JP4963831B2 - Semiconductive structure, conductive and / or thermally conductive structure, method for producing the structure, and use thereof - Google Patents
Semiconductive structure, conductive and / or thermally conductive structure, method for producing the structure, and use thereof Download PDFInfo
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- JP4963831B2 JP4963831B2 JP2005369205A JP2005369205A JP4963831B2 JP 4963831 B2 JP4963831 B2 JP 4963831B2 JP 2005369205 A JP2005369205 A JP 2005369205A JP 2005369205 A JP2005369205 A JP 2005369205A JP 4963831 B2 JP4963831 B2 JP 4963831B2
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
- Sliding-Contact Bearings (AREA)
Description
本発明は、半導電性構造体、導電性及び/又は熱伝導性構造体、該構造体の製造方法、およびその用途に関する。詳細には、導電性および/または熱伝導性フィラーとしての炭素フィラーをポリマー中に分散させてなるプラスチック構造体において、従来と同一の配合量でも従来より高い導電性および/または熱伝導性を発揮する若しくは従来よりも少ない配合量で従来と同等もしくはそれ以上の高い導電性および/または熱伝導性を発揮し、高温高荷重に耐え、摩擦係数が小さく、摩耗しにくい構造体、および該構造体の製造方法、並びにその用途に関する。 The present invention relates to a semiconductive structure, a conductive and / or thermally conductive structure, a method for producing the structure, and uses thereof. Specifically, a plastic structure in which carbon filler as conductive and / or thermally conductive filler is dispersed in a polymer exhibits higher conductivity and / or thermal conductivity than the conventional one even with the same blending amount. Or a structure that exhibits high electrical conductivity and / or thermal conductivity equivalent to or higher than that of conventional ones with a smaller blending amount than the conventional one, can withstand high temperature and high load, has a small friction coefficient, and is not easily worn, and the structure This invention relates to the manufacturing method of
自動車や航空機等には半導体部品や精密電気機器が多く用いられている。半導体部品は静電気によって破損することがあるので、半導体製造現場や半導体部品を組み込んだ機器では静電気の発生を防止する措置が必要である。また精密電気機器などでは外部からの電磁波によって誤動作することがあるので、電磁波を遮蔽する措置が必要になる場合がある。そのために、静電気の発生防止や電磁波の遮蔽を目的として半導電性樹脂成形品が用いられている。
半導電性/導電性樹脂成形品としては、樹脂やエラストマーに導電性フィラーを練りこんだ材料を成形したものが知られている。
樹脂やゴムなどに充填する導電性フィラー量を増やしていくと、緩やかに導電性が増加し、ある臨界充填量(閾値)を超えると導電性が劇的に増加し、導電性の劇的増加の後は再び緩やかに導電性が増加していく。
Semiconductor parts and precision electrical equipment are often used in automobiles and aircraft. Since semiconductor components can be damaged by static electricity, measures must be taken to prevent the generation of static electricity at semiconductor manufacturing sites and devices incorporating semiconductor components. In addition, since precision electrical equipment and the like may malfunction due to external electromagnetic waves, measures for shielding electromagnetic waves may be required. Therefore, semiconductive resin molded products are used for the purpose of preventing the generation of static electricity and shielding electromagnetic waves.
As a semiconductive / conductive resin molded product, a product obtained by molding a material obtained by kneading a conductive filler in a resin or an elastomer is known.
Increasing the amount of conductive filler to be filled in resin, rubber, etc. will increase the conductivity gradually, and if it exceeds a certain critical filling amount (threshold), the conductivity will increase dramatically and the conductivity will increase dramatically. After that, the conductivity gradually increases again.
樹脂等に導電性フィラーを練りこんだ材料を用いて、帯電防止に適した体積固有抵抗値にするためには、導電性フィラーを閾値以上添加する必要がある。しかし、導電性フィラーを閾値以上に添加すると、樹脂の溶融流動性が低下し成形加工が困難となり、ショートショットになりやすい。また導電性フィラーを多量に添加して成形加工できたとしても成形品の表面外観が悪くなりやすく、またショット毎の質量のばらつき等で満足な成形品が得られず、さらに衝撃強度等の機械的性質に劣った成形品しか得られない場合があった。 In order to obtain a volume specific resistance value suitable for antistatic using a material in which a conductive filler is kneaded into a resin or the like, it is necessary to add the conductive filler above a threshold value. However, when the conductive filler is added to a threshold value or more, the melt fluidity of the resin is lowered and the molding process becomes difficult, and a short shot is likely to occur. Even if a large amount of conductive filler can be added and molded, the surface appearance of the molded product tends to deteriorate, and satisfactory molded products cannot be obtained due to variations in the mass of each shot. In some cases, only molded articles with inferior physical properties can be obtained.
このようなことから少量の導電性フィラーの配合で、高い導電性を有する成形品を得るために種々検討がなされている。例えば、導電性フィラーの粒子径、アスペクト比、比表面積などを調整することが提案されているが、成形加工時の流動性を悪化させることがあり、適用可能な導電性フィラーに制限がある。導電性フィラーとの親和性が高い樹脂と、親和性が低い樹脂とをブレンドし、海島構造のミクロドメインを形成することが提案されている(特許文献1及び2)。しかしながら、樹脂ブレンドによって性質が変化するのを許容できない用途等の場合には、この方法は適用できない。また、導電性フィラーの表面を処理して、樹脂/導電性フィラー間の界面エネルギーを大きくする方法が提案されている(非特許文献1)。しかし、この方法を適用できる樹脂が限定され、また導電性フィラーの表面処理は、導電性フィラー本来の特性を損なう場合がありその適用が限定される。
このように、導電性以外の物性低下、成形時の流動性低下などを引き起こさずに、少量の導電性フィラーで高い導電性を持つ成形品を得るための満足できる方法は見出されていない。
For this reason, various studies have been made to obtain a molded article having high conductivity by blending a small amount of conductive filler. For example, it has been proposed to adjust the particle diameter, aspect ratio, specific surface area, and the like of the conductive filler, but the fluidity at the time of molding may be deteriorated, and applicable conductive fillers are limited. It has been proposed to blend a resin having a high affinity with the conductive filler and a resin having a low affinity to form a microdomain having a sea-island structure (
As described above, no satisfactory method has been found for obtaining a molded product having high conductivity with a small amount of conductive filler without causing deterioration in physical properties other than conductivity, fluidity during molding, and the like.
一方、ハードディスクなどの摺動部分を持つ機器では、摺動部分の摩擦によって発生する静電気や熱が機器の動作を誤らせることがある。また、摺動部分の磨耗によって発生する微粉等が精密機器に入り込みやはり誤動作の原因となることがある。そのために、静電気による帯電防止や摩擦熱の放散を目的として導電性及び/又は熱伝導性樹脂成形品が用いられている。摺動部材等に用いられる導電性及び/又は熱伝導性樹脂成形品としては、例えば、炭素繊維を樹脂に混合して得られるものが提案されている(特許文献3及び4)。しかし、上述したように、導電性/熱伝導性を得るためには多量のフィラーを配合する必要がある。そのために配合したフィラーが磨耗によって微粉となって飛散することがある。このように、導電性/熱伝導性以外の物性低下、成形時の流動性低下などを引き起こさずに、少量の導電性/熱伝導性フィラーで高い導電性/熱伝導性を持つ成形品を得るための満足できる方法は見出されていない。 On the other hand, in a device having a sliding portion such as a hard disk, static electricity or heat generated by friction of the sliding portion may cause the device to malfunction. In addition, fine powder generated by wear of the sliding portion may enter into precision equipment and cause malfunction. Therefore, conductive and / or thermally conductive resin molded products are used for the purpose of preventing static electricity due to static electricity and dissipating frictional heat. As a conductive and / or thermally conductive resin molded product used for a sliding member or the like, for example, a product obtained by mixing carbon fiber with a resin has been proposed (Patent Documents 3 and 4). However, as described above, it is necessary to add a large amount of filler in order to obtain conductivity / thermal conductivity. For this reason, the blended filler may be scattered as fine powder due to wear. In this way, a molded article having high conductivity / thermal conductivity is obtained with a small amount of conductive / thermal conductive filler without causing deterioration in physical properties other than conductivity / thermal conductivity, fluidity reduction during molding, and the like. No satisfactory method has been found for this.
本発明の目的は、導電性および/または熱伝導性フィラーとしての炭素フィラーをポリマー中に分散させてなるプラスチック構造体において、従来と同一の配合量でも従来より高い導電性および/または熱伝導性を発揮する若しくは従来よりも少ない配合量で従来と同等もしくはそれ以上の高い導電性および/または熱伝導性を発揮し、高温高荷重に耐え、摩擦係数が小さく、摩耗しにくい構造体、および該構造体の製造方法、並びにその用途を提供することにある。 An object of the present invention is to provide a plastic structure in which a carbon filler as a conductive and / or heat conductive filler is dispersed in a polymer. A structure that exhibits high electrical conductivity and / or thermal conductivity equivalent to or higher than that of a conventional material with a blending amount less than that of the prior art, withstands high temperature and high load, has a low coefficient of friction, and is not easily worn. It is in providing the manufacturing method of a structure, and its use.
本発明者らは鋭意検討を重ねた結果、ポリマー粒子および炭素フィラーを乾式混合して、 ポリマー粒子表面の少なくとも一部に炭素フィラーが存在し、ひとつのポリマー粒子と他のポリマー粒子との間に炭素フィラーが介在している混合物を得、その混合物を1〜500kgf/cm2の圧力で且つポリマー粒子の荷重たわみ温度、融点またはガラス転移温度以上の温度で加圧成形することによって、ポリマーだけからなるA相と、炭素フィラーを主成分として含有するB相とを含み、前記B相が前記A相それぞれの周囲を取り囲み、ひとつのA相と他のA相との間にB相が介在し、該B相が3次元網目構造又は断面がマーブル模様状に分布している構造体が得られ、この構造体が従来と同一の配合量でも従来より高い導電性および/または熱伝導性を発揮する若しくは従来よりも少ない配合量で従来と同等もしくはそれ以上の高い導電性および/または熱伝導性を発揮することを見出した。さらにこの構造体を摺動部材に適用すると、高温高荷重に耐え、摩擦係数が小さく、摩耗しにくく、かつ熱伝導性が良好で、発生する熱を速やかに放出することができ、さらに、相手材がアルミニウムであっても、アルミニウムを損傷させることなく、摺動性能を長期間保持することができることを見出した。本発明はこれらの知見に基づいて完成したものである。 As a result of intensive studies, the inventors of the present invention dry-mixed the polymer particles and the carbon filler so that the carbon filler is present on at least a part of the surface of the polymer particle, and between one polymer particle and another polymer particle. A mixture in which carbon fillers are present is obtained, and the mixture is pressure-molded at a pressure of 1 to 500 kgf / cm 2 and at a temperature equal to or higher than the deflection temperature under load, melting point, or glass transition temperature of the polymer particles. And a B phase containing a carbon filler as a main component, the B phase surrounds each of the A phases, and a B phase is interposed between one A phase and another A phase. , A structure in which the B phase is distributed in a three-dimensional network structure or in a marble pattern is obtained. Exhibits thermal conductivity or was found to exhibit a conventional equal to or more high conductivity and / or thermal conductivity with a smaller amount than before. Furthermore, when this structure is applied to a sliding member, it can withstand high temperatures and high loads, has a low friction coefficient, is not easily worn, has good thermal conductivity, and can quickly release the generated heat. It has been found that even if the material is aluminum, the sliding performance can be maintained for a long time without damaging the aluminum. The present invention has been completed based on these findings.
かくして本発明によれば、
〔1〕 ポリマー粒子表面の少なくとも一部に炭素フィラーが存在し、ひとつのポリマー粒子と他のポリマー粒子との間に炭素フィラーが介在している混合物。
〔2〕 前記〔1〕に記載の混合物をポリマー粒子の荷重たわみ温度、融点またはガラス転移温度以上の温度で加熱することにより、ポリマー粒子を軟化させ、ひとつの炭素フィラーと他の炭素フィラーとの隙間に軟化ポリマーを浸み込ませてなる、ポリマーだけから成るA相と炭素フィラーを主成分として含有するB相とを含み、B相が3次元網目構造を形成している、構造体。
〔3〕 ポリマーだけからなるA相と、炭素フィラーを主成分として含有するB相とを含み、前記B相が前記A相それぞれの周囲を取り囲み、ひとつのA相と他のA相との間にB相が介在し、該B相がマーブル模様状に分布している構造体。
〔4〕 ポリマー粒子は、熱可塑性樹脂、熱可塑性エラストマー、未架橋の熱硬化性樹脂および未架橋のエラストマーからなる群から選ばれる少なくとも1つのポリマーから成る粒子である前記〔2〕に記載の構造体。
〔5〕 ポリマー粒子は、その平均粒径が1μmから500μmである前記〔2〕に記載の構造体。
Thus, according to the present invention,
[1] A mixture in which a carbon filler is present on at least a part of the surface of the polymer particle, and the carbon filler is interposed between one polymer particle and another polymer particle.
[2] By heating the mixture according to the above [1] at a temperature equal to or higher than the deflection temperature under load, melting point or glass transition temperature of the polymer particles, the polymer particles are softened, and one carbon filler and another carbon filler A structure in which a softening polymer is soaked in a gap, and includes a phase A made of only a polymer and a phase B containing a carbon filler as a main component, and the phase B forms a three-dimensional network structure.
[3] A phase comprising only a polymer and a B phase containing a carbon filler as a main component, the B phase surrounding each of the A phases, and between one A phase and another A phase A structure in which the B phase intervenes and the B phase is distributed in a marble pattern.
[4] The structure according to [2], wherein the polymer particles are particles composed of at least one polymer selected from the group consisting of a thermoplastic resin, a thermoplastic elastomer, an uncrosslinked thermosetting resin, and an uncrosslinked elastomer. body.
[5] The structure according to [2], wherein the polymer particles have an average particle diameter of 1 μm to 500 μm.
〔6〕 炭素フィラーは、カーボンブラック、炭素繊維、および黒鉛からなる群から選ばれる少なくとも1つのものである前記〔2〕又は〔3〕に記載の構造体。
〔7〕 炭素フィラーが気相法炭素繊維であり、
該気相法炭素繊維は、平均繊維径が20〜500nm、アスペクト比が20〜1000、BET比表面積が4〜100m2/g、X線回折法によるd002が0.345nm以下、ラマン散乱スペクトルの1341〜1349cm-1のバンドのピーク高さ(Id)と1570〜1578cm-1のバンドのピーク高さ(Ig)の比:(Id/Ig)が0.1〜2である前記〔2〕又は〔3〕に記載の構造体。
〔8〕 炭素フィラーが気相法炭素繊維であり、
該気相法炭素繊維は、不活性雰囲気下、2000〜3500℃の温度で熱処理したものである前記〔2〕又は〔3〕に記載の構造体。
〔9〕 気相法炭素繊維は、その平均繊維径が50〜200nmである前記〔7〕又は〔8〕に記載の構造体。
〔10〕 ポリマー粒子および炭素フィラーを乾式混合し、次いで1〜500kgf/cm2の圧力で且つポリマー粒子の荷重たわみ温度、融点またはガラス転移温度以上の温度で加圧成形して得られた前記〔2〕又は〔3〕に記載の構造体。
[6] carbon fillers include carbon black, structure according to the carbon fibers, and that the at least one thing selected from black lead or Ranaru group [2] or [3].
[7] The carbon filler is vapor grown carbon fiber,
The vapor grown carbon fiber has an average fiber diameter of 20 to 500 nm, an aspect ratio of 20 to 1000, a BET specific surface area of 4 to 100 m 2 / g, an X-ray diffraction d 002 of 0.345 nm or less, and a Raman scattering spectrum. the ratio of the peak height of the band 1341~1349cm -1 (I d) and the band peak height 1570~1578cm -1 (I g): ( I d / I g) is 0.1 to 2 The structure according to [2] or [3].
[8] The carbon filler is vapor grown carbon fiber,
The structure according to [2] or [3], wherein the vapor grown carbon fiber is heat-treated at a temperature of 2000 to 3500 ° C. in an inert atmosphere.
[9] The structure according to [7] or [8], wherein the vapor grown carbon fiber has an average fiber diameter of 50 to 200 nm.
[10] The above-mentioned obtained by dry-mixing polymer particles and carbon filler, and then press-molding at a pressure of 1 to 500 kgf / cm 2 and at a temperature higher than the deflection temperature under load, melting point or glass transition temperature of the polymer particles [ [2] or [3].
〔11〕 ポリマー粒子および炭素フィラーを乾式混合し、次いで1〜500kgf/cm2の圧力で且つポリマー粒子の荷重たわみ温度、融点またはガラス転移温度以上の温度で加圧成形することを含む前記〔2〕又は〔3〕に記載の構造体の製造方法。
〔12〕 加圧成形する際の保持時間が15分以上である前記〔11〕に記載の構造体の製造方法。
〔13〕 加圧成形した後、所望の形状に切削加工することをさらに含む前記〔11〕に記載の構造体の製造方法。
〔14〕 所望の形状になる金型を用いて加圧成形する前記〔11〕に記載の構造体の製造方法。
〔15〕 乾式混合をポリマー粒子の荷重たわみ温度、融点またはガラス転移温度未満の温度で行う、前記〔11〕に記載の構造体の製造方法。
[11] The method comprising dry-mixing polymer particles and carbon filler, and then press-molding at a pressure of 1 to 500 kgf / cm 2 and at a temperature equal to or higher than the deflection temperature under load, melting point or glass transition temperature of the polymer particles [2 ] Or the manufacturing method of the structure as described in [3].
[12] The method for producing a structure according to [11], wherein a holding time at the time of pressure molding is 15 minutes or more.
[13] The method for manufacturing a structure according to [11], further including cutting into a desired shape after the pressure forming.
[14] The method for producing a structure according to [11], wherein pressure molding is performed using a mold having a desired shape.
[15] The method for producing a structure according to [11], wherein the dry mixing is performed at a temperature lower than the deflection temperature under load, the melting point, or the glass transition temperature of the polymer particles.
〔16〕 構造体100質量部に対して、ポリマーを99.5〜90質量部、炭素フィラーを0.5〜10質量部含み、体積固有抵抗が102〜1010Ωcmである、前記〔2〕又は〔3〕に記載の半導電性構造体。
〔17〕 炭素フィラーが気相法炭素繊維である前記〔16〕に記載の半導電性構造体。
〔18〕 構造体100質量部に対して、ポリマーを80〜50質量部、炭素フィラーを20〜50質量部含み、体積固有抵抗が10−4〜102Ωcmであり、且つ熱伝導率が7W/mK以上である、前記〔2〕又は〔3〕に記載の導電性及び/又は熱伝導性構造体。
〔19〕 炭素フィラー20〜50質量部が、気相法炭素繊維0.5〜30質量部、黒鉛粉体0〜20質量部および黒鉛化炭素繊維0〜30質量部からなる、前記〔18〕に記載の導電性及び/又は熱伝導性構造体。
[16] The above-mentioned [2], containing 99.5 to 90 parts by mass of a polymer and 0.5 to 10 parts by mass of a carbon filler with respect to 100 parts by mass of the structure, and having a volume resistivity of 10 2 to 10 10 Ωcm. ] Or the semiconductive structure according to [3].
[17] The semiconductive structure according to [16], wherein the carbon filler is vapor grown carbon fiber.
[18] 80 to 50 parts by mass of the polymer and 20 to 50 parts by mass of the carbon filler with respect to 100 parts by mass of the structure, the volume resistivity is 10 −4 to 10 2 Ωcm, and the thermal conductivity is 7 W. The conductive and / or thermally conductive structure according to [2] or [3], which is / mK or more.
[19] The above [18], wherein 20 to 50 parts by mass of carbon filler comprises 0.5 to 30 parts by mass of vapor grown carbon fiber, 0 to 20 parts by mass of graphite powder, and 0 to 30 parts by mass of graphitized carbon fiber. The electrically conductive and / or thermally conductive structure described in 1.
〔20〕 前記〔16〕又は〔17〕に記載の半導電性構造体からなる帯電防止部材。
〔21〕 半導体、半導体部品、ハードディスクヘッド、又はハードディスクを搬送するためのトレー用である前記〔20〕に記載の帯電防止部材
〔22〕 前記〔16〕又は〔17〕に記載の半導電性構造体からなる帯電防止摺動部材。
〔23〕 クリーンルーム内で使用される部品用である前記〔22〕に記載の帯電防止摺動部材。
〔24〕 クリーンルーム内で使用される製造機械部品用である前記〔22〕に記載の帯電防止摺動部材。
[20] An antistatic member comprising the semiconductive structure according to [16] or [17].
[21] The antistatic member according to [20], which is for a semiconductor, a semiconductor component, a hard disk head, or a tray for transporting a hard disk. [22] The semiconductive structure according to [16] or [17] An antistatic sliding member comprising a body.
[23] The antistatic sliding member according to [22], which is for a part used in a clean room.
[24] The antistatic sliding member according to [22], which is used for manufacturing machine parts used in a clean room.
〔25〕 前記〔18〕又は〔19〕に記載の導電性及び/又は熱伝導性構造体からなる導電性部材。
〔26〕 燃料電池のセパレーター用である前記〔25〕に記載の導電性部材。
〔27〕 前記〔18〕又は〔19〕に記載の導電性及び/又は熱伝導性構造体からなる耐熱摺動部材。
〔28〕 高温高荷重環境下で使用される部品用である前記〔27〕に記載の耐熱摺動部材。
〔29〕 高温高荷重環境下で使用される製造装置部品、OA機器部品又は自動車部品用である、前記〔27〕に記載の耐熱摺動部材。
が提供される。
[25] A conductive member comprising the conductive and / or thermally conductive structure according to [18] or [19].
[26] The conductive member according to [25], which is for a fuel cell separator.
[27] A heat-resistant sliding member comprising the conductive and / or thermally conductive structure according to [18] or [19].
[28] The heat-resistant sliding member according to [27], which is for parts used in a high-temperature and high-load environment.
[29] The heat-resistant sliding member according to [27], which is used for manufacturing equipment parts, OA equipment parts, or automobile parts used in a high temperature and high load environment.
Is provided.
導電性フィラーおよび/または熱伝導性フィラーを、1種のポリマー中に分散させて導電性能および/または熱伝導性能に優れるプラスチックを得るに際し、通常は導電性フィラーと樹脂を溶融混練し、更に射出成形される場合が多い。その場合、溶融樹脂中の導電性フィラーはせん断力で分散されるため、導電および伝熱ネットワークが破壊されたり、導電性フィラーの破壊が起こり、特に繊維状導電性フィラーではアスペクト比が小さくなる傾向があり、所望の導電性又は伝熱性を得るためにフィラーを多量に添加する必要があることが知られている。本発明では、軟化ポリマー中でせん断力が加わらないので、効果的なネットワーク構造を形成でき、所望の導電性又は伝熱性を得るために必要な炭素フィラーの添加量を劇的に少なくすることが可能になり、その産業上の利用価値は極めて高い。 When a conductive filler and / or thermally conductive filler is dispersed in one kind of polymer to obtain a plastic having excellent conductive performance and / or thermal conductive performance, the conductive filler and resin are usually melt-kneaded and then injected. Often molded. In that case, since the conductive filler in the molten resin is dispersed by shearing force, the conductive and heat transfer networks are broken, or the conductive filler is broken. Especially, the aspect ratio tends to be small in the fibrous conductive filler. It is known that a large amount of filler needs to be added in order to obtain the desired conductivity or heat conductivity. In the present invention, since no shear force is applied in the softened polymer, an effective network structure can be formed, and the amount of carbon filler added to obtain the desired conductivity or heat conductivity can be dramatically reduced. It becomes possible, and its industrial utility value is extremely high.
本発明の(半導電性、導電性および/または熱伝導性)構造体は、ポリマー本来が有していた機械的強度を持ち、且つ導電性、帯電防止性などの電気的特性および熱伝導性などの熱的特性が優れている。また、本発明の構造体は、機械的強度、塗装性、熱安定性、衝撃強度に優れ、かつ導電性、帯電防止性に優れているので、電気電子部品の搬送、包装用部品、電気電子分野やOA機器用部品、静電塗装用の自動車部品など、多くの分野に有用である。さらに本発明の構造体は、熱伝導性に優れているので、温度や荷重の許容範囲が広くなり、高温高荷重で使用される摺動部材に好適である。本発明の構造体はその産業上の利用価値は極めて高い。 The (semiconductive, conductive and / or thermally conductive) structure of the present invention has the mechanical strength inherent to the polymer, and has electrical characteristics such as conductivity and antistatic properties, and thermal conductivity. Excellent thermal characteristics. In addition, since the structure of the present invention is excellent in mechanical strength, paintability, thermal stability, impact strength, and excellent in conductivity and antistatic properties, it is possible to transport electric and electronic parts, packaging parts, electric and electronic parts. It is useful in many fields such as fields, parts for office automation equipment, and automotive parts for electrostatic coating. Furthermore, since the structure of the present invention is excellent in thermal conductivity, the allowable range of temperature and load is wide, and it is suitable for a sliding member used at high temperature and high load. The structure of the present invention has a very high industrial utility value.
本発明の構造体において、アスペクト比の高い気相法炭素繊維を用いた場合でも、炭素繊維の破壊が抑制されアスペクト比の低下がほとんどない。炭素繊維を高充填することによって、高温高荷重に耐え、摩擦係数が小さく、摩耗しにくく且つフィラーの脱離が少なく、かつ熱伝導性が良好で、発生する熱を速やかに放出することができる。さらに、相手材がアルミニウムであっても、アルミニウムを損傷させることなく、性能を長期間保持することができる摺動部材を得ることができる。本発明はその産業上の利用価値は極めて高い。
本発明の摺動部材は、力学的特性、耐熱性、熱伝導性に優れている。特に摺動性に関しては、摩擦係数および摩耗量ともに小さく、限界PV値が非常に大きい。そのため、自動車、電気・電子分野等の摺動部材として広範な用途に使用できる。
In the structure of the present invention, even when vapor-grown carbon fiber having a high aspect ratio is used, the destruction of the carbon fiber is suppressed and the aspect ratio is hardly lowered. By high-filling carbon fiber, it can withstand high temperatures and high loads, has a low coefficient of friction, is hard to wear, has little filler detachment, has good thermal conductivity, and can quickly release generated heat. . Furthermore, even if the counterpart material is aluminum, a sliding member that can maintain the performance for a long time without damaging the aluminum can be obtained. The present invention has an extremely high industrial utility value.
The sliding member of the present invention is excellent in mechanical properties, heat resistance, and thermal conductivity. In particular, with regard to slidability, both the coefficient of friction and the amount of wear are small, and the limit PV value is very large. Therefore, it can be used for a wide range of applications as a sliding member in automobiles, electrical / electronic fields and the like.
(ポリマー粒子と炭素フィラーとの混合物)
本発明の混合物は、 ポリマー粒子表面の少なくとも一部に炭素フィラーが存在し、ひとつのポリマー粒子と他のポリマー粒子との間に炭素フィラーが介在しているものである。図4(1)は本発明の混合物の一例を概念的に示した図である。図中、黒線で示した炭素フィラーの中に白丸で示したポリマー粒子が浮かんで分散しているようになっている。この混合物中ではポリマー粒子は自由に動くことができ相互に結合していない。
(Mixture of polymer particles and carbon filler)
In the mixture of the present invention, a carbon filler is present on at least a part of the surface of the polymer particle, and the carbon filler is interposed between one polymer particle and another polymer particle. FIG. 4 (1) is a diagram conceptually showing an example of the mixture of the present invention. In the figure, polymer particles indicated by white circles are floated and dispersed in the carbon filler indicated by black lines. In this mixture, the polymer particles can move freely and are not bonded to each other.
本発明に用いるポリマー粒子はその粒子径が通常1〜500μm、好ましくは5〜200μmである。この粒子径が大きすぎると分散不良を起こしやすくなる。ポリマー粒子を構成するポリマーは、特に制限されず、例えば、熱可塑性樹脂、熱可塑性エラストマー、未架橋の熱硬化性樹脂、未架橋のエラストマーから選択することができる。 The polymer particles used in the present invention have a particle size of usually 1 to 500 μm, preferably 5 to 200 μm. If this particle size is too large, poor dispersion tends to occur. The polymer constituting the polymer particles is not particularly limited, and can be selected from, for example, a thermoplastic resin, a thermoplastic elastomer, an uncrosslinked thermosetting resin, and an uncrosslinked elastomer.
熱可塑性樹脂としては、成形分野で使用される熱可塑性樹脂であれば特に制限はなく、例えば、ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)、ポリトリメチレンテレフタレート(PTT)、ポリエチレンナフタレート(PEN)、液晶ポリエステル(LCP)等のポリエステル;ポリエチレン(PE)、ポリプロピレン(PP)、ポリブテンー1(PB−1)、ポリブチレン等のポリオレフィン;スチレン系樹脂;ポリオキシメチレン(POM)、ポリアミド(PA)、ポリカーボネート(PC),ポリメチレメタクリレート(PMMA)、ポリ塩化ビニル(PVC)、ポリフェニレンエーテル(PPE)、ポリフェニレンスルフィド(PPS)、ポリイミド(PI)、ポリアミドイミド(PAI)、ポリエーテルイミド(PEI)、ポリスルフォン(PSU)、ポリエーテルスルフォン、ポリケトン(PK)、ポリエーテルケトン(PEK)、ポリエーテルエーテルケトン(PEEK)、ポリエーテルケトンケトン(PEKK)、ポリアリレート(PAR)、ポリエーテルニトリル(PEN);フェノール(ノボラック型など)フェノキシ樹脂;ポリテトラフルオロエチレン(PTFE)などのフッ素系樹脂;熱可塑性ポリイミド、ポリベンズイミダゾール、液晶ポリマー、シクロオレフィンポリマー、ポリアセタール、ポリフェニレンオキサイド、熱可塑性ポリエステル、超高分子量ポリエチレンなどが挙げられる。そしてこれらは共重合体や変性体であってもよいし、2種類以上をブレンドした樹脂であってもよい。また、更に耐衝撃性向上のために、上記熱可塑性樹脂にその他のエラストマーもしくはゴム成分を添加した樹脂であってもよい。
超高分子量ポリエチレンなどの分子量が非常に高い樹脂や、ポリテトラフルオロエチレンなどの成形加工条件幅が狭く溶融混練ができない樹脂、ポリベンズイミダゾールなどの非常に耐熱性が高く溶融流動性を示さない樹脂であっても、本発明の方法を用いれば、容易に半導電性、導電性及び/又は熱伝導性の構造体を得ることができる。
熱可塑性エラストマーとしてはポリスチレン系、ポリオレフィン系、ポリウレタン系、ポリエステル系、ポリアミド系、ポリブタジエン系、ポリイソプレン系、フッ素系等の熱可塑性エラストマー等が挙げられる。
The thermoplastic resin is not particularly limited as long as it is a thermoplastic resin used in the molding field. For example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate ( PEN), polyesters such as liquid crystal polyester (LCP); polyolefins such as polyethylene (PE), polypropylene (PP), polybutene 1 (PB-1), polybutylene; styrene resins; polyoxymethylene (POM), polyamide (PA) , Polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyimide (PI), polyamideimide (PAI), poly Etherimide (PEI), polysulfone (PSU), polyethersulfone, polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), Polyether nitrile (PEN); Phenol (novolak type, etc.) phenoxy resin; Fluorine resin such as polytetrafluoroethylene (PTFE); Thermoplastic polyimide, polybenzimidazole, liquid crystal polymer, cycloolefin polymer, polyacetal, polyphenylene oxide, heat Examples thereof include plastic polyester and ultrahigh molecular weight polyethylene. These may be copolymers or modified products, or may be a resin in which two or more types are blended. Further, in order to further improve impact resistance, a resin obtained by adding another elastomer or a rubber component to the thermoplastic resin may be used.
Resins with very high molecular weight such as ultra-high molecular weight polyethylene, resins such as polytetrafluoroethylene that cannot be melt kneaded with a narrow range of molding conditions, and resins that do not show melt fluidity such as polybenzimidazole Even so, if the method of the present invention is used, a semiconductive, conductive and / or thermally conductive structure can be easily obtained.
Examples of the thermoplastic elastomer include thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluorine.
熱硬化性樹脂としては、成形分野で使用される熱硬化性樹脂であれば特に制限はなく、例えば、不飽和ポリエステル、ビニルエステル、エポキシ、フェノール(レゾール型)、ユリア・メラミン、ポリイミド等が挙げられる。これらは共重合体や変性体であってもよいし、2種類以上をブレンドした樹脂であってもよい。また、更に耐衝撃性向上のために、上記熱硬化性樹脂にエラストマーもしくはゴム成分を添加した樹脂であってもよい。熱可塑性樹脂、熱硬化性樹脂又はエラストマーからなるポリマー粒子は混合物中では未架橋/未硬化のものである。そして、後述するように混合物を加圧成形する際に熱可塑性樹脂、熱硬化性樹脂又はエラストマーを架橋/硬化してもよい。
エラストマーとしては、天然ゴム、イソプレンゴム、スチレンブタジエンゴム、ブタジエンゴム、クロロプレンゴム、二トリルゴム、ブチルゴム、エチレンプロピレンゴム、ウレタンゴム、シリコンゴム、アクリルゴム、クロルスルホン化ポリエチレンゴム、フッ素ゴム、水素化二トリルゴム、エピクロルヒドリンゴム、多硫化ゴムなどが挙げられる。
The thermosetting resin is not particularly limited as long as it is a thermosetting resin used in the molding field, and examples thereof include unsaturated polyester, vinyl ester, epoxy, phenol (resole type), urea melamine, polyimide, and the like. It is done. These may be copolymers or modified products, or may be a resin in which two or more types are blended. Further, in order to further improve the impact resistance, a resin obtained by adding an elastomer or a rubber component to the thermosetting resin may be used. The polymer particles made of thermoplastic resin, thermosetting resin or elastomer are uncrosslinked / uncured in the mixture. Then, as will be described later, the thermoplastic resin, thermosetting resin or elastomer may be crosslinked / cured when the mixture is pressure-molded.
Elastomers include natural rubber, isoprene rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, acrylic rubber, chlorosulfonated polyethylene rubber, fluoro rubber, hydrogenated hydrogen Examples include tolyl rubber, epichlorohydrin rubber and polysulfide rubber.
これらポリマーのうち、ポリエーテルエーテルケトン、ポリエーテルケトン、熱可塑性ポリイミド、ポリベンズイミダゾール、液晶ポリマー、ポリエーテルサルフォン、ポリサルフォン、ポリエーテルイミド、ポリアミドイミド、ポリフェニレンサルファイド、シクロオレフィンポリマー、ポリカーボネート、ポリアミド、ポリアセタール、ポリフェニレンオキサイド、熱可塑性ポリエステル、ポリテトラフルオロエチレン、超高分子量ポリエチレンが好適である。 Among these polymers, polyetheretherketone, polyetherketone, thermoplastic polyimide, polybenzimidazole, liquid crystal polymer, polyethersulfone, polysulfone, polyetherimide, polyamideimide, polyphenylene sulfide, cycloolefin polymer, polycarbonate, polyamide, Polyacetal, polyphenylene oxide, thermoplastic polyester, polytetrafluoroethylene, and ultrahigh molecular weight polyethylene are preferred.
本発明で用いる炭素フィラーは、導電性又は伝熱性を付与することができる炭素材料であれば特に制限はない。例えば、カーボンブラック、炭素繊維、黒鉛などが挙げられる。これらのうち炭素繊維、特に気相法炭素繊維が好適である。 If the carbon filler used by this invention is a carbon material which can provide electroconductivity or heat conductivity, there will be no restriction | limiting in particular. For example, carbon black, carbon fiber, graphite and the like can be mentioned. Of these, carbon fibers, particularly vapor grown carbon fibers are preferred.
本発明で用いる気相法炭素繊維は、例えば、高温の不活性ガス雰囲気下で、触媒となる鉄と共にガス化された有機化合物を吹き込むことにより製造することができる(特開平7−150419号公報等)。
本発明で使用する気相法炭素繊維は、その平均繊維径が20〜500nmであることが好ましく、50〜200nmであることがさらに好ましい。平均繊維径が小さくなると表面エネルギーが指数関数的に大きくなり、繊維同士の凝集力が増大する傾向がある。平均繊維径の小さい気相法炭素繊維とポリマー粒子とを単純に乾式ブレンドしても、炭素繊維の凝集が解けず、十分に分散されず、効果的な導電または熱伝導ネットワークの形成が困難になる。そのために炭素繊維の添加量を多くしなければならなくなり、構造体の機械的特性、特に衝撃性が低下傾向になる。一方、平均繊維径が大きくなると、炭素繊維は容易に分散するが、微視的に均一なものができないばかりでなく、成形品表面にも炭素繊維が出やすくなり、摺動特性を低下させることがある。
The vapor grown carbon fiber used in the present invention can be produced, for example, by blowing an organic compound gasified with iron serving as a catalyst in a high-temperature inert gas atmosphere (Japanese Patent Laid-Open No. 7-150419). etc).
The vapor grown carbon fiber used in the present invention preferably has an average fiber diameter of 20 to 500 nm, and more preferably 50 to 200 nm. When the average fiber diameter decreases, the surface energy increases exponentially, and the cohesion between fibers tends to increase. Simple dry blending of vapor-grown carbon fibers and polymer particles with a small average fiber diameter does not dissolve the carbon fibers and does not fully disperse, making it difficult to form an effective conductive or heat conductive network Become. Therefore, it is necessary to increase the amount of carbon fiber added, and the mechanical properties of the structure, in particular, impact properties tend to be lowered. On the other hand, when the average fiber diameter is increased, the carbon fibers are easily dispersed, but not only microscopically uniform cannot be obtained, but also the carbon fibers are likely to appear on the surface of the molded product, thereby reducing the sliding characteristics. There is.
本発明で使用する気相法炭素繊維は、そのアスペクト比が好ましくは20〜1000であり、より好ましくは40〜500である。
アスペクト比が大きくなる(すなわち、繊維長が長くなる)と炭素繊維同士が絡まりあい、容易にほぐすことができなくなり、十分な分散が得られなくなる。一方、アスペクト比が小さくなると、導電ネットワークを形成するために10質量%以上のフィラーを添加しなければならず、ポリマーの流動性や引張強度の低下が顕著になるので好ましくない。
The vapor grown carbon fiber used in the present invention preferably has an aspect ratio of 20 to 1000, more preferably 40 to 500.
When the aspect ratio is large (that is, the fiber length is long), the carbon fibers are entangled and cannot be easily loosened, and sufficient dispersion cannot be obtained. On the other hand, when the aspect ratio is small, it is not preferable because a filler of 10% by mass or more must be added to form a conductive network, and the fluidity and tensile strength of the polymer are significantly reduced.
本発明で使用する気相法炭素繊維は、その分岐度が、好ましくは0.3個/μm以下、より好ましくは0.2個/μm以下、さらに好ましくは0.1個/μm以下である。分岐度が0.3個/μmを超えると、炭素繊維が強固な凝集体を形成してしまい、少量で効率的な導電性付与が困難な傾向になる。 The degree of branching of the vapor grown carbon fiber used in the present invention is preferably 0.3 pieces / μm or less, more preferably 0.2 pieces / μm or less, and further preferably 0.1 pieces / μm or less. . If the degree of branching exceeds 0.3 / μm, the carbon fiber forms a strong aggregate, and it tends to be difficult to efficiently impart conductivity in a small amount.
本発明で使用する気相法炭素繊維は、X線回折法による平均面間隔d002が、好ましくは0.345nm以下、より好ましくは0.343nm以下、さらに好ましくは0.340nm以下である。平均面間隔d002が0.345nmを超えるものは、グラファイト結晶が十分発達していないため、炭素繊維単身の抵抗率が大きくなる傾向がある。さらに、ポリマーなどに混合したときの、炭素繊維−ポリマー−炭素繊維間の電子の移動が困難な傾向になり、所望の導電性を得るための炭素繊維添加量が多くなる傾向がある。 The vapor grown carbon fiber used in the present invention has an average interplanar spacing d 002 by an X-ray diffraction method of preferably 0.345 nm or less, more preferably 0.343 nm or less, and further preferably 0.340 nm or less. When the average interplanar spacing d 002 exceeds 0.345 nm, the graphite crystal is not sufficiently developed, so that the resistivity of the carbon fiber alone tends to increase. Furthermore, when mixed with a polymer or the like, the movement of electrons between carbon fiber-polymer-carbon fiber tends to be difficult, and the amount of carbon fiber added to obtain desired conductivity tends to increase.
本発明で使用する気相法炭素繊維は、そのBET比表面積が、好ましくは4〜100m2/g、より好ましくは10〜40m2/gである。BET比表面積が大きい炭素繊維は、その表面エネルギーが大きくなり、付着・凝集力が強くなるために分散が困難な傾向になる。さらに、マトリックスポリマーと炭素繊維の界面積が大きくなり、マトリックスポリマーが十分に繊維を被覆することができなくなったり、炭素繊維がマトリックスポリマーから剥離する確率が増大傾向になる。その結果、ポリマーとの複合体を作製した場合、電気伝導性のみならず機械的強度の劣化を招くことがある。 Vapor grown carbon fiber employed in the present invention has a BET specific surface area is preferably 4~100m 2 / g, more preferably 10 to 40 m 2 / g. A carbon fiber having a large BET specific surface area tends to be difficult to disperse because its surface energy increases and adhesion / cohesion force increases. Furthermore, the interfacial area between the matrix polymer and the carbon fiber increases, and the matrix polymer cannot sufficiently cover the fiber, or the probability that the carbon fiber peels from the matrix polymer tends to increase. As a result, when a composite with a polymer is produced, not only electrical conductivity but also mechanical strength may be deteriorated.
本発明で使用する気相法炭素繊維は、そのラマン散乱スペクトルの1341〜1349cm−1のバンドのピーク高さ(Id)と1570〜1578cm−1のバンドのピーク高さ(Ig)の比(Id/Ig)は、好ましくは0.1〜2、より好ましくは0.1〜1.4、さらに好ましくは0.15〜1.3、特に好ましくは0.2〜1.2である。 Vapor grown carbon fiber employed in the present invention, the ratio of the band peak height of the Raman scattering spectrum of 1341~1349cm -1 (I d) and the band peak height 1570~1578cm -1 (I g) (I d / I g ) is preferably 0.1 to 2, more preferably 0.1 to 1.4, still more preferably 0.15 to 1.3, and particularly preferably 0.2 to 1.2. is there.
本発明で使用する気相法炭素繊維は、有機遷移金属化合物の存在下、炭素源(有機化合物)を熱分解することにより製造することができる。
炭素繊維の原料となる炭素源(有機化合物)としては、トルエン、ベンゼン、ナフタレン、エチレン、アセチレン、エタン、天然ガス、一酸化炭素等のガスが挙げられ、それらを単独でまたは2以上を組み合わせて用いることができる。これらの中でもトルエン、ベンゼン等の芳香族炭化水素が好ましい。
The vapor grown carbon fiber used in the present invention can be produced by thermally decomposing a carbon source (organic compound) in the presence of an organic transition metal compound.
Examples of the carbon source (organic compound) used as the raw material for the carbon fiber include gases such as toluene, benzene, naphthalene, ethylene, acetylene, ethane, natural gas, carbon monoxide, and the like, alone or in combination of two or more. Can be used. Among these, aromatic hydrocarbons such as toluene and benzene are preferable.
有機遷移金属化合物は、触媒となる遷移金属を含む化合物である。触媒として用いる遷移金属としては周期律表第4〜10族の元素が挙げられる。好ましい有機遷移金属化合物としてはフェロセン、ニッケロセンが挙げられる。
熱分解反応雰囲気下で、遷移金属触媒粒子表面に吸着した水素などのガスを効率的に除去し、触媒活性を高めるための助触媒として、硫黄、チオフェンなどの硫黄化合物を用いることができる。
An organic transition metal compound is a compound containing a transition metal serving as a catalyst. Examples of the transition metal used as the catalyst include elements in groups 4 to 10 of the periodic table. Preferable organic transition metal compounds include ferrocene and nickelocene.
Sulfur compounds such as sulfur and thiophene can be used as a co-catalyst for efficiently removing gas such as hydrogen adsorbed on the surface of the transition metal catalyst particles and enhancing the catalytic activity in a pyrolysis reaction atmosphere.
水素などの還元性ガスをキャリアガスに用い、上記有機化合物と有機遷移金属化合物、及び硫黄化合物を800〜1300℃に加熱した反応炉へ供給し、熱分解反応させることによって炭素繊維を得ることができる。 A carbon fiber can be obtained by using a reducing gas such as hydrogen as a carrier gas, supplying the organic compound, the organic transition metal compound, and the sulfur compound to a reaction furnace heated to 800 to 1300 ° C. and performing a thermal decomposition reaction. it can.
原料の形態としては、芳香族炭化水素に有機遷移金属化合物および硫黄化合物を溶解させたもの(液体原料)や、500℃以下で気化させたもの(気体原料)を用いることができる。しかし、液体原料は、反応管壁において気化・分解を起こし、反応管内で局所的に原料濃度分布が生じ、その結果、生成した炭素繊維同士が凝集する傾向を示す。したがって、原料の形態としては、反応管中における原料濃度分布を生じ難い気体原料が好ましい。 As the form of the raw material, a material obtained by dissolving an organic transition metal compound and a sulfur compound in an aromatic hydrocarbon (liquid raw material), or a material vaporized at 500 ° C. or lower (gas raw material) can be used. However, the liquid raw material is vaporized and decomposed on the reaction tube wall, and the concentration distribution of the raw material is locally generated in the reaction tube. As a result, the generated carbon fibers tend to aggregate. Therefore, as a form of the raw material, a gaseous raw material that hardly causes a raw material concentration distribution in the reaction tube is preferable.
遷移金属触媒と硫黄化合物助触媒との割合は、遷移金属/(遷移金属+硫黄)×100[質量%]の計算式において15〜35質量%が好ましい。15質量%以下になると、触媒活性が高まり、繊維の分岐数が増大したり、放射状に繊維が生成したりする等、繊維同士の相互作用が増加して強固な凝集体を形成しやすい。また、35質量%以上になると、触媒に吸着した水素を十分除去できなくなり、触媒への炭素源供給が阻害され炭素繊維以外の炭素粒子が発生しやすくなる。 The ratio of the transition metal catalyst and the sulfur compound co-catalyst is preferably 15 to 35% by mass in the formula of transition metal / (transition metal + sulfur) × 100 [% by mass]. When the amount is 15% by mass or less, the catalytic activity increases, the number of fiber branches increases, the fibers are generated radially, and the like, and the interaction between the fibers increases to form a strong aggregate. On the other hand, when it is 35% by mass or more, hydrogen adsorbed on the catalyst cannot be sufficiently removed, and the supply of the carbon source to the catalyst is hindered, and carbon particles other than carbon fibers are likely to be generated.
炭素繊維の分岐数および凝集体のほぐれ具合は、炭素繊維合成時の原料濃度により決定される。すなわち、気相中の原料濃度が高いと、生成した炭素繊維表面に触媒粒子の不均一な核が発生し、炭素繊維表面からさらに炭素繊維が成長し、樹氷状の炭素繊維が形成される。また、高濃度で生成した炭素繊維同士が絡み合い、容易にほぐすことができない。したがって、反応管中の原料供給量とキャリアガス流量の比は、1g/リットル以下が好ましく、0.5g/リットル以下がより好ましくは、0.2g/リットル以下が特に好ましい。 The number of branches of the carbon fiber and the degree of loosening of the aggregate are determined by the raw material concentration at the time of carbon fiber synthesis. That is, when the raw material concentration in the gas phase is high, non-uniform nuclei of the catalyst particles are generated on the surface of the produced carbon fiber, and the carbon fiber grows further from the surface of the carbon fiber to form a frost-like carbon fiber. Moreover, carbon fibers produced at a high concentration are entangled and cannot be easily loosened. Therefore, the ratio of the raw material supply amount in the reaction tube to the carrier gas flow rate is preferably 1 g / liter or less, more preferably 0.5 g / liter or less, and particularly preferably 0.2 g / liter or less.
炭素繊維表面に付着したタールなどの有機物を除去するために不活性雰囲気中で900〜1300℃で熱処理することが好ましい。炭素繊維の導電率を向上させるためには、さらに不活性雰囲気下で2000〜3500℃で熱処理を行い、結晶を発達させることが好ましい。 In order to remove organic substances such as tar adhering to the carbon fiber surface, heat treatment is preferably performed at 900 to 1300 ° C. in an inert atmosphere. In order to improve the electrical conductivity of the carbon fiber, it is preferable to further develop a crystal by performing a heat treatment at 2000 to 3500 ° C. in an inert atmosphere.
結晶を発達させるために使用する熱処理炉は、2000℃以上、好ましくは2300℃以上の所望する温度に保持できる炉であればよく、通常の、アチソン炉、抵抗炉、高周波炉他の何れの装置でもよい。また、場合によっては、粉体または成形体に直接通電して加熱する方法も使用できる。 The heat treatment furnace used to develop the crystal may be any furnace that can be maintained at a desired temperature of 2000 ° C. or higher, preferably 2300 ° C. or higher, and any ordinary apparatus such as an Atchison furnace, a resistance furnace, a high-frequency furnace, or the like. But you can. Moreover, depending on the case, the method of heating by energizing powder or a molded object directly can also be used.
熱処理の雰囲気は非酸化性の雰囲気、好ましくはアルゴン、ヘリウム、ネオン等の1種もしくは2種以上の希ガス雰囲気がよい。熱処理の時間は、生産性の面からは出来るだけ、短い方が好ましい。長時間加熱を続けると、焼結し固まってくるので、製品収率も悪化する。従って、成形体等の中心部の温度が目標温度に達した後、その温度に10分〜1時間保持すれば十分である。 The atmosphere for the heat treatment is a non-oxidizing atmosphere, preferably an atmosphere of one or more rare gases such as argon, helium and neon. The heat treatment time is preferably as short as possible from the viewpoint of productivity. If heating is continued for a long time, the product yield deteriorates because it sinters and hardens. Therefore, after the temperature of the center part of the molded body or the like reaches the target temperature, it is sufficient to hold the temperature for 10 minutes to 1 hour.
炭素繊維の結晶をさらに発達させ、導電性を向上させるために、不活性雰囲気下で2000〜3500℃で加熱する黒鉛化処理を行う際に、炭化ホウ素(B4C)、酸化ホウ素(B2O3)、元素状ホウ素、ホウ酸(H3BO3)、ホウ酸塩等のホウ素化合物を混合してもよい。 Boron carbide (B 4 C), boron oxide (B 2 ) when performing graphitization treatment in which heating is performed at 2000 to 3500 ° C. in an inert atmosphere in order to further develop carbon fiber crystals and improve conductivity. Boron compounds such as O 3 ), elemental boron, boric acid (H 3 BO 3 ), and borate may be mixed.
ホウ素化合物の添加量は、用いるホウ素化合物の化学的特性、物理的特性に依存するため一概に規定できないが、例えば炭化ホウ素(B4C)を使用した場合には、炭素繊維に対して0.05〜10質量%、好ましくは0.1〜5質量%の範囲がよい。 The amount of boron compound added depends on the chemical and physical properties of the boron compound used, and thus cannot be specified unconditionally. For example, when boron carbide (B 4 C) is used, the amount of boron compound added is 0. The range is from 05 to 10% by mass, preferably from 0.1 to 5% by mass.
ホウ素化合物との熱処理により、炭素繊維の結晶性が向上し、導電性が向上する。炭素繊維の結晶内あるいは結晶表面に含まれるホウ素量は0.01〜5質量%がよい。炭素繊維の導電性やポリマーとの親和性を改善するために、0.1質量%以上のホウ素を含むことがより好ましい。また、グラフェンシートに置換し得るホウ素量は3質量%程度であり、それ以上、特に5質量%以上のホウ素はホウ素炭化物やホウ素酸化物として存在し、導電性を低下させる傾向になる。 By the heat treatment with the boron compound, the crystallinity of the carbon fiber is improved and the conductivity is improved. The amount of boron contained in the carbon fiber crystal or on the crystal surface is preferably 0.01 to 5% by mass. In order to improve the conductivity of the carbon fiber and the affinity with the polymer, it is more preferable to contain 0.1% by mass or more of boron. Further, the amount of boron that can be substituted for the graphene sheet is about 3% by mass, and more than that, especially 5% by mass or more of boron exists as boron carbide or boron oxide, and tends to lower the conductivity.
また、炭素繊維とポリマーとの親和性を向上させるために炭素繊維を酸化処理して繊維表面にフェノール性水酸基、カルボキシル基、キノン基、ラクトン基を導入することもできる。さらに、シラン系あるいはチタネート系、アルミニウム系、リン酸エステル系のカップリング剤等により、表面処理を施してもよい。 In order to improve the affinity between the carbon fiber and the polymer, the carbon fiber can be oxidized to introduce a phenolic hydroxyl group, a carboxyl group, a quinone group, or a lactone group on the fiber surface. Furthermore, surface treatment may be performed with a silane-based, titanate-based, aluminum-based, or phosphate ester-based coupling agent.
本発明の混合物には、本発明の目的、効果を損なわない範囲で、他の各種ポリマー添加剤を配合することができる。配合できるポリマー添加剤としては、例えば、着色剤、可塑剤、滑剤、熱安定剤、光安定剤、紫外線吸収剤、充填剤、発泡剤、難燃剤、防錆剤などが挙げられる。これらの各種ポリマー添加剤は、ポリマー粒子と炭素フィラーとを乾式混合する際に添加するのが好ましい。 Various other polymer additives can be blended in the mixture of the present invention within a range not impairing the object and effects of the present invention. Examples of the polymer additive that can be blended include a colorant, a plasticizer, a lubricant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a filler, a foaming agent, a flame retardant, and a rust inhibitor. These various polymer additives are preferably added when the polymer particles and the carbon filler are dry-mixed.
本発明の混合物は、ポリマー粒子と炭素フィラーとを乾式混合することによって得られる。
ポリマー粒子と炭素フィラーとの混合割合は特に制限されないが、帯電防止性に優れた構造体を得る観点から、構造体100質量部に対して、ポリマー99.5〜90質量部、炭素フィラー0.5〜10質量部となる割合であることが好ましい。
The mixture of the present invention is obtained by dry-mixing polymer particles and carbon filler.
The mixing ratio of the polymer particles and the carbon filler is not particularly limited, but from the viewpoint of obtaining a structure excellent in antistatic properties, 99.5 to 90 parts by mass of the polymer and 0. The ratio is preferably 5 to 10 parts by mass.
導電性及び/又は熱伝導性に優れた構造体を得る観点から、構造体100質量部に対して、ポリマー80〜50質量部、炭素フィラー20〜50質量部となる割合であることが好ましい。また、本発明において導電性と熱伝導性とを兼ね備えた構造体を得る観点から、炭素フィラー20〜50質量部を、気相法炭素繊維0.5〜30質量部、黒鉛粉体0〜20質量部および黒鉛化炭素繊維0〜30質量部からなるものにすることが好ましい。 From the viewpoint of obtaining a structure excellent in electrical conductivity and / or thermal conductivity, the ratio is preferably 80 to 50 parts by mass of the polymer and 20 to 50 parts by mass of the carbon filler with respect to 100 parts by mass of the structure. Moreover, from a viewpoint of obtaining the structure which has electroconductivity and heat conductivity in this invention, 20-50 mass parts of carbon fillers, 0.5-30 mass parts of vapor-grown carbon fiber, and graphite powder 0-20 It is preferable to consist of a mass part and 0-30 mass parts of graphitized carbon fiber.
乾式混合はポリマー粒子の荷重たわみ温度、融点またはガラス転移温度未満の温度で行うことが好ましい。この乾式混合によって、ポリマー粒子それぞれの周囲を炭素フィラーが取り囲むようになる。そして、ひとつのポリマー粒子と他のポリマー粒子との間に炭素フィラーが介在し、該炭素フィラーが3次元網目構造状に分布するようになる。 Dry mixing is preferably performed at a temperature below the deflection temperature under load, melting point or glass transition temperature of the polymer particles. By this dry mixing, a carbon filler surrounds each of the polymer particles. A carbon filler is interposed between one polymer particle and another polymer particle, and the carbon filler is distributed in a three-dimensional network structure.
(構造体)
本発明の構造体は、ポリマーだけからなるA相と、炭素フィラーを主成分として含有するB相とを含み、前記B相が前記A相それぞれの周囲を取り囲み、ひとつのA相と他のA相との間にB相が介在し、該B相がマーブル模様状に分布しているものである。
また、本発明の構造体は、前記の混合物をポリマー粒子の荷重たわみ温度、融点またはガラス転移温度以上の温度で加熱することにより、ポリマー粒子を軟化させ、ひとつの炭素フィラーと他の炭素フィラーとの隙間に軟化ポリマーを浸み込ませてなる、ポリマーだけから成るA相と炭素フィラーを主成分として含有するB相とを含み、B相が3次元網目構造を形成しているものである。なお、加熱する温度は、結晶性ポリマーでは融点を、非晶性ポリマーでは、ガラス転移温度を、融点及びガラス転移温度が不明又は無い場合は荷重たわみ温度を基準に用いる。
(Structure)
The structure of the present invention includes an A phase composed only of a polymer and a B phase containing a carbon filler as a main component. The B phase surrounds each of the A phases, and one A phase and another A phase. The B phase intervenes between the phases, and the B phase is distributed in a marble pattern.
Further, the structure of the present invention softens the polymer particles by heating the mixture at a temperature equal to or higher than the deflection temperature under load, melting point or glass transition temperature of the polymer particles, and one carbon filler and another carbon filler And a B phase containing a carbon filler as a main component, and the B phase forms a three-dimensional network structure. The heating temperature is based on the melting point for crystalline polymers, the glass transition temperature for amorphous polymers, and the deflection temperature under load when the melting point and glass transition temperature are unknown or absent.
図1は本発明構造体の一例の光学顕微鏡像を示す図である。図中、黒色部分は炭素フィラーを主成分として含有するB相であり、白色部分はポリマーだけからなるA相である。
図1に示すように構造体の断面を観察すると、A相の周りをB相が取り囲み、B相はマーブル模様状に分布している。そして構造体中のB相は3次元網目構造を形成している。
3次元網目構造又は断面観察においてマーブル模様状に分布したB相の平均幅は通常0.5〜100μmであり、A相の大きさは、平均相当直径で、通常0.1〜1000μm、好ましくは1〜500μmである。
FIG. 1 is a view showing an optical microscope image of an example of the structure of the present invention. In the figure, the black portion is a B phase containing a carbon filler as a main component, and the white portion is an A phase consisting only of a polymer.
When the cross section of the structure is observed as shown in FIG. 1, the B phase surrounds the A phase, and the B phase is distributed in a marble pattern. The B phase in the structure forms a three-dimensional network structure.
The average width of the B phase distributed in a marble pattern in a three-dimensional network structure or cross-sectional observation is usually 0.5 to 100 μm, and the size of the A phase is an average equivalent diameter, usually 0.1 to 1000 μm, preferably 1 to 500 μm.
本発明の構造体は、前記混合物を1〜500kgf/cm2の圧力で且つポリマー粒子の荷重たわみ温度、融点またはガラス転移温度以上の温度で加圧成形することによって得られる。図4(2)は構造体の構造を模式的に示した図である。加圧成形においては炭素フィラーにかかるせん断力が弱いので、混合物(図4(1))の3次元網目構造を維持したまま、構造体(図4(2))を形成することができる。加圧成形する際の保持時間は好ましくは15分以上である。 The structure of the present invention can be obtained by pressure-molding the mixture at a pressure of 1 to 500 kgf / cm 2 and a temperature higher than the deflection temperature under load, melting point or glass transition temperature of the polymer particles. FIG. 4B is a diagram schematically showing the structure of the structure. In the pressure molding, since the shearing force applied to the carbon filler is weak, the structure (FIG. 4 (2)) can be formed while maintaining the three-dimensional network structure of the mixture (FIG. 4 (1)). The holding time at the time of pressure molding is preferably 15 minutes or more.
加圧成形において所望の形状になる金型を用いることによって、用途に応じた形状の構造体を容易に得ることができる。また、加圧成形した後で所望の形状に切削加工することによって用途に応じた形状の構造体を得てもよい。 By using a mold having a desired shape in the pressure molding, a structure having a shape corresponding to the application can be easily obtained. Moreover, you may obtain the structure of a shape according to a use by cutting into a desired shape after press-molding.
本発明の導電性構造体は、構造体100質量部に対して、ポリマーを99.5〜90質量部、炭素フィラーを0.5〜10質量部含み、体積固有抵抗が102〜1010Ωcmである。
また本発明の導電性/熱伝導性構造体は、構造体100質量部に対して、ポリマーを80〜50質量部、炭素フィラーを20〜50質量部含み、体積固有抵抗が10−4〜102Ωcmであり、且つ熱伝導率が7W/mK以上である。
The conductive structure of the present invention contains 99.5 to 90 parts by mass of a polymer and 0.5 to 10 parts by mass of a carbon filler with respect to 100 parts by mass of the structure, and has a volume resistivity of 10 2 to 10 10 Ωcm. It is.
In addition, the conductive / thermally conductive structure of the present invention includes 80 to 50 parts by mass of a polymer and 20 to 50 parts by mass of a carbon filler with respect to 100 parts by mass of the structure, and has a volume resistivity of 10 −4 to 10. 2 Ωcm and the thermal conductivity is 7 W / mK or more.
本発明の構造体は炭素フィラーの添加量によって、半導電性構造体、又は導電性/熱伝導性構造体にすることができる。そして半導電性構造体は、帯電防止部材、帯電防止摺動部材として好適である。本発明の帯電防止部材は、特に半導体、半導体部品、ハードディスクヘッド、ハードディスクを搬送するためのトレー用途に好適である。また本発明の帯電防止摺動部材はクリーンルーム内で使用される部品用や、クリーンルーム内で使用される製造機械部品用に好適である。本発明の導電性及び/又は熱伝導性構造体は、導電性部材、耐熱摺動部材として利用され、導電性部材は燃料電池のセパレーターに好適であり、耐熱摺動部材は高温高荷重環境下で使用される部品用や、高温高荷重環境下で使用される製造装置部品、OA機器部品又は自動車部品用に好適である。 The structure of the present invention can be made into a semiconductive structure or a conductive / thermally conductive structure depending on the amount of carbon filler added. The semiconductive structure is suitable as an antistatic member or an antistatic sliding member. The antistatic member of the present invention is particularly suitable for tray applications for transporting semiconductors, semiconductor components, hard disk heads, and hard disks. Further, the antistatic sliding member of the present invention is suitable for parts used in a clean room and for manufacturing machine parts used in a clean room. The conductive and / or thermally conductive structure of the present invention is used as a conductive member and a heat-resistant sliding member, and the conductive member is suitable for a fuel cell separator. It is suitable for parts used in the above, manufacturing equipment parts used in high temperature and high load environments, OA equipment parts or automobile parts.
以下に本発明を実施例によって、詳しく説明するが、本発明はこれらの範囲に限定されるものではない。
実施例1
ポリエーテルエーテルケトン(PEEK)粒子99.5質量部と、気相法炭素繊維(VGCF−S)0.5質量部とをヘンシェルミキサー(容量10リットル)で室温で10分間乾式混合し、巨視的に均一な混合物を得た。この混合物は、図4(1)に示すようにポリマー粒子それぞれの周囲を炭素フィラーが取り囲み、ひとつのポリマー粒子と他のポリマー粒子との間に炭素フィラーが介在していた。
この混合物を金型に充填し、温度360℃、圧力200kgf/cm2で30分間加圧成形して構造体(200×200×60mm厚)を得た。この構造体を各種評価試験に必要な形状に切削加工して試験片を得た。評価結果を表1に示した。この構造体は光学顕微鏡観察で図1に示すようなマーブル模様状にPEEK相(白色部)と炭素フィラー相(黒色部)とが分布していた。B相の平均幅が約10μm、A相の平均相当直径が約30μmであった。
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these ranges.
Example 1
Macroscopically, 99.5 parts by mass of polyether ether ketone (PEEK) particles and 0.5 parts by mass of vapor grown carbon fiber (VGCF-S) were dry-mixed at room temperature for 10 minutes with a Henschel mixer (capacity 10 liters). A homogeneous mixture was obtained. In this mixture, as shown in FIG. 4 (1), the carbon filler surrounds each of the polymer particles, and the carbon filler is interposed between one polymer particle and another polymer particle.
This mixture was filled in a mold and subjected to pressure molding at a temperature of 360 ° C. and a pressure of 200 kgf / cm 2 for 30 minutes to obtain a structure (200 × 200 × 60 mm thickness). This structure was cut into a shape necessary for various evaluation tests to obtain a test piece. The evaluation results are shown in Table 1. In this structure, the PEEK phase (white portion) and the carbon filler phase (black portion) were distributed in a marble pattern as shown in FIG. The average width of the B phase was about 10 μm, and the average equivalent diameter of the A phase was about 30 μm.
実施例2〜5
表1に示す配合処方に代えた他は実施例1と同様にして構造体を得た。評価結果を表1に示した。これらの構造体の断面は光学顕微鏡観察で図1に示すようなマーブル模様状にPEEK相(白色部)と炭素フィラー相(黒色部)とが分布していた。
実施例6〜8
表1に示す配合処方に代え、加圧成形時の温度を310℃にした他は実施例1と同様にして構造体を得た。評価結果を表1に示した。これらの構造体は実施例1と同様のマーブル模様状にPPS相(白色部)と炭素フィラー相(黒色部)とが分布していた。
実施例9〜10
表1に示す配合処方に代え、加圧成形時の温度を500℃にした他は実施例1と同様にして構造体を得た。評価結果を表1に示した。これらの構造体は実施例1と同様のマーブル模様状にPBI相(白色部)と炭素フィラー相(黒色部)とが分布していた。
Examples 2-5
A structure was obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was used. The evaluation results are shown in Table 1. In the cross section of these structures, the PEEK phase (white portion) and the carbon filler phase (black portion) were distributed in a marble pattern as shown in FIG.
Examples 6-8
A structure was obtained in the same manner as in Example 1 except that the temperature at the time of pressure molding was changed to 310 ° C. instead of the formulation shown in Table 1. The evaluation results are shown in Table 1. In these structures, the PPS phase (white portion) and the carbon filler phase (black portion) were distributed in the same marble pattern as in Example 1.
Examples 9-10
A structure was obtained in the same manner as in Example 1 except that the temperature at the time of pressure molding was changed to 500 ° C. instead of the formulation shown in Table 1. The evaluation results are shown in Table 1. In these structures, the PBI phase (white portion) and the carbon filler phase (black portion) were distributed in the same marble pattern as in Example 1.
比較例1
ポリエーテルエーテルケトン(PEEK)粒子93質量部と気相法炭素繊維(VGCF−S)7質量部とを同方向2軸押出機を用いて360℃で練り合わせ、次いで380℃で射出成形して成形体(100×100×3mm厚、フィルムゲート)を得た。この成形体を各種評価試験に必要な形状に切削加工して試験片を得た。評価結果を表2に示した。この成形体の透過型電子顕微鏡像は図3に示すように炭素フィラーがポリマーマトリックス中に均一分散していた。
比較例2〜3
表2に示す配合処方に代えた他は比較例1と同様にして構造体を得た。評価結果を表2に示した。この成形体は炭素フィラーがポリマーマトリックス中に均一分散していた。
比較例4〜5
表2に示す配合処方に代え、310℃で練り合わせ、320℃で射出成形した他は比較例1と同様にして成形体を得た。評価結果を表2に示した。この成形体は炭素フィラーがポリマーマトリックス中に均一分散していた。この成形体は透過型電子顕微鏡像が図3に示すように、炭素フィラーがポリマーマトリックス中に均一分散していた。
Comparative Example 1
93 parts by mass of polyetheretherketone (PEEK) particles and 7 parts by mass of vapor grown carbon fiber (VGCF-S) were kneaded at 360 ° C. using the same direction twin screw extruder, and then injection molded at 380 ° C. A body (100 × 100 × 3 mm thick, film gate) was obtained. The molded body was cut into a shape necessary for various evaluation tests to obtain a test piece. The evaluation results are shown in Table 2. In the transmission electron microscope image of this molded product, as shown in FIG. 3, the carbon filler was uniformly dispersed in the polymer matrix.
Comparative Examples 2-3
A structure was obtained in the same manner as in Comparative Example 1 except that the formulation shown in Table 2 was used. The evaluation results are shown in Table 2. In this molded body, the carbon filler was uniformly dispersed in the polymer matrix.
Comparative Examples 4-5
A molded body was obtained in the same manner as in Comparative Example 1 except that it was mixed at 310 ° C. and injection molded at 320 ° C. instead of the formulation shown in Table 2. The evaluation results are shown in Table 2. In this molded body, the carbon filler was uniformly dispersed in the polymer matrix. As shown in the transmission electron microscope image of this molded product, the carbon filler was uniformly dispersed in the polymer matrix.
実施例11〜15
表3に示す配合処方に代えた他は実施例1と同様にして構造体を得た。評価結果を表3に示した。これらの構造体はマーブル模様状にPEEK相(白色部)と炭素フィラー相(黒色部)とが分布していた。
実施例16〜18
表3に示す配合処方に代え、加圧成形時の温度を310℃にした他は実施例1と同様にして構造体を得た。評価結果を表3に示した。これらの構造体はマーブル模様状にPPS相(白色部)と炭素フィラー相(黒色部)とが分布していた。
実施例19〜21
表3に示す配合処方に代え、加圧成形時の温度を220℃にした他は実施例1と同様にして構造体を得た。評価結果を表3に示した。これらの構造体はマーブル模様状にPP相(白色部)と炭素フィラー相(黒色部)とが分布していた。
Examples 11-15
A structure was obtained in the same manner as in Example 1 except that the formulation shown in Table 3 was used. The evaluation results are shown in Table 3. In these structures, a PEEK phase (white portion) and a carbon filler phase (black portion) were distributed in a marble pattern.
Examples 16-18
A structure was obtained in the same manner as in Example 1 except that the temperature at the time of pressure molding was changed to 310 ° C. instead of the formulation shown in Table 3. The evaluation results are shown in Table 3. In these structures, a PPS phase (white portion) and a carbon filler phase (black portion) were distributed in a marble pattern.
Examples 19-21
A structure was obtained in the same manner as in Example 1 except that the temperature at the time of pressure molding was changed to 220 ° C. instead of the formulation shown in Table 3. The evaluation results are shown in Table 3. In these structures, a PP phase (white portion) and a carbon filler phase (black portion) were distributed in a marble pattern.
比較例6
ポリエーテルエーテルケトン(PEEK)粒子70質量部と気相法炭素繊維(VGCF−S)30質量部とを同方向2軸押出機を用いて360℃で練り合わせ、次いで380℃で射出成形して成形体(100×100×3mm厚、フィルムゲート)を得た。この成形体を各種評価試験に必要な形状に切削加工して試験片を得た。評価結果を表4に示した。この成形体は図2に示すように、炭素フィラーがポリマーマトリックス中に均一分散していた。
比較例7〜8
表4に示す配合処方に代えた他は比較例6と同様にして構造体を得た。評価結果を表4に示した。この成形体は炭素フィラーがポリマーマトリックス中に均一分散していた。
Comparative Example 6
70 parts by mass of polyether ether ketone (PEEK) particles and 30 parts by mass of vapor grown carbon fiber (VGCF-S) are kneaded at 360 ° C. using the same direction twin screw extruder, and then injection molded at 380 ° C. to form. A body (100 × 100 × 3 mm thick, film gate) was obtained. The molded body was cut into a shape necessary for various evaluation tests to obtain a test piece. The evaluation results are shown in Table 4. As shown in FIG. 2, in this molded body, the carbon filler was uniformly dispersed in the polymer matrix.
Comparative Examples 7-8
A structure was obtained in the same manner as in Comparative Example 6, except that the formulation shown in Table 4 was used. The evaluation results are shown in Table 4. In this molded body, the carbon filler was uniformly dispersed in the polymer matrix.
本実施例、比較例で使用した炭素フィラーは次に示すとおりのものである。
〔気相法炭素繊維〕
イ)VGCF(登録商標):昭和電工製気相法炭素繊維(平均繊維径:150nm、平均繊維長:10μm、比表面積:13m2/g、アスペクト比:67、I0=0.2)を使用した。
ロ)VGCF−S:昭和電工製気相法炭素繊維(平均繊維径:100nm、平均繊維長:11μm、比表面積:20m2/g、アスペクト比:110、I0=0.2)を使用した。
〔炭素繊維〕
黒鉛化炭素繊維
グレード名:XN−100(チョップドファイバー) 日本グラファイトファイバー社製
〔黒鉛〕
グレード名:UFG−30 昭和電工社製
The carbon fillers used in the examples and comparative examples are as follows.
[Vapor grown carbon fiber]
A) VGCF (registered trademark): Showa Denko's vapor grown carbon fiber (average fiber diameter: 150 nm, average fiber length: 10 μm, specific surface area: 13 m 2 / g, aspect ratio: 67, I 0 = 0.2) used.
B) VGCF-S: Showa Denko vapor phase carbon fiber (average fiber diameter: 100 nm, average fiber length: 11 μm, specific surface area: 20 m 2 / g, aspect ratio: 110, I 0 = 0.2) was used. .
〔Carbon fiber〕
Graphitized carbon fiber Grade name: XN-100 (chopped fiber) manufactured by Nippon Graphite Fiber Co., Ltd. [ graphite]
Grade name: UFG-30 Showa Denko
本実施例、比較例で使用したポリマー粒子は次に示すとおりのものである。
1)PEEK
グレード名:450P ビクトレックス・エムシー社製
平均粒子径20μm、融点343℃
2)PPS
グレード名:LD−10 大日本インキ社製
平均粒子径20μm、融点280℃
3)PBI
100MESH POLYMER PBI PERFORMANCE PRODUCTS,INC社製
平均粒子径20μm、荷重たわみ温度435℃(ASTM D−648、荷重1.82MPa)
4)PP
グレード名:PM801A(ホモ) サンアロマー社製
平均粒子径20μm、融点160℃
The polymer particles used in the examples and comparative examples are as follows.
1) PEEK
Grade name: 450P Victrex MC, Inc.
2) PPS
Grade name: LD-10 Dainippon Ink Co., Ltd.
3) PBI
100MESH POLYMER PBI PERFORMANCE PRODUCTS, INC.
4) PP
Grade name: PM801A (homo) Sun Allomer's
評価物性 物性の測定方法
1)体積固有抵抗
JIS K7194に準拠し、四探針法により測定した。
2)ノッチ付アイゾット衝撃試験
ASTM D256により、測定した。
3)熱伝導率
京都電子工業社製迅速熱伝導率計を使用し、熱線法で測定した。
Measurement method of physical properties of evaluation 1) Volume resistivity Based on JIS K7194, it was measured by a four-probe method.
2) Measured by notched Izod impact test ASTM D256.
3) Thermal conductivity A rapid thermal conductivity meter manufactured by Kyoto Electronics Industry Co., Ltd. was used and measured by a hot wire method.
A:ポリマー相;B:炭素フィラー相; A: polymer phase; B: carbon filler phase;
Claims (24)
該混合物を1〜500kgf/cm2の圧力で且つポリマー粒子の荷重たわみ温度、融点またはガラス転移温度以上の温度で加圧成形することによって、 ポリマー粒子を軟化させ、ひとつの炭素フィラーと他の炭素フィラーとの隙間に軟化ポリマーを浸み込ませる、
ポリマーだけから成るA相と炭素フィラーを主成分として含有するB相とを含み、B相が3次元網目構造を形成しており且つ前記炭素フィラーが炭素繊維を含むものである、構造体の製造方法。 The polymer particles and the carbon filler are dry mixed to obtain a mixture in which the carbon filler is present on at least a part of the surface of the polymer particles and the carbon filler is interposed between one polymer particle and the other polymer particle,
By pressing the mixture at a pressure of 1 to 500 kgf / cm 2 and at a temperature higher than the deflection temperature, melting point or glass transition temperature of the polymer particles, the polymer particles are softened, and one carbon filler and another carbon Soaking the softening polymer in the gap with the filler,
And a B phase mainly containing A-phase and the carbon filler consisting of only the polymer and the carbon filler B phase forms a three-dimensional network structure is intended to include carbon fibers, the manufacturing method of the structure.
該気相法炭素繊維は、平均繊維径が20〜500nm、アスペクト比が20〜1000、BET比表面積が4〜100m2/g、X線回折法によるd002が0.345nm以下、ラマン散乱スペクトルの1341〜1349cm-1のバンドのピーク高さ(Id)と1570〜1578cm-1のバンドのピーク高さ(Ig)の比:(Id/Ig)が0.1〜2である請求項1〜4のいずれかひとつに記載の構造体の製造方法。 The carbon fiber is a vapor grown carbon fiber,
The vapor grown carbon fiber has an average fiber diameter of 20 to 500 nm, an aspect ratio of 20 to 1000, a BET specific surface area of 4 to 100 m 2 / g, an X-ray diffraction d 002 of 0.345 nm or less, and a Raman scattering spectrum. the ratio of the peak height of the band 1341~1349cm -1 (I d) and the band peak height 1570~1578cm -1 (I g): ( I d / I g) is 0.1 to 2 The manufacturing method of the structure as described in any one of Claims 1-4 .
該気相法炭素繊維は、不活性雰囲気下、2000〜3500℃の温度で熱処理したものである請求項1〜4のいずれかひとつに記載の構造体の製造方法。 The carbon fiber is a vapor grown carbon fiber,
The method for producing a structure according to any one of claims 1 to 4 , wherein the vapor grown carbon fiber is heat-treated at a temperature of 2000 to 3500 ° C in an inert atmosphere.
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