WO2018168833A1 - Multilayer carbon nanotubes, method for producing multilayer carbon nanotubes, liquid dispersion, resin composition, and coating film - Google Patents

Abstract

Provided are: multilayer carbon nanotubes which make it possible to produce a resin composition having high blackness; and a method for synthesizing multilayer carbon nanotubes. Multilayer carbon nanotubes characterized by satisfying the requirements (1) and (2): (1) the average outer diameter of the multilayer carbon nanotubes is 10 nm or less; and (2) the standard deviation of the outer diameters of the multilayer carbon nanotube is 4 nm or less.

Description

Multi-walled carbon nanotube, method for producing multi-walled carbon nanotube, dispersion, resin composition, and coating film

The present invention relates to multi-walled carbon nanotubes and a method for producing multi-walled carbon nanotubes. More specifically, the present invention relates to multi-walled carbon nanotubes, a resin composition containing multi-walled carbon nanotubes and a resin, a dispersion thereof, and a coating film excellent in jet blackness coated with the same.

Carbon nanotube is a cylindrical carbon material having an outer diameter of several nanometers to several tens of nanometers. Carbon nanotubes have high electrical conductivity and mechanical strength. For this reason, carbon nanotubes are expected to be used in a wide range of fields including electronic engineering and energy engineering as functional materials. Examples of functional materials include fuel cells, electrodes, electromagnetic shielding materials, conductive resins, field emission display (FED) members, and various gas storage materials such as hydrogen.

On the other hand, as examples of the development of the functional material, there are few examples using carbon nanotubes as a coloring material. Carbon black is used as the color material instead of carbon nanotubes. For example, as disclosed in Patent Documents 1 and 2, carbon black is used in order to obtain a jet black resin coated product, film, or molded product. Carbon black is uniformly dispersed in a resin solution or a solid resin.

However, a color material made of carbon black tends to have a high lightness (L ^* ) (that is, gray / white). Further, the chromaticity (a ^* , b ^* ) is in the plus direction (+ a ^* : red, + b ^* : yellow). Here, L ^* , a ^*, and b ^* represent values in the L ^* a ^* b ^* color system defined by JIS Z8781-4. For this reason, it has been difficult for carbon black to express jet blackness such as so-called “piano black” and “wet crow wings”.

Also, the color tone of a molded product using carbon black tends to change depending on the primary particle diameter of carbon black. Specifically, when carbon black having a small primary particle diameter is used, bluishness is exhibited while blackness is lowered. Thus, in the conventional black color material, there is a trade-off relationship between blackness and blueness. For this reason, it was difficult to reproduce a color tone having a bluish color and a high blackness, that is, a jet black color tone.

Patent Documents 3, 4 and 5 relate to adjustment of blackness of a color material made of carbon black. In adjusting the blackness, for example, colloidal characteristics such as the particle size and aggregate size of carbon black are changed. Further, surface treatment such as ozone oxidation and nitric acid oxidation is applied to the carbon black. With this process, the dispersion state in the dispersion is controlled.

Also known is a method of adding an organic pigment such as phthalocyanine blue to carbon black. By this method, the color material can exhibit a bluish color in addition to black. However, the blackness decreases with the addition of the organic pigment in the coloring material. For this reason, when the molded object containing such a coloring material is observed under direct sunlight, a reddish color is observed on the molded object. This problem is recognized as the occurrence of a so-called bronze phenomenon.

Patent Documents 6 and 7 are investigating a laminate of carbon nanotubes in order to solve these problems. However, in these means, it is necessary to form a layer so that the gloss of the resin composition containing carbon nanotubes can be obtained. Further, in Patent Document 8, carbon nanotubes as jet-black pigments are also studied, but the outer diameter is large and jet-black properties when used as a coating film are insufficient. Furthermore, development of single-walled carbon nanotubes and double-walled carbon nanotubes having a small outer diameter has been promoted, but it has been difficult to disperse and it has been difficult to achieve a sufficient jet black feeling.

Further, in Patent Document 9, by making the catalyst finer, the entanglement at the time of carbon nanotube synthesis is suppressed, thereby widening the voids inside the carbon nanotube aggregate structure and producing carbon nanotubes with excellent dispersibility in the resin. is doing. However, carbon nanotubes having a small outer diameter could not be obtained efficiently.

JP 2001-179176 A JP 2004-098033 A Japanese Patent Laid-Open No. 6-122834 JP-A-6-136287 JP 2008-285632 A Japanese Unexamined Patent Publication No. 2016-13680 Japanese Patent Laid-Open No. 2016-22664 Japanese Patent Laid-Open No. 2015-229706 JP 2008-173608 A

The problem to be solved by the present invention is to solve the above-mentioned conventional problems, and to provide a multi-walled carbon nanotube and a method for synthesizing the multi-walled carbon nanotube from which a resin composition having high jetness is obtained.

As a result of intensive studies, the present inventors have found that the above problems can be solved by specific multi-walled carbon nanotubes.

That is, the present invention relates to a multi-walled carbon nanotube characterized by satisfying the following requirements (1) and (2).
(1) The average outer diameter of the multi-walled carbon nanotube is 10 nm or less. (2) The standard deviation of the outer diameter of the multi-walled carbon nanotube is 4 nm or less.

In one embodiment of the multi-walled carbon nanotube, a powder X-ray diffraction analysis has a peak at a diffraction angle 2θ = 25 ° ± 2 °, and the half width of the peak is 3 ° or more and 5 ° or less.

Another embodiment of the multi-walled carbon nanotube has a peak at a diffraction angle 2θ = 25 ° ± 2 ° in a powder X-ray diffraction analysis, and the half width of the peak exceeds 5.5 ° to 5.5 °. It is as follows.

In one embodiment of the multi-walled carbon nanotube, X ± 2σ is 2.5 nm ≦ X ± 2σ ≦ 15, where X is the average outer diameter of the multi-walled carbon nanotube and σ is the standard deviation of the outer diameter of the multi-walled carbon nanotube. .5 nm is satisfied.

One embodiment of the above-mentioned multi-walled carbon nanotube is G / G when the maximum peak intensity in the range of 1560 to 1600 cm ⁻¹ is G and the maximum peak intensity in the range of 1310 to 1350 cm ⁻¹ is D in the Raman spectrum. The D ratio is 2.0 or less, preferably 1.0 or less.

The method for producing a multi-walled carbon nanotube of the present invention includes the following steps.
(1) An active ingredient containing at least one selected from cobalt, nickel and iron and a catalyst carrier containing at least one selected from magnesium, aluminum and silicon are mixed and / or pulverized and calcined. Step for obtaining catalyst (2) Step for obtaining multi-walled carbon nanotube by bringing the catalyst into contact with a carbon source containing at least one selected from hydrocarbon and alcohol under heating

In one embodiment of the method for producing a multi-walled carbon nanotube, in the step (2), the carbon source contains a hydrocarbon, and the production amount of the multi-walled carbon nanotube per 1 g of the carbon nanotube synthesis catalyst is Y (g), When the contact reaction time of the catalyst for carbon nanotube synthesis and the hydrocarbon is Z (min), Y / Z (g / min) satisfies 1.5 ≦ Y / Z ≦ 2.7. Adjust catalyst amount and / or hydrocarbon flow rate.

In one embodiment of the method for producing a multi-walled carbon nanotube, the hydrocarbon is ethylene.

The dispersion of the present invention contains the multi-walled carbon nanotube of the present invention and a dispersant.

The resin composition of the present invention contains the multi-walled carbon nanotube of the present invention and a resin.

Moreover, the coating film of the present invention is formed by the resin composition of the present invention.

By using the multi-walled carbon nanotube of the present invention, a resin composition excellent in jetness can be obtained. Therefore, it is possible to use the multi-walled carbon nanotube and the method for producing the multi-walled carbon nanotube of the present invention in various applications that require high jetness.

FIG. 1 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes when 300 multi-walled carbon nanotubes are arbitrarily observed using the transmission electron microscope obtained in Example 1. FIG. 2 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes when 300 multi-walled carbon nanotubes are arbitrarily observed using the transmission electron microscope obtained in Example 4. FIG. 3 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes when 300 multi-walled carbon nanotubes are arbitrarily observed using the transmission electron microscope obtained in Comparative Example 1. FIG. 4 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes when 300 multi-walled carbon nanotubes are arbitrarily observed using the transmission electron microscope obtained in Comparative Example 2. FIG. 5 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes when 300 multi-walled carbon nanotubes are arbitrarily observed using the transmission electron microscope obtained in Comparative Example 3. FIG. 6 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes when 300 multi-walled carbon nanotubes are arbitrarily observed using the transmission electron microscope obtained in Comparative Example 4. FIG. 7 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes when 300 carbon nanotubes were arbitrarily observed using a transmission electron microscope for the multi-walled carbon nanotubes obtained in Example 12. is there. FIG. 8 is a graph showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes obtained by observing 300 carbon nanotubes arbitrarily using a transmission electron microscope for the multi-walled carbon nanotubes obtained in Example 13. is there.

Hereinafter, the multi-walled carbon nanotube, the dispersion, the resin composition and the coating film thereof according to the present invention will be described in detail.
(1) Multi-walled carbon nanotube (A)
The multi-walled carbon nanotube (A) has a shape obtained by winding planar graphite into a cylindrical shape. The multi-walled carbon nanotube (A) may be a mixture of single-walled carbon nanotubes. Single-walled carbon nanotubes have a structure in which a single layer of graphite is wound. The multi-walled carbon nanotube (A) has a structure in which two or more layers of graphite are wound. Further, the side wall of the multi-walled carbon nanotube (A) may not have a graphite structure. For example, a carbon nanotube having a sidewall having an amorphous structure can be used as the multi-walled carbon nanotube (A).

The shape of the multi-walled carbon nanotube (A) is not limited. Examples of such a shape include various shapes including a needle shape, a cylindrical tube shape, a fish bone shape (fishbone or cup laminated type), a trump shape (platelet), and a coil shape. In this embodiment, the shape of the multi-walled carbon nanotube (A) is preferably a needle shape or a cylindrical tube shape. The multi-walled carbon nanotube (A) may be a single shape or a combination of two or more shapes.

Examples of the multi-walled carbon nanotube (A) include graphite whiskers, filamentous carbon, graphite fibers, ultrafine carbon tubes, carbon tubes, carbon fibrils, carbon microtubes, and carbon nanofibers. It is not limited. The multi-walled carbon nanotube (A) may have a single form or a combination of two or more kinds.

The average outer diameter of the multi-walled carbon nanotube (A) of the present embodiment is 10 nm or less, and the standard deviation of the outer diameter is 4 nm or less. When the multi-walled carbon nanotube (A) has such a specific outer diameter, a resin composition having high jetness can be obtained.
The average outer diameter of the multi-walled carbon nanotube (A) is preferably 3 to 10 nm, more preferably 4 to 10 nm, and further preferably 4 to 8 nm, from the viewpoint of ease of dispersion and hue. preferable.
The standard deviation of the outer diameter of the multi-walled carbon nanotube (A) may be 4 nm or less, and from the viewpoint of ease of dispersion and hue, it is preferably 3 nm or less, more preferably 2.5 nm or less. Further, the standard deviation of the outer diameter is preferably 0.7 nm or more, and more preferably 1.4 nm or more.
Further, when the average outer diameter of the carbon nanotube is X [nm] and the standard deviation of the outer diameter of the carbon nanotube is σ [nm], a resin composition having high jetness can be obtained, so that X ± σ [nm] is 5.0 nm ≦ X ± σ ≦ 14.0 nm is preferable.
Moreover, it is preferable that X ± 2σ [nm] is 2.0 nm ≦ X ± 2σ ≦ 17.0 nm, and 2.5 nm ≦ X ± 2σ ≦ 15. 5 nm is more preferable, and 3.0 nm ≦ X ± 2σ ≦ 12.0 nm is still more preferable.

The outer diameter and average outer diameter of the multi-walled carbon nanotube (A) are obtained as follows. First, the multi-walled carbon nanotube (A) is observed and imaged with a transmission electron microscope. Next, in the observation photograph, arbitrary 300 multi-walled carbon nanotubes (A) are selected, and the respective outer diameters are measured. Next, the average outer diameter (nm) of the multi-walled carbon nanotube (A) is calculated as the number average of outer diameters.

The fiber length of the multi-walled carbon nanotube (A) of the present embodiment is preferably from 0.1 to 150 μm, more preferably from 1 to 10 μm, from the viewpoint of ease of dispersion and hue.

The carbon purity of the multi-walled carbon nanotube (A) is represented by the carbon atom content (% by mass) in the multi-walled carbon nanotube (A). The carbon purity is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more with respect to 100% by mass of the multi-walled carbon nanotube (A).

In this embodiment, the multi-walled carbon nanotube (A) usually exists as secondary particles. The shape of the secondary particles may be, for example, a state in which multi-walled carbon nanotubes (A) that are general primary particles are intertwined in a complicated manner. An aggregate of the multi-walled carbon nanotubes (A) may be used. Secondary particles, which are aggregates of linear multi-walled carbon nanotubes (A), are easier to loosen than those intertwined. Moreover, since the linear thing has a good dispersibility compared with the thing intertwined, it can be utilized suitably as a multi-walled carbon nanotube (A).

The multi-walled carbon nanotube (A) may be a carbon nanotube subjected to surface treatment. The multi-walled carbon nanotube (A) may be a carbon nanotube derivative provided with a functional group represented by a carboxyl group. In addition, a multi-walled carbon nano-nanotube (A) in which a substance typified by an organic compound, a metal atom, or fullerene is included can also be used.

The multi-walled carbon nanotube (A) of the present embodiment is preferably a carbon nanotube having a relatively small number of layers. In particular, when a powder X-ray diffraction analysis is performed, a peak exists at a diffraction angle 2θ = 25 ° ± 2 °, and the half width of the peak is preferably 3 ° or more and 5.5 ° or less, and more than 5 °. More preferably, the angle is 5.5 ° or less. By using such a multi-walled carbon nanotube (A) having a relatively small number of layers, the lightness is low and the specular gloss is improved, so that a coating film with high jetness can be obtained.
The layer structure of the multi-walled carbon nanotube (A) can be analyzed by powder X-ray diffraction analysis by the following method.

The half width of the multi-walled carbon nanotube (A) is obtained as follows. First, the multi-walled carbon nanotubes (A) are packed in a predetermined sample holder so that the surface is flat, set in a powder X-ray diffraction analyzer, and measured by changing the irradiation angle of the X-ray source from 5 ° to 80 °. . For example, CuKα rays are used as the X-ray source. The step width is 0.010 ° and the measurement time is 1.0 second. The multi-walled carbon nanotube (A) can be evaluated by reading the diffraction angle 2θ at which the peak appears. In graphite, a peak is usually detected when 2θ is around 26 °, and this is known to be a peak due to interlayer diffraction. Since the multi-walled carbon nanotube (A) also has a graphite structure, a peak due to graphite interlayer diffraction is detected in the vicinity thereof. However, since the carbon nanotube has a cylindrical structure, its value is different from that of graphite. A peak appears at a position where the value 2θ is 25 ° ± 2 °, so that it can be determined that a composition having a multilayer structure is included instead of a single layer. Since the peak appearing at this position is a peak due to interlayer diffraction of the multilayer structure, the number of layers of the multilayer carbon nanotube (A) can be determined. Since the single-walled carbon nanotube has only one layer, a peak does not appear at a position of 25 ° ± 2 ° with the single-walled carbon nanotube alone. However, even single-walled carbon nanotubes are not 100% single-walled carbon nanotubes, and when multi-walled carbon nanotubes or the like are mixed, a peak may appear at a position where 2θ is 25 ° ± 2 °. .

In the multi-walled carbon nanotube (A), a peak appears at a position where 2θ is 25 ° ± 2 °. The layer structure can also be analyzed from the half width of the 25 ° ± 2 ° peak detected by powder X-ray diffraction analysis. That is, it is considered that the number of multi-walled carbon nanotubes (A) is larger as the half width of this peak is smaller. Conversely, it is considered that the larger the half width of this peak, the smaller the number of carbon nanotube layers.

The multi-walled carbon nanotube (A) of the present embodiment has a maximum peak intensity in the range of 1560 to 1600 cm ⁻¹ in the Raman spectrum as G and a maximum peak intensity in the range of 1310 to 1350 cm ⁻¹ as D. The G / D ratio is preferably 4.9 to 0.3, more preferably 2.0 to 0.3, and still more preferably 1.0 to 0.5. The G / D ratio of the multi-walled carbon nanotube (A) is determined by Raman spectroscopy.

Although there are various laser wavelengths used in the Raman spectroscopic analysis, 532 nm and 632 nm are used here. The Raman shift observed in the vicinity of 1590 cm ⁻¹ in the Raman spectrum is called a G band derived from graphite, and the Raman shift observed in the vicinity of 1350 cm ⁻¹ is called a D band derived from defects in amorphous carbon or graphite. The higher the G / D ratio, the higher the degree of graphitization.

The Raman spectrum of 150 to 350 cm ^-1 is called RBM (radial breathing mode), and the peak observed in this region has the following correlation with the outer diameter of the carbon nanotube, and the outer diameter of the carbon nanotube is estimated. Is possible. If the outer diameter of the carbon nanotube is d (nm) and the Raman shift is ν (cm ⁻¹ ), d = 248 / ν holds. ^140cm -1 in Raman spectroscopic analysis of wavelength 532nm Considering ^{now, 160cm -1, 180cm -1, 210cm} -1, 270cm -1, the peak at 320 cm ^-1 is observed, i.e. 1.77nm, 1.55nm , 1.38 nm, 1.18 nm, 0.92 nm, and 0.78 nm, suggesting the presence of carbon nanotubes.

Since the wave number of Raman spectroscopic analysis may vary depending on the measurement conditions, the wave number specified here is specified as wave number ± 10 cm ⁻¹ .

[Method for producing multi-walled carbon nanotube (A)]
In the present embodiment, the multi-walled carbon nanotube (A) is not particularly limited as long as the average outer diameter of the multi-walled carbon nanotube is 10 nm or less and the standard deviation of the outer diameter is 4 nm or less. Carbon nanotubes manufactured in (1) may be used. The multi-walled carbon nanotube (A) can be generally produced by a laser ablation method, an arc discharge method, a thermal CVD method, a plasma CVD method and a combustion method. For example, the multi-walled carbon nanotube (A) can be produced by causing a carbon source to contact with a catalyst at 500 to 1000 ° C. in an atmosphere having an oxygen concentration of 1% by volume or less.

In the present embodiment, a method including the following steps is preferable as the method for producing the multi-walled carbon nanotube (A).
(1) Step of obtaining a catalyst for carbon nanotube synthesis by mixing and / or pulverizing cobalt and a metal salt containing magnesium, and (2) heating the carbon nanotube synthesis catalyst from hydrocarbon and alcohol under heating. A step of obtaining a multi-walled carbon nanotube by contacting with a carbon source containing one or more selected types

Any conventionally known source gas can be used as the carbon source. For example, hydrocarbon, carbon monoxide, alcohol, etc. are mentioned, It can use individually by 1 type or in combination of 2 or more types. In the present embodiment, the carbon source preferably includes one or more selected from hydrocarbons and alcohols, and more preferably includes hydrocarbons. Examples of the hydrocarbon include methane, propane, butane, acetylene, etc. Among them, ethylene is preferable.

When ethylene is used as the carbon source, it is preferable to produce the multi-walled carbon nanotube (A) by contacting the carbon source with the catalyst at 600 to 800 ° C. in an atmosphere having an oxygen concentration of 1% by volume or less. More preferably, the multi-walled carbon nanotube (A) is produced by reacting a carbon source with a catalyst at 650 to 750 ° C.

The amount of hydrocarbon may be appropriately changed according to the size of the reaction vessel and the amount of catalyst in the reaction vessel. The amount of carbon nanotubes produced per gram of catalyst is Y (g), and the contact reaction time of the catalyst and hydrocarbon is determined. It is preferable to adjust the catalyst amount and / or the hydrocarbon flow rate so that Y / Z (g / min) satisfies 1.5 ≦ Y / Z ≦ 2.7 when Z (min) is set.

If necessary, after activating the catalyst in a reducing gas atmosphere, it is preferable to cause the source gas and the catalyst to contact with each other in an atmosphere having an oxygen concentration of 1% by volume or less. In addition to the reducing gas, the raw material gas may be contacted with the catalyst. The atmosphere having an oxygen concentration of 1% by volume or less is not particularly limited, but an atmosphere of an inert gas typified by a rare gas such as argon gas and a nitrogen gas is preferable. As the reducing gas used for the activation of the catalyst, hydrogen or ammonia can be used, but is not limited thereto. As the reducing gas, hydrogen is particularly preferable.

As the catalyst, various conventionally known metals can be used. Specifically, it is a metal oxide obtained by mixing and / or pulverizing an active ingredient typified by cobalt, nickel or iron and a catalyst carrier typified by magnesium, aluminum or silicon. In particular, a metal oxide obtained by mixing and / or grinding a metal containing cobalt as an active component and magnesium as a catalyst support is preferable. By using cobalt as the active component and magnesium as the catalyst support, it is easy to obtain multi-walled carbon nanotubes having an average outer diameter of 10 nm or less and a standard deviation of the outer diameter of 4 nm or less.

As active ingredients, specifically, iron (III) ammonium citrate, iron (II) ammonium sulfate hexahydrate, iron (III) chloride hexahydrate, iron (II) chloride tetrahydrate, iron citrate (III) n hydrate, iron (III) nitrate nonahydrate, iron (II) oxalate dihydrate, iron (III) oxide, cobalt hydroxide, cobalt acetate (II) tetrahydrate, base Cobalt (II) carbonate, cobalt (II) chloride, cobalt (II) chloride hexahydrate, cobalt nitrate (II) hexahydrate, cobalt (II) oxide, cobalt oxide (II, III), cobalt stearate (II), cobalt sulfate (II) heptahydrate, cobalt sulfide (II), cobalt acetate (II), nickel sulfate (II) ammonium hexahydrate, nickel acetate (II) tetrahydrate, nickel chloride ( II), nickel chloride (II) hexahydrate, nickel hydroxide (II), nickel nitrate (II) hexahydrate, nitric oxide Examples include nickel (II) and nickel (II) sulfate hexahydrate. Particularly preferred are cobalt hydroxide, cobalt (II) acetate tetrahydrate, iron (III) citrate n hydrate, and iron (III) nitrate nonahydrate. Two or more of these active ingredients may be combined.

The catalyst carrier contains magnesium, preferably exhibits adsorption and catalytic activity, and can carry a catalyst metal on the surface of the catalyst carrier, and may be organic or inorganic.

Conventionally known magnesium compounds can be used as the catalyst support magnesium. For example, magnesium, magnesium chloride, magnesium hydroxide, magnesium oxide, magnesium sulfate, magnesium acetate tetrahydrate, basic magnesium carbonate, magnesium chloride hexahydrate. In particular, it is preferable to use magnesium acetate tetrahydrate, magnesium hydroxide, or magnesium oxide.

As the catalyst support, in addition to magnesium, for example, silicon oxide, aluminum, basic aluminum acetate, aluminum bromide, aluminum chloride, aluminum hydroxide, aluminum lactate, aluminum oxide, zeolite, titanium oxide, zirconium, calcium oxide, oxidation It is preferable that titanium etc. are included. By combining two kinds of raw materials having different melting points, fusion of particles can be prevented at the time of catalyst preparation. For example, catalytic activity can be improved by combining organic substances such as magnesium acetate and aluminum acetate with inorganic substances such as silicon oxide, aluminum oxide, zeolite, titanium oxide, zirconium, and magnesium oxide. In particular, when magnesium acetate tetrahydrate is used for the catalyst support, it is preferable to combine silicon oxide, zeolite, and aluminum oxide. Particularly preferred are silicon oxide and zeolite.

Examples of the silicon oxide, zeolite, and aluminum oxide used for the catalyst carrier include AEROSIL (registered trademark) 50, AEROSIL (registered trademark) 130, AEROSIL (registered trademark) 200, and AEROSIL (registered trademark) manufactured by Nippon Aerosil Co., Ltd. (Trademark) 300, AEROSIL (registered trademark) 380, AEROXIDE (registered trademark) AluC, AEROXIDE (registered trademark) TiO2P25, Alumina C10W, C20, C40, C50, C500 manufactured by Nippon Light Metal Co., Ltd. 940HOA, 980HOA, Mordenite type zeolite 640HOA, 690HOA, Y type zeolite 320HOA, 331HSA, 350HUA, 360HUA, 385HUA, 390H It is preferable to use the A. Among these, AEROSIL (registered trademark) is preferable.

The content of silica and aluminum in the catalyst support is preferably 1 to 50 mol%, more preferably 1 to 25 mol%, when the magnesium content is 100 mol%.

The bulk density of silica or aluminum in the catalyst support is preferably 0.04 to 0.5 g / mL. When silica is used, it is more preferably 0.04 to 0.1 g / mL.

The bulk density is a bulk density before performing a treatment for reducing the volume such as deaeration and granulation, and is a value obtained by measurement according to JIS-K-5101.

The BET specific surface area of silica or alumina of the catalyst support is preferably 50 to 1000 m ² / g, more preferably 150 to 350 m ² / g.

The catalyst carrier preferably contains a cocatalyst having a function of enhancing the catalytic action of the catalyst. For example, it is preferable that manganese, molybdenum, and tungsten are included. Particularly preferred are manganese and molybdenum. By including these in the catalyst carrier, the catalyst activity and the catalyst life can be improved. These promoters may be used alone or in combination.

The content of the promoter in the catalyst carrier is preferably 5 to 100 mol%, more preferably 5 to 30 mol%, when the magnesium content is 100 mol%.

Various conventionally known salts can be used as the manganese salt or molybdenum salt used for the catalyst carrier. For example, manganese acetate (II) tetrahydrate, manganese carbonate (II) n hydrate, manganese chloride (II) tetrahydrate, manganese nitrate (II) hexahydrate, manganese (IV) oxide, manganese sulfate (II) pentahydrate, ammonium molybdate, molybdenum, potassium molybdate, hexaammonium hexamolybdate tetrahydrate, molybdenum chloride (V), molybdenum oxide (VI), molybdenum sulfide (IV), ammonium tungstate para Examples include pentahydrate, potassium tungstate, sodium tungsten (VI) dihydrate, tungsten, and tungsten (VI) oxide. In particular, manganese (II) acetate tetrahydrate, manganese (II) carbonate n-hydrate, ammonium molybdate, and molybdenum (VI) oxide are preferable.

It is preferable that the raw materials for the catalyst carrier are mixed uniformly. Mixing may be wet or dry, but when using a water-insoluble salt, dry mixing is preferred. When the raw materials are mixed in a wet manner, it is preferable to mix after drying in the range of 100 to 200 ° C.

The catalyst carrier is preferably low in moisture. When the catalyst support is 100% by mass, the water content is preferably 5% by mass or less, and preferably 3% by mass or less. The amount of water in the catalyst carrier can be measured using, for example, a heat drying moisture meter (MS-70, A & D Corporation).

The catalyst carrier preferably has a small particle size. Specifically, in the particle size distribution, D50 (μm) is preferably 1.0 to 10.0 μm, and more preferably 1.0 to 5.0 μm. Further, D90 (μm) is preferably 5.0 to 70.0 μm, and more preferably 5.0 to 20.0 μm.

The particle size distributions D50 (μm) and D90 (μm) of the catalyst carrier are obtained as follows. First, the particle size distribution of the catalyst carrier is measured by a laser diffraction dry particle size distribution measuring device. In the measurement results, the particle size when the cumulative distribution is 50 vol% can be calculated as D50 (μm), and the particle size when the cumulative distribution is 90 vol% can be calculated as D90 (μm).

As a method for reducing the particle size of the catalyst carrier, various conventionally known methods can be used. Among these, it is preferable to use a pulverizer that can apply a compressive force, an impact force, a shearing force, and a frictional force to the catalyst carrier.

A pulverizer is a device that applies a force such as compressive force, impact force, shear force or friction force to a sample to refine the sample. Equipment for miniaturization includes mortar, pin mill, hammer mill, pulverizer, attritor, jet mill, cutter mill, ball mill, bead mill, colloid mill, conical mill, disc mill, edge mill, one dark lasher, vibration mill, ultrasonic homogenizer, etc. Can be used. Preferred are an attritor, a pin mill, a hammer mill, a jet mill, a cutter mill, a ball mill, a bead mill, a one-dark lasher, and a vibration mill, which are easily composited, mechanically alloyed and amorphized. Particularly preferable are an attritor, a ball mill, a bead mill, and a vibration mill using beads as a grinding medium.

Various conventionally known beads can be used as the grinding media. For example, steel beads, zirconia beads, alumina beads, and glass beads. Among them, it is preferable to use steel beads having high specific gravity or zirconia beads having high hardness.

Although various conventionally known beads can be used, it is preferable to use beads having a diameter of 1 to 10 mm from the viewpoint of workability. More preferably, 2-5 mm beads are used.

The catalyst is preferably prepared by uniformly mixing and / or pulverizing the active component, the catalyst carrier and the promoter component. Various conventionally known methods can be used as the mixing and / or grinding method. Examples of the mixing and / or pulverizing apparatus include the same ones as described above.

The catalyst is preferably made into an oxide by mixing and pulverizing an active component, a catalyst carrier and a metal salt as a promoter component, followed by firing in air.

The firing temperature varies depending on the oxygen concentration at the time of firing, but is preferably 300 to 900 ° C., more preferably 300 to 750 ° C. in the presence of oxygen.

The catalyst is preferably calcined and then pulverized to a solid particle size of 50 μm or less, more preferably less than 20 μm. A homogenous catalyst can be obtained by pulverizing the solid and making the particle diameter uniform.

(2) Resin composition (B)
The resin composition (B) of this embodiment contains at least a multi-walled carbon nanotube (A) and a resin (C). The resin composition of this embodiment can be suitably used for forming a coating film with high jetness by containing the multi-walled carbon nanotube (A) of the present invention.

In order to obtain the resin composition (B) of the present embodiment, it is preferable to perform a treatment of dispersing the multi-walled carbon nanotube (A) and the resin (C) in a solvent. The equipment used for performing such processing is not particularly limited. For example, paint conditioner (manufactured by Red Devil), ball mill, sand mill ("Dyno mill" manufactured by Shinmaru Enterprises), attritor, pearl mill ("DCP mill" manufactured by Eirich), ultrasonic homogenizer (Advanced Digital Sonifier ( (Registered trademark), MODEL 450DA, manufactured by BRANSON), coball mill, basket mill, homomixer, homogenizer (“CLEAMIX” manufactured by M Technique), wet jet mill (“GENUS PY” manufactured by Genus, “Nanomizer manufactured by Nanomizer) "), Hoover Mahler, 3 roll mills and extruders.

Further, a high-speed stirrer can be used to obtain the resin composition (B). Examples of the high-speed stirrer include, but are not limited to, homodisper (manufactured by PRIMIX), fillmix (manufactured by PRIMIX), dissolver (manufactured by Inoue Seisakusho) and hyper HS (manufactured by Ashizawa Finetech).

Resin (C)
The resin (C) is selected from natural resins and synthetic resins. Resin (C) may be a single resin. As the resin (C), two or more kinds of resins may be selected from natural resins and synthetic resins. Two or more kinds of resins can be used in combination.

Natural resins include, but are not limited to, natural rubber, gelatin, rosin, shellac, polysaccharides and gilsonite. Synthetic resins include phenolic resin, alkyd resin, petroleum resin, vinyl resin, olefin resin, synthetic rubber, polyester resin, polyamide resin, acrylic resin, styrene resin, epoxy resin, melamine resin, polyurethane resin, amino resin, Examples include, but are not limited to, amide resins, imide resins, fluorine resins, vinylidene fluoride resins, vinyl chloride resins, ABS resins, polycarbonates, silicone resins, nitrocellulose, rosin-modified phenol resins, and rosin-modified polyamide resins.

Among these resins, it is preferable that at least one of an acrylic resin and a polyester resin is included from the viewpoint of light resistance. At this time, it is preferable that at least one of acrylic resin and polyester resin is also contained in the base coating material.

The water-soluble resin used in the resin composition (B) of the present embodiment is preferably a water-soluble resin having an acid value of 20 to 70 mgKOH / g and a hydroxyl value of 20 to 160 mgKOH / g. Specifically, polyester resin, acrylic resin, and polyurethane resin are particularly preferably used as the water-soluble resin.

The polyester resin is a resin using polyhydric alcohol and polybasic acid as raw materials. The acid value of the polyester resin is 20 to 70 mgKOH / g, preferably 25 to 60 mgKOH / g, particularly preferably 30 to 55 mgKOH / g. The hydroxyl value of the polyester resin is 20 to 160 mgKOH / g, preferably 80 to 130 mgKOH / g.

In this embodiment, an acid value means the mass (mg) of potassium hydroxide required in order to neutralize 1 g of resin. The hydroxyl value refers to the mass (mg) of potassium hydroxide required to react the hydroxyl group of the resin with phthalic anhydride and neutralize 1 g of the resin with the acid required for the reaction.
In this embodiment, the acid value and hydroxyl value of the resin can be measured according to the method of JIS K0070.

The water-soluble polyester resin can be easily obtained by a known esterification reaction. The water-soluble polyester resin is a resin produced using a polyhydric alcohol and a polybasic acid as raw materials. The raw material may be a compound constituting a normal polyester resin. You may add fats and oils to water-soluble polyester resin as needed.

Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, diethylene glycol, Examples include, but are not limited to, propylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol and dipentaerythritol. These polyhydric alcohols may be used alone or in combination of two or more.
Examples of the polybasic acid include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, maleic anhydride, fumaric acid, itaconic acid and trimellitic anhydride. However, it is not limited to these. These polybasic acids may be used alone or in combination of two or more.
Examples of the fats and oils include soybean oil, coconut oil, safflower oil, bran oil, castor oil, persimmon oil, linseed oil and tall oil, and fatty acids obtained therefrom. It is not limited.

The acrylic resin is a resin made from a vinyl monomer. The acid value of the acrylic resin is 20 to 70 mgKOH / g, preferably 22 to 50 mgKOH / g, particularly preferably 23 to 40 mgKOH / g. The acrylic resin is a water-soluble resin having a hydroxyl value of 20 to 160 mgKOH / g, preferably 80 to 150 mgKOH / g.

The water-soluble acrylic resin can be easily obtained by a known solution polymerization method or other methods. The water-soluble acrylic resin is a resin produced using a vinyl monomer as a raw material. The raw material may be a compound constituting a normal acrylic resin. In the above method, the organic peroxide is used as an initiator for the polymerization reaction.

Examples of vinyl monomers include ethylenically unsaturated carboxylic acids represented by acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid; methyl, ethyl, propyl, butyl, isobutyl, tertiary butyl, Alkyl esters of acrylic acid or methacrylic acid represented by 2-ethylhexyl, lauryl, cyclohexyl, stearyl; acrylics represented by 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, polyethylene glycol having a molecular weight of 1000 or less Hydroxyalkyl esters of acid or methacrylic acid; amides of acrylic acid or methacrylic acid; or alkyl ethers thereof include, but are not limited to. Examples include, but are not limited to, acrylamide, methacrylamide, N-methylol acrylamide, diacetone acrylamide, diacetone methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide and N-butoxymethyl acrylamide.

Furthermore, glycidyl (meth) acrylate having an epoxy group can be mentioned. Also included are monomers containing a tertiary amino group. Examples thereof include, but are not limited to, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate. In addition, aromatic monomers represented by styrene, α-methylstyrene, vinyltoluene and vinylpyridine; acrylonitrile; methacrylonitrile; vinyl acetate; and mono- or dialkyl esters of maleic acid or fumaric acid, It is not limited to. Organic peroxides include, for example, acyl peroxides (eg, benzoyl peroxide), alkyl hydroperoxides (eg, t-butyl hydroperoxide and p-methane hydroperoxide), and dialkyl peroxides ( Examples thereof include, but are not limited to, di-t-butyl peroxide.

The polyurethane resin is a resin made from polyol and polyisocyanate. The acid value of the polyurethane resin is 20 to 70 mgKOH / g, preferably 22 to 50 mgKOH / g, particularly preferably 23 to 35 mgKOH / g. The hydroxyl value of the polyurethane resin is 20 to 160 mgKOH / g, preferably 25 to 50 mgKOH / g.

The water-soluble polyurethane resin can be easily obtained by addition polymerization of polyol and polyisocyanate. The raw material may be a polyol and a polyisocyanate constituting an ordinary polyurethane resin.

Polyols include, but are not limited to, polyester polyols, polyether polyols, and acrylic polyols. Polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate. , Trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, and trimethylhexane diisocyanate, but are not limited thereto.

Water-soluble polyester resin, acrylic resin, and polyurethane resin are rendered water-soluble by neutralization with a basic substance. Under the present circumstances, it is preferable to use the basic substance of the quantity which can neutralize 40 mol% or more of the acidic group contained in water-soluble resin. Examples of the basic substance include ammonia, dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, morpholine, monoisopropanol. Examples include, but are not limited to amines, diisopropanolamine, and dimethylethanolamine.

The number average molecular weight of the water-soluble resin is not particularly limited. The number average molecular weight is preferably 500 to 50,000, more preferably 800 to 25,000, and particularly preferably 1,000 to 12,000.

Also, the resin (C) is classified into a curable type and a lacquer type. In the present embodiment, a curable resin is preferably used. The curable resin (C) is used with an amino resin typified by melamine resin or a crosslinking agent typified by (block) polyisocyanate compound amine compound, polyamide compound and polyvalent carboxylic acid. After the resin (C) and the cross-linking agent are mixed, the curing reaction proceeds by being heated or at room temperature. Moreover, while using resin of the type which does not have curability as resin for film-forming, it can also use together with resin of the type which has curability.

The resin composition (B) of this embodiment should just contain the said multi-walled carbon nanotube (A) and resin (C) at least, and may contain another component as needed. is there.
Examples of other components include a dispersant and a solvent.

As the dispersant, a surfactant, a resin-type dispersant, or an organic pigment derivative can be used. Surfactants are mainly classified into anionic, cationic, nonionic and amphoteric. Depending on the properties required for the dispersion of the multi-walled carbon nanotube (A), a suitable type of dispersant can be appropriately used in a suitable blending amount. A preferable dispersant is a resin-type dispersant.

When selecting an anionic surfactant, the kind is not particularly limited. Specifically, fatty acid salt, polysulfonate, polycarboxylate, alkyl sulfate ester salt, alkylaryl sulfonate, alkylnaphthalene sulfonate, dialkyl sulfonate, dialkyl sulfosuccinate, alkyl phosphate, polyoxy Examples include ethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphoric acid sulfonate, glycerol borate fatty acid ester and polyoxyethylene glycerol fatty acid ester. It is not limited to. Specific examples include sodium dodecylbenzenesulfonate, sodium laurate sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene nonylphenyl ether sulfate ester salt, and sodium salt of β-naphthalenesulfonic acid formalin condensate. However, it is not limited to these.

In addition, examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts. Specifically, stearylamine acetate, trimethyl cocoammonium chloride, trimethyl tallow ammonium chloride, dimethyl dioleyl ammonium chloride, methyl oleyl diethanol chloride, tetramethyl ammonium chloride, lauryl pyridinium chloride, lauryl pyridinium bromide, lauryl pyridinium disulfate, cetyl pyridinium bromide , 4-alkylmercaptopyridine, poly (vinylpyridine) -dodecyl bromide and dodecylbenzyltriethylammonium chloride. Examples of amphoteric surfactants include, but are not limited to, aminocarboxylates.

Nonionic surfactants include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and alkyl allyl ethers. Specific examples include, but are not limited to, polyoxyethylene lauryl ether, sorbitan fatty acid ester, and polyoxyethylene octyl phenyl ether.

The selected surfactant is not limited to a single surfactant. For this reason, it is also possible to use 2 or more types of surfactant in combination. For example, a combination of an anionic surfactant and a nonionic surfactant, or a combination of a cationic surfactant and a nonionic surfactant can be used. The blending amount at that time is preferably set to a suitable blending amount for each surfactant component. As a combination, a combination of an anionic surfactant and a nonionic surfactant is preferable. The anionic surfactant is preferably a polycarboxylate. The nonionic surfactant is preferably polyoxyethylene phenyl ether.

Specific examples of the resin-type dispersant include polyurethane; polyacrylate ester of polyacrylate; unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid alkylamine salt. , Polysiloxanes, long-chain polyaminoamide phosphates and hydroxyl group-containing polycarboxylic acid esters and modified products thereof; amides formed by reaction with lower alkyleneimine polymers and polyesters having free carboxyl groups or salts thereof Oil-based dispersant: water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol and polyvinylpyrrolidone Resin or water-soluble polymer compound; Ester resin; modified polyacrylate resin, ethylene oxide / propylene oxide addition compound; and phosphate ester-based resin used but not limited thereto. These can be used alone or in admixture of two or more, but are not necessarily limited thereto.

Among the above dispersants, resin type dispersants having an acidic functional group such as polycarboxylic acid are preferable. This is because such a resin-type dispersant reduces the viscosity of the dispersion composition with a small addition amount and increases the spectral transmittance of the dispersion composition. The resin-type dispersant is preferably used in an amount of about 3 to 300% by mass with respect to the multi-walled carbon nanotube (A). From the viewpoint of film formability, it is more preferable to use about 5 to 100% by mass.

Commercially available resin-type dispersants include ANTI-TERRA (registered trademark) -U / U100, ANTI-TERRA (registered trademark) -204, ANTI-TERRA (registered trademark) -250 *, DISPERBYK (by Big Chemie Japan) Registered trademark), DISPERBYK (registered trademark) -102, DISPERBYK (registered trademark) -103, DISPERBYK (registered trademark) -106, DISPERBYK (registered trademark) -108, DISPERBYK (registered trademark) -109, DISPERBYK (registered trademark)- 110/111, DISPERBYK (registered trademark) -118 *, DISPERBYK (registered trademark) -140, DISPERBYK (registered trademark) -142, DISPERBYK (registered trademark) -145, DISPERBYK (registered trademark)- 61, DISPERBYK (registered trademark) -162/163, DISPERBYK (registered trademark) -164, DISPERBYK (registered trademark) -167, DISPERBYK (registered trademark) -168, DISPERBYK (registered trademark) -170/171, DISPERBYK (registered trademark) ) -174, DISPERBYK (registered trademark) -180, DISPERBYK (registered trademark) -182, DISPERBYK (registered trademark) -184, DISPERBYK (registered trademark) -185, DISPERBYK (registered trademark) -187, DISPERBYK (registered trademark)- 190, DISPERBYK (registered trademark) -191, DISPERBYK (registered trademark) -192, DISPERBYK (registered trademark) -193, DISPERBYK (registered trademark) -194N * DISPERBYK (R) -198 *, DISPERBYK (R) -199 *, DISPERBYK (R) -2000, DISPERBYK (R) -2001, DISPERBYK (R) -2008, DISPERBYK (R) -2009, DISPERBYK (registered trademark) -2010, DISPERBYK (registered trademark) -2012 *, DISPERBYK (registered trademark) -2013 *, DISPERBYK (registered trademark) -2015, DISPERBYK (registered trademark) -2022 *, DISPERBYK (registered trademark) -2025 DISPERBYK (R) -2050, DISPERBYK (R) -2096, DISPERBYK (R) -2150, DISPERBYK (R) -2152 *, DISPERBYK (registered trademark) -2155, DISPERBYK (registered trademark) -2163, DISPERBYK (registered trademark) -2164, DISPERBYK (registered trademark) -2200 *, BYK (registered trademark) -P104 / P104S, BYK (registered) Trademark) -P105, BYK (registered trademark) -9076, BYK (registered trademark) -9077, BYK (registered trademark) -220S, SOLPERSE-3000, 5000, 9000, 11200, 12000, 13240, 13650, manufactured by Nippon Lubrizol Corporation 13940, 16000, 17000, 18000, 20000, 21000, 24000GR, 26000, 27000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35 00, 35200, 36000, 36600, 37500, 38500, 39000, 41000, 41090, 43000, 44000, 46000, 47000, 53095, 55000, 56000, 71000 and 76500, Dispex (registered trademark) UltraPA4550, Dispex (registered by BASF) (Trademark) UltraPA4560, Dispex (registered trademark) UltraPX4575, Dispex (registered trademark) UltraPX4585, Efka (registered trademark) FA4608, Efka (registered trademark) FA4620, Efka (registered trademark) FA4644, Efka (registered trademark) FA4654, Efk ) FA4663, Efka (registered trademark) FA4665, Efka (registered trademark) FA4666, Efka (Registered trademark) FA4672, Efka (registered trademark) FA4673, Efka (registered trademark) PA4400, Efka (registered trademark) PA4401, Efka (registered trademark) PA4403, Efka (registered trademark) PA4450, Efka (registered trademark) PU4063, Efka (registered trademark) (Trademark) PX4300, Efka (registered trademark) PX4310, Efka (registered trademark) PX4320, Efka (registered trademark) PX4330, Efka (registered trademark) PX4340, Efka (registered trademark) PX4700, Efka (registered trademark) PX4701, Efka (registered trademark) ) PX4731, Efka (registered trademark) PX4732, Dispex (registered trademark) UltraPA4550, Efka (registered trademark) PA4560, Efka (registered trademark) PX4575, Efka (registered trademark) PX4585, Efka (registered trademark) FA4600, Efka (registered trademark) FA4601, Efka (registered trademark) FA4608, Efka (registered trademark) FA4620, Efka (registered trademark) FA4644, Efka (registered trademark) FA4654, Efka (registered trademark) ) FA4663, Efka (registered trademark) FA4665, Efka (registered trademark) FA4666, Efka (registered trademark) FA4672, Efka (registered trademark) FA4673, Efka (registered trademark) PA4400, Efka (registered trademark) PA4401, Efka (registered trademark) PA4403, Efka (registered trademark) PA4450, Efka (registered trademark) PU4063, Efka (registered trademark) PX4300, Efka (registered trademark) PX4310, Efka (registered trademark) PX4320, E ka (registered trademark) PX4330, Efka (registered trademark) PX4340, Efka (registered trademark) PX4700, Efka (registered trademark) PX4701, Efka (registered trademark) PX4731, Efka (registered trademark) PX4732, Kyoeisha Chemical Co., Ltd. 15B, FLOREN DOPA-15BHFS, FLOREN DOPA-17HF, FLOREN DOPA-22, FLOREN DOPA-35, FLOREN G-700, FLOREN G-820XF, FLOREN GW-1500, FLOREN G-100SF, FLOREN AF-1000, FLOREN AF- 1005, Floren KDG-2400, Floren D-90, and Ajinomoto Finetechno Ajisper PA111, PN411, PB821, PB822, PB824, PB 81 including but not limited to.

Examples of the organic pigment derivative include an organic dye derivative having an acidic functional group represented by the following general formula (2) and a triazine derivative having an acidic functional group represented by the following general formula (1).

The symbol in a formula represents the following meaning.
Q ₁ : an organic dye residue, an anthraquinone residue, an optionally substituted heterocyclic ring, or an optionally substituted aromatic ring R ₁ : —O—R ₂ , —NH —R ₂ , halogen group, —X ₁ —R ₂ , —X ₂ —Y ₁ —Z ₁ (R ₂ represents a hydrogen atom or an alkyl group or alkenyl group which may have a substituent)
_{X 1: -NH -, - O} -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or _{-X 3 -Y 1 -X 4 - (} X 3 and X ₄ each independently represents —NH— or —O—.
_{X 2: -CONH -, - SO} 2 NH -, - CH 2 NH -, - NHCO- or -NHSO ₂ -
Y ₁ : an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent Z ₁ :- SO ₃ M, —COOM (M represents one equivalent of a monovalent to trivalent cation)

The general formula (1) phthalocyanine as organic colorant residue dye in to Q _1, azo dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone And pigments or dyes such as trichromatic pigments and triphenylmethane pigments.

Examples of the heterocyclic ring or aromatic ring in Q ₁ of the general formula (1) include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, and indole. Quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene and the like.

General formula (2)
Q ₂ -(-X ₅ -Z ₂ ) _n
The symbol in a formula represents the following meaning.
Q _2: organic pigment residue or anthraquinone residue _{X 5:} a direct _{bond, -NH -, - O -,} - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH- or - X ₆ —Y ₂ —X ₇ — (X ₆ and X ₇ each independently represent —NH— or —O—, and Y ₂ represents an alkylene group or an arylene group which may have a substituent.)
Z ₂ : —SO ₃ M, —COOM (M represents one equivalent of a monovalent to trivalent cation)
n: an integer from 1 to 4

The general formula phthalocyanine as organic pigment residue at Q ₂ (2) dyes, azo dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone And pigments or dyes such as dyes, perylene dyes, perinone dyes, thioindico dyes, isoindolinone dyes, and triphenylmethane dyes.

Resin composition (B) may contain a solvent. As the solvent, any of an aqueous solvent and an organic solvent can be used.

An aqueous solvent is water or a solvent containing water. As the solvent containing water, a water-soluble liquid can be used. Specific examples of water-soluble liquids include, for example, acetaldehyde, propylene oxide, acetone, pyridine, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, acetic acid, propionic acid, acrylic acid, ethylene glycol, glycerin and the like. The water-soluble flammable liquid represented is mentioned.

Among organic solvents, organic solvents having a boiling point of 50 to 250 ° C. are easy to use. Such an organic solvent is excellent in workability during coating and drying before and after curing. Specific examples of the solvent include alcohol solvents typified by methanol, ethanol and isopropyl alcohol; ketone solvents typified by acetone, butyl diglycol acetate and MEK (methyl ethyl ketone); typified by ethyl acetate and butyl acetate. Ester solvents such as dibutyl ether, ethylene glycol, and monobutyl ether; and dipolar aprotic solvents such as N-methyl-2-pyrrolidone, but are not limited thereto. These solvents can be used alone or in admixture of two or more.

Aromatic hydrocarbon solvents represented by toluene, xylene, Solvesso # 100 (manufactured by TonenGeneral) and Solvesso # 150 (manufactured by TonenGeneral); aliphatic carbonization represented by hexane, heptane, octane and decane Hydrogen solvents; or amide solvents represented by cellosolve acetate, ethyl cellosolve, and butyl cellosolve can also be used. These solvents can also be used alone or in admixture of two or more.

In addition, an additive can be appropriately blended with the solvent as necessary within a range not impairing the object of the present embodiment. Examples of additives include pigments, wetting and penetrating agents, anti-skinning agents, ultraviolet absorbers, antioxidants, crosslinking agents, preservatives, antifungal agents, viscosity modifiers, pH adjusters, leveling agents, and antifoaming agents. However, it is not limited to these.

(3) Coating film (D)

The coating film of the present embodiment is a coating film formed from the resin composition (B) of the present embodiment, and includes a multi-walled carbon nanotube (A) and a resin (C). Although the base material (E) is provided under this coating film (D), you may remove a base material after coating film (D) preparation.
The coating film (D) of this embodiment has high jetness by including the multi-walled carbon nanotube (A).

The coating film (D) of this embodiment can be formed by applying the resin composition (B) by a general technique. Specific techniques include wet coating methods including casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, print transfer, and inkjet. Can be, but is not limited to. A coating film can be formed by coating the resin composition (B) on the substrate (E) by the above technique.

What is necessary is just to select suitably the addition rate of the multi-walled carbon nanotube (A) in a coating film (D) according to a use. The addition rate is preferably in the range of 0.1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 2 to 15% by mass. In particular, if the addition rate is within such a range, a coating film having excellent jetness can be obtained.

In the range not impairing the object of the present invention, carbon black can be added to the coating film (D) in addition to the multi-walled carbon nanotube (A). Specific examples of carbon black include ketjen black, acetylene black, furnace black and channel black. Carbon black may be by-produced when producing a synthesis gas containing hydrogen and carbon monoxide by partially oxidizing a hydrocarbon typified by naphtha in the presence of hydrogen and oxygen. Carbon black may be obtained by oxidizing or reducing such a by-product. The above is not intended to limit the carbon black according to the present invention. These carbon blacks may be used alone or in combination of two or more. From the viewpoint of improving blackness, carbon black having an average particle diameter of 20 nm or less and a DBP oil absorption of 80 mL / 100 g or less is preferably used. In the present embodiment, the DBP oil absorption represents the amount (mL) of dibutyl phthalate (DBP) that can be contained per 100 g of carbon black. The DBP oil absorption is a measure for quantifying the structure of carbon black. The structure is a complex aggregated form due to chemical or physical bonding between carbon black particles.

The average particle diameter of carbon black is obtained in the same manner as the outer diameter of the multi-walled carbon nanotube (A). Specifically, carbon black is observed and imaged with a transmission electron microscope. Next, in the observation photograph, arbitrary 300 carbon blacks are selected, and the respective particle sizes are measured. Next, the average particle diameter (nm) of carbon black is calculated as the number average of the particle diameter.

The amount of carbon black used is preferably 1 to 25 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the multi-walled carbon nanotube (A).

The film thickness of the coating film (D) is preferably 5 μm or more, more preferably 10 μm or more.

In the coating film (D), a clear layer may be further formed on the coating film (D). By forming the clear layer, a coating film (D) having gloss, light resistance and jetness is obtained.

The lightness (L) exhibited by the coating film (D) is preferably 5.7 or less, more preferably 5.5 or less, still more preferably 5.3 or less, and 5.2 or less. It is particularly preferred. This lightness (L) is obtained by measuring using a color difference meter. The measurement is performed on the surface of the coating film (D) from the side on which the coating film (D) is formed. As a color difference meter, you may use NIPPONDENSHOKU Co., Ltd. and SpectroColorMeterSE6000.

The 60 ° specular gloss of the coating film (D) is preferably 60 or more, more preferably 80 or more, and even more preferably 85 or more. A gloss meter GM-26D (manufactured by Murakami Color Research Laboratory) may be used as the gloss meter.

Base material (E)
The base material (E) used in order to form the coating film (D) in this embodiment is not specifically limited. As the material of the substrate (E), metals represented by iron, aluminum and copper or alloys thereof; inorganic materials represented by glass, cement and concrete; polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer Resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin and epoxy resin represented by plastics; plastic materials represented by various FRPs; wood; and fiber materials (including paper and cloth) Examples include, but are not limited to, natural or synthetic materials.

Of the above materials, metals such as iron, aluminum and copper or their alloys are preferred. A resin containing a pigment typified by carbon black and carbon nanotubes is also preferable.

The shape of the substrate (E) may be a plate shape, a film shape, a sheet shape, or a molded body shape. For example, an injection molding method such as an insert injection molding method, an in-mold molding method, an overmold molding method, a two-color injection molding method, a core back injection molding method, and a sandwich injection molding method; Typified by extrusion, multilayer extrusion, coextrusion and extrusion coating; and multilayer blow molding, multilayer calendering, multilayer press molding, slush molding and melt casting. Other molding methods can be used.

(4) Multi-walled carbon nanotube (CNT) dispersion (F)
Although the preparation method of the resin composition (B) of this embodiment mentioned above is not specifically limited, As one method, the method of preparing CNT dispersion liquid (F) and adding resin to the said CNT dispersion liquid (F) is mentioned. Can be mentioned. The CNT dispersion liquid (F) contains at least the multi-walled carbon nanotube (A) and a dispersant, and usually further contains a solvent. The dispersion liquid (F) does not contain the resin (C).

In order to obtain the CNT dispersion liquid (F), it is preferable to perform a treatment of dispersing the multi-walled carbon nanotubes (A) in a solvent. The equipment used for performing such processing is not particularly limited. For example, paint conditioner (manufactured by Red Devil), ball mill, sand mill ("Dyno mill" manufactured by Shinmaru Enterprises), attritor, pearl mill ("DCP mill" manufactured by Eirich), ultrasonic homogenizer (Advanced Digital Sonifier ( (Registered trademark), MODEL 450DA, manufactured by BRANSON), coball mill, basket mill, homomixer, homogenizer (“CLEAMIX” manufactured by M Technique), wet jet mill (“GENUS PY” manufactured by Genus, “Nanomizer manufactured by Nanomizer) )), Hoover Mahler, 3 roll mills, and extruders.

As the dispersant that the CNT dispersion liquid (F) has, a surfactant, a resin-type dispersant, or an organic pigment derivative can be used. Surfactants are mainly classified into anionic, cationic, nonionic and amphoteric. A preferable dispersant is a resin-type dispersant. Since the specific example of a dispersing agent is the same as that of what was demonstrated by the said resin composition (B), description here is abbreviate | omitted.
Moreover, since the solvent contained in the CNT dispersion liquid (F) is the same as that described in the resin composition (B), description thereof is omitted here.

It was found that the resin composition (B) and the coating film (D) using the multi-walled carbon nanotube (A) as described above have good jetness.

The reason why the jetness is good is that multi-walled carbon nanotubes (A) with a small outer diameter are stronger in interaction between carbon nanotubes than in general carbon nanotubes, and form and hold bundles firmly. This is probably because of this. Therefore, the specific surface area is reduced, and the wettability to the solvent and the dispersant is improved. Moreover, also in the resin composition (B) and coating film (D) after dispersion | distribution, it is easy to maintain the orientation of a carbon nanotube, and the light confinement effect is large.

The present invention will be described more specifically with reference to the following examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. In Examples, unless otherwise specified, “part” means “part by mass” and “%” means “mass%”. Further, “carbon nanotube” may be abbreviated as “CNT”, and “carbon black” may be abbreviated as “CB”.

<Method of measuring physical properties>
The physical properties of the CNTs or CNT coatings used in the examples and comparative examples described later were measured by the following methods.

<Raman spectroscopic analysis of CNT>
CNTs were placed on a Raman microscope (XploRA, manufactured by Horiba, Ltd.), and measurement was performed using a laser wavelength of 532 nm. The measurement conditions were an acquisition time of 60 seconds, an integration count of 2 times, a neutral density filter of 10%, an objective lens magnification of 20 times, a diffraction grating score of 1200 lines / minute, a confocal hole 500, and a slit width of 100 μm. CNTs for measurement were collected on a slide glass and flattened using a spatula. Among the obtained peaks, the maximum peak intensity is G in the range of 1560 to 1600 cm ⁻¹ in the spectrum, the maximum peak intensity is D in the range of 1310 to 1350 cm ⁻¹ , and the ratio of G / D is the G / The D ratio was used.

<Powder X-ray diffraction analysis of CNT>
CNTs were installed in an X-ray diffractometer (Ultima 2100, manufactured by Rigaku Corporation) and operated from 1.5 ° to 80 ° for analysis. The X-ray source is CuKα ray. The step width was 0.01 ° and the measurement time was 1.0 second. The plots appearing at the diffraction angle 2θ = 25 ° ± 2 ° obtained at this time were each subjected to a simple moving average of 11 points, and the half width of the peak was defined as the half width of the CNT.

<Preparation of CNT dispersion>
Weigh 0.2 g of carbon nanotubes in a 450 mL SM sample bottle (manufactured by Sansho Co., Ltd.) and 0.2 g of polyvinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) as a resin-type dispersant, add 200 mL of isopropyl alcohol, Using a sonic homogenizer (Advanced Digital Sonifer (registered trademark), MODEL 450DA, manufactured by BRANSON), dispersion treatment was carried out at 50% amplitude for 5 minutes under ice cooling to prepare a CNT dispersion.

<Transmission electron microscope analysis of CNT>
The CNT dispersion was appropriately diluted, dropped by several μL onto the collodion membrane, dried at room temperature, and then observed using a direct transmission electron microscope (H-7650, manufactured by Hitachi, Ltd.). Observations were taken at a magnification of 50,000 times, taking a plurality of photographs containing 10 or more CNTs in the field of view, measuring the outer diameters of 300 CNTs arbitrarily extracted, and calculating the average value of the average outer diameters of CNTs ( nm). The standard deviation was calculated using the measured outer diameter of 300 CNTs as a population.
For reference, FIGS. 1 to 8 are graphs showing the relationship between the outer diameter and the number of multi-walled carbon nanotubes of Examples 1, 4 and 12 to 13 and Comparative Examples 1 to 4 described later.

<Measurement method of lightness (L) of CNT coating film>
About the CNT coating film, the lightness (L) was measured from the surface on which the CNT resin composition was applied using a color difference meter (manufactured by NIPONDENSHOKU, SpectroColorMeterSE6000).

<Gloss measurement of CNT coating film>
With respect to the CNT coating film, the 60 ° specular gloss was measured with a gloss meter GM-26D (Murakami Color Research Co., Ltd.) according to JIS Z8741 from the surface coated with the CNT resin composition.

[First Example Group]
<Example of production of catalyst for CNT synthesis>
The CNT synthesis catalyst used in each of the examples and comparative examples described later was prepared by the following method.

Catalyst for CNT synthesis (A)
Weigh 60 parts of cobalt hydroxide, 138 parts of magnesium acetate tetrahydrate, and 16.2 parts of manganese acetate in a heat-resistant container and dry them at a temperature of 170 ± 5 ° C. for 1 hour using an electric oven. After evaporating, the SPEED dial was adjusted to 3 using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.), and pulverized for 1 minute. Then, using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.), adjust the SPPED dial to 2 and mix for 30 seconds for each pulverized powder. Catalyst precursor for CNT synthesis (A) Was made. Then, after transferring the catalyst precursor for CNT synthesis (A) to a heat-resistant container, using a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.), and firing for 30 minutes in an air atmosphere at 450 ± 5 ° C., The catalyst for CNT synthesis (A) was obtained by pulverization in a mortar.

CNT synthesis catalyst (B)
60 parts of cobalt hydroxide, 138 parts of magnesium acetate tetrahydrate and 8.1 parts of manganese carbonate were weighed in a heat-resistant container and dried using an electric oven at a temperature of 170 ± 5 ° C. for 1 hour. After evaporating, the SPEED dial was adjusted to 3 using a pulverizer (One Dark Rusher WC-3, Osaka Chemical Co., Ltd.) and pulverized for 1 minute. Then, using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.), adjust the SPEED dial to 2 and mix for 30 seconds to pulverize each pulverized powder. Catalyst precursor for CNT synthesis (B) Was made. Then, after transferring the catalyst precursor for CNT synthesis (B) to a heat-resistant container, using a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.), and firing for 30 minutes in an air atmosphere at 450 ± 5 ° C., A CNT synthesis catalyst (B) was obtained by pulverization in a mortar.

Catalyst for CNT synthesis (C)
Weigh 60 parts of cobalt hydroxide, 138 parts of magnesium acetate tetrahydrate, 16.2 parts of manganese carbonate, and 4.0 parts of zeolite (HSZ-940HOA, manufactured by Tosoh Corporation) in a heat-resistant container. After drying for 1 hour at a temperature of 170 ± 5 ° C. and evaporating moisture, the SPEED dial was adjusted to 3 using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.). Milled for minutes. Then, using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.), adjust the SPEED dial to 2 and mix for 30 seconds to pulverize each pulverized powder. Catalyst precursor for CNT synthesis (C) Was made. Then, after transferring the catalyst precursor for CNT synthesis (C) to a heat-resistant container and using a muffle furnace (FO510, manufactured by Yamato Kagaku Co., Ltd.), firing in an air atmosphere at 450 ± 5 ° C. for 30 minutes, A CNT synthesis catalyst (C) was obtained by pulverization in a mortar.

Catalyst for CNT synthesis (D)
60 parts of cobalt hydroxide, 138 parts of magnesium acetate tetrahydrate, 16.2 parts of manganese carbonate, 4.0 parts of Aerosil (AEOSIL (registered trademark) 200, manufactured by Nippon Aerosil Co., Ltd.) are weighed in a heat-resistant container. After drying for 1 hour at a temperature of 170 ± 5 ° C. using an electric oven to evaporate the moisture, the SPEED dial is set to 3 using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.). Adjust and grind for 1 minute. Then, using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.), adjust the SPEED dial to 2 and mix for 30 seconds to pulverize each pulverized powder. Catalyst precursor for CNT synthesis (D) Was made. Then, the catalyst precursor for CNT synthesis (D) was transferred to a heat-resistant container, and after using a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.) and baked for 30 minutes in an air atmosphere at 450 ± 5 ° C., A CNT synthesis catalyst (D) was obtained by pulverization in a mortar.

Catalyst for CNT synthesis (E)
Weigh 60 parts of cobalt hydroxide, 166 parts of magnesium acetate tetrahydrate, 16.2 parts of manganese carbonate, and 4.0 parts of Aerosil (AEOSIL (registered trademark) 200, manufactured by Nippon Aerosil Co., Ltd.) in a heat-resistant container. After drying for 1 hour at a temperature of 170 ± 5 ° C. using an electric oven to evaporate the moisture, the SPEED dial is set to 3 using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.). Adjust and grind for 1 minute. Then, using a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.), adjust the SPEED dial to 2 and mix for 30 seconds to pulverize each pulverized powder. Catalyst precursor for CNT synthesis (E) Was made. Then, the catalyst precursor for CNT synthesis (E) was transferred to a heat-resistant container, and after using a muffle furnace (FO510, manufactured by Yamato Kagaku Co., Ltd.) and calcined for 30 minutes in an air atmosphere at 450 ± 5 ° C., A CNT synthesis catalyst (E) was obtained by pulverization in a mortar.

CNT synthesis catalyst (F)
60 parts of cobalt hydroxide, 138 parts of magnesium acetate tetrahydrate and 16.2 parts of manganese acetate are weighed in one heat-resistant container and dried at 170 ± 5 ° C. for 1 hour using an electric oven. After evaporating the water, the particle size was made uniform through 80 mesh to prepare a catalyst precursor (F) for CNT synthesis. Then, the catalyst precursor for CNT synthesis (F) was transferred to a heat-resistant container, and after using a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.) and calcined for 30 minutes in an air atmosphere at 450 ± 5 ° C., A CNT synthesis catalyst (F) was obtained by pulverization in a mortar.

(Example 1) Production of CNT (A) 2.0 g of the CNT synthesis catalyst (A) was sprayed on the center of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 L. A quartz glass bakeware was installed. Exhaust was performed while injecting nitrogen gas, the air in the reaction tube was replaced with nitrogen gas, and the atmosphere in the horizontal reaction tube was adjusted to an oxygen concentration of 1 vol% or less. Subsequently, it heated with the external heater and it heated until the center temperature in a horizontal type reaction tube became 680 degreeC. After reaching 680 ° C., propane gas as a carbon source was introduced into the reaction tube at a flow rate of 2 L / min, and contact reaction was performed for 1 hour. After completion of the reaction, the gas in the reaction tube was replaced with nitrogen gas, the gas in the reaction tube was replaced with nitrogen gas, and the temperature of the reaction tube was cooled to 100 ° C. or less to obtain CNT (A). .

Examples 2 to 5 Preparation of CNTs (B) to (E) Same as Example 1 except that CNT synthesis catalysts (B) to (E) were used instead of CNT synthesis catalyst (A). Thus, CNTs (B) to (E) were obtained.

Comparative Example 1 Preparation of CNT (F) CNT (F) was obtained in the same manner as in Example 1 except that the CNT synthesis catalyst (F) was used instead of the CNT synthesis catalyst (A). It was.

(Comparative Example 2) Production of CNT (G) 2.0 g of the CNT synthesis catalyst (F) was sprayed on the center of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 L. A quartz glass bakeware was installed. Exhaust was performed while injecting nitrogen gas, the air in the reaction tube was replaced with nitrogen gas, and the atmosphere in the horizontal reaction tube was adjusted to an oxygen concentration of 1% by volume or less. Subsequently, it heated with the external heater and it heated until the center temperature in a horizontal type reaction tube became 680 degreeC. After reaching 680 ° C., ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 2 L / min, and contact reaction was performed for 1 hour. After completion of the reaction, the gas in the reaction tube was replaced with nitrogen gas, the gas in the reaction tube was replaced with nitrogen gas, and the temperature of the reaction tube was cooled to 100 ° C. or less to obtain CNT (G). .

(Comparative Examples 3 to 4) CNT (H) to (I)
Multi-walled carbon nanotubes (NC7000, manufactured by Nanosil Corporation) were designated as CNT (H), and multi-walled carbon nanotubes (Flotube 9000, produced by Cano Corporation) were designated as CNT (I).

Table 1 shows the evaluation results of CNTs (A) to (I). The average outer diameter of CNT was expressed as X, and the standard deviation of the CNT outer diameter was expressed as σ.

(Example 6) Production of CNT resin composition and coating film 5.6 g of CNT (A), resin type dispersant (DISPERBYK (registered trademark) -111, manufactured by BYK Chemie, nonvolatile content 100%) 11.2 g as a dispersant , 48.8 g of Solvesso 150 (manufactured by TonenGeneral Sekiyu KK), 73.5 g of toluene, 73.5 g of xylene, and 48.8 g of butyl acetate as a solvent are added to a plastic container (Descup 1L, manufactured by Tokyo Glass Instrument Co., Ltd.) (TK KHOMODERS MODEL2.5, manufactured by Primix Co., Ltd.) was used, and the mixture was stirred for 5 minutes at a rotation speed of 1500 rpm. Thereafter, using a high-speed stirrer (TKHOMOMIXER MARKII MODEL2.5, manufactured by Primix Co., Ltd.), a dispersion treatment was performed for 5 minutes at a rotational speed of 5000 rpm to obtain a CNT coarse dispersion (A). 100 parts of this CNT coarse dispersion (A) and 175 parts of zirconia beads (bead diameter 1.0 mmφ) are charged into a 200 mL SM sample bottle (manufactured by Sansho Co., Ltd.) and dispersed for 3 hours using a paint conditioner manufactured by Red Devil. Processing was performed to obtain a CNT dispersion (A). Thereafter, 92.6 parts of acrylic resin (DIC Corporation, ACRYDIC 47-712, 50% non-volatile content) was added, and a high-speed stirrer (TK HOMODERS MODEL2.5, Primix Co., Ltd.) was used. The mixture was stirred at the rotation speed for 5 minutes. Further, after that, 19.3 parts of melamine resin (manufactured by DIC, Super Becamine L-117-60, non-volatile content 60%) is added to the CNT dispersion (A), and dispersed for 30 minutes using a paint conditioner manufactured by Red Devil. Processing was performed to obtain a CNT resin composition (A). Next, using a PET (polyethylene terephthalate) film (manufactured by Toray Industries Inc., Lumirror 100, T60) as a base material, the CNT resin composition (A) was spray-coated on one side so that the film thickness after drying was 20 μm. Spray coating was performed using an air spray gun (W-61-2G manufactured by Anest Iwata). The coated PET film was allowed to stand at room temperature for 30 minutes and then dried at 140 ± 5 ° C. for 30 minutes to produce a CNT coating film (A).

(Examples 7 to 10), (Comparative Examples 5 to 8)
CNT resin compositions (B) to (I), CNT dispersions (B) to (I), and CNT coating film (B) by the same method as in Example 6 except that the CNTs listed in Table 2 were changed. To (I) were obtained.

Table 3 shows the evaluation results of the CNT coating films produced in Examples 6 to 10 and Comparative Examples 5 to 8. The jet blackness evaluation criteria were as follows. When the lightness (L) of the coating film is 5.5 or less and the 60 ° specular gloss is 80 or more ++ (excellent), the brightness (L) of the coating film is 5.7 or less and the 60 ° specular gloss is 80 or more (good) ), A lightness (L) of the coating film exceeding 5.7 or a 60 ° specular gloss of less than 80 was defined as “-” (bad).

(Comparative Example 9)
A CB resin composition (A), a CB dispersion (A), a CB coating film (A) were prepared in the same manner as in Example 6 except that Degussa carbon black (COLOR Black FW-200) was used instead of CNT. )

Table 4 shows the evaluation results of the CB coating film produced in Comparative Example 9. The jet blackness evaluation criteria were as follows. When the lightness (L) of the coating film is 5.5 or less and the 60 ° specular gloss is 80 or more ++ (excellent), the brightness (L) of the coating film is 5.7 or less and the 60 ° specular gloss is 80 or more (good) ), A lightness (L) of the coating film exceeding 5.7 or a 60 ° specular gloss of less than 80 was defined as “-” (bad).

From the results of the first example group, the coating films of Examples 6 to 10 using the multi-walled carbon nanotubes of Examples 1 to 5 having an average outer diameter of 10 nm or less and a standard deviation of the outer diameter of 4 nm or less are as follows: It was revealed that the lightness was particularly low and the jet blackness was superior to the coating films of Comparative Examples 5 to 8 using multi-walled carbon nanotubes having a large outer diameter and Comparative Example 9 using carbon nanoblack.

[Second Example Group]
<Example of production of catalyst for CNT synthesis>
A catalyst carrier for CNT synthesis, a cobalt composition, and a catalyst for CNT synthesis used in each of Examples and Comparative Examples described later were prepared by the following methods.

<Preparation of CNT synthesis catalyst carrier>
1000 parts of magnesium acetate tetrahydrate was weighed in a heat-resistant container, dried for 6 hours at 170 ± 5 ° C. using an electric oven, and then pulverized (sample mill KIIW-I type, Dalton Co., Ltd.). 1 mm screen was used and pulverized to obtain a magnesium acetate dry pulverized product. Magnesium acetate dry pulverized product 45.8 parts, manganese carbonate 8.1 parts, silicon oxide (SiO ₂ , made by Nippon Aerosil Co., Ltd .: AEROSIL (registered trademark) 200), steel beads (bead diameter 2.0 mmφ) 200 The part was charged into an SM sample bottle (manufactured by Sansho Co., Ltd.), and pulverized and mixed for 30 minutes using a paint conditioner manufactured by Red Devil. Thereafter, using a stainless steel sieve, the pulverized and mixed powder and the steel beads (bead diameter 2.0 mmφ) were separated to obtain a catalyst support for CNT synthesis.

<Preparation of CNT synthesis catalyst>
30 parts of cobalt (II) hydroxide was weighed in a heat-resistant container and dried at 170 ± 5 ° C. for 2 hours to obtain a cobalt composition containing CoHO ₂ . Thereafter, 54.9 parts of the catalyst carrier for CNT synthesis and 29 parts of the cobalt composition were charged into a pulverizer (One Dark Rusher WC-3, manufactured by Osaka Chemical Co., Ltd.), a standard lid was attached, and the SPEED dial was adjusted to 2. The mixture was pulverized and mixed for 30 seconds to obtain a catalyst precursor for CNT synthesis. The catalyst precursor for CNT synthesis is transferred to a heat-resistant container, baked in a muffle furnace (FO510, manufactured by Yamato Scientific Co., Ltd.) for 30 minutes in an air atmosphere at 450 ± 5 ° C., and then pulverized in a mortar A catalyst for CNT synthesis was obtained.

(Example 11) Production of CNT (J) Quartz glass bakeware in which 1 g of the CNT synthesis catalyst was dispersed in the central part of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 L Was installed. Evacuation was performed while injecting nitrogen gas, the air in the reaction tube was replaced with nitrogen gas, and heating was performed until the atmospheric temperature in the horizontal reaction tube reached 710 ° C. After reaching 710 ° C., ethylene gas as hydrocarbon was introduced into the reaction tube at a flow rate of 2 L / min, and contact reaction was performed for 7 minutes. After completion of the reaction, the gas in the reaction tube was replaced with nitrogen gas, and the reaction tube was cooled to 100 ° C. or lower and taken out to obtain CNT (J).

(Examples 12 to 16)
CNTs (K) to (O) were obtained in the same manner as in Example 11 except that the catalyst amount, temperature, and reaction time listed in Table 5 were changed.

(Examples 17 to 19)
CNTs (Q) to (S) were obtained in the same manner as in Example 11 except that the temperatures and reaction times listed in Table 6 were changed.

(Examples 20 to 21)
CNT (T) and (U) were obtained in the same manner as in Example 11 except that the catalyst amount, temperature, reaction time, and hydrocarbon listed in Table 7 were changed.

Table 8 shows the evaluation results of the CNTs produced in Examples 11 to 21.

(Example 22) Preparation of CNT resin composition and coating film 5.6 g of CNT (K), 11.2 g of resin type dispersant (DISPERBYK (registered trademark) -111, manufactured by BYK Chemie, nonvolatile content 100%) as a dispersant , 48.8 g of Solvesso 150 (manufactured by TonenGeneral Sekiyu KK), 73.5 g of toluene, 73.5 g of xylene, and 48.8 g of butyl acetate as a solvent are added to a plastic container (Descup 1L, manufactured by Tokyo Glass Instrument Co., Ltd.) (TK KHOMODERS MODEL2.5, manufactured by Primix Co., Ltd.) was used, and the mixture was stirred for 5 minutes at a rotation speed of 1500 rpm. Thereafter, using a high-speed stirrer (TK HOMOMIXER MARKII MODEL2.5, manufactured by Primix Co., Ltd.), a dispersion treatment was performed for 5 minutes at a rotational speed of 5000 rpm to obtain a CNT coarse dispersion (K). 100 parts of the CNT coarse dispersion (K) and 175 parts of zirconia beads (bead diameter 1.0 mmφ) are charged into a 200 mL SM sample bottle (manufactured by Sansho Co., Ltd.) and dispersed for 3 hours using a paint conditioner manufactured by Red Devil. Processing was performed to obtain a CNT dispersion A. Thereafter, 92.6 parts of acrylic resin (DIC Corporation, ACRYDIC 47-712, 50% non-volatile content) was added, and a high-speed stirrer (TK HOMODERS MODEL2.5, Primix Co., Ltd.) was used. The mixture was stirred at the rotation speed for 5 minutes. Further, after that, 19.3 parts of melamine resin (manufactured by DIC, Super Becamine L-117-60, non-volatile content 60%) is added to the CNT dispersion (K), and dispersed for 30 minutes using a paint conditioner made by Red Devil. Processing was performed to obtain a CNT resin composition (K). Next, using a PET (polyethylene terephthalate) film (manufactured by Toray Industries Inc., Lumirror 100, T60) as a base material, the CNT resin composition (K) was spray-coated on one side so that the film thickness after drying was 20 μm. Spray coating was performed using an air spray gun (W-61-2G manufactured by Anest Iwata). The coated PET film was allowed to stand at room temperature for 30 minutes and then dried at 140 ± 5 ° C. for 30 minutes to produce a CNT coating film (K).

(Examples 23 to 32)
A CNT resin composition (L) to (U), a CNT dispersion (L) to (U), a CNT coating film (L) in the same manner as in Example 22 except that the CNTs listed in Table 9 were changed. To (U) was obtained.

Table 10 shows the evaluation results of the CNT coating films produced in Examples 22 to 32. For jetness evaluation, the lightness (L) of the coating film is 5.2 or less and the 60 ° specular gloss is 80 or more +++ (excellent), and the brightness (L) of the coating film is 5.3 or less and the 60 ° specular gloss is 60 °. ++ (excellent) when 80 or more, brightness (L) of coating film is 5.5 or less and 60 ° specular gloss is ++ (good) when shining is 80 or more, brightness (L) of coating film is 5.7 or less and 60 ° specular A glossiness of 80 or higher was evaluated as + (possible), and a lightness (L) of the coating film of more than 5.7 or a 60 ° specular gloss of less than 80 was evaluated as-(bad).

From the results of the second example group, the average outer diameter is 10 nm or less, the standard deviation of the outer diameter is 4 nm or less, and the half-width of the peak is at a diffraction angle 2θ = 25 ° ± 2 ° in the powder X-ray diffraction analysis. It was revealed that the coating films of Examples 22 to 27 using the multi-walled carbon nanotubes of Examples 11 to 16 having an angle of 5 ° to 5.5 ° have particularly excellent jetness.

The present invention has been described above with reference to the embodiment, but the present invention is not limited to the above. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the invention.

This application claims priority based on Japanese Patent Application No. 2017-49759 filed on March 15, 2017 and Japanese Patent Application No. 2017-243686 filed on December 20, 2017, the entire disclosure of which is incorporated herein by reference. Capture here.

Claims (12)

1. A multi-walled carbon nanotube characterized by satisfying the following requirements (1) and (2):
   (1) The average outer diameter of the multi-walled carbon nanotube is 10 nm or less. (2) The standard deviation of the outer diameter of the multi-walled carbon nanotube is 4 nm or less.
2. 2. The multilayer carbon according to claim 1, wherein a peak exists at a diffraction angle 2θ = 25 ° ± 2 ° in a powder X-ray diffraction analysis, and a half width of the peak is 3 ° or more and 5 ° or less. Nanotubes.
3. In the powder X-ray diffraction analysis, a peak exists at a diffraction angle 2θ = 25 ° ± 2 °, and the half width of the peak is more than 5 ° and not more than 5.5 °. The multi-walled carbon nanotube described.
4. X ± 2σ satisfies 2.5 nm ≦ X ± 2σ ≦ 15.5 nm, where X is the average outer diameter of the multi-walled carbon nanotubes, and σ is the standard deviation of the outer diameter of the multi-walled carbon nanotubes, The multi-walled carbon nanotube according to any one of claims 1 to 3.
5. G / D ratio is 2.0 or less when the maximum peak intensity in the range of 1560 to 1600 cm ⁻¹ is G and the maximum peak intensity in the range of 1310 to 1350 cm ⁻¹ is D in the Raman spectrum. The multi-walled carbon nanotube according to any one of claims 1 to 4, wherein:
6. G / D ratio is 1.0 or less when the maximum peak intensity in the range of 1560 to 1600 cm ⁻¹ is G and the maximum peak intensity in the range of 1310 to 1350 cm ⁻¹ is D in the Raman spectrum. The multi-walled carbon nanotube according to any one of claims 1 to 5, wherein
7. The method for producing a multi-walled carbon nanotube according to any one of claims 1 to 6, comprising the following steps.
   (1) An active ingredient containing at least one selected from cobalt, nickel and iron and a catalyst carrier containing at least one selected from magnesium, aluminum and silicon are mixed and / or pulverized and calcined. Step for obtaining catalyst (2) Step for obtaining multi-walled carbon nanotube by bringing the catalyst into contact with a carbon source containing at least one selected from hydrocarbon and alcohol under heating
8. In the step (2), the carbon source contains hydrocarbons, the production amount of multi-walled carbon nanotubes per gram of the catalyst is Y (g), and the contact reaction time of the catalyst and the hydrocarbons is Z (minutes). The multi-walled carbon nanotube according to claim 7, wherein the amount of catalyst and / or the flow rate of hydrocarbon is adjusted so that Y / Z (g / min) satisfies 1.5 ≦ Y / Z ≦ 2.7. Manufacturing method.
9. The method for producing a multi-walled carbon nanotube according to claim 8, wherein the hydrocarbon is ethylene.
10. A dispersion containing the multi-walled carbon nanotubes according to any one of claims 1 to 5 and a dispersant.
11. A resin composition comprising the multi-walled carbon nanotube according to any one of claims 1 to 5 and a resin.
12. A coating film formed from the resin composition according to claim 11.

Images