KR102591669B1 - Compositions, polymers for capacitors and capacitors - Google Patents
Compositions, polymers for capacitors and capacitors Download PDFInfo
- Publication number
- KR102591669B1 KR102591669B1 KR1020227016295A KR20227016295A KR102591669B1 KR 102591669 B1 KR102591669 B1 KR 102591669B1 KR 1020227016295 A KR1020227016295 A KR 1020227016295A KR 20227016295 A KR20227016295 A KR 20227016295A KR 102591669 B1 KR102591669 B1 KR 102591669B1
- Authority
- KR
- South Korea
- Prior art keywords
- capacitor
- phosphate
- composition
- ethylenedioxythiophene
- structural formula
- Prior art date
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 118
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- -1 phosphoric acid ester compound Chemical class 0.000 claims abstract description 27
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- DEZUSZMWEWAYSI-UHFFFAOYSA-N methyl 2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carboxylate Chemical group O1CCOC2=C(C(=O)OC)SC=C21 DEZUSZMWEWAYSI-UHFFFAOYSA-N 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 6
- MLXAPRJMRAWNHH-UHFFFAOYSA-N CCCCOC(=O)C1=C2C(=CS1)OCCO2 Chemical compound CCCCOC(=O)C1=C2C(=CS1)OCCO2 MLXAPRJMRAWNHH-UHFFFAOYSA-N 0.000 claims description 4
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 4
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 claims description 4
- UAEWCWCMYQAIDR-UHFFFAOYSA-N diethyl methyl phosphate Chemical compound CCOP(=O)(OC)OCC UAEWCWCMYQAIDR-UHFFFAOYSA-N 0.000 claims description 4
- JQVXMIPNQMYRPE-UHFFFAOYSA-N ethyl dimethyl phosphate Chemical compound CCOP(=O)(OC)OC JQVXMIPNQMYRPE-UHFFFAOYSA-N 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 4
- FCTINJHSYHFASK-UHFFFAOYSA-N tris(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OCC#C)OCC#C FCTINJHSYHFASK-UHFFFAOYSA-N 0.000 claims description 4
- BTVLERZSQCGLGL-UHFFFAOYSA-N CC(C)OC(=O)C1=C2C(=CS1)OCCO2 Chemical compound CC(C)OC(=O)C1=C2C(=CS1)OCCO2 BTVLERZSQCGLGL-UHFFFAOYSA-N 0.000 claims description 3
- RUIKQPWKVGWNHX-UHFFFAOYSA-N CCCOC(C1=C2OCCOC2=CS1)=O Chemical compound CCCOC(C1=C2OCCOC2=CS1)=O RUIKQPWKVGWNHX-UHFFFAOYSA-N 0.000 claims description 3
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- WGKIXRIZQOQWTB-UHFFFAOYSA-N ethyl 2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carboxylate Chemical compound O1CCOC2=C(C(=O)OCC)SC=C21 WGKIXRIZQOQWTB-UHFFFAOYSA-N 0.000 claims description 3
- XMNQCSOOUOJOLR-UHFFFAOYSA-N ethyl methyl hydrogen phosphate Chemical compound CCOP(O)(=O)OC XMNQCSOOUOJOLR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 claims description 3
- QVKQJEWZVQFGIY-UHFFFAOYSA-N dipropyl hydrogen phosphate Chemical compound CCCOP(O)(=O)OCCC QVKQJEWZVQFGIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011888 foil Substances 0.000 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000004815 dispersion polymer Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- DRSDCRSCGFTJCE-UHFFFAOYSA-N ethanol;4-methylbenzenesulfonic acid Chemical compound CCO.CC1=CC=C(S(O)(=O)=O)C=C1 DRSDCRSCGFTJCE-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DCCRIIFBJZOPAV-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carboxylic acid Chemical compound O1CCOC2=C(C(=O)O)SC=C21 DCCRIIFBJZOPAV-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-M thiophene-2-carboxylate Chemical compound [O-]C(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/0425—Electrodes or formation of dielectric layers thereon characterised by the material specially adapted for cathode
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3242—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more oxygen atoms as the only heteroatom, e.g. benzofuran
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
종래의 전해 커패시터에 금속박 산화막 부식으로 인한 전압 저항 강하 및 누설 전류 증가의 문제를 극복하기 위해, 본 발명은 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 포함하는 조성물을 제공한다. 상기 중합 단량체는 3,4-에틸렌디옥시티오펜류 중합 단량체를 포함하며, 상기 말단 캡핑제는 구조식 1로 표시되는 화합물을 포함한다.
구조식 1
여기에서 R4는 H 또는 탄소 원자수가 1 내지 6인 탄화수소기이다. 동시에 본 발명은 상기 조성물을 중합하여 획득한 커패시터용 중합체 및 상기 커패시터용 중합체를 포함하는 커패시터를 더 개시한다. 본 발명에서 제공하는 조성물 중합에 의해 획득된 중합체는 금속박 상의 산화막에 대해 복구 및 보호의 역할을 하므로, 커패시터 금속박 상의 산화막이 파손되는 것을 현저하게 감소시킨다.In order to overcome the problems of voltage resistance drop and leakage current increase due to corrosion of the metal foil oxide film in conventional electrolytic capacitors, the present invention provides a composition containing a polymeric monomer, a phosphoric acid ester compound, and an end capping agent. The polymerization monomer includes a 3,4-ethylenedioxythiophene polymerization monomer, and the end capping agent includes a compound represented by Structural Formula 1.
Structural formula 1
Here, R 4 is H or a hydrocarbon group having 1 to 6 carbon atoms. At the same time, the present invention further discloses a capacitor polymer obtained by polymerizing the composition and a capacitor containing the capacitor polymer. The polymer obtained by polymerizing the composition provided by the present invention plays a role in repairing and protecting the oxide film on the metal foil, thereby significantly reducing damage to the oxide film on the capacitor metal foil.
Description
본 발명은 고체 상태 커패시터 재료 기술 분야에 관한 것으로, 더욱 상세하게는 조성물, 커패시터용 중합체 및 커패시터에 관한 것이다.The present invention relates to the field of solid state capacitor material technology, and more particularly to compositions, polymers for capacitors and capacitors.
고체 상태 전해 커패시터는 전도율이 높고 열안정성이 우수한 전도성 고분자를 전해질로 사용하여, 일반적인 액체 상태 커패시터에 비해 높은 신뢰성, 긴 사용 수명, 고주파의 낮은 임피던스, 초대형 리플 전류 내성 등의 특징을 가지고 있다. 또한 액체 상태 전해 커패시터 전해액이 액체가 누출되기 쉬운 단점을 극복하였다. 국내 전자 정보 산업이 급성장하면서 최근 몇 년간의 발전 추세에서 고체 상태 전해 커패시터가 점차 액체 상태 저전압 전해 커패시터를 대체하며 21세기 전자 정보 산업의 주류 제품 중 하나가 되고 있음을 알 수 있다.Solid-state electrolytic capacitors use conductive polymers with high conductivity and excellent thermal stability as electrolytes, and have features such as high reliability, long service life, low impedance at high frequencies, and ultra-large ripple current resistance compared to general liquid-state capacitors. In addition, the disadvantage of liquid electrolytic capacitor electrolyte, which is prone to liquid leakage, was overcome. With the rapid growth of the domestic electronic information industry, the development trend of recent years shows that solid-state electrolytic capacitors are gradually replacing liquid-state low-voltage electrolytic capacitors and are becoming one of the mainstream products of the 21st century electronic information industry.
사람들이 고체 상태 전해 커패시터 성능에 대한 요건이 증가함에 따라, 고전도성 고분자 커패시터에 내전압이 더욱 향상되고 누설 전류가 낮아져 커패시터 성능 및 사용 수명을 향상시키는 것은 연구원들의 공통 목표가 되었다. 알루미늄 전해 커패시터의 내전압은 산화알루미늄 산화막층의 두께에 비례하므로, 산화알루미늄 산화막층이 얇아지면 알루미늄박의 내전압이 낮아짐을 의미한다. 알루미늄박 산화막층 두께가 어느 정도까지 얇아지면, 양극박 내전압은 성능 요건을 충족하지 못하게 되며, 커패시터 사용 과정에서 양음극 도통, 소위 절연파괴(electrical breakdown) 현상이 발생한다. 부식이 상술한 가혹한 조건에 도달하지 않으면 누설 전류가 커질 수 있다. 누설 전류 크기 제어는 주요 고체 상태 알루미늄 전해 커패시터 제조업체가 제어해야 할 핵심이 되었다. 동시에, 최근 몇 년 동안 커패시터를 축소하려는 시장 수요 및 알루미늄 고체 상태 전해 커패시터 비용 절감에 대한 수요로 인해, 커패시터 제조업체에서 사용하는 양극박 내전압이 더욱 낮아지는 추세이다. 따라서 양극박의 부식을 완화시키고 커패시터 누설 전류 등 측면의 성능을 낮추기 위한 요건이 더욱 높아졌다.As people's requirements for solid-state electrolytic capacitor performance increase, it has become a common goal for researchers to provide high-conductivity polymer capacitors with further improved withstand voltage and lower leakage current to improve capacitor performance and service life. Since the withstand voltage of an aluminum electrolytic capacitor is proportional to the thickness of the aluminum oxide oxide film layer, this means that the withstand voltage of the aluminum foil decreases as the aluminum oxide oxide film layer becomes thinner. If the thickness of the aluminum foil oxide layer becomes thinner to a certain extent, the withstand voltage of the anode foil does not meet the performance requirements, and anode conduction, a so-called electrical breakdown phenomenon, occurs during the process of using a capacitor. If corrosion does not reach the severe conditions described above, the leakage current may become large. Leakage current magnitude control has become a key issue for major solid-state aluminum electrolytic capacitor manufacturers. At the same time, in recent years, due to the market demand for shrinking capacitors and the demand for reducing the cost of aluminum solid-state electrolytic capacitors, the withstand voltage of the anode foil used by capacitor manufacturers is trending lower. Therefore, the requirements to alleviate corrosion of the anode foil and reduce performance of aspects such as capacitor leakage current have increased.
현재, 고체 상태 알루미늄 전해 커패시터에는 3,4-에틸렌디옥시티오펜을 단량체로 사용하여 제조된 폴리-3,4-에틸렌디옥시티오펜(PEDOT) 중합체 재료가 일반적으로 사용된다. 상술한 중합체 재료는 우수한 도전성과 우수한 환경 안정성으로 인해 고체 상태 전해 커패시터 음극으로 널리 사용된다. 그러나 중합 반응에 사용되는 강산성 물질은 생성된 중합체 재료에 잔류할 수 있다. 커패시터 사용 시, 알루미늄박 산화막층을 부식시켜 이를 얇아지게 만들어 커패시터 내전압 강하 및 누설 전류 증가 문제를 야기할 수 있다. 따라서 단순히 3,4-에틸렌디옥시티오펜 단량체를 사용하여 제조된 고체 상태 알루미늄 전해 커패시터는 그 내전압 및 누설 전류 성능이 사람들의 증가하는 요건을 충족시킬 수 없다.Currently, poly-3,4-ethylenedioxythiophene (PEDOT) polymer material prepared using 3,4-ethylenedioxythiophene as a monomer is commonly used in solid-state aluminum electrolytic capacitors. The above-described polymer materials are widely used as solid-state electrolytic capacitor cathodes due to their excellent conductivity and excellent environmental stability. However, strongly acidic substances used in the polymerization reaction may remain in the resulting polymer material. When using a capacitor, the aluminum foil oxide layer can corrode and become thinner, causing problems such as a drop in the capacitor's withstand voltage and an increase in leakage current. Therefore, the solid-state aluminum electrolytic capacitor simply manufactured using 3,4-ethylenedioxythiophene monomer, its withstand voltage and leakage current performance cannot meet people's increasing requirements.
종래의 전해 커패시터에 금속박 산화막 부식으로 인해 내전압 강하 및 누설 전류 증가의 문제를 해결하기 위해, 본 발명은 조성물, 커패시터용 중합체 및 커패시터를 제공한다.In order to solve the problems of withstand voltage drop and leakage current increase due to corrosion of the metal foil oxide film in conventional electrolytic capacitors, the present invention provides a composition, a polymer for capacitors, and a capacitor.
본 발명은 상기 기술적 문제를 해결하기 위해 하기 기술적 해결책을 채택한다.The present invention adopts the following technical solutions to solve the above technical problems.
일 양상에 있어서, 본 발명은 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 포함하는 조성물을 제공한다.In one aspect, the present invention provides a composition comprising a polymerizable monomer, a phosphoric acid ester type compound, and an endcapping agent.
상기 중합 단량체는 3,4-에틸렌디옥시티오펜류 중합 단량체이다.The polymerization monomer is a 3,4-ethylenedioxythiophene type polymerization monomer.
상기 말단 캡핑제는 구조식 1로 표시되는 화합물을 포함한다.The end capping agent includes a compound represented by structural formula 1.
구조식 1Structural formula 1
여기에서 R4는 H 또는 탄소 원자수가 1 내지 6인 탄화수소기이다.Here, R 4 is H or a hydrocarbon group having 1 to 6 carbon atoms.
선택적으로, 상기 조성물은,Optionally, the composition:
중합 단량체 96 내지 99.9998부, 말단 캡핑제 0.0001 내지 1부, 인산 에스테르류 화합물 0.0001 내지 3부의 중량 성분을 포함한다.It contains 96 to 99.9998 parts of polymerizable monomer, 0.0001 to 1 part of end capping agent, and 0.0001 to 3 parts of phosphoric acid ester compound.
선택적으로, 상기 말단 캡핑제는 메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트(methyl 3,4-ethylenedioxythiophene-2-carboxylate), 에틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트(ethyl 3,4-ethylenedioxythiophene-2-carboxylate), 프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트(propyl 3,4-ethylenedioxythiophene-2-carboxylate), 이소프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트(ispropyl 3,4-ethylenedioxythiophene-2-carboxylate), 부틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트(butyl 3,4-ethylenedioxythiophene-2-carboxylate) 중 하나 이상을 포함한다.Optionally, the end capping agent is methyl 3,4-ethylenedioxythiophene-2-carboxylate, ethyl 3,4-ethylenedioxythiophene-2-carboxylate ethyl 3,4-ethylenedioxythiophene-2-carboxylate, propyl 3,4-ethylenedioxythiophene-2-carboxylate, isopropyl 3,4-ethylenediox One of ispropyl 3,4-ethylenedioxythiophene-2-carboxylate, butyl 3,4-ethylenedioxythiophene-2-carboxylate Includes more.
선택적으로, 상기 인산 에스테르류 화합물은 구조식 2로 표시되는 화합물을 포함한다.Optionally, the phosphoric acid ester compound includes a compound represented by structural formula 2.
구조식 2Structural formula 2
여기에서 R1, R2 및 R3은 H 또는 수소 원자가 치환 또는 비치환된 탄소 원자수가 1 내지 6인 탄화수소기, 에테르기, 카르보닐기 또는 방향족기로부터 선택되고, R1, R2 및 R3은 동시에 H가 아니다.Here, R 1 , R 2 and R 3 are H or a hydrogen atom selected from a substituted or unsubstituted hydrocarbon group, an ether group, a carbonyl group or an aromatic group having 1 to 6 carbon atoms, and R 1 , R 2 and R 3 are At the same time, it is not H.
선택적으로, R1, R2 및 R3 중 2개는 서로 연결되어 고리를 형성한다.Optionally, two of R 1 , R 2 and R 3 are linked to each other to form a ring.
선택적으로, 상기 인산 에스테르류 화합물은 트리메틸 포스페이트(trimethyl phosphate), 디메틸 포스페이트(ditrimethyl phosphate), 메틸 에틸 포스페이트(methyl ethyl phosphate), 트리에틸 포스페이트(triethyl phosphate), 디에틸 포스페이트(diethyl phosphate), 디메틸 에틸 포스페이트(dimethyl ethyl phosphate), 메틸 디에틸 포스페이트(methyl diethyl phosphate), 트리프로필 포스페이트(tripropyl phosphate), 트리프로파길 포스페이트(tripropargyl phosphate), 디프로필 포스페이트(dipropyl phosphate), 트리부틸 포스페이트(tripropyl phosphate), 디부틸 포스페이트(dibutyl phosphate), 모노부틸 포스페이트(monobutyl phosphate) 및 트리펜틸 포스페이트(tripentyl phosphate) 중 하나 이상을 포함한다.Optionally, the phosphate ester compound is trimethyl phosphate, dimethyl phosphate, methyl ethyl phosphate, triethyl phosphate, diethyl phosphate, dimethyl ethyl. Phosphate (dimethyl ethyl phosphate), methyl diethyl phosphate, tripropyl phosphate, tripropargyl phosphate, dipropyl phosphate, tributyl phosphate, It includes one or more of dibutyl phosphate, monobutyl phosphate, and tripentyl phosphate.
선택적으로, 상기 중합 단량체는 구조식 3으로 표시되는 화합물을 포함한다.Optionally, the polymerization monomer includes a compound represented by structural formula 3.
구조식 3Structural formula 3
다른 일 양상에 있어서, 본 발명은 커패시터용 중합체를 제공하며, 이는 상술한 조성물을 중합하여 획득한다.In another aspect, the present invention provides a polymer for capacitors, which is obtained by polymerizing the composition described above.
다른 일 양상에 있어서, 본 발명은 커패시터 소자 및 커패시터 소자에 부착된 양극 재료를 포함하는 알루미늄 전해 커패시터를 제공한다. 상기 음극 재료는 상술한 바와 같은 커패시터용 중합체를 포함한다.In another aspect, the present invention provides an aluminum electrolytic capacitor including a capacitor element and an anode material attached to the capacitor element. The cathode material includes a polymer for capacitors as described above.
선택적으로, 상기 커패시터는 고체 상태 알루미늄 전해 커패시터 또는 고체 상태 탄탈륨 전해 커패시터이다.Optionally, the capacitor is a solid state aluminum electrolytic capacitor or a solid state tantalum electrolytic capacitor.
본 발명에서 제공하는 조성물은 인산 에스테르류 화합물, 중합 단량체 및 말단 캡핑제를 중합 원료로 사용한다. 인산 에스테르류 화합물은 일정한 윤활성을 가지므로 금속박과 직접 접촉시키기 용이하며 어느 정도 금속박 서방제로 사용되어 부식을 방지하고 금속박 상의 산화막에 대해 복구 및 보호의 역할을 수행하여 커패시터 금속박 상의 산화막이 파손되는 것을 현저하게 감소시킬 수 있다. 또한 구조식 1로 표시되는 화합물을 말단 캡핑제로 사용하면 중합 단량체의 중합 반응에서 중합도를 낮추고 단량체 중합 속도를 완화시켜 시스템의 산도를 낮춰 부식이 발생하는 것을 더욱 방지할 수 있다.The composition provided by the present invention uses phosphoric acid ester compounds, polymerization monomers, and end capping agents as polymerization raw materials. Since phosphoric acid ester compounds have a certain lubricity, they are easy to come into direct contact with metal foil, and are used as a metal foil release agent to some extent to prevent corrosion and play a role in restoring and protecting the oxide film on the metal foil, significantly preventing the oxide film on the capacitor metal foil from being damaged. can be reduced significantly. In addition, using the compound represented by structural formula 1 as an end capping agent can lower the degree of polymerization in the polymerization reaction of polymerized monomers and alleviate the monomer polymerization rate, thereby lowering the acidity of the system and further preventing corrosion from occurring.
본 발명이 해결하고자 하는 기술적 과제, 기술적 해결책 및 유익한 효과를 보다 명확하게 설명하기 위하여, 이하에서는 실시예를 참조하여 본 발명을 더욱 상세하게 설명한다. 본원에 설명된 구체적인 실시예는 본 발명을 설명하기 위해 사용된 것일 뿐, 본 발명을 제한하지 않음을 이해해야 한다.In order to more clearly explain the technical problems, technical solutions and beneficial effects to be solved by the present invention, the present invention will be described in more detail below with reference to examples. It should be understood that the specific examples described herein are only used to illustrate the invention and do not limit the invention.
본 발명의 일 실시예는 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 포함하는 조성물을 제공한다.One embodiment of the present invention provides a composition comprising a polymerizable monomer, a phosphoric acid ester compound, and an endcapping agent.
상기 중합 단량체는 3,4-에틸렌디옥시티오펜류 중합 단량체이다.The polymerization monomer is a 3,4-ethylenedioxythiophene type polymerization monomer.
상기 말단 캡핑제는 구조식 1로 표시되는 화합물을 포함한다.The end capping agent includes a compound represented by structural formula 1.
구조식 1Structural formula 1
여기에서 R4는 H 또는 탄소 원자수가 1 내지 6인 탄화수소기이다.Here, R 4 is H or a hydrocarbon group having 1 to 6 carbon atoms.
인산 에스테르류 화합물은 일정한 윤활성을 가지므로 금속박과 직접 접촉시키기 용이하며 어느 정도 금속박 서방제로 사용되어 부식을 방지하고 금속박 상의 산화막에 대해 복구 및 보호의 역할을 수행하여 커패시터 금속박 상의 산화막이 파손되는 것을 현저하게 감소시킬 수 있다. 또한 구조식 1로 표시되는 화합물을 말단 캡핑제로 사용하면 중합 단량체의 중합 반응에서 중합도를 낮추고 단량체 중합 속도를 완화시켜 시스템의 산도를 낮춰 부식이 발생하는 것을 더욱 방지할 수 있다.Since phosphoric acid ester compounds have a certain lubricity, they are easy to come into direct contact with metal foil, and are used as a metal foil release agent to some extent to prevent corrosion and play a role in restoring and protecting the oxide film on the metal foil, significantly preventing the oxide film on the capacitor metal foil from being damaged. can be reduced significantly. In addition, using the compound represented by structural formula 1 as an end capping agent can lower the degree of polymerization in the polymerization reaction of polymerized monomers and alleviate the monomer polymerization rate, thereby lowering the acidity of the system and further preventing corrosion from occurring.
일부 실시예에 있어서, 상기 조성물은,In some embodiments, the composition:
중합 단량체 96 내지 99.9998부, 말단 캡핑제 0.0001 내지 1부, 인산 에스테르류 화합물 0.0001 내지 3부의 중량 성분을 포함한다.It contains 96 to 99.9998 parts of polymerizable monomer, 0.0001 to 1 part of end capping agent, and 0.0001 to 3 parts of phosphoric acid ester compound.
보다 바람직한 실시예에 있어서, 상기 조성물은,In a more preferred embodiment, the composition:
중합 단량체 98 내지 99.9899부, 말단 캡핑제 0.0001 내지 0.5부, 인산 에스테르류 화합물 0.01 내지 1.5부의 중량 성분을 포함한다.It contains 98 to 99.9899 parts of polymerizable monomer, 0.0001 to 0.5 part of end capping agent, and 0.01 to 1.5 part of phosphoric acid ester compound.
상기 인산 에스테르류 화합물의 첨가량이 너무 적으면 알루미늄박 산화막에 대한 보호 효과가 현저하지 않다. 반면 상기 인산 에스테르류 화합물의 첨가량이 너무 많으면 중합 후 중합체의 도전성이 열화되고 중합체와 금속박의 부착 효과가 떨어진다.If the amount of the phosphoric acid ester compound added is too small, the protective effect on the aluminum foil oxide film is not significant. On the other hand, if the amount of the phosphoric acid ester compound added is too large, the conductivity of the polymer deteriorates after polymerization and the adhesion effect between the polymer and the metal foil deteriorates.
상기 말단 캡핑제의 첨가량이 너무 적으면 중합 반응의 중합도 저하는 현저하지 않다. 반면 상기 말단 캡핑제의 첨가량이 너무 많으면 중합 후 중합체의 중합도가 너무 낮아 중합체의 구조적 강도에 영향을 미치므로 커패시터의 안전 성능 향상에 도움이 되지 않는다.If the amount of the end capping agent added is too small, the degree of polymerization in the polymerization reaction is not significantly reduced. On the other hand, if the amount of the end capping agent added is too large, the polymerization degree of the polymer after polymerization is too low, which affects the structural strength of the polymer and does not help improve the safety performance of the capacitor.
일부 실시예에 있어서, 상기 말단 캡핑제는 메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 에틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 이소프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 부틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 중 하나 이상을 포함한다.In some embodiments, the end capping agent is methyl 3,4-ethylenedioxythiophene-2-carboxylate, ethyl 3,4-ethylenedioxythiophene-2-carboxylate, propyl 3,4-ethylenedioc It includes one or more of thiophene-2-carboxylate, isopropyl 3,4-ethylenedioxythiophene-2-carboxylate, and butyl 3,4-ethylenedioxythiophene-2-carboxylate.
일부 실시예에 있어서, 상기 인산 에스테르류 화합물은 구조식 2로 표시되는 화합물을 포함한다.In some embodiments, the phosphoric acid ester compound includes a compound represented by structural formula 2.
구조식 2Structural formula 2
여기에서 R1, R2 및 R3은 H 또는 수소 원자가 치환 또는 비치환된 탄소 원자수가 1 내지 6인 탄화수소기, 에테르기, 카르보닐기 또는 방향족기로부터 선택되고, 치환기는 할로겐, 히드록실 또는 카르복실이며, R1, R2 및 R3은 동시에 H가 아니다.Here, R 1 , R 2 and R 3 are H or a hydrogen atom selected from a substituted or unsubstituted hydrocarbon group, an ether group, a carbonyl group or an aromatic group having 1 to 6 carbon atoms, and the substituent is halogen, hydroxyl or carboxyl. and R 1 , R 2 and R 3 are not H at the same time.
일부 실시예에 있어서, R1, R2 및 R3 중 2개는 서로 연결되어 고리를 형성한다.In some embodiments, two of R 1 , R 2 and R 3 are connected to each other to form a ring.
보다 바람직한 실시예에 있어서, 상기 인산 에스테르류 화합물은 트리메틸 포스페이트, 디메틸 포스페이트, 메틸 에틸 포스페이트, 트리에틸 포스페이트, 디에틸 포스페이트, 디메틸 에틸 포스페이트, 메틸 디에틸 포스페이트, 트리프로필 포스페이트, 트리프로파길 포스페이트, 디프로필 포스페이트, 트리부틸 포스페이트, 디부틸 포스페이트, 모노부틸 포스페이트 및 트리펜틸 포스페이트 중 하나 이상을 포함한다.In a more preferred embodiment, the phosphoric acid ester compound is trimethyl phosphate, dimethyl phosphate, methyl ethyl phosphate, triethyl phosphate, diethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, tripropyl phosphate, tripropargyl phosphate, dimethyl phosphate, It includes one or more of propyl phosphate, tributyl phosphate, dibutyl phosphate, monobutyl phosphate and tripentyl phosphate.
본 발명의 설명에서 3,4-에틸렌디옥시티오펜류 중합 단량체는 티오펜 고리에서 2 및 5 위치에서 중합 반응을 일으킬 수 있는 3,4-에틸렌디옥시티오펜 및 그 유도체를 의미함에 유의한다.Note that in the description of the present invention, the 3,4-ethylenedioxythiophene polymerization monomer refers to 3,4-ethylenedioxythiophene and its derivatives that can undergo polymerization at the 2 and 5 positions of the thiophene ring.
일부 실시예에 있어서, 상기 중합 단량체는 구조식 3으로 표시되는 화합물을 포함한다.In some embodiments, the polymerization monomer includes a compound represented by Structural Formula 3.
구조식 3Structural formula 3
본 발명의 다른 일 실시예는 커패시터용 중합체를 제공하며, 이는 상술한 조성물의 중합에 의해 획득된다.Another embodiment of the present invention provides a polymer for capacitors, which is obtained by polymerization of the composition described above.
종래의 커패시터용 중합체와 비교하여, 상기 조성물을 중합하여 획득한 커패시터용 중합체는 낮아진 금속박 부식성을 가지며, 커패시터의 누설 전류를 효과적으로 감소시킬 수 있으며, 고체 커패시터의 성능 안정성을 향상시킬 수 있다.Compared to conventional polymers for capacitors, the polymer for capacitors obtained by polymerizing the composition has lower corrosion resistance to metal foil, can effectively reduce the leakage current of the capacitor, and can improve the performance stability of the solid capacitor.
본 발명의 다른 일 실시예는 커패시터 소자 및 커패시터 소자에 부착된 양극 재료를 포함하는 알루미늄 전해 커패시터를 제공한다. 상기 음극 재료는 상술한 바와 같은 커패시터용 중합체를 포함한다.Another embodiment of the present invention provides an aluminum electrolytic capacitor including a capacitor element and an anode material attached to the capacitor element. The cathode material includes a polymer for capacitors as described above.
일부 실시예에 있어서, 상기 커패시터는 고체 상태 알루미늄 전해 커패시터 또는 고체 상태 탄탈륨 전해 커패시터이다.In some embodiments, the capacitor is a solid state aluminum electrolytic capacitor or a solid state tantalum electrolytic capacitor.
이하에서는 실시예를 참고하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to examples.
실시예 1Example 1
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 하기 조작 단계가 포함된다.This example is intended to illustrate the composition disclosed in the present invention, the polymer for capacitors, and the method for producing the capacitor, which includes the following operating steps.
트리부틸 포스페이트 0.07중량%, 메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.01중량%, 3,4-에틸렌디옥시티오펜 99.92중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.The three substances, 0.07% by weight of tributyl phosphate, 0.01% by weight of methyl 3,4-ethylenedioxythiophene-2-carboxylate, and 99.92% by weight of 3,4-ethylenedioxythiophene, are uniformly mixed to produce polymerized monomer, phosphoric acid. A composition containing an ester compound and an endcapping agent is prepared.
상기 조성물을 중합 원료로 사용하여 자유기 중합 방식을 통해 중합체 수분산체를 제조한다. 구체적인 실시 공정은 다음과 같다. 즉, 물 1753g과 폴리스티렌 술폰산나트륨 90.32g을 취하여, 분산기에서 고속으로 균일하게 혼합하고, 질소 분위기 보호 하에서 반응기 내 온도를 22℃로 제어하며, 황산철 수용액(1.3% 농도) 17.54g 및 상술한 중합 원료 7.25g을 첨가하여 24시간 동안 계속해서 반응시켜, 중합체 분산체 PEDOT/PSS 중간체를 수득한다. 상기 중합체 분산체 PEDOT:PSS 중간체를 음이온 및 양이온 교환 수지와 혼합하여 불순물 이온을 제거한다. 불순물 이온이 제거된 중합체 분산체 PEDOT:PSS 중간체 500g에 폴리에틸렌글리콜 1000 53.2g을 첨가하고 8시간 동안 혼합 교반한 후 호모지나이저로 균질화하여 중합체 분산액을 수득한다.A polymer aqueous dispersion is prepared through free radical polymerization using the composition as a polymerization raw material. The specific implementation process is as follows. That is, 1753 g of water and 90.32 g of sodium polystyrene sulfonate are mixed uniformly at high speed in a disperser, the temperature in the reactor is controlled to 22°C under the protection of a nitrogen atmosphere, and 17.54 g of an aqueous iron sulfate solution (1.3% concentration) and the above-described polymerization are added. 7.25 g of raw materials were added and the reaction was continued for 24 hours to obtain a polymer dispersion PEDOT/PSS intermediate. The polymer dispersion PEDOT:PSS intermediate is mixed with an anion and cation exchange resin to remove impurity ions. 53.2 g of polyethylene glycol 1000 was added to 500 g of the polymer dispersion PEDOT:PSS intermediate from which impurity ions were removed, mixed and stirred for 8 hours, and then homogenized with a homogenizer to obtain a polymer dispersion.
건조된 커패시터 소자를 상온에서 진공도가 -0.09MPa인 조건에서 중합체 분산액을 20min 동안 함침시켜 소자를 꺼내고 그 표면의 중합체 분산액을 닦은 후 125℃에서 1시간 소성하여 함침시킨 후, 베이킹 공정을 3번 순환한다. 함침 완료 후, 커패시터 소자는 입구를 밀봉하여 고체 상태 전해 커패시터로 조립한다.The dried capacitor element was impregnated with a polymer dispersion for 20 minutes at room temperature and the vacuum degree was -0.09 MPa. The element was taken out, the polymer dispersion on its surface was wiped, baked at 125°C for 1 hour to be impregnated, and the baking process was cycled three times. do. After completion of impregnation, the capacitor element is assembled into a solid-state electrolytic capacitor by sealing the inlet.
실시예 2Example 2
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This Example is intended to illustrate the composition, capacitor polymer, and method of making the capacitor disclosed herein, and includes most of the operational steps in Example 1. The differences are as follows.
메틸 디에틸 포스페이트 0.2중량%, 에틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.1중량%, 3,4-에틸렌디옥시티오펜 99.7중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.The three substances, 0.2% by weight of methyl diethyl phosphate, 0.1% by weight of ethyl 3,4-ethylenedioxythiophene-2-carboxylate, and 99.7% by weight of 3,4-ethylenedioxythiophene, were uniformly mixed to produce polymerized monomers, A composition containing a phosphoric acid ester type compound and an endcapping agent is prepared.
실시예 3Example 3
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This Example is intended to illustrate the composition, capacitor polymer, and method of making the capacitor disclosed herein, and includes most of the operational steps in Example 1. The differences are as follows.
디메틸 에틸 포스페이트 1.0중량%, 프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.3중량%, 3,4-에틸렌디옥시티오펜 98.7중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.The three substances, 1.0% by weight of dimethyl ethyl phosphate, 0.3% by weight of propyl 3,4-ethylenedioxythiophene-2-carboxylate, and 98.7% by weight of 3,4-ethylenedioxythiophene, are uniformly mixed to produce polymerized monomer, phosphoric acid. A composition containing an ester compound and an endcapping agent is prepared.
실시예 4Example 4
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This Example is intended to illustrate the composition, capacitor polymer, and method of making the capacitor disclosed herein, and includes most of the operational steps in Example 1. The differences are as follows.
트리프로필 포스페이트 0.62중량%, 부틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.0002중량%, 3,4-에틸렌디옥시티오펜 99.3798중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.The three substances, 0.62% by weight of tripropyl phosphate, 0.0002% by weight of butyl 3,4-ethylenedioxythiophene-2-carboxylate, and 99.3798% by weight of 3,4-ethylenedioxythiophene, are uniformly mixed to form a polymer monomer, phosphoric acid. A composition containing an ester compound and an endcapping agent is prepared.
실시예 5Example 5
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This Example is intended to illustrate the composition, capacitor polymer, and method of making the capacitor disclosed herein, and includes most of the operational steps in Example 1. The differences are as follows.
트리프로파길 포스페이트 0.006중량%, 메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.006중량%, 3,4-에틸렌디옥시티오펜 99.988중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.Three substances, 0.006% by weight of tripropargyl phosphate, 0.006% by weight of methyl 3,4-ethylenedioxythiophene-2-carboxylate, and 99.988% by weight of 3,4-ethylenedioxythiophene, were uniformly mixed to produce polymerized monomers, A composition containing a phosphoric acid ester type compound and an endcapping agent is prepared.
실시예 6Example 6
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This Example is intended to illustrate the composition, capacitor polymer, and method of making the capacitor disclosed herein, and includes most of the operational steps in Example 1. The differences are as follows.
트리에틸 포스페이트 0.05중량%, 이소프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.024중량%, 3,4-에틸렌디옥시티오펜 99.926중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.Three substances, 0.05% by weight of triethyl phosphate, 0.024% by weight of isopropyl 3,4-ethylenedioxythiophene-2-carboxylate, and 99.926% by weight of 3,4-ethylenedioxythiophene, are uniformly mixed to produce polymerized monomers, A composition containing a phosphoric acid ester type compound and an endcapping agent is prepared.
실시예 7Example 7
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This Example is intended to illustrate the composition, capacitor polymer, and method of making the capacitor disclosed herein, and includes most of the operational steps in Example 1. The differences are as follows.
모노부틸 포스페이트 0.37중량%, 메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.052중량%, 3,4-에틸렌디옥시티오펜 99.578중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.The three substances, 0.37% by weight of monobutyl phosphate, 0.052% by weight of methyl 3,4-ethylenedioxythiophene-2-carboxylate, and 99.578% by weight of 3,4-ethylenedioxythiophene, are uniformly mixed to obtain polymerized monomer, phosphoric acid. A composition containing an ester compound and an endcapping agent is prepared.
실시예 8Example 8
본 실시예는 본 발명에서 개시하는 조성물, 커패시터용 중합체 및 커패시터의 제조 방법을 설명하기 위한 것이며, 여기에는 하기 조작 단계가 포함된다.This example is intended to illustrate the composition disclosed in the present invention, the polymer for capacitors, and the method for producing the capacitor, which includes the following operating steps.
트리부틸 포스페이트 0.06중량%, 메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.04중량%, 3,4-에틸렌디옥시티오펜 99.9중량%의 세 가지 물질을 균일하게 혼합하여 중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 함유하는 조성물을 제조한다.The three substances, 0.06% by weight of tributyl phosphate, 0.04% by weight of methyl 3,4-ethylenedioxythiophene-2-carboxylate, and 99.9% by weight of 3,4-ethylenedioxythiophene, are uniformly mixed to obtain polymerized monomer, phosphoric acid. A composition containing an ester compound and an endcapping agent is prepared.
에탄올을 용매로 사용하여 상기 조성물을 25% 단량체 용액으로 제조하고, 커패시터 소자를 사용하여 상기 단량체 용액을 2min 동안 함침시키며, 커패시터 소자를 꺼내 60℃ 오븐 내에서 30min 동안 건조한 후 상온으로 냉각한다.The composition is prepared as a 25% monomer solution using ethanol as a solvent, a capacitor element is impregnated with the monomer solution for 2 min, the capacitor element is taken out, dried in a 60°C oven for 30 min, and then cooled to room temperature.
상술한 단계를 처리한 커패시터 소자는 상온, 진공도가 -0.085MPa인 조건에서 60% 농도의 p-톨루엔술폰산 에탄올 산화제 용액을 함침시키며, 함침 시간은 5min이다.The capacitor element processed in the above-described steps is impregnated with a 60% concentration p-toluenesulfonic acid ethanol oxidizing agent solution at room temperature and a vacuum degree of -0.085 MPa, and the impregnation time is 5 minutes.
함침이 완료되면 커패시터 소자를 꺼내어 항온항습 상자에 넣고 중합 반응을 수행한다. 온도 40℃, 습도 40% 조건에서 1h 동안 반응시킨다. 온도는 60℃, 습도는 25%로 조절하여 2h 동안 반응시킨다. 온도는 70℃, 습도는 20%로 조절하여 1h 동안 반응시킨다. 온도는 150℃, 습도는 0%로 조절하여 1h 동안 반응시킨다. 온도는 110℃, 습도는 0%로 조절하여 3h 동안 반응시킨다. 중합 반응을 완료하고, 커패시터를 고체 상태 전해 커패시터로 패키징한다.When impregnation is complete, the capacitor element is taken out and placed in a constant temperature and humidity box to perform a polymerization reaction. React for 1 h at a temperature of 40°C and humidity of 40%. The temperature was adjusted to 60°C and humidity to 25% and allowed to react for 2 h. The temperature was adjusted to 70°C and humidity to 20% and allowed to react for 1 h. The temperature was adjusted to 150°C and the humidity was 0% and allowed to react for 1 h. The temperature was adjusted to 110°C and the humidity was 0% and allowed to react for 3 h. The polymerization reaction is completed, and the capacitor is packaged as a solid-state electrolytic capacitor.
비교예 1Comparative Example 1
본 비교예는 본 발명에서 개시하는 커패시터용 중합체 및 커패시터의 제조 방법을 비교하여 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This comparative example is intended to compare and explain the capacitor polymer disclosed in the present invention and the manufacturing method of the capacitor, and includes most of the operating steps in Example 1. The differences are as follows.
순수한 단량체 3,4-에틸렌디옥시티오펜을 채택해 실시예 1의 중합 원료를 대체한다.The pure monomer 3,4-ethylenedioxythiophene was adopted to replace the polymerization raw material in Example 1.
비교예 2Comparative Example 2
본 실시예는 본 발명에서 개시하는 커패시터용 중합체 및 커패시터의 제조 방법을 비교하여 설명하기 위한 것이며, 여기에는 하기 조작 단계가 포함된다.This example is intended to compare and illustrate the polymer for capacitors disclosed in the present invention and the manufacturing method of the capacitor, which includes the following operating steps.
에탄올을 용매로 사용하여 3,4-에틸렌디옥시티오펜을 25% 단량체 용액으로 제조하고, 커패시터 소자를 사용하여 단량체 용액을 2min 동안 함침시키며, 커패시터 소자를 꺼내 60℃ 오븐 내에서 30min 동안 건조한 후 상온으로 냉각한다.Prepare 3,4-ethylenedioxythiophene as a 25% monomer solution using ethanol as a solvent, impregnate the capacitor element with the monomer solution for 2 minutes, take out the capacitor element, dry it in an oven at 60°C for 30 minutes, and then place it at room temperature. Cool down.
상술한 단계를 처리한 커패시터 소자는 상온, 진공도가 -0.085MPa인 조건에서 60% 농도의 p-톨루엔술폰산 에탄올 산화제 용액을 함침시키며, 함침 시간은 5min이다.The capacitor element processed in the above-described steps is impregnated with a 60% concentration p-toluenesulfonic acid ethanol oxidizing agent solution at room temperature and a vacuum degree of -0.085 MPa, and the impregnation time is 5 minutes.
함침이 완료되면 커패시터 소자를 꺼내어 항온항습 상자에 넣고 중합 반응을 수행한다. 온도 40℃, 습도 40% 조건에서 1h 동안 반응시킨다. 온도는 60℃, 습도는 25%로 조절하여 2h 동안 반응시킨다. 온도는 70℃, 습도는 20%로 조절하여 1h 동안 반응시킨다. 온도는 150℃, 습도는 0%로 조절하여 1h 동안 반응시킨다. 온도는 110℃, 습도는 0%로 조절하여 3h 동안 반응시킨다. 중합 반응을 완료하고, 커패시터를 고체 상태 전해 커패시터로 패키징한다.When impregnation is complete, the capacitor element is taken out and placed in a constant temperature and humidity box to perform a polymerization reaction. React for 1 h at a temperature of 40°C and humidity of 40%. The temperature was adjusted to 60°C and humidity to 25% and allowed to react for 2 h. The temperature was adjusted to 70°C and humidity to 20% and allowed to react for 1 h. The temperature was adjusted to 150°C and the humidity was 0% and allowed to react for 1 h. The temperature was adjusted to 110°C and the humidity was 0% and allowed to react for 3 h. The polymerization reaction is completed, and the capacitor is packaged as a solid-state electrolytic capacitor.
비교예 3Comparative Example 3
본 비교예는 본 발명에서 개시하는 커패시터용 중합체 및 커패시터의 제조 방법을 비교하여 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This comparative example is intended to compare and explain the capacitor polymer disclosed in the present invention and the manufacturing method of the capacitor, and includes most of the operating steps in Example 1. The differences are as follows.
트리부틸 포스페이트 0.07중량% 및 3,4-에틸렌디옥시티오펜 99.93 중량%으로 상기 두 물질을 균일하게 혼합하여 중합 단량체 및 인산 에스테르류 화합물을 함유하는 조성물을 제조한다.A composition containing a polymerizable monomer and a phosphoric acid ester compound is prepared by uniformly mixing 0.07% by weight of tributyl phosphate and 99.93% by weight of 3,4-ethylenedioxythiophene.
비교예 4Comparative Example 4
본 비교예는 본 발명에서 개시하는 커패시터용 중합체 및 커패시터의 제조 방법을 비교하여 설명하기 위한 것이며, 여기에는 실시예 1 중 대부분의 조작 단계가 포함된다. 차이점은 하기와 같다.This comparative example is intended to compare and explain the capacitor polymer disclosed in the present invention and the manufacturing method of the capacitor, and includes most of the operating steps in Example 1. The differences are as follows.
메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 0.01중량% 및 3,4-에틸렌디옥시티오펜 99.99중량%를 사용하여 상기 두 물질을 혼합하여 중합 단량체와 말단 캡핑제를 함유하는 중합체를 제조한다.0.01% by weight of methyl 3,4-ethylenedioxythiophene-2-carboxylate and 99.99% by weight of 3,4-ethylenedioxythiophene were mixed to prepare a polymer containing polymerization monomers and an end capping agent. manufacture.
성능 테스트performance test
상기 실시예 1 내지 7 및 비교예 1 내지 4에서 제조된 고체 상태 전해 커패시터에 대해 다음과 같은 성능 테스트를 수행하였다.The following performance tests were performed on the solid-state electrolytic capacitors manufactured in Examples 1 to 7 and Comparative Examples 1 to 4.
자동 전자 부품 분석기 및 누설 전류 시험기를 이용하여 고체 상태 전해 커패시터의 정전용량, 손실값, 등가 직렬 저항 및 누설 전류를 시험한다. 여기에서 용량 및 손실값은 120Hz 주파수에서 시험하고, 등가 직렬 저항은 100KHz의 주파수에서 시험하며, 누설 전류는 정격전압으로 1min 동안 충전한 후 누설 전류 시험기로 시험한다. 시험 방법은 일반적인 자동 전자 부품 분석기와 누설 전류 시험기의 시험 방법으로, 여기에서 반복하여 설명하지 않는다.Test the capacitance, loss value, equivalent series resistance, and leakage current of solid-state electrolytic capacitors using an automatic electronic component analyzer and leakage current tester. Here, the capacity and loss values are tested at a frequency of 120Hz, the equivalent series resistance is tested at a frequency of 100KHz, and the leakage current is tested with a leakage current tester after charging at the rated voltage for 1 min. The test method is that of a general automatic electronic component analyzer and leakage current tester, and will not be repeated here.
테스트 결과는 표 1과 같다.The test results are shown in Table 1.
표 1 고체 상태 알루미늄 전해 커패시터 각 항목 성능 테스트 결과(16V680μF 코어)Table 1 Performance test results of each item of solid-state aluminum electrolytic capacitor (16V680μF core)
표 1의 시험 결과로부터 알 수 있듯이, 본 발명에서 제공하는 커패시터용 중합체로 제조된 고체 상태 전해 커패시터는 비교적 낮은 누설 전류값을 가지며, 최대가 7.3μA에 불과하다. 반면, 비교예 1 내지 4의 단량체로 제조된 고체 상태 전해 커패시터는 그 누설 전류값이 현저하게 크며 최소가 모두 12.5μA이다. 이는 인산 에스테르류 물질과 말단 캡핑제의 첨가가 고체 전해질의 알루미늄박에 대한 부식을 효과적으로 완화하며, 커패시터의 누설 전류를 낮추고 커패시터의 내전압 성능을 향상시켜 고체 상태 전해 커패시터의 성능 안정성을 보장하고 고체 상태 전해 커패시터의 사용 수명을 크게 향상시킬 수 있음을 설명한다.As can be seen from the test results in Table 1, the solid-state electrolytic capacitor made from the polymer for capacitors provided by the present invention has a relatively low leakage current value, with a maximum of only 7.3 μA. On the other hand, the solid-state electrolytic capacitors manufactured from the monomers of Comparative Examples 1 to 4 had significantly higher leakage current values, with a minimum of 12.5 μA. This means that the addition of phosphate ester-type materials and end capping agents effectively alleviates the corrosion of the aluminum foil in the solid electrolyte, lowers the leakage current of the capacitor and improves the withstand voltage performance of the capacitor, ensuring the performance stability of the solid-state electrolytic capacitor and solid-state electrolytic capacitor. It explains that the service life of electrolytic capacitors can be greatly improved.
비교예 1, 비교예 3 및 비교예 4의 시험 결과에서 알 수 있듯이, 인산 에스테르류 화합물과 말단 캡핑제는 모두 고체 전해질의 알루미늄박에 대한 부식을 완화하는 역할을 하며, 커패시터의 누설 전류를 낮춘다.As can be seen from the test results of Comparative Example 1, Comparative Example 3, and Comparative Example 4, both the phosphoric acid ester compound and the end capping agent play a role in alleviating corrosion of the aluminum foil of the solid electrolyte and lower the leakage current of the capacitor. .
상기 내용은 본 발명의 비교적 바람직한 실시예일 뿐이므로 본 발명을 제한하지 않는다. 또한 본 발명의 사상과 원칙 내에서 이루어진 모든 수정, 동등한 대체, 개선 등은 본 발명의 보호 범위에 포함되어야 한다.The above contents are only relatively preferred embodiments of the present invention and do not limit the present invention. Additionally, all modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.
Claims (10)
중합 단량체, 인산 에스테르류 화합물 및 말단 캡핑제를 포함하고,
상기 중합 단량체는 3,4-에틸렌디옥시티오펜류 중합 단량체이고,
상기 말단 캡핑제는 구조식 1로 표시되는 화합물을 포함하고,
구조식 1
여기에서 R4는 H 또는 탄소 원자수가 1 내지 6인 탄화수소기이고,
상기 조성물은,
중합 단량체 96 내지 99.9998부, 말단 캡핑제 0.0001 내지 1부, 인산 에스테르류 화합물 0.0001 내지 3부의 중량 성분을 포함하는 것을 특징으로 하는 조성물.In the composition,
Contains polymerization monomers, phosphoric acid ester compounds and end capping agents,
The polymerization monomer is a 3,4-ethylenedioxythiophene type polymerization monomer,
The end capping agent includes a compound represented by structural formula 1,
Structural formula 1
Here, R 4 is H or a hydrocarbon group having 1 to 6 carbon atoms,
The composition is,
A composition comprising 96 to 99.9998 parts of polymerizable monomers, 0.0001 to 1 part of an end capping agent, and 0.0001 to 3 parts of a phosphoric acid ester compound.
상기 말단 캡핑제는 메틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 에틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 이소프로필 3,4-에틸렌디옥시티오펜-2-카르복실레이트, 부틸 3,4-에틸렌디옥시티오펜-2-카르복실레이트 중 하나 이상을 포함하는 것을 특징으로 하는 조성물.According to paragraph 1,
The end capping agent is methyl 3,4-ethylenedioxythiophene-2-carboxylate, ethyl 3,4-ethylenedioxythiophene-2-carboxylate, propyl 3,4-ethylenedioxythiophene-2-carboxylate A composition comprising at least one of boxylate, isopropyl 3,4-ethylenedioxythiophene-2-carboxylate, and butyl 3,4-ethylenedioxythiophene-2-carboxylate.
상기 인산 에스테르류 화합물은 구조식 2로 표시되는 화합물을 포함하고,
구조식 2
여기에서 R1, R2 및 R3은 H 또는 수소 원자가 치환 또는 비치환된 탄소 원자수가 1 내지 6인 탄화수소기, 에테르기, 카르보닐기 또는 방향족기로부터 선택되고, R1, R2 및 R3은 동시에 H가 아닌 것을 특징으로 하는 조성물.According to paragraph 1,
The phosphoric acid ester compounds include compounds represented by structural formula 2,
Structural formula 2
Here, R 1 , R 2 and R 3 are H or a hydrogen atom selected from a substituted or unsubstituted hydrocarbon group, an ether group, a carbonyl group or an aromatic group having 1 to 6 carbon atoms, and R 1 , R 2 and R 3 are A composition characterized in that it is not H at the same time.
R1, R2 및 R3 중 2개는 서로 연결되어 고리를 형성하는 것을 특징으로 하는 조성물.According to paragraph 4,
A composition wherein two of R 1 , R 2 and R 3 are connected to each other to form a ring.
상기 인산 에스테르류 화합물은 트리메틸 포스페이트, 디메틸 포스페이트, 메틸 에틸 포스페이트, 트리에틸 포스페이트, 디에틸 포스페이트, 디메틸 에틸 포스페이트, 메틸 디에틸 포스페이트, 트리프로필 포스페이트, 트리프로파길 포스페이트, 디프로필 포스페이트, 트리부틸 포스페이트, 디부틸 포스페이트, 모노부틸 포스페이트 및 트리펜틸 포스페이트 중 하나 이상을 포함하는 것을 특징으로 하는 조성물.According to paragraph 4,
The phosphoric acid ester compounds include trimethyl phosphate, dimethyl phosphate, methyl ethyl phosphate, triethyl phosphate, diethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, tripropyl phosphate, tripropargyl phosphate, dipropyl phosphate, tributyl phosphate, A composition comprising one or more of dibutyl phosphate, monobutyl phosphate and tripentyl phosphate.
상기 중합 단량체는 구조식 3으로 표시되는 화합물을 포함하는 것을 특징으로 하는 조성물.
구조식 3According to paragraph 1,
A composition characterized in that the polymerization monomer includes a compound represented by structural formula 3.
Structural formula 3
제1항 및 제3항 내지 제7항 중 어느 한 항에 따른 조성물 중합을 통해 획득하는 것을 특징으로 하는 커패시터용 중합체.In the polymer for capacitors,
A polymer for capacitors, characterized in that it is obtained through polymerization of the composition according to any one of claims 1 and 3 to 7.
커패시터 소자와 상기 커패시터 소자 상에 부착된 음극 재료를 포함하고, 상기 음극 재료는 제8항에 따른 커패시터용 중합체를 포함하는 것을 특징으로 하는 커패시터.In a capacitor,
A capacitor comprising a capacitor element and a cathode material deposited on the capacitor element, the cathode material comprising a polymer for a capacitor according to claim 8.
상기 커패시터는 고체 상태 알루미늄 전해 커패시터 또는 고체 상태 탄탈륨 전해 커패시터인 것을 특징으로 하는 커패시터.According to clause 9,
A capacitor, characterized in that the capacitor is a solid-state aluminum electrolytic capacitor or a solid-state tantalum electrolytic capacitor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911303518.1A CN112979927B (en) | 2019-12-17 | 2019-12-17 | Composition, polymer for capacitor and capacitor |
| CN201911303518.1 | 2019-12-17 | ||
| PCT/CN2020/136011 WO2021121174A1 (en) | 2019-12-17 | 2020-12-14 | Composition, polymer for capacitor, and capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20220086613A KR20220086613A (en) | 2022-06-23 |
| KR102591669B1 true KR102591669B1 (en) | 2023-10-20 |
Family
ID=76342423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020227016295A KR102591669B1 (en) | 2019-12-17 | 2020-12-14 | Compositions, polymers for capacitors and capacitors |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7392143B2 (en) |
| KR (1) | KR102591669B1 (en) |
| CN (1) | CN112979927B (en) |
| WO (1) | WO2021121174A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113363078A (en) * | 2021-07-28 | 2021-09-07 | 深圳市金富康电子有限公司 | Solid-liquid mixed state winding type aluminum electrolytic capacitor and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5788127B1 (en) * | 2014-02-27 | 2015-09-30 | テイカ株式会社 | Oxidizing agent / dopant for conductive polymer production, solution thereof, conductive polymer produced using any of them, and electrolytic capacitor using the conductive polymer as electrolyte |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005037903A (en) * | 2003-06-30 | 2005-02-10 | Fuji Denki Gazo Device Kk | Electrophotographic photoreceptor and electrophotographic apparatus using the same |
| CN1816535A (en) * | 2003-06-30 | 2006-08-09 | 富士电机影像器材有限公司 | Quinone based compound, photosensitive article for electrophotography and electrophotographic device using the same |
| US7361728B1 (en) * | 2004-09-30 | 2008-04-22 | Tda Research, Inc. | Electrically conducting materials from branched end-capping intermediates |
| CN101486839B (en) * | 2008-01-18 | 2011-08-17 | 郑州泰达电子材料科技有限公司 | Conductive polymer composition, solid electrolyte and solid electrolyte capacitor using the conductive polymer |
| CN101350252B (en) * | 2008-09-17 | 2012-06-27 | 中国振华（集团）新云电子元器件有限责任公司 | Conductive polyelectrolyte polymerization liquid prescription stored in normal temperature steadily and use thereof |
| JP2010095469A (en) * | 2008-10-16 | 2010-04-30 | Tama Kagaku Kogyo Kk | Method for producing 3,4-dialkoxy (or alkylenedioxy) thiophene |
| WO2012112676A2 (en) * | 2011-02-15 | 2012-08-23 | Kemet Electronics Corporation | Materials and methods for improving corner and edge coverage of solid electrolytic capacitors |
| CN103295785B (en) * | 2012-02-22 | 2016-05-18 | 尼吉康株式会社 | Solid electrolytic capacitor |
| CN102779653B (en) * | 2012-07-18 | 2015-09-02 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of two step manufacture methods of high-conductivity polymer electrolytic capacitor |
| JP6250340B2 (en) * | 2013-09-18 | 2017-12-20 | テイカ株式会社 | Hole transport material, electroluminescence device and thin film solar cell |
| TWI506031B (en) * | 2014-11-05 | 2015-11-01 | Ind Tech Res Inst | Ferric salt oxidant, solid electrolytic capacitor, and method for fabricating the same |
| JP2017101104A (en) * | 2015-11-30 | 2017-06-08 | Ｎｅｃトーキン株式会社 | Conductive polymer, conductive polymer solution, conductive polymer material, electrolytic capacitor, and method of manufacturing the same |
| JP6977246B2 (en) * | 2015-12-04 | 2021-12-08 | 東ソー株式会社 | Antistatic thin film and antistatic aqueous solution |
| US10737101B2 (en) * | 2016-11-14 | 2020-08-11 | Avx Corporation | Medical device containing a solid electrolytic capacitor |
| TW201908363A (en) * | 2017-07-12 | 2019-03-01 | 鈺邦科技股份有限公司 | Polymer composite material applied to a solid capacitor, capacitor package structure using the same and manufacturing method thereof |
| CN109741858B (en) * | 2018-12-04 | 2020-07-14 | 广州中国科学院先进技术研究所 | Green printed all-polymer flexible transparent electrode and preparation method thereof |
-
2019
- 2019-12-17 CN CN201911303518.1A patent/CN112979927B/en active Active
-
2020
- 2020-12-14 WO PCT/CN2020/136011 patent/WO2021121174A1/en active Application Filing
- 2020-12-14 KR KR1020227016295A patent/KR102591669B1/en active IP Right Grant
- 2020-12-14 JP JP2022528069A patent/JP7392143B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5788127B1 (en) * | 2014-02-27 | 2015-09-30 | テイカ株式会社 | Oxidizing agent / dopant for conductive polymer production, solution thereof, conductive polymer produced using any of them, and electrolytic capacitor using the conductive polymer as electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7392143B2 (en) | 2023-12-05 |
| WO2021121174A1 (en) | 2021-06-24 |
| JP2023502945A (en) | 2023-01-26 |
| KR20220086613A (en) | 2022-06-23 |
| CN112979927A (en) | 2021-06-18 |
| CN112979927B (en) | 2021-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2622616B1 (en) | A method for improving electrical parameters in capacitors comprising pedot/pss as a solid electrolyte through a polyalkylene glycol | |
| CN110692115B (en) | Hybrid aluminum electrolytic capacitor and manufacturing method thereof | |
| CN110730994B (en) | Hybrid aluminum electrolytic capacitor and manufacturing method thereof | |
| CN105405661A (en) | Manufacturing method of solid-state electrolytic capacitor | |
| CN112563033B (en) | Novel solid-state aluminum electrolytic capacitor and preparation method thereof | |
| KR102591669B1 (en) | Compositions, polymers for capacitors and capacitors | |
| JP2015129309A (en) | Electrolyte material formulation, electrolyte material composition formed therefrom and use thereof | |
| CN109786137B (en) | Preparation method of solid capacitor | |
| US8197886B2 (en) | Method of manufacturing solid electrolytic capacitor | |
| TW201131601A (en) | Solid electrolytic capacitor and method for producing same | |
| JP2019172770A (en) | Conductive polymer composition, manufacturing method of conductive polymer thin film | |
| CN111909362A (en) | Conductive polymer, capacitor and preparation method thereof | |
| JP5656127B2 (en) | Electrolyte material composition, electrolyte material composition formed therefrom, and use thereof | |
| JP6030628B2 (en) | Iron salt oxidizing agent composition, solid electrolytic capacitor, and method for producing the same | |
| CN113113234B (en) | Method for reducing core loss of PEDOT solid aluminum electrolytic capacitor | |
| CN112582175B (en) | Solid-state aluminum electrolytic capacitor and preparation method thereof | |
| CN116364436A (en) | Manufacturing method of solid-liquid mixed aluminum electrolytic capacitor | |
| CN102321341B (en) | Conductive polymer material and capacitor comprising the same | |
| CN110853927A (en) | Preparation method of low-leakage-current solid aluminum capacitor | |
| CN113192757A (en) | Method for reducing core loss and high-frequency impedance of PEDOT solid aluminum electrolytic capacitor | |
| JP2024509119A (en) | Dispersion for aluminum electrolytic capacitors and aluminum electrolytic capacitors | |
| CN111875935A (en) | Conductive polymer composition and solid aluminum electrolytic capacitor | |
| CN102321342B (en) | Conductive polymer material and capacitor comprising same | |
| CN118299187A (en) | Solid-liquid mixed aluminum electrolytic capacitor and preparation method thereof | |
| CN115410828A (en) | Method for improving high-temperature flashover voltage of working electrolyte of medium-high voltage aluminum electrolytic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |