WO2017033838A1 - カーボンナノチューブ凝集体及びその製造方法ならびにそれを含む熱可塑性樹脂組成物 - Google Patents

カーボンナノチューブ凝集体及びその製造方法ならびにそれを含む熱可塑性樹脂組成物 Download PDF

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Publication number
WO2017033838A1
WO2017033838A1 PCT/JP2016/074165 JP2016074165W WO2017033838A1 WO 2017033838 A1 WO2017033838 A1 WO 2017033838A1 JP 2016074165 W JP2016074165 W JP 2016074165W WO 2017033838 A1 WO2017033838 A1 WO 2017033838A1
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Prior art keywords
water
carbon nanotube
carbon nanotubes
thermoplastic resin
nanotube aggregate
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PCT/JP2016/074165
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English (en)
French (fr)
Japanese (ja)
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剛士 扇
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ハリマ化成株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin

Definitions

  • the present invention relates to a carbon nanotube aggregate containing carbon nanotubes and a water-soluble rosin resin, and a thermoplastic resin composition containing the same.
  • Carbon nanotubes can be composited with a thermoplastic resin to produce a high performance composite material.
  • thermoplastic resin since carbon nanotubes have a low bulk density and a large amount of air is contained per unit volume, there is a problem that uniform mixing with pellets and powders of thermoplastic resin is difficult.
  • the carbon nanotubes and thermoplastic resin may be separated into layers, so it is necessary to contact the carbon nanotubes with the thermoplastic resin at a higher pressure than usual.
  • the dispersibility is poor and the filling amount cannot be increased.
  • the carbon nanotube has a problem that it is difficult to handle because it has a low bulk density and is easily scattered.
  • Patent Documents 1 to 9 various attempts have been made to granulate carbon nanotubes.
  • Carbon nanotube aggregates that improve the wettability of carbon nanotubes, are easy to knead, can suppress scattering, and are excellent in dispersibility and filling properties in thermoplastic resins. It is an object to provide a granular carbon nanotube) and a resin composition containing the same.
  • the present invention is as follows.
  • Carbon nanotube aggregates A carbon nanotube aggregate comprising carbon nanotubes and a water-soluble rosin resin.
  • Thermoplastic resin composition A thermoplastic resin composition comprising a thermoplastic resin and the carbon nanotube aggregate.
  • Carbon nanotube aggregates containing carbon nanotubes and a water-soluble rosin resin improve workability such that the carbon nanotubes do not scatter when melt-mixed with a thermoplastic resin. Furthermore, the carbon nanotubes and the water-soluble rosin resin Therefore, carbon nanotubes mixed with a water-soluble rosin resin have good dispersibility in the molded product, and the resulting molded product has not only high tensile stress and elongation but also conductivity. high.
  • FIG. 1 is a schematic diagram of a wettability evaluation method.
  • FIG. 2 shows the results of the wettability test of carbon nanotubes. A case where an aqueous solution containing 1% of a water-soluble rosin resin (REO30) is used, a case where only water is used, and a case where an emulsion rosin (rosin solid content with respect to water is 1%) are shown.
  • the result using an aqueous solution containing 1% of a water-soluble rosin resin is a curve of ⁇
  • the result of using only water is the curve of ⁇
  • the result of using an emulsion rosin is a curve of ⁇ .
  • the vertical axis represents penetration weight (g)
  • the horizontal axis represents time (minutes).
  • the carbon nanotube aggregate of the present invention contains carbon nanotubes and a water-soluble rosin resin.
  • the carbon nanotube is a tube-like fiber made of carbon.
  • the length of the carbon nanotube is usually 0.1 to 100 ⁇ m, preferably 5 to 50 ⁇ m, and the diameter is 1 to 80 nm, preferably 5 to 30 nm. It is a tubular fiber.
  • the water-soluble rosin resin used for the carbon nanotube aggregate of the present invention is a rosin obtained by modifying rosin so as to be water-soluble. Rosin is a non-volatile component of pine resin that is contained in a large amount in Pinaceae plants. Abietic acid, which is the main component, has a conjugated double bond, and consists of a highly hydrophobic site and a hydrophilic carboxyl group.
  • the water-soluble rosin resin is not particularly limited, and can be obtained, for example, by adding alkylene oxide to this carboxyl group and esterifying it.
  • the polyethylene oxide is: -(CH 2 -CH 2 -O) n-
  • polypropylene oxide is: — (CH 2 —CH (CH 3 ) —O) n —
  • n is 5 to 50, preferably 10 to 45.
  • One molecule of the polyalkylene oxide is added to each carboxyl group of the compound constituting the rosin resin, and the polyalkylene oxide is added to most of the carboxyl groups.
  • water-soluble rosin resins made water-soluble obtained by adding polyethylene oxide include trade names REO15, REO30, and REO40 (all manufactured by Harima Chemical Co., Ltd.).
  • Rosin can be made water-soluble by other methods.
  • As a method for making rosin water-soluble it can be made water-soluble by, for example, saponification using an alkali.
  • the saponification can be performed by a usual method, and examples thereof include a method of saponifying rosin with caustic soda, alcohol amine, ammonia and the like.
  • Specific examples of the saponified rosin include RX-20 manufactured by Harima Kasei Co., Ltd.
  • the ratio of the carbon nanotube to the water-soluble rosin resin is usually 0.1 to 50% by weight, preferably 0.5 to 0.5% as the water-soluble rosin resin relative to the carbon nanotube. 20% by weight, more preferably 0.5 to 15% by weight. If the amount of the water-soluble rosin resin is too large, the amount of carbon nanotubes is relatively small, and the characteristics of the carbon nanotubes are difficult to appear. On the other hand, when the amount of the water-soluble rosin resin is too small, it becomes difficult to improve wettability and physical properties of the thermoplastic resin composition.
  • the carbon nanotube aggregate can be added within the range that does not impair the original purpose, but it is preferable not to add it.
  • the additive include a filler and a binder. If these additives are added too much, the physical properties deteriorate, so even if they are added, they are 0.1 to 5% by weight, for example, 0.1 to 1% by weight with respect to the carbon nanotubes.
  • the aggregate of carbon nanotubes can be obtained by mixing carbon nanotubes, a water-soluble rosin resin, and, if necessary, other additives. When mixing, add water and mix to form a clay-like kneaded product.
  • the mixing method is not particularly limited, but is performed at a high speed of about 2000 rpm using a Henschel mixer or the like.
  • the amount of water is not particularly limited as long as it becomes a clay-like kneaded material. For example, about 5 to 10 times as much water as the weight of the carbon nanotube is used.
  • a water-soluble rosin resin When adding water, a water-soluble rosin resin may be dissolved in water to prepare an aqueous rosin solution and then mixed with carbon nanotubes, or after mixing a water-soluble rosin resin with carbon nanotubes, Water may be added.
  • the kneaded product obtained by mixing is formed into pellets of a predetermined shape by a wet extrusion granulator and dried to obtain carbon nanotube aggregates.
  • thermoplastic resin composition In order to obtain a high-performance composite material, the obtained carbon nanotube aggregate can be mixed with a thermoplastic resin to prepare a thermoplastic resin composition.
  • the thermoplastic resin is a thermoplastic resin that adds a function by an aggregate of carbon nanotubes, and is not particularly limited.
  • examples of the thermoplastic resin include polycarbonate resin and polyphenyl sulfide resin.
  • Carbon nanotubes (C TUBE- 199 manufactured by CNT Co., Ltd.) and 600 g of water were added to a 20 L Henschel mixer to make the volume about half that of the Henschel mixer.
  • 100 g of water-soluble rosin (trade name: REO30 Harima Kasei Co., Ltd., 30 mol of polyethylene oxide added) was added at a ratio of 5% by weight of water-soluble rosin to carbon nanotubes.
  • the system resin was added and stirred and mixed at 2000 rpm for 2 minutes at high speed.
  • the obtained mixture was a clay-like kneaded product, and this was put into a wet extrusion granulator manufactured by Dalton Co. to obtain a columnar granulated product (pellet).
  • the obtained granulated product was dried at 90 ° C. for 2 hours with a blast dryer manufactured by Yamato Scientific Co., Ltd., to obtain a carbon nanotube aggregate.
  • the obtained carbon nanotube aggregates were classified using a sieve having a nominal aperture of 2.36 mm as defined in JIS Z8801-1.
  • the carbon nanotube aggregates that passed through the sieve were further classified using a sieve having a nominal opening of 1.18 mm.
  • the carbon nanoaggregate remaining on the sieve was vacuum-dried at 80 ° C. to obtain the target carbon nanotube aggregate.
  • Examples 2 to 5 Carbon nanotubes and water-soluble rosin resin were mixed in the same procedure as in Example 1, and carbon nanotube aggregates of Examples 2 to 5 were prepared according to the ratios shown in Table 1.
  • REO15 and REO40 are obtained by adding 15 mol% and 40 mol% of polyethylene oxide to rosin, respectively.
  • the number of repeating units n of polyethylene oxide is about 15, about 30, and about 40, respectively.
  • Example 6 Using the water-soluble rosin resin obtained by saponification (trade name: RX-20, manufactured by Harima Kasei Co., Ltd.) as the water-soluble rosin resin, the carbon nanotube aggregate of Example 6 was prepared in the same manner as in Example 1. Was made. The blending ratio was created based on Table 1.
  • Comparative Example 1 A carbon nanotube aggregate of Comparative Example 1 was produced in the same manner as in Example 1 using emulsion rosin (ER) instead of the water-soluble rosin resin.
  • ER was produced by the following method. That is, first, 100 g of modified rosin (trade name “135GN” manufactured by Harima Chemicals Co., Ltd.) was dissolved in 300 g of toluene to prepare a toluene solution of modified rosin. Next, 900 mL of an aqueous solution having an active ingredient concentration of 10% by mass in a surfactant (trade name “New Coal 2320-SN” manufactured by Nippon Emulsifier Industry Co., Ltd.) was separately prepared.
  • a surfactant trade name “New Coal 2320-SN” manufactured by Nippon Emulsifier Industry Co., Ltd.
  • a funnel 1 having a diameter of 15 mm was closed with a mesh 5 (hole size: 60 ⁇ m), and then powdered carbon nanotubes 2 (CNT Co., Ltd., C TUBE- 199 manufactured by CNT Co.) were applied to the neck of the funnel. Stuffed. Thereafter, the mesh 5 was brought into contact with water or 1% binder solution 3. From the point of contact, measurement of the permeation time was started, and the wettability of the CNT and the binder was compared by measuring the weight of the solution immersed in the sample for each permeation time.
  • CNT Co., Ltd., C TUBE- 199 manufactured by CNT Co. powdered carbon nanotubes 2
  • the experiment was conducted using an aqueous solution containing 1% of a water-soluble rosin resin (REO30), water, and an emulsion rosin (with a solid content ratio of rosin of 1%; ER1%). It was found that the aqueous solution containing the functional rosin resin penetrates the carbon nanotubes very quickly and in large quantities (high wettability) (see FIG. 2). That is, it was found that the water-soluble rosin-based resin intervenes very easily.
  • a water-soluble rosin resin REO30
  • water emulsion rosin
  • thermoplastic resin compositions 1 to 11 The carbon nanotube aggregates of Example 1 were mixed with polycarbonate resin (PC) or polyphenyl sulfide (PPS) in the proportions shown in Table 2, and were extruded by an extruder (PCM45) at a temperature in the range of 290 ° C. to 330 ° C. Then, extrusion molding was performed to obtain molded articles of the thermoplastic resin compositions 1 to 11 (prototype numbers 1 to 11).
  • Table 3 shows the properties of the obtained thermoplastic resin composition.
  • the thermoplastic resin composition 8 and the thermoplastic resin composition 9 have CNT Co. as carbon nanotubes. , Ltd. compression type carbon nanotubes (Comparative Example 2, trade name C tube- 199P) and Kumho Petrochemical Co., Ltd. , Ltd. compression type carbon nanotubes (Comparative Example 3, trade name K-Nanos-100T) were used.
  • the water-soluble rosin resin as a raw material shows neutrality when dissolved in water, for example, it exhibits alkalinity, tensile stress, elongation, etc. than a water-soluble rosin resin obtained by saponification
  • the mechanical properties of are even better.
  • the water-soluble rosin resin is a polyethylene oxide adduct of rosin, a resin composition having high mechanical properties can be obtained.
  • the number of repeating units n of polyethylene oxide in the ethylene oxide adduct is 5 to 50, the water-soluble rosin resin is easy to handle and has an appropriate hydrophilicity, which is preferable.
  • thermoplastic resin composition obtained by melt-mixing the thermoplastic resin and the carbon nanotube aggregate according to any one of (1) to (5) includes a conventional granulated carbon nanotube. It is a resin composition having excellent mechanical properties as compared with the case of use.
  • a method of granulating carbon nanotubes comprising a step of mixing carbon nanotubes, water, and a water-soluble rosin resin, a step of extruding the mixture, and a step of drying the molded product.
  • the carbon nanotubes can be granulated by a very simple method, and the functional resin composition produced using the obtained granulated carbon nanotubes has high mechanical properties and electrical conductivity. have.
  • FIG. 1 Funnel 2 Powder 3 Binder solution or water 4 Container 5 Mesh part

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2016/074165 2015-08-21 2016-08-19 カーボンナノチューブ凝集体及びその製造方法ならびにそれを含む熱可塑性樹脂組成物 WO2017033838A1 (ja)

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JP2018177586A (ja) * 2017-04-12 2018-11-15 株式会社ＤＲ．ｇｏｏ カーボンナノチューブの造粒方法
JP2019039001A (ja) * 2017-08-25 2019-03-14 ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ カーボンナノチューブ強化ポリマー及びその製造方法
JP2020079342A (ja) * 2018-11-12 2020-05-28 株式会社ＤＲ．ｇｏｏ カーボンナノチューブ粒状物およびその製造方法
CN113773598A (zh) * 2021-09-17 2021-12-10 宁波信远炭材料股份有限公司 碳基复合材料的制备方法

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EP3980375A1 (en) 2019-06-05 2022-04-13 Cabot Corporation Densified reduced graphene oxide and methods of production

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JP2014218403A (ja) * 2013-05-09 2014-11-20 ハリマ化成株式会社 黒鉛造粒物の製造方法および黒鉛造粒物
WO2015030056A1 (ja) * 2013-08-30 2015-03-05 ハリマ化成株式会社 シリカ造粒物、ゴム組成物、タイヤ、シリカ造粒物の製造方法およびゴム組成物の製造方法

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018177586A (ja) * 2017-04-12 2018-11-15 株式会社ＤＲ．ｇｏｏ カーボンナノチューブの造粒方法
JP2019039001A (ja) * 2017-08-25 2019-03-14 ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ カーボンナノチューブ強化ポリマー及びその製造方法
JP7268975B2 (ja) 2017-08-25 2023-05-08 ザ・ボーイング・カンパニー カーボンナノチューブ強化ポリマー及びその製造方法
JP2020079342A (ja) * 2018-11-12 2020-05-28 株式会社ＤＲ．ｇｏｏ カーボンナノチューブ粒状物およびその製造方法
KR20210090604A (ko) 2018-11-12 2021-07-20 가부시키가이샤 닥터 구 카본 나노 튜브 입상물 및 그 제조 방법
CN113773598A (zh) * 2021-09-17 2021-12-10 宁波信远炭材料股份有限公司 碳基复合材料的制备方法

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