TWI429662B - An electret and an electrostatic induction type conversion element comprising the same - Google Patents
An electret and an electrostatic induction type conversion element comprising the same Download PDFInfo
- Publication number
- TWI429662B TWI429662B TW097106483A TW97106483A TWI429662B TW I429662 B TWI429662 B TW I429662B TW 097106483 A TW097106483 A TW 097106483A TW 97106483 A TW97106483 A TW 97106483A TW I429662 B TWI429662 B TW I429662B
- Authority
- TW
- Taiwan
- Prior art keywords
- electret
- ring structure
- main chain
- fluoropolymer
- decane
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 title claims description 11
- 230000006698 induction Effects 0.000 title claims description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 82
- 229910052731 fluorine Inorganic materials 0.000 claims description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 36
- 239000011737 fluorine Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 34
- 229920002313 fluoropolymer Polymers 0.000 claims description 32
- 239000004811 fluoropolymer Substances 0.000 claims description 32
- 239000007822 coupling agent Substances 0.000 claims description 23
- -1 decane compound Chemical group 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 5
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- KTGXWDZUZLWXOF-UHFFFAOYSA-N NCCNCCCC(C(OC)(OC)C)CCCCCCCC Chemical compound NCCNCCCC(C(OC)(OC)C)CCCCCCCC KTGXWDZUZLWXOF-UHFFFAOYSA-N 0.000 description 2
- DCIXGUPVOHOLTK-UHFFFAOYSA-N NCCNCCCC(C(OCC)(OCC)C)CCCCCCCC Chemical compound NCCNCCCC(C(OCC)(OCC)C)CCCCCCCC DCIXGUPVOHOLTK-UHFFFAOYSA-N 0.000 description 2
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical class FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 description 2
- 229920005548 perfluoropolymer Polymers 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- OTGGHZUEAWMAAK-UHFFFAOYSA-N (1,1-dimethoxy-1-phenyldecan-2-yl)benzene Chemical compound C1(=CC=CC=C1)C(C(OC)(OC)C1=CC=CC=C1)CCCCCCCC OTGGHZUEAWMAAK-UHFFFAOYSA-N 0.000 description 1
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- LQSJUQMCZHVKES-UHFFFAOYSA-N 6-iodopyrimidin-4-amine Chemical compound NC1=CC(I)=NC=N1 LQSJUQMCZHVKES-UHFFFAOYSA-N 0.000 description 1
- 101150030352 Arsi gene Proteins 0.000 description 1
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- XYSNGNNDJGSUMY-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCC)(OCC)C)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCC)(OCC)C)CCCCCCCC XYSNGNNDJGSUMY-UHFFFAOYSA-N 0.000 description 1
- MTDLVDBRMBSPBJ-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC MTDLVDBRMBSPBJ-UHFFFAOYSA-N 0.000 description 1
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- PEXBBTCNDBSFHT-UHFFFAOYSA-N NCCNCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound NCCNCCCC(C(OC)(OC)OC)CCCCCCCC PEXBBTCNDBSFHT-UHFFFAOYSA-N 0.000 description 1
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- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- KQNSPSCVNXCGHK-UHFFFAOYSA-N [3-(4-tert-butylphenoxy)phenyl]methanamine Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1=CC=CC(CN)=C1 KQNSPSCVNXCGHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- 229950008618 perfluamine Drugs 0.000 description 1
- 229950011087 perflunafene Drugs 0.000 description 1
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- BPHQIXJDBIHMLT-UHFFFAOYSA-N perfluorodecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BPHQIXJDBIHMLT-UHFFFAOYSA-N 0.000 description 1
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- JAJLKEVKNDUJBG-UHFFFAOYSA-N perfluorotripropylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F JAJLKEVKNDUJBG-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
- H01G7/021—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric
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- 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
- C08F16/00—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/24—Monomers containing halogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L27/00—Compositions of homopolymers or 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 halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or 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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
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- H01—ELECTRIC ELEMENTS
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- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
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Description
本發明係關於一種駐極體及包含其之靜電感應型轉換元件之改良。
先前以來,已提出有使用將電荷注入至絕緣材料中之駐極體的發電裝置、麥克風等靜電感應型轉換元件。作為此種駐極體之材料,例如,可使用下述專利文獻1所記載之含氟聚合物。
[專利文獻1]日本專利特開平4-189880號公報
然而,上述先前之含氟聚合物存在如下問題:無法提高注入至駐極體中之電荷之密度,因而表面電位不充分,且無法提高使用駐極體之靜電感應型轉換元件之電能與動能的轉換效率。
本發明係鑒於上述先前之課題研製而成者,其目的在於提供一種表面電位提高之駐極體及包含其之靜電感應型轉換元件。
為了達成上述目的,請求項1所述之駐極體之發明的特徵在於,含有主鏈上具有環結構之含氟聚合物與矽烷偶合劑之混合物。
請求項2所述之發明如請求項1所述之駐極體,其中上述
主鏈上具有環結構之含氟聚合物含有羧基作為端基。
請求項3所述之發明如請求項1或2所述之駐極體,其中此駐極體含有與上述羧基鍵結之矽烷化合物。
請求項4所述之發明如請求項1至3中任一項所述之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有環結構之含氟脂肪族聚合物。
請求項5所述之發明如請求項1至4中任一項所述之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有含醚性氧原子之環結構的含氟脂肪族聚合物。
請求項6所述之靜電感應型轉換元件之發明的特徵在於,包含如請求項1至5中任一項所述之駐極體。
根據本發明,可提供一種表面電位提高之駐極體及包含其之靜電感應型轉換元件。
以下,就用以實施本發明之最佳形態(以下稱為實施形態)加以說明。
本實施形態之特徵在於,由含有主鏈上具有環結構之含氟聚合物與矽烷偶合劑之混合物的材料來構成駐極體。又,較佳的是上述主鏈上具有環結構之含氟聚合物含有羧基作為端基,且矽烷化合物可與該羧基鍵結。
又,較佳的是上述主鏈上具有環結構之含氟聚合物係主鏈上具有環結構之含氟脂肪族聚合物,進而,尤佳的是上述主鏈上具有環結構之含氟聚合物係主鏈上具有含醚性氧
原子之環結構的含氟脂肪族聚合物。
本實施形態之駐極體可藉由將如下塗佈用含氟聚合物組合物進行製膜而獲得,該塗佈用含氟聚合物組合物係將上述主鏈上具有環結構之含氟聚合物以及矽烷偶合劑、非質子性含氟溶劑及作為質子性含氟溶劑之含氟醇作為必需成分。上述製膜例如藉由將上述塗佈用含氟聚合物組合物旋塗於銅基板上、並加以燒成而進行。
上述本實施形態之駐極體適合作為致動器、感測器等、將電能與動能進行轉換之靜電感應型轉換元件。
此處,主鏈上具有環結構之含氟聚合物係可溶於溶劑之聚合物,作為其較佳例,可列舉可溶於含氟溶劑之主鏈上具有含氟脂肪族環結構之非晶質全氟聚合物。含氟聚合物較好的是非晶質者,但可使用結晶度為30%以下、較好的是20%以下者。
作為上述非晶質全氟聚合物之具體例,可列舉:CF2
=CFO(CF2
)n
CF=CF2
(n=1~3)之環化聚合物,全氟(2,2-二甲基-1,3-二氧雜環戊烯)、全氟(1,3-二氧雜環戊烯)、全氟(4-甲氧基-1,3-二氧雜環戊烯)等之均聚物或共聚物。亦較佳的是使用2種以上該等單體而得之共聚物。又,亦較佳的是與四氟乙烯、氯三氟乙烯、偏二氟乙烯等氟烯烴之共聚物。再者,上述環化聚合、均聚合及共聚合,例如可使用日本專利特開平4-189880號公報等所記載之先前公知之方法。
又,作為溶解上述主鏈上具有環結構之含氟聚合物之非
質子性含氟溶劑,可例示以下含氟化合物。
全氟苯、五氟苯、1,3-雙(三氟甲基)苯、1,4-雙(三氟甲基)苯等多氟芳香族化合物,全氟三丁胺、全氟三丙胺等多氟三烷基胺化合物,全氟萘烷、全氟環己烷、全氟(1,3,5-三甲基環己烷)等多氟環烷烴化合物,全氟(2-丁基四氫呋喃)等多氟環狀醚化合物,含氟低分子量聚醚等。
全氟己烷、全氟辛烷、全氟癸烷、全氟十二烷、全氟(2,7-二甲基辛烷)、1,1,2-三氯-1,2,2-三氟乙烷、1,1,1-三氯-2,2,2-三氟乙烷、1,3-二氯-1,1,2,2,3-五氟丙烷、1,1,1,3-四氯-2,2,2,3-四氟丙烷、1,1,3,4-四氯-1,2,2,3,4,4-六氟丁烷、全氟(1,2-二甲基己烷)、全氟(1,3-二甲基己烷)、2H,3H-全氟戊烷、1H-全氟己烷、1H-全氟辛烷、1H-全氟癸烷、1H,1H,1H,2H,2H-全氟己烷、1H,1H,1H,2H,2H-全氟辛烷、1H,1H,1H,2H,2H-全氟癸烷、3H,4H-全氟-2-甲基戊烷、2H,3H-全氟-2-甲基戊烷、1H-1,1-二氯全氟丙烷、1H-1,3-二氯全氟丙烷等多氟烷烴化合物等。
該等非質子性含氟溶劑可單獨使用或混合使用,又,除該等以外亦可使用廣泛之化合物。例如,較佳的是氫氟醚(HFE,Hydrofluoroether)等含氟溶劑。此種含氟溶劑係通式R1
-O-R2
(R1
為可具有醚鍵之碳數5~12之直鏈狀或支鏈狀多氟烷基,R2
為碳數1~5之直鏈狀或支鏈狀烷基。)所示之含氟溶劑。
當R1
之碳數為4以下時,則難以溶解具有含氟環結構之聚合物,當R1
之碳數為13以上時,工業上獲取困難,因此
R1
之碳數係選自5~12之範圍內。R1
之碳數較好的是6~10,更好的是6~7及9~10。
所謂多氟烷基,係指烷基之2個以上的氫原子經氟原子取代之基,包括烷基之所有氫原子經氟原子取代之全氟烷基、及烷基之2個以上的氫原子經氟原子取代且烷基之1個以上的氫原子經除氟原子以外之鹵素原子取代之基。作為除氟原子以外之鹵素原子,較好的是氯原子。
作為多氟烷基,較好的是所對應之烷基的氫原子數之60%以上經氟原子取代之基,更好的是氫原子數之80%以上經氟原子取代之基。尤其好的多氟烷基為全氟烷基。
當R1
具有醚鍵時,若醚鍵數過多則會阻礙溶解性,故R1
中之醚鍵較好的是1~3個,更好的是1~2個。當R2
之碳數為6以上時,則會顯著阻礙具有含氟環結構之聚合物之溶解性。R2
之較好例為甲基或乙基。
若含氟溶劑之分子量過大,則不僅會使含氟聚合物組合物之黏度上升,而且具有含氟環結構之聚合物之溶解性亦會下降,故含氟溶劑之分子量較好的是1000以下。又,為了提高具有含氟環結構之聚合物之溶解性,較好的是含氟溶劑之氟含量為60~80重量%。作為較好之含氟溶劑,可例示下述者。
F(CF2
)5
OCH3
、F(CF2
)6
OCH3
、F(CF2
)7
OCH3
、F(CF2
)8
OCH3
、F(CF2
)9
OCH3
、F(CF2
)10
OCH3
、H(CF2
)6
OCH3
、(CF3
)2
CF(OCH3
)CFCF2
CF3
、F(CF2
)3
OCF(CF3
)CF2
OCH3
、F(CF2
)3
OCF(CF3
)CF2
OCF(CF3
)CF2
OCH3
、F(CF2
)8
OCH2
CH2
CH3
、(CF3
)2
CFCF2
CF2
OCH3
、F(CF2
)2
O(CF2
)4
OCH2
CH3
。
該等含氟溶劑中,尤其好的是(CF3
)2
CF(OCH3
)CFCF2
CF3
。
又,作為上述矽烷偶合劑,於包含先前以來公知或周知者之廣範圍內,可例示下述者。
三甲基甲氧基矽烷、三甲基乙氧基矽烷、二甲基乙烯基甲氧基矽烷、二甲基乙烯基乙氧基矽烷等單烷氧基矽烷類。
γ-氯丙基甲基二甲氧基矽烷、γ-氯丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、甲基二甲氧基矽烷、甲基二乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、甲基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、3,3,3-三氟丙基甲基二甲氧基矽烷、3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛基甲基二甲氧基矽烷、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸基甲基二甲氧基矽烷等二烷氧基矽烷類。
γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基
丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-氯丙基三甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛基三甲氧基矽烷、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-十七氟癸基三甲氧基矽烷、四甲氧基矽烷、四乙氧基矽烷等三或四烷氧基矽烷類。
具有芳香族胺結構之矽烷偶合劑即芳香族胺系矽烷偶合劑(可看出,使用此矽烷偶合劑時,即使該矽烷偶合劑為三烷氧基化合物亦難以引起凝膠化或增稠。若使用此矽烷偶合劑,則烷氧基矽烷經縮合反應之後可形成不具有碳數為2以上之烷基或伸烷基結構之結構,因此可提高耐熱性。)。
較好的芳香族胺系矽烷偶合劑係通式ArSi(OR1
)(OR2
)(OR3
)、ArSiR4
(OR1
)(OR2
)或ArSiR4
R5
(OR1
)[式中,R1
~R5
分別獨立,表示氫原子、碳數1~20之烷基或芳基,Ar表示對、間或鄰胺基苯基。]所示之化合物。以下列舉具體例。
胺基苯基三甲氧基矽烷、胺基苯基三乙氧基矽烷、胺基苯基三丙氧基矽烷、胺基苯基三異丙氧基矽烷、胺基苯基甲基二甲氧基矽烷、胺基苯基甲基二乙氧基矽烷、胺基苯基甲基二丙氧基矽烷、胺基苯基甲基二異丙氧基矽烷、胺基苯基苯基二甲氧基矽烷、胺基苯基苯基二乙氧基矽烷、胺基苯基苯基二丙氧基矽烷、胺基苯基苯基二異丙氧基矽
烷等。
胺基之氫原子可經烷基或芳基取代。例如可列舉:N,N-二甲基胺基苯基三烷氧基矽烷或N,N-二甲基胺基苯基甲基二烷氧基矽烷等。除此之外,例如可使用美國專利第3,481,815號說明書所記載之芳香族胺系矽烷偶合劑等。
該等矽烷偶合劑可單獨使用或組合使用,又,亦較好的是使用其共(部分)水解物。進而,亦較好的是使用上述矽烷偶合劑與四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷等四烷氧基矽烷之共(部分)水解物。其中,作為不損及含氟聚合物之透明性、且使含氟聚合物之接著性提高者,可例示尤其佳的是:作為具有胺基之矽烷偶合劑的(γ-胺基丙基三乙氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基三乙氧基矽烷、N-(β-胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、胺基苯基三甲氧基矽烷、胺基苯基三乙氧基矽烷、胺基苯基甲基二甲氧基矽烷、胺基苯基甲基二乙氧基矽烷等),或作為具有環氧基之矽烷偶合劑的(γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷等)。更好的是具有胺基之矽烷偶合劑。
對於預先於主鏈末端或側鏈上導入有羧基之含氟聚合物
而言,尤其有效的是具有胺基或環氧基之烷氧基矽烷類,而對於預先於主鏈末端或側鏈上導入有酯基之含氟聚合物而言,尤其有效的是具有胺基或胺基苯基之烷氧基矽烷類。
於上述非質子性含氟溶劑中,具有胺基或環氧基之三烷氧基矽烷類與具有相同之基之二烷氧基矽烷類相比,更容易使本發明之液狀組合物經時性黏度上升或凝膠化。又,三烷氧基矽烷類與二烷氧基矽烷類相比,含氟聚合物於非質子性含氟溶劑中之溶解性亦更小。因此,使用三烷氧基矽烷類時,較好的是添加質子性含氟溶劑、尤其是含氟醇。
使用二烷氧基矽烷類之情況下,其溶解性並不小於三烷氧基矽烷類,但同樣可藉由添加質子性含氟溶劑、尤其是含氟醇而提高溶解性。使用二烷氧基矽烷類之情形時,液狀組合物之經時性黏度上升並不像使用三烷氧基矽烷類時那般顯著,故不一定要添加含氟醇等質子性含氟溶劑,但添加含氟醇等質子性含氟溶劑卻會可靠地抑制黏度上升。
如上所述,若於含氟聚合物溶液中添加質子性含氟溶劑,則可增大矽烷偶合劑於含氟聚合物溶液中之溶解性。進而,可抑制一般認為是由於矽烷偶合劑間之反應而導致的黏度上升或凝膠化。作為此種質子性含氟溶劑,可例示下述者。
三氟乙醇、2,2,3,3,3-五氟-1-丙醇、2-(全氟丁基)乙醇、2-(全氟己基)乙醇、2-(全氟辛基)乙醇、2-(全氟癸基)乙
醇、2-(全氟-3-甲基丁基)乙醇、1H,1H,3H-四氟-1-丙醇、1H,1H,5H-八氟-1-戊醇、1H,1H,7H-十二氟-1-庚醇、1H,1H,9H-十六氟-1-壬醇、2H-六氟-2-丙醇、1H,1H,3H-六氟-2-丁醇等含氟醇。
三氟乙酸、全氟丙酸、全氟丁酸、全氟戊酸、全氟己酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟癸酸、3H-四氟丙酸、5H-八氟戊酸、7H-十二氟庚酸、9H-十六氟壬酸等含氟羧酸,該等含氟羧酸之醯胺,三氟甲磺酸、十七氟辛磺酸等含氟磺酸等。
該等質子性含氟溶劑亦可單獨使用,或可製成2種以上之混合物使用。
非質子性含氟溶劑與質子性含氟溶劑之混合物中之含氟聚合物濃度,通常為0.1~30重量%,較好的是0.5~20重量%。相對於含氟聚合物每100重量份,矽烷偶合劑之調配量為0.01~50重量份,較好的是0.1~30重量份。非質子性含氟溶劑與質子性含氟溶劑之混合物中之質子性含氟溶劑的調配量為0.01~50重量%,較好的是0.1~30重量%。
以下,以上述實施形態之具體例作為實施例來加以說明,再者,本發明並不限定於以下實施例。
依照以下順序製造本實施例之駐極體。
(1)塗佈用含氟聚合物組合物之製造
使全氟聚丁烯基乙烯基醚以13%之濃度溶解於全氟三丁
胺中,而獲得聚合物溶液B。對溶解於該聚合物溶液B中之聚合物之壓縮成形薄膜的紅外線吸收光譜進行測定,結果可確認源自-COOH基之1775 cm-1
、1810 cm-1
之特性吸收,又,所溶解之聚合物的於全氟(2-丁基四氫呋喃)溶液中所測定之固有黏度[η]為0.23。
再者,對於全氟聚丁烯基乙烯基醚而言,係將過氧化二碳酸二異丙酯(((CH3
)2
CHOCOO)2
)作為聚合起始劑而使全氟丁烯基乙烯基醚(CF2
=CFOCF2
CF2
CF=CF2
)進行環化聚合,並藉由熱處理使源自起始劑之不穩定末端成為-COF,其後進行水解而成為-COOH。
(2)與矽烷偶合劑之混合物之製造
於84.6 g之上述聚合物溶液B中,加入4.7 g之2-(全氟己基)乙醇及10.6 g之全氟三丁胺,進而加入0.4 g之γ-胺基丙基甲基二乙氧基矽烷並進行混合,而獲得均勻之聚合物溶液A。
又,於84.6 g之上述聚合物溶液B中,加入4.7 g之2-(全氟己基)乙醇及10.6 g之全氟三丁胺,進而加入0.4 g之γ-胺基丙基三乙氧基矽烷並進行混合,而獲得均勻之聚合物溶液C。
又,於84.6 g之上述聚合物溶液B中,加入0.4 g之N-(β-胺基乙基)-γ-胺基丙基三乙氧基矽烷並進行混合,而獲得均勻之聚合物溶液D。
(3)於3 cm見方、350 μm厚之銅基板上,以1000 rpm、20秒鐘之條件旋塗上述聚合物溶液A,並於100℃下進行10分鐘
之預烘烤,其後以1080 rpm、20秒鐘之條件實施旋塗,並於100℃下進行10分鐘之預烘烤,重複進行2次上述一系列積層膜形成操作之後,進行100℃下1小時、200℃下1小時的後烘烤,藉此獲得15 μm厚之塗佈膜。依照實施例2之順序對該塗佈膜注入電荷而獲得駐極體A。
又,除了使用上述聚合物溶液C、及聚合物溶液D以外,以與上述相同之方式,重複進行2次之旋塗、預烘烤、旋塗、預烘烤之一系列積層膜形成操作,其後,藉由進行後烘烤而獲得15 μm厚之塗佈膜。依照實施例2之順序對該等塗佈膜注入電荷,而分別獲得駐極體C、及駐極體D。
依照以下順序來製造作為比較例之駐極體。
(1)於3 cm見方、350 μm厚之銅基板上,以1000 rpm、20秒鐘之條件旋塗上述聚合物溶液B,並於100℃下進行10分鐘之預烘烤,其後以1850 rpm、20秒鐘之條件實施旋塗,並於100℃下進行10分鐘之預烘烤,重複進行2次上述一系列之積層膜形成操作後,最後進行100℃下1小時、200℃下1小時的後烘烤,藉此獲得15 μm厚之塗佈膜。依照實施例2之順序對該塗佈膜注入電荷,而製成駐極體B。
依照以下順序,對上述駐極體A、B、C、D進行帶電試驗。
圖1表示帶電試驗中所用之電暈帶電裝置之概念圖。圖1
中,藉由電暈放電將電荷注入至在銅基板(基極)10上塗佈聚合物溶液A、B、C、D而形成之膜,藉此形成駐極體A、B、C、D。電荷之注入係藉由如下方式而進行:將銅基板10作為電極,藉由直流高壓電源裝置12(HAR-20R5:Matsusada Precision製造)於電暈針14與銅基板10之間施加-8 kV之高電壓。由電暈針14所放電之負離子藉由柵極16而變均勻之後,紛紛降至塗佈膜上,而注入電荷。再者,由柵極用電源18對柵極16施加-600 V之電壓。又,塗佈膜係藉由熱板19加熱至玻璃轉移溫度(Tg)以上,而謀求所注入之電荷之穩定化。
本實施例中,於大氣環境下,於溫度為120℃、帶電電壓為-8 kV、帶電時間為3分鐘之條件下對各塗佈膜之樣品進行電暈帶電,其後,使樣品回到常溫,藉由表面電位計(model279;Monroe Electronics製造)自膜之中心開始以3 mm之間隔格子狀地測定9處之表面電位,求出其平均值。
圖2表示上述9處測定點之設定例。
又,各塗佈膜之樣品係保管於20℃、65%RH(相對濕度)之條件下,經時實施電位測定直至達到2500小時為止。
圖3表示上述各塗佈膜(駐極體A、B)所保持之電荷之經時變化狀況。圖3中,橫軸為經過時間,縱軸為表面電位。駐極體所保持之電荷之密度越高則表面電位亦越高。
由圖3可知,混合胺基矽烷而成之駐極體A與未混合胺基矽烷之比較例的駐極體B相比,電荷密度、經時穩定性均大幅提高。
同樣,由圖4可知,駐極體C、D之電荷密度、經時穩定性亦均大幅提高。
表1中表示各駐極體之表面電位經時變化後大致達到固定之後的值。由表1可知,駐極體A、C、D經時變化後之表面電位均高於駐極體B。
依照以下順序,對上述駐極體A、B、C、D進行熱穩定性試驗。
圖5表示熱穩定性試驗中所使用之裝置的概念圖。圖5中,與駐極體A、B對向而配置對向電極20,該駐極體A、B係藉由電暈放電將電荷注入至在銅基板10上塗佈聚合物溶液A、B所形成之膜而形成。藉此由各駐極體A、B與對向電極20形成電容器。因此,對各駐極體A、B進行加熱時,膜中所捕獲(trap)之電荷變得不穩定,若表面附近之電荷由於擴散等而消失,則儲存於對向電極20中之電荷亦會減少。因此,可根據自對向電極20所流出之電流值之大小來測定各駐極體A、B的熱穩定性。
因此,以固定速度(1℃/分鐘)使圖5之虛線所示部分之溫度升高,使用電流計22測定自各駐極體A、B所釋放之電荷量,來作為自對向電極20所流出之電流值i。再者,電
流計22係使用微小電流計(Keithley製造之Model6517A)。
圖6表示利用圖5之裝置所進行之各駐極體A、B的熱穩定性試驗之結果。由圖6可知,混合胺基矽烷而成之駐極體A相對於未混合胺基矽烷之比較例的駐極體B,熱穩定性提高。駐極體A之峰值位置之溫度(185℃)高於駐極體B的峰值位置之溫度(145℃),顯示出較高之熱穩定性。
以與上述相同之方式,利用圖5之裝置對駐極體C、D進行熱穩定性試驗。駐極體C及駐極體D之峰值位置之溫度分別為176℃及168℃,可知耐熱性優於駐極體B。將各駐極體之峰值位置之溫度記載於表2中。
於0.7 mm厚之Pyrex(註冊商標)製玻璃基板28上,依照Cr/Au/Cr(50/200/50 nm厚)之順序進行蒸鍍而形成電極之後,藉由光微影術如圖7所示般進行圖案化。電極之圖案係由在上表面形成駐極體之基極(150 μm寬,間距為300 μm)24及屏蔽電極26所形成。以1000 rpm、20秒鐘之條件旋塗上述聚合物溶液A,並於100℃下進行10分鐘之預烘烤,其後以1080 rpm、20秒鐘之條件實施旋塗,並於100℃下進行10分鐘之預烘烤,重複進行2次上述一系列積層膜形成操作,其後,進行100℃下1小時、200℃下1小時的後烘烤,藉此獲得16 μm厚之塗佈膜(膜A)。
繼而,於該膜A上蒸鍍Cu並藉由光微影術進行圖案化而製成金屬掩模,以100 W之RF(Radio Freqency,射頻)功率使用O2
電漿對膜A進行乾式蝕刻60~70分鐘。藉由以上製程,獲得僅圖案化於基極24上的聚合物A塗佈膜(膜E)。以實施例2中記載之方法對該膜E實施電暈放電處理,而獲得表面電位為-640 V之駐極體膜(膜F)。
又,藉由相同之製程而同樣地於0.7 μm厚之Pyrex製玻璃基板上製成經圖案化之Cr/Au/Cr電極(對向電極A),如圖8所示般以30 μm之間隔來配置膜F與對向電極A,固定膜F並使對向電極A以20 Hz之頻率、1.2 mm之寬度於圖中之箭頭方向上進行水平振動,藉此獲得最大為0.698毫瓦特之電功率。
10‧‧‧銅基板
12‧‧‧直流高壓電源裝置
14‧‧‧電暈針
16‧‧‧柵極
18‧‧‧柵極用電源
19‧‧‧熱板
20‧‧‧對向電極
22‧‧‧電流計
24‧‧‧基極電極
26‧‧‧屏蔽電極
28‧‧‧玻璃基板
圖1係帶電試驗中所使用之電暈帶電裝置之概念圖。
圖2係表示表面電位之測定點之設定例的圖。
圖3係表示駐極體A、B所保持之電荷之經時變化狀況的圖。
圖4係表示駐極體C、D所保持之電荷之經時變化狀況的圖。
圖5係熱穩定性試驗中所使用之裝置之概念圖。
圖6係表示駐極體A、B之熱穩定性試驗之結果的圖。
圖7係表示經圖案化之電極之圖。
圖8係振動發電試驗之裝置之概念圖。
Claims (12)
- 一種駐極體,其特徵在於含有主鏈上具有環結構之含氟聚合物與矽烷偶合劑之混合物。
- 如請求項1之駐極體,其中上述矽烷偶合劑係具有胺基之矽烷偶合劑。
- 如請求項1之駐極體,其中上述主鏈上具有環結構之含氟聚合物含有羧基作為端基。
- 如請求項2之駐極體,其中上述主鏈上具有環結構之含氟聚合物含有羧基作為端基。
- 如請求項1至4中任一項之駐極體,其中含有與上述羧基鍵結之矽烷化合物。
- 如請求項1至4中任一項之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有環結構之含氟脂肪族聚合物。
- 如請求項5之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有環結構之含氟脂肪族聚合物。
- 如請求項1至4中任一項之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有含醚性氧原子之環結構的含氟脂肪族聚合物。
- 如請求項5之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有含醚性氧原子之環結構的含氟脂肪族聚合物。
- 如請求項6之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有含醚性氧原子之環結構的含氟脂 肪族聚合物。
- 如請求項7之駐極體,其中上述主鏈上具有環結構之含氟聚合物係主鏈上具有含醚性氧原子之環結構的含氟脂肪族聚合物。
- 一種靜電感應型轉換元件,其特徵在於包含如請求項1至11中任一項之駐極體。
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RU2009138001A (ru) | 2011-04-27 |
RU2465673C2 (ru) | 2012-10-27 |
TW200904833A (en) | 2009-02-01 |
KR20100014895A (ko) | 2010-02-11 |
CN101641752A (zh) | 2010-02-03 |
WO2008114489A1 (ja) | 2008-09-25 |
US20100127595A1 (en) | 2010-05-27 |
KR101366146B1 (ko) | 2014-02-24 |
JP2008266563A (ja) | 2008-11-06 |
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