TWI450282B - Transparent conductive film with adhesive layer and manufacturing method thereof - Google Patents
Transparent conductive film with adhesive layer and manufacturing method thereof Download PDFInfo
- Publication number
- TWI450282B TWI450282B TW097107241A TW97107241A TWI450282B TW I450282 B TWI450282 B TW I450282B TW 097107241 A TW097107241 A TW 097107241A TW 97107241 A TW97107241 A TW 97107241A TW I450282 B TWI450282 B TW I450282B
- Authority
- TW
- Taiwan
- Prior art keywords
- transparent conductive
- adhesive layer
- film
- conductive film
- substrate
- Prior art date
Links
- 239000012790 adhesive layer Substances 0.000 title claims description 124
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000758 substrate Substances 0.000 claims description 90
- 239000010410 layer Substances 0.000 claims description 69
- 239000002985 plastic film Substances 0.000 claims description 60
- 229920003023 plastic Polymers 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 13
- 229910003437 indium oxide Inorganic materials 0.000 claims description 11
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000003522 acrylic cement Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 214
- 238000000034 method Methods 0.000 description 32
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 8
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- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
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- 239000000203 mixture Substances 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
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- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
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- 241001422033 Thestylus Species 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
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- 238000004804 winding Methods 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical class [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/12—Layered products comprising a layer of natural or synthetic rubber comprising natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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Description
本發明係關於附黏著劑層之透明導電性膜及其製造方法。附黏著劑層之透明導電性膜,於經過適當加工處理後,可用於液晶顯示器、電激發光顯示器等新型顯示方式或觸控面板等的透明電極中。另外,附黏著劑層之透明導電性膜,可用於透明物品之抗靜電或電磁波隔離、液晶調光玻璃、透明加熱器等。
先前,作為透明導電性薄膜,眾所周知的是於玻璃上形成有氧化銦薄膜之所謂導電性玻璃,因導電性玻璃之基材為玻璃,故而可撓性、加工性差,於有些用途中無法使用。因此,近年來,就可撓性、加工性優異,及耐衝擊性優異、重量輕等優點而言,使用有以聚對苯二甲酸乙二酯膜所代表的各種塑膠膜為基材的透明導電性膜。
上述透明導電性膜係作為一種透明導電性積層體而使用,該透明導電性積層體於透明塑膠膜基材之一個側面上設置有透明導電性膜,且,於透明塑膠膜基材之另一個側面上經由黏著劑層而黏附有透明基體(專利文獻1、2)。
專利文獻1:日本專利特開平2-66809號公報專利文獻2:日本專利特開平2-129808號公報
人們期待上述透明導電性膜不僅可用於觸控面板,亦可
用於各種用途。然而,若透明導電性膜為如上所述之透明導電性積層體,則加工性差,難以充分地展開用途。
又,於將透明導電性膜用於電極等用途時,多用作晶質透明導電性膜,但眾所周知的是非晶質透明導電性薄膜之蝕刻等加工性優異。一般而言,為了自非晶質狀態轉換為晶質狀態,要進行加熱處理。然而,於將透明導電性膜黏合於液晶面板或觸控面板等黏附體後進行加熱處理之情形時,有時會因加熱處理而導致黏附體產生不良情形。
又,若考慮到黏合步驟,相較於加熱處理後另外於透明導電性膜上形成黏著劑層之情形,較好的是首先將脫模薄膜經由黏著劑層而設置於透明導電性膜上。
另一方面,要求透明導電性膜薄型化,但薄型之透明導電性膜,容易因加熱處理而產生捲縮,因此業界謀求一種即使經過加熱處理,亦產生較少捲縮的附黏著劑層之透明導電性膜。
本發明之目的在於提供一種加工性良好之透明導電性膜及其製造方法。
本案發明者等,為了解決上述問題而進行潛心研究,結果發現:藉由採用下述構成,可實現上述目的,從而完成了本發明。
即,本發明係關於一種附黏著劑層之透明導電性膜,其特徵在於包括:非晶質透明導電性積層體,其係於透明塑膠膜基材一方之面上設置有非晶質透明導電性薄膜;脫模
薄膜,其係經由黏著劑層而設置於上述透明塑膠膜基材另一方之面上,且至少具有薄膜基材;上述脫模薄膜之厚度大於上述非晶質透明導電性積層體之厚度;從上述非晶質透明導電性積層體之MD方向之熱收縮率減去上述脫模薄膜之MD方向之熱收縮率之值為-0.3~0.45%。
此處,上述所謂「MD方向」,係指使用王子測量機器製造之商品名「KOBRA21-ADH」,於23℃、波長590 nm之條件下分別對非晶質透明導電性積層體及脫模薄膜進行測定時面內相位差值最大之方向。再者,於對非晶質透明導電性積層體進行測定時,係自透明塑膠膜基材側進行測定。又,於對脫模薄膜進行測定時,係自薄膜基材側進行測定。
又,上述所謂「熱收縮率」,係指分別自非晶質透明導電性積層體及脫模薄膜,取得於MD方向為100(L1
)mm、該MD方向之正交方向(TD方向)為100 mm之正方形樣品,於140℃、1.5小時之條件下對該樣品進行加熱,對加熱後樣品於MD方向的長度(L2
)進行測定,並根據下述式而算出之值。
熱收縮率(%)+(L1
-L2
)/L1
×100
再者,本發明中之所謂「非晶質」,係指使用場發射穿透式電子顯微鏡(FE-TEM,Field Emission Transmission Electron Microscope),對透明導電性膜之表面進行觀察時,於該透明導電性膜之整個表面上,多邊形或橢圓形結
晶所占之面積比率為50%以下(較好的是0~30%)。
於上述附黏著劑層之透明導電性膜中,非晶質透明導電性薄膜係經由至少1層底塗層而設置於透明塑膠膜基材一方之面上。
於上述附黏著劑層之透明導電性膜中,非晶質透明導電性薄膜,可使用由含有90~99重量%之氧化銦及1~10重量%之氧化錫的金屬氧化物所形成者。
於上述附黏著劑層之透明導電性膜中,較好的是,上述透明塑膠膜基材之厚度為10~40 μm,上述脫模薄膜之厚度為50~100 μm。
於上述附黏著劑層之透明導電性膜中,較好的是,脫模薄膜之彎曲模量為1500~8000 MPa。
於上述附黏著劑層之透明導電性膜中,脫模薄膜可使用在脫模薄膜之薄膜基材配置於黏著劑層之側具有剝離層及/或防止寡聚物移動之層者。
於上述附黏著劑層之透明導電性膜中,較好的是,黏著劑層之厚度為5~50 μm。
於上述附黏著劑層之透明導電性膜中,較好的是,黏著劑層為丙烯酸系黏著劑層。
於上述附黏著劑層之透明導電性膜中,較好的是,脫模薄膜之薄膜基材之材料與透明塑膠膜基材之材料係同種材料。
又,較好的是,附黏著劑層之透明導電性膜於140℃下加熱1.5小時後之捲縮為25 mm以下。
又,附黏著劑層之透明導電性膜,可較佳地用於自黏著劑層剝離脫模薄膜後貼合於其他基材上之態樣。
又,附黏著劑層之透明導電性膜,可較佳地用於對非晶質透明導電性薄膜進行結晶化加工處理後,自黏著劑層剝離脫模薄膜,貼合於其他基材上之態樣。
又,本發明係關於上述附黏著劑層之透明導電性膜之製造方法,其特徵在於包括如下步驟:
將設置於脫模薄膜上之黏著劑層貼合於非晶質透明導電性積層體之透明塑膠膜基材一方之面上,該非晶質透明導電性積層體係於上述透明塑膠膜基材另一方之面上設置有非晶質透明導電性薄膜者。
本發明之附黏著劑層之透明導電性膜,於透明塑膠膜基材之一個側面具有非晶質透明導電性薄膜。就透明導電性膜而言,通常使用結晶性透明導電性薄膜作為透明導電性膜,而本發明中係使用非晶質透明導電性薄膜作為透明導電性膜。非晶質透明導電性薄膜,與結晶性透明導電性薄膜相比,加工性優異,可擴大透明導電性膜之用途。
又,於上述透明塑膠膜基材之另一個側面上設置有黏著劑層,且於該黏著劑層上設置有脫模薄膜。設置有脫模薄膜之黏著劑層,可藉由剝離脫模薄膜而容易地使黏著劑層成為表面層。該黏著劑層,可黏合於其他基材上,加工性優異,故而可擴大透明導電性膜之用途。
如此,本發明之透明導電性膜,係使用非晶質透明導電
性薄膜作為透明導電性膜,並且將設置有脫模薄膜之黏著劑層配置於表面層,藉此可飛躍性地提高透明導電性膜之加工性,從而可大幅度擴大透明導電性膜之使用形態。具體而言,無論是否將黏著劑層黏合於其他基材上,均可對非晶質透明導電性薄膜進行蝕刻。進而,可於對非晶質透明導電性薄膜進行結晶化加熱處理之後,再將黏著劑層黏合於其他基材上。藉此,可將經結晶化之透明導電性膜供於不適合加熱處理之基材。
再者,先前,如專利文獻1、2般,於透明導電性膜中,有時會於透明塑膠膜基材之另一個側面上設置有黏著劑層,此情形時,透明導電性膜係作為於該黏著劑層上設置有透明基體之透明導電性積層體而使用。即,先前之透明導電性膜,即使於具有黏著劑層之情形時,亦於該黏著劑層上黏合有透明基體。又,於將透明導電性膜(透明導電性積層體)用於觸控面板等之情形時,於透明塑膠膜基材中,未設置有透明導電性膜之側,係成為透明導電性膜(透明導電性積層體)之外表面側。由此,即使如專利文獻1般,將硬塗層設置於該外表面之情形時,亦不會考慮於該表面上設置黏著劑層。如以上般,先前之透明導電性膜,於透明塑膠膜基材中,於未設置有透明導電性膜之側,並未經由黏著劑層而設置脫模薄膜。
以下參照圖式對本發明之實施形態進行說明。圖1係表示本發明之附黏著劑層之透明導電性膜之一例的剖面圖。圖1之附黏著劑層之透明導電性膜包括:透明導電性積層
體10,其於透明塑膠膜基材1之一個側面上設置有透明導電性膜2;及脫模薄膜4,其經由黏著劑層3而設置於透明塑膠膜基材1之另一面上。圖2係如下情形,即於圖1之附黏著劑層之透明導電性膜中,於透明塑膠膜基材1之一個側面,經由底塗層5而設置有透明導電性膜2的情形。再者,圖2中所記載之底塗層5為1層,但底塗層5可設置多層。
又,就本發明之附黏著劑層之透明導電性膜而言,脫模薄膜4之厚度,厚於透明導電性積層體10之厚度。藉此,於進行附黏著劑層之透明導電性膜之製造步驟、或將該附黏著劑層之透明導電性膜黏合於黏附體時,可提高作業性,並且可使透明導電性積層體10之厚度變薄。
又,就本發明之附黏著劑層之透明導電性膜而言,自透明導電性積層體10於MD方向之熱收縮率減去脫模薄膜4於MD方向之熱收縮率而獲得之值為-0.3~0.45%(較好的是-0.15~0.45%)。藉此,可將後述之於140℃下加熱1.5小時後之捲縮抑制為例如25 mm以下,因此,即使透明導電性積層體10之厚度變薄,亦可製成加工性良好之薄膜。
作為上述透明塑膠膜基材1,並無特別限制,可使用具有透明性之各種塑膠膜。該塑膠膜,通常由1層薄膜形成。作為其材料,例如可列舉:聚對苯二甲酸乙二酯及聚萘二甲酸乙二酯等聚酯系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、聚氯乙烯系樹
脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚苯硫醚系樹脂等。該等中尤其好的是聚酯系樹脂、聚醯亞胺系樹脂及聚醚碸系樹脂。
又,作為上述塑膠膜之材料,可列舉日本專利特開2001-343529號公報(WO10/37007)中所揭示之高分子薄膜,例如如下樹脂組成物,該樹脂組成物含有於側鏈具有取代及/或非取代醯亞胺基之熱可塑性樹脂、及於側鏈具有取代及/或非取代苯基及腈基之熱可塑性樹脂。具體而言,可使用含有如下樹脂組成物之高分子膜,該樹脂組成物含有由異丁烯及N-甲基順丁烯二醯亞胺所形成之交替共聚物、及丙烯腈-苯乙烯共聚物。
上述透明塑膠膜基材1之厚度,較好的是10~40 μm,更好的是20~30 μm。若透明塑膠膜基材1之厚度小於10 μm,則有如下情形,即透明塑膠膜基材1之機械強度不足,難以進行將該透明塑膠膜基材1形成輥狀,並連續地形成透明導電性膜2之操作。另一方面,若透明塑膠膜基材1之厚度超過40 μm,則進行透明導電性膜2之製膜加工時,有可能使透明塑膠膜基材1之投入量降低,又,於除去氣體或水分之步驟中產生不良影響,而有損生產性。又,難以實現透明導電性積層體10之薄型化。
亦可預先對上述透明塑膠膜基材1之表面實施濺鍍、電暈放電、火焰處理、照射紫外線、照射電子束、轉化處理、氧化處理等蝕刻處理或底塗處理,藉此提高設置於其上之透明導電性膜2或底塗層5,與上述透明塑膠膜基材1
之密接性。又,亦可於設置透明導電性膜2或底塗層5之前,根據需要藉由溶劑清洗或超音波清洗等而對上述透明塑膠膜基材1之表面進行除塵、清潔。
作為上述透明導電性膜2之構成材料,並無特別限定,例如可較佳地使用含氧化錫之氧化銦、含銻之氧化錫等氧化物。又,透明導電性膜2為非晶質透明導電性薄膜。於藉由上述材料而形成透明導電性膜2之情形時,可藉由對上述材料中之氧化錫進行控制(使上述材料中之氧化錫之含量為特定量),而使透明導電性膜2成為非晶質。
作為上述透明導電性膜2之構成材料,較好的是含氧化錫之氧化銦。於藉由該金屬氧化物而形成非晶質透明導電性薄膜之情形時,該金屬氧化物,較好的是含有90~99重量%之氧化銦及1~10重量%之氧化錫。更好的是含有95~98重量%之氧化銦及2~5重量%之氧化錫。
透明導電性膜2之厚度,並無特別限制,為了形成具有表面電阻為1×103
Ω/以下之良好導電性之連續被覆膜,其厚度較好的是10 nm以上。若膜厚過厚,則會導致透明性降低等,因此,更好的是15~35 nm,更好的是處於20~30 nm之範圍內。若厚度小於115 nm,則表面電阻會變高,且難以形成連續被覆膜。又,若厚度超過35 nm,則會導致透明性降低等。
作為透明導電性膜2之形成方法,並無特別限定,可採用先前眾所周知之方法。具體而言,例如可例示:真空蒸鍍法、濺鍍法、離子電鍍法。又,亦可根據所需之膜厚而
採用適當方法。
底塗層5,可由無機物、有機物、或無機物與有機物之混合物所形成。例如,作為無機物,可列舉:NaF(1.3)、Na3
AlF6
(1.35)、LiF(1.36)、MgF2
(1.38)、CaF2
(1.4)、BaF2
(1.3)、SiO2
(1.46)、LaF3
(1.55)、CeF3
(1.63)、Al2
O3
(1.63)等無機物[上述各材料之括號內之數值為光之折射率]。該等中,較好的是使用SiO2
、MgF2
、Al2
O3
等。尤其好的是SiO2
。除上述之外,可使用相對於100重量份之氧化銦,含有10~40重量份左右之氧化鈰、及0~20重量份左右之氧化錫的複合氧化物。
由無機物所形成之底塗層,可藉由真空蒸鍍法、濺鍍法、離子電鍍法等乾式製程、或濕式法(塗敷法)等而形成。作為形成底塗層之無機物,如上所述,較好的是SiO2
。就濕式法而言,可藉由塗敷矽溶膠等而形成SiO2
膜。
又,作為有機物,可列舉:丙烯酸系樹脂、胺基甲酸酯樹脂、三聚氰胺樹脂、醇酸樹脂、矽氧烷系聚合物、有機矽烷縮合物等。至少使用該等有機物中之1種。尤其理想的是,作為有機物,使用包含三聚氰胺樹脂、醇酸樹脂及有機矽烷縮合物之混合物的熱固化型樹脂。
於形成複數層底塗層5之情形時,就所獲得之附黏著劑層之透明導電性膜之加工性方面而言,較好的是距離透明塑膠膜基材1最近之底塗層係由有機物形成,而距離透明塑膠膜基材1最遠之底塗層係由無機物形成。因此,於有
兩層底塗層5之情形時,較好的是,距離透明塑膠膜基材1最近之底塗層係由有機物形成,而另一層底塗層係由無機物形成。
底塗層5之厚度,並無特別限制,自光學設計、防止自上述透明塑膠膜基材1產生寡聚物之效果方面而言,通常為1~300 nm左右,較好的是5~300 nm。再者,於設置兩層以上底塗層5之情形時,各層之厚度為5~250 nm左右,較好的是10~250 nm。
於形成有上述透明導電性膜2的透明塑膠膜基材1之另一個側面上,經由黏著劑層3而設置有脫模薄膜4。此情形時,較好的是於透明塑膠膜基材1與黏著劑層3之間設置有防止寡聚物移動之層。
再者,作為該防止移動層之形成材料,使用可形成透明膜之適當材料,亦可為無機物、有機物或該等之複合材料。較好的是其膜厚為0.01~20 μm。又,形成該防止移動層時,常使用利用塗佈機之塗佈法或噴霧法、旋塗法、線上塗佈法等,但亦可使用真空蒸鍍法、濺鍍法、離子電鍍法、噴霧熱分解法、化學電鍍法、電氣電鍍法之類的方法。就塗佈法而言,亦可使用丙烯酸系樹脂、胺基甲酸酯系樹脂、三聚氰胺系樹脂、UV(ultraviolet,紫外線)固化型樹脂、環氧系樹脂等樹脂成分或該等與氧化鋁、二氧化矽、雲母等無機粒子之混合物。或者,亦可使用藉由兩層以上之複合擠壓而形成之包含防止移動層之積層基材。又,對於真空蒸鍍法、濺鍍法、離子電鍍法、噴霧熱分解
法、化學電鍍法、電氣電鍍法之類的方法,可使用包括金、銀、鉑、鈀、銅、鋁、鎳、鉻、鈦、鐵、鈷或者錫、或該等之合金等之金屬,或包括氧化銦、氧化錫、氧化鈦、氧化鎘或者該等之混合物的金屬氧化物,及包括碘化鋼等之其他金屬化合物。
作為黏著劑層3,只要為具有透明性者,則可無特別限制地使用。具體而言,可適當地選用以例如丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺基甲酸酯、聚醯胺、聚乙烯醚、乙酸乙烯酯/氯乙烯共聚物、改性聚烯烴、環氧系、氟系、天然橡膠及合成橡膠等橡膠系等聚合物為基礎聚合物而成者。尤其是,自光學透明性優異、顯示出適度之濡濕性、凝聚性及接著性等黏著特性,且耐候性及耐熱性等亦優異之方面而言,較好的是使用丙烯酸系黏著劑。
根據作為黏著劑層3之構成材料之黏著劑之種類而使用適當之黏著用底塗劑,藉此可提高固著力。因此,於使用如此之黏著劑時,較好的是使用黏著用底塗劑。黏著用底塗劑,通常係設置於透明塑膠膜基材1側。
作為上述黏著用底塗劑,只要為可提高黏著劑之固著力之層,則並無特別限制。具體而言,例如可使用:於同一分子內具有胺基、乙烯基、環氧基、巰基、氯基等反應性官能基、及水解性烷氧基矽烷基之矽烷系偶合劑,於同一分子內具有含鈦之水解性親水性基、及有機官能性基之鈦酸酯系偶合劑,及於同一分子內具有含鋁之水解性親水性基、及有機官能性基之鋁酸鹽系偶合劑等所謂偶合劑;環
氧系樹脂、異氰酸酯系樹脂、胺基甲酸酯系樹脂、酯-氨基甲酸酯系樹脂等具有有機反應性基之樹脂。自工業上易於處理之觀點而言,尤其好的是含有矽烷系偶合劑之層。
又,上述黏著劑層3中可含有基礎聚合物所相對應之交聯劑。又,亦可根據需要,於黏著劑層3中調配入例如包括天然物或合成物之樹脂類、玻璃纖維或玻璃珠粒、金屬粉或其他無機粉末等之填充劑,顏料,著色劑,抗氧化劑等適當之添加劑。又,亦可形成含有透明微粒子而賦予光擴散性之黏著劑層3。
再者,上述之透明微粒子,例如可使用:平均粒徑為0.5~20 μm之二氧化矽、氧化鈣、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等具有導電性之無機系微粒子,或包括如聚甲基丙烯酸甲酯、聚胺基甲酸酯之適當聚合物的經交聯或未經交聯之有機系微粒子等適當者中之1種或2種以上。
上述黏著劑層3,通常係由將基質聚合物或其組成物溶解或分散於溶劑中而成之黏著劑溶液(固形分濃度:10~50重量%左右)所形成。作為上述溶劑,可適當地選用甲苯或醋酸乙酯等有機溶劑、或水等對應於黏著劑之種類者。
上述黏著劑層3,於將本發明之附黏著劑層之透明導電性膜(剝離去脫模薄膜者)接著於各種黏附體後,藉由其緩衝效果而發揮如下功能:提高設置於透明塑膠膜基材1之一個側面上之透明導電性膜之耐擦傷性或用於觸控面板時之打點特性,即提高所謂之觸筆輸入耐久性及面壓耐久
性。就更好地發揮該功能之觀點而言,較理想的是,將黏著劑層3之彈性模數設定為1~100 N/cm2
之範圍,將厚度設定為5~50 μm、較好的是設定為10~30 μm之範圍。若為上述厚度,則可充分發揮上述效果,且與黏附體之密接力亦充分。若厚度薄於上述範圍,則無法充分地確保上述耐久性或密接性,又,若厚度厚於上述範圍,則有可能滲出糊、產生缺陷等、加工性變差、進而於透明性等外觀方面產生不良情況。
若上述之彈性模數小於1 N/cm2
,則黏著劑層3會變為非彈性,因此,容易因加壓而產生變形,導致於透明塑膠膜基材1進而透明導電性膜2中會產生凹凸。又,容易產生黏著劑自加工切斷面滲出等情況,而且,提高該透明導電性膜2之耐擦傷性或用於觸控面板時之打點特性之效果會降低。另一方面,若彈性模數超過100 N/cm2
,則黏著劑層3會變硬,無法期待其緩衝效果,因此,存在難以提高透明導電性膜2之耐擦傷性或用於觸控面板時之觸筆輸入耐久性之傾向。
又,若黏著劑層3之厚度小於5 μm,則無法期待其緩衝效果,因此,存在難以提高透明導電性膜2之耐擦傷性或用於觸控面板時之觸筆輸入耐久性之傾向。另一方面,若厚度過厚,則有損透明性,或使黏著劑層3之形成步驟或向各種黏附體之黏合步驟之作業性變差,進而使成本提高。
上述脫模薄膜4,至少具有薄膜基材。作為上述薄膜基
材之材料,例如可使用:聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂,聚丙烯等聚烯烴系樹脂,紙等。其中,上述薄膜基材較好的是聚酯系樹脂、聚烯烴系樹脂、紙。
脫模薄膜4,可於將脫模薄膜之薄膜基材配置於黏著劑層之側,設置剝離層及/或防止寡聚物移動之層。
作為上述剝離層,可由聚矽氧系、長鏈烷基系、氟系、硫化鉬等適當剝離劑所形成。就脫模效果之方面而言,剝離層之厚度可適當設定。一般而言,就柔軟性等處理性方面而言,該厚度較好的是20 μm以下,更好的是0.01~10 μm之範圍,尤其好的是0.1~5 μm之範圍。作為剝離層之形成方法,並無特別限定,例如可使用:塗敷法、噴霧法、旋塗法、線上塗佈法等。又,亦可使用真空蒸鍍法、濺鍍法、離子電鍍法、噴霧熱分解法、化學電鍍法、電氣電鍍法等。
上述防止移動層,與剝離層共同設置之情形時,較好的是設置於剝離層與脫模薄膜之薄膜基材之間。作為上述防止移動層,可由用以防止脫模薄膜之薄膜基材(例如,聚酯膜)中之移動成分,尤其是聚酯之低分子量寡聚物成分之移動的適當材料所形成。作為防止移動層之形成材料,可使用無機物或者有機物、或該等之複合材料。防止移動層之厚度可於0.01~20 μm之範圍內進行適當地設定。藉由設置上述防止寡聚物移動之層,可將以與黏著劑主成分之莫耳比所表示的黏著劑層中之寡聚物之比例抑制在0.2以
下。再者,莫耳比可藉由對1
H-NMR(proton nuclear magnetic resonance,質子核磁共振)(分析裝置:日本電子(股)製造之JNM-EX400,測定溶劑:CDCl3
)所測出之來自寡聚物之峰積分值與來自黏著劑之峰積分值加以比較而算出。
防止移動層之形成方法,並無特別限定,可採用與剝離層之形成方法相同之方法。對於上述塗敷法、噴霧法、旋塗法、線上塗佈法,可使用丙烯酸系樹脂、胺基甲酸酯系樹脂、三聚氰胺系樹脂、環氧系樹脂等電離輻射固化型樹脂,或於上述樹脂中混合有氧化鋁、二氧化矽、雲母等而成者。又,於使用真空蒸鍍法、濺鍍法、離子電鍍法、噴霧熱分解法、化學電鍍法或電氣電鍍法之情形時,可使用包含金、銀、鉑、鈀、銅、鋁、鎳、鉻、鈦、鐵、鈷或錫或該等之合金等之金屬氧化物,包括碘化鋼等之其他金屬化合物。
脫模薄膜4之厚度,於具有上述薄膜基材或剝離層、防止移動層之情形時,為薄膜基材之厚度加上該等厚度而得之合計厚度,較好的是50~100 μm,更好的是60~85 μm。藉由將厚度設為50 μm以上,可於進行附黏著劑層之透明導電性膜之製造步驟、或向黏附體進行黏合時,提高作業性。又,藉由將厚度設為100 μm以下,可使剝離脫模薄膜4之前之附黏著劑層之透明導電性膜之捲繞性良好。再者,若脫模薄膜之厚度小於50 μm,則存在黏著劑層之變形(凹痕)增大之傾向。另一方面,即使厚度超過100 μm,
亦不會有尤其有利之效果,且就附黏著劑層之透明導電性膜之加工性之方面而言欠佳。又,若脫模薄膜4之薄膜基材之厚度過厚,則導致價格上升,而且若變厚,則輥捲取量變少,就經濟性、生產率之方面而言欠佳。脫模薄膜4係最終被廢棄者,因此,可於上述範圍內,即附黏著劑層之透明導電性膜之加工性良好之範圍內加以有效利用。
又,較好的是,脫模薄膜4之彎曲模量為1500~8000 MPa。更好的是2000~5000 MPa,更好的是3000~4000 MPa。彎曲模量係根據JIS K-7203進行測定。若彎曲模量小於1500 MPa,則黏著劑層容易產生變形(凹痕),於外觀方面欠佳。若彎曲模量處於上述範圍,則可抑制黏著劑層之變形(凹痕),外觀良好。
又,對於本發明之附黏著劑層之透明導電性膜,較好的是,脫模薄膜4之薄膜基材之材料與透明塑膠膜基材1之材料係同種材料。作為上述各膜之材料,較好的是使用聚酯系樹脂,尤其好的是使用聚對苯二甲酸乙二酯。
又,較好的是,本發明之附黏著劑層之透明導電性膜,以100 mm×100 mm尺寸、且於140℃下加熱5小時後之捲縮為25 mm以下,更好的是10 mm以下。又,較好的是於相同條件下進行加熱後之熱收縮率於MD、TD方向均為1.5%以內。捲縮係將加熱處理後之附黏著劑層之透明導電性膜,以於平板上成為凹狀之方式,於23℃之條件下放置3小時後附黏著劑層之透明導電性膜之4個頂點各自與平板之距離的平均值。如上所述,本發明之附黏著劑層之透明
導電性膜,於加熱後之捲縮較小,可獲得加工性良好之透明導電性膜。如此,捲縮較小之附黏著劑層之透明導電性膜,例如可藉由將脫模薄膜之薄膜基材之材料與透明塑膠膜基材之材料選擇同種材料而獲得。
本發明之附黏著劑層之透明導電性膜之製造方法,只要為可獲得上述構成者之方法,則並無特別限制。通常,可於透明塑膠膜基材1之一個側面上形成透明導電性膜2(包含底塗層5之情形)而製造透明導電性積層體10之後,於透明塑膠薄膜基材1之另一個側面上形成上述黏著劑層3。黏著劑層3可直接形成於透明塑膠薄膜基材1上,亦可預先於脫模薄膜4上設置黏著劑層3,之後將該黏著劑層3黏合於上述透明塑膠薄膜基材1上。對於後一方法,可藉由使透明塑膠膜基材1製成輥狀,而連續地形成黏著劑層3,從而於生產率之方面更為有利。
以下,使用實施例對本發明進行詳細說明,本發明於不脫離其主旨之範圍內並不限定於以下實施例。
對於透明塑膠膜基材等具有1 μm以上之厚度者,係使用Mitutoyo製造之尺寸測量器式厚度計進行測定。於為難以直接測量黏著劑層等之厚度之層之情形時,可對包括設置有該層之基材在內的總厚度進行測定,減去基材之厚度,藉此計算出該層之膜厚。
底塗層、ITO(Indium Tin Oxides,氧化銦錫)膜之厚度,係使用大塚電子(股)製造之瞬時多通道測光系統
(internsified multichannel photodetector)MCPD2000(商品名),基於干涉光譜之波形而算出。
根據JIS K-7105測定總透光率。再者,本發明之附黏著劑層之透明導電性膜,於未含有脫模薄膜之狀態下,就透明性之觀點而言,總透光率較好的是80%以上,更好的是85%以上。
使用三菱化學公司製造之Loresta電阻測定器,測定表面電阻值(Ω/)。再者,本發明之附黏著劑層之透明導電性膜,作為導電面之透明導電性膜之表面電阻值,較好的是100~1000 Ω/,更好的是200~700 Ω/。尤其是,用於觸控面板之情形時,就消耗電力之觀點而言,較好的是電阻不太低。
作為透明塑膠膜基材,係使用於厚度為25 μm之聚對苯二甲酸乙二酯膜(以下,稱作PET(polyethylene terephthalate)膜)之一個側面上設置防止移動層(由胺基甲酸酯-丙烯酸系紫外線固化性樹脂所形成,厚度為1 μm)而成者。再者,所用之PET膜於MD方向之熱收縮率為0.5%。於該薄膜基材之另一個側面上,由三聚氰胺樹脂:醇酸樹脂:有機矽烷縮合物之重量比為2:2:1之熱固化型樹脂形成有厚度為180 nm之第一層底塗層。繼而,於第一層
底塗層上,以電子束加熱法,於1.33×10-2
~2.67×10-2
Pa之真空中真空蒸鍍SiO2
,而形成厚度為40 nm之第二層底塗層(SiO2
膜)。
繼而,於第二層之底塗層上,於包含80%之氬氣及20%之氧氣的5.33×10-2
Pa之氣體環境中,藉由使用95重量%之氧化銦、5重量%之氧化錫之反應性濺鍍法,而形成厚度為20 nm之ITO膜,從而獲得透明導電性積層體。上述ITO膜為非晶質。再者,對所得之透明導電性積層體之一部分進行取樣,並測定於MD方向之熱收縮率,結果為,於MD方向之熱收縮率為0.5%。又,透明導電性積層體之厚度(總厚度)為26.24 μm。
作為脫模薄膜,係使用於厚度為75 μm之PET膜之一個側面上,設置防止移動層(由胺基甲酸酯-丙烯酸系紫外線固化性樹脂所形成,厚度為1 μm),繼而設置聚矽氧系剝離層(厚度為1 μm)而成者(總厚度為77 μm)。再者,所用之PET膜於MD方向之熱收縮率為0.4%。又,脫模薄膜之彎曲模量為3000 MPa。又,對脫模薄膜之一部分進行取樣,並對MD方向之熱收縮率進行測定,結果為,MD方向之熱收縮率為0.4%。繼而,於上述剝離層上形成厚度為25 μm、彈性模數為10 N/cm2
之透明丙烯酸系黏著劑層。作為黏著劑層組成物,係使用於丙烯酸丁酯:丙烯酸:乙酸乙烯酯之重量比為100:2:5之100重量份之丙烯酸系共聚物
中,調配1重量份之異氰酸酯系交聯劑而成者。將上述透明導電性積層體之未形成有透明導電性膜之側面黏合於上述黏著劑層側,而製成附黏著劑層之透明導電性膜。該附黏著劑層之透明導電性膜於140℃下加熱1.5小時後之捲縮,以4頂點平均值表示時為5 mm。又,透明導電性膜之表面電阻值為300 Ω/。進而,將脫模薄膜剝離,測定經由黏著劑層黏合於玻璃板上之狀態下透明導電性膜的總透光率,結果為89.0%。
作為實施例2~5,將透明塑膠膜基材之PET膜及脫模薄膜之PET膜變更為具有表1記載之熱收縮率之PET'膜,除此以外,以與實施例1相同之方式製作附黏著劑層之透明導電性膜,並測定捲縮。將結果表示於表1。
作為比較例1~3,將透明塑膠膜基材之PET膜及脫模薄膜之PET膜變更為具有表1記載之熱收縮率之PET膜,除此以外,以與實施例1相同之方式製作附黏著劑層之透明導電性膜,並測定捲縮。將結果表示於表1。
由表1可知,本發明之實施例1~5,與比較例1~3相比,可抑制捲縮。
1‧‧‧透明塑膠膜基材
2‧‧‧透明導電性膜(非晶質透明導電性薄膜)
3‧‧‧黏著劑層
4‧‧‧脫模薄膜
5‧‧‧底塗層
10‧‧‧透明導電性積層體(非晶質透明導電性積層體)
圖1係表示本發明之一實施形態之附黏著劑層之透明導電性膜之剖面圖。
圖2係表示本發明之一實施形態之附黏著劑層之透明導電性膜之剖面圖。
1‧‧‧透明塑膠膜基材
2‧‧‧透明導電性膜(非晶質透明導電性薄膜)
3‧‧‧黏著劑層
4‧‧‧脫模薄膜
10‧‧‧透明導電性積層體(非晶質透明導電性積層體)
Claims (12)
- 一種附黏著劑層之透明導電性膜,其特徵在於包括:非晶質透明導電性積層體,其係於透明塑膠膜基材一方之面上設置有非晶質透明導電性薄膜;脫模薄膜,其係經由黏著劑層而設置於上述透明塑膠膜基材另一方之面上,且至少具有薄膜基材;上述脫模薄膜之厚度大於上述非晶質透明導電性積層體之厚度;從上述非晶質透明導電性積層體之MD方向之熱收縮率減去上述脫模薄膜之MD方向之熱收縮率之值為-0.3~0.45%;上述透明塑膠膜基材之厚度為10~40μm;上述脫模薄膜之厚度為50~100μm。
- 如請求項1之附黏著劑層之透明導電性膜,其中非晶質透明導電性薄膜係經由至少1層底塗層而設置於透明塑膠膜基材一方之面上。
- 如請求項1之附黏著劑層之透明導電性膜,其中非晶質透明導電性薄膜係由含有90~99重量%之氧化銦及1~10重量%之氧化錫之金屬氧化物所形成。
- 如請求項1之附黏著劑層之透明導電性膜,其中脫模薄膜之彎曲模量為1500~8000MPa。
- 如請求項1之附黏著劑層之透明導電性膜,其中脫模薄膜於脫模薄膜之薄膜基材配置於黏著劑層之側上具有剝離層及/或防止寡聚物移動之層。
- 如請求項1之附黏著劑層之透明導電性膜,其中黏著劑層之厚度為5~50μm。
- 如請求項1之附黏著劑層之透明導電性膜,其中黏著劑層為丙烯酸系黏著劑層。
- 如請求項1之附黏著劑層之透明導電性膜,其中脫模薄膜之薄膜基材之材料與透明塑膠膜基材之材料係同種材料。
- 如請求項1之附黏著劑層之透明導電性膜,其中附黏著劑層之透明導電性膜於140℃下加熱1.5小時後之捲縮為25mm以下。
- 如請求項1之附黏著劑層之透明導電性膜,其中黏著劑層係剝離脫模薄膜後貼合於其他基材上者。
- 如請求項1之附黏著劑層之透明導電性膜,其中非晶質透明導電性薄膜係進行結晶化加工處理之後,將脫模薄膜自黏著劑層剝離,貼合於其他基材上者。
- 一種附黏著劑層之透明導電性膜之製造方法,其特徵在於:該附黏著劑層之透明導電性膜係如請求項1至11中任一項者;其製造方法係包括如下步驟:將設置於脫模薄膜上之黏著劑層貼合於非晶質透明導電性積層體之透明塑膠膜基材一方之面上,該非晶質透明導電性積層體係於上述透明塑膠膜基材另一方之面上設置有非晶質透明導電性薄膜者。
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TW200849284A (en) | 2008-12-16 |
CN101622680B (zh) | 2011-12-14 |
US20100136276A1 (en) | 2010-06-03 |
CN101622680A (zh) | 2010-01-06 |
KR101181682B1 (ko) | 2012-09-19 |
KR20110102515A (ko) | 2011-09-16 |
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JP2008251529A (ja) | 2008-10-16 |
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