JP4008978B2 - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP4008978B2 JP4008978B2 JP04082697A JP4082697A JP4008978B2 JP 4008978 B2 JP4008978 B2 JP 4008978B2 JP 04082697 A JP04082697 A JP 04082697A JP 4082697 A JP4082697 A JP 4082697A JP 4008978 B2 JP4008978 B2 JP 4008978B2
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- Prior art keywords
- resin composition
- resin
- polyimide
- conductive
- filler
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/034—Organic insulating material consisting of one material containing halogen
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は樹脂組成物に関する。さらに詳しくは、導電性フィラーと非導電性無機フィラーを添加し、その体積抵抗率が108〜1015Ω・cmであることを特徴とする樹脂組成物に関する。
【0002】
【従来の技術】
ポリイミドフィルムは優れた耐熱性・低温特性・耐薬品性・機械特性・電気特性等を有していることから特に電気・電子機器用途の材料として広く用いられており、また、このポリイミドフィルムの優れた特性を利用して種々の用途への応用がはかられている。これに対し、フッ素樹脂はその優れた耐熱性、耐薬品性、低摩擦係数から潤滑剤や容器等に広く用いられている。
【0003】
【発明が解決しようとする課題】
これらの樹脂は完全な非伝導性であり、導電性が必要な用途に使用する場合には、これらの樹脂に導電性を有するフィラーを添加したり、表面に帯電防止剤を塗布したりすることにより導電性を得ていた。しかし、この導電性を有するフィラーの特性として、少量の添加では導電性を示さず、ある閾値を超えた量を添加すると急激に抵抗が下がるという傾向がある。例えば、導電性を有するフィラーとしてカーボンブラックを使用した場合には、樹脂に対し重量換算で数%以下の添加では1015〜1016Ω・cm程度の体積抵抗率を示すが、それ以上添加していくとある閾値の領域では1%増量するにつれて2〜4桁も抵抗値が変化し、ある一定量以上ではその体積抵抗率が106〜108Ω・cmとなり、ほとんど変化がなくなるという傾向を示す。したがって、レーザープリンターの転写体や定着ローラーに使用する場合に要求される108〜1014Ω・cmという領域は、単純にカーボンブラックを添加することによっては安定的に実現できず、樹脂の表面もしくは内部に導電層を形成し、フィルム全体としてこの領域の体積抵抗率を実現するという方法が主流である。
【0004】
しかし、この方法では複数層の樹脂が必要であるため、コストが高く、また、微妙な抵抗値の制御が難しいという難点を有していた。
そこで、本発明者らは上記実状に鑑み、鋭意研究の結果、樹脂に導電性カーボンと非導電性無機フィラーを添加することにより、上記課題が解決されることを見い出し、本発明を完成させたものである。
【0005】
【課題を解決するための手段】
本発明に係る樹脂組成物の要旨とするところは、樹脂に導電性フィラーと少なくとも1種の非導電性無機フィラーを添加し、その体積抵抗率が108〜1015Ω・cmであることを特徴とする樹脂組成物であることにあり、(請求項1)
樹脂がポリイミド単独、あるいはポリイミドとフッ素樹脂からなることを特徴とする請求項1記載の樹脂組成物であり(請求項2)、
さらに、ポリイミドの構造が一般式(1)
【0006】
【化6】
【0007】
(Ar1は4価の有機基を、Ar2は2価の有機基を、nは1以上の整数をあらわす。)で表されることを特徴とする請求項1又は2いずれか記載の樹脂組成物であり(請求項3)、
一般式(1)中のAr1が
【0008】
【化7】
【0009】
【化8】
【0010】
で表される少なくとも一種からなることを特徴とする請求項1〜3いずれかに記載の樹脂組成物であり(請求項4)、
一般式(1)中のAr2が
【0011】
【化9】
【0012】
【化10】
【0013】
で表される少なくとも一種からなることを特徴とする請求項1〜4いずれかに記載の樹脂組成物である(請求項5)。
【0014】
【発明の実施の形態】
本発明に係る樹脂組成物は、ポリイミド単独あるいはポリイミド及びフッ素樹脂を主成分とし、特に一般式(1)で表されるポリイミドを主成分とする樹脂及びフッ素樹脂を主成分とするものである。本発明に係る樹脂の主成分であるポリイミドは、優れた耐熱性、耐薬品性、及び耐磨耗性を併せ有している。また、このうちエステル基を有するポリイミドは熱可塑性を示し、非常に良好な加工性を有するとともに低吸水率という特性を有している。このポリイミドは従来用いられている方法でモノマーから重合し得ることができる。また、この樹脂組成物の成分であるフッ素樹脂は、フッ素原子を有するその構造から非粘着性や溌水性を有する。また、低摩擦係数や耐薬品性、耐熱性を有している。この2種の優れた樹脂を主成分として作製した樹脂は、両者の優れた特性を損なうことなく優れた特性を示す。
【0015】
添加する導電性フィラーはどのような形態のものを使用しても良い。例えばカーボンブラックや金属、金属酸化物、金属窒化物である。また、その添加量は、非導電性無機フィラーを添加せず、単独で添加した場合に樹脂の体積抵抗率が1012〜1016Ω・cmを示すような少量の添加量でよい。例えばカーボンブラックの場合、好ましくは0.5〜5%であり、さらに好ましくは2〜5%である。また、非導電性無機フィラーとしては、あらゆるものが考えられるが、樹脂に単独で添加した場合、樹脂中に含まれる非導電性無機フィラーの量が20wt%の場合にその樹脂の体積抵抗率が1014Ω・cm以上となるものが良い。好ましくは雲母、ガラスビーズ、スメクタイト、窒化ボロン、チタン酸ウィスカー等が良い。その添加量は好ましくは10〜40%、さらに好ましくは15〜35%である。ただし、導電性フィラーと非導電性フィラーの量はそれぞれの種類の組み合わせにより最適な領域があり、例えばカーボンブラックと膨潤性雲母との組み合わせの場合にはカーボンブラック3〜5%、膨潤性雲母15〜25%である。また、フッ素樹脂は特に限定されないが、ポリテトラフルオロエチレンの場合は、どのような融点のものを使用しても良いが、融点が325℃以上であるものが望ましい。ポリテトラフルオロエチレンはその分子量により融点が決まるが、融点が325℃以下の場合、熱分解温度が低く耐熱性に劣る。
【0016】
これらの樹脂およびフィラーを混合し、均一な樹脂を得るためにはどのような方法を用いても良いが、その方法により均一さに違いがあり、したがって得られた樹脂の体積抵抗率に違いがある。例えばポリイミドを従来の方法のようにモノマーを重合しその前駆体であるポリアミド酸溶液を得、それにフィラーを混合し、その後三本ロールにて混練を繰り返したものは、そのフィラーの分散性が非常に良く、効果的に体積抵抗率を制御することができる。また、ポリイミドを重合するための溶媒に事前にフィラーを添加しておき、その溶媒を用いて重合を行い、フィラーを分散したポリアミド酸溶液を得ても良い。この方法ではフィラーの凝集が起こりにくい利点がある。また、その後このポリアミド酸溶液を三本ロールにて混練を繰り返しても良い。これらの方法で得られたポリアミド酸溶液は従来用いられている方法でイミド化を行い、フィルムやチューブ、その他成形体に加工できる。また、押出成形により、ポリイミドにフィラーを混合し、成形体を得ても良い。この場合事前にポリイミド粉体にフィラーを混合してもよいし、押出時に添加しても良い。
【0017】
このようにして得られた樹脂組成物は、非導電性無機フィラーの量を変化させることによりその体積抵抗率を108〜1015Ω・cmに制御することができる。
また、ポリイミド及びフッ素樹脂の性能を著しく低下させず、体積抵抗率が本願の範囲外にならない場合には、安定剤、滑材、界面活性剤、顔料、相溶剤、ポリイミド系樹脂及びフッ素樹脂以外の樹脂等を添加しても良く、このことは特に制限されない。
また、ポリイミドとフッ素樹脂の混合比は特に規定されない。
【0018】
以上、本発明に係る樹脂組成物の有用性を明らかにすべく、応用例を説明したが、本発明はこれによって限定されるものではなく、本発明はその主旨を逸脱しない範囲で当業者の知識に基づき、種々なる改良、変更、修正を加えた態様で実施しうるものである。
【0019】
【実施例】
初めに、本発明の実施例において用いるポリイミドの製造方法について具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。
(実施例1)
50mlメスフラスコ(1)に2,2−ビス[4−(4−アミノフェノキシ)フェニル]プロパン(以下、BAPPという。)15.6gおよびジメチルホルムアミド(以下、DMFという)25.4gを採り、スターラーを用いて攪拌し、充分溶かした。さらに、他の50mlメスフラスコ(2)にBAPP1.0g、DMF10.0gを採り、十分溶かした。他方、攪拌機を備えた500ml三口フラスコに2,2−ビス(4−ヒドロキシフェニル)プロパンジベンゾエート−3,3´,4,4´−テトラカルボキシリックアシッドジアンヒドライド(以下、ESDAという。)11.9gと3,3´,4,4´−ベンゾフェニルテトラカルボキシリックアシッドジアンヒドライド(以下、BTDAという。)6.4g、およびDMF25.0gを入れ、氷水で冷やしつつ、かつフラスコ中の雰囲気を窒素置換しながら攪拌し充分溶かした。そして、まず事前に得られた50mlメスフラスコ(1)中のBAPP溶液を攪拌しながら前記500ml三口フラスコ中に徐々に投入した。約30分間攪拌しながら放置した後、50mlメスフラスコ(2)中のBAPP溶液を三口フラスコ中の溶液の粘度に注目しながら三口フラスコ中に徐々に投入した。粘度が1500poiseに達したところで、さらにDMF85.2gを加え、均一になるまで攪拌を続けた。さらに、50mlメスフラスコ(2)中のBAPP溶液を三口フラスコ中の溶液の粘度に注目しながら三口フラスコ中に徐々に投入した。最大粘度に達した後、BAPP溶液の投入を終了し、1時間攪拌しながら放置し、ポリアミド酸重合体溶液を得た。次に、200mlビーカー中に三菱化学(株)製導電性カーボンブラック3030Bを1.40g、コープケミカル(株)製膨潤性雲母ソマシフME−100を6.98g、DMFを55.7g採り、良く攪拌した後、1時間超音波洗浄した。その後、この溶液を前述のポリアミド酸重合体溶液と混合し、良く攪拌した後、ロール間の距離を1000μmとした三本ロールを5回通し、良く混練した。
【0020】
このようにして得られたポリアミド酸重合体溶液をPETフィルム上に塗布し、80℃で25分加熱した後、PETフィルムから剥し、金属支持体に固定した後、150℃、200℃、250℃、270℃、300℃で各5分加熱し、熱可塑ポリイミドフィルムを得た。このフィルムの体積抵抗率を測定したところ、3.0×1010Ω・cmであった。
(実施例2)
実施例1において導電性カーボンブラック3030Bの量を1.05gとし、導電性カーボンブラックとソマシフMEー100とを事前に500ml三口フラスコ中に添加しておくこと以外には実施例1と同様にしてポリアミド酸溶液を得、さらにフィルムを作製し、その体積抵抗率を測定したところ6.1×1014Ω・cmであった。
(比較例1)
実施例1で作製したフィラーを添加する前のポリアミド酸重合体溶液をPETフィルム上に塗布し、実施例1と同様にして熱可塑ポリイミドフィルムを得た。このフィルムの体積抵抗率は1016Ω・cm以上であった。
(比較例2)
実施例1においてコープケミカル(株)製ソマシフME−100を使用しないこと以外は同じようにして熱可塑ポリイミドフィルムを作製し、その体積抵抗率を測定したところ1016Ω・cm以上であった。
【0021】
【発明の効果】
以上に示すように、本発明に係る樹脂組成物は、導電性フィラーと非導電性無機フィラーとを樹脂に添加することにより従来は制御が困難であった体積抵抗率を容易に制御することができる。この樹脂組成物をキャスト法あるいは押出成形、射出成形により、フィルム状、チューブ状あるいは成形体に加工でき、種々の用途に使用することができる。
また、本発明の樹脂組成物は、特に一般式(1)で表されるポリイミド及びフッ素樹脂からなるため、優れた特性を有し、耐熱性、耐放射線性、機械的特性、寸法安定性、製膜精度、難燃性、耐磨耗性、低摩擦係数、溌水性、オフセット性、電気特性等に優れ、特に吸水率が低く、溶融押出法により製膜するとさらに寸法精度・膜厚精度に優れたフィルムとなる。このため係る樹脂組成物は、例えばFPC(フレキシブルプリント基板)、電線の絶縁用フィルム、シートベルト、食品用トレー、カテーテル等医療用部品、光学部品機材、さらに、耐熱性を利用した精密電気電子部材、例えば、複写機、プリンターの各種ベルト、定着ローラーに好適である。また、寸法精度が良好であるため、精密機材等の駆動ベルトに利用可能である。さらに、その他あらゆる分野で各種の用途が期待できるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition characterized by adding a conductive filler and a non-conductive inorganic filler and having a volume resistivity of 10 8 to 10 15 Ω · cm.
[0002]
[Prior art]
Polyimide film has excellent heat resistance, low temperature properties, chemical resistance, mechanical properties, electrical properties, etc., so it is widely used especially as a material for electrical and electronic equipment applications. Utilizing these characteristics, they are being applied to various purposes. In contrast, fluororesins are widely used in lubricants and containers because of their excellent heat resistance, chemical resistance, and low friction coefficient.
[0003]
[Problems to be solved by the invention]
These resins are completely non-conductive, and when used for applications that require electrical conductivity, add conductive fillers to these resins or apply antistatic agents to the surface. Therefore, conductivity was obtained. However, as a characteristic of this conductive filler, there is a tendency that when a small amount is added, the conductivity is not exhibited, and when an amount exceeding a certain threshold is added, the resistance rapidly decreases. For example, when carbon black is used as a conductive filler, a volume resistivity of about 10 15 to 10 16 Ω · cm is shown when added to the resin at a few percent in terms of weight, but more than that is added. As the amount increases by 1% in a certain threshold region, the resistance value changes by 2 to 4 digits. Above a certain amount, the volume resistivity becomes 10 6 to 10 8 Ω · cm, and there is a tendency for almost no change. Indicates. Therefore, the area of 10 8 to 10 14 Ω · cm, which is required for use in laser printer transfer bodies and fixing rollers, cannot be stably achieved by simply adding carbon black, and the resin surface Alternatively, a method in which a conductive layer is formed inside and the volume resistivity in this region as a whole film is realized is the mainstream.
[0004]
However, since this method requires a plurality of layers of resin, the cost is high, and it is difficult to control a delicate resistance value.
Therefore, in view of the above situation, the present inventors have found that the above-mentioned problems can be solved by adding conductive carbon and non-conductive inorganic filler to the resin as a result of intensive studies and completed the present invention. Is.
[0005]
[Means for Solving the Problems]
The gist of the resin composition according to the present invention is that a conductive filler and at least one non-conductive inorganic filler are added to the resin, and the volume resistivity is 10 8 to 10 15 Ω · cm. The resin composition is characterized in that (Claim 1).
The resin composition according to claim 1, wherein the resin is composed of polyimide alone or polyimide and fluororesin (claim 2),
Furthermore, the structure of the polyimide has the general formula (1)
[0006]
[Chemical 6]
[0007]
3. The resin according to claim 1, wherein Ar 1 is a tetravalent organic group, Ar 2 is a divalent organic group, and n is an integer of 1 or more. A composition (claim 3);
Ar 1 in the general formula (1) is
[Chemical 7]
[0009]
[Chemical 8]
[0010]
It consists of at least 1 type represented by these, It is a resin composition in any one of Claims 1-3 (Claim 4),
Ar 2 in the general formula (1) is
[Chemical 9]
[0012]
Embedded image
[0013]
The resin composition according to any one of claims 1 to 4, wherein the resin composition is at least one type represented by the formula (Claim 5).
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The resin composition according to the present invention is mainly composed of a polyimide alone or a polyimide and a fluororesin as a main component, and particularly a resin mainly composed of a polyimide represented by the general formula (1) and a fluororesin. The polyimide that is the main component of the resin according to the present invention has excellent heat resistance, chemical resistance, and wear resistance. Of these, polyimide having an ester group exhibits thermoplasticity, has very good processability and has a characteristic of low water absorption. This polyimide can be polymerized from the monomer by a conventionally used method. Moreover, the fluororesin which is a component of this resin composition has non-adhesiveness and hydrophobicity due to its structure having a fluorine atom. In addition, it has a low coefficient of friction, chemical resistance, and heat resistance. Resins prepared using these two kinds of excellent resins as the main components exhibit excellent characteristics without impairing the excellent characteristics of both.
[0015]
Any form of conductive filler may be used. For example, carbon black, metal, metal oxide, and metal nitride. The addition amount may be such a small addition amount that the volume resistivity of the resin exhibits 10 12 to 10 16 Ω · cm when the non-conductive inorganic filler is not added and it is added alone. For example, in the case of carbon black, it is preferably 0.5 to 5%, more preferably 2 to 5%. Any non-conductive inorganic filler can be considered, but when added alone to the resin, when the amount of non-conductive inorganic filler contained in the resin is 20 wt%, the volume resistivity of the resin is low. It should be 10 14 Ω · cm or higher. Preferably, mica, glass beads, smectite, boron nitride, titanate whiskers and the like are preferable. The addition amount is preferably 10 to 40%, more preferably 15 to 35%. However, the amount of conductive filler and non-conductive filler has an optimum region depending on the combination of each type. For example, in the case of a combination of carbon black and swellable mica, 3 to 5% of carbon black, swellable mica 15 ~ 25%. The fluororesin is not particularly limited. In the case of polytetrafluoroethylene, any melting point may be used, but the melting point is preferably 325 ° C. or higher. Polytetrafluoroethylene has a melting point determined by its molecular weight, but when the melting point is 325 ° C. or lower, the thermal decomposition temperature is low and the heat resistance is poor.
[0016]
Any method may be used to obtain a uniform resin by mixing these resins and fillers, but there is a difference in uniformity depending on the method, and thus there is a difference in the volume resistivity of the obtained resin. is there. For example, when polyimide is polymerized as in the conventional method to obtain a polyamic acid solution that is a precursor of the polyimide, filler is mixed with it, and then kneading is repeated with three rolls, the dispersibility of the filler is very high. The volume resistivity can be controlled effectively. Alternatively, a filler may be added in advance to a solvent for polymerizing polyimide, and polymerization may be performed using the solvent to obtain a polyamic acid solution in which the filler is dispersed. This method has an advantage that filler aggregation is less likely to occur. Further, the kneading of the polyamic acid solution with three rolls may be repeated thereafter. The polyamic acid solution obtained by these methods is imidized by a conventionally used method, and can be processed into a film, a tube, or other molded body. Alternatively, a molded body may be obtained by mixing a filler with polyimide by extrusion molding. In this case, a filler may be mixed with the polyimide powder in advance, or may be added at the time of extrusion.
[0017]
The resin composition thus obtained can be controlled to have a volume resistivity of 10 8 to 10 15 Ω · cm by changing the amount of the non-conductive inorganic filler.
In addition, if the volume resistivity does not fall outside the scope of the present application without significantly degrading the performance of polyimide and fluororesin, other than stabilizers, lubricants, surfactants, pigments, compatibilizers, polyimide resins and fluororesins These resins may be added, and this is not particularly limited.
Further, the mixing ratio of polyimide and fluororesin is not particularly specified.
[0018]
In the above, application examples have been described in order to clarify the usefulness of the resin composition according to the present invention, but the present invention is not limited thereto, and the present invention is within the scope of the gist of those skilled in the art. Based on the knowledge, the present invention can be implemented in a mode with various improvements, changes, and modifications.
[0019]
【Example】
First, the method for producing polyimide used in the examples of the present invention will be described in detail, but the present invention is not limited to these examples.
Example 1
Into a 50 ml volumetric flask (1), 15.6 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as BAPP) and 25.4 g of dimethylformamide (hereinafter referred to as DMF) were taken. Was sufficiently dissolved. Further, 1.0 g of BAPP and 10.0 g of DMF were taken into another 50 ml volumetric flask (2) and dissolved sufficiently. On the other hand, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic acid dianhydride (hereinafter referred to as ESDA) 11 was added to a 500 ml three-necked flask equipped with a stirrer. .9 g, 3,3 ′, 4,4′-benzophenyltetracarboxylic acid dianhydride (hereinafter referred to as BTDA) 6.4 g, and DMF 25.0 g were added, and the atmosphere in the flask was cooled with ice water. Was stirred and dissolved sufficiently with nitrogen. First, the BAPP solution obtained in advance in the 50 ml volumetric flask (1) was gradually put into the 500 ml three-necked flask while stirring. After being left stirring for about 30 minutes, the BAPP solution in the 50 ml volumetric flask (2) was gradually put into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. When the viscosity reached 1500 poise, 85.2 g of DMF was further added, and stirring was continued until it became uniform. Further, the BAPP solution in the 50 ml volumetric flask (2) was gradually put into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. After reaching the maximum viscosity, the addition of the BAPP solution was terminated and the mixture was allowed to stand with stirring for 1 hour to obtain a polyamic acid polymer solution. Next, 1.40 g of conductive carbon black 3030B manufactured by Mitsubishi Chemical Corporation, 6.98 g of swellable mica Somasif ME-100 manufactured by Corp Chemical Co., and 55.7 g of DMF were taken in a 200 ml beaker and stirred well. And ultrasonic cleaning for 1 hour. Thereafter, this solution was mixed with the above-described polyamic acid polymer solution and stirred well, and then a three-roll roll with a distance between the rolls of 1000 μm was passed five times and kneaded well.
[0020]
The polyamic acid polymer solution thus obtained was applied on a PET film, heated at 80 ° C. for 25 minutes, then peeled off from the PET film and fixed on a metal support, and then 150 ° C., 200 ° C., 250 ° C. Each was heated at 270 ° C. and 300 ° C. for 5 minutes to obtain a thermoplastic polyimide film. The volume resistivity of this film was measured and found to be 3.0 × 10 10 Ω · cm.
(Example 2)
In Example 1, the amount of conductive carbon black 3030B was set to 1.05 g, and conductive carbon black and Somasif ME-100 were added in advance to a 500 ml three-necked flask in the same manner as in Example 1. A polyamic acid solution was obtained, a film was further produced, and its volume resistivity was measured and found to be 6.1 × 10 14 Ω · cm.
(Comparative Example 1)
The polyamic acid polymer solution before adding the filler prepared in Example 1 was applied onto a PET film, and a thermoplastic polyimide film was obtained in the same manner as in Example 1. The volume resistivity of this film was 10 16 Ω · cm or more.
(Comparative Example 2)
A thermoplastic polyimide film was prepared in the same manner as in Example 1 except that Somasif ME-100 manufactured by Co-op Chemical Co., Ltd. was not used, and its volume resistivity was measured to be 10 16 Ω · cm or more.
[0021]
【The invention's effect】
As described above, the resin composition according to the present invention can easily control the volume resistivity that has been difficult to control by adding a conductive filler and a non-conductive inorganic filler to the resin. it can. This resin composition can be processed into a film shape, a tube shape, or a molded body by a casting method, extrusion molding, or injection molding, and can be used for various applications.
In addition, the resin composition of the present invention is particularly composed of polyimide and fluorine resin represented by the general formula (1), and thus has excellent characteristics, heat resistance, radiation resistance, mechanical properties, dimensional stability, Excellent film forming accuracy, flame retardancy, abrasion resistance, low coefficient of friction, water repellency, offset property, electrical properties, etc., especially low water absorption, and film formation by melt extrusion method further improves dimensional accuracy and film thickness accuracy Excellent film. For this reason, such resin compositions include, for example, FPC (Flexible Printed Circuit Board), insulation films for electric wires, seat belts, food trays, medical parts such as catheters, optical parts, and precision electric and electronic members using heat resistance. For example, it is suitable for various belts and fixing rollers of copying machines and printers. Further, since the dimensional accuracy is good, it can be used for a driving belt of precision equipment or the like. Furthermore, various uses can be expected in all other fields.
Claims (3)
当該樹脂組成物の体積抵抗率が108〜1015Ω・cmに制御されており、かつ、
上記樹脂がポリイミド単独からなるものであり、
上記ポリイミドの構造が下記一般式(1)
上記導電性フィラーはカーボンブラックであり、上記非導電性無機フィラーは膨潤性雲母であり、
上記カーボンブラックは3〜5重量%、上記膨潤性雲母は15〜25重量%添加されているものであることを特徴とする樹脂組成物。A resin composition comprising a combination of a conductive filler and at least one non-conductive inorganic filler added to a resin,
The volume resistivity of the resin composition is controlled to 10 8 to 10 15 Ω · cm, and
The resin is made of polyimide alone,
The structure of the polyimide is the following general formula (1)
The conductive filler is carbon black, the non-conductive inorganic filler is swellable mica,
3. A resin composition comprising 3 to 5% by weight of the carbon black and 15 to 25% by weight of the swellable mica .
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WO2000061658A1 (en) * | 1999-04-09 | 2000-10-19 | Kaneka Corporation | Polyimide resin, resin composition with improved moisture resistance comprising the same, adhesive solution, filmy bonding member, layered adhesive film, and processes for producing these |
US20080317523A1 (en) * | 2005-02-16 | 2008-12-25 | Sumitomo Electric Fine Polymer, Inc. | Fixing Belt |
JP5285567B2 (en) * | 2009-10-09 | 2013-09-11 | 株式会社カネカ | Insulating polyimide film, coverlay film, and flexible printed wiring board |
JP5285578B2 (en) * | 2009-11-13 | 2013-09-11 | 株式会社カネカ | Insulating polyimide film, coverlay film and flexible printed wiring board |
CN113527738B (en) * | 2020-04-13 | 2023-04-14 | 达迈科技股份有限公司 | Polyimide composite film for flexible metal-clad substrate and manufacturing method thereof |
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JPS6250344A (en) * | 1985-08-29 | 1987-03-05 | Sumitomo Bakelite Co Ltd | Transparent and electrically conductive plastic film |
JP3461005B2 (en) * | 1992-01-29 | 2003-10-27 | グンゼ株式会社 | Seamless semiconductive belt and method of manufacturing the same |
JPH0825232B2 (en) * | 1992-06-12 | 1996-03-13 | グンゼ株式会社 | Seamless semi-conductive belt |
JPH06240138A (en) * | 1993-02-17 | 1994-08-30 | Ntn Corp | Polyimide resin composition for sliding material |
JPH06254941A (en) * | 1993-03-09 | 1994-09-13 | Gunze Ltd | Seamless-type semi-conductive belt |
JP2516310B2 (en) * | 1993-04-16 | 1996-07-24 | 日東電工株式会社 | Tubular |
JP3451738B2 (en) * | 1993-09-22 | 2003-09-29 | 株式会社ブリヂストン | Charging member and charging device |
JPH07173325A (en) * | 1993-12-17 | 1995-07-11 | Citizen Watch Co Ltd | Antistatic resin composition |
JPH0881628A (en) * | 1994-09-14 | 1996-03-26 | Toshiba Chem Corp | Heat-resistant electrically conductive paste |
JP3409226B2 (en) * | 1995-03-27 | 2003-05-26 | 日東電工株式会社 | Semiconductive resin sheet and method for producing the same |
JP3646824B2 (en) * | 1996-03-26 | 2005-05-11 | 東洋紡績株式会社 | Thermoplastic resin composition and molded article thereof |
JPH10204305A (en) * | 1996-11-25 | 1998-08-04 | Cosmo Sogo Kenkyusho:Kk | Electromagnetic-wave-shielding resin composition and molding made therefrom |
JP3721768B2 (en) * | 1997-01-24 | 2005-11-30 | 宇部興産株式会社 | Photosensitive polyimide siloxane composition and insulating film |
JP3744634B2 (en) * | 1997-02-17 | 2006-02-15 | 株式会社カネカ | Polyimide resin film |
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