WO2011016536A1 - 導電性樹脂組成物 - Google Patents
導電性樹脂組成物 Download PDFInfo
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- WO2011016536A1 WO2011016536A1 PCT/JP2010/063333 JP2010063333W WO2011016536A1 WO 2011016536 A1 WO2011016536 A1 WO 2011016536A1 JP 2010063333 W JP2010063333 W JP 2010063333W WO 2011016536 A1 WO2011016536 A1 WO 2011016536A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
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- 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
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a novel conductive resin composition. Specifically, the present invention relates to a conductive resin composition in which fine carbon fibers and / or fine short carbon fibers are blended as a conductivity-imparting material in a resin component containing a polyamide resin and a polyphenylene ether resin.
- the conductive resin composition of the present invention has stable conductivity, low water absorption, excellent dimensional stability and molding processability, and mechanical properties such as impact properties, chemical resistance, and hydrolysis resistance. Therefore, it can be used for a wide range of applications such as automobile parts, industrial parts, industrial materials, and electric / electronic parts.
- Crystalline polyamide resins represented by nylon 6 and nylon 66 are widely used as engineering plastics due to their excellent mechanical properties and ease of melt molding, but they point out insufficient heat resistance and poor dimensional stability due to water absorption. Has been.
- polyphenylene ether resin is excellent in heat resistance and dimensional stability, it has been pointed out that it has problems such as high viscosity at the time of melting and extremely poor moldability and chemical resistance. Therefore, conventionally, a technique for blending a polyamide resin and a polyphenylene ether resin has been proposed (Patent Document 1: Japanese Patent Application Laid-Open No. Sho 62-270654), and studies have been made to create new materials having excellent characteristics inherent in each. I came.
- Patent Document 2 Japanese Patent Laid-Open No. 02-201811
- a conductive filler is kneaded and dispersed to impart electrical conductivity to an electrically insulating resin for antistatic purposes and other purposes.
- the conductive filler to be kneaded with the resin generally used are ion conductive organic surfactants, metal fibers and powders, conductive metal oxide powders, carbon black, carbon fibers, graphite powders, and the like.
- a molded product having a volume resistance value of 10 ⁇ 1 to 10 12 ⁇ ⁇ cm can be obtained by molding the conductive resin composition melt-kneaded and dispersed in
- the conductive filler by using a flaky, whisker or fibrous material having a large aspect ratio (length / outer diameter), conductivity can be imparted to the resin with a relatively small amount. it can. This is because the conductive filler having a larger aspect ratio can effectively form the connection between the fillers with the same blending amount, so that the conductivity can be obtained with a smaller amount.
- metal fillers are inferior in corrosion resistance and chemical resistance. Since the inorganic conductive filler is generally granular, it requires a large amount of blending exceeding 50% by mass with respect to the total mass of the composition, so that the physical properties of the resin are lowered and molding becomes difficult. As carbon black, ketjen black and acetylene black, which form a conductive circuit with a chain structure, can be used, so high conductivity can be obtained with a blending ratio of 15% by mass or less, but these are difficult to control dispersion in resin and stable. A unique blending and mixing technique is required in order to obtain high conductivity.
- Patent Document 4 Special.
- Kaihei 01-131251 Patent Document 5: Japanese Patent Laid-Open No. 03-74465
- Patent Document 6 Japanese Patent Laid-Open No. 02-235945 are considered as effective conductive fillers that eliminate the drawbacks of conventional conductive fillers.
- carbon nanofibers or carbon nanotubes which are collectively referred to as carbon nanofibers, (1) Multi-walled carbon nanotubes (graphite layer is multi-layer concentric cylinder) (non-fishbone) JP-B 3-64606, 3-77288 JP 2004-299986 A (2) Cup-stacked carbon nanotubes (fishbone) USP 4,855,091 M.Endo, YAKim etc.:Appl.Phys.Lett.,vol80(2002)1267 ⁇ JP2003-073928 JP 2004-36099 A (3) Platelet type carbon nanofiber (Trump shape) H.Murayama, T.maeda: Nature, vol345 [No.28] (1990) 791-793 JP-A-2004-300631 The three nanostructured carbon materials are roughly classified as follows.
- the multi-walled carbon nanotube is good because the conductivity in the length direction of the carbon nanotube is an electron flow in the direction of the graphite network surface (C axis).
- the conductivity between the carbon nanotube fibers is perpendicular to the graphite network surface (C-axis) direction, and electrons flow when the fibers are in direct contact with each other.
- the fibers are loosely contacted with each other. Rather than the flow of electrons, the flow of electrons from the surface layer of the conductive filler plays an important role. The ease of electron emission is related to the conductive performance of the filler.
- the jumping effect tunnel effect theory
- JP-A-62-270654 Japanese Patent Laid-Open No. 02-201811 JP 2006-57033 A Japanese Patent Laid-Open No. 01-131251 Japanese Patent Laid-Open No. 03-74465 Japanese Patent Laid-Open No. 02-235945 JP 2004-323738 A
- An object of the present invention is to provide a conductive resin composition having low water absorption, excellent dimensional stability and moldability, and excellent mechanical properties such as impact properties, chemical resistance, and hydrolysis resistance. That is. Furthermore, even without using a special kneading / mixing method or compounding recipe, mixing and dispersion of ultrafine carbon fibers in the resin is achieved, and the resin composition has stable conductivity while maintaining the original physical properties of the resin. Is to provide.
- the present invention relates to the following matters.
- A polyamide resin
- B a polyphenylene ether resin
- c a bell-shaped structural unit having a closed top portion and a trunk portion having a closed top portion, wherein the graphite net surface is composed of only carbon atoms and is dispersed in the resin.
- the bell-shaped structural units are stacked to share 2 to 30 with a common central axis to form an aggregate, and the aggregate is connected with a space in a head-to-tail manner to form a fiber.
- the fine carbon fiber is produced by a vapor phase growth method using a catalyst containing an element selected from the group consisting of Fe, Co, Ni, Al, Mg and Si, and the ash content in the fine carbon fiber is 4 mass.
- Item 2 The conductive resin composition according to Item 1, wherein the composition is% or less.
- Item 4 The conductive resin composition according to Item 3, wherein the fine carbon short fibers are produced by applying shear stress to shorten the fibers.
- Item 5 The conductive resin composition according to any one of Items 1 to 4, wherein the (b) polyphenylene ether resin is a polyphenylene ether resin modified with an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof.
- Item 6 The conductive resin composition according to any one of Items 1 to 5, wherein the (a) polyamide resin is an aliphatic polyamide resin.
- Item 7 The conductive resin composition according to any one of Items 1 to 6, wherein the polyamide resin (a) is a polyamide resin obtained by polycondensation of oxalic acid and a diamine having 4 to 12 carbon atoms.
- a resin composition having high moldability and conductivity while maintaining the original physical properties of the polyamide-polyphenylene ether resin.
- high conductivity is achieved by adding a small amount of fine carbon fibers and / or fine carbon short fibers. Therefore, the conductive resin composition can be obtained without significantly impairing the original properties of the resin, such as moldability and mechanical properties.
- the fine carbon fiber contained in the composition of the present invention is a conductive carbon fiber that does not belong to the above-mentioned three categories of carbon nanotubes (1) to (3).
- the electron flow in the longitudinal direction of the fiber itself can be handled by a bell-shaped body that is slightly inclined outward, and the electron flow between fibers can be performed by the emission of electrons from the open end of the bell-shaped body. Yes, it is estimated that the conductive performance in the resin is improved.
- fine carbon short fiber is a concept included in “fine carbon fiber”, and means “short carbon fiber” having a short fiber length as described later.
- fine carbon fiber usually means “fine carbon fiber” that has not been shortened.
- fine carbon fiber and fine carbon short fiber mean a carbon fiber having a specific structure described below, and not a carbon fiber having a known structure unless explicitly indicated.
- Conductive Resin Composition In the conductive resin composition of the present invention, fine carbon fibers (including fine carbon short fibers) are dispersed in a polyamide-polyphenylene ether resin.
- the fine carbon fiber, polyamide resin, polyphenylene ether resin and the like used in the present invention will be described in detail later.
- the amount of fine carbon fibers is varied in a wide range compared to “conventional ultrafine carbon fibers”. be able to.
- the blending amount of fine carbon fibers can be appropriately changed within a range in which the desired conductivity can be obtained, and within a range that does not cause deterioration of moldability and mechanical properties of the molded product.
- the blending amount is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass with respect to the total mass of the composition.
- the conductive resin composition of the present invention by blending fine carbon fibers with the polyamide-polyphenylene ether resin, merits can be obtained in the following applications.
- molding processing applications processability is improved and deformation and shrinkage are suppressed.
- electrical and electronic applications charging is prevented, and conductivity imparting and electromagnetic wave shielding are manifested.
- reinforcement applications the modulus, stiffness, tensile strength and impact resistance are improved.
- thermal applications low expansion, thermal conductivity and heat resistance are improved.
- vibration damping and vibrator characteristics such as speakers are improved.
- tribological applications wear resistance, slidability and powder fall-off prevention are improved.
- flame-retardant applications a drip prevention effect can be imparted.
- the conductive resin composition of the present invention is prepared by mixing (a) a polyamide resin component, (b) a polyphenylene ether resin component, (c) fine carbon fibers and an optional component as an optional component by a known mixing method.
- fine carbon fibers including fine carbon short fibers
- kneading method or kneader are excellent in dispersibility and can be produced by a known kneading method or kneader.
- a melt blender Bosset blender
- a single screw or twin screw extruder kneader a single screw or twin screw extruder kneader
- the method for supplying the fine carbon fibers and the additional components may be one step or multiple steps.
- fine carbon fibers When kneading as described above, fine carbon fibers have an open end which is an active site, so the affinity with the resin is high, dispersibility in kneading is improved, and at the same time, maintaining and improving the physical properties of the resin Presumed to contribute.
- the connecting portion of the assembly of bell-shaped structural units that are joined by a weak van der Waals force is easily separated at the joint by shearing force in kneading.
- the catalytic vapor phase growth method which is currently most promising as a method for mass production, produces agglomerates (fuzz balls of several ⁇ m to 1 mm) in which long filaments of 1 ⁇ m or more are intertwined in a complicated manner.
- the fine carbon fibers used in the present invention are cut to an appropriate length by adjusting the shearing force, and the shortening and opening of the fiber assembly proceeds.
- a conductive resin composition can be obtained without using an apparatus.
- fine carbon short fibers are cut at the joints to make short fibers, and are further excellent in dispersibility.
- Fine carbon fiber and fine carbon short fiber The typical characteristics and typical production methods of fine carbon fibers and short carbon fibers blended in the composition of the present invention are summarized in the following items.
- fine carbon fibers produced by a vapor deposition method Graphite mesh surface composed of only carbon atoms forms a bell-shaped structural unit having a closed top and a trunk that is open at the bottom, preferably the angle ⁇ formed by the busbar of the trunk and the fiber axis Is less than 15 °,
- the bell-shaped structural units are stacked with 2 to 30 in common sharing the central axis to form an aggregate,
- a fine carbon fiber characterized in that the aggregates are connected to each other at intervals in a head-to-tail manner to form fibers.
- the outer diameter D of the end of the aggregate body is 5 to 40 nm, the inner diameter d is 3 to 30 nm, and the aspect ratio (L / D) of the aggregate is 2 to 30 Fine carbon fiber.
- the peak half width W (unit: degree) of the 002 plane of fine carbon fiber measured by X-ray diffraction method is 2-4, Fine carbon fiber.
- a method for producing fine carbon fibers characterized by supplying gas and reacting them to grow fine carbon fibers.
- the volume ratio of CO / H 2 in the mixed gas is in the range of 70/30 to 99.9 / 0.1, and the reaction temperature is in the range of 400 to 650 ° C.
- a fine carbon short fiber obtained by shortening fine carbon fibers produced by a vapor deposition method, wherein the graphite net has a closed top portion and a trunk portion having an open bottom portion.
- a structural unit is formed, and the bell-shaped structural units are stacked in layers of 2 to 30 sharing a central axis to form an aggregate, and the aggregate is one to several tens in a head-to-tail manner.
- Fine carbon short fibers characterized by being connected individually.
- the outer diameter D at the end of the aggregate body is 5 to 40 nm, the inner diameter d is 3 to 30 nm, and the aspect ratio (L / D) of the aggregate is 2 to 30, 11.
- the peak half width W (unit: degree) of the 002 plane of the fine carbon fiber measured by X-ray diffraction method is 2 to 4, wherein any one of the above 10 to 13 Fine carbon short fiber.
- a fine short carbon fiber produced by applying shear stress to the carbon fiber described in any one of 1 to 5 above to make a short fiber.
- a method for producing a fine short carbon fiber comprising producing a fine carbon fiber by the production method according to any one of 6 to 9 above and then applying a shear stress to further shorten the fiber.
- the temple bell (temple ⁇ ⁇ bell) is found in Japanese temples, has a relatively cylindrical body, and is different in shape from a conical Christmas bell.
- the structural unit 11 has a top portion 12 and a trunk portion 13 having an open end, like a bell, and has a rotating body shape rotated about the central axis. It has become.
- the structural unit 11 is formed of a graphite network surface made of only carbon atoms, and the circumferential portion of the body portion open end is the open end of the graphite network surface.
- the central axis and the body portion 13 are shown as straight lines for convenience, but they are not necessarily straight lines and may be curved as shown in FIGS.
- the trunk portion 13 gently spreads toward the open end.
- the bus bar of the trunk portion 13 is slightly inclined with respect to the central axis of the bell-shaped structural unit, and the angle ⁇ formed by both is smaller than 15 °. More preferably, 1 ° ⁇ ⁇ 15 °, and further preferably 2 ° ⁇ ⁇ 10 °. If ⁇ is too large, fine fibers composed of the structural unit exhibit a fishbone-like carbon fiber-like structure, and the conductivity in the fiber axis direction is impaired.
- the fine carbon fiber and the fine carbon short fiber have defects and irregular turbulence, but if the irregular shape is eliminated and the shape of the whole is grasped, the trunk portion 13 is on the open end side. It can be said that it has a bell-shaped structure that gently spreads.
- the fine carbon fiber and the fine short carbon fiber of the present invention do not mean that ⁇ is in the above range in all parts, but exclude the defective part and the irregular part, and the structural unit 11 Means that ⁇ generally satisfies the above range. Therefore, in the measurement of ⁇ , it is preferable to exclude the vicinity of the crown 12 where the thickness of the trunk may be irregularly changed. More specifically, for example, if the length of the bell-shaped structural unit aggregate 21 (see below) is L as shown in FIG.
- 1B, (1/4) L, (1/2 ) L and (3/4) L may be measured at three points to obtain an average, and the value may be used as the overall ⁇ for the structural unit 11.
- the body part 13 is often a curved line in practice, it may be closer to the actual value when measured along the curve of the body part 13. .
- the shape of the top of the head when manufactured as fine carbon fibers (the same applies to fine carbon short fibers), is smoothly continuous with the trunk and has a convex curve on the upper side (in the figure).
- the length of the top of the head is typically about D (FIG. 1 (b)) or less and about d (FIG. 1 (b)) for explaining the bell-shaped structural unit aggregate.
- FIG. 1B In the fine carbon fiber and the fine short carbon fiber of the present invention, as shown in FIG. 1B, 2 to 30 such bell-shaped structural units are stacked to share the central axis, and the bell-shaped structural unit is stacked.
- An aggregate 21 (hereinafter sometimes simply referred to as an aggregate) is formed.
- the number of stacked layers is preferably 2 to 25, and more preferably 2 to 15.
- the outer diameter D of the body portion of the aggregate 21 is 5 to 40 nm, preferably 5 to 30 nm, and more preferably 5 to 20 nm.
- D is increased, the diameter of the fine fibers formed is increased, so that a large amount of addition is required in order to impart functions such as conductive performance in the composite with the polymer.
- D becomes small, the diameter of the fine fibers formed becomes thin and the aggregation of the fibers becomes strong. For example, in preparing a composite with a polymer, it becomes difficult to disperse.
- the measurement of the outer diameter D of the torso is preferably measured and averaged at three points (1/4) L, (1/2) L, and (3/4) L from the top of the aggregate.
- drum outer diameter D is shown for convenience in FIG.1 (b), the value of actual D has the preferable average value of the said 3 points
- the inner diameter d of the aggregate body is 3 to 30 nm, preferably 3 to 20 nm, more preferably 3 to 10 nm.
- the inner diameter d of the torso also measure and average at three points (1/4) L, (1/2) L, and (3/4) L from the top of the bell-shaped structural unit assembly. Is preferred.
- drum internal diameter d is shown in FIG.1 (b) for convenience, the actual value of d has the preferable average value of the said 3 points
- the aspect ratio (L / D) calculated from the length L of the aggregate 21 and the body outer diameter D is 2 to 150, preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 10. is there.
- the aspect ratio is large, the structure of the formed fiber approaches a cylindrical tube shape, and the conductivity in the fiber axis direction of one fiber is improved.
- the open end of the graphite network surface constituting the structural unit body is a fiber. Since the frequency of exposure to the outer peripheral surface is reduced, the conductivity between adjacent fibers is deteriorated.
- the aspect ratio is small, the open end of the graphite mesh surface constituting the structural unit body portion is more frequently exposed to the outer peripheral surface of the fiber, so that the conductivity between adjacent fibers is improved. Since many short graphite mesh surfaces are connected in the axial direction, conductivity in the fiber axial direction of one fiber is impaired.
- the fine carbon fiber and the fine carbon short fiber have essentially the same configuration with respect to the bell-shaped structural unit and the bell-shaped structural unit aggregate, but have different fiber lengths as follows.
- fine carbon fibers are formed by connecting the aggregates in a head-to-tail manner.
- the joining parts of the adjacent aggregates are the top part (Head) of one aggregate and the lower end part (Tail) of the other aggregate.
- the shape of the joint portion is the top of the bell-shaped structural unit of the outermost layer of the second aggregate 21b, further inside the bell-shaped structural unit of the innermost layer, at the lower end opening of the first aggregate 21a. Is inserted, and the top of the third assembly 21c is inserted into the lower end opening of the second assembly 21b, and this is further continued to form a fiber.
- Each joint part forming one fine fiber of fine carbon fibers does not have structural regularity, for example, the fiber axis direction of the joint part of the first aggregate and the second aggregate
- the length of is not necessarily the same as the length of the junction of the second assembly and the third assembly.
- the two assemblies to be joined may be connected linearly sharing the central axis, but the bell-shaped structural unit assemblies 21b and 21c in FIG. As described above, the central axis may be joined without being shared, resulting in a bent structure at the joint.
- the length L of the bell-shaped structural unit assembly is generally constant for each fiber.
- the fine carbon fiber thus configured, at least a part of the open end of the graphite net surface at the lower end of the bell-shaped structural unit is exposed on the outer peripheral surface of the fiber according to the connection interval of the aggregate.
- the conductivity between adjacent fibers can be improved by the jumping effect (tunnel effect) caused by the jumping out of the ⁇ electrons without impairing the conductivity in the fiber axis direction of one fiber.
- the fine carbon fiber structure as described above can be observed by a TEM image.
- the effect of the fine carbon fiber has almost no influence even when the aggregate itself bends and there is a bend in the connecting portion of the aggregate. Therefore, in the TEM image, an assembly having a shape that is relatively close to a straight line is observed to obtain each parameter relating to the structure, and the structure parameter ( ⁇ , D, d, L) for the fiber may be obtained.
- the fine carbon short fiber is obtained by further shortening the fine carbon fiber thus constituted. Specifically, by applying shear stress to the fine carbon fiber, a slip occurs between the graphite base surfaces at the aggregate joint, and the fine carbon fiber is cut at a part of the aggregate joint and is short fiber. It becomes.
- the fine short carbon fibers obtained by shortening such a short fiber have about 1 to several tens of aggregates (that is, 100 or less, up to about 80, preferably up to about 70), preferably 1 To 20 connected fibers are shortened.
- the aspect ratio of the fine carbon short fiber aggregate is about 2 to 150.
- the aspect ratio of the aggregate of fine carbon short fibers suitable for mixing is 2 to 50. Even if shear stress is applied, the fiber straight body portion composed of carbon SP2 bonds of the aggregate does not cause fiber cutting, and cannot be cut smaller than the aggregate.
- the peak half width W (unit: degree) of the 002 plane measured is in the range of 2-4.
- W exceeds 4 the graphite crystallinity is low and the conductivity is low.
- W is less than 2 the graphite crystallinity is good, but at the same time, the fiber diameter becomes large, and a large amount of addition is required to impart a function such as conductivity to the polymer.
- the graphite interplanar spacing d002 obtained by XRD measurement by the Gakushin method of fine carbon fibers and short carbon short fibers is 0.350 nm or less, preferably 0.341 to 0.348 nm. If d002 exceeds 0.350 nm, the graphite crystallinity is lowered and the conductivity is lowered. On the other hand, the fiber of less than 0.341 nm has a low yield in production.
- the ash contained in fine carbon fibers and short carbon short fibers is 4% by mass or less, and no refining is required for normal use. Usually, it is 0.3 mass% or more and 4 mass% or less, More preferably, it is 0.3 mass% or more and 3 mass% or less.
- the ash content is determined from the weight of the oxide remaining after burning 0.1 g or more of the fiber.
- the fine short carbon fiber preferably has a fiber length of 100 to 1000 nm, more preferably 100 to 300 nm. Having such a length, the above-described 002 plane peak half-value width W (unit: degree) is 2 to 4, and the graphite plane spacing d002 is 0.350 nm or less, preferably 0.341 to 0.00.
- a fine short carbon fiber having a wavelength of 348 nm is a novel fiber that has not existed conventionally.
- Fine carbon short fibers are produced by shortening fine carbon fibers.
- the method for producing fine carbon fibers is as follows. Fine carbon fibers are produced by vapor phase growth using a catalyst.
- a catalyst containing an element selected from the group consisting of Fe, Co, Ni, Al, Mg and Si is preferably used, and the supply gas is preferably a mixed gas containing CO and H 2 .
- the catalyst a catalyst containing an element selected from the group consisting of Fe, Co, Ni, Al, Mg and Si is preferably used, and the supply gas is preferably a mixed gas containing CO and H 2 .
- a mixed gas containing CO and H 2 is supplied to the catalyst particles to form fine particles by vapor deposition.
- the spinel crystal structure of cobalt in which Mg is substituted and dissolved is represented by Mg x Co 3-x O y .
- x is a number indicating the replacement of Co by Mg, and formally 0 ⁇ x ⁇ 3.
- y is a number selected so that the entire expression is neutral in terms of charge, and formally represents a number of 4 or less. That is, in the spinel-type oxide Co 3 O 4 of cobalt, there are divalent and trivalent Co ions, where the divalent and trivalent cobalt ions are represented by Co II and Co III , respectively.
- a cobalt oxide having a spinel crystal structure is represented by Co II Co III 2 O 4 .
- Mg displaces both Co II and Co III sites and forms a solid solution.
- the value of y becomes smaller than 4 in order to maintain charge neutrality.
- both x and y take values in a range where the spinel crystal structure can be maintained.
- the solid solution range of Mg is such that the value of x is 0.5 to 1.5, more preferably 0.7 to 1.5.
- the value of x is less than 0.5, the catalyst activity is low and the amount of fine carbon fibers produced is small.
- the value of x exceeds 1.5, it is difficult to prepare a spinel crystal structure.
- the spinel oxide crystal structure of the catalyst can be confirmed by XRD measurement, and the crystal lattice constant a (cubic system) is in the range of 0.811 to 0.818 nm, more preferably 0.812. ⁇ 0.818 nm. If “a” is small, the solid solution substitution of Mg is not sufficient, and the catalytic activity is low. Also, the spinel oxide crystal having a lattice constant exceeding 0.818 nm is difficult to prepare.
- the particle size of the catalyst can be appropriately selected.
- the median diameter is 0.1 to 100 ⁇ m, preferably 0.1 to 10 ⁇ m.
- Catalyst particles are generally used by being applied to a suitable support such as a substrate or a catalyst bed by a method such as spraying.
- the catalyst particles may be sprayed directly onto the substrate or the catalyst bed, but the catalyst particles may be sprayed directly, but a desired amount may be sprayed by suspending in a solvent such as ethanol and drying.
- the catalyst particles are preferably activated before reacting with the raw material gas. Activation is usually performed by heating in a gas atmosphere containing H 2 or CO. These activation operations can be performed by diluting with an inert gas such as He or N 2 as necessary.
- the temperature at which the activation is performed is preferably 400 to 600 ° C., more preferably 450 to 550 ° C.
- the reactor for the vapor phase growth method there are no particular limitations on the reactor for the vapor phase growth method, and the reaction can be carried out using a reactor such as a fixed bed reactor or a fluidized bed reactor.
- a mixed gas containing CO and H 2 is used as a source gas that becomes a carbon source for vapor phase growth.
- the H 2 gas addition concentration ⁇ (H 2 / (H 2 + CO) ⁇ is preferably 0.1 to 30 vol%, more preferably 2 to 20 vol%. If the addition concentration is too low, a cylindrical graphitic network is used. On the other hand, if the surface exceeds 30 vol%, the angle of inclination of the bell-shaped structure with respect to the fiber axis increases with respect to the fiber axis, resulting in a fishbone shape. This causes a decrease in conductivity in the fiber direction.
- the raw material gas may contain an inert gas.
- the inert gas include CO 2 , N 2 , He, Ar, and the like.
- the content of the inert gas is preferably such that the reaction rate is not significantly reduced, for example, 80 vol% or less, preferably 50 vol% or less.
- waste gas such as synthesis gas or converter exhaust gas containing H 2 and CO can be appropriately treated and used as necessary.
- the reaction temperature for carrying out the vapor phase growth is preferably 400 to 650 ° C., more preferably 500 to 600 ° C. If the reaction temperature is too low, fiber growth does not proceed. On the other hand, if the reaction temperature is too high, the yield decreases.
- reaction time is not specifically limited, For example, it is 2 hours or more, and is about 12 hours or less.
- the reaction pressure for carrying out the vapor phase growth is preferably normal pressure from the viewpoint of simplifying the reaction apparatus and operation, but is carried out under pressure or reduced pressure as long as Boudardo equilibrium carbon deposition proceeds. It doesn't matter.
- the amount of fine carbon fiber produced per unit weight of the catalyst was much larger than that of the conventional production method.
- the amount of fine carbon fibers produced by this fine carbon fiber production method is 40 times or more per unit weight of the catalyst, for example, 40 to 200 times. As a result, it is possible to produce fine carbon fibers with less impurities and ash as described above.
- the catalyst has a balance between the exothermic Boudouard equilibrium and the heat removal by the flow of the raw material gas. Since the temperature in the vicinity of the cobalt fine particles formed from oscillates up and down, it is considered that carbon deposition is formed by intermittent progress. That is, [1] formation of the top of the bell-shaped structure, [2] growth of the trunk of the bell-shaped structure, [3] growth stop due to temperature rise due to heat generated in the processes [1] and [2], [4] It is presumed that a fine junction of the carbon fiber structure is formed by repeating the four processes of cooling with the flow gas on the catalyst fine particles.
- a fine carbon fiber can be manufactured.
- fine carbon short fibers can be produced by separating the fine carbon fibers into short fibers. Preferably, it manufactures by applying a shear stress to a fine carbon fiber.
- a crusher, a rotating ball mill, a centrifugal ball mill, a centrifugal planetary ball mill, a bead mill, a microbead mill, an attritor type high-speed ball mill, a rotating rod mill, a vibrating rod mill, a roll mill, a three-roll mill, etc. are suitable. It is.
- the shortening of fine carbon fibers can be performed either dry or wet.
- the atmosphere for dry fiber shortening can be selected from an inert atmosphere and an oxidizing atmosphere depending on the purpose.
- the fine carbon fibers are formed by connecting the bell-shaped structural unit aggregates at intervals in the head-to-tail manner to form fibers.
- shear stress is applied to the fiber, the fiber is pulled in the direction of the fiber axis in the direction of the arrow in FIG. 4 to cause slippage between the carbon base surfaces constituting the joint (A in FIG. 4: “C” portion of Katakana).
- the bell-shaped structural unit aggregate is pulled out from one to several tens of units at the head-to-tail connection portion, and short fiber formation occurs.
- the head-to-tail joint is not formed of continuous carbon double bonds in the fiber axis direction as in the case of concentric fine carbon fibers, but mainly consists of van der Waals forces with low binding energy. This is because it is formed by bonding.
- the crystallinity of the fine carbon fiber and the fine carbon short fiber obtained by shortening the fine carbon fiber are compared in terms of the carbon layer spacing and the true specific gravity, there is no difference in carbon crystallinity between the two.
- the surface area of the fine carbon short fiber after shortening is increased by about 2 to 5% as compared with the fine carbon fiber.
- the resin component in which fine carbon fibers or fine carbon short fibers are dispersed preferably includes a polyamide resin and a polyphenylene ether resin.
- the polyamide resin used in the present invention is obtained by polycondensation of diamine and dicarboxylic acid, self-condensation of ⁇ -aminocarboxylic acid, ring-opening polymerization of lactams, etc., and has a sufficient molecular weight.
- the number average molecular weight of the polyamide resin used in the present invention is not particularly limited, and those having a molecular weight in the range of usually 10,000 to 50,000, preferably 13,000 to 30,000 can be arbitrarily used. If the molecular weight of the polyamide resin is too small, the mechanical properties of the finally obtained resin composition are deteriorated, and if it is too large, the melt viscosity is increased and the molding processability is deteriorated.
- the polyamide resin used in the present invention includes, for example, nylon 6, nylon 4, nylon 6,6, nylon 11, nylon 12, nylon 6,10, nylon 6,12, nylon 6 / 6,6, nylon 6 / 6,6 / 12, nylon 6, MXD (MXD represents m-xylylenediamine component), nylon 6,6T (T represents terephthalic acid component), nylon 6,6I (I represents isophthalic acid component) These are not intended to limit the scope of the present invention.
- the diamine include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 1,9-nonane diamine, 2-methyl-1 , 8-octanediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, m-xylylenediamine, p-xylylenediamine and the like, and aliphatic, alicyclic and aromatic diamines.
- dicarboxylic acid examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene.
- Aliphatic, alicyclic, and aromatic dicarboxylic acids such as dicarboxylic acid, dimer acid, oxalic acid, and oxalic acid ester may be mentioned.
- One aspect of obtaining a polyamide resin by polycondensation of a diamine and a dicarboxylic acid is the case of using a diamine having 4 to 12 carbon atoms as the diamine component and oxalic acid as the dicarboxylic acid component. Will be described.
- the polyamide resin obtained by polycondensation of the compound is characterized by improved water absorption and chemical resistance as compared with conventional polyamide resins.
- diamine having 4 to 12 carbon atoms aliphatic diamine, alicyclic diamine and aromatic diamine having 4 to 12 carbon atoms are preferable, and among them, nonane diamine, decane diamine, dodecane diamine and isomers thereof are more preferable. These may be used alone or in admixture of two or more.
- Examples of the case where two or more kinds of diamines are mixed and used include a case where a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is used.
- the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 1:99 to 99: 1, more preferably 5:95 to 40:60 or 60:40 to 95: 5, particularly preferably 5:95 to 30:70 or 70:30 to 90:10.
- oxalic acid diester As the oxalic acid source used for the production, oxalic acid diester is used, and there is no particular limitation as long as it has reactivity with an amino group. Dimethyl oxalate, diethyl oxalate, di-n-oxalate (or i-) Aliphatic monohydric alcohol oxalic acid diesters such as propyl, di-n- (or i-, or t-) butyl oxalate, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, diphenyl oxalate, etc.
- Examples include oxalic acid diesters of aromatic alcohols, and among the above oxalic acid diesters, oxalic acid diesters of aliphatic monohydric alcohols having more than 3 carbon atoms, alicyclic alcohol oxalic acid diesters, and aromatic alcohol oxalates. Acid diesters are preferred, with dibutyl oxalate and diphenyl oxalate being particularly preferred. Arbitrariness.
- Examples of the ⁇ -aminocarboxylic acid include 6-aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like.
- Examples of the lactam include ⁇ -caprolactam and ⁇ -laurolactam.
- these diamines, dicarboxylic acids, or ⁇ -aminocarboxylic acids, or lactams are used for polycondensation or the like alone or in the form of a mixture of two or more, and thus obtained polyamide homopolymer, Any of the copolymers and mixtures of homopolymers and / or copolymers can be used.
- the polyphenylene ether resin used in the present invention is not particularly limited, and examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-diethyl-1,4-phenylene) ether.
- a commercially available polyphenylene ether resin containing a styrenic polymer may be used.
- the intrinsic viscosity [ ⁇ ] of these polyphenylene ether resins measured in chloroform at 25 ° C. is 0.2 to 1.0 dl / g, preferably 0.3 to 0.7 dl / g. If this intrinsic viscosity is too small, the effect of improving the heat resistance of the resulting resin composition is not sufficient, and if it is too large, the moldability is lowered.
- the above-mentioned polyphenylene ether resin can be used after being modified with ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof in order to develop compatibility with the polyamide resin.
- Specific examples of the ⁇ , ⁇ -unsaturated carboxylic acid include monobasic unsaturated carboxylic acids such as acrylic acid and methacrylic acid, dibasic unsaturated carboxylic acids such as array acid, itaconic acid and fumaric acid, and citric acid. And tribasic unsaturated carboxylic acids such as acids.
- Examples of the derivatives of ⁇ , ⁇ -unsaturated carboxylic acids include acid halamides, amides, imides, anhydrides, salts and esters, and specific examples include maleic anhydride and itaconic anhydride.
- ⁇ Polyamide-polyphenylene ether resin In the present invention, the above polyamide resin and polyphenylene ether resin are mixed and used. These mixing methods are not particularly limited, and the polyphenylene ether resin may be previously modified with ⁇ , ⁇ -unsaturated carboxylic acid and then mixed with the polyamide resin, or the polyphenylene ether resin may be mixed with ⁇ , ⁇ -unsaturated. You may mix with a polyamide resin sequentially in the process modified
- the mixing ratio of the polyamide resin and the polyphenylene ether resin can be appropriately adjusted according to the use, but for example, in the range of 1/99 to 99/1, preferably 30/70 to 95/5, more preferably 50/50 to 90 /.
- the range is 10.
- thermoplastic resins and elastomers can be mixed as long as the object of the present invention is not impaired, and these may be used alone or in combination of two or more. Good.
- thermoplastic resins to be mixed include polyolefin resins (polyethylene, polypropylene, ethylene-vinyl acetate copolymer resins, ethylene-vinyl copolymer resins, ethylene-ethyl acrylate copolymer resins, ionomers, etc.), polyvinyl resins (Polyvinyl chloride, styrene, ABS resin, etc.), polyester resins (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphtholate, polycarbonate, liquid crystal polymer, etc.), polyether resins (polyoxymethylene, aromatic polysulfone, polyether Ketones, polyphenylene sulfide, polyether / imide, etc.) and fluororesins (polytetrafluoroethylene, polyvinylidene fluoride, etc.).
- polyolefin resins polyethylene, polypropylene, ethylene-vinyl acetate copoly
- polyvinyl resins particularly aromatic vinyl compound-aliphatic hydrocarbon copolymers, particularly hydrogenated or non-hydrogenated products of styrene-butadiene copolymers and styrene-isoprene copolymers are preferably used.
- the conductive resin composition of the present invention can be used in combination with an additional component in order to more effectively express the intended function.
- additional components include various additives such as various pigments, heat-resistant agents such as copper compounds, ultraviolet absorbers, light stabilizers, antioxidants, flame retardants, crystallization accelerators, plasticizers, lubricants, and fillers. Etc.
- pigments examples include extender pigments (transparent white pigments such as barium sulfate, calcium carbonate, silica, aluminum oxide), black pigments (carbon black, magnetite, etc.), white pigments (titanium dioxide, zinc oxide, tin dioxide, zirconium oxide, etc.) ), Black and colored pigments (cobalt blue, titanium yellow, etc.).
- extender pigments transparent white pigments such as barium sulfate, calcium carbonate, silica, aluminum oxide
- black pigments carbon black, magnetite, etc.
- white pigments titanium dioxide, zinc oxide, tin dioxide, zirconium oxide, etc.
- Black and colored pigments cobalt blue, titanium yellow, etc.
- conductive filler As filler, conductive filler ⁇ metal (silver, copper, nickel, stainless fiber, etc.), oxide filler (ZnO, ITO, ATO, nitride, carbide, boride), carbon, organic ⁇ , magnetic filler (Ferrite, Sm / Co, Nd / Fe / B, etc.), piezoelectric filler, thermal conductive filler (Ag, h-BN, AlN, Al 2 O 3 ), reinforcing filler (glass fiber, carbon fiber, MOS, Talc, mica, etc.), moldable filler, impact resistant filler, wear resistant filler, heat resistant filler (clay mineral, talc, calcium carbonate, precipitated barium sulfate, etc.), flame retardant filler (zinc borate, red phosphorus) , Ammonium phosphate, magnesium hydroxide, etc.), soundproof and vibration-proof filler (iron powder, barium sulfate, mica, ferrite, etc.), solid lubric
- the filler shape is granular, spherical (improved easy processability and fracture toughness), flat (flaky) (rigidity, vibration control, surface lubricity), needle (mechanical thermal reinforcement, conductivity efficiency) ), And can be used according to the purpose.
- These additional components can be appropriately added according to the purpose of use of the conductive resin composition. Typically, the additional component is added in the range of 2% by mass to 40% by mass with respect to the total mass of the conductive resin composition.
- Preferred reinforcing fillers are glass fiber and carbon fiber, but the effect of improving the physical properties such as strength and creep resistance of the conductive polyamide resin composition of the present invention is particularly remarkable by blending glass fiber.
- the glass fiber is not particularly limited, and the glass fiber diameter is not limited, but those of 5 to 15 ⁇ m are preferable.
- the fiber length may be a short fiber or a long fiber depending on the application, but is preferably 5 to 1000 ⁇ m.
- the blending ratio of the glass fiber is preferably 3 to 50% by mass, more preferably 5 to 35% by mass with respect to the total mass of the conductive resin composition. If the blending ratio of the glass fiber is small, the effect of improving the strength and creep resistance is small, while if the blending amount of the glass fiber is large, the moldability and surface smoothness may be deteriorated.
- the molding method of the conductive resin composition of the present invention and the shape of the molded product are not particularly limited.
- various methods such as melt spinning, extrusion molding, blow molding, injection molding, press molding and the like can be used, and the method is appropriately selected according to the shape and composition of the molded product.
- the shape of the molded product include a film, a sheet, a filament, a rod, a tube, a belt, and a three-dimensional molded product.
- the conductive molded product obtained from the conductive composition of the present invention can be used in a wide range of applications such as the electric / electronic field, the automobile field, the civil engineering and building field, the medical field, the information and communication field, and household goods.
- engine parts such as air intake manifolds and air cleaners in the engine compartment, oil pumps, oil coolers, oil pans, radiators, water pumps, impellers, engine pumps, fuel tanks, Peripheral parts, fuel tank valves, fuel system parts such as fuel tubes and fuel tube connectors, gears and other transmission parts used in transmissions and steering parts, brakes, clutch parts, electromagnetic shielding members, antistatic parts
- electrostatic coating members such as automobile body outer plates can be mentioned.
- non-aqueous solvent power storage device electrodes such as consumer devices and automobile batteries, capacitors and electrochemical capacitors, conductive binders for electrodes, current collectors, other electromagnetic wave shielding members in the electric and electronic fields, antistatic components, etc.
- Useful for applications such as manufacturing of semiconductor devices, trays in packaging processes, packaging materials, building materials for clean rooms, dust-free clothing, and conductive materials for electronic devices (belts, sheaths, rolls, connectors, gears, tubes, etc.) is there.
- Relative viscosity ( ⁇ r) ⁇ r was measured at 25 ° C. using an Ostwald viscometer using a 96% polyamide sulfuric acid solution (concentration: 1.0 g / dl).
- volume resistivity of the resin composition was measured with a low resistivity meter Loresta GP (MCP-T610) and a high resistivity meter Hiresta UP (MCP-HT450) (manufactured by Dia Instruments Co., Ltd.).
- Production Example A1 Production of Fine Carbon Fiber ⁇ Production Example A1>
- magnesium nitrate [Mg (NO 3 ) 2 .6H 2 O: molecular weight 256.41 102 g (0.40 mol) was dissolved to prepare a raw material solution (1).
- 220 g (2.78 mol) of ammonium bicarbonate [(NH 4 ) HCO 3 : molecular weight 79.06] powder was dissolved in 1100 mL of ion-exchanged water to prepare a raw material solution (2).
- the raw material solutions (1) and (2) were mixed at a reaction temperature of 40 ° C., and then stirred for 4 hours. The produced precipitate was filtered, washed and dried.
- the yield was 53.1 g, and the ash content was 1.5% by mass.
- the peak half-value width W (degree) observed by XRD analysis of the product was 3.156, and d002 was 0.3437 nm.
- the number of bell-shaped structural units forming the aggregate was 4 to 5.
- about D, d, and (theta) three points, (1/4) L, (1/2) L, and (3/4) L, were measured from the tower top of the aggregate.
- FIG. 3 shows a TEM image of the obtained fine carbon fiber.
- Fine carbon fibers obtained as described above were treated with a ceramic ball mill having a diameter of 2 mm for a predetermined time to prepare fine short carbon fibers.
- a TEM image of fine carbon short fibers after 20 hours is shown in FIG.
- ⁇ shown here is the average value of the slopes of the left and right carbon layers with respect to the fiber axis center of the TEM image.
- the number of stacked bell-shaped structural units forming the aggregate was 10 to 20.
- Production Example B1 Production of polyamide resin using oxalic acid as dicarboxylic acid component ⁇ Production Example B1> Oxalic acid in a 150 liter pressure vessel with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator and polymer outlet After charging 28.40 kg (140.4 mol) of dibutyl, pressurizing to 0.5 MPa with nitrogen gas having a purity of 99.9999% inside the pressure vessel, and then releasing nitrogen gas to atmospheric pressure 5 After repeated nitrogen substitution, the system was heated while stirring under a sealing pressure. After adjusting the temperature of dibutyl oxalate to 100 ° C.
- the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port.
- butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was raised to 260 ° C. over about 1 hour, and the reaction was carried out at 260 ° C. for 4.5 hours. .
- the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes, then released to an internal pressure of 0.5 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
- the string-like polycondensate was immediately cooled, and the water-cooled string-like resin was pelletized by a pelletizer.
- Polyamide 66 Polyamide 66 resin having a relative viscosity of 2.75 (2020B manufactured by Ube Industries, Ltd.)
- Polyamide 6 Polyamide 6 resin having a relative viscosity of 2.70 (Ube Industries, Ltd., 1015B)
- Polyphenylene ether resin a poly (2,6-dimethyl-1,4-phenylene ether) resin having a polymer concentration of 0.5% by mass in chloroform at 25 ° C. and a relative viscosity of 0.45.
- Maleic anhydride-modified polyphenylene ether resin melt-kneaded with maleic anhydride at 280 ° C.
- Aromatic vinyl compound-aliphatic hydrocarbon copolymer hydrogenated styrene-isoprene block copolymer (Kuraray Septon 2104)
- Examples 1 to 7 A predetermined amount of fine carbon fibers produced in the same manner as in Production Example A1 are blended with the polyamide 66 resin (1) and the polyphenylene ether resin (3), premixed with a Henschel mixer, and the blended product is then mixed with a twin-screw extruder. The mixture was melted and mixed at 260 ° C., and the molten mixture was pelletized to obtain a conductive polyamide resin composition. This pellet was melt press-molded at 260 ° C., and the volume resistance value ( ⁇ ⁇ cm) (applied voltage 10 V) was measured. The results are shown in Table 1 together with the composition.
- Example 1 Evaluation was performed in the same manner as in Example 1 except that ketjen black (EC600JD manufactured by ketjen black international) was used instead of fine carbon fibers. The results are shown in Table 1.
- Examples 1 to 7 using fine carbon fibers which are the characteristics of the present invention, are more conductive and mechanical than the composition using Ketjen Black shown in Comparative Example 1. Excellent mechanical properties, especially tensile elongation at break and impact strength.
- Example 8 Evaluation was performed in the same manner as in Example 1 except that the polyamide 6 resin (2) was used. The results are shown in Table 2 together with the composition.
- Example 2 Evaluation was performed in the same manner as in Example 2 except that ketjen black (EC600JD manufactured by ketjen black international) was used instead of fine carbon fibers. The results are shown in Table 2.
- Example 9 Evaluation was conducted in the same manner as in Example 2 except that the polyamide resin produced in the same manner as in Production Example B1 was used. The results are shown in Table 2 together with the composition.
- Example 10 The polyamide 66 resin (1), the polyphenylene ether resin (3) and the aromatic vinyl compound-aliphatic hydrocarbon copolymer (4) are blended with a predetermined amount of fine carbon fibers produced in the same manner as in Production Example A1, After premixing with a Henschel mixer, the blend was melted and mixed at 260 ° C. with a twin-screw extruder, and the molten mixture was pelletized to obtain a conductive polyamide resin composition. The pellet was melt press-molded at 260 ° C. and the volume resistance value ( ⁇ ⁇ cm) (applied voltage: 10 V) was measured. The results are shown in Table 2 together with the composition.
- Examples 8 to 10 using fine carbon fibers which is a feature of the present invention, are more conductive than the compositions using Ketjen Black shown in Comparative Examples 2 to 4. Excellent mechanical properties, especially tensile elongation at break and impact strength.
- the conductive resin composition of the present invention has stable conductivity while maintaining the original physical properties of the polyamide-polyphenylene ether resin, has low water absorption, excellent dimensional stability and moldability, and has impact characteristics. Excellent mechanical properties, chemical resistance, and hydrolysis resistance. Therefore, the conductive molded product obtained from the conductive resin composition of the present invention can be used in a wide range of applications such as the electric / electronic field, the automobile field, the civil engineering / building field, the medical field, the information communication field, and the household goods.
- engine parts such as air intake manifolds and air cleaners in the engine compartment, oil pumps, oil coolers, oil pans, radiators, water pumps, impellers, engine pumps, fuel tanks, Peripheral parts, fuel tank valves, fuel system parts such as fuel tubes and fuel tube connectors, gears and other transmission parts used in transmissions and steering parts, brakes, clutch parts, electromagnetic shielding members, antistatic parts
- electrostatic coating members such as automobile body outer plates can be mentioned.
- Electromagnetic wave shielding member, antistatic component, electrostatic coating member in electrical and electronic fields and automotive field, as well as trays, packaging materials, clean room building materials, dust-free garments, and electronic devices in semiconductor device manufacturing and transportation processes It is useful for applications such as equipment conductive members (belts, sheaths, rolls, connectors, gears, tubes, etc.).
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Abstract
Description
(1)多層カーボンナノチューブ(グラファイト層が多層同心円筒状)(非魚骨状)
特公平3-64606、同3-77288
特開2004-299986
(2)カップ積層型カーボンナノチューブ(魚骨状(フィッシュボーン))
USP 4,855,091
M.Endo, Y.A.Kim etc.:Appl.Phys.Lett.,vol80(2002)1267~
特開2003-073928
特開2004-360099
(3)プレートレット型カーボンナノファイバー(トランプ状)
H.Murayama, T.maeda:Nature, vol345[No.28](1990)791~793
特開2004-300631
の3つのナノ構造炭素材料に大別される。
(b)ポリフェニレンエーテル樹脂、及び
(c)前記樹脂中に分散され、炭素原子のみから構成されるグラファイト網面が、閉じた頭頂部と、下部が開いた胴部とを有する釣鐘状構造単位を形成し、前記釣鐘状構造単位が、中心軸を共有して2~30個積み重なって集合体を形成し、前記集合体が、Head-to-Tail様式で間隔をもって連結して繊維を形成している微細な炭素繊維
を含有する導電性樹脂組成物。
本発明の導電性樹脂組成物は、ポリアミド-ポリフェニレンエーテル樹脂中、微細な炭素繊維(微細な炭素短繊維を包含する)が分散されている。本発明に用いる微細な炭素繊維、ポリアミド樹脂、ポリフェニレンエーテル樹脂等については、後で詳細に説明する。
本発明の導電性樹脂組成物は、(a)ポリアミド樹脂成分、(b)ポリフェニレンエーテル樹脂成分、(c)微細な炭素繊維及び任意成分として付加成分を、公知の混合方法によって混合して調製される。特に、微細な炭素繊維(微細な炭素短繊維を包含する)は、分散性に優れるため、公知の混練方法、混練機で製造することができる。
本発明の組成物中に配合される微細な炭素繊維及び微細な炭素短繊維の代表的な特徴及び代表的な製造方法は、次の項目にまとめられる。
炭素原子のみから構成されるグラファイト網面が、閉じた頭頂部と、下部が開いた胴部とを有する釣鐘状構造単位を形成し、好ましくは前記胴部の母線と繊維軸とのなす角θが15°より小さく、
前記釣鐘状構造単位が、中心軸を共有して2~30個積み重なって集合体を形成し、
前記集合体が、Head-to-Tail様式で間隔をもって連結して繊維を形成していることを特徴とする微細な炭素繊維。
まず、微細な炭素繊維の製造方法は、次のとおりである。微細な炭素繊維は、触媒を用いて、気相成長法により製造される。触媒としては、好ましくはFe、Co、Ni、Al、Mg及びSiからなる群より選ばれる元素を含む触媒が使用され、供給ガスは、好ましくはCO及びH2を含む混合ガスである。最も好ましくは、コバルトのスピネル型結晶構造を有する酸化物に、マグネシウムが固溶置換した触媒を用いて、CO及びH2を含む混合ガスを触媒粒子に供給して気相成長法により、微細な炭素繊維を製造する。
以上により、微細な炭素繊維を製造することができる。次に、微細な炭素短繊維は、微細な炭素繊維を分離して短繊維とすることで製造することができる。好ましくは、微細な炭素繊維にずり応力を加えることにより製造する。具体的な短繊維化処理方法としては擂潰機、回転ボールミル、遠心ボールミル、遠心遊星ボールミル、ビーズミル、マイクロビーズミル、アトライタータイプの高速ボールミル、回転ロッドミル、振動ロッドミル、ロールミル、3本ロールミルなどが好適である。微細な炭素繊維の短繊維化は乾式でも、湿式でも行うことが可能である。湿式で行う場合、樹脂を共存させて、或は樹脂とフィラーを共存させて行うことも出来る。また短繊維化前の微細な炭素繊維は凝集した毛玉のような状態を構成しているので、このような状態を解きほぐす微小なメディアを共存させると解砕、短繊維化が進みやすい。また、微細なフィラーを共存させることで、微細な炭素繊維の短繊維化と、フィラーの混合および分散とを同時に行うことも出来る。乾式短繊維化における雰囲気は不活性雰囲気も酸化雰囲気も目的によって選択することが出来る。
本発明において、微細な炭素繊維または微細な炭素短繊維が分散される樹脂成分は、ポリアミド樹脂とポリフェニレンエーテル樹脂を含むことが好ましい。
本発明に用いるポリアミド樹脂は、ジアミンとジカルボン酸の重縮合、ω-アミノカルボン酸の自己縮合、ラクタム類の開環重合などによって得られ、十分な分子量を有するものである。
本発明に用いるポリフェニレンエーテル樹脂は、特に限定されないが、例えば、ポリ(2,6-ジメチル-1,4-フェニレン)エーテル、ポリ(2,6-ジエチル-1,4-フェニレン)エーテルなどが挙げられ、また当業界で周知のごとく、市販品としてのスチレン系重合体を含んだポリフェニレンエーテル樹脂を用いてもよい。
本発明において、これらのポリフェニレンエーテル樹脂の25℃クロロホルム中で測定した極限粘度[η]は、0.2~1.0dl/g、好ましくは0.3~0.7dl/gである。この極限粘度が小さすぎると、得られる樹脂組成物の耐熱性改善効果が十分でなく、また、大きすぎると成形加工性が低下する。
本発明においては、上記ポリアミド樹脂およびポリフェニレンエーテル樹脂を混合して用いる。これらの混合方法においては、特に制限はなく、あらかじめポリフェニレンエーテル樹脂をα,β-不飽和カルボン酸により変性した後、ポリアミド樹脂と混合してもよいし、ポリフェニレンエーテル樹脂をα,β-不飽和カルボン酸で変性する工程で、逐次ポリアミド樹脂と混合してもよい。ポリアミド樹脂とポリフェニレンエーテル樹脂の混合比は、用途に応じて適宜調整できるが、例えば1/99~99/1の範囲、好ましくは30/70~95/5、さらに好ましくは50/50~90/10の範囲である。
本発明の導電性樹脂組成物には、本発明の目的を損なわない範囲で、他の熱可塑性樹脂やエラストマーなどを混合することができ、これらは単独でも2種類以上を混合して用いてもよい。
本発明の導電性樹脂組成物は、目的とする機能をさらに効果的に発現するために、付加成分を併用することができる。このような付加成分としては、各種顔料、銅化合物などの耐熱剤、紫外線吸収剤、光安定剤、酸化防止剤、難燃剤、結晶化促進剤、可塑剤、潤滑剤などの各種添加剤、フィラー等が挙げられる。
本発明の導電性樹脂組成物の成形法及び成形品の形状は、特に限定されない。成形法としては、溶融紡糸、押出成形、ブロー成形、射出成形、プレス成形等各種方法が利用でき、成形品の形状及び組成物に応じて適宜選択する。成形品の形状としては、フィルム、シート、フィラメント、棒、チューブ、ベルト、立体成形品などが挙げられる。
ηrはポリアミドの96%硫酸溶液(濃度:1.0g/dl)を使用してオストワルド型粘度計を用いて25℃で測定した。
実施例及び比較例により得られたポリアミド樹脂ペレットを、23℃65%Rh雰囲気中に放置し、飽和吸水率をカールフィッシャー型水分計を用いてJIS規格に準拠して測定した。
以下に示す[1]~[4]の測定は、下記の試験片を樹脂温度260℃(ナイロン12を用いた場合は230℃)、金型温度80℃で射出成形した試験片を用いて行った。
[1]引張降伏点強度及び破断点伸び:ISOタイプA試験片を用い、ISO527-1,2に準拠して測定した。測定は23℃50%Rh雰囲気下で行った。
[2]曲げ弾性率:ISOタイプB試験片を用い、ISO178に準拠して測定した。測定は23℃50%Rh雰囲気下で行った。
[3]吸水時曲げ弾性率:ISOタイプB試験片を23℃50%Rh雰囲気下中に放置し、飽和吸水率まで吸水した試験片をISO178に準拠して測定した。測定は23℃50%Rh雰囲気下で行った。
[4]シャルピー衝撃試験:ISOタイプB試験片を用い、ISO179/1eAに準拠してノッチ付きの衝撃試験を23℃50%Rh雰囲気下で行った。
樹脂組成物の体積抵抗値は、低抵抗率計ロレスタGP(MCP-T610)及び高抵抗率計ハイレスタUP(MCP-HT450)((株)ダイヤインスツルメンツ製)で測定した。
<製造例A1>
イオン交換水500mLに硝酸コバルト〔Co(NO3)2・6H2O:分子量291.03〕115g(0.40モル)、硝酸マグネシウム〔Mg(NO3)2・6H2O:分子量256.41〕102g(0.40モル)を溶解させ、原料溶液(1)を調製した。また、重炭酸アンモニウム〔(NH4)HCO3:分子量79.06〕粉末220g(2.78モル)をイオン交換水1100mLに溶解させ、原料溶液(2)を調製した。次に、反応温度40℃で原料溶液(1)と(2)を混合し、その後4時間攪拌した。生成した沈殿物のろ過、洗浄を行い、乾燥した。
<製造例B1>
攪拌機、温度計、トルクメーター、圧力計、ダイアフラムポンプを直結した原料投入口、窒素ガス導入口、放圧口、圧力調整装置及びポリマー放出口を備えた内容積が150リットルの圧力容器にシュウ酸ジブチル28.40kg(140.4モル)を仕込み、圧力容器の内部の純度が99.9999%の窒素ガスで0.5MPaに加圧した後、次に常圧まで窒素ガスを放出する操作を5回繰返し、窒素置換を行った後、封圧下、攪拌しながら系内を昇温した。約30分間かけてシュウ酸ジブチルの温度を100℃にした後、1,9-ノナンジアミン18.89kg(119.3モル)と2-メチル-1,8-オクタンジアミン3.34kg(21.1モル)の混合物(1,9-ノナンジアミンと2-メチル-1,8-オクタンジアミンのモル比が85:15)をダイアフラムポンプにより流速1.49リットル/分で約17分間かけて反応容器内に供給すると同時に昇温した。供給直後の圧力容器内の内圧は、重縮合反応によって生成したブタノールによって0.35MPaまで上昇し、重縮合物の温度は約170℃まで上昇した。その後、1時間かけて温度を235℃まで昇温した。その間、生成したブタノールを放圧口より抜き出しながら、内圧を0.5MPaに調節した。重縮合物の温度が235℃に達した直後から放圧口よりブタノールを約20分間かけて抜き出し、内圧を常圧にした。常圧にしたところから、1.5リットル/分で窒素ガスを流しながら昇温を開始し、約1時間かけて重縮合物の温度を260℃にし、260℃で4.5時間反応させた。その後、攪拌を止めて系内を窒素で1MPaに加圧して約10分間静置した後、内圧0.5MPaまで放圧し、重縮合物を圧力容器下部抜出口より紐状に抜き出した。紐状の重縮合物は直ちに冷却し、水冷した紐状の樹脂はペレタイザーによってペレット化した。得られたポリアミドは白色の強靭なポリマーであり、ηr=3.20であった。
実施例、比較例で使用した材料は次のとおりである。
(1)ポリアミド66:相対粘度2.75のポリアミド66樹脂(宇部興産(株)製2020B)
(2)ポリアミド6:相対粘度2.70のポリアミド6樹脂(宇部興産(株)製1015B)
(3)ポリフェニレンエーテル樹脂:25℃クロロホルム中におけるポリマー濃度0.5質量%の相対粘度が0.45であるポリ(2,6-ジメチル-1,4-フェニレンエーテル)樹脂で、当該ポリフェニレンエーテルと無水マレイン酸とを280℃で溶融混練した無水マレイン酸変性ポリフェニレンエーテル樹脂(前もって作成した赤外吸収スペクトルの検量線より求めた無水マレイン酸量が0.2%のもの)
(4)芳香族ビニル化合物-脂肪族炭化水素共重合体:水素添加のスチレン-イソプレンブロック共重合体(クラレ製セプトン2104)
ポリアミド66樹脂(1)及びポリフェニレンエーテル樹脂(3)に、製造例A1と同様にして製造した微細な炭素繊維を所定量配合し、ヘンシェルミキサーで予備混合した後、配合物を二軸押出機により260℃で溶融混合し、溶融混合物をペレット化して導電性ポリアミド樹脂組成物を得た。このペレットを260℃にて溶融プレス成形し、体積抵抗値(Ω・cm)(印加電圧10V)を測定した。結果を配合組成と共に表1に示す。
微細な炭素繊維のかわりに、ケッチェンブラック(ケッチェンブラックインターナショナル製EC600JD)を用いた以外は、実施例1と同様に評価した。結果を表1に示す。
ポリアミド6樹脂(2)を用いた以外は、実施例1と同様に評価した。結果を配合組成と共に表2に示す。
微細な炭素繊維のかわりに、ケッチェンブラック(ケッチェンブラックインターナショナル製EC600JD)を用いた以外は、実施例2と同様に評価した。結果を表2に示す。
製造例B1と同様に製造したポリアミド樹脂を用いた以外は、実施例2と同様に評価した。結果を配合組成とともに表2に示す。
微細な炭素繊維のかわりに、ケッチェンブラック(ケッチェンブラックインターナショナル製EC600JD)を用いた以外は、実施例9と同様に評価した。結果を表2に示す。
ポリアミド66樹脂(1)、ポリフェニレンエーテル樹脂(3)及び芳香族ビニル化合物-脂肪族炭化水素共重合体(4)に、製造例A1と同様にして製造した微細な炭素繊維を所定量配合し、ヘンシェルミキサーで予備混合した後、配合物を二軸押出機により260℃で溶融混合し、溶融混合物をペレット化して導電性ポリアミド樹脂組成物を得た。このペレット260℃にて溶融プレス成形し体積抵抗値(Ω・cm)(印加電圧10V)を測定した。結果を配合組成とともに表2に示す。
微細な炭素繊維のかわりに、ケッチェンブラック(ケッチェンブラックインターナショナル製EC600JD)を用いた以外は、実施例10と同様に評価した。結果を表2に示す。
12 頭頂部
13 胴部
21、21a、21b、21c 集合体
Claims (7)
- (a)ポリアミド樹脂、
(b)ポリフェニレンエーテル樹脂、及び
(c)前記樹脂中に分散され、炭素原子のみから構成されるグラファイト網面が、閉じた頭頂部と、下部が開いた胴部とを有する釣鐘状構造単位を形成し、前記釣鐘状構造単位が、中心軸を共有して2~30個積み重なって集合体を形成し、前記集合体が、Head-to-Tail様式で間隔をもって連結して繊維を形成している微細な炭素繊維
を含有する導電性樹脂組成物。 - 前記微細な炭素繊維が、Fe、Co、Ni、Al、Mg及びSiからなる群より選ばれる元素を含む触媒を用いた気相成長法により製造され、前記微細な炭素繊維中の灰分が4質量%以下であることを特徴とする請求項1記載の導電性樹脂組成物。
- 前記微細な炭素繊維が、100個以下の前記集合体が連結して構成されている微細な炭素短繊維であることを特徴とする請求項1または2記載の導電性樹脂組成物。
- 前記微細な炭素短繊維が、ずり応力を加えて短繊維化されて製造されたことを特徴とする請求項3記載の導電性樹脂組成物。
- 前記(b)ポリフェニレンエーテル樹脂が、α、β-不飽和カルボン酸またはその誘導体で変性されたポリフェニレンエーテル樹脂であることを特徴とする請求項1~4のいずれか1項に記載の導電性樹脂組成物。
- 前記(a)ポリアミド樹脂が、脂肪族ポリアミド樹脂であることを特徴とする請求項1~5のいずれか1項に記載の導電性樹脂組成物。
- 前記(a)ポリアミド樹脂が、シュウ酸と炭素数4~12のジアミンとの重縮合により得られるポリアミド樹脂であることを特徴とする請求項1~6のいずれか1項に記載の導電性樹脂組成物。
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Also Published As
Publication number | Publication date |
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EP2463341A4 (en) | 2015-01-28 |
US9236163B2 (en) | 2016-01-12 |
EP2463341A1 (en) | 2012-06-13 |
CN102575098B (zh) | 2013-10-23 |
JPWO2011016536A1 (ja) | 2013-01-17 |
US20120132866A1 (en) | 2012-05-31 |
JP5605364B2 (ja) | 2014-10-15 |
CN102575098A (zh) | 2012-07-11 |
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