JP4877637B2 - Conductive resin - Google Patents
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- JP4877637B2 JP4877637B2 JP2006323889A JP2006323889A JP4877637B2 JP 4877637 B2 JP4877637 B2 JP 4877637B2 JP 2006323889 A JP2006323889 A JP 2006323889A JP 2006323889 A JP2006323889 A JP 2006323889A JP 4877637 B2 JP4877637 B2 JP 4877637B2
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- 229920005989 resin Polymers 0.000 title claims description 60
- 239000011347 resin Substances 0.000 title claims description 60
- 239000002134 carbon nanofiber Substances 0.000 claims description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 40
- 229920005992 thermoplastic resin Polymers 0.000 claims description 22
- 239000011342 resin composition Substances 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
本発明は、引張強度に優れると共に、破断伸度および衝撃強度の低下が少ない導電性樹脂に関する。本発明の導電性樹脂はキャリアーテープやトレイ、さらには複写機、ファクシミリ、ブリンター等の電子写真装置に用いられる導電性樹脂として好適である。 The present invention relates to a conductive resin that is excellent in tensile strength and has little decrease in elongation at break and impact strength. The conductive resin of the present invention is suitable as a conductive resin used in carrier tapes and trays, and electrophotographic apparatuses such as copying machines, facsimiles, and printers.
従来から、導電性カーボン粉末を多量に含有した樹脂によって形成した導電性樹脂が知られている。例えば、カーボンブラックなどの炭素粉末や炭素繊維、これらを混合した導電性樹脂組成物が知られており（特許文献１、２）、また、炭素粉末や炭素繊維に代えてカーボンナノチューブを用いたものや、炭素繊維と共にカーボンナノチューブを配合した導電性樹脂組成物が知られており（特許文献３、４）、これらの樹脂組成物によって導電性シートが形成されている。 Conventionally, a conductive resin formed of a resin containing a large amount of conductive carbon powder is known. For example, carbon powders such as carbon black, carbon fibers, and conductive resin compositions in which these are mixed are known (Patent Documents 1 and 2), and carbon nanotubes are used instead of carbon powders and carbon fibers. In addition, conductive resin compositions in which carbon nanotubes are blended with carbon fibers are known (Patent Documents 3 and 4), and a conductive sheet is formed of these resin compositions.
しかし、従来の導電フィラー含有樹脂組成物によって形成された導電性シートは、フィラーの含有量が多いために機械的強度に劣り、しかも伸びが殆どないので二次加工が困難であり、実用性に限界がある。この欠点を解消するため、親油性の高いカーボンナノファイバーを用いることによって機械的強度を高め、破断伸度の劣化を抑制した導電性樹脂シートが提案されている（特許文献５）。
親油性の高いカーボンナノファイバーを用いた導電性樹脂シート（特許文献５）は、導電性に優れており、高い引張強度を有し、破断伸度の低下も少ないが、衝撃強度については改善の余地がある。本発明は高い引張強度を有すると共に破断伸度および衝撃強度の低下が少ない導電性樹脂を提供する。 The conductive resin sheet using the highly lipophilic carbon nanofiber (Patent Document 5) has excellent electrical conductivity, high tensile strength, and little decrease in elongation at break, but improved impact strength. There is room. The present invention provides a conductive resin having a high tensile strength and a small decrease in elongation at break and impact strength.
本発明は以下に示す構成を有することによって上記課題を解決した導電性樹脂とその用途に関する。
（１）カーボンナノファイバーを分散させた熱可塑性樹脂組成物によって形成した導電性樹脂であって、第一族及び第ニ族元素残量が１００ppm以下のカーボンナノファイバーを用い、原熱可塑性樹脂に対する衝撃強度の強度比が７０％以上であることを特徴とする導電性樹脂。
（２）ＤＢＰ吸油量１５０ml/100g以上のカーボンナノファイバーを分散させた熱可塑性樹脂組成物によって形成した導電性樹脂であって、成型品破断伸度が４０％以上、原熱可塑性樹脂に対する引張強度比１００％以上である上記(１)の導電性樹脂。
（３） 表面抵抗値が１０3Ω/□以下、引張強度５５ＭＰａ以上である上記(１)または上記(２)の導電性樹脂シート。
（４）上記(１)〜上記(３)の何れかに記載する導電性を用いた電子部品包装体、電子部品搬送容器、または複写機、印刷機、ないしファクシミリに使用される帯電、除電、転写、または定着シート。
The present invention relates to a conductive resin that has solved the above-described problems by having the following configuration and its use.
(1) A conductive resin formed of a thermoplastic resin composition in which carbon nanofibers are dispersed, wherein carbon nanofibers having a remaining amount of the first group and second group elements of 100 ppm or less are used, and the raw thermoplastic resin is used. A conductive resin having a strength ratio of impact strength of 70% or more.
(2) A conductive resin formed from a thermoplastic resin composition in which carbon nanofibers having a DBP oil absorption of 150 ml / 100 g or more are dispersed, and has a molded product breaking elongation of 40% or more and a tensile strength against the original thermoplastic resin. The conductive resin according to (1), wherein the ratio is 100% or more.
(3) The conductive resin sheet according to (1) or (2) above, having a surface resistance value of 10 3 Ω / □ or less and a tensile strength of 55 MPa or more.
(4) Charging, static elimination used in electronic component packaging, electronic component transport containers, or copiers, printing machines, or facsimiles using the conductivity described in any one of (1) to (3) above. Transfer or fixing sheet.
本発明の導電性樹脂は、第一族及び第ニ族元素残量を１００ppm以下に低減したカーボンナノファイバーを用いることによって、原熱可塑性樹脂に対する衝撃強度の強度比を７０％以上に高めたものであり、本発明の導電性樹脂シートによれば衝撃に強い導電性樹脂製品を得ることができる。 The conductive resin of the present invention has a strength ratio of impact strength with respect to the raw thermoplastic resin increased to 70% or more by using carbon nanofibers in which the remaining amounts of the first group and second group elements are reduced to 100 ppm or less. Thus, according to the conductive resin sheet of the present invention, a conductive resin product resistant to impact can be obtained.
また、第一族及び第ニ族元素残量を低減すると共に、ＤＢＰ吸油量１５０ml/100g以上のカーボンナノファイバーを用いることによって、衝撃強度および破断伸度の低下が少なく、かつ原熱可塑性樹脂に対する引張強度比の高い導電性樹脂を得ることができる。具体的には、原熱可塑性樹脂に対する衝撃強度の強度比を７０％以上、および破断伸度４０％以上、引張強度比１００％以上の導電性樹脂を得ることができる。さらに、体積抵抗値１.０Ωcm以下のカーボンナノファイバーを用い、表面抵抗値が１０3Ω/□以下の導電性樹脂を得ることができる。 In addition, the carbon nanofibers having a DBP oil absorption amount of 150 ml / 100 g or more are reduced by reducing the remaining amount of the first group and second group elements, so that the impact strength and the elongation at break are small and the raw thermoplastic resin is reduced. A conductive resin having a high tensile strength ratio can be obtained. Specifically, it is possible to obtain a conductive resin having a strength ratio of impact strength with respect to the raw thermoplastic resin of 70% or more, a breaking elongation of 40% or more, and a tensile strength ratio of 100% or more. Furthermore, a conductive resin having a surface resistance value of 10 3 Ω / □ or less can be obtained using carbon nanofibers having a volume resistance value of 1.0 Ωcm or less.
本発明の導電性樹脂は高い導電性と共に優れた加工性を有するので、本発明の導電性樹脂を用いることによって、電子部品包装体、電子部品搬送容器、または複写機、印刷機、ないしファクシミリに使用される帯電、除電、転写、または定着シートなどの製品について、高品質の導電性製品を得ることができる。 Since the conductive resin of the present invention has high conductivity and excellent processability, the use of the conductive resin of the present invention allows the electronic component package, the electronic component transport container, or the copying machine, printing machine, or facsimile to be used. High quality conductive products can be obtained for products such as charging, static elimination, transfer or fixing sheets used.
本発明の導電性樹脂は、カーボンナノファイバーを分散させた熱可塑性樹脂組成物によって形成したものである。このカーボンナノファイバーは、例えば、直径が数十ナノメータ以下、長さが数百ミクロンメータ以下であるナノサイズの極微細炭素繊維であって、内部が中空構造のカーボンナノチューブに限らず、内部が充填された構造のものを含む。 The conductive resin of the present invention is formed by a thermoplastic resin composition in which carbon nanofibers are dispersed. This carbon nanofiber is, for example, a nano-sized ultrafine carbon fiber having a diameter of several tens of nanometers or less and a length of several hundreds of micrometers or less. Including those with a structured structure.
熱可塑性樹脂組成物は、ポリエチレン系、ポリプロピレン系、ポリスチレン系、ポリ塩化ビニル、ポリメタクリル酸メチル、ナイロン(ポリアミド)系、ポリエステル系、ポリカーボネート系、ポリアセタール系、酢酸セルロース、ABS系の樹脂やそれらの混合物などを用いることができる。 Thermoplastic resin compositions include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polymethyl methacrylate, nylon (polyamide), polyester, polycarbonate, polyacetal, cellulose acetate, ABS resins and their A mixture or the like can be used.
本発明の導電性樹脂は、第一族及び第ニ族元素残量が１００ppm以下のカーボンナノファイバーを用いる。一般にカーボンナノファイバーの製造工程において、マグネシウムなどの第ニ族元素を含む触媒が使用されるが、不純物の第一族元素やカーボンナノファイバーに残る触媒量が多いと衝撃強度が低下する傾向がみられる。触媒成分である第ニ族元素の残量は１００ppm以下が良く、１０ppm以下がさらに好ましい。 For the conductive resin of the present invention, carbon nanofibers having a remaining amount of the first group and second group elements of 100 ppm or less are used. In general, a catalyst containing a Group II element such as magnesium is used in the manufacturing process of carbon nanofibers. However, if there is a large amount of impurities remaining in Group I elements or carbon nanofibers, the impact strength tends to decrease. It is done. The remaining amount of the Group II element as the catalyst component is preferably 100 ppm or less, and more preferably 10 ppm or less.
不純物の第一族元素や触媒成分の第ニ族元素を除去するには塩化水素や希硫酸などで洗浄すれば良い。具体的には、例えば、希硫酸にカーボンナノファイバーを投入し、加温下で攪拌して第一族及び第ニ族元素の不純物を溶解させる。その後、濾過洗浄して上記不純物を除去する。処理条件としては、例えば、濃度０.５〜１０.０重量％の希硫酸を使用し、処理温度室温〜８０℃、処理時間０.５〜６.０時間程度で良い。 In order to remove the first group element of impurities and the second group element of the catalyst component, it may be washed with hydrogen chloride or dilute sulfuric acid. Specifically, for example, carbon nanofibers are added to dilute sulfuric acid and stirred under heating to dissolve impurities of the first group and second group elements. Thereafter, the impurities are removed by filtration and washing. As the treatment conditions, for example, dilute sulfuric acid having a concentration of 0.5 to 10.0% by weight is used, the treatment temperature is room temperature to 80 ° C., and the treatment time is about 0.5 to 6.0 hours.
第一族及び第ニ族元素残量を１００ppm以下に低減したカーボンナノファイバーを用いることによって、原熱可塑性樹脂によって形成した樹脂の衝撃強度（ＳO）に対して、樹脂の衝撃強度（ＳH）の強度比（ＳH／ＳO）が７０％以上の導電性樹脂を得ることができる。この衝撃強度の比（ＳH／ＳO）は、同一条件で作成した樹脂について、カーボンナノファイバーを含有しない熱可塑性樹脂によって形成した樹脂の衝撃強度ＳOに対して、同一の熱可塑性樹脂にカーボンナノファイバーを配合した本発明の熱可塑性樹脂組成物によって形成した樹脂の衝撃強度ＳHの比（ＳH／ＳO）を％値で示したものである。なお、衝撃強度は例えばシャルピー衝撃強度である。 By using the carbon nanofibers having reduced first family and Second group elements remaining in 100ppm or less, with respect to the impact strength of the resin formed by Haranetsu thermoplastic resin (S O), impact strength of the resin (S H ) Strength ratio (S H / S O ) of 70% or more can be obtained. This ratio of impact strength (S H / S O ) is the same for the resins made under the same conditions, with respect to the impact strength S O of the resin formed by the thermoplastic resin not containing carbon nanofibers. It illustrates the ratio of the impact strength S H of resin formed of a thermoplastic resin composition of the present invention obtained by blending carbon nanofibers (S H / S O) a percentage value. The impact strength is, for example, Charpy impact strength.
また、上記カーボンナノファイバーは、ＤＢＰ吸油量１５０ml/100g以上である親油性の高いカーボンナノファイバーを用いることが好ましい。ＤＢＰ吸油量が上記範囲よりも少ないカーボンナノファイバーは樹脂中の分散性が劣り、凝集しやすいので樹脂組成物の導電性が不均一になり、さらに樹脂組成物の加工性が低下する。ＤＢＰ吸油量が上記範囲のカーボンナノファイバーは樹脂中で分散性が良く、樹脂に配合したときに樹脂の機械的強度や粘性等を損なうことなく、導電性と共に強度および破断伸度に優れた導電性樹脂を得ることができる。具体的には、例えば、破断伸度が４０％以上、原熱可塑性樹脂に対する引張強度比１００％以上の導電性樹脂を得ることができる。 The carbon nanofiber is preferably a highly lipophilic carbon nanofiber having a DBP oil absorption of 150 ml / 100 g or more. Carbon nanofibers having a DBP oil absorption amount less than the above range are poor in dispersibility in the resin and easily aggregate, so that the conductivity of the resin composition becomes non-uniform and the processability of the resin composition is further lowered. Carbon nanofibers with DBP oil absorption in the above range have good dispersibility in the resin, and when blended in the resin, the conductivity and strength and breaking elongation are excellent without impairing the mechanical strength and viscosity of the resin. Can be obtained. Specifically, for example, a conductive resin having a breaking elongation of 40% or more and a tensile strength ratio of 100% or more to the original thermoplastic resin can be obtained.
原熱可塑性樹脂に対する引張強度比とは、同一条件で作成した樹脂試験片について、カーボンナノファイバーを含有しない熱可塑性樹脂によって形成した樹脂試験片の引張強度ＰOに対して、同一の熱可塑性樹脂にカーボンナノファイバーを配合した熱可塑性樹脂組成物によって形成した樹脂試験片の引張強度ＰXの比（ＰX／ＰO）を％値で示したものである。破断伸度は、試験前の長さＬ0に対して、破断時の長さＬXの比（ＬX／ＬO）を％値で示したものである。 Tensile strength ratio Haranetsu thermoplastic resin, the resin specimens prepared in the same conditions, with respect to tensile strength P O of the resin specimens were formed by a thermoplastic resin containing no carbon nanofiber, the same thermoplastic resin The ratio (P X / P O ) of the tensile strength P X of a resin test piece formed from a thermoplastic resin composition in which carbon nanofibers are blended is shown as a% value. The elongation at break is the ratio (L X / L O ) of the length L X at break to the length L 0 before the test, expressed as a% value.
また、表面抵抗値が１０3Ω/□以下の導電性の高い樹脂を得るには体積抵抗値１.０Ωcm以下のカーボンナノファイバーを用いると良い。 In order to obtain a highly conductive resin having a surface resistance value of 10 3 Ω / □ or less, carbon nanofibers having a volume resistance value of 1.0 Ωcm or less are preferably used.
体積抵抗値が低く、かつＤＢＰ吸油量が高いカーボンナノチューブは、触媒を用いた気相成長法において、触媒および原料の混合ガス組成を調整することによって製造することができる。具体的には、例えば、触媒粒子としてＦｅ、Ｎｉ、Ｃｏ、Ｍｎ、Ｃｕの酸化物から選ばれた１種または２種以上と、Ｍｇ、Ｃa、Ａｌ、Ｓｉの酸化物から選ばれた１種または２種以上の混合酸化物粉末を用い、４００℃〜８００℃の温度で、一酸化炭素または二酸化炭素と水素の混合ガスを上記触媒粒子に接触させて、カーボンナノファイバーを製造する気相成長法において、触媒としてＣｏ酸化物とＭｇ酸化物の混合酸化物あるいは、Ｍｇ酸化物にＣｏ酸化物が被覆された複合酸化物を用い、原料混合ガスを一酸化炭素および/または二酸化炭素と水素とし、その混合比をＣＯ/Ｈ2＝５０／５０〜９９／１に調整することによって、体積抵抗値が低く、ＤＢＰ吸油量が高いカーボンナノチューブを製造することができる。 Carbon nanotubes having a low volume resistivity and a high DBP oil absorption can be produced by adjusting the mixed gas composition of the catalyst and the raw material in the vapor phase growth method using the catalyst. Specifically, for example, the catalyst particles are one or more selected from oxides of Fe, Ni, Co, Mn, and Cu and one selected from oxides of Mg, Ca, Al, and Si. Alternatively, vapor phase growth in which carbon nanofibers are produced by using two or more mixed oxide powders and contacting carbon monoxide or a mixed gas of carbon dioxide and hydrogen with the catalyst particles at a temperature of 400 ° C. to 800 ° C. In this method, a mixed oxide of Co oxide and Mg oxide or a composite oxide in which a Mg oxide is coated with a Co oxide is used as a catalyst, and the raw material mixed gas is carbon monoxide and / or carbon dioxide and hydrogen. By adjusting the mixing ratio to CO / H 2 = 50/50 to 99/1, carbon nanotubes having a low volume resistance value and a high DBP oil absorption can be produced.
本発明の導電性樹脂において、カーボンナノファイバーの含有量は、熱可塑性樹脂１００重量部に対する該カーボンナノファイバーの表面積換算値（カーボン含有量×比表面積の値）で２５００ｍ2以下が好ましい。カーボンナノファイバーの含有量がこれより多いと引張強度や伸度などの樹脂物性が大きく低下するので好ましくない。 In the conductive resin of the present invention, the content of the carbon nanofibers is preferably 2500 m 2 or less in terms of the surface area of the carbon nanofibers (carbon content × specific surface area) with respect to 100 parts by weight of the thermoplastic resin. If the carbon nanofiber content is higher than this, the resin physical properties such as tensile strength and elongation are greatly lowered, which is not preferable.
本発明の導電性樹脂を形成するカーボンナノファイバー分散樹脂組成物は、機械的強度等を大きく損なわない範囲内で、他の導電性微粒子や難燃剤、分散安定剤などを含有してもよい。 The carbon nanofiber-dispersed resin composition forming the conductive resin of the present invention may contain other conductive fine particles, a flame retardant, a dispersion stabilizer and the like within a range that does not significantly impair mechanical strength and the like.
以下に本発明の実施例を比較例と共に示す。なお、ＰＣ樹脂の作成方法および評価方法は下記のとおりである。また、本発明の導電性樹脂において、引張強度および破断伸度は引張試験機を用いて測定した。試験片は、JIS K7113準拠の１号形試験片を作成し測定に用いた。引張強度は、断面積あたりの強度に換算して計算した。
〔ＰＣ樹脂試験片の作成方法〕：予め所定量のカーボンナノファイバーを分散させたポリカーボネート樹脂（ＰＣ樹脂）コンパウンドを作成し、それを射出圧縮成型及び、熱プレス加工で所定の形に成形することにより各種試験片得た。
〔体積抵抗値〕：抵抗率計（デジタルマルチメーター）を用い、試料に対して１００kg/cm2の加圧時の抵抗を測定する。
〔表面抵抗値〕：市販の測定装置（油化電子社製：ロレスタ−ＡＰ）を用い、４端子法により体積抵抗を求めた。
〔衝撃強度〕：JIS K7110準拠の試験片を作成し、シャルピー衝撃試験法により測定した。
Examples of the present invention are shown below together with comparative examples. In addition, the preparation method and evaluation method of PC resin are as follows. In the conductive resin of the present invention, the tensile strength and the breaking elongation were measured using a tensile tester. As the test piece, a JIS K7113 compliant type 1 test piece was prepared and used for measurement. The tensile strength was calculated in terms of strength per cross-sectional area.
[Preparation method of PC resin test piece]: A polycarbonate resin (PC resin) compound in which a predetermined amount of carbon nanofibers is dispersed in advance is prepared, and then molded into a predetermined shape by injection compression molding and hot pressing. Thus, various test pieces were obtained.
[Volume resistance value]: A resistance meter (digital multimeter) is used to measure the resistance when a sample is pressurized to 100 kg / cm 2 .
[Surface Resistance Value] Volume resistance was determined by a four-terminal method using a commercially available measuring device (Yureka Electronics Co., Ltd .: Loresta AP).
[Impact strength]: JIS K7110-compliant test pieces were prepared and measured by the Charpy impact test method.
〔実施例１〜２〕
第一族及び第ニ族元素残量２ppmのカーボンナノファイバー（ＣＮＦ：ＤＢＰ吸油量２５０ml/100ｇ）をポリカーボネート樹脂（二種Ｉ,II）に分散させた樹脂組成物（ＣＮＦ量５重量％）を用い、射出圧縮成型及び、熱プレス成型により試験片を調製した。この試験片の、表面抵抗値、引張強度、破断伸度、衝撃強度を測定した。この結果を表１に示した。カーボンナノファイバーを含有しない以外は同様にして調製した試験片について表面抵抗値等を測定した。この結果を比較対象（ＮＡ）として表１に示した。
[Examples 1-2]
A resin composition (CNF amount 5% by weight) in which carbon nanofibers (CNF: DBP oil absorption 250 ml / 100 g) having a residual amount of Group 1 and Group 2 elements are dispersed in a polycarbonate resin (Type I, II) A test piece was prepared by injection compression molding and hot press molding. The test piece was measured for surface resistance, tensile strength, elongation at break, and impact strength. The results are shown in Table 1. Surface resistance values and the like were measured for test pieces prepared in the same manner except that no carbon nanofibers were contained. The results are shown in Table 1 as a comparison target (NA).
〔比較例１〜３〕
触媒除去を行わないカーボンナノファイバー（アルカリ土類残量５０００ppm）を用いた以外は実施例１〜２と同様にして樹脂シートを調製し、この樹脂シートについて表面抵抗値等を測定した。この結果を比較例１〜２として表１に示した。また、カーボンナノファイバーに代えてカーボンブラックを同量用いた以外は実施例１〜２と同様にして樹脂シートを調製し、この樹脂シートについて表面抵抗値等を測定した。この結果を比較例３として表１に示した。
[Comparative Examples 1-3]
A resin sheet was prepared in the same manner as in Examples 1 and 2 except that carbon nanofibers (alkaline earth residual amount: 5000 ppm) without catalyst removal were used, and the surface resistance value and the like of this resin sheet were measured. The results are shown in Table 1 as Comparative Examples 1-2. A resin sheet was prepared in the same manner as in Examples 1 and 2 except that the same amount of carbon black was used instead of carbon nanofibers, and the surface resistance value and the like of this resin sheet were measured. The results are shown in Table 1 as Comparative Example 3.
表１に示すように、本発明に係る樹脂（実施例１〜２）は、カーボンナノファイバーを含まない樹脂シート（ＮＡ）に対してシャルピー衝撃強度が約２０％程度しか低下せず、樹脂の有する衝撃強度を大きく損なわずに維持することができる。また、本発明のカーボンナノファイバーを含む樹脂試験片の破断伸度ＨSは４０％以上であり、カーボンナノファイバーを含まない樹脂試験片の破断伸度Ｈ0に対する伸度比（ＨS／Ｈ0）は７０％以上であり、破断伸度の低下も小さい。一方、引張強度比（ＰX／ＰO）は何れも１００％以上であり、優れた機械的強度を有する。また、比較例３より、同量のカーボンブラックを入れた時は、破断伸度、衝撃強度が著しく低下し、表面抵抗に関しても、６×１０15Ω/□以上で導電性は得られなかった。 As shown in Table 1, the resin according to the present invention (Examples 1 and 2) has a Charpy impact strength that is only about 20% lower than the resin sheet (NA) that does not contain carbon nanofibers. The impact strength possessed can be maintained without significant loss. In addition, the elongation at break H S of the resin test piece containing the carbon nanofibers of the present invention is 40% or more, and the elongation ratio (H S / H) of the resin test piece not containing the carbon nanofibers to the break elongation H 0 . 0 ) is 70% or more, and the decrease in elongation at break is small. On the other hand, the tensile strength ratio (P X / P O ) is 100% or more, and has excellent mechanical strength. Further, from Comparative Example 3, when the same amount of carbon black was added, the elongation at break and impact strength were remarkably lowered, and the surface resistance was not obtained at 6 × 10 15 Ω / □ or more. .
Claims (4)
A conductive resin formed from a thermoplastic resin composition in which carbon nanofibers with a DBP oil absorption of 150 ml / 100 g or more are dispersed, and has a molded product breaking elongation of 40% or more and a tensile strength ratio of 100% with respect to the raw thermoplastic resin. The conductive resin according to claim 1, which is as described above.
The conductive resin according to claim 1 or 2, having a surface resistance value of 10 3 Ω / □ or less and a tensile strength of 55 MPa or more.
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| CN108586926B (en) * | 2018-04-23 | 2020-11-17 | 江门市三硕新材料有限公司 | Plastic for high-strength conductive PP/MLLDPE flat filament and preparation method thereof |
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