being made of a silicone rubber elastic body having an Hs rubber hardness in the range of 10 to 55 and having fine irregularities formed on the surface.
- the above-mentioned silicone rubber elastic body used in the present invention is an ultraviolet curable silicone rubber or a thermosetting silicone rubber.
- the total light transparency of the silicone rubber (measured with a sheet having a thickness of 250 ⁇ m according to JISK7105) is 60% or more, preferably 80% or more, and it is preferable that the transparency is higher.
- the above-mentioned nanoimprint mold can be used alone with an elastic body of silicone rubber having an Hs rubber hardness of 10 to 55, but can also be formed on the surface of a transparent support.
- the transparent support is preferably a curved body having a curved surface portion with a radius of curvature of 500 mm or less.
- the curved body of the present invention preferably has a curved surface portion with a radius of curvature of 500 mm or less, and the surface of the curved surface portion has irregularities with an interval in the range of 50 to 100,000 nm.
- the nanoprint mold of the present invention fine irregularities formed on the mother mold can be transferred from the mother mold to the surface of the silicone rubber elastic body having a specific hardness.
- This mother mold is made of a hard member such as silicone, glass, metal, etc., and is very expensive, so that nano-order irregularities may be worn or damaged. Therefore, the resin mold is transferred from the mother mold, and a transfer plate having fine irregularities formed on the surface is formed using the resin mold.
- Many of these transfer plates are made of thermoplastic resin, so there is no particular problem when used as a flat plate. However, when irregularities are formed on a curved surface like a lens, the shape follows. Sex matters. Moreover, since it is a resin mold and transfers the uneven
- silicone rubber having an Hs rubber hardness of 10 to 55 is used in consideration of such applications. By using such silicone rubber, repeated stamping can be performed.
- FIG. 1 is a photograph showing an example of a curved body according to the present invention.
- the attached Reference Example 1 is a photograph of this curved body, and the part where the color has changed is the interference wave of the sheet formed by the unevenness formed using the nanoimprint mold.
- FIG. 2 is an electron micrograph of irregularities formed on the sheet.
- FIG. 3 is a cross-sectional view of the laminate 20 for forming irregularities formed when transferring fine irregularities from the mother mold 11 to the silicone rubber 13 with the support 11.
- FIG. 4 is a cross-sectional view when fine irregularities are transferred from the mother mold 11 to the silicone rubber 13 with the support 11.
- FIG. 5 is a cross-sectional view in which fine irregularities are formed on the silicone rubber 13 with the support 11.
- FIG. 6 is a cross-sectional view showing an example of a state in which the silicone rubber 13 is attached to a curved body.
- the mold for nanoimprinting of the present invention abuts a mother mold having fine irregularities on a silicone rubber elastic body having an Hs rubber hardness in the range of 10 to 55, preferably in the range of 20 to 40. It is obtained by printing or photoimprinting (see FIGS. 3 to 5).
- reference numeral 11 is a mother mold
- reference numeral 13 is uncured silicone rubber.
- Reference numeral 15 denotes a support, which is preferably used to support uncured silicone rubber.
- the mother mold 11 is not limited as long as it is a known mold for nanoimprinting. In addition to those made from silicone, glass, metal, etc., the mother mold 11 is a replica mold as described in JP 2011-25677 A. Also good.
- the resin used for the support 15 is not particularly limited, but it is preferable to use a light-transmitting resin for photocuring the silicone rubber, such as polycarbonate (PC), polyethylene terephthalate (PET), polymethyl. It is preferable to use methacrylate (PMMA) or the like. Further, since the support 15 is used after being peeled off, it is preferable that the support 15 is peeled at least on the side where the silicone rubber layer is provided.
- a light-transmitting resin for photocuring the silicone rubber such as polycarbonate (PC), polyethylene terephthalate (PET), polymethyl. It is preferable to use methacrylate (PMMA) or the like.
- An uncured silicone rubber layer 13 is formed on the surface of such a support 15.
- This silicone rubber layer 13 is a mixture of a tetrafunctional, trifunctional, bifunctional, or monofunctional organosiloxane and a catalyst, which is cured by light (ultraviolet rays) or heat to form a ladder polymer and has a specific Hs rubber hardness.
- Form silicone rubber In particular, in the present invention, as shown in FIG. 4, the imprint shape formed on the surface of the mother mold is transferred by contacting the mother mold with heat imprinting or optical imprinting, so that the Hs rubber hardness is 10 to 10%. It is preferable to adjust the type of organosiloxane so that it is within the range of 55, preferably within the range of 20-40.
- the thickness of the silicone rubber layer is in the range of 50 to 5000 ⁇ m, preferably 100 to 1000 ⁇ m, both before and after curing. Further, a release layer can be further laminated on the silicone rubber layer.
- the Hs rubber hardness in the present invention is derived from the following equation.
- G is a transverse elastic modulus (Pa) of the silicone elastic body after being cured by heat or light
- G 50 is a rubber constant having a hardness of 50
- “" Based on the description of “Mech D & A NewsLatter Vol.1997-1, Mechanical Design Co., Ltd.”, 7.45 ⁇ 10 5 ⁇ 1.0197 (Pa). A specific method for measuring the transverse elastic modulus will be described later in the example section.
- a pattern 14 opposite to that formed in the mother mold 11 is formed on the surface of the silicone rubber layer cured by irradiating the silicone rubber layer with light.
- the reverse pattern 14 is attached to a curved body such as a lens, preferably a curved body having a curved portion with a radius of curvature of 500 mm or less, thereby forming the nanoimprint mold of the present invention. can do.
- the nanoimprint mold of the present invention thus formed is suitably used for imprinting thermoplastic resins and thermosetting resins.
- the imprinted transcript is not only a flat body (film shape) as in the conventional nanoimprint, but also the mold for nanoimprinting of the present invention has an appropriate shape following property and hardness. It is possible to prepare a minute curved body having a curved surface portion of 500 mm or less and having irregularities on the surface of the curved surface portion in the range of 50 to 200,000 nm, preferably 100 to 100,000 nm. .
- the nanoimprint mold of the present invention is stretched, so that the unevenness formed on the surface of the mold is set at the peripheral edge according to the Hs rubber hardness of the silicone rubber elastic body. It is preferable to make it narrower than the center.
- the silicone rubber used in the present invention has an Hs rubber hardness in the above range, it has good shape followability with respect to a curved surface, and can adhere to the curved surface without voids.
- Various characteristics of the nanoimprint mold of the present invention can be measured using the following apparatus.
- Sample Rubber hardness: sample thickness
- Transverse elastic modulus Using a rheometer (Anton Paar, device name: PHYSICA MCR300), the transverse elastic modulus was measured under the following conditions.
- Temperature controller TC30 / CTD600 Measuring jig: PP8 Number of measurement points: 10 points Measurement interval: 10 sec Measurement time: 100 sec Measurement mode: Rotational strain ( ⁇ ): 0 ⁇ 0.1 (Linear) Normal force: 10N Temperature: 23 ° C (Total light transmittance) Using a haze meter (Murakami Color Research Laboratory, model: HM-150), the total light transmittance was measured according to JISK7105.
- Example 1 Preparation of mold
- Uncured silicone rubber (KE-103) was spin-coated on a glass substrate (rotation speed: 500 rpm, time: 20 sec) to prepare a resin layer.
- a master mold (quartz mold after release treatment, transfer surface 30 mm square 150 nmL & S) was pressed against the laminate of the substrate and the resin layer, and the resin layer deposit was heated to 140 ° C. to perform thermosetting transfer.
- the press pressure during thermosetting transfer was 1 MPa and the holding time was 20 minutes. Then, it cooled, the master mold was removed, and the 100-micrometer-thick silicone rubber mold was obtained.
- Example 3 Using KE-106, a silicone mold was prepared in the same manner as in Example 2 to obtain a 1 mm thick silicone mold. Thereafter, transfer was performed under the same conditions as those for transfer to the curved surface of Example 1 to obtain a lens having the same shape as the master mold transferred to the entire surface.
- [Comparative Example 1] Using SIM-260, a silicone mold was prepared in the same manner as in Example 2 to obtain a 1 mm thick silicone mold.
- a curved body was manufactured by sticking the nanoimprint mold obtained as described above to the surface of the spherical lens shown in FIG.
Abstract
Description
[試料]
未硬化シリコーンゴムからなる厚さ250μmのシートを4種類用意し、以下の方法により横弾性係数ならびに全光線透過率を測定した。サンプル(ゴム硬度:サンプル厚)
(横弾性係数)
レオメーター(Anton Paar社製、装置名:PHYSICA MCR300)を用い、以下の条件により横弾性係数を測定した。
温調装置 :TC30/CTD600
測定冶具 :PP8
測定点数 :10点
測定間隔 :10sec
測定時間 :100sec
測定モード :回転
ひずみ(γ) :0→0.1(Linear)
ノーマルフォース:10N
温度 :23℃
(全光線透過率)
ヘーズメーター(村上色彩技術研究所製、型式:HM-150)を用いて、JISK7105に準拠して、全光線透過率を測定した。
〔実施例1〕
・シリコーンゴムモールドの調製
ガラス基板上に未硬化シリコーンゴム(KE-103)をスピンコート(回転数500rpm、時間20sec)し、樹脂層を作製した。上記基板及び樹脂層の積層物にマスターモールド(離型処理済み石英モールド、転写面30mm角 150nmL&S)を押し付け、樹脂層の堆積物を140℃に加熱し、熱硬化転写した。熱硬化転写時のプレス圧力は1MPa、保持時間20分間であった。その後、冷却を行い、マスターモールドを外し、100μm厚のシリコーンゴムモールドを得た。
・曲面への転写
曲率半径40mmの曲面レンズ形状の表面にUV硬化樹脂を適量滴下し、前記シリコーンモールドを、滴下した液がレンズの表面全体に広がるように押し当てるようにして固定し、シリコーンモールド越しにUV照射し、UV硬化樹脂を硬化させ、レンズ全面にマスターモールドと同形状を転写させた。
〔実施例2〕
・シリコーンゴムモールドの調製
二枚のガラス基板フィルムマスターモールドおよび、未硬化のKE-103を挟んで、未硬化のKE-103がフィルムマスターモールドの全面に広がった時点で、ガラス基板同士を動かないように固定し、そのまま固定した状態で、150℃に調整した乾燥機中で1時間静置し、KE-103を硬化させ、1mm厚のシリコーンモールドを得た。
〔実施例3〕
KE-106を用いて、実施例2と同様にシリコーンモールドを調製し、1mm厚のシリコーンモールドを得た。その後、実施例1の曲面への転写と同条件で転写を行い、マスターモールドと同形状が全面に転写されたレンズを得た。
〔比較例1〕
SIM-260を用いて、実施例2と同様にシリコーンモールドを調製し、1mm厚のシリコーンモールドを得た。その後、実施例1の曲面への転写と同条件で転写を行い、レンズ全面に追従することが困難であり、曲面レンズの端部ではマスターモールドと同形状を転写させることができなかった。
〔比較例2〕
KE-1204を用いて、実施例2と同様にシリコーンモールドを調製し、1mm厚のシリコーンモールドを得た。その後、実施例1の曲面への転写と同条件で転写を行い、レンズ全面に追従することが困難であり、また、透明性も低いため、UV硬化樹脂を硬化させることが困難であった。
13・・・熱可塑性樹脂
14・・・凹凸
15・・・支持体
18・・・曲面体
20・・・凹凸を形成するための積層体
Claims (7)
- Hsゴム硬度が10~55の範囲内のシリコーンゴム弾性体からなり、表面に微細な凹凸が形成されていることを特徴とするナノインプリント用モールド。
- 上記シリコーンゴム弾性体が、紫外線硬化性シリコーンゴムまたは熱硬化性シリコーンゴムであることを特徴とする請求項第1項記載のナノインプリント用モールド。
- 上記シリコーンゴムの全光線透過率(JISK7105に準拠して250μm厚のシートで測定)が60%以上であることを特徴とする請求項第1項記載のナノインプリント用モールド。
- 上記シリコーンゴム弾性体が、透明支持体表面に形成されていることを特徴とする請求項第1項記載のナノインプリント用モールド。
- 上記透明支持体が、曲率半径が500mm以下の曲面部を有する曲面体であることを特徴とする請求項第4項記載のナノインプリント用モールド。
- 曲率半径が500mm以下の曲面部を有し、かつ、前記曲面部の表面には間隔が50~100000nmの範囲にある凹凸を有することを特徴とする曲面体。
- 請求項第1項から第5項のいずれかの項に記載のナノインプリント用モールドを用いて得られることを特徴とする請求項第6項記載の曲面体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/118,360 US20140099474A1 (en) | 2011-05-19 | 2012-05-15 | Nanoimprint Mold and Curved Surface Body |
KR20137022137A KR20140010386A (ko) | 2011-05-19 | 2012-05-15 | 나노 임프린트용 몰드 및 곡면체 |
EP12785578.1A EP2711161A4 (en) | 2011-05-19 | 2012-05-15 | NANOPRUCTIVE FORM AND CURVED BODY |
CN2012800141418A CN103429417A (zh) | 2011-05-19 | 2012-05-15 | 纳米压印用模具及曲面体 |
JP2013515161A JP5868393B2 (ja) | 2011-05-19 | 2012-05-15 | ナノインプリント用モールドおよび曲面体の製造方法 |
Applications Claiming Priority (2)
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JP2011112187 | 2011-05-19 | ||
JP2011-112187 | 2011-05-19 |
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WO2012157636A1 true WO2012157636A1 (ja) | 2012-11-22 |
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PCT/JP2012/062391 WO2012157636A1 (ja) | 2011-05-19 | 2012-05-15 | ナノインプリント用モールドおよび曲面体 |
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US (1) | US20140099474A1 (ja) |
EP (1) | EP2711161A4 (ja) |
JP (1) | JP5868393B2 (ja) |
KR (1) | KR20140010386A (ja) |
CN (1) | CN103429417A (ja) |
TW (1) | TW201300218A (ja) |
WO (1) | WO2012157636A1 (ja) |
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JP2018161798A (ja) * | 2017-03-27 | 2018-10-18 | 株式会社ダイセル | シリコーンモールド |
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- 2012-05-15 JP JP2013515161A patent/JP5868393B2/ja not_active Expired - Fee Related
- 2012-05-15 KR KR20137022137A patent/KR20140010386A/ko not_active Application Discontinuation
- 2012-05-15 WO PCT/JP2012/062391 patent/WO2012157636A1/ja active Application Filing
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JP2017501568A (ja) * | 2013-11-29 | 2017-01-12 | エーファウ・グループ・エー・タルナー・ゲーエムベーハー | スタンパ構造を備えたスタンパ並びにその製造方法 |
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JP2020115579A (ja) * | 2020-04-08 | 2020-07-30 | エーファウ・グループ・エー・タルナー・ゲーエムベーハー | スタンパ構造を備えたスタンパ並びにその製造方法 |
Also Published As
Publication number | Publication date |
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TW201300218A (zh) | 2013-01-01 |
KR20140010386A (ko) | 2014-01-24 |
CN103429417A (zh) | 2013-12-04 |
JP5868393B2 (ja) | 2016-02-24 |
EP2711161A4 (en) | 2015-06-17 |
EP2711161A1 (en) | 2014-03-26 |
US20140099474A1 (en) | 2014-04-10 |
JPWO2012157636A1 (ja) | 2014-07-31 |
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