JP5415929B2 - Isolation method of carbon nanotube columnar structure from carbon nanotube composite structure - Google Patents

Description

  The present invention relates to a method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure. Specifically, the present invention relates to a method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure including a plurality of carbon nanotube columnar structures on a substrate.

  Carbon nanotubes are expected to be developed into various functional materials because of their excellent thermal and electrical characteristics. For this reason, various studies have been made on carbon nanotubes, such as productivity and use. In order to put carbon nanotubes into practical use as a functional material, for example, a carbon nanotube aggregate composed of a plurality of carbon nanotube columnar structures can be used, and the characteristics of the aggregate can be improved.

  Examples of the use of the carbon nanotube aggregate include an adhesive (Patent Document 1 and Patent Document 2). Various materials are used as pressure-sensitive adhesives for industrial use, and most of them are viscoelastic bodies designed flexibly in bulk. The viscoelastic body wets and adheres to the adherend due to its low modulus and exhibits adhesive strength. On the other hand, since the diameter of the carbon nanotube is nano-sized, it has been revealed that the carbon nanotube follows the surface unevenness of the adherend and exhibits an adhesive force by van der Waals force.

  A carbon nanotube composite structure provided with a carbon nanotube aggregate composed of a plurality of carbon nanotube columnar structures on a substrate can be applied to various uses such as an adhesive member.

  A carbon nanotube composite structure is generally produced by growing and forming carbon nanotubes on a substrate by a chemical vapor deposition method (CVD method). The growth and formation of carbon nanotubes by chemical vapor deposition (CVD) is generally performed at a high temperature around 400 to 800 ° C. For this reason, as the base material, a highly heat-resistant material exhibiting high durability even at high temperatures is used.

  A substrate made of such a high heat-resistant material has low adhesion to carbon nanotubes. For this reason, a carbon nanotube columnar structure can be peeled from a base material, transferred to another adherend, and handled.

  However, particularly when a long or large-area substrate is used, cohesive failure occurs in the carbon nanotube columnar structure when the carbon nanotube columnar structure is peeled from the substrate in this way. There is a problem that it is difficult to perform uniform transfer without unevenness to the adherend.

US Patent Application Publication No. 2004/0071870 US Patent Application Publication No. 2006/0068195

  An object of the present invention is a method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure having a plurality of carbon nanotube columnar structures on a substrate, and coagulating and destroying the carbon nanotube columnar structures Another object of the present invention is to provide a method for peeling and transferring to other adherends easily and uniformly without any unevenness.

The isolation method of the present invention is a method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure comprising a plurality of carbon nanotube columnar structures on a substrate, the carbon nanotube composite structure comprising: An intermediate layer is provided between the base material and the carbon nanotube columnar structure, and the adhesion between the base material provided with the intermediate layer and the carbon nanotube columnar structure is less than 5 N / cm ² , After the tip of the structure has a shear adhesive force to glass at 25 ° C. of 10 N / cm ² or more, the tip of the carbon nanotube columnar structure provided in the carbon nanotube composite structure is bonded to the adherend by bonding, Peeling the base material provided with the intermediate layer at a peeling angle of 45 ° or more causes the carbon nanotube columnar structure to cohesively break. Release transfer without any problems.

  In a preferred embodiment, the substrate is a substrate made of a metal material having a melting point of 700 ° C. or higher.

  In preferable embodiment, the said metal material consists of either copper or the copper alloy containing 50 weight% or more of copper.

  In a preferred embodiment, the intermediate layer is made of an inorganic oxide.

  In a preferred embodiment, the intermediate layer has a thickness of 10 nm or more.

  According to the present invention, there is provided a method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure having a plurality of carbon nanotube columnar structures on a substrate, the method comprising coagulating and destroying the carbon nanotube columnar structure Thus, it is possible to provide a method of peeling and transferring to other adherends easily and uniformly without unevenness.

It is a schematic sectional drawing of the carbon nanotube composite structure in preferable embodiment of this invention. It is a schematic sectional drawing of the carbon nanotube aggregate manufacturing apparatus in preferable embodiment of this invention. It is a schematic sectional drawing which shows the Young's modulus measuring method. It is a schematic sectional drawing of a volume resistivity measuring device. It is a schematic sectional drawing which shows the mode of peeling in the isolation method of this invention.

  FIG. 1 shows a schematic cross-sectional view of a representative carbon nanotube composite structure that can be used in the isolation method of the present invention (the scale is not accurately described to clearly show each component). The carbon nanotube composite structure 10 includes a base material 1, a plurality of carbon nanotube columnar structures 2, and an intermediate layer 3.

In the carbon nanotube composite structure that can be used in the isolation method of the present invention, the adhesion between the base material provided with the intermediate layer and the carbon nanotube columnar structure is less than 5 N / cm ² . It said seal adhesive strength is preferably 0.01~3N / cm ^2, more preferably 0.05~1.5N / cm ^2. Since the adhesion between the base material provided with the intermediate layer and the carbon nanotube columnar structure is within the above range, the carbon nanotube columnar structure can be easily peeled and transferred to another adherend without causing cohesive failure.

In the carbon nanotube composite structure that can be used in the isolation method of the present invention, the shear bond strength to glass at 25 ° C. at the tip of the carbon nanotube columnar structure is preferably 10 N / cm ² or more, more preferably 15 to 200 N / cm. ² , more preferably 20 to 200 N / cm ² , particularly preferably 25 to 200 N / cm ² , most preferably 30 to 200 N / cm ² . When the tip of the carbon nanotube columnar structure has a shear adhesive force to glass at 25 ° C. within the above range, the carbon nanotube columnar structure can be easily peeled and transferred to another adherend without causing cohesive failure of the carbon nanotube columnar structure.

  The carbon nanotube columnar structure may be a single layer or a multilayer. Further, the diameter, specific surface area, and density of the carbon nanotube columnar structure can be set to any appropriate values.

  As the shape of the carbon nanotube columnar structure, it is sufficient that the cross section thereof has any appropriate shape. For example, the cross section may be substantially circular, elliptical, n-gonal (n is an integer of 3 or more), and the like.

  The length of the carbon nanotube columnar structure can be set to any appropriate length. The length of the carbon nanotube columnar structure is preferably 300 to 10000 μm, more preferably 400 to 1000 μm, and still more preferably 500 to 1000 μm. When the length of the carbon nanotube columnar structure is within the above range, the carbon nanotube columnar structure can be easily peeled and transferred to another adherend without causing cohesive failure of the carbon nanotube columnar structure.

  The carbon nanotube columnar structure provided in the carbon nanotube composite structure that can be used in the isolation method of the present invention has an arbitrary distribution width of the wall number distribution, a mode value of the wall number distribution, and a relative frequency of the mode value. Appropriate values can be taken. Here, the distribution width of the layer number distribution refers to the difference between the maximum number and the minimum number of layers of the carbon nanotube columnar structure. What is necessary is just to measure these layer numbers and layer number distribution by arbitrary appropriate apparatuses. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, 20 or more carbon nanotube columnar structures may be measured by SEM or TEM.

  The carbon nanotube columnar structure provided in the carbon nanotube composite structure that can be used in the isolation method of the present invention can take, for example, the following first preferred embodiment or second preferred embodiment.

<First Preferred Embodiment of Carbon Nanotube Columnar Structure>
In the first preferred embodiment of the carbon nanotube columnar structure provided in the carbon nanotube composite structure that can be used in the isolation method of the present invention, the distribution width of the wall number distribution is preferably 10 or more, The relative frequency of the mode value is preferably 25% or less. The distribution width of the layer number distribution is more preferably 10 to 30 layers, still more preferably 10 to 25 layers, and particularly preferably 10 to 20 layers. The maximum number of layers in the layer number distribution is preferably 5 to 30 layers, more preferably 10 to 30 layers, still more preferably 15 to 30 layers, and particularly preferably 15 to 25 layers. The number is preferably 1 to 10 layers, more preferably 1 to 5 layers. The relative frequency of the mode value of the layer number distribution is more preferably 1 to 25%, further preferably 5 to 25%, particularly preferably 10 to 25%, and most preferably 15 to 25%. The mode value of the layer number distribution is preferably in 2 to 10 layers, more preferably in 3 to 10 layers. The carbon nanotube columnar structure provided in the carbon nanotube composite structure that can be used in the isolation method of the present invention adopts the embodiment as described above, so that the carbon nanotube columnar structure can be easily deposited without causing cohesive failure. It can be peeled and transferred to the body.

<Second Preferred Embodiment of Carbon Nanotube Columnar Structure>
In a second preferred embodiment of the carbon nanotube columnar structure provided in the carbon nanotube composite structure that can be used in the isolation method of the present invention, the mode value of the layer number distribution is preferably present in 10 layers or less, The relative frequency of the mode value is preferably 30% or more. The mode value of the layer number distribution is more preferably 9 layers or less, still more preferably 1 to 9 layers, particularly preferably 2 to 8 layers, and most preferably 3 to 8 layers. Exists. The maximum number of layers in the layer number distribution is preferably 1 to 20 layers, more preferably 2 to 15 layers, and further preferably 3 to 10 layers. The minimum number of layers in the layer number distribution is preferably 1 to 10 layers, more preferably 1 to 5 layers. The relative frequency of the mode value of the layer number distribution is more preferably 30 to 100%, further preferably 30 to 90%, particularly preferably 30 to 80%, and most preferably 30 to 70%. The mode value of the layer number distribution is preferably in 1 to 10 layers, more preferably in 2 to 8 layers, and still more preferably in 2 to 6 layers. The carbon nanotube columnar structure provided in the carbon nanotube composite structure that can be used in the isolation method of the present invention adopts the embodiment as described above, so that the carbon nanotube columnar structure can be easily deposited without causing cohesive failure. It can be peeled and transferred to the body.

  Any appropriate base material can be adopted as the base material included in the carbon nanotube composite structure that can be used in the isolation method of the present invention as long as the base material is made of a high heat resistant material. For example, the base material which consists of inorganic materials, and the base material which consists of metal materials are mentioned. Preferably, it is a base material made of a metal material, more preferably a base material made of a metal material having a melting point of 700 ° C. or higher, more preferably from copper or a copper alloy containing 50% by weight or more of copper. It is the base material which becomes.

  An example of the inorganic material is graphite.

  Examples of the metal material having a melting point of 700 ° C. or higher include, for example, copper, nickel, iron, chromium, zinc, tin, silicon, manganese, magnesium, titanium, zirconium, silver, cobalt, brass, white copper, bronze, western white, and kovar alloy. Invar (Ni36Fe64), Elinvar (Ni36Fe52Co12), stainless steel and the like.

  The copper alloy containing 50% by weight or more of copper may contain any appropriate other metal as long as it contains 50% by weight or more of copper as long as the effect of the present invention can be exhibited. Examples of such other metals include nickel, iron, chromium, zinc, tin, silicon, manganese, magnesium, titanium, zirconium, silver, and cobalt. Specific examples of the copper alloy include brass, white copper, bronze, white, Kovar alloy, and the like.

  The Young's modulus of the substrate contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention is preferably 250 GPa or less, more preferably 1 to 200 GPa, and still more preferably 10 to 150 GPa.

  If the Young's modulus of the base material contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention is 250 GPa or less, it can have excellent flexibility.

  The substrate included in the carbon nanotube composite structure that can be used in the isolation method of the present invention has a thermal conductivity of preferably 1 to 5000 W / mK or more, more preferably 10 to 4000 W / mK, and still more preferably. Is 50 to 3000 W / mK, particularly preferably 150 to 3000 W / mK. Provided is a carbon nanotube composite structure capable of exhibiting better thermal conductivity when the thermal conductivity of the substrate contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention is within the above range. Can do.

The base material contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention has an electrical conductivity of preferably 1.0 × 10 ⁷ m ⁻¹ · Ω ⁻¹ or more, more preferably 1.0. × 10 ⁷ to 50 × 10 ⁷ m ⁻¹ · Ω ⁻¹ , more preferably 1.0 × 10 ^{7 to} 20 × 10 ⁷ m ⁻¹ · Ω ⁻¹ , and particularly preferably 1.0 × 10 9. ⁷ to 10 × 10 ⁷ m ⁻¹ · Ω ⁻¹ . When the conductivity of the base material contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention is within the above range, it is possible to provide a carbon nanotube composite structure that can exhibit more excellent conductivity. .

  Arbitrary appropriate thickness can be employ | adopted for the thickness of the base material contained in the carbon nanotube composite structure which can be used with the isolation method of this invention according to the objective. Preferably it is 200 micrometers or less, More preferably, it is 0.01-200 micrometers, More preferably, it is 0.1-100 micrometers, Most preferably, it is 1-100 micrometers. By setting the thickness of the base material contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention within the above range, a carbon nanotube composite structure having more excellent flexibility can be provided.

Any appropriate material can be adopted as the intermediate layer contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention. An inorganic oxide is preferable. Examples of such inorganic oxides include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), silica-alumina (SiO ₂ -Al ₂ O ₃ ), titania (TiO ₂ ), zirconia (ZrO), and magnesia. (MgO). Such inorganic oxides may be used alone or in combination of two or more.

  The thickness of the intermediate layer contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention is preferably 10 nm or more, more preferably 10 nm to 100 nm, and still more preferably 10 to 50 nm. By making the thickness of the intermediate layer contained in the carbon nanotube composite structure usable in the isolation method of the present invention within the above range, the carbon nanotube columnar structure can be easily peeled off to another adherend without causing cohesive failure. Can be transcribed.

  Any appropriate method can be adopted as a method for producing the intermediate layer contained in the carbon nanotube composite structure that can be used in the isolation method of the present invention. For example, the method of forming a thin film on a base material by sputtering is mentioned.

  The carbon nanotube composite structure that can be used in the isolation method of the present invention preferably has an intermediate layer formed on the surface of a substrate, a catalyst layer is formed on the intermediate layer, and a chemical vapor deposition method (Chemical Vapor Deposition). Obtained by growing carbon nanotubes on the catalyst layer by a CVD method).

  Any appropriate apparatus can be adopted as an apparatus that can be used when producing a carbon nanotube composite structure that can be used in the isolation method of the present invention. For example, as a thermal CVD apparatus, as shown in FIG. 2, a hot wall type configured by surrounding a cylindrical reaction vessel with a resistance heating type electric tubular furnace can be cited. In that case, for example, a heat-resistant quartz tube is preferably used as the reaction vessel.

  Any appropriate method can be adopted as a method of forming the catalyst layer on the intermediate layer. For example, a method of depositing a metal catalyst by EB (electron beam), sputtering, or the like, a method of applying a suspension of metal catalyst fine particles on a substrate, and the like can be mentioned.

  Any appropriate catalyst can be used as the catalyst (catalyst layer material) that can be used in the production of the carbon nanotube composite structure that can be used in the isolation method of the present invention. For example, metal catalysts, such as iron, cobalt, nickel, gold, platinum, silver, copper, are mentioned.

  The thickness of the catalyst layer is preferably 0.01 to 20 nm, more preferably 0.1 to 10 nm, still more preferably 0.1 to 5 nm, and particularly preferably 1 to 3 nm. When the thickness of the catalyst layer is within the above range, the adhesive force between the plurality of carbon nanotube columnar structures and the substrate can be more fully expressed.

  Any appropriate carbon source can be used as a carbon source used as a raw material for carbon nanotubes, which can be used in producing a carbon nanotube composite structure that can be used in the isolation method of the present invention. For example, hydrocarbons such as methane, ethylene, acetylene, and benzene; alcohols such as methanol and ethanol;

  The isolation method of the present invention is a method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure having a plurality of carbon nanotube columnar structures on a substrate, the carbon nanotube composite structure described above The carbon nanotube columnar structure provided in the carbon nanotube composite structure is adhered to the adherend by pressure bonding, and then the substrate provided with the intermediate layer is peeled at a peeling angle of 45 ° or more. Thus, the carbon nanotube columnar structure is peeled and transferred without causing cohesive failure.

  Any appropriate method can be adopted as a method of pressure bonding the tip of the carbon nanotube columnar structure provided in the carbon nanotube composite structure to the adherend. For example, there is a method in which a carbon nanotube composite structure is placed on an adherend so that the tip of the carbon nanotube columnar structure provided in the carbon nanotube composite structure faces downward, and is bonded by pressure bonding. .

  Any appropriate method can be adopted as a method of pressure bonding. For example, a method of pressure bonding only by its own weight or a method of pressure bonding by an external force using a roller or the like can be mentioned.

  As the adherend, any appropriate material can be adopted as long as the carbon nanotube columnar structure can be transferred.

  As a peel method, a substrate provided with an intermediate layer is peeled from a laminate obtained by bonding an adherend and a carbon nanotube composite structure to obtain an adherend to which a carbon nanotube columnar structure is transferred. Like that.

  In the isolation method of the present invention, the peel angle of the peel is set to 45 ° or more. The peeling angle is preferably 45 ° to 180 °, more preferably 60 ° to 180 °, and still more preferably 90 ° to 180 °. By setting the peel angle of the peel within the above range, the carbon nanotube columnar structure can be easily peeled and transferred to another adherend without causing cohesive failure. In addition, the peeling angle said to this invention means the angle which a base material and a to-be-adhered body make at the time of peeling.

  According to the isolation method of the present invention, the carbon nanotube columnar structure is not cohesively broken even when a long or large area substrate is used as well as when a small area substrate is used. It can be peeled and transferred to other adherends easily and uniformly without any unevenness.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on weight (mass).

≪Measurement method of adhesion between substrate and carbon nanotube columnar structure≫
The glass (MATUNAMI slide glass 27 mm × 56 mm) was placed so that the tips of the plurality of carbon nanotube columnar structures in the carbon nanotube composite structure cut into a 1 cm ² unit area were in contact with each other, and a 5 kg roller was reciprocated once. The tip of the carbon nanotube was crimped to glass. Then, it was left for 30 minutes. Unit area after confirming that the peeled surface is an interface between the base material provided with the intermediate layer and the carbon nanotube columnar structure by pulling with a tensile tester (Instron Tensil Tester) at 25 ° C. and a tensile speed of 50 mm / min. The shear adhesive strength per hit was determined.

≪Measurement of Young's modulus≫
The deflection (hmm) generated when a load (PN) is applied to the center of a plate-like sample (d × b × Lmm) supported at both ends as shown in FIG. N / m ² ) was calculated from the following formula.
E = (1/4) (L ³ / (d ³ · b)) (P / h) × 10 ⁶

≪Evaluation of thermal conductivity≫
Using a “LE / TCM-FA8510B” apparatus manufactured by Rigaku Corporation, a laser flash method adopts thermal diffusivity (t1 / 2 method) and specific heat (extrapolation method) as measurement items, and a measurement temperature of 25 The thermal conductivity of the substrate at ° C was measured.

≪Evaluation of conductivity≫
The volume resistivity was measured as an evaluation of conductivity. The volume resistivity in the vertical direction was measured using the apparatus shown in FIG. That is, a base material is cut out to 10 mmφ and a thickness of 35 μm, and both ends of the base material are sandwiched between conductive rubber electrodes (Ag-containing, volume resistivity = 5.07 × 10 ⁻³ Ωcm), and on the upper rubber electrode A weight (65 g) of SUS was placed, voltage (1.0 V) was applied, and volume resistivity (ρV) was obtained from the amount of current (volume resistivity ρV (Ωcm) = [voltage (V) / current (A ]] × [area (cm ² ) / thickness (cm)]). The reciprocal of the measured volume resistivity (ρV) was defined as conductivity.

≪Evaluation of peeling transfer≫
It is placed on glass (MATUNAMI slide glass 27 mm × 56 mm) so that the tips of a plurality of carbon nanotube columnar structures in a carbon nanotube composite structure with an area of 20 mm × 50 mm are in contact with each other, and a carbon nanotube is reciprocated once by a 5 kg roller. The tip of was crimped to glass. Then, it was left for 30 minutes. The base material was peeled at a predetermined peeling angle, and only the base material was removed to obtain a glass / carbon nanotube structure. The transfer state at that time was evaluated.

[Example 1]
An Al ₂ O ₃ thin film (thickness 20 nm) was formed on a copper base material (manufactured by Nippon Mining & Metals Co., Ltd., JTCS, thickness 35 μm) by a sputtering apparatus (manufactured by ULVAC, RFS-200). This _Al 2 _{O 3} thin film, a sputtering apparatus (ULVAC Ltd., RFS-200) were in by further depositing a Fe thin film (having a thickness of 1 nm) to form a catalyst layer.
Next, the copper substrate with the catalyst layer is cut and placed in a 30 mmφ quartz tube, and a helium / hydrogen (120/80 sccm) mixed gas maintained at a moisture content of 350 ppm is allowed to flow through the quartz tube for 30 minutes to replace the inside of the tube. did. Thereafter, the inside of the tube was gradually raised to 765 ° C. in 35 minutes using an electric tubular furnace, and stabilized at 765 ° C. After leaving at 765 ° C. for 10 minutes, while maintaining the temperature, the tube was filled with a mixed gas of helium / hydrogen / ethylene (105/80/15 sccm, moisture content 350 ppm) and left for 30 minutes to place the carbon nanotubes on the substrate. To obtain a carbon nanotube composite structure (1).
The carbon nanotube columnar structure (1) in the obtained carbon nanotube composite structure (1) has a length of 750 μm, the mode value of the layer number distribution exists in two layers, and the relative value of the mode value The frequency was 65%.
As shown in FIG. 5, the carbon nanotube composite structure (1) is placed on the glass as the adherend (MATUNAMI slide glass 27 mm × 56 mm) so that the tip of the carbon nanotube columnar structure (1) faces downward. And bonded by pressing with a 5 kg roller. Next, the base material provided with the intermediate layer was peeled at a peeling angle of 45 °.
The results are summarized in Table 1.

[Example 2]
An Al ₂ O ₃ thin film (thickness 15 nm) is formed on a brass base material (manufactured by Nikko Metals, C2680, thickness 35 μm, copper: zinc = 66: 34 (weight ratio)) by a sputtering device (ULVAC, RFS-200). A carbon nanotube composite structure (2) was obtained in the same manner as in Example 1 except that.
The carbon nanotube columnar structure (2) in the obtained carbon nanotube composite structure (2) has a length of 710 μm, the mode value of the layer number distribution exists in two layers, and the relative value of the mode value The frequency was 68%.
As shown in FIG. 5, the carbon nanotube composite structure (2) is placed on the glass as the adherend (MATUNAMI slide glass 27 mm × 56 mm) so that the tip of the carbon nanotube columnar structure (2) faces downward. And bonded by pressing with a 5 kg roller. Next, the base material provided with the intermediate layer was peeled at a peeling angle of 90 °.
The results are summarized in Table 1.

Example 3
The carbon nanotube composite structure was carried out in the same manner as in Example 1 except that an Al ₂ O ₃ thin film (thickness 20 nm) was formed on SUS304 (Morimatsu Kogyo Co., Ltd., thickness 35 μm) by a sputtering apparatus (ULVAC, RFS-200). Body (3) was obtained.
The carbon nanotube columnar structure (3) in the obtained carbon nanotube composite structure (3) has a length of 640 μm, the mode value of the layer number distribution exists in two layers, and the relative value of the mode value The frequency was 60%.
As shown in FIG. 5, the carbon nanotube composite structure (3) is placed on the glass as the adherend (MATUNAMI slide glass 27 mm × 56 mm) so that the tip of the carbon nanotube columnar structure (3) faces downward. And bonded by pressing with a 5 kg roller. Next, the base material provided with the intermediate layer was peeled at a peeling angle of 90 °.
The results are summarized in Table 1.

[Comparative Example 1]
The same operation as in Example 1 was performed except that the peeling angle was changed from 45 ° to 20 °.
The results are summarized in Table 1.

[Comparative Example 2]
A carbon nanotube composite structure (C2) was obtained in the same manner as in Example 2 except that the substrate was a silicon wafer (manufactured by KST, thickness 525 μm).
The carbon nanotube columnar structure (C2) in the obtained carbon nanotube composite structure (C2) has a length of 750 μm, the mode value of the layer number distribution exists in two layers, and the relative value of the mode value The frequency was 71%.
As shown in FIG. 5, the carbon nanotube composite structure (C2) is placed on the glass (MATUNAMI slide glass 27 mm × 56 mm) as the adherend so that the tip of the carbon nanotube columnar structure (C2) faces downward. And bonded by pressing with a 5 kg roller. Next, the base material provided with the intermediate layer was peeled at a peeling angle of 30 °.
The results are summarized in Table 1.

[Comparative Example 3]
Except that an Al ₂ O ₃ thin film (thickness 3 nm) was formed on a copper base material (manufactured by Nikko Metal Co., Ltd., JTCS, thickness 35 μm) by a sputtering apparatus (manufactured by ULVAC, RFS-200), A carbon nanotube composite structure (C3) was obtained.
The carbon nanotube columnar structure (C3) in the obtained carbon nanotube composite structure (C3) has a length of 680 μm, the mode value of the layer number distribution exists in two layers, and the relative value of the mode value The frequency was 63%.
As shown in FIG. 5, the carbon nanotube composite structure (C3) is placed on the glass as the adherend (MATUNAMI slide glass 27 mm × 56 mm) so that the tip of the carbon nanotube columnar structure (C3) faces downward. And bonded by pressing with a 5 kg roller. Next, the base material provided with the intermediate layer was peeled at a peeling angle of 90 °.
The results are summarized in Table 1.

[Comparative Example 4]
The same operation as in Example 3 was performed except that the peeling angle was changed from 90 ° to 30 °.
The results are summarized in Table 1.

  As shown in the results of Table 1, according to the isolation method of the present invention, the carbon nanotube columnar structure can be peeled and transferred to another adherend easily and uniformly without cohesive failure. .

  The isolation method of this invention can be utilized suitably in manufacture of adhesive members, such as an adhesive sheet and an adhesive film.

DESCRIPTION OF SYMBOLS 1 Base material 2 Carbon nanotube columnar structure 3 Intermediate | middle layer 10 Carbon nanotube composite structure 20 Adhering body

Claims (5)

A method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure comprising a plurality of carbon nanotube columnar structures on a substrate,
The carbon nanotube composite structure includes an intermediate layer between the base material and the carbon nanotube columnar structure, the base material has a thickness of 200 μm or less, and the intermediate layer has a thickness of 10 nm to 100 nm. The adhesion between the base material provided with the intermediate layer and the carbon nanotube columnar structure is less than 5 N / cm ² , and the shearing adhesive force to glass at 25 ° C. at the tip of the carbon nanotube columnar structure is 10 N / cm ² or more. And
After the tip of the carbon nanotube columnar structure provided in the carbon nanotube composite structure is pressure-bonded and adhered to an adherend, the base material provided with the intermediate layer is peeled at a peeling angle of 45 ° or more, whereby the carbon Exfoliating and transferring nanotube columnar structures without cohesive failure,
A method for isolating a carbon nanotube columnar structure from a carbon nanotube composite structure.   The isolation method according to claim 1, wherein the base material is a base material made of a metal material having a melting point of 700 ° C. or higher.   The isolation method according to claim 2, wherein the metal material is made of either copper or a copper alloy containing 50% by weight or more of copper.   The isolation method according to any one of claims 1 to 3, wherein the intermediate layer is made of an inorganic oxide. The isolation method according to any one of claims 1 to 4, wherein the intermediate layer has a thickness of 10 nm or more.