JPS6136540B2 - - Google Patents
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- Publication number
- JPS6136540B2 JPS6136540B2 JP8876078A JP8876078A JPS6136540B2 JP S6136540 B2 JPS6136540 B2 JP S6136540B2 JP 8876078 A JP8876078 A JP 8876078A JP 8876078 A JP8876078 A JP 8876078A JP S6136540 B2 JPS6136540 B2 JP S6136540B2
- Authority
- JP
- Japan
- Prior art keywords
- complex salt
- polymer
- conductive polymer
- film
- polymer composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 39
- 229920001940 conductive polymer Polymers 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 33
- 125000000524 functional group Chemical group 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 229920006158 high molecular weight polymer Polymers 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 23
- 239000003990 capacitor Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000002001 electrolyte material Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N cinnamyl alcohol Chemical compound OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- -1 vinylpyridine Chemical compound 0.000 description 2
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Description
本発明は電導体の製法に関し、とくに固体電解
コンデンサの電解質材料に適した電導性重合体組
成物の製造方法に関する。
電導性重合体組成物を電子部品材料に適用する
ためには、(イ)電導度が高いことは言うまでもな
く、さらに(ロ)熱的、経時的に安定であること、(ハ)
成膜性、密着性に優れ、機械的、熱的シヨツクに
よる剥離、あるいは経時的な剥離の少ないことが
要求される。従来の重合体および７・７・８・８
−テトラシアノキノジメタン（以下、TCNQと略
す）錯塩より成る電導性重合体組成物の中にも、
以上の条件を一応満足し、たとえば固体電解コン
デンサの固体電解質材料を形成し得るものもあ
る。しかし、一般に熱的な安定性、成膜性、密着
性にやや難があり、近年の電子部品の高信頼化要
求には即応しかねているのが実情である。
本発明の目的は、高電導性、高安定性であり、
しかも成膜性、密着性に富んだ電導性重合体組成
物の製造方法を提供することにある。
本発明によれば、官能基を有する高分子重合体
にTCNQ錯塩を分散させ、フイルム形成時、ある
いはフイルム形成後に多官能性の架橋剤で架橋、
硬化させ、機械的な特性を向上させたことを特徴
とする導電性重合体組成物の製造方法が得られ
る。
本発明による電導性重合体組成物は、従来の重
合体とTCNQ錯塩とから成る電導性重合体組成物
と比較し、三次すなわち、重合体主鎖間の架橋反
応による網目構造化により、成膜性および熱安定
性が向上する。したがつて固体電解コンデンサの
電解質材料、印刷された配線導体、抵抗体、その
他電子部品材料に適用するに充分な電導度、安定
性、成膜性を兼ねそなえている。官能基を有する
重合体としては、たとえばｐ−アミノスチレンの
重合体のように、官能基を有する単量体の単独重
合体、またはTCNQ錯塩との相溶性の良い、たと
えばビニルピリジンなどの窒素原子を有する単量
体と官能基を有する単量体との共重合体などがあ
る。本発明による電導性重合体組成物は、TCNQ
錯塩、および前述の重合体あるいは共重合体およ
びジイソシアネートなどの多官能性の架橋剤の三
者を溶解する溶液からフイルムを形成、これを加
熱、硬化させて得る。TCNQ錯塩と重合体からフ
イルムを形成し、その後架橋剤を含浸、硬化させ
て、本発明の電導性重合体組成物を得ることもで
きる。
TCNQ錯塩を重合体に分散させ、均一な電導性
重合体組成物を形成するには、両者の間に適当な
相互作用の存在が要求される。一般にTCNQ錯塩
を重合体に分散させ、溶液からフイルムを形成す
ると、フイルム形成時にTCNQ錯塩の結晶が析
出、成長する。TCNQ錯塩の結晶が析出すると、
電導性重合体組成物の電導度分布が不均一とな
り、高度な信頼性を要求される電子材料としては
不適当である。TCNQ錯塩と重合体との相互作用
としては、日本化学会誌1977、(9)P1385にあるよ
うに電荷移動相互作用等が考えられている。均一
な電導性重合体組成物としては、TCNQ錯塩とビ
ニルピリジンの重合体あるいは共重合体等の窒素
を含む重合体との組合せ等が発明され、効果を上
げている。
しかし、TCNQ錯塩と重合体との相互作用は電
導性重合体組成物の均一化に寄与している反面、
電導性重合体組成物の安定性を減退させている。
日本化学会誌1977(9)P1388のFig5に見られるよう
に、TCNQ錯塩およびこれとの相互作用を有する
重合体とから成る電導性重合体組成物では、重合
体の組成比の増大とともに比抵抗の経時変化が増
大し、熱安定性も低下して行く傾向が認められ
る。さらに、相互作用が強くなるとこの傾向も増
大する。したがつて、安定性を確保するために
は、TCNQ錯塩の組成比が高い方が好ましい。
電導性重合体組成物の電導性と組成比の間に
も、同様な傾向が認められる。すなわち、同じく
日本化学会誌1977(9)、P1387に見られるように、
重合体の組成比の増大とともに比抵抗が増大し、
TCNQ錯塩の組成比の増大とともに比抵抗は低下
する。したがつて、安定性を向上させるためにも
電導性を向上させるためにもTCNQ錯塩の組成比
を増大させる必要がある。しかし、これは電導性
重合体組成物膜の成膜性、密着性を向上させる方
向とは相反している。バインダーとなる重合体組
成比を低下させながら、しかも成膜性、密着性を
向上させるためには、本発明が著しい効果を示
す。
本発明の電導性重合体組成物の一応用例とし
て、固体電解コンデンサの半導体層としての応用
が挙げられる。従来の固体電解コンデンサの固体
電解質としては、通常、二酸化マンガンが用いら
れており、これは主に、硝酸マンガンの熱分解に
より形成されている。この時に加わる高熱および
発生するガスのため、誘電体であるTa、Al、等
の弁作用を有する金属の酸化皮膜は損傷を受け、
この損傷を修復するために再度陽極酸化、熱分解
を行う必要がある。したがつて、高い信頼性を得
るためにはこの修復操作をさらに数回繰り返す必
要があり、作業工程が複雑となるばかりでなく、
酸化皮膜を形成させる時の印加電圧に比し、耐電
圧が低下し、固体電解コンデンサの小型大容量
比、高耐圧化の障害となつている。さらに上述の
修復操作を数回繰り返しても酸化皮膜の損傷を完
全に修復することはできない。特に、もれ電流を
小さく抑えることが困難であつた。これらの欠点
を捕うために、電導性重合体組成物を用いると、
高温を負荷せずに固体電解質を形成することがで
きるため、酸化皮膜の損傷がなく、再度陽極酸化
をする必要がない。従つて、作業工程は大幅に短
縮化され、耐電圧は上昇し、漏れ電流は低下す
る。具体的には、陽極酸化されたTa、Al等の弁
作用を有する金属の細孔に電導性重合体組成物の
溶液をしみ込ませ、溶媒を乾燥除去して、Taあ
るいはAlの酸化皮膜を電導性重合体組成物で覆
うものである。ここでは、電導性重合体組成物の
溶液が細孔の奥までしみ込むことが必要条件であ
り、重合体の分子量が大きいと粘度が高くなり、
形状的にも進入しにくくなるので、分子量は数万
程度以下であることが望ましい。均一性を増すと
いう見地から、TCNQ錯塩と重合体との組合せを
決定した場合、電導性、安定性等を考慮し、(a)
TCNQ錯塩の組成比は大きい方が好ましい、(b)重
合体の分子量は小さい方が好ましい。しかし、電
導性重合体の成膜性、密着性、さらに熱安定性を
増すには重合体の組成比を増やすか、重合体の分
子量を増大させることが必要であり、これは上述
の方向と相反している。したがつて、TCNQ錯塩
と重合体の組合せが決定すると、その成膜性、密
着性だけを独立に向上させることは困難である。
しかも、均一な電導性重合体組成物を形成し得る
TCNQ錯塩と重合体との組合せは極めて限定され
ていることから、電導性重合体組成物の成膜性、
密着性をさらに向上させることは従来困難であつ
た。
本発明では、均一な膜を形成し得るTCNQ錯塩
と重合体との組合せに着目し、均一性をくずさな
い限度内で重合体に官能基を持たせ、あるいは、
官能基を有する単量体と共重合させ、これに
TCNQ錯塩を分散させ、重合体あるいは共重合体
に導入した官能基を利用し、三次元化するもので
ある。この方法では、TCNQ錯塩と重合体との組
成比あるいは重合体の分子量を変化させずに、電
導性重合体組成物の成膜性、密着性を向上させる
ことができる。すなわち、均一性、電導性、安定
性をそこなわずに成膜性、密着性を独立に向上す
ることができる。さらに、重合体の三次元化によ
り熱安定性も向上する。
さらに具体的には、所定量のTCNQ錯塩、官能
基を有する重合体あるいは共重合体および多官能
性の架橋剤をＮ・Ｎジメチルホルムアミド（以下
DMFと略す。）等の溶媒に完全に溶解する。この
溶液を、基盤上に塗布又は含浸、乾燥し、所定の
電導性重合体組成物を電解質として形成する。溶
液状態においては、官能基濃度が希薄であること
から反応速度が遅く、重合体の三次元化反応は進
行せず、細孔の細部にまで溶液をしみ込ますこと
が可能である。DMFの蒸発とともに電導性重合
体組成物の膜が形成して行くが、同時に、官能基
濃度も上昇し、架橋反応は促進され、形成された
膜は三次元化され、成膜性、密着性さらには熱安
定性も上昇する。
TCNQ錯塩と重合体とから電導性の膜を形成
し、その後、膜に架橋剤を含浸し、架橋、三次元
化することも可能である。また、本発明の三次元
化の効果は固体電解コンデンサの電解質材料のみ
ならず、広く、電子部品、電気部品材料に適用し
た場合にも発現するものである。
以下に実施例を示し、本発明をさらに詳細に説
明する。
実施例 １
Ｎメチルアクリジニウム−TCNQ2錯塩800mg、
４ビニルピリジン（4VP）とパラアミノメチルス
チレン（PAmMSt）との共重合体（共重合組成
比4VP／PAmMSt＝90／10）200mg、ヘキサメチ
レンジイソシアネート（HMDI）16mgを38c.c.の
DMFに溶解し、60℃、30分間加熱した後、DMF
をエバポレートし、乾固した。これを再びDMF
に溶解し、不溶部を分離、充分乾燥させ、その収
量を測定した。TCNQ錯塩、共重合体および架橋
剤を混合し、加熱反応、溶媒除去した時点で三次
元化反応がおこつていれば、その後TCNQ錯塩、
未反応共重合体、未反応架橋剤は再びDMFに溶
解するが、三次元化した共重合体はDMFには不
溶となる。従つて、DMF不溶部の量は、共重合
体の三次元化した量を意味する。
The present invention relates to a method for producing an electrical conductor, and particularly to a method for producing a conductive polymer composition suitable as an electrolyte material for a solid electrolytic capacitor. In order to apply a conductive polymer composition to an electronic component material, it must not only (a) have high conductivity, but also (b) be thermally and temporally stable; and (c)
It is required to have excellent film formability and adhesion, and to have little peeling due to mechanical or thermal shock or peeling over time. Conventional polymers and 7, 7, 8, 8
- Among conductive polymer compositions consisting of tetracyanoquinodimethane (hereinafter abbreviated as TCNQ) complex salts,
Some materials satisfy the above conditions and can be used as solid electrolyte materials for solid electrolytic capacitors, for example. However, they generally have some difficulties in thermal stability, film formability, and adhesion, and the reality is that they cannot immediately meet the recent demands for high reliability of electronic components. The purpose of the present invention is high conductivity, high stability,
Moreover, it is an object of the present invention to provide a method for producing a conductive polymer composition having excellent film-forming properties and adhesive properties. According to the present invention, a TCNQ complex salt is dispersed in a polymer having a functional group, and crosslinked with a polyfunctional crosslinking agent during or after film formation.
A method for producing a conductive polymer composition characterized in that it is cured and has improved mechanical properties is obtained. The conductive polymer composition according to the present invention, in comparison with conventional conductive polymer compositions composed of a polymer and a TCNQ complex salt, has a tertiary structure, that is, a network structure formed by a crosslinking reaction between the main chains of the polymer. properties and thermal stability are improved. Therefore, it has sufficient conductivity, stability, and film formability to be applied to electrolyte materials for solid electrolytic capacitors, printed wiring conductors, resistors, and other electronic component materials. Examples of the polymer having a functional group include a homopolymer of a monomer having a functional group, such as a polymer of p-aminostyrene, or a nitrogen atom such as vinylpyridine, which has good compatibility with the TCNQ complex salt. There are copolymers of a monomer having a functional group and a monomer having a functional group. The conductive polymer composition according to the present invention is TCNQ
A film is formed from a solution in which the complex salt, the aforementioned polymer or copolymer, and a polyfunctional crosslinking agent such as a diisocyanate are dissolved, and the film is heated and cured. The conductive polymer composition of the present invention can also be obtained by forming a film from the TCNQ complex salt and the polymer, and then impregnating it with a crosslinking agent and curing it. In order to disperse the TCNQ complex salt in a polymer and form a uniform conductive polymer composition, the presence of appropriate interaction between the two is required. Generally, when a TCNQ complex salt is dispersed in a polymer and a film is formed from the solution, crystals of the TCNQ complex salt precipitate and grow during film formation. When crystals of TCNQ complex salt precipitate,
The electrical conductivity distribution of the electrically conductive polymer composition becomes non-uniform, making it unsuitable for electronic materials requiring high reliability. As for the interaction between the TCNQ complex salt and the polymer, charge transfer interaction and the like are considered as described in Journal of the Chemical Society of Japan 1977, (9) P1385. As a uniform conductive polymer composition, a combination of a TCNQ complex salt and a nitrogen-containing polymer such as a vinylpyridine polymer or copolymer has been invented and has been effective. However, while the interaction between the TCNQ complex salt and the polymer contributes to the homogenization of the conductive polymer composition,
This reduces the stability of the conductive polymer composition.
As seen in Fig. 5 of Journal of the Chemical Society of Japan 1977(9) P1388, in a conductive polymer composition consisting of a TCNQ complex salt and a polymer that interacts with it, the specific resistance increases as the composition ratio of the polymer increases. There is a tendency that the change over time increases and the thermal stability also decreases. Moreover, this tendency increases as the interaction becomes stronger. Therefore, in order to ensure stability, it is preferable that the composition ratio of the TCNQ complex salt is high. A similar tendency is observed between the conductivity and the composition ratio of the conductive polymer composition. In other words, as also seen in Journal of the Chemical Society of Japan 1977(9), P1387,
As the composition ratio of the polymer increases, the specific resistance increases,
The specific resistance decreases as the composition ratio of TCNQ complex salt increases. Therefore, it is necessary to increase the composition ratio of the TCNQ complex salt in order to improve stability and conductivity. However, this is contrary to the direction of improving the film formability and adhesion of the conductive polymer composition film. The present invention exhibits a remarkable effect in improving film formability and adhesion while reducing the composition ratio of the polymer serving as the binder. One application example of the conductive polymer composition of the present invention is application as a semiconductor layer of a solid electrolytic capacitor. Manganese dioxide is usually used as the solid electrolyte in conventional solid electrolytic capacitors, and this is mainly formed by thermal decomposition of manganese nitrate. Due to the high heat applied and the gas generated at this time, the oxide film of the valve metal such as Ta, Al, etc., which is a dielectric, is damaged.
In order to repair this damage, it is necessary to perform anodization and thermal decomposition again. Therefore, in order to obtain high reliability, it is necessary to repeat this repair operation several more times, which not only complicates the work process but also
Compared to the voltage applied when forming the oxide film, the withstand voltage is lower, which is an obstacle to achieving small size, large capacity, and high withstand voltage of solid electrolytic capacitors. Furthermore, even if the above-mentioned repair operation is repeated several times, the damage to the oxide film cannot be completely repaired. In particular, it has been difficult to suppress leakage current. To address these drawbacks, using conductive polymer compositions,
Since a solid electrolyte can be formed without applying high temperatures, there is no damage to the oxide film and there is no need to perform anodic oxidation again. Therefore, the working process is significantly shortened, the withstand voltage increases, and the leakage current decreases. Specifically, a solution of a conductive polymer composition is infiltrated into the pores of an anodized metal such as Ta or Al that has valve action, and the solvent is dried and removed to make the oxide film of Ta or Al conductive. It is covered with a polymer composition. Here, the necessary condition is that the solution of the conductive polymer composition penetrates deep into the pores, and the larger the molecular weight of the polymer, the higher the viscosity.
Since it becomes difficult to enter due to the shape, it is desirable that the molecular weight is about tens of thousands or less. When determining the combination of TCNQ complex salt and polymer from the standpoint of increasing uniformity, considering electrical conductivity, stability, etc., (a)
The composition ratio of the TCNQ complex salt is preferably larger, and the molecular weight of the (b) polymer is preferably smaller. However, in order to improve the film formability, adhesion, and thermal stability of conductive polymers, it is necessary to increase the composition ratio of the polymer or increase the molecular weight of the polymer. It's contradictory. Therefore, once the combination of TCNQ complex salt and polymer is determined, it is difficult to independently improve its film formability and adhesion.
Moreover, it is possible to form a uniform conductive polymer composition.
Since the combinations of TCNQ complex salts and polymers are extremely limited, the film-forming properties of conductive polymer compositions are
Conventionally, it has been difficult to further improve adhesion. In the present invention, we focus on the combination of TCNQ complex salt and polymer that can form a uniform film, and add functional groups to the polymer within the limit that does not destroy the uniformity, or
Copolymerize with a monomer having a functional group, and add
The TCNQ complex salt is dispersed and functional groups introduced into the polymer or copolymer are used to make it three-dimensional. With this method, the film formability and adhesion of the conductive polymer composition can be improved without changing the composition ratio of the TCNQ complex salt and the polymer or the molecular weight of the polymer. That is, film formability and adhesion can be independently improved without impairing uniformity, conductivity, and stability. Furthermore, thermal stability is also improved by making the polymer three-dimensional. More specifically, a predetermined amount of TCNQ complex salt, a polymer or copolymer having a functional group, and a polyfunctional crosslinking agent are mixed with N.N dimethylformamide (hereinafter referred to as
Abbreviated as DMF. ) and other solvents. This solution is applied or impregnated onto a substrate and dried to form a predetermined conductive polymer composition as an electrolyte. In a solution state, the reaction rate is slow because the concentration of functional groups is dilute, and the three-dimensional reaction of the polymer does not proceed, making it possible for the solution to penetrate into the details of the pores. A film of the conductive polymer composition is formed as DMF evaporates, but at the same time, the concentration of functional groups increases, the crosslinking reaction is promoted, and the formed film becomes three-dimensional, improving film formability and adhesion. Furthermore, thermal stability also increases. It is also possible to form a conductive film from a TCNQ complex salt and a polymer, and then impregnate the film with a crosslinking agent to crosslink it and make it three-dimensional. Further, the three-dimensional effect of the present invention is manifested not only when applied to electrolyte materials of solid electrolytic capacitors, but also when applied to a wide range of electronic components and electrical component materials. EXAMPLES The present invention will be explained in further detail by way of Examples below. Example 1 N-methylacridinium-TCNQ dicomplex salt 800 mg,
200 mg of a copolymer of 4-vinylpyridine (4VP) and para-aminomethylstyrene (PAmMSt) (copolymer composition ratio 4VP/PAmMSt = 90/10) and 16 mg of hexamethylene diisocyanate (HMDI) were added to 38 c.c.
After dissolving in DMF and heating at 60℃ for 30 minutes, DMF
was evaporated to dryness. DMF this again
The insoluble portion was separated and thoroughly dried, and the yield was measured. If a three-dimensional reaction occurs when the TCNQ complex salt, copolymer, and crosslinking agent are mixed, heated, and the solvent removed, then the TCNQ complex salt,
The unreacted copolymer and unreacted crosslinking agent dissolve in DMF again, but the three-dimensional copolymer becomes insoluble in DMF. Therefore, the amount of DMF-insoluble portion means the amount of three-dimensional copolymer.
【表】
第１表に見られるように、不溶部の収量は共重
合体と架橋剤の重量の和のほぼ等しく、三次元化
反応は完全にすすんでいることは明らかである。
ここで、DMF溶液を蒸発乾固する以前には不溶
部は認められないことから、DMFを蒸発乾固す
る際に溶液が濃縮され、官能基濃度が上昇したた
めに架基反応が進行したと解釈できる。共重合体
としてヒドロキシアルキル基、アミノ基等の官能
基を有する単量体と、4VP、2VP、アクリロニト
リル等窒素原子を有する単量体との共重合体、こ
れらに、この他の単量体の加わつた多元共重合体
あるいは、前述の官能基を有する単量体の単独重
合体（ホモポリマー）にも同様な傾向が認めら
れ、一般に、本発明の方法により架橋、三次元化
が可能であり、成膜性の向上が認められる。ま
た、本実施例では活性水素とイソシアネートとの
反応を取り上げたが、この他エポキシと活性水素
の反応、アミンと酸又は酸無水物の反応、その他
これに類似の多くの縮合反応を利用しても本発明
の効果を発現することができる。
実施例 ２
Ｎメチルアクリジニウム−TCNQ2（MAc−
TCNQ2）錯塩85に対し、4VPとヒドロキシメチル
スチレン（HMSt）から成る共重合体（共重合組
成比85／15）15共重合体の官能基（ヒドロキシメ
チル基）と官能基濃度にして等モルの架橋剤
HMDIをDMF溶液とし、これをガラス基盤上に
流延、温度60℃で乾燥し、電導性重合体組成物の
膜を形成した。形成された電導性重合体組成物の
膜にはMAc−TCNQ2錯塩の結晶の析出は認めら
れなかつた。形成された膜は溶剤に不溶であり、
極めて均一、良好であつた。[Table] As shown in Table 1, the yield of the insoluble portion is approximately equal to the sum of the weights of the copolymer and the crosslinking agent, and it is clear that the three-dimensional reaction has proceeded completely.
Here, since no insoluble parts were observed before the DMF solution was evaporated to dryness, it is interpreted that the cross-group reaction progressed because the solution was concentrated when DMF was evaporated to dryness and the concentration of functional groups increased. can. A copolymer of a monomer having a functional group such as a hydroxyalkyl group or an amino group, and a monomer having a nitrogen atom such as 4VP, 2VP, or acrylonitrile. A similar tendency is observed for multi-component copolymers or homopolymers of monomers having the above-mentioned functional groups, and in general, crosslinking and three-dimensionalization are possible by the method of the present invention. , an improvement in film formability was observed. In addition, although this example deals with the reaction between active hydrogen and isocyanate, it is also possible to use the reaction between epoxy and active hydrogen, the reaction between amine and acid or acid anhydride, and many other condensation reactions similar to this. can also exhibit the effects of the present invention. Example 2 N-methylacridinium-TCNQ 2 (MAc-
TCNQ 2 ) Complex salt 85 is equivalent to the functional group concentration (hydroxymethyl group) of a copolymer (copolymer composition ratio 85/15) 15 consisting of 4VP and hydroxymethylstyrene (HMSt) in terms of functional group concentration. crosslinking agent
A DMF solution of HMDI was cast on a glass substrate and dried at a temperature of 60°C to form a film of the conductive polymer composition. No crystal precipitation of MAc-TCNQ 2 complex salt was observed in the formed film of the conductive polymer composition. The formed film is insoluble in solvents,
It was extremely uniform and good.
【表】
第２表に見られるように、形成された膜の電導
度は、従来の三次元化しないP4VP−MAc.
TCNQ2とほぼ同等であり、熱分解温度は約10℃
上昇した。すなわち、電導性、安定性等の特性は
従来通り維持しつつ成膜性、密着性さらには熱安
定性を向上することができた。
同様な結果が、4VPとPAmMStの共重合体、
4VPとヒドロキシエチルメタアクリレートとの共
重合体等にも認められ、本発明の効果が認められ
た。
実施例 ３
MAc−TCNQ2錯塩85に対し、種々の重合体あ
るいは共重合体15、これら重合体の官能基と等モ
ルの架橋剤HMDIとをDMFに溶解する。この溶
液に陽極酸化したTa素子を浸漬、乾燥する。こ
の浸漬、乾燥の操作を繰り返し、Ta酸化皮膜上
に固体電解質層を形成したのち、陰極電極を取り
出し、外装処理して固体電解コンデンサを形成し
た。そのときの諸特性を第３表に示す。ここで、
P4VPは４ビニルピリジンの単独重合体、4VP−
HMStは４ビニルピリジンとヒドロキシメチルス
チレンの共重合体、4VP−PAmMStは4VPとＰ−
アミノメチルスチレンの共重合体、4VP−HEMA
は4VPとヒドロキシエチルメタアクリレートとの
共重合体である。[Table] As shown in Table 2, the conductivity of the formed film is higher than that of conventional P4VP-MAc, which is not three-dimensional.
Almost equivalent to TCNQ 2 , thermal decomposition temperature is approximately 10℃
Rose. That is, it was possible to improve film formability, adhesion, and thermal stability while maintaining properties such as conductivity and stability as before. Similar results were obtained for copolymers of 4VP and PAmMSt,
This was also observed in copolymers of 4VP and hydroxyethyl methacrylate, and the effects of the present invention were observed. Example 3 MAc-TCNQ 2 complex salt 85, various polymers or copolymers 15, and equimolar amounts of the functional groups of these polymers and the crosslinking agent HMDI are dissolved in DMF. The anodized Ta element is immersed in this solution and dried. After repeating this dipping and drying operation to form a solid electrolyte layer on the Ta oxide film, the cathode electrode was taken out and packaged to form a solid electrolytic capacitor. Table 3 shows the various characteristics at that time. here,
P4VP is a homopolymer of 4 vinyl pyridine, 4VP-
HMSt is a copolymer of 4vinylpyridine and hydroxymethylstyrene, and 4VP-PAmMSt is a copolymer of 4VP and P-
Aminomethylstyrene copolymer, 4VP-HEMA
is a copolymer of 4VP and hydroxyethyl methacrylate.
【表】
第３表に見られるように、架橋三次元化した試
料は容量の出現が大きく、tanδが小さい。さら
に、高温負荷寿命試験の結果、1000時間後の容量
変化率が小さい。これは、共重合体の三次元化に
より電導性重合体組成物の成膜性、密着性が向上
し、Ta酸化皮膜との接触が良好となつたために
容量が出現し、tanδが小さくなり、剥離の減少
により、容量変化率が低下したものである。固体
電解質の剥離の減少には、三次元化による電導性
重合体組成物の熱安定性向上も寄与している。上
記以外の特性についても、従来の電導性重合体組
成物を用いた固体電解コンデンサの特性と比較
し、劣るものは全く無く、従来の無機化合物を用
いた固体電解コンデンサに比較し、高耐圧、小型
大容量、低漏れ電流、高耐逆電圧等数々の利点を
有していることは言うまでもない。なお、実施例
ではタンタルの固体電解コンデンサについてその
効果を述べたが、アルミやニオブなどの他の弁作
用を有する金属の酸化皮膜から形成される固体電
解コンデンサについても本発明は同様に極めてす
ぐれた効果が得られることを確認した。
また、本発明による電導性重合体組成物を固体
電解コンデンサの電解質材料以外にも、たとえば
印刷された配線導体、抵抗体、その他の電子部品
材料に適用した場合にも優れた電導性、安定性、
成膜性、密着性を示し、著しい効果を発現する。[Table] As seen in Table 3, the three-dimensional crosslinked sample has a large capacity and a small tan δ. Furthermore, as a result of a high-temperature load life test, the rate of change in capacity after 1000 hours was small. This is due to the three-dimensional copolymerization, which improves the film-forming properties and adhesion of the conductive polymer composition, and improves contact with the Ta oxide film, resulting in the appearance of capacity and a decrease in tanδ. The capacitance change rate decreased due to the decrease in peeling. Improvement in the thermal stability of the conductive polymer composition due to three-dimensionalization also contributes to the reduction in peeling of the solid electrolyte. In terms of properties other than those listed above, there is no inferiority at all compared to the properties of solid electrolytic capacitors using conventional conductive polymer compositions, and compared to solid electrolytic capacitors using conventional inorganic compounds, they have higher withstand voltage, Needless to say, it has many advantages such as small size, large capacity, low leakage current, and high reverse voltage resistance. In addition, although the effects of tantalum solid electrolytic capacitors have been described in the examples, the present invention is also extremely effective for solid electrolytic capacitors formed from oxide films of other valve-acting metals such as aluminum and niobium. We confirmed that it was effective. Furthermore, when the conductive polymer composition of the present invention is applied not only to electrolyte materials for solid electrolytic capacitors, but also to printed wiring conductors, resistors, and other electronic component materials, it exhibits excellent conductivity and stability. ,
It exhibits excellent film-forming properties and adhesion, and exhibits remarkable effects.
Claims (1)
ノキノジメタン錯塩を分散させて得る電導性重合
体組成物の製造方法において、前記高分子重合体
がアミノ基、イソシアネート基、ヒドロキシアル
キル基、エポキシ基等の反応性に富む官能基を有
しており、これに前記７・７・８・８−テトラシ
アノキノジメタン錯塩を両者の共通溶媒中で分散
させた後、溶媒を除去する工程あるいは溶媒除去
後、前記官能基との反応性に富む官能基を少なく
とも２個有する架橋剤で前記高分子重合体を三次
元化することを特徴とした電導性重合体組成物の
製造方法。1. A method for producing a conductive polymer composition obtained by dispersing a 7,7,8,8-tetracyanoquinodimethane complex salt in a polymer, wherein the polymer contains amino groups, isocyanate groups, hydroxyalkyl The 7,7,8,8-tetracyanoquinodimethane complex is dispersed in a common solvent for both, and then the solvent is removed. or after removing the solvent, the high molecular weight polymer is made three-dimensional using a crosslinking agent having at least two functional groups highly reactive with the functional group. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8876078A JPS5516034A (en) | 1978-07-19 | 1978-07-19 | Conductive polymer composition and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8876078A JPS5516034A (en) | 1978-07-19 | 1978-07-19 | Conductive polymer composition and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5516034A JPS5516034A (en) | 1980-02-04 |
| JPS6136540B2 true JPS6136540B2 (en) | 1986-08-19 |
Family
ID=13951826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8876078A Granted JPS5516034A (en) | 1978-07-19 | 1978-07-19 | Conductive polymer composition and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5516034A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58105363U (en) * | 1982-01-07 | 1983-07-18 | 関 鉄夫 | Wooden golf club head |
| JPS60132573A (en) * | 1983-12-20 | 1985-07-15 | 旭テック株式会社 | Insert for golf club head |
| JPS61176372A (en) * | 1985-01-29 | 1986-08-08 | ヤマハ株式会社 | Club head for golf |
| JPS63153076A (en) * | 1986-12-17 | 1988-06-25 | 株式会社 遠藤製作所 | Head for golf club |
| US4768787A (en) * | 1987-06-15 | 1988-09-06 | Shira Chester S | Golf club including high friction striking face |
-
1978
- 1978-07-19 JP JP8876078A patent/JPS5516034A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5516034A (en) | 1980-02-04 |
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