KR102291539B1 - Carbon nanotube-containing composition and method for producing a thermosetting product of carbon nanotube-containing composition - Google Patents

Abstract

An object of the present invention is to enable conduction inspection even when the wiring of a circuit device to be inspected is narrowed in pitch and the wiring is thinned. It is to provide the manufacturing method of the composition which can be used as an electroconductive member, and the thermosetting material of each composition.
(A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin; ), the absolute value of the difference is 70 ° C. or less, the composition containing carbon nanotubes.

Description

Carbon nanotube-containing composition and method for producing a thermosetting product of carbon nanotube-containing composition

The present invention can, for example, be electrically connected to an electrode to be inspected of a circuit device to conduct conduction inspection of the inspected electrode, and can be used as a conductive member for conduction inspection that does not contain a metal component as a conductive material. The present invention relates to a composition and a method for producing a thermosetting product thereof.

BACKGROUND ART Conventionally, an electrical connector called a contact probe is used to confirm normal continuity of wirings such as semiconductor packages. In recent years, with the miniaturization of electronic components, such as semiconductors, wirings, such as a semiconductor package, are narrowing in pitch, and wiring is also becoming thin. Accordingly, there is a demand for miniaturization of the contact probe. However, the contact probe is a precision mechanical part including a spring, a metal tube, and the like, and there is a limit to its miniaturization. Accordingly, in some cases, conductive members for conduction inspection such as an anisotropic conductive sheet are used as electrical connectors instead of contact probes as the pitch of wirings such as semiconductor packages is narrowed.

As a conductive member for conduction inspection such as the anisotropic conductive sheet, for example, a core sheet including a plurality of metal wires arranged in parallel on the same plane in a sheet-like member is provided in a plurality of forms, and the direction of the metal wires included in the core sheet Anisotropic conductivity obtained by stacking two or more core sheets in a form in which the directions of metal wires included in other core sheets coincide with each other, and cutting the laminate in directions perpendicular to the longitudinal direction of the metal wires A sheet has been proposed (Patent Document 1).

However, in the conductive member for conduction inspection of Patent Document 1, in order to cope with narrower pitch of wirings such as semiconductor packages, it is necessary to narrow the distance between the metal wires arranged in parallel by that much. However, when the space between the metal wires is narrowed and arranged, there is a fear that the metal wires come into contact with each other. Therefore, as the conductive member for conduction inspection of Patent Document 1, there is also a limit in responding to narrower pitch of wirings such as semiconductor packages.

Further, as another example of the conductive member for the continuity inspection, an insulating sheet body made of an elastic polymer material having a plurality of through holes formed therein, and a conductive path formed in the plurality of through holes, the conductive member being contained in the elastic polymer material is formed. An anisotropically conductive sheet having a negative portion has been proposed (Patent Document 2). As the conductive member contained in the elastic polymer material, conductive metal particles are used.

However, in the conductive member for conduction inspection in Patent Document 2, in order to cope with narrower pitch of wirings such as semiconductor packages, it is necessary to reduce the width of the through-holes filled with the elastic polymer material containing conductive particles. It is necessary to use the small electrically-conductive particle with a uniform particle diameter as electroconductive particle. As a result, it becomes easy to aggregate electroconductive particle, and it becomes difficult to fill a through hole with electroconductive particle uniformly, As a result, there exists a problem that sufficient electroconductivity cannot be obtained.

In addition, in patent documents 1 and 2, in order to provide electroconductivity to the electroconductive member for conduction|electrical_connection test|inspection, in all, the metal member is used. When a metallic material is used for the electroconductive member for continuity|electrical_connection test|inspection, it may become a problem that the electrode or circuit device which is an inspection object is contaminated with a metallic material. Then, development of the electroconductive member for a conduction test|inspection which does not use a metal component as an electroconductive member is calculated|required.

[Prior art literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 6026321

[Patent Document 2] Japanese Patent No. 5018612

In view of the above, it is an object of the present invention to have excellent conductivity and to not contain a metal component as a conductive member that allows conducting a continuity test even when the wiring of the circuit device to be inspected becomes narrower and the wiring becomes thinner. It is to provide the manufacturing method of the composition and the thermosetting material of each composition which can be used as a conductive member for the non-conductive test|inspection.

In order to solve the above problems, there is provided a composition containing carbon nanotubes. The summary of the structure of this invention is as follows.

[1] Initiation of thermosetting reaction between (B) the boiling point (T1) of the organic solvent and the (C) thermosetting resin, comprising (A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin The carbon nanotube-containing composition, wherein the absolute value of the difference in temperature (T2) is 70°C or less.

[2] In the (A) carbon nanotube, the intensity ratio G/D of the G band and the D band of the Raman spectrum obtained by Raman spectroscopy is 1.0 or more, and the (A) carbon nanotube has an average length of 1.0 The carbon nanotube-containing composition according to [1], which is not less than μm.

[3] The carbon nanotube-containing composition according to [1] or [2], wherein the (C) thermosetting resin is an epoxy resin.

[4] The carbon nanotube according to any one of [1] to [3], wherein the (A) carbon nanotube is contained in an amount of 0.1 mass% or more and 15 mass% or less in 100 mass% of the total solid component of the carbon nanotube-containing composition. containing composition.

[5] A thermosetting product of the carbon nanotube-containing composition according to any one of [1] to [4].

[6] The thermosetting product according to [5], wherein the volume resistivity is 0.1 Ω·m or less.

[7] (A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin, wherein the (B) boiling point (T1) of the organic solvent and the thermosetting reaction of the (C) thermosetting resin are initiated a step of applying a carbon nanotube-containing composition having an absolute value of a difference from the temperature T2 of 70° C. or less on the film; and

A thermosetting product of a carbon nanotube-containing composition comprising the steps of: volatilizing the (B) organic solvent by heat-treating the carbon nanotube-containing composition, and further (C) initiating a thermosetting reaction of the thermosetting resin; manufacturing method.

[8] The manufacturing method according to [7], wherein the thermosetting material constitutes a conductive sheet having a thickness of 1 µm or more and 50 µm or less.

In the composition of the present invention, carbon nanotubes, not metal components, are used as conductive materials. Therefore, in the composition of the present invention, a metal component is not blended as a conductive material. In addition, in this specification, the thermosetting reaction initiation temperature (T2) means a temperature measured as follows: a thermosetting resin is put into a sample container of a differential scanning calorimeter (DSC), and the temperature increase rate is under a nitrogen atmosphere as an airtight container The temperature is raised from room temperature to 300°C at 5°C/mｎn, the curing exothermic behavior is shown by DSC measurement, and the reaction initiation temperature is determined. As shown in FIG. 1, the first rising temperature (DSC on set) of the curing exothermic peak is obtained from the obtained DSC chart, and this is called the thermosetting reaction initiation temperature (T2).

Carbon nanotubes have a property that, when aggregation, ie, dispersibility, decreases, properties such as conductivity decrease. On the other hand, according to the aspect of the composition of the present invention, an organic solvent is blended as a dispersion medium of carbon nanotubes and a thermosetting resin, and the absolute value of the difference between the boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the thermosetting resin Since it is limited to this 70 degreeC or less, in the thermosetting process of a composition, volatilization of an organic solvent and thermosetting of a thermosetting resin are synchronized. From the above, even if the composition of the present invention is subjected to a thermosetting treatment, it is possible to maintain the excellent dispersibility of the carbon nanotubes in the thermosetting product. Therefore, by thermosetting the composition of the present invention in a predetermined form, even if the wiring of the circuit device to be inspected is narrowed in pitch and the wiring is thinned, the conduction inspection can be performed appropriately and the conductivity is improved. It is possible to obtain an excellent conductive member for conduction inspection.

In addition, according to the aspect of the composition of the present invention, by using carbon nanotubes rather than a metallic component as the conductive material, it is possible to prevent the electrode or circuit device to be inspected from being contaminated by the metallic material during the conduction inspection.

According to the aspect of the composition of the present invention, when the intensity ratio G/D of the G band and the D band of the Raman spectrum of the carbon nanotube is 1.0 or more, and the average length of the carbon nanotube is 1.0 μm or less, the thermosetting product of the composition It is possible to further increase the conductivity of

According to the aspect of the composition of the present invention, the carbon nanotubes are contained in an amount of 0.1 mass % or more and 15 mass % or less in 100 mass % of the total solid components included in the composition, so that excellent conductivity for thermosetting materials and excellent carbon nanotubes are present. It imparts dispersibility and it is possible to obtain good formability.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing explaining the measuring method of the thermosetting reaction initiation temperature.

Hereinafter, the carbon nanotube-containing composition, which is the composition of the present invention, will be described in detail. The composition of the present invention includes (A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin, wherein (B) a boiling point (T1) of the organic solvent and (C) a thermosetting resin The present invention relates to a carbon nanotube-containing composition in which the absolute value of the difference from the thermosetting reaction initiation temperature (T2) is 70° C. or less.

(Carbon Nanotubes)

Although it does not specifically limit as a carbon nanotube, It is possible to use a well-known carbon nanotube. Specifically, for example, single-walled carbon nanotubes in which one graphite sheet is wound on one layer, multi-walled carbon nanotubes wound around multiple layers, and the like can be mentioned. As the carbon nanotube-containing composition of the present invention, the diameter (fiber diameter) and average length of the carbon nanotubes are not particularly limited, but carbon nanotubes with a long average length are used from the viewpoints of conductivity, moldability, etc. It is preferable, and it is particularly preferable to use single-walled carbon nanotubes with a long average length. Further, if necessary, a combination of single-walled carbon nanotubes and multi-walled carbon nanotubes may be used.

The lower limit of the average length of the single-walled carbon nanotubes is preferably 1.0 µm, more preferably 5.0 µm, and particularly preferably 10 µm from the viewpoint of further improving conductivity. On the other hand, the upper limit of the average length of the single-walled carbon nanotubes is preferably 200 µm, more preferably 150 µm, particularly preferably 100 µm, from the viewpoint of preventing deterioration of the surface appearance when a molded article or a film is formed.

The lower limit of the diameter of the single-walled carbon nanotubes is preferably 0.5 nm, particularly preferably 1.0 nm, from the viewpoint of suppressing aggregation when the thermosetting resin and the organic solvent are dispersed. On the other hand, the upper limit of the diameter of the single-walled carbon nanotubes is preferably 15 nm, particularly preferably 10 nm, from the viewpoint of improving the mechanical properties by the nano-effect.

The aspect ratio of the single-walled carbon nanotubes is not particularly limited, and can be appropriately selected from the viewpoints of conductivity, dispersibility, and the like. Among these, as for the lower limit of the aspect ratio of single-walled carbon nanotubes, conductivity is ensured with a small number of electrical contacts, and the number of electrical contacts with other carbon nanotubes in one carbon nanotube increases, making it possible to form a high-dimensional electrical network From the viewpoint of saying that, 1000 is preferable, and 5000 is particularly preferable. On the other hand, the upper limit of the aspect ratio of the single-walled carbon nanotubes is preferably 200000, particularly preferably 100000, from the viewpoint of obtaining excellent dispersibility in an organic solvent and a thermosetting resin.

Although the intensity ratio G/D (hereinafter referred to as [G/D band ratio]) of the G band and the D band of the Raman spectrum obtained by Raman spectroscopy of the single-walled carbon nanotube is not particularly limited, the G/D band ratio From a viewpoint of further improving electroconductivity, 1.0 is preferable, 4.0 is more preferable, and, as for the lower limit of, 6.0 is especially preferable. On the other hand, although it is so preferable that the upper limit of G/D band ratio is high, for example, 100 is mentioned. Here, G band, 1590cm in the Raman ^spectrum is a Raman shift seen in the vicinity of ^1, derived from graphite. ^{The D band is a Raman shift seen in the vicinity of 135 nm -1} in the Raman spectrum, and is derived from defects in amorphous carbon or graphite. That is, the higher the G/D ratio, which is the ratio of the peak heights of the G band and the D band, is, the higher the linearity and crystallinity, and the higher the quality. Moreover, in the Raman spectroscopy method of a solid, a measurement value may be disturbed by sampling. Therefore, the G/D band ratio is measured by Raman spectroscopy at at least three places and other places, and the value of the additive average is referred to as the G/D ratio in the present specification.

The multi-walled carbon nanotube may be a double-walled carbon nanotube (DWNT) or a multi-layered carbon nanotube (MWNT) having three or more layers. The lower limit of the average length of the multi-walled carbon nanotubes is preferably 1.0 µm, more preferably 5.0 µm, and particularly preferably 10 µm, from the viewpoint of further improving the conductivity, similarly to the above-mentioned single-walled carbon nanotubes. On the other hand, the upper limit of the average length of the multi-walled carbon nanotubes is preferably 200 µm, more preferably 150 µm, from the viewpoint of preventing deterioration of the surface appearance of the molded article or film at one time, similar to the above-mentioned single-walled carbon nanotubes, 100 μm is particularly preferred.

The lower limit of the diameter of the multi-walled carbon nanotubes is preferably 0.5 nm, particularly preferably 1.0 nm, from the viewpoint of suppressing aggregation when dispersed in a thermosetting resin and an organic solvent, similarly to the single-walled carbon nanotubes. On the other hand, the upper limit of the diameter of the multi-walled carbon nanotubes is preferably 15 nm, particularly preferably 10 nm, from the viewpoint of improving the mechanical properties due to the nano-effect, similarly to the above-mentioned single-walled carbon nanotubes.

The aspect ratio of the multilayer carbon nanotube is not particularly limited, and can be appropriately selected from the viewpoints of conductivity, dispersibility, and the like. At this time, the lower limit of the aspect ratio of the multi-walled carbon nanotube is the same as the above-mentioned single-walled carbon nanotube. In addition to ensuring conductivity with a small number of electrical contacts, one carbon nanotube has a large number of electrical contacts with other carbon nanotubes. From the viewpoint of being able to form a high-dimensional electrical network, 1000 is preferable, and 5000 is particularly preferable. On the other hand, the upper limit of the aspect ratio of the multi-walled carbon nanotubes is preferably 200000, particularly preferably 100000, from the viewpoint of obtaining excellent dispersibility in organic solvents and thermosetting resins, similarly to the above-mentioned single-walled carbon nanotubes.

Although the G/D ratio of the multi-walled carbon nanotubes is not particularly limited, the lower limit of the G/D ratio is preferably 1.0, more preferably 4.0, from the viewpoint of further improving the conductivity, as in the above-mentioned single-walled carbon nanotubes. and 6.0 is particularly preferred. On the other hand, the upper limit of the G/D band ratio is preferably as high as it is as in the above single-walled carbon nanotubes, but, for example, 100 is exemplified.

The content of the carbon nanotubes is not particularly limited, but the lower limit thereof is 100% by mass of the total solid component of the carbon nanotube-containing composition from the viewpoint of imparting excellent conductivity with a volume resistivity of 0.1 Ω·nm or less to the thermosetting product. 0.1 mass % is preferable, 1.0 mass % is more preferable, 3.0 mass % is still more preferable, and 5.0 mass % is especially preferable. On the other hand, the upper limit of the carbon nanotube content is preferably 15% by mass based on 100% by mass of the total solid component of the carbon nanotube-containing composition from the viewpoint of obtaining excellent dispersibility of the carbon nanotubes in the thermosetting product, and is easily From the viewpoint of being able to form in a sheet shape and easily obtaining a sheet-like thermosetting product having excellent conductivity, 12% by mass is preferable, more preferably 10% by mass, among 100% by mass of the total solid component of the carbon nanotube-containing composition, 7.0 mass % is especially preferable. In addition, [total solid component] means the component which removed volatile components, such as an organic solvent, from a carbon nanotube containing composition.

Although the BET specific surface area of a carbon nanotube is not specifically limited, From a viewpoint of electroconductivity, it is preferable that it is ^{600 m<2>/g or more.} In addition, [BET specific surface area] means the nitrogen adsorption specific surface area measured using the BET method.

(organic solvent)

The organic solvent is blended as a dispersion medium for carbon nanotubes and a thermosetting resin to be described later. In the composition of the present invention, the type of the organic solvent is selected so that the absolute value of the difference between the boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the thermosetting resin described later is 70° C. or less. Therefore, according to the value of the thermosetting reaction initiation temperature (T2) of the thermosetting resin to be blended, the type of the organic solvent is selected so that the boiling point (T1) of the organic solvent is in the range of T2-70°C≤T1≤T2+70°C.

By controlling the absolute value of the difference between the boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the thermosetting resin to be 70° C. or less, in the thermosetting treatment of the carbon nanotube-containing composition, the organic solvent is volatilized. The thermosetting of the thermosetting resin is synchronized. From the above, even if the carbon nanotube-containing composition of the present invention is subjected to thermosetting, it is possible to maintain the excellent dispersibility of the carbon nanotube in the thermosetting product. Therefore, by thermosetting the carbon nanotube-containing composition of the present invention, it is possible to obtain uniform conductivity throughout the entire thermosetting process, and it is possible to obtain excellent conductivity with a volume resistivity of 0.1 Ω·cm or less, Even if the wiring of the circuit device to be inspected has a narrow pitch and the wiring is thinned, it is possible to appropriately conduct a conduction inspection and obtain a conductive member for conduction inspection.

When the absolute value of the difference between the boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the thermosetting resin is 70° C. or less, the boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the thermosetting resin are also Although not particularly limited, from the viewpoint of further improving the dispersibility of carbon nanotubes during thermosetting, it is preferable that the boiling point (T1) of the organic solvent is higher than the thermosetting reaction initiation temperature (T2) of the thermosetting resin. Moreover, if the absolute value of the difference of the boiling point (T1) of an organic solvent and the thermosetting reaction initiation temperature (T2) of a thermosetting resin is 70 degrees C or less, although it will not specifically limit, 65 degrees C or less is especially preferable.

The content of the organic solvent in the carbon nanotube-containing composition is not particularly limited, but preferably 80 mass% or more and 98 mass% or less, and 85 mass% or more and 95 mass% or less in the carbon nanotube-containing composition Especially preferred.

(thermosetting resin)

A thermosetting resin functions as binder resin. Examples of the thermosetting resin include epoxy resins, other phenolic resins, amino resins, unsaturated polyester resins, polyurethane resins, silicone resins, and thermosetting polyimide resins. A thermosetting resin may be used independently and may use 2 or more types together. Among these thermosetting resins, an epoxy resin and a silicone resin are particularly preferable.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol AF type epoxy resin, bisphenol type Epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, tris hydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, biphenyl aralkyl type epoxy resin , bifunctional epoxy resins such as phenyl aralkyl type epoxy resins and dicyclopentadiene type epoxy resins, polyfunctional epoxy resins, hydantoin type epoxy resins, glycidyl ester type epoxy resins, etc. can be mentioned as examples.

The content of the thermosetting resin in the carbon nanotube-containing composition is not particularly limited, but the thermosetting resin is contained so that the total content of the thermosetting resin and the carbon nanotube is 2% by mass or more and 20% by weight or less in the carbon nanotube-containing composition. It is preferable that a thermosetting resin is contained so that it may become 5 mass % or more and 15 mass % or less.

When using an epoxy resin as a thermosetting resin, it is possible to use a hardening|curing agent (epoxy resin hardening|curing agent). As the epoxy resin curing agent, for example, known curing agents such as amines, acid anhydrides, and polyhydric phenols can be cited, and a latent curing agent that exhibits curability at a predetermined temperature above room temperature and exhibits rapid curing is preferable. do. As the latent curing agent, dicyandiamide, imidazoles, hydrazides, boron trifluoride-amine complexes, amineimides, polyamic acids and modified products thereof, particularly microcapsules can be used. These may be used independently and may use 2 or more types together. Content of an epoxy resin hardening|curing agent is not specifically limited, For example, 0.5 mass part or more and 50 mass parts or less are mentioned with respect to 100 mass parts of epoxy resins.

Moreover, when using a silicone resin as a thermosetting resin, it is possible to use a hardening|curing agent (silicone resin hardening|curing agent). As a silicone resin hardening|curing agent, an alkoxysilane compound is mentioned, for example. As an alkoxysilane compound, it is possible to mention the silane compound which has alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, Specifically, For example, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane , dimethyldiethoxysilane, tetraethoxysilane, glycidyloxypropyl trimethoxysilane, and the like. These may be used independently and may use 2 or more types together. Silicone resin curing agent content is not specifically limited, For example, 1.0 mass part or more and 100 mass parts or less are mentioned with respect to 100 mass parts of silicone resins.

In the carbon nanotube-containing composition of the present invention, in addition to each of the above components, if necessary, a crosslinking agent such as an isocyanate type, an epoxy type, a melamine type, a peroxide type, a dispersant such as a silane coupling agent, a surfactant, and electrical conductivity It is possible to blend a filler (filler), a flame retardant, an ion trapping agent, a thickener, an anti-aging agent, an antioxidant, and the like.

Next, the manufacturing method of the carbon nanotube containing composition of this invention is demonstrated. The method for producing the carbon nanotube-containing composition of the present invention is not particularly limited, but for example, first, the carbon nanotube is dispersed in an organic solvent to obtain the organic solvent-dispersed carbon nanotube. The method of dispersing the carbon nanotubes in the organic solvent is not particularly limited, and for example, a homogenizer, a thin film turning, a jaw crusher, an automatic induction, an ultracentrifugal grinding, a jet mill, a cutting mill, a disk mill, a ball mill, It is possible to cite methods such as rotational agitation and ultrasonic dispersion as examples. Next, a carbon nanotube-containing composition can be produced by adding a thermosetting resin and, if necessary, a curing agent to the obtained organic solvent-dispersed carbon nanotubes, and stirring at room temperature for a predetermined time using a stirring device. As said stirring apparatus, a jet mill, a cutting mill, a disk mill, a ball mill etc. are mentioned, for example.

Next, the manufacturing method of the thermosetting material of the carbon nanotube containing composition of this invention is demonstrated. A method for producing a thermosetting product of a carbon nanotube-containing composition includes, for example, (A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin, wherein (B) the boiling point of the organic solvent ( T1) and (C) a step of applying a carbon nanotube-containing composition having an absolute value of 70 ° C or less between the thermosetting reaction initiation temperature (T2) of the thermosetting resin and the film on the film, and heat-treating the carbon nanotube-containing composition and volatilizing the (B) organic solvent and initiating the thermosetting reaction of the (C) thermosetting resin.

(The process of applying to the film)

By applying the carbon nanotube-containing composition prepared as described above on the film, it is possible to obtain a laminated structure of the coating film of the carbon nanotube-containing composition and the film. At this time, if the carbon nanotube-containing composition is applied to a sheet, it is possible to obtain a sheet-like laminated structure. The coating method of the carbon nanotube-containing composition is not particularly limited, and for example, a comma coater method, a screen printing method, an inkjet method, a roll coater method, a bar coater method, a spray coater method, a curtain flow coater method, a squeegee method, It is possible to use well-known methods, such as the applicator method, the blade coater method, the knife coater method, and the gravure coater method. Although the thickness of the coating film of a carbon nanotube containing composition is not specifically limited, For example, the range of 5-100 micrometers is mentioned.

Also, when the film is used as a release film, the material of the film may include, for example, polyimide, polyester (polyethylene, polypropylene, polyethylene terephthalate, etc.).

(heat treatment process)

It is possible to thermoset the coating film of the carbon nanotube-containing composition by thermosetting the thermosetting resin while volatilizing the organic solvent by heat treatment. The temperature of the heat treatment can be appropriately selected depending on the thermosetting start temperature of the thermosetting resin. For example, when an epoxy resin or a silicone resin is used as the thermosetting resin, 70 to 250° C. is exemplified. As the time of , it is possible to cite, for example, 1 to 60 minutes.

Next, by peeling the film from the laminated structure, it is possible to obtain a thermosetting product (eg, a sheet-like thermosetting product) of the carbon nanotube-containing composition.

[Example]

Next, although an embodiment of the present invention is described, the present invention is not limited to these examples as long as it does not exceed the gist of the present invention.

(Example 1)

<Preparation of carbon nanotube-containing composition>

9 parts by mass of bisphenol A epoxy resin (brand name: YD-128, manufactured by Shin-Nika Epoxy Co., Ltd., mass average molecular weight: 400, softening point: 25° C. or less, liquid, epoxy equivalent: 190) as a thermosetting resin as a binder resin, 9 parts by mass, epoxy resin 1 part by mass of diethylenetriamine (manufactured by Mitsui Chemical Fine Co., Ltd., purity: 99% or more, specific gravity: 0.95) as a curing agent, single-walled carbon nanotubes dispersed in N-methyl-2-pyrroline as an organic solvent (trade name: ZEONANO ( Registered trademark) 03DS-NPD-R, manufactured by Nippon Zeon Corporation, solid content 0.3% by mass, average length 100 μm or more, G/D band ratio 5.0 or more) 177 parts by mass in a 250 ml plastic container (brand name: Pack AIDS P-250, Terra Co., Ltd.) Okaze) and stirred for 10 minutes in a planetary stirring/degassing apparatus (trade name: Mazel Star-KK-250, manufactured by Kurabo Spinning Co., Ltd.) to obtain a carbon nanotube-containing composition.

<Manufacture of an electroconductive member>

10 g of the carbon nanotube-containing composition is applied on the polyimide film by a comma coater method to form a coating film, and then heated at 200° C. for 30 minutes to volatilize the organic solvent from the coating film, and further thermoset the coating film to a thickness A thermosetting coating film of 100 μm was formed. Thereby, the sheet-like conductive member according to Example 1 was obtained.

(Example 2)

In the production of a carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrroline (trade name: ECP1.5P-NMP, manufactured by Myeongseong Nano Carbon Co., Ltd., solid content 0.2% by mass, average length 5-10 μm, G/D band ratio 50 or more) was used in the same manner as in Example 1 except that 265 parts by mass was used to obtain a sheet-shaped conductive member according to Example 2.

(Example 3)

In the production of a carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrroline (trade name: EPC22.0P-NMP, manufactured by Myeongseong Nanocarbon Co., Ltd., solid content 0.2% by mass, average length 10-15 μm , G/D band ratio 50 or more) was used in the same manner as in Example 1 except that 265 parts by mass was used to obtain a sheet-shaped conductive member according to Example 3.

(Example 4)

In the production of a carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrroline (trade name: EPC22.0P-NMP, manufactured by Myeongseong Nanocarbon Co., Ltd., solid content 0.2% by mass, average length 10-15 μm , G/D band ratio 50 or more) was used in the same manner as in Example 1 except that 375 parts by mass was used to obtain a sheet-shaped conductive member according to Example 4.

(Example 5)

In the production of a carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrroline (trade name: EPC22.0P-NMP, manufactured by Myeongseong Nanocarbon Co., Ltd., solid content 0.2% by mass, average length 10-15 μm , G/D band ratio 50 or more) was used in the same manner as in Example 1 except that 555 parts by mass was used to obtain a sheet-shaped conductive member according to Example 5.

(Example 6)

Regarding the production of the carbon nanotube-containing composition, in place of the bisphenol A epoxy resin, a non-crystalline liquid epoxy resin (trade name ZX-1059, manufactured by Shin-Nika Epoxy Co., Ltd.; A sheet-shaped conductive member according to Example 6 was obtained in the same manner as in Example 2 except that 9 parts by mass of epoxy equivalent: 165) was used.

(Example 7)

Regarding the production of the carbon nanotube-containing composition, instead of the bisphenol A epoxy resin, a cyclic aliphatic diglycidyl ether-based epoxy resin (trade name ZX-16, manufactured by Shin-Nika Epoxy Co., Ltd., viscosity 50 mM, softening point 25 ° C. Hereinafter, a sheet-like conductive member according to Example 7 was obtained in the same manner as in Example 2, except that 9 parts by mass of liquid, epoxy equivalent: 133) was used.

(Example 8)

Regarding the production of the carbon nanotube-containing composition, 7 parts by mass of polydimethylsiloxane containing a silanol group as a silicone resin (trade name: XP1434, manufactured by JNC Corporation, viscosity of 50 mM, liquid) in place of the bisphenol A-type epoxy resin, Example 2 was carried out in the same manner as in Example 2, except that 3 parts by mass of alkoxyepoxysilane (trade name: S-510, manufactured by JNC Corporation, 3-glycidyloxypropyl trimethoxysilane) was used instead of diethylenetriamine. 8 was obtained.

(Example 9)

Regarding the production of a carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in N-methyl-2-pyrroline as carbon nanotubes (trade name: ZEONANO (registered trademark) 03DS-NPD-R, manufactured by Nippon Zeon Corporation, solid content 0.3) A sheet-like conductive member according to Example 9 was obtained in the same manner as in Example 1 except that 500 parts by mass (mass%, average length 100 µm or more, G/D band ratio 5.0 or more) was used.

(Example 10)

Regarding the production of the carbon nanotube-containing composition, instead of the bisphenol A epoxy resin, polydimethylsiloxane containing a silanol group as a silicone resin (trade name: FM-915, manufactured by JNC Co., Ltd., viscosity 130 mM, liquid) was added to 7 In the same manner as in Example 2, except that 3 parts by mass of alkoxyepoxysilane (trade name: S-510, manufactured by JNC Corporation, 3-glycidyloxypropyl trimethoxysilane) was used in place of diethylenetriamine in parts by mass , a sheet-like conductive member according to Example 10 was obtained.

(Comparative Example 1)

Regarding the production of a carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in methyl ethyl ketone (trade name: 03DS-MK-RD, manufactured by Zeo Corporation, Japan, solid content 0.35 mass%, average length 100 µm or more, G/D band ratio 5.0) was used in the same manner as in Example 1 except that 151 parts by mass was used to obtain a sheet-like conductive member according to Comparative Example 1.

(Comparative Example 2)

Regarding the production of the carbon nanotube-containing composition, single-walled carbon nanotubes dispersed in methyl ethyl ketone (trade name: EC1.5P-MEK, manufactured by Myungsung Nano Carbon Co., Ltd., solid content 0.2% by mass, average length 5 to 10 µm, G/D A sheet-like conductive member according to Comparative Example 2 was obtained in the same manner as in Example 1 except that 265 parts by mass was used (band ratio 50 or more).

The following measurement and evaluation were performed about each electroconductive member of the Example and the comparative example obtained as mentioned above.

(organic solvent boiling point (T1))

For the organic solvent used for the organic solvent-dispersed carbon nanotubes used in each Example and Comparative Example, the boiling point of the organic solvent ( T1) was measured. The results are shown in Tables 1 and 2 below.

(thermal curing reaction initiation temperature (T2))

For the thermosetting resin and curing agent used in each Example and Comparative Example, the amounts indicated in Tables 1 and 2 were weighed into a 250 ml plastic container (brand name: PAX P-250, manufactured by Teraoka Co., Ltd.), and a planetary stirring and defoaming device ( Brand name: Majerusta-KK-250, Kurashiki Spinning Co., Ltd. product) was stirred for 10 minutes and performed. In accordance with the measurement method described above, the sample was heated from room temperature to 300°C in a differential scanning calorimeter (model number: DSC7000, manufactured by Hitachi High-Tech Sciences Co., Ltd.) at a temperature increase rate of 5°C/mｉｎ. From the obtained exothermic peak, thermosetting reaction The onset temperature (T2) was measured.

(Film property evaluation)

When peeling a polyimide film from the electroconductive member which concerns on each Example and a comparative example, the fracture|rupture condition of the thermosetting coating film was observed and evaluated. What the thermosetting coating film fractured|ruptured was evaluated as O, and the thing which was peelable without fracture|rupture of a thermosetting coating film was evaluated as Х. The results are shown in Tables 1 and 2.

(Evaluation of carbon nanotube (CNT) dispersion morphology)

The conductive members obtained in Examples and Comparative Examples were cut into halves in the thickness direction with an ultra-microtome (trade name: EMUC7, manufactured by Leica), and the cross section was observed with a transmission electron microscope (trade name: JEM-ARM300F, manufactured by Nippon Electronics Co., Ltd.) By doing so, the dispersion form of CNTs was observed. A single dispersion of CNTs on all observation surfaces was evaluated as O, and observations of aggregates of CNTs were evaluated as Х. The results are shown in Tables 1 and 2.

(volume resistivity)

The conductive members obtained in Examples and Comparative Examples were cut out with a hole punch having a diameter of 12.5 mm to obtain a disk-shaped test piece having a diameter of 12.5 mm and a thickness of 10 µm. With respect to this test piece, the volume resistivity was measured by a four-terminal method with a high-accuracy, high-function, low-resistivity meter (model number: Lorestar GX, manufactured by Mitsubishi Chemical Analytech Co., Ltd., measurement terminal: PSP probe MCP-P06P 112). The results are shown in Tables 1 and 2.

[Table 1]

[Table 2]

From Table 1, in Examples 1 to 10, in which the absolute value of the difference between the boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the thermosetting resin is 70° C. or less, aggregation of carbon nanotubes is prevented and a single It is dispersed. In these Examples 1 to 10, the volume resistivity can be reduced, and it is possible to obtain excellent conductivity throughout the conductive member. Accordingly, in Examples 1 to 10, it was confirmed that even if the wiring of the circuit device to be inspected was narrowed in pitch and the wiring was thinned, it was possible to perform a high-accuracy conduction inspection. In particular, in Examples 1 to 8 and 10 in which the carbon nanotubes contain 5 mass% or more and 10 mass% or less in 100 mass% of the total solid content of the carbon nanotube-containing composition, the carbon nanotubes are the total amount of the carbon nanotube-containing composition. Compared with Example 9 containing 13 mass % in 100 mass % of the solid component, it was confirmed that the film formability was also excellent and that it could be easily molded into a sheet form.

Further, in Examples 1 to 10, carbon nanotubes are used as the conductive material and no metal components are mixed. Therefore, even when used as a conductive member for continuity inspection, it is possible to prevent contamination of the electrode or circuit device to be inspected by the metal material. can be prevented

On the other hand, from Table 2, in Comparative Examples 1 and 2 in which the absolute value of the difference between the boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the thermosetting resin exceeds 70°C, aggregation of carbon nanotubes is occurred. In the said Comparative Examples 1-2, the volume resistivity increased and it was impossible to obtain favorable electroconductivity as an electroconductive member.

[Industrial Applicability]

The carbon nanotube-containing composition of the present invention can obtain excellent conductivity over the entire conductive member, which is a thermosetting material, and thus can be used as a conductive member for conduction inspection that does not contain a metal component as a conductive material. Further, since the conductive member, which is a thermosetting product of the carbon nanotube-containing composition, can be molded into a sheet shape, it is also possible to form a conductive sheet for continuity inspection. It is also possible to form an anisotropically conductive sheet by filling and curing the carbon nanotube-containing composition of the present invention in the through-holes of an insulating sheet body having a plurality of penetrating through-holes penetrating in the thickness direction.

Claims (8)

(A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin, wherein the (B) boiling point (T1) of the organic solvent and the thermosetting reaction initiation temperature (T2) of the (C) thermosetting resin ), the carbon nanotube-containing composition for use as an electroconductive member for continuity inspection, wherein the absolute value of the difference is 70° C. or less. The carbon nanotube according to claim 1, wherein the (A) carbon nanotube has an intensity ratio G/D of 1.0 or more between the G band and the D band of a Raman spectrum obtained by Raman spectroscopy, and (A) the average length of the carbon nanotube is 1.0 μm or more, a composition containing carbon nanotubes. The carbon nanotube-containing composition according to claim 1, wherein the (C) thermosetting resin is an epoxy resin. The carbon according to any one of claims 1 to 3, wherein the carbon nanotubes (A) contain 0.1 mass% or more and 15 mass% or less in 100 mass% of the total solid components of the carbon nanotube-containing composition. A composition containing nanotubes. A thermosetting product of the carbon nanotube-containing composition according to any one of claims 1 to 3. The thermosetting product according to claim 5, wherein the volume resistivity is 0.1 Ω·m or less. (A) carbon nanotubes, (B) an organic solvent, and (C) a thermosetting resin, wherein (B) the boiling point of the organic solvent (T1) and (C) the thermosetting reaction initiation temperature of the thermosetting resin (T2) ) and the step of applying a carbon nanotube-containing composition having an absolute value of 70 ° C or less on the film, and
for use as a conductive member for continuity inspection, comprising a step of volatilizing the (B) organic solvent and initiating a thermosetting reaction of the (C) thermosetting resin by subjecting the carbon nanotube-containing composition to heat treatment, A method for producing a thermosetting product of a carbon nanotube-containing composition. The method for producing a thermosetting product according to claim 7, wherein the thermosetting product constitutes a conductive sheet having a thickness of 1 µm or more and 500 µm or less.

Images