WO2017159661A1

WO2017159661A1 - Conveying fixing jig

Info

Publication number: WO2017159661A1
Application number: PCT/JP2017/010140
Authority: WO
Inventors: 将太郎増田; 智昭市川; 前野　洋平; 義治畠山
Original assignee: 日東電工株式会社
Priority date: 2016-03-18
Filing date: 2017-03-14
Publication date: 2017-09-21

Abstract

Provided is a conveying fixing jig that has excellent grip strength, does not readily contaminate a workpiece (object being conveyed), and has exceptional heat resistance. This conveying fixing jig is provided with a first base member, a carbon nanotube assembly, and an adhesive layer arranged between the first base member and the carbon nanotube assembly. The first base member and the carbon nanotube assembly are bonded with the adhesive layer interposed therebetween, and the ratio of the linear expansion coefficient of the first base member and the linear expansion coefficient of the adhesive layer (adhesive layer/base member) is 0.7-1.8.

Description

Transport fixture

The present invention relates to a conveyance fixing jig.

When transporting materials, intermediate products, products, etc. (hereinafter also referred to as workpieces) in the manufacturing process of semiconductor elements, etc., the workpieces are transported using a transport base such as a movable arm or a movable table. (For example, refer to Patent Documents 1 and 2). When performing such conveyance, the member (conveyance fixing jig) on which the workpiece is placed is required to have a strong grip force so that the workpiece does not shift during conveyance. In addition, such a demand is increasing year by year together with a demand for speeding up the manufacturing process.

However, the conventional conveyance fixing jig has a problem that the workpiece is held by an elastic material such as a resin, and the elastic material is likely to adhere and remain on the workpiece. In addition, an elastic material such as a resin has a problem that heat resistance is low, and grip force is reduced under a high temperature environment.

If a material such as ceramics is used for the conveyance fixture, contamination of the workpiece is prevented and the temperature dependence of the grip force is reduced. However, the conveyance fixture composed of such a material has a problem that the gripping force is essentially low and the workpiece cannot be sufficiently held even at room temperature.

Also, as a method of holding the workpiece under a high temperature environment, there are a method of suctioning under reduced pressure, a method of fixing the workpiece by the shape of the conveyance fixing jig (for example, chucking, counterboring, etc.) and the like. However, the method of adsorbing under reduced pressure is effective only under an air atmosphere and cannot be employed under vacuum in a CVD process or the like. Further, in the method of fixing the workpiece by the shape of the conveyance fixing jig, there is a problem that the workpiece is damaged or particles are generated due to contact between the workpiece and the conveyance fixing jig.

JP 2001-351196 A JP 2013-138152 A

An object of the present invention is to provide a conveyance fixing jig which has a high grip force, hardly contaminates a workpiece (conveyed object) and is excellent in heat resistance.

The conveyance fixture of the present invention includes a first base material, a carbon nanotube aggregate, and an adhesive layer disposed between the first base material and the carbon nanotube aggregate. 1 substrate and the aggregate of carbon nanotubes are bonded via the adhesive layer, and the ratio of the linear expansion coefficient of the first substrate to the linear expansion coefficient of the adhesive layer (adhesive layer / Base material) is 0.7 to 1.8.
In one embodiment, the aggregate of carbon nanotubes is formed on a second base material, and the first base material and the second base material are bonded via the adhesive layer. Has been.
In one embodiment, the adhesive constituting the adhesive layer is an inorganic adhesive or a carbon adhesive.
In one embodiment, the inorganic adhesive is a ceramic adhesive.
In one embodiment, the elastic modulus change of the adhesive layer is 50% or less when the conveyance fixture is left at 450 ° C. for 1 hour.
In one embodiment, the adhesive layer has a linear expansion coefficient of 5 ppm / ° C. to 12 ppm / ° C.
In one embodiment, the material which comprises the said 1st base material is an alumina.
In one embodiment, the coefficient of static friction at 23 ° C. with respect to the glass surface of the carbon nanotube aggregate surface is 1 to 50.
According to another situation of this invention, the manufacturing method of the said conveyance fixing jig is provided. In this manufacturing method, an adhesive is applied on a first substrate to form an application layer, an aggregate of carbon nanotubes is disposed on the application layer, the application layer is cured, and an adhesive layer is formed. Forming and bonding the first substrate and the aggregate of carbon nanotubes via the adhesive layer, the linear expansion coefficient of the first substrate, and the line of the adhesive layer The ratio of the expansion coefficient (adhesive layer / base material) is 0.7 to 1.8.

According to the present invention, it is possible to provide a conveyance fixing jig that has a high grip force, hardly contaminates a workpiece (conveyed object), and is excellent in heat resistance. More specifically, the conveyance fixing jig of the present invention includes a carbon nanotube aggregate disposed on the first base material, and the workpiece can be fixed by the carbon nanotube aggregate. High, difficult to contaminate work piece (conveyed object) and excellent in heat resistance. Furthermore, the first base material and the carbon nanotube aggregate are joined via an adhesive layer, and the ratio of the linear expansion coefficient of the first base material to the linear expansion coefficient of the adhesive layer (adhesive layer / By setting the base material to a specific range, the aggregate of carbon nanotubes is hardly detached even at high temperatures, and the work piece (conveyed object) can be fixed well.

It is a schematic sectional drawing of the conveyance fixing jig by one Embodiment of this invention. It is a schematic sectional drawing of the conveyance fixing jig by another embodiment of this invention. It is a schematic perspective view of the conveyance fixing jig by one Embodiment of this invention. It is a schematic sectional drawing of the manufacturing apparatus of the carbon nanotube aggregate in one embodiment of this invention.

A. Overview Figure 1 of the transport fixture is a schematic cross-sectional view of the transport fixture according to one embodiment of the present invention. The conveyance fixture 100 includes a first base material 10, a carbon nanotube aggregate 31, and an adhesive layer 20 disposed between the first base material 10 and the carbon nanotube aggregate 31. The first base material 10 and the carbon nanotube aggregate 31 are bonded via the adhesive layer 20. The carbon nanotube aggregate 31 may be provided on the entire surface of the first base material 10 or may be provided on a part of the surface of the first base material 10.

The carbon nanotube aggregate 31 is composed of a plurality of carbon nanotubes 32. The carbon nanotubes 32 are oriented in the direction of the length L, and the carbon nanotube aggregate 31 is configured as a fibrous columnar structure. The carbon nanotubes 32 are preferably oriented in a substantially vertical direction with respect to the first base material 10. Here, the “substantially perpendicular direction” means that the angle with respect to the surface of the substrate 20 is preferably 90 ° ± 20 °, more preferably 90 ° ± 15 °, and further preferably 90 ° ± 10 °. And particularly preferably 90 ° ± 5 °.

FIG. 2 is a schematic cross-sectional view of a conveyance fixing jig according to another embodiment of the present invention. In the conveyance fixing jig 200 of FIG. 2, the carbon nanotube aggregate 31 is formed on the second base material 33. The adhesive layer 20 is disposed on the side of the second base material 33 where the carbon nanotube aggregate 31 is not formed. The first base material 10 and the second base material 32 are joined via the adhesive layer 20.

The conveyance fixing jig of the present invention can be suitably used in, for example, a semiconductor element manufacturing process, an optical member manufacturing process, and the like. More specifically, the conveyance fixing jig of the present invention is a material, an intermediate product, a product, etc. (specifically, a semiconductor material, a wafer) between processes in a semiconductor element manufacturing process or within a predetermined process. , Chips, films, etc.). Moreover, it can be used for transferring a glass substrate or the like between processes in manufacturing an optical member or within a predetermined process. Hereinafter, materials, intermediate products, products, and the like that can be transported by the transport apparatus of the present invention may be referred to as workpieces or transported objects.

The coefficient of static friction at 23 ° C. with respect to the glass surface of the carbon nanotube assembly side surface of the conveyance fixture is preferably 1.0 or more. The upper limit value of the static friction coefficient is preferably 50. If it is such a range, the conveyance fixing jig excellent in grip property can be obtained. In addition, it cannot be overemphasized that the said conveyance fixing jig with a large friction coefficient with respect to the glass surface can express strong grip property also to the mounted object (for example, semiconductor wafer) comprised from materials other than glass.

B. 1st base material The said 1st base material functions as a conveyance base material at the time of conveying a semiconductor material, an electronic material, etc. Examples of the form of the first base material include a transport arm, a transport table, a transport ring, a transport guide rail, a storage cassette, a hook, and a transport frame. The size and shape of the first substrate can be appropriately selected according to the purpose. The first substrate may be a part of a transfer arm, a transfer table, a transfer ring, a transfer guide rail, a storage cassette, a hook, a transfer frame, and the like. An example of the case where the first substrate is a transfer arm is shown in the schematic perspective view of FIG. In the transport fixing jig 100 of FIG. 3, a carbon nanotube aggregate 31 is disposed at one end of the first base material 10 as a transport arm. Note that FIG. 1 described above is a cross-sectional view taken along the line II of the conveyance fixing jig 100.

Any appropriate material can be adopted as the material constituting the first base material. In one embodiment, a ceramic material such as alumina or silicon nitride; a heat resistant material such as stainless steel is used as a material constituting the conveyance base material. Preferably, alumina is used.

The linear expansion coefficient of the first base material is preferably 2 ppm / ° C. to 12 ppm / ° C., more preferably 3 ppm / ° C. to 12 ppm / ° C., further preferably 5 ppm / ° C. to 12 ppm / ° C., More preferably, it is 6 ppm / ° C. to 9 ppm / ° C. If it is such a range, the conveyance fixing jig which can function satisfactorily also under high temperature can be obtained. In this specification, the linear expansion coefficient can be measured by a thermomechanical analyzer (TMA).

The volume expansion coefficient of the first base material is preferably 15 ppm / ° C. to 36 ppm / ° C., more preferably 18 ppm / ° C. to 27 ppm / ° C. If it is such a range, the conveyance fixing jig which can function satisfactorily also under high temperature can be obtained.

The ratio of the linear expansion coefficient of the first base material to the linear expansion coefficient of the adhesive layer (adhesive layer / base material) is 0.7 to 1.8. In the present invention, by setting the ratio of the linear expansion coefficients in such a range, the aggregate of carbon nanotubes is hardly detached even at a high temperature (for example, 450 ° C.), and the workpiece (conveyed object) is A conveyance fixing jig that can be fixed satisfactorily can be obtained. By using the carbon nanotube aggregate, it is possible to improve the tackiness and cleanliness at high temperature, and further, as described above, the linear expansion coefficient of the adhesive layer (ratio to the linear expansion coefficient of the first substrate) It is a great achievement of the present invention that the carbon nanotube aggregate, which is an aggregate of fibrous materials, can be satisfactorily bonded to the first base material by appropriately adjusting. The ratio of the linear expansion coefficient of the first base material to the linear expansion coefficient of the adhesive layer (adhesive layer / base material) is preferably 0.8 to 1.7. If it is such a range, the said effect will become more remarkable.

C. Adhesive Layer The adhesive layer can be composed of any appropriate adhesive. As the adhesive constituting the adhesive layer, an inorganic adhesive or a carbon adhesive is preferably used. These adhesives are preferable in terms of excellent heat resistance. Among these, an inorganic adhesive or a carbon adhesive is preferable.

Examples of the inorganic adhesive include ceramic adhesive and silica adhesive.

Ceramic adhesive is an adhesive that can exhibit adhesiveness by curing a curing component such as alkali metal silicate, phosphate, and metal alkoxide. Preferably, a ceramic adhesive containing an alkali metal silicate or phosphate (eg, aluminum phosphate) is used as the curing component.

The silica-based adhesive is an adhesive that can exhibit adhesiveness by curing silica-based curing components such as silicic acid fine particles having silanol groups on the particle surface and organopolysiloxane. As the silica-based curing component, for example, fused silica, ultrafine silica (for example, particle size: 10 nm to 100 nm), silicone-based materials such as organopolysiloxane, silane compound, and organosilicon compound can be used.

The ceramic adhesive and the silica-based adhesive may further include a curing agent (curing accelerator) and / or a filler (filler). The ceramic adhesive can also include any suitable dispersion medium.

Examples of the curing agent (curing accelerator) used in combination with the alkali metal silicate in the ceramic adhesive include oxides or hydroxides such as zinc, magnesium, and calcium; And phosphates such as aluminum and zinc; borate salts such as calcium, barium and magnesium; and the like. Examples of the curing agent (curing accelerator) used in combination with the above phosphate include oxides or hydroxides such as magnesium, calcium, zinc, and aluminum; silicates such as magnesium and calcium; Group II boric acid Salt; and the like.

Examples of the filler (filler) include alumina, silica, zirconia, and magnesium oxide. The linear expansion coefficient of the adhesive layer is adjusted by one embodiment, the type and / or addition amount of the filler (filler).

Any appropriate solvent is used as the dispersion medium. As the solvent, an aqueous solvent or an organic solvent may be used. The aqueous solvent is preferable in that it can form a higher heat-resistant adhesive layer. Moreover, an organic solvent is preferable at the point which is excellent in affinity with a carbon nanotube aggregate.

The components in the ceramic adhesive can be appropriately selected according to the material constituting the first substrate, the material constituting the second substrate, the desired heat-resistant temperature, and the like. In one embodiment, when the first substrate is made of alumina, a metal alkoxide is used as a curing component, alumina is used as a filler, and an alcohol such as methanol is used as a dispersion medium.

In one embodiment, the carbon-based adhesive includes a binder, a carbon-based filler, and a solvent. Examples of the binder include alkali metal silicate, phosphate, metal alkoxide and the like, and alkali metal silicate is preferable. Examples of the carbon filler include graphite powder and carbon black, and carbon black is preferable. Examples of the solvent include water.

In another embodiment, the carbon-based adhesive may include a predetermined resin and a carbon-based filler. As the resin, a resin that becomes non-graphitizable carbon by heating can be used. Examples of such a resin include a phenol resin and a polycarbodiimide resin. Examples of the carbon filler include graphite powder and carbon black. The carbon-based adhesive may contain any appropriate solvent. Examples of the solvent contained in the carbon-based adhesive include water, phenol, formaldehyde, ethanol, and the like.

The linear expansion coefficient of the adhesive layer is preferably 5 ppm / ° C. to 12 ppm / ° C., more preferably 6 ppm / ° C. to 9 ppm / ° C. Within such a range, it is possible to obtain a conveyance fixing jig in which the aggregate of carbon nanotubes is not easily detached even at high temperatures. In addition, the linear expansion coefficient of an adhesive bond layer is a linear expansion coefficient after hardening an adhesive agent.

The volume expansion coefficient of the adhesive layer is preferably 15 ppm / ° C. to 36 ppm / ° C., more preferably 18 ppm / ° C. to 27 ppm / ° C. Within such a range, it is possible to obtain a conveyance fixing jig in which the aggregate of carbon nanotubes is not easily detached even at high temperatures. The volume expansion coefficient of the adhesive layer is a volume expansion coefficient after the adhesive is cured.

Change in elastic modulus of the adhesive layer (adhesive layer elastic modulus after 450 ° C x 1 hour-adhesive layer immediately after formation of adhesive layer (immediately after adhesive curing)) when the conveyance fixture is left at 450 ° C for 1 hour The agent layer elastic modulus) is preferably 50% or less, more preferably 30% or less. By forming an adhesive layer with little change in properties at high temperatures in this way, it is possible to obtain a conveyance fixing jig in which the aggregate of carbon nanotubes is not easily detached even at high temperatures. The elastic modulus can be determined from the slope of the load-displacement curve and the projected area of the indenter on the sample by single indentation measurement using a nanoindenter. In addition, the measurement conditions of the single indentation measurement by a nano indenter are as follows.
Apparatus: Hysitron Inc. Made by Triboindenter
Working indenter: Berkovich (triangular pyramid type)
Measuring method: Single indentation measurement Measuring temperature: 25 ° C (room temperature)
Pushing depth setting: 5μm

The thickness of the adhesive layer is preferably 0.1 μm to 100 μm, more preferably 0.5 μm to 50 μm, and further preferably 1.0 μm to 20 μm. If it is such a range, a carbon nanotube aggregate or a 2nd base material and a 1st base material can be firmly joined via this adhesive bond layer.

D. Carbon nanotube aggregate The carbon nanotube aggregate is composed of a plurality of carbon nanotubes.

The length of the carbon nanotube is preferably 50 μm to 3000 μm, more preferably 200 μm to 2000 μm, still more preferably 300 μm to 1500 μm, particularly preferably 400 μm to 1000 μm, and most preferably 500 μm to 1000 μm. is there. Within such a range, it is possible to form a conveyance fixing jig that has a high grip force and that hardly contaminates the object to be conveyed.

The aggregate of carbon nanotubes can take, for example, embodiments described later (first embodiment and second embodiment).

The first embodiment of the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes have a plurality of layers, the distribution width of the number distribution of the carbon nanotubes is 10 or more, and the number distribution of the carbon nanotubes The relative frequency of the mode value is 25% or less. By adopting such a configuration of the carbon nanotube aggregate, it is possible to form a conveyance fixing jig that has a high grip force and is difficult to contaminate the object to be conveyed.

In the first embodiment, the distribution width of the number distribution of carbon nanotubes is preferably 10 or more, more preferably 10 to 30 layers, still more preferably 10 to 25 layers, and particularly preferably. Is 10 to 20 layers. By adjusting the distribution width of the number distribution of the carbon nanotubes within such a range, it is possible to form a conveyance fixing jig that has a high grip force and hardly contaminates the object to be conveyed.

The “distribution width” of the number distribution of carbon nanotubes refers to the difference between the maximum number and the minimum number of carbon nanotube layers. By adjusting the distribution width of the number distribution of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and further, the carbon nanotubes have excellent adhesive properties. It can be the carbon nanotube aggregate shown.

The number of carbon nanotube layers and the number distribution of the carbon nanotubes may be measured by any appropriate apparatus. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes may be taken out from the aggregate of carbon nanotubes and measured by SEM or TEM to evaluate the number of layers and the number distribution of the layers.

In the first embodiment, the maximum number of carbon nanotube layers is preferably 5 to 30 layers, more preferably 10 to 30 layers, and even more preferably 15 to 30 layers. Particularly preferred are 15 to 25 layers. By adjusting the maximum number of the carbon nanotube layers within such a range, it is possible to form a conveyance fixing jig that has a high grip force and is difficult to contaminate the object to be conveyed.

In the first embodiment, the minimum number of carbon nanotube layers is preferably 1 to 10 layers, and more preferably 1 to 5 layers. By adjusting the minimum number of the carbon nanotube layers within such a range, it is possible to form a conveyance fixing jig that has a high grip force and hardly contaminates the object to be conveyed.

In the first embodiment, by adjusting the maximum number and the minimum number of the carbon nanotube layers within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area. The carbon nanotubes can be a carbon nanotube aggregate exhibiting excellent adhesive properties.

In the first embodiment, the relative frequency of the mode value of the number distribution of the carbon nanotubes is preferably 25% or less, more preferably 1% to 25%, and further preferably 5% to 25%. Yes, particularly preferably 10% to 25%, most preferably 15% to 25%. By adjusting the relative frequency of the mode value of the wall number distribution of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area. It can be an aggregate of carbon nanotubes exhibiting excellent adhesive properties.

In the first embodiment, the mode value of the number distribution of carbon nanotubes preferably exists in the number of layers 2 to 10 and more preferably in the number of layers 3 to 10. By adjusting the mode of the number distribution of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes have excellent adhesive properties. It can become the carbon nanotube aggregate which shows.

In the first embodiment, as the shape of the carbon nanotube, it is sufficient that its cross section 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.

In the first embodiment, the length of the carbon nanotube is preferably 50 μm or more, more preferably 100 μm to 3000 μm, still more preferably 300 μm to 1500 μm, still more preferably 400 μm to 1000 μm, and particularly preferably. Is 500 μm to 1000 μm. By adjusting the length of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes can exhibit excellent adhesion properties. It can be a body.

In the first embodiment, the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm. By adjusting the diameter of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area. Furthermore, the carbon nanotube aggregates exhibit excellent adhesive properties. Can be.

In the first embodiment, the specific surface area and density of the carbon nanotubes can be set to any appropriate values.

The second embodiment of the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes have a plurality of layers, and the mode of the number distribution of the carbon nanotubes is present in the number of layers of 10 or less. The relative frequency of the mode value is 30% or more. By adopting such a configuration of the carbon nanotube aggregate, it is possible to form a conveyance fixing jig that has a high grip force and is difficult to contaminate the object to be conveyed.

In the second embodiment, the distribution width of the number distribution of carbon nanotubes is preferably 9 or less, more preferably 1 to 9 layers, still more preferably 2 to 8 layers, and particularly preferably. Is 3 to 8 layers. By adjusting the distribution width of the number distribution of the carbon nanotubes within such a range, it is possible to form a conveyance fixing jig that has a high grip force and hardly contaminates the object to be conveyed.

In the second embodiment, the maximum number of carbon nanotube layers is preferably 1 to 20 layers, more preferably 2 to 15 layers, and further preferably 3 to 10 layers. By adjusting the maximum number of the carbon nanotube layers within such a range, it is possible to form a conveyance fixing jig that has a high grip force and is difficult to contaminate the object to be conveyed.

In the second embodiment, the minimum number of carbon nanotube layers is preferably 1 to 10 layers, and more preferably 1 to 5 layers. By adjusting the minimum number of the carbon nanotube layers within such a range, it is possible to form a conveyance fixing jig that has a high grip force and hardly contaminates the object to be conveyed.

In the second embodiment, by adjusting the maximum number and the minimum number of the carbon nanotube layers within the above ranges, the carbon nanotubes can have excellent mechanical properties and a high specific surface area. The carbon nanotubes can be a carbon nanotube aggregate exhibiting excellent adhesive properties.

In the second embodiment, the relative frequency of the mode value of the number distribution of the carbon nanotubes is preferably 30% or more, more preferably 30% to 100%, and further preferably 30% to 90%. Particularly preferably 30% to 80%, most preferably 30% to 70%. By adjusting the relative frequency of the mode value of the wall number distribution of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area. It can be an aggregate of carbon nanotubes exhibiting excellent adhesive properties.

In the second embodiment, the mode value of the number distribution of carbon nanotubes is preferably present in the number of layers of 10 or less, more preferably in the number of layers from 1 to 10, and more preferably in the number of layers. The number of layers is from 2 to 8 and particularly preferably from 2 to 6 layers. By adjusting the mode of the number distribution of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes have excellent adhesive properties. It can become the carbon nanotube aggregate which shows.

In the second embodiment, as the shape of the carbon nanotube, the cross section may have 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.

In the second embodiment, the length of the carbon nanotube is preferably 50 μm or more, more preferably 550 μm to 3000 μm, still more preferably 600 μm to 2000 μm, still more preferably 650 μm to 1000 μm, and particularly preferably. Is 700 μm to 1000 μm. By adjusting the length of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area, and the carbon nanotubes can exhibit excellent adhesion properties. It can be a body.

In the second embodiment, the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm. By adjusting the diameter of the carbon nanotubes within the above range, the carbon nanotubes can have excellent mechanical properties and a high specific surface area. Furthermore, the carbon nanotube aggregates exhibit excellent adhesive properties. Can be.

In the second embodiment, the specific surface area and density of the carbon nanotubes can be set to any appropriate values.

In one embodiment, at least a portion including the tip of the carbon nanotube is coated with an inorganic material. The “part including at least the tip” as used herein means a portion including at least the tip of the carbon nanotube, that is, the tip of the carbon nanotube opposite to the first substrate.

All of the above carbon nanotubes may be covered with an inorganic material at least at a portion including the tip, or a portion thereof may be covered with an inorganic material at least a portion including the tip. The content ratio of the carbon nanotube in which at least the portion including the tip of the carbon nanotube is coated with an inorganic material is preferably 50 wt% to 100 wt%, more preferably 60 wt% to 100 wt%. % By weight, more preferably 70% by weight to 100% by weight, further preferably 80% by weight to 100% by weight, particularly preferably 90% by weight to 100% by weight, and most preferably substantially 100% by weight. If it is such a range, the conveyance fixing jig | tool which has high grip force and cannot contaminate a to-be-conveyed object can be formed.

The thickness of the coating layer is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, further preferably 7 nm or more, particularly preferably 9 nm or more, and most preferably 10 nm. That's it. The upper limit of the thickness of the coating layer is preferably 50 nm, more preferably 40 nm, still more preferably 30 nm, particularly preferably 20 nm, and most preferably 15 nm. Within such a range, it is possible to form a conveyance fixing jig that has a high grip force and that hardly contaminates the object to be conveyed.

The length of the coating layer is preferably 1 nm to 1000 nm, more preferably 5 nm to 700 nm, still more preferably 10 nm to 500 nm, particularly preferably 30 nm to 300 nm, and most preferably 50 nm to 100 nm. is there. If it is such a range, the conveyance fixing jig | tool which has high grip force and cannot contaminate a to-be-conveyed object can be formed.

As said inorganic material, arbitrary appropriate inorganic materials can be employ | adopted in the range which does not impair the effect of this invention. Examples of such inorganic materials include SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , TiO ₂ , MgO, Cu, Ag, and Au.

Any appropriate method can be adopted as a method for producing a carbon nanotube aggregate.

As a method for producing a carbon nanotube aggregate, for example, a chemical vapor phase is formed in which a catalyst layer is formed on a flat plate, a carbon source is filled in a state where the catalyst is activated by heat, plasma, etc., and carbon nanotubes are grown. Examples thereof include a method of producing an aggregate of carbon nanotubes oriented substantially vertically from a flat plate by a growth method (Chemical Vapor Deposition: CVD method).

Any appropriate flat plate can be adopted as a flat plate that can be used in the method for producing a carbon nanotube aggregate. For example, the material which has smoothness and the high temperature heat resistance which can endure manufacture of a carbon nanotube is mentioned. Examples of such materials include quartz glass, silicon (such as a silicon wafer), and a metal plate such as aluminum.

Any appropriate apparatus can be adopted as an apparatus for producing the carbon nanotube aggregate. For example, as a thermal CVD apparatus, as shown in FIG. 4, a hot wall type configured by surrounding a cylindrical reaction vessel with a resistance heating type electric tubular furnace, and the like can be mentioned. In that case, for example, a heat-resistant quartz tube is preferably used as the reaction vessel.

Any suitable catalyst can be used as a catalyst (catalyst layer material) that can be used in the production of the carbon nanotube aggregate. For example, metal catalysts, such as iron, cobalt, nickel, gold, platinum, silver, copper, are mentioned.

When producing the carbon nanotube aggregate, an alumina / hydrophilic film may be provided between the flat plate and the catalyst layer as necessary.

Any appropriate method can be adopted as a method for producing the alumina / hydrophilic film. For example, it can be obtained by forming a SiO ₂ film on a flat plate, depositing Al, and then oxidizing it by raising the temperature to 450 ° C. According to such a manufacturing method, _Al 2 _{O 3} interacts with the SiO ₂ film hydrophilic, different _Al 2 _{O 3} surface particle diameters than those deposited _Al 2 _{O 3} directly formed. Even if Al is heated up to 450 ° C. and oxidized without forming a hydrophilic film on a flat plate, Al ₂ O ₃ surfaces having different particle diameters may not be formed easily. Moreover, even if a hydrophilic film is prepared on a flat plate and Al ₂ O ₃ is directly deposited, Al ₂ O ₃ surfaces having different particle diameters may not be easily formed.

The thickness of the catalyst layer that can be used in the production of the carbon nanotube aggregate is preferably 0.01 nm to 20 nm, more preferably 0.1 nm to 10 nm in order to form fine particles. By adjusting the thickness of the catalyst layer that can be used in the production of the carbon nanotube aggregate within the above range, the formed carbon nanotubes can have both excellent mechanical properties and a high specific surface area. It can be a carbon nanotube aggregate exhibiting excellent adhesive properties.

Any appropriate method can be adopted as a method for forming the catalyst 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 flat plate, and the like can be mentioned.

Any appropriate carbon source can be used as the carbon source that can be used for the production of the carbon nanotube aggregate. For example, hydrocarbons such as methane, ethylene, acetylene, and benzene; alcohols such as methanol and ethanol;

Arbitrary appropriate temperature can be employ | adopted as manufacturing temperature in manufacture of a carbon nanotube aggregate. For example, in order to form catalyst particles that can sufficiently exhibit the effects of the present invention, the temperature is preferably 400 ° C to 1000 ° C, more preferably 500 ° C to 900 ° C, and further preferably 600 ° C to 800 ° C. .

E. Second Base Material The second base material may be a flat plate used when forming the carbon nanotube aggregate. That is, the conveyance fixing jig provided with the second base material is obtained by laminating the flat plate on which the carbon nanotube aggregate is formed as it is on the first base material.

F. Manufacturing method of conveyance fixing jig The conveyance fixing jig can be manufactured by any appropriate method. In one embodiment, the adhesive constituting the adhesive layer is applied on the first substrate, the carbon nanotube aggregate is disposed on the applied layer formed by the application, and then the applied layer is cured. Thereby, an adhesive bond layer can be formed and a conveyance fixing jig can be obtained. Examples of the method of arranging the carbon nanotube aggregate on the coating layer include a method of transferring the carbon nanotube aggregate to the coating layer from the flat plate with the carbon nanotube aggregate obtained by the method described in the above section D. It is done.

In another embodiment, a flat plate (second substrate) in which an adhesive constituting an adhesive layer is applied on a first substrate, and an aggregate of carbon nanotubes is formed on the coating layer formed by the application. ), And then the coating layer is cured to obtain a transport fixture.

Any appropriate method can be adopted as an adhesive application method. Examples of the application method include application using a comma coater or a die coater, application using a dispenser, application using a squeegee, and the like.

Any appropriate method may be adopted as a method for curing the adhesive application layer. A method of curing by heating is preferably used. The curing temperature can be appropriately set according to the type of adhesive. The curing temperature is, for example, 90 ° C. to 400 ° C. In one embodiment, when a carbon-based adhesive is used as the adhesive, it is baked at a high temperature after curing. The firing temperature is preferably higher than the use temperature of the adhesive, for example, 350 ° C. to 3000 ° C.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Various evaluations and measurements were performed by the following methods.

[Production Example 1] Production of aggregate of carbon nanotubes Al ₂ O ₃ by a sputtering apparatus (trade name “CFS-4ES” manufactured by Shibaura Mechatronics Co., Ltd.) on a silicon flat plate (manufactured by VALQUA EFT Co., Ltd., thickness 700 μm) A thin film (degree of ultimate vacuum: 8.0 × 10 ⁻⁴ Pa, sputtering gas: Ar, gas pressure: 0.50 Pa, growth rate: 0.12 nm / sec, thickness: 20 nm) was formed. On this Al ₂ O ₃ thin film, an Fe thin film was further formed as a catalyst layer (sputtering gas: Ar, gas pressure: 0.75 Pa, growth rate: 0) using a sputtering apparatus (trade name “CFS-4ES” manufactured by Shibaura Mechatronics). .012 nm / sec, thickness: 1.0 nm).
Thereafter, this flat plate was placed in a 30 mmφ quartz tube, and a mixed gas of helium / hydrogen (105/80 sccm) maintained at a moisture content of 700 ppm was allowed to flow through the quartz tube for 30 minutes to replace the inside of the tube. Thereafter, the inside of the tube was heated to 765 ° C. using an electric tubular furnace and stabilized at 765 ° C. While maintaining the temperature at 765 ° C., a mixed gas of helium / hydrogen / ethylene (105/80/15 sccm, moisture content 700 ppm) was filled into the tube and left for 60 minutes to form a carbon nanotube aggregate on the flat plate. It was.

[Example 1]
An adhesive (manufactured by Three Bond, trade name “TB3732”, binder: metal alkoxide, filler: alumina) was applied onto the first base material (manufactured by Ceramics; linear expansion coefficient: 8 ppm / ° C.) using a squeegee. .
The carbon nanotube aggregate obtained in Production Example 1 was collected from the flat plate and placed on the adhesive coating layer. At this time, it arrange | positioned so that the side which was in contact with the flat plate of the carbon nanotube aggregate may contact the adhesive application layer.
Then, a weight is placed on the opposite side of the carbon nanotube aggregate from the adhesive coating layer through a clean wafer, and a load of 50 g / cm ² is applied for 1 minute to bring the carbon nanotube aggregate and the adhesive coating layer into close contact with each other. I let you.
Next, the laminate obtained as described above was placed at room temperature for 1 hour and further in an environment of 100 ° C. for 30 minutes to cure the adhesive.
As described above, a conveyance fixing jig composed of the first base material / adhesive layer (thickness: 10 μm) / carbon nanotube aggregate was obtained.

[Example 2]
Instead of adhesive (trade name “TB3732” manufactured by ThreeBond Co., Ltd., binder: metal alkoxide, filler: alumina), adhesive (trade name “G7716” manufactured by EM Japan Co., Ltd., binder: silicate, filler: carbon) A laminate was obtained in the same manner as in Example 1 except that was used. The laminate is placed at room temperature for 2 hours and further in an environment of 100 ° C. for 2 hours to cure the adhesive, and from the first substrate / adhesive layer (thickness: 10 μm) / carbon nanotube aggregate A configured transport fixture was obtained.

[Example 3]
Instead of adhesive (trade name “TB3732”, manufactured by ThreeBond Co., Ltd., binder: metal alkoxide, filler: alumina), adhesive (trade name “RG-57-2-3”, manufactured by Ein Co., Ltd.); binder: organopolysiloxane A laminate was obtained in the same manner as in Example 1 except that filler: silicon dioxide (silica), titanium dioxide (titania), potassium titanate, solvent: ethylene glycol dibutyl ether was used. The laminate is placed in an environment at 80 ° C. for 30 minutes, further in an environment at 150 ° C. for 30 minutes, and further in an environment at 400 ° C. for 2 hours to cure and fire the adhesive. A conveyance fixing jig composed of a material / adhesive layer (thickness: 20 μm) / carbon nanotube aggregate was obtained.

[Example 4]
The first base material (made of ceramics; linear expansion coefficient: 3 ppm / ° C.) was used instead of the first base material (made of ceramics; linear expansion coefficient: 8 ppm / ° C.), and an adhesive (Three Bond Co., Ltd.) Manufactured, trade name “TB3732”, binder: metal alkoxide, filler: alumina, adhesive (trade name “RG-12-6-2, manufactured by Ein Co., Ltd.); binder: organopolysiloxane, filler: silicon dioxide A laminate was obtained in the same manner as in Example 1 except that (silica), titanium dioxide (titania), solvent: ethylene glycol monobutyl ether) were used. The laminate is placed in an environment at 80 ° C. for 30 minutes, further in an environment at 150 ° C. for 30 minutes, and further in an environment at 400 ° C. for 2 hours to cure and fire the adhesive. A conveyance fixing jig composed of a material / adhesive layer (thickness: 20 μm) / carbon nanotube aggregate was obtained.

[Comparative Example 1]
Instead of the adhesive (trade name “TB3732” manufactured by Three Bond Co., Ltd., binder: metal alkoxide, filler: alumina), the adhesive (trade name “Aron Ceramic C” manufactured by Toagosei Co., Ltd.), binder: silicate, filler: A laminate was obtained in the same manner as in Example 1 except that (silica) was used. The laminate was placed at room temperature for 24 hours, at 90 ° C. for 2 hours, and further at 150 ° C. for 1 hour to cure the adhesive, and the first substrate / adhesive layer (thickness) : 10 μm) / a conveyance fixing jig composed of an aggregate of carbon nanotubes was obtained.

[Comparative Example 2]
Instead of the adhesive (trade name “TB3732” manufactured by Three Bond Co., Ltd., binder: metal alkoxide, filler: alumina), the adhesive (trade name “Aron Ceramic E” manufactured by Toa Gosei Co., Ltd.), binder: silicate, filler: A laminate was obtained in the same manner as in Example 1 except that zirconia and silica) were used. The laminate was placed at room temperature for 24 hours, at 90 ° C. for 2 hours, and further at 150 ° C. for 1 hour to cure the adhesive, and the first substrate / adhesive layer (thickness) : 10 μm) / a conveyance fixing jig composed of an aggregate of carbon nanotubes was obtained.

[Evaluation]
The conveyance fixtures obtained in the examples and comparative examples were subjected to the following evaluation. The results are shown in Table 1.

(1) Linear expansion coefficient The linear expansion coefficient was measured with a thermomechanical analyzer (TMA) (manufactured by Shimadzu Corporation, "TMA-60").

(2) Adhesion strength About the conveyance fixture immediately after manufacture, the adhesion strength (tensile shear strength) between the first substrate and the carbon nanotube aggregate was measured at room temperature (23 ° C.). The adhesion strength was measured by using an autograph (manufactured by Shimadzu Corporation, trade name “Shimadzu Autograph AG-120 kN”) at a tensile speed of 50 mm / min.
Further, the adhesion strength of the conveyance fixture after the high temperature treatment (450 ° C. for 1 hour) was measured by the same method as described above.

DESCRIPTION OF SYMBOLS 10 First base material 20 Adhesive layer 31 Carbon nanotube aggregate 32 Carbon nanotube 33

Second base material

100, 200 Conveying and fixing jig

Claims

A first base, a carbon nanotube aggregate, and an adhesive layer disposed between the first base and the carbon nanotube aggregate,
The first substrate and the carbon nanotube aggregate are bonded via the adhesive layer,
The ratio of the linear expansion coefficient of the first base material to the linear expansion coefficient of the adhesive layer (adhesive layer / base material) is 0.7 to 1.8.
Transport fixture.
The aggregate of carbon nanotubes is formed on a second substrate;
The first substrate and the second substrate are bonded via the adhesive layer,
The conveyance fixing jig according to claim 1.
The conveyance fixing jig according to claim 1 or 2, wherein the adhesive constituting the adhesive layer is an inorganic adhesive or a carbon adhesive.
The conveyance fixing jig according to claim 3, wherein the inorganic adhesive is a ceramic adhesive.
The conveyance fixing jig according to any one of claims 1 to 4, wherein the elastic modulus change of the adhesive layer is 50% or less when the conveyance fixing jig is left at 450 ° C for 1 hour.
The conveyance fixing jig according to any one of claims 1 to 5, wherein the adhesive layer has a linear expansion coefficient of 5 ppm / ° C to 12 ppm / ° C.
The conveyance fixing jig according to any one of claims 1 to 6, wherein a material constituting the first base material is alumina.
The conveyance fixture according to any one of claims 1 to 7, wherein a coefficient of static friction at 23 ° C with respect to the glass surface of the carbon nanotube aggregate surface is 1 to 50.
On the first substrate, an adhesive is applied to form a coating layer,
Disposing a carbon nanotube aggregate on the coating layer,
The coating layer is cured to form an adhesive layer;
Bonding the first substrate and the aggregate of carbon nanotubes via the adhesive layer,
The ratio of the linear expansion coefficient of the first base material to the linear expansion coefficient of the adhesive layer (adhesive layer / base material) is 0.7 to 1.8.
The manufacturing method of the conveyance fixing jig in any one of Claim 1 to 8.