JP2006225454A - Polyimide-based resin - Google Patents
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Abstract
Description
本発明は新規なポリイミド系樹脂に関する。特に、耐熱性や親水性が強く、密着性や顔料分散性に優れ、電磁波遮蔽、導電インキ、磁気記録媒体などのバインダーに有用なポリイミド系樹脂に関する。 The present invention relates to a novel polyimide resin. In particular, the present invention relates to a polyimide resin having strong heat resistance and hydrophilicity, excellent adhesion and pigment dispersibility, and useful as a binder for electromagnetic wave shielding, conductive ink, magnetic recording medium and the like.
現在、ポリイミド系樹脂は耐熱性や機械的強度に優れており主にフレキシブルプリント回路板の絶縁フィルムや半導体用封止材などの電子材料用途に広く応用されている。しかしながらポリイミド系樹脂は一般に極性に乏しいため接着しにくいという問題があった。また、極性が乏しいため、顔料などの分散が不十分なため電磁波遮蔽インキや半導電フィルム、磁気記録媒体などへの応用が困難であった。
しかしながら近年、電子・情報産業の高度化、軽薄短小化に伴い電磁波遮蔽、複写機やプリンターの転写ベルト、磁気記録媒体などにも高耐熱性の要求が高まりつつある。
従来、ポリイミド系樹脂、特にポリアミドイミド樹脂に極性基を導入して染色性を改良する試み（特許文献１）、カーボンの分散性を改良してプリンターベルト用に応用する試み（特許文献２）が行われているが、極性基としてスルホン酸ナトリウム基やリン酸ナトリウム基を用いていたため、ポリイミド系樹脂の耐久性が低下したり、金属イオンが溶出することによる導電性の経時変化等の問題があった。
Currently, polyimide resins are excellent in heat resistance and mechanical strength, and are widely applied to electronic materials such as insulating films for flexible printed circuit boards and sealing materials for semiconductors. However, polyimide resins generally have a problem that they are difficult to bond because of their poor polarity. Further, since the polarity is poor, the dispersion of pigments and the like is insufficient, making it difficult to apply to electromagnetic wave shielding ink, semiconductive film, magnetic recording medium and the like.
However, in recent years, with the advancement of the electronics and information industry, the reduction in thickness, the demand for high heat resistance is increasing for electromagnetic wave shielding, transfer belts for copying machines and printers, magnetic recording media, and the like.
Conventionally, there are attempts to improve dyeability by introducing polar groups into polyimide resins, particularly polyamideimide resins (Patent Document 1), and attempts to improve carbon dispersibility and apply it to printer belts (Patent Document 2). However, since the sodium sulfonate group and the sodium phosphate group were used as polar groups, the durability of the polyimide-based resin decreased, and problems such as changes in conductivity due to elution of metal ions occurred. there were.
本発明はこれらの欠点を改良して、カーボンや磁性粉などの顔料分散性に優れるとともに他素材に対する密着性に優れる極性の高いポリイミド系樹脂を提供することを目的とする。 An object of the present invention is to improve these disadvantages and provide a highly polar polyimide resin which is excellent in dispersibility of pigments such as carbon and magnetic powder and has excellent adhesion to other materials.
本発明者は上記目的を達成するために、鋭意検討を重ねた結果、本発明に到達した。即ち本発明は以下のポリイミド系樹脂等に関する。 As a result of intensive studies to achieve the above object, the present inventor has reached the present invention. That is, the present invention relates to the following polyimide resins and the like.
下記一般式（Ｉ）に示す化合物が共重合されたポリイミド系樹脂に関する。
上記に記載のポリイミド系樹脂にカーボンを配合したことを特徴とする燃料電池用セパレーターに関する。 It is related with the separator for fuel cells characterized by mix | blending carbon with the polyimide resin as described above.
上記に記載のポリイミド系樹脂にカーボン及び／または銀粉を配合したことを特徴とする導電インキ組成物に関する。 The present invention relates to a conductive ink composition characterized in that carbon and / or silver powder is blended with the polyimide resin described above.
非磁性支持体上に、上記に記載のポリイミド系樹脂に磁性粉を配合した磁性層を有することを特徴とする磁気記録媒体に関する。 The present invention relates to a magnetic recording medium having a magnetic layer in which magnetic powder is blended with the polyimide resin described above on a nonmagnetic support.
上記に記載のポリイミド系樹脂にカーボンを配合したことを特徴とする半導電性ベルトに関する。 The present invention relates to a semiconductive belt characterized in that carbon is blended with the polyimide resin described above.
本発明は、塩基性窒素化合物を分子内に導入することにより、分子間力を増加させることができるような極性を付与し、顔料などの分散性を改良した新規なポリイミド系樹脂を提供することができる。本発明のポリイミド系樹脂を用いることにより、耐熱性や強靭性を維持しつつ、電気、磁気特性などに優れる燃料電池用セパレーターや電磁波遮蔽用導電インキ、半導電性ベルト、磁気記録媒体などを提供することができる。 The present invention provides a novel polyimide resin which imparts polarity capable of increasing intermolecular force by introducing a basic nitrogen compound into the molecule, and has improved dispersibility of pigments and the like. Can do. By using the polyimide resin of the present invention, it is possible to provide a separator for a fuel cell, a conductive ink for electromagnetic wave shielding, a semiconductive belt, a magnetic recording medium, etc. that have excellent electrical and magnetic properties while maintaining heat resistance and toughness. can do.
以下本発明を詳細に説明する。
本発明の塩基性窒素化合物が分子内に導入されたポリイミド系樹脂は耐熱性の点から芳香族系または脂環族系ポリイミド系樹脂が好ましい。なお、ポリイミド系樹脂とは、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリエステルイミド樹脂等が挙げられ、溶剤溶解性や加工性の点からポリアミドイミド樹脂が好ましい。
The present invention will be described in detail below.
The polyimide resin in which the basic nitrogen compound of the present invention is introduced into the molecule is preferably an aromatic or alicyclic polyimide resin from the viewpoint of heat resistance. The polyimide resin includes polyimide resin, polyamideimide resin, polyetherimide resin, polyesterimide resin, and the like, and polyamideimide resin is preferable from the viewpoint of solvent solubility and workability.
ポリイミド系樹脂の合成は、例えば多価カルボン酸無水物とジアミンまたはジイソシアネートをＮ−メチル−２−ピロリドンなどの極性有機溶剤中で室温または加熱下攪拌すること等一般的な方法により製造することができる。この場合、酸成分の一部または全部をトリメリット酸無水物やジカルボン酸に置き換えるとポリアミドイミドが製造される。 The synthesis of the polyimide-based resin can be produced by a general method such as stirring polyvalent carboxylic acid anhydride and diamine or diisocyanate in a polar organic solvent such as N-methyl-2-pyrrolidone at room temperature or under heating. it can. In this case, when part or all of the acid component is replaced with trimellitic anhydride or dicarboxylic acid, polyamideimide is produced.
本発明のポリイミド系樹脂の合成に用いられる酸成分は主としてトリメリット酸無水物を用いることが好ましいが、その一部または全部を他の多塩基酸またはその無水物に置き換えることができる。例えば、ピロメリット酸、ビフェニルテトラカルボン酸、ビフェニルスルホンテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ビフェニルエーテルテトラカルボン酸、エチレングリコールアンヒドロビストリメリテート、プロピレングリコールアンヒドロビストリメリテート等のテトラカルボン酸及びこれらの無水物を共重合することによって達成される。これらの中では反応性、溶解性、価格などの点からピロメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物、エチレングリコールアンヒドロビストリメリテート、プロピレングリコールアンヒドロビストリメリテートが好ましい。また、本発明のポリイミド系樹脂の特性を損なわない範囲でシュウ酸、アジピン酸、マロン酸、セバチン酸、アゼライン酸、ドデカンジカルボン酸、ジカルボキシポリブタジエン、ジカルボキシポリ（アクリロニトリル−ブタジエン）、ジカルボキシポリ（スチレン−ブタジエン）等の脂肪族ジカルボン酸、１，４−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、４，４’−ジシクロヘキシルメタンジカルボン酸、ダイマー酸等の脂環族ジカルボン酸、テレフタル酸、イソフタル酸、ジフェニルスルホンジカルボン酸、ジフェニルエーテルジカルボン酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸等を共重合しても良い。これらの中では各種基材への密着性や溶剤溶解性の点からはダイマー酸やアクリロニトリルブタジエン系ジカルボン酸が好ましい。 The acid component used for the synthesis of the polyimide resin of the present invention is preferably mainly trimellitic anhydride, but part or all of it can be replaced with other polybasic acid or anhydride thereof. For example, tetracarboxylic acids such as pyromellitic acid, biphenyl tetracarboxylic acid, biphenyl sulfone tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl ether tetracarboxylic acid, ethylene glycol anhydrobis trimellitate, propylene glycol anhydro bis trimellitate and the like This is accomplished by copolymerizing the anhydrides. Among these, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydride, ethylene glycol anhydrobis trimellitate, propylene glycol anhydro bis trimellitate in terms of reactivity, solubility, price, etc. Is preferred. In addition, oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), dicarboxypoly, as long as the characteristics of the polyimide resin of the present invention are not impaired. Aliphatic dicarboxylic acids such as (styrene-butadiene), 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4′-dicyclohexylmethanedicarboxylic acid, alicyclic dicarboxylic acids such as dimer acid, terephthalic acid An aromatic dicarboxylic acid such as isophthalic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and the like may be copolymerized. Among these, dimer acid and acrylonitrile butadiene dicarboxylic acid are preferable from the viewpoint of adhesion to various base materials and solvent solubility.
また、酸成分の一部をグリコールに置き換えてウレタン基を分子内に導入することもできる。グリコールとしてはエチレングリコール、プロピレングリコール、テトラメチレングリコール、ネオペンチルグリコール、１，６−ヘキサンジオール等のアルキレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリアルキレングリコールや上記ジカルボン酸の１種又は２種以上と上記グリコールの１種又は２種以上とから合成される末端水酸基のポリエステル等が挙げられ、これらの中では基材への密着性や溶剤溶解性の点からポリエチレングリコール、末端水酸基のポリエステルが好ましい。また、これらの数平均分子量は５００以上が好ましく、１０００以上がより好ましい。上限は特に限定されないが８０００未満が好ましい。 In addition, a urethane group can be introduced into the molecule by replacing part of the acid component with glycol. As the glycol, ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, alkylene glycol such as 1,6-hexanediol, polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and one of the above dicarboxylic acids Alternatively, polyesters of terminal hydroxyl groups synthesized from two or more types and one or more of the above-mentioned glycols may be mentioned, and among these, polyethylene glycol, terminal hydroxyl groups from the viewpoint of adhesion to a substrate and solvent solubility The polyester is preferred. Moreover, these number average molecular weights are preferably 500 or more, and more preferably 1000 or more. The upper limit is not particularly limited, but is preferably less than 8000.
本発明のポリイミド系樹脂の合成に用いられるジアミン（ジイソシアネート）成分としては、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン及びこれらのジイソシアネート、１，４−シクロヘキサンジアミン、１，３−シクロヘキサンジアミン、ジシクロヘキシルメタン−４，４’−ジアミン、イソホロンジアミン等の脂環族ジアミン及びこれらのジイソシアネート、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルスルホン、ベンジジン、３，３’−ジメチルベンジジン、キシリレンジアミン、ナフタレンジアミン等の芳香族ジアミン及びこれらのジイソシアネート等が挙げられ、これらの中では反応性、コスト、溶剤溶解性の点から４，４’−ジアミノジフェニルメタン、３，３’−ジメチルベンジジン、イソホロンジアミン、ジシクロヘキシルメタン−４，４’−ジアミン及びこれらのジイソシアネートが好ましい。 Examples of the diamine (diisocyanate) component used for the synthesis of the polyimide resin of the present invention include aliphatic diamines such as ethylenediamine, propylenediamine, and hexamethylenediamine, and their diisocyanates, 1,4-cyclohexanediamine, and 1,3-cyclohexanediamine. Alicyclic diamines such as dicyclohexylmethane-4,4′-diamine and isophoronediamine, and diisocyanates thereof, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylether, Aromatic diamines such as 4,4′-diaminodiphenylsulfone, benzidine, 3,3′-dimethylbenzidine, xylylenediamine, naphthalenediamine, and their diisocyanates, and the like. Among these, 4,4′-diaminodiphenylmethane, 3,3′-dimethylbenzidine, isophoronediamine, dicyclohexylmethane-4,4′-diamine and diisocyanates thereof are preferable from the viewpoint of reactivity, cost, and solvent solubility. .
本発明のポリイミド系樹脂に塩基性窒素化合物を導入するには２級又は３級窒素を含有するジアミン、ジカルボン酸、ジオール化合物等を共重合すればよい。具体的には一般式（Ｉ）にて表される成分を共重合することで得られる。
一般式（Ｉ）において、Ｒ1、Ｒ2はアミノ基、水酸基、カルボキシル基のいずれかを有する置換基であり、同一でも異なっていても良い。Ｒ3は水素またはアルキル基である。また、Ｒ1、Ｒ2、Ｒ3はアミノ基、水酸基、カルボキシル基のいずれかを有する置換基であり、同一でも異なっていても良い。特にＲ1、Ｒ2は水酸基を有する置換基であり、同一でも異なっていても良く、Ｒ3は水素またはアルキル基であるものが好ましい。 In the general formula (I), R 1 and R 2 are substituents having any of an amino group, a hydroxyl group, and a carboxyl group, and may be the same or different. R 3 is hydrogen or an alkyl group. R 1 , R 2 and R 3 are substituents having any one of an amino group, a hydroxyl group and a carboxyl group, and may be the same or different. In particular, R 1 and R 2 are substituents having a hydroxyl group and may be the same or different, and R 3 is preferably a hydrogen atom or an alkyl group.
アミノ基、水酸基、カルボキシル基のいずれかを有する置換基とは、アミノ基、水酸基、カルボキシル基を有するアルキル基、アルキレン基等であり、もちろんこれ以外の官能基を有していても良い。アミノ基を有する置換基としては、例えばアミノメチル基、アミノエチル基、アミノブチル基、アミノヘキセン基等が挙げられる。水酸基やカルボキシル基についても同様である。好ましいＲ3としては水素、メチル基、エチル基、イソプロピル基等が例示される。その中でもＲ1とＲ2が水酸基を有する置換基であるジオール化合物が反応性などの点から好ましく、具体的にはジエタノールアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミンなどが挙げられ、塩基性の強さや重合性の点からＮ−メチルジエタノールアミンが好ましい。これらの共重合量は酸成分を１００モル％としたときに、０．５モル〜５０モル％、好ましくは１〜３０モル％、更に好ましくは２〜２０モル％である。共重合量が０．５モル％以下では目的とする密着性や顔料分散性の改良が不十分になることがあり、５０モル％を超えると耐熱性が低下するなどの問題が生じる場合がある。 The substituent having any of an amino group, a hydroxyl group, and a carboxyl group is an amino group, a hydroxyl group, an alkyl group having a carboxyl group, an alkylene group, or the like, and of course may have other functional groups. Examples of the substituent having an amino group include an aminomethyl group, an aminoethyl group, an aminobutyl group, and an aminohexene group. The same applies to the hydroxyl group and carboxyl group. Preferred examples of R 3 include hydrogen, methyl group, ethyl group, isopropyl group and the like. Among them, a diol compound in which R 1 and R 2 are a substituent having a hydroxyl group is preferable from the viewpoint of reactivity, and specific examples include diethanolamine, triethanolamine, N-methyldiethanolamine, and the like. N-methyldiethanolamine is preferred from the viewpoint of polymerizability. These copolymerization amounts are 0.5 mol-50 mol%, Preferably it is 1-30 mol%, More preferably, it is 2-20 mol% when an acid component is 100 mol%. If the copolymerization amount is 0.5 mol% or less, the desired adhesion and pigment dispersibility may not be improved, and if it exceeds 50 mol%, problems such as reduced heat resistance may occur. .
本発明に用いるポリイミド系樹脂はＮ，Ｎ’−ジメチルホルムアミド、Ｎ，Ｎ’−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン等の極性溶剤中、室温〜２００℃に加熱しながら攪拌することで容易に製造することができる。この場合、必要に応じてトリエチルアミン、ジエチレントリアミン等のアミン類、フッ化ナトリウム、フッ化カリウム、フッ化セシウム、ナトリウムメトキシド等のアルカリ金属塩等を触媒として用いることもできる。 The polyimide resin used in the present invention is stirred while heating at room temperature to 200 ° C. in a polar solvent such as N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. By doing so, it can be easily manufactured. In this case, amines such as triethylamine and diethylenetriamine, alkali metal salts such as sodium fluoride, potassium fluoride, cesium fluoride, sodium methoxide, and the like can be used as a catalyst as necessary.
上述のように合成されたポリイミド系樹脂の塩基性窒素を４級アンモニウム塩化することにより、さらに極性が増加し、さらに密着性や顔料分散性を向上させることが出来る。４級アンモニウム塩にする方法は例えば、ヨウ化メチルなどのハロゲン化アルキルを加えて、室温で攪拌する方法等を挙げることができる。 By subjecting the basic nitrogen of the polyimide resin synthesized as described above to quaternary ammonium chloride, the polarity is further increased, and adhesion and pigment dispersibility can be further improved. Examples of the method for forming a quaternary ammonium salt include a method of adding an alkyl halide such as methyl iodide and stirring at room temperature.
本発明の塩基性窒素化合物が分子内に導入されたポリイミド系樹脂はその極性に起因して、顔料分散性が改良されており、種々用途に応用できる。例えばカーボンを配合分散した燃料電池用セパレーターや複写機、プリンター用の半導電性転写ベルト、カーボンと銀や銅などの金属粒子を分散させた電磁波遮蔽用や回路形成用の導電インキ、或いは磁性粉を分散させた磁気記録媒体用塗料などに用いることができる。 The polyimide resin in which the basic nitrogen compound of the present invention is introduced into the molecule has improved pigment dispersibility due to its polarity, and can be applied to various uses. For example, fuel cell separators, copiers, and printers with semi-conductive transfer belts with carbon mixed, conductive ink for electromagnetic wave shielding or circuit formation with carbon and silver or copper metal particles dispersed, or magnetic powder Can be used as a coating material for magnetic recording media in which is dispersed.
以下、実施例で本発明を更に詳細に説明するが、本発明はこれらの実施例で制限されるものではない。尚、実施例中の測定値は以下の方法で測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples. In addition, the measured value in an Example was measured with the following method.
（１）吸水率
固形樹脂を１２０℃、１時間乾燥して重量（Ｗ０）を測定し、その固形樹脂を２５ ℃の水に２０時間浸漬して表面付着水を拭き取ったあとの重量（Ｗ１）を測定して 次式によって求めた。
吸水率（％）＝１００×（Ｗ１−Ｗ０）／Ｗ１
（２）引っ張り強伸度
ポリエステルフィルム上に樹脂溶液を塗布、１５０℃で２０時間乾燥した後剥離し た約３０μｍのフィルムを東洋ボールドウイン社の引張り試験機を用いて、２５℃ ７０％ＲＨの条件下、引っ張り速度２０ｍｍ／分で測定した。
（３）耐酸性
ｐＨ３の硫酸水溶液に９０℃で２０時間浸漬した後の外観を観察した。
（４）顔料分散性：
塗膜表面を堀場製作所製グロスチェッカＩＢ−３２０により測定した。
（５）表面抵抗値
横河ヒューレットパッカード社のＨＩＧＨ ＲＥＳＩＳＴＡＮＣＥ ＭＥＴＥＲを 用いて、室温で測定した。
（６）比抵抗
ポリエステルフィルムにスクリーン印刷法で塗膜が約７μｍとなるように印刷して 、１００℃で１０分、１５０℃で１時間乾燥後タテ、ヨコともに２５ｍｍ長さの回 路のシート抵抗値を測定して膜厚を乗じて計算した。
（７）接触角
塗膜表面に水滴を滴下して協和界面科学社製接触角計（ＣＡ−Ｘ型）を用いて室温 で測定した。
(1) Water absorption The solid resin was dried at 120 ° C. for 1 hour, the weight (W0) was measured, and the solid resin was immersed in water at 25 ° C. for 20 hours to wipe off the water adhering to the surface (W1). Was obtained by the following equation.
Water absorption (%) = 100 × (W1-W0) / W1
(2) Tensile strength and elongation A resin solution is applied onto a polyester film, dried at 150 ° C. for 20 hours, and then peeled off, using a Toyo Baldwin tensile tester at 25 ° C. and 70% RH. Under the conditions, the measurement was performed at a pulling speed of 20 mm / min.
(3) Acid resistance The appearance after being immersed in a sulfuric acid aqueous solution of pH 3 at 90 ° C. for 20 hours was observed.
(4) Pigment dispersibility:
The surface of the coating film was measured with a gloss checker IB-320 manufactured by Horiba.
(5) Surface resistance value It measured at room temperature using HIGH RESISTANCE METER of Yokogawa Hewlett Packard.
(6) Specific resistance Printed on a polyester film by a screen printing method so that the coating film is about 7 μm, dried at 100 ° C. for 10 minutes, and then dried at 150 ° C. for 1 hour. The resistance value was measured and calculated by multiplying the film thickness.
(7) Contact angle A drop of water was dropped on the surface of the coating film and measured at room temperature using a contact angle meter (CA-X type) manufactured by Kyowa Interface Science Co., Ltd.
［実施例１］
温度計、冷却管、窒素ガス導入管のついた４ツ口フラスコにトリメリット酸無水物（ＴＭＡ）０．９５モル、Ｎ−メチルジエタノールアミン０．０５モル、ジフェニルメタンジイソシアネート（ＭＤＩ）１モルを固形分濃度が２５％となるようにＮ−メチル−２−ピロリドンと共に仕込み、１３０℃で５時間攪拌して反応させた。得られたポリアミドイミド樹脂Ａの特性を表１に示す。
[Example 1]
In a four-necked flask equipped with a thermometer, a condenser tube, and a nitrogen gas inlet tube, 0.95 mol of trimellitic anhydride (TMA), 0.05 mol of N-methyldiethanolamine, and 1 mol of diphenylmethane diisocyanate (MDI) are solid components. The mixture was charged with N-methyl-2-pyrrolidone so as to have a concentration of 25%, and reacted at 130 ° C. with stirring for 5 hours. Table 1 shows the properties of the obtained polyamideimide resin A.
［実施例２］
実施例１でＴＭＡを０．９モル、Ｎ−メチルジエタノールアミンを０．１モルとした以外は実施例１と同じ方法でポリアミドイミド樹脂Ｂを製造した。特性を表１に示す。
[Example 2]
Polyamideimide resin B was produced in the same manner as in Example 1 except that TMA was 0.9 mol and N-methyldiethanolamine was 0.1 mol in Example 1. The characteristics are shown in Table 1.
［実施例３］
実施例１でＴＭＡを０．８モル、Ｎ−メチルジエタノールアミンを０．２モルとした以外は実施例１と同じ方法でポリアミドイミド樹脂Ｃを製造した。特性を表１に示す。
[Example 3]
Polyamideimide resin C was produced in the same manner as in Example 1 except that TMA was 0.8 mol and N-methyldiethanolamine was 0.2 mol in Example 1. The characteristics are shown in Table 1.
［実施例４］
実施例１のポリアミドイミド樹脂Ａ溶液に室温でポリアミドイミド樹脂中のＮ−メチルジエタノールアミンと等量の沃化メチルを１２時間かけて添加して三級窒素を四級化した。得られたポリアミドイミドＤの特性を表１に示す。
[Example 4]
Tertiary nitrogen was quaternized by adding the same amount of methyl iodide as N-methyldiethanolamine in the polyamideimide resin over 12 hours to the polyamideimide resin A solution of Example 1 at room temperature. The properties of the obtained polyamideimide D are shown in Table 1.
［実施例５］
実施例２のポリアミドイミド樹脂溶液１００部に２５部のグラファイトを配合して３本ロールミルで均一に分散させた。
この分散液を厚みが０．３ｍｍのステンレス（ＳＵＳ３０４）に乾燥膜厚が０．３ｍｍとなるように塗布、２００℃で１時間乾燥した後プレス成型してガス流路用の溝を形成した。この積層板の塗布面の表面抵抗値は２．１×１０-2Ω／□、グロスは１１５％と優れた電気特性と分散性を示し、またポリアミドイミド樹脂クリア塗膜表面の接触角が６２度と低いため燃料ガス供給性に優れた燃料電池用セパレーターが得られた。
[Example 5]
25 parts of graphite was blended with 100 parts of the polyamideimide resin solution of Example 2 and uniformly dispersed by a three-roll mill.
This dispersion was applied to stainless steel (SUS304) having a thickness of 0.3 mm so as to have a dry film thickness of 0.3 mm, dried at 200 ° C. for 1 hour, and then press-molded to form a gas channel groove. The coated surface of this laminate has a surface resistance value of 2.1 × 10 −2 Ω / □, a gloss of 115% and excellent electrical characteristics and dispersibility, and a polyamideimide resin clear coating surface contact angle of 62 Therefore, a fuel cell separator having excellent fuel gas supply performance was obtained.
［実施例６］
実施例２のポリアミドイミド樹脂溶液１００部にカーボンブラック（コロンビアンカーボン社のコンダクテックスＳＣ）を５部配合して３本ロールミルで混練りした溶液をアルミ製の円筒状金型内に吹きつけ流延し、回転させながら１５０℃で３０分、更に２５０℃で１時間乾燥させたあと、金型から剥離して厚みが９０μｍの無端ベルトを得た。このベルトのグロスは１２５％、表面抵抗は５．３×１０-11Ω／□と表面が平滑で、電気特性に優れたプリンター及び複写機用転写ベルトが製造出来た。
[Example 6]
100 parts of the polyamideimide resin solution of Example 2 and 5 parts of carbon black (Conductex SC of Colombian Carbon) were mixed and kneaded with a three-roll mill, and the solution was sprayed into an aluminum cylindrical mold. It was stretched and rotated at 150 ° C. for 30 minutes and further at 250 ° C. for 1 hour, and then peeled from the mold to obtain an endless belt having a thickness of 90 μm. This belt has a gloss of 125%, a surface resistance of 5.3 × 10 −11 Ω / □, a smooth surface, and excellent transfer characteristics for printers and copiers.
［実施例７］
実施例２のポリアミドイミド樹脂溶液１００部にグラファイト３部、銀粉１００部、レベリング剤としてＫＳ６６（信越化学製）を０．１部配合してデイゾルバーで３０分攪拌後、３本ロールミルで２回混練して導電性インキを製造した。このインキをポリエステルフィルム上にスクリーン印刷を行い１００℃で１０分、１８０℃で３０分乾燥した。ポリエステルフィルムへのインキ層の密着性は良好で比抵抗値を測定したところ３．２×１０-4Ω・ｃｍであり電磁波遮蔽用インキ及び電気回路形成用インキに好適であった。
[Example 7]
100 parts of the polyamideimide resin solution of Example 2 was mixed with 3 parts of graphite, 100 parts of silver powder, and 0.1 part of KS66 (manufactured by Shin-Etsu Chemical) as a leveling agent, stirred for 30 minutes with a dissolver, and then kneaded twice with a three-roll mill. Thus, a conductive ink was produced. This ink was screen printed on a polyester film and dried at 100 ° C. for 10 minutes and at 180 ° C. for 30 minutes. The adhesion of the ink layer to the polyester film was good and the specific resistance value was measured to be 3.2 × 10 −4 Ω · cm, which was suitable for electromagnetic wave shielding ink and electric circuit forming ink.
［比較例１］
実施例１でトリメリット酸無水物を１モル、ジフェニルメタン−４，４’−ジイソシアネート１モルとした以外は実施例１と同じ条件でポリアミドイミド樹脂を合成した。得られたポリアミドイミド樹脂Ｅの特性を表１に示す。
[Comparative Example 1]
A polyamideimide resin was synthesized under the same conditions as in Example 1 except that 1 mol of trimellitic anhydride and 1 mol of diphenylmethane-4,4′-diisocyanate were used in Example 1. Table 1 shows the properties of the obtained polyamideimide resin E.
［比較例２］
比較例１のポリアミドイミド樹脂Ｅを用いて、実施例５と同じ条件で燃料電池用セパレーターを作成したが、接触角が８５度と高く、グラファイトの分散が不十分なため表面抵抗値が５．２×１０-5Ω・ｃｍと高く、成型時に微小なクラックが発生した。
[Comparative Example 2]
A separator for a fuel cell was prepared using the polyamideimide resin E of Comparative Example 1 under the same conditions as in Example 5. However, the contact angle was as high as 85 degrees, and the dispersion of graphite was insufficient, so that the surface resistance value was 5. It was as high as 2 × 10 −5 Ω · cm, and minute cracks occurred during molding.
［比較例３］
比較例１のポリアミドイミド樹脂Ｅを用いて実施例６と同じ方法で無端ベルトを作成した。このベルトのグロスは９２％と低く、表面抵抗値は２．８×１０-14Ω／□と高く分散不良に基づくと思われた。
[Comparative Example 3]
An endless belt was prepared in the same manner as in Example 6 using the polyamideimide resin E of Comparative Example 1. The gloss of this belt was as low as 92%, and the surface resistance value was as high as 2.8 × 10 −14 Ω / □, which seemed to be due to poor dispersion.
本発明は、親水性に優れた熱可塑性樹脂、特に極性基含有ポリイミド系樹脂と炭素粉体の混合物を用いることにより、燃料ガスが安定に供給され、耐酸性に優れた燃料電池用セパレーターを供給できる。また、電磁波遮蔽用導電インキ、半導電性ベルト、磁気記録媒体などを提供することもできる。 The present invention provides a fuel cell separator having a stable supply of fuel gas and excellent acid resistance by using a thermoplastic resin excellent in hydrophilicity, particularly a mixture of a polar group-containing polyimide resin and carbon powder. it can. In addition, a conductive ink for shielding electromagnetic waves, a semiconductive belt, a magnetic recording medium, and the like can be provided.
Claims (9)
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| JP2005038627A JP2006225454A (en) | 2005-02-16 | 2005-02-16 | Polyimide-based resin |
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| JP2005038627A JP2006225454A (en) | 2005-02-16 | 2005-02-16 | Polyimide-based resin |
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| JP2006225454A true JP2006225454A (en) | 2006-08-31 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170071812A (en) * | 2015-12-16 | 2017-06-26 | 주식회사 엘지화학 | Polyimide precursor resin solution and transparent polyimide film prepared by using same |
| WO2020203417A1 (en) * | 2019-03-29 | 2020-10-08 | 国立大学法人大阪大学 | Conductive ink and carbon wiring board |
| US11346801B2 (en) | 2018-07-04 | 2022-05-31 | Murata Manufacturing Co., Ltd. | Composite sensor |
| US11913896B2 (en) | 2018-07-04 | 2024-02-27 | Murata Manufacturing Co., Ltd. | Humidity sensor and RFID tag including the same |
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| JPH05255504A (en) * | 1992-03-13 | 1993-10-05 | Toyobo Co Ltd | Polyamide-imide containing ionic group |
| JPH0945333A (en) * | 1995-07-31 | 1997-02-14 | Toyobo Co Ltd | Nonaqueous electrolyte secondary battery and its manufacture |
| JPH10247315A (en) * | 1997-03-04 | 1998-09-14 | Sony Corp | Magnetic recording medium |
| JP2002348470A (en) * | 2001-05-25 | 2002-12-04 | Hitachi Chem Co Ltd | Heat-resistant resin composition and paint |
| JP2003151121A (en) * | 2001-11-12 | 2003-05-23 | Toyobo Co Ltd | Magnetic recording medium |
| JP2003261768A (en) * | 2002-03-12 | 2003-09-19 | Hitachi Chem Co Ltd | Semiconductive tubular polyamide-imide film and method for producing the same |
| JP2004039379A (en) * | 2002-07-02 | 2004-02-05 | Sumitomo Electric Ind Ltd | Conductive paste, conductive membrane, and manufacturing method of conductive membrane |
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| JPH0191315A (en) * | 1987-10-01 | 1989-04-11 | Sony Corp | Magnetic recording medium |
| JPH05255504A (en) * | 1992-03-13 | 1993-10-05 | Toyobo Co Ltd | Polyamide-imide containing ionic group |
| JPH0945333A (en) * | 1995-07-31 | 1997-02-14 | Toyobo Co Ltd | Nonaqueous electrolyte secondary battery and its manufacture |
| JPH10247315A (en) * | 1997-03-04 | 1998-09-14 | Sony Corp | Magnetic recording medium |
| JP2002348470A (en) * | 2001-05-25 | 2002-12-04 | Hitachi Chem Co Ltd | Heat-resistant resin composition and paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170071812A (en) * | 2015-12-16 | 2017-06-26 | 주식회사 엘지화학 | Polyimide precursor resin solution and transparent polyimide film prepared by using same |
| KR102020091B1 (en) | 2015-12-16 | 2019-10-18 | 주식회사 엘지화학 | Polyimide precursor resin solution and transparent polyimide film prepared by using same |
| US11346801B2 (en) | 2018-07-04 | 2022-05-31 | Murata Manufacturing Co., Ltd. | Composite sensor |
| US11913896B2 (en) | 2018-07-04 | 2024-02-27 | Murata Manufacturing Co., Ltd. | Humidity sensor and RFID tag including the same |
| WO2020203417A1 (en) * | 2019-03-29 | 2020-10-08 | 国立大学法人大阪大学 | Conductive ink and carbon wiring board |
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