JP2016522277A - 光硬化コーティング組成物、これを用いてなるコーティングフィルム及び偏光板 - Google Patents
光硬化コーティング組成物、これを用いてなるコーティングフィルム及び偏光板 Download PDFInfo
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- JP2016522277A JP2016522277A JP2016508860A JP2016508860A JP2016522277A JP 2016522277 A JP2016522277 A JP 2016522277A JP 2016508860 A JP2016508860 A JP 2016508860A JP 2016508860 A JP2016508860 A JP 2016508860A JP 2016522277 A JP2016522277 A JP 2016522277A
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- Prior art keywords
- meth
- acrylate
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- photocurable
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- 239000008199 coating composition Substances 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 81
- 229920000728 polyester Polymers 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 10
- 230000001681 protective effect Effects 0.000 abstract description 3
- -1 hydroxypropyl Chemical group 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
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- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
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- CZRTVSQBVXBRHS-UHFFFAOYSA-N ethyl carbamate prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(N)=O CZRTVSQBVXBRHS-UHFFFAOYSA-N 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000012719 thermal polymerization Methods 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
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- 239000003039 volatile agent Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
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- 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
- G03F7/004—Photosensitive materials
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
- Polarising Elements (AREA)
- Laminated Bodies (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
下記の表1に表すような割合(単位:重量%)で各成分を混合して光硬化コーティング組成物を製造した。
ポリエステルアクリレート(6官能):ポリエステルヘキサアクリレート(PS610)
ポリエステルアクリレート(4官能):ポリエステルテトラアクリレート(PS420)
モノマー:ペンタエリスリトールトリアクリレート(M340)
溶剤:メチルエチルケトン、2−メトキシエタノール
光開始剤:1−ヒドロキシシクロヘキシルフェニルケトン
添加剤:変性シリコンポリマー(BYK−3530)
(実験例1)
前記実施例1−7と比較例1−6で製造した光硬化コーティング組成物を、それぞれ1時間撹拌した後、透明基材フィルム(80μm、PMMA)上に厚さが6μmになるようにマイアバ(グラビアコータの一種)にて塗布した後、70℃で1分間乾燥してから、500mJ/cm2で硬化させてコーティングフィルムを製造した。
光硬化コーティング組成物をUV硬化させながら、組成物の貯蔵弾性率G'をレオメータ(Physica MCR−3xx、Anton Paar)で測定した。
分光光度計(HZ−1、日本のスガ社製)を利用して、PMMA面を光源(D65)に向けて全光線透過率(Total Transmittance)及び全ヘイズ(Haze)を測定した。
製造されたコーティングフィルムの表面を鉛筆硬度試験機器(PHT、韓国のソックボ科学社製)で500gの荷重をかけて鉛筆硬度を測定した。鉛筆は三菱社製を使用し、1鉛筆硬度当たり5回実施した。傷が2個以上であれば不良と判定し、不良が発生する以前の鉛筆で鉛筆硬度を表示した。
傷1:OK
傷2以上:NG
(4)耐スクラッチ性
スチールウールテスト機(WT−LCM100、韓国のプロテック社製)を利用して、1kg/(2cm×2cm)下で、10回往復運動させて耐スクラッチ性を試験した。スチールウールは#0000を使用した。
A':スクラッチが1〜10個
B:スクラッチが11〜20個
C:スクラッチが21〜30個
D:スクラッチが31個以上
(5)密着性
フィルムの塗布された面に1mm間隔で横縦それぞれ11本の直線を引いて100個の正四角形を画成した後、テープ(CT−24、日本のニチバン社製)を利用して3回の剥離テストを実施した。100個の四角形3個をテストしてその平均値を記録した。密着性は以下のように記録した。
n:全四角形のうち、剥離されていない四角形の数
100:全四角形の個数
よって、1個も剥離されなかったときを100/100と記録した。
JIS−K5600−5−1に従って耐屈曲性測定法(Mandrel)を用いて、マンドレルφ(直径、mm)毎にクラック発生の有無を測定した。測定試料サイズを2.5cm×20cm(横×縦)として試料を用意し、フィルムの塗布された面が外方に向くようにして評価した。
上述した方法にて測定した結果を下記の表2に表した。
Claims (17)
- 貯蔵弾性率G'が4.0E+07〜7.0E+07Paの範囲である光硬化コーティング組成物。
- 光硬化型(メタ)アクリレートオリゴマーを含むことを特徴とする請求項1に記載の光硬化コーティング組成物。
- 光硬化型(メタ)アクリレートオリゴマーが、ウレタン(メタ)アクリレートとポリエステル(メタ)アクリレートとの混合物、または2種のポリエステル(メタ)アクリレートの混合物であることを特徴とする請求項2に記載の光硬化コーティング組成物。
- 光硬化型(メタ)アクリレートオリゴマーが、光硬化コーティング組成物(固形分基準)100重量部に対して、92〜99重量部の範囲で含まれることを特徴とする請求項2に記載の光硬化コーティング組成物。
- 光硬化型(メタ)アクリレートオリゴマーが、4官能ポリエステル(メタ)アクリレートと6官能ポリエステル(メタ)アクリレートとの混合物であることを特徴とする請求項2に記載の光硬化コーティング組成物。
- 光硬化コーティング組成物(固形分基準)100重量部に対して、4官能ポリエステル(メタ)アクリレートが20〜50重量部の範囲で含まれ、また6官能ポリエステル(メタ)アクリレートは45〜75重量部の範囲で含まれることを特徴とする請求項5に記載の光硬化コーティング組成物。
- 光硬化型(メタ)アクリレートオリゴマーが、4官能ポリエステル(メタ)アクリレートと4〜6官能ウレタン(メタ)アクリレートとの混合物であることを特徴とする請求項2に記載の光硬化コーティング組成物。
- 光硬化コーティング組成物(固形分基準)100重量部に対して、4官能ポリエステル(メタ)アクリレートが20〜50重量部の範囲で含まれ、また4〜6官能ウレタン(メタ)アクリレートは45〜85重量部の範囲で含まれることを特徴とする請求項7に記載の光硬化コーティング組成物。
- 光硬化型モノマーをさらに含むことを特徴とする請求項2に記載の光硬化コーティング組成物。
- 光硬化型モノマーが(メタ)アクリロイル基を持つモノマーであることを特徴とする請求項9に記載の光硬化コーティング組成物。
- 混合物中の6官能ポリエステル(メタ)アクリレートの一部を光硬化型モノマーで代替して用いることを特徴とする請求項6に記載の光硬化コーティング組成物。
- 混合物中の4〜6官能ウレタン(メタ)アクリレートの一部を光硬化型モノマーで代替して用いることを特徴とする請求項8に記載の光硬化コーティング組成物。
- 光開始剤及び溶剤をさらに含むことを特徴とする請求項2に記載の光硬化コーティング組成物。
- 光硬化コーティング組成物100重量部に対して、光開始剤が0.05〜10重量部の範囲で含まれ、また溶剤が0.1〜85重量部の範囲で含まれることを特徴とする請求項13に記載の光硬化コーティング組成物。
- 透明基材の片面または両面に、請求項1〜14のいずれかに記載の光硬化コーティング組成物の硬化物を含むコーティング層が形成されてなるコーティングフィルム。
- 請求項15に記載のコーティングフィルムが備えられていることを特徴とする偏光板。
- 請求項15に記載のコーティングフィルムが備えられていることを特徴とする表示装置。
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WO2014171678A1 (ko) | 2014-10-23 |
WO2014171678A9 (ko) | 2014-12-11 |
CN105121565A (zh) | 2015-12-02 |
TWI627238B (zh) | 2018-06-21 |
KR20140123779A (ko) | 2014-10-23 |
JP6348972B2 (ja) | 2018-06-27 |
CN105121565B (zh) | 2018-01-02 |
TW201500487A (zh) | 2015-01-01 |
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