Resin composition and cured product

Abstract

The present invention aims to provide a resin composition capable of inhibiting settling and excessive thickening of fillers, and capable of exerting excellent electrical conductivity. The resin composition of the present invention comprises a base resin, and a primary electrically conductive filler (A) having a metal at least on a part of a surface. The resin composition comprises the primary electrically conductive filler (A) at a prescribed content ratio. The resin composition further comprises at least one of a carbon-based electrically conductive filler (B) having an aspect ratio of 50 or more, and a carbon-based electrically conductive filler (C) having a specific surface area of 10 m 2 / g or more, respectively, at prescribed content ratios.

Description

Technical Field

[0001] This invention relates to resin compositions and cured products obtained by curing the resin compositions. Background Technology

[0002] In recent years, in order to improve properties such as electrical conductivity, thermal conductivity, and mechanical strength, techniques for preparing resin compositions by adding various fillers to the matrix resin have been explored.

[0003] For example, Patent Document 1 proposes adding specified fillers to a cured polymer such as a siloxane polymer to produce a cured polymer composite material. Furthermore, according to Patent Document 1, this polymer composite material exhibits excellent tensile strength, hardness, and electrical conductivity.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Publication No. 2023-516923 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] In the past, to impart electrical conductivity to resin compositions and their cured products, fillers with at least a portion of their surface being metallic have been added to the matrix resin. However, such resin compositions suffer from problems such as filler settling or excessive thickening of the resin composition itself, leading to impaired workability.

[0009] Therefore, the object of the present invention is to provide a resin composition and a cured product. In some embodiments, the object of the present invention is to provide a resin composition capable of suppressing filler sedimentation and excessive thickening and exhibiting excellent electrical conductivity, and a cured product formed by curing the resin composition.

[0010] Solution for solving the problem

[0011] To achieve the above-mentioned objective, the inventors conducted in-depth research. Furthermore, the inventors discovered that by comprising a resin composition containing a matrix resin and a filler having at least a portion of its surface metal, a carbon-based conductive filler with an aspect ratio of 50 or more and a specific surface area of ​​10 m² can be achieved. 2 The present invention is completed by using at least one of the carbon-based conductive fillers of / g or more, under specified conditions, thereby enabling the resin composition to exhibit excellent conductivity while suppressing both filler sedimentation and excessive thickening.

[0012] That is, according to the present invention, the resin composition of [1] to

[14] described below and the cured product of

[15] are provided.

[0013] [1] A resin composition comprising a matrix resin and a primary conductive filler (A) having a metallic component at least in a portion of its surface, wherein,

[0014] When the total volume of the resin composition is set to 100% by volume, the content of the main conductive filler (A) is 19.80% by volume or more and 35.20% by volume or less, and,

[0015] The following conditions (1), (2), or (3) must be met:

[0016] Condition (1): The resin composition comprises a carbon-based conductive filler (B) with an aspect ratio of 50 or greater and a specific surface area of ​​10 m². 2 Both of these are carbon-based conductive fillers (C) with a content of / g or more, and

[0017] When the total volume of the resin composition is set to 100% by volume...

[0018] The carbon-based conductive filler (B) is present in a concentration of 0.01% by volume or more but less than 1.00% by volume.

[0019] The carbon-based conductive filler (C) is present in a proportion exceeding 0.10% by volume and less than 2.00% by volume.

[0020] The total content of the main conductive filler (A), the carbon-based conductive filler (B), and the carbon-based conductive filler (C) exceeds 20.60% by volume and is less than 36.50% by volume.

[0021] Condition (2): The resin composition contains a specific surface area of ​​10 m². 2 Carbon-based conductive fillers (C) with a length-to-diameter ratio of 50 or higher, excluding carbon-based conductive fillers (B) with a length-to-diameter ratio of 50 or higher, and

[0022] When the total volume of the resin composition is set to 100% by volume...

[0023] The carbon-based conductive filler (C) is present in a proportion exceeding 1.00% by volume and less than 6.00% by volume.

[0024] The combined content of the main conductive filler (A) and the carbon-based conductive filler (C) exceeds 21.00% by volume and is less than 38.00% by volume.

[0025] Condition (3): The resin composition contains a carbon-based conductive filler (B) with an aspect ratio of 50 or more, but does not contain a specific surface area of ​​10 m². 2 / g or more of carbon-based conductive filler (C), and

[0026] When the total volume of the resin composition is set to 100% by volume...

[0027] The carbon-based conductive filler (B) is present in a concentration of 0.10% by volume or more and less than 2.50% by volume.

[0028] The combined content of the main conductive filler (A) and the carbon-based conductive filler (B) exceeds 20.20% by volume and is less than 36.00% by volume.

[0029] [2] The resin composition according to [1] above, wherein the main conductive filler (A) comprises nickel-plated graphite.

[0030] [3] The resin composition according to [1] or [2] above, wherein the carbon-based conductive filler (B) comprises carbon nanostructures.

[0031] [4] The resin composition according to any one of [1] to [3] above, wherein the carbon-based conductive filler (C) comprises carbon black.

[0032] [5] The resin composition according to any one of [1] to [4] above, wherein the matrix resin comprises at least one selected from the group consisting of silicone resin, epoxy resin, acrylic resin, polyolefin oxide resin and polyurethane resin.

[0033] [6] The resin composition according to any one of [1] to [4] above, wherein the matrix resin comprises at least one selected from the group consisting of silicone resin, epoxy resin and polyurethane resin.

[0034] [7] The resin composition according to any one of [1] to [6] above further comprises a curing catalyst capable of curing the matrix resin.

[0035] [8] The resin composition according to any one of [1] to [7] above further comprises a reinforcing filler.

[0036] [9] The resin composition according to any one of [1] to [8] above further comprises an adhesion promoter comprising both 3-methacryloyloxypropyltrimethoxysilane and tetraethoxysilane.

[0037]

[10] The resin composition according to any one of [1] to [9] above satisfies the conditions (1) or (2).

[0038]

[11] The resin composition according to any one of [1] to [9] above satisfies the condition (1).

[0039]

[12] The resin composition according to any one of [1] to

[11] above is a two-component type.

[0040]

[13] The resin composition according to any one of [1] to

[12] above has curable properties.

[0041]

[14] The resin composition according to any one of [1] to

[13] above has room temperature curing properties.

[0042]

[15] A cured product formed by curing the resin composition described in

[13] or

[14] above.

[0043] The effects of the invention

[0044] According to the present invention, a resin composition capable of suppressing filler sedimentation and excessive thickening and exhibiting excellent electrical conductivity is provided, as well as a cured product formed by curing the resin composition. Detailed Implementation

[0045] The embodiments of the present invention will now be described in detail.

[0046] (Resin composition)

[0047] The resin composition of the present invention comprises a matrix resin and a primary conductive filler (A) having a metallic component at least in a portion of its surface. Furthermore, the resin composition of the present invention comprises a carbon-based conductive filler (B) with an aspect ratio of 50 or more and / or a specific surface area of ​​10 m². 2 / g or more of carbon-based conductive filler (C). In addition, the resin composition of the present invention may optionally contain components other than the matrix resin, the main conductive filler (A), and the carbon-based conductive fillers (B) and (C) (hereinafter referred to as "optional components"). Furthermore, the resin composition of the present invention satisfies any one of the conditions (1) to (3) described below.

[0048] The resin composition of the present invention, through the above-described configuration, suppresses both filler sedimentation and excessive thickening, and as a resin composition and / or its cured product, exhibits excellent electrical conductivity.

[0049] <Matrix Resin>

[0050] The matrix resin included in the resin composition of the present invention is one of the main components of the resin composition. The matrix resin is not particularly limited as long as it enables good dispersion of the main conductive filler (A) and the carbon-based conductive filler (B) and / or (C), and can be selected appropriately according to the intended use of the resin composition. The preferred structure, properties, type, and proportion of the matrix resin in one embodiment of the present invention are described below, but the present invention is not limited thereto.

[0051] <<Structure and Properties>>

[0052] The molecular structure of the matrix resin is not particularly limited, and examples include linear, partially branched linear, branched, cyclic, network, and dendritic structures. Furthermore, when the resin composition of the present invention comprises multiple matrix resins, their respective molecular structures may be the same or different.

[0053] In one aspect of the present invention, the matrix resin may contain reactive functional groups in its molecules. By having reactive functional groups in the matrix resin, various curing reactions can proceed well to obtain a cured product. Furthermore, known functional groups capable of participating in chemical reactions such as condensation and addition reactions can be used as reactive functional groups. Examples of such reactive functional groups include alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl; trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl; and epoxy groups. Furthermore, the matrix resin may have only one type of reactive functional group in one molecule, or it may have two or more reactive functional groups.

[0054] The location of reactive functional groups in these matrix resins is not particularly limited. The polymers constituting the matrix resins may, for example, have reactive functional groups at the ends of their molecular chains.

[0055] Furthermore, from the viewpoint of improving reactivity and enabling good curing, the matrix resin preferably has at least two reactive functional groups in one molecule.

[0056] The viscosity of the base resin is not particularly limited, but is preferably 20 mPa·s or more, more preferably 100 mPa·s or more, further preferably 500 mPa·s or more, and preferably 1,000,000 mPa·s or less, more preferably 100,000 mPa·s or less, further preferably 10,000 mPa·s or less, and particularly preferably 5,000 mPa·s or less. If the viscosity of the base resin is 20 mPa·s or more, filler sedimentation in the resin composition can be further suppressed, and the softness and elongation of the cured product obtained by curing the resin composition can be improved. On the other hand, if the viscosity of the base resin is 1,000,000 mPa·s or less, excessive thickening of the resin composition can be sufficiently suppressed.

[0057] Furthermore, in this specification, the “viscosity” of the matrix resin refers to the value measured at 25°C using a type B viscometer in accordance with JIS K 7117-1:1999.

[0058] <<Types of Matrix Resins>>

[0059] As mentioned above, there is no particular limitation on the type of matrix resin. In addition, a single matrix resin can be used alone, or two or more can be combined in any proportion.

[0060] For example, when the resin composition of the present invention is used as an adhesive, from the viewpoint of exhibiting adhesive properties, silicone resins (such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.; these may have the aforementioned reactive functional groups, and some or all of the hydrogen atoms may be replaced by halogen atoms such as fluorine), epoxy resins, acrylic resins, polyolefin oxide resins, polyurethane resins, and combinations thereof are preferably used as the base resin. Furthermore, in some embodiments, silicone resins, epoxy resins, polyurethane resins, and combinations thereof are preferably used as the base resin.

[0061] <<Proportion of Matrix Resin>>

[0062] Furthermore, the proportion of the matrix resin in the resin composition, based on 100% by mass of the total resin composition, is preferably 10.00% by mass or more, more preferably 15.00% by mass or more, even more preferably 20.00% by mass or more, even more preferably 25.00% by mass or more, particularly preferably 30.00% by mass or more, and preferably 60.00% by mass or less, more preferably 50.00% by mass or less, and even more preferably 40.00% by mass or less. If the proportion of the matrix resin in the resin composition is 10.00% by mass or more, the resin composition can exhibit excellent adhesive properties. On the other hand, if the proportion of the matrix resin in the resin composition is 60.00% by mass or less, the conductivity of the resin composition will not be excessively reduced.

[0063] <Main conductive filler (A)>

[0064] The primary conductive filler (A) is a conductive filler with at least a portion of its surface having a metallic appearance, and is a component capable of imparting conductivity to the resin composition of the present invention. Furthermore, the primary conductive filler (A) can be used alone or in combination of two or more in any proportion.

[0065] Here, the main conductive filler (A) is not particularly limited as long as at least a portion of its outer surface is provided with metal. It can be a filler whose entire structure is made of metal, or a filler whose surface of a non-metallic component is partially or entirely covered by metal.

[0066] The metal that can constitute the main conductive filler (A) is not particularly limited, and examples include nickel, silver, copper, tin, and cobalt. One of these metals can be used alone, or two or more can be combined in any proportion. Of these, nickel is preferred from the viewpoint of further enhancing the conductivity of the resin composition.

[0067] Furthermore, there are no particular limitations on the non-metallic components that can constitute the main conductive filler (A), and examples include graphite, silicon dioxide, alumina, talc, glass, plastic particles, and diamond. These non-metallic components can be used individually or in combination of two or more in any proportion. Of these, graphite is preferred from the viewpoint of further enhancing the conductivity of the resin composition.

[0068] Furthermore, as the main conductive filler (A), from the viewpoint of enabling the resin composition to exhibit excellent conductivity, graphite (i.e., nickel-plated graphite) with at least a portion of its surface coated with nickel is preferred.

[0069] In addition, the shape of the main conductive filler (A) is not particularly limited and can be any shape such as spherical, fibrous, plate-like, or amorphous.

[0070] In addition, when the two-dimensional cross-sectional image of the main conductive filler (A) is confirmed by scanning electron microscopy (SEM), it is preferable that at least one cross section, based on the length of the outer perimeter (surface) as 100%, preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 90% or more, is composed of metal (coated by metal).

[0071] Furthermore, the volume average particle size of the main conductive filler (A) is preferably 1 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, and preferably 1,000 μm or less, more preferably 700 μm or less, and even more preferably 500 μm or less. If the volume average particle size of the main conductive filler (A) is within the above range, it is possible to further suppress filler sedimentation and thickening in the resin composition while simultaneously enabling the resin composition to exhibit even better conductivity.

[0072] Furthermore, in this specification, the “volume average particle size” of various fillers refers to the particle size that accounts for 50% of the cumulative volume calculated from the smallest particle size side in a volume-based particle size distribution determined by laser diffraction.

[0073] Furthermore, the proportion of the main conductive filler (A) in the resin composition, based on the total volume of the resin composition (100% by volume), should be 19.80% or more and 35.20% or less, preferably 20.00% or more, more preferably 22.00% or more, even more preferably 24.00% or more, and preferably 35.00% or less, more preferably 32.00% or less, and even more preferably 29.00% or less. If the proportion of the main conductive filler (A) in the resin composition is less than 19.80% by volume, the resin composition cannot exhibit sufficient conductivity. On the other hand, if the proportion of the main conductive filler (A) in the resin composition exceeds 35.20% by volume, filler sedimentation in the resin composition cannot be suppressed, and adhesion is reduced.

[0074] <Carbon-based conductive fillers (B) and (C)>

[0075] The resin composition of the present invention needs to contain a carbon-based conductive filler (B) with an aspect ratio of 50 or more and a specific surface area of ​​10 m². 2 At least one of the carbon-based conductive fillers (C) of / g or above.

[0076] These carbon-based conductive fillers are carbonaceous materials with carbon as the main component (e.g., the carbon content is 90% by mass or more), and like the main conductive filler (A) described above, they are components capable of imparting conductivity to the resin composition of the present invention. Furthermore, through the inventors' investigation, it has been clarified that by adding carbon-based conductive fillers (B) and / or (C) to the resin composition, the sedimentation of the main conductive filler (A) can be suppressed, thereby improving the adhesiveness of the resin composition. The reason for achieving this effect is not yet clear, but it is speculated that this is because these carbon-based conductive fillers have an aspect ratio or specific surface area of ​​a specified value or higher, thereby producing a reinforcing effect when dispersed in the matrix resin.

[0077] <<Carbon-based conductive fillers (B)>>

[0078] The aspect ratio of the carbon-based conductive filler (B) should be 50 or more, preferably 100 or more, more preferably 500 or more, and even more preferably 1,000 or more, as described above. It is anticipated that if the aspect ratio of the carbon-based conductive filler (B) is less than 50, the aforementioned reinforcing effect will not occur, and filler sedimentation in the resin composition cannot be suppressed; furthermore, the adhesiveness of the resin composition will decrease. Furthermore, there is no particular upper limit to the aspect ratio of the carbon-based conductive filler (B), and it can be set to 30,000 or less, for example.

[0079] Furthermore, in this specification, the "length-to-diameter ratio" of the filler can be determined as follows: observe the filler with SEM, for any 50 primary particles, measure the maximum diameter (length diameter) and the diameter of the particle in the direction orthogonal to the maximum diameter (short diameter), and calculate the average value of the ratio of the length diameter to the short diameter (length diameter / short diameter).

[0080] The carbon-based conductive filler (B) having the aforementioned aspect ratio can be, for example, any branched fibrous or cylindrical carbon material, preferably a carbon nanostructure with a nanoscale outer diameter. There are no particular limitations on the carbon nanostructure; examples include carbon nanotubes (single-walled, multi-walled), carbon nanofibers, carbon nanorods, carbon nanofibers, carbon nanoneedles, carbon nanohorns, carbon nanocones, and carbon nanorolls. Furthermore, the carbon-based conductive filler (B) can be used alone or in combination of two or more in any proportion.

[0081] <<Carbon-based conductive fillers (C)>>

[0082] The specific surface area of ​​the carbon-based conductive filler (C) needs to be 10 m², as mentioned above. 2 / g or more, preferably 100m 2 / g or more, preferably 300m 2 / g or more, further preferably 600m 2 / g or more, with 800m being particularly preferred. 2 / g or more. It is speculated that if the specific surface area of ​​the carbon-based conductive filler (C) is less than 10m²... 2 If the specific surface area is less than 1 g, the aforementioned reinforcing effect will not occur, and the settling of fillers in the resin composition cannot be suppressed. Furthermore, the adhesiveness of the resin composition will decrease. Additionally, there is no particular upper limit to the specific surface area of ​​the carbon-based conductive filler (C); for example, it can be set to 2,000 m². 2 / g or less.

[0083] Furthermore, in this specification, the "specific surface area" of the packing material refers to the nitrogen adsorption specific surface area determined using the BET method.

[0084] In addition, the shape of carbon-based conductive filler (C) is not particularly limited and can be set to any shape, but the aspect ratio is usually less than 50.

[0085] Carbon black is preferred as the carbon-based conductive filler (C) having the aforementioned specific surface area. There is no particular limitation on the type of carbon black; examples include pyrolysis carbon black, acetylene black, channel black, furnace black, lampblack, and bone black. Furthermore, one type of carbon-based conductive filler (C) may be used alone, or two or more may be used in any combination.

[0086] <Conditions (1) to (3)>

[0087] The resin composition of the present invention shall satisfy any one of the following conditions (1), (2) or (3) regarding the main conductive filler (A), carbon-based conductive filler (B) and (C).

[0088] -Condition (1)-

[0089] The resin composition that satisfies condition (1) satisfies all of the following items [1-1] to [1-4].

[0090] [1-1] The resin composition comprises both a carbon-based conductive filler (B) and a carbon-based conductive filler (C).

[0091] [1-2] When the total volume of the resin composition is set to 100% by volume, the content of carbon-based conductive filler (B) is 0.01% by volume or more and less than 1.00% by volume.

[0092] [1-3] When the total volume of the resin composition is set to 100% by volume, the content of carbon-based conductive filler (C) is greater than 0.10% by volume and less than 2.00% by volume.

[0093] [1-4] When the total volume of the resin composition is set to 100% by volume, the combined content of the main conductive filler (A), carbon-based conductive filler (B) and carbon-based conductive filler (C) exceeds 20.60% by volume and is less than 36.50% by volume.

[0094] In condition (1), the content ratio of the carbon-based conductive filler (B) specified in the above items [1-2], based on the total volume of the resin composition as 100% by volume, is as described above, which requires to be 0.01% by volume or more and less than 1.00% by volume, which can be 0.02% by volume or more, which can be 0.05% by volume or more, which can be more than 0.10% by volume, which is preferably 0.15% by volume or more, which is more preferably 0.20% by volume or more, which is even more preferably 0.25% by volume or more, which is preferably 0.85% by volume or less, which is even more preferably 0.70% by volume or less, which is even more preferably 0.55% by volume or less. In condition (1), if the content ratio of the carbon-based conductive filler (B) is less than 0.01% by volume, the filler sedimentation in the resin composition cannot be suppressed, and the conductivity of the resin composition is impaired. In addition, the adhesion of the resin composition is reduced. On the other hand, if the content ratio of the carbon-based conductive filler (B) is 1.00% by volume or more, the thickening of the resin composition cannot be suppressed.

[0095] In condition (1), the content ratio of the carbon-based conductive filler (C) specified in the above items [1-3], based on the total volume of the resin composition of 100 vol%, shall be more than 0.10 vol% and less than 2.00 vol%, as described above, preferably more than 0.50 vol%, more preferably more than 0.80 vol%, further preferably more than 1.10 vol%, and preferably less than 1.90 vol%, more preferably less than 1.80 vol%, and further preferably less than 1.70 vol%. In condition (1), if the content ratio of the carbon-based conductive filler (C) is less than 0.10 vol%, filler sedimentation in the resin composition cannot be suppressed, and the conductivity of the resin composition is impaired. In addition, the adhesiveness of the resin composition is reduced. On the other hand, if the content ratio of the carbon-based conductive filler (C) is more than 2.00 vol%, thickening of the resin composition cannot be suppressed.

[0096] In condition (1), the total content ratio of the main conductive filler (A), carbon-based conductive filler (B), and (C) specified in the above items [1-4], based on the total volume of the resin composition as 100% by volume, shall be more than 20.60% by volume and less than 36.50% by volume, as described above. Preferably, it shall be 23.00% by volume or more, more preferably 25.00% by volume or more, further preferably 27.00% by volume or more, and preferably 34.00% by volume or less, more preferably 32.00% by volume or less, and further preferably 30.00% by volume or less. In condition (1), if the total content ratio of the main conductive filler (A), carbon-based conductive filler (B), and (C) is 20.60% by volume or less, the conductivity of the resin composition is impaired; if it is 36.50% by volume or more, the thickening of the resin composition cannot be suppressed.

[0097] Furthermore, in condition (1), the total content of carbon-based conductive fillers (B) and (C), based on 100% of the total volume of the resin composition, is preferably 0.50% by volume or more, more preferably 1.00% by volume or more, even more preferably 1.30% by volume or more, and preferably 2.50% by volume or less, more preferably 2.20% by volume or less, and even more preferably 2.00% by volume or less. In condition (1), if the total content of carbon-based conductive fillers (B) and (C) is 0.50% by volume or more, filler sedimentation in the resin composition can be further suppressed, and the conductivity of the resin composition can be further improved. In addition, the resin composition can exhibit excellent adhesion. On the other hand, if the total content of carbon-based conductive fillers (B) and (C) is 2.50% by volume or less, thickening of the resin composition can be further suppressed.

[0098] Furthermore, in condition (1), the volume ratio of the carbon-based conductive filler (C) to the carbon-based conductive filler (B) ((C) / (B)) can be more than 1.0 times, more than 2.0 times, or more than 3.0 times, and can be less than 100.0 times, less than 50.0 times, less than 30.0 times, less than 20.0 times, less than 10.0 times, less than 8.0 times, or less than 6.0 times. If the volume ratio of (C) / (B) is within the above range, it is presumed that both the carbon-based conductive filler (B) and (C) effectively exert the above-mentioned reinforcing effect, which can further suppress filler sedimentation and thickening of the resin composition while improving the adhesion of the resin composition.

[0099] -Condition (2)-

[0100] The resin composition that meets condition (2) satisfies all of the following items [2-1] to [2-3].

[0101] [2-1] The resin composition contains carbon-based conductive filler (C) but does not contain carbon-based conductive filler (B).

[0102] [2-2] When the total volume of the resin composition is set to 100% by volume, the content of carbon-based conductive filler (C) is greater than 1.00% by volume and less than 6.00% by volume.

[0103] [2-3] When the total volume of the resin composition is set to 100% by volume, the combined content of the main conductive filler (A) and the carbon-based conductive filler (C) exceeds 21.00% by volume and is less than 38.00% by volume.

[0104] In condition (2), the content ratio of the carbon-based conductive filler (C) specified in item [2-2] above, based on the total volume of the resin composition of 100 vol%, shall be greater than 1.00 vol% and less than 6.00 vol%, as described above, preferably 1.10 vol% or more, more preferably 1.20 vol% or more, further preferably 1.30 vol% or more, and preferably 5.00 vol% or less, more preferably 4.00 vol% or less, further preferably 3.00 vol% or less, and particularly preferably 2.50 vol% or less. In condition (2), if the content ratio of the carbon-based conductive filler (C) is less than 1.00 vol%, filler sedimentation in the resin composition cannot be suppressed, and the conductivity of the resin composition is impaired. In addition, the adhesiveness of the resin composition is reduced. On the other hand, if the content ratio of the carbon-based conductive filler (C) is 6.00 vol% or more, thickening of the resin composition cannot be suppressed.

[0105] In condition (2), the total proportion of the main conductive filler (A) and the carbon-based conductive filler (C) specified in the above items [2-3], based on the total volume of the resin composition as 100% by volume, shall, as described above, exceed 21.00% by volume and be less than 38.00% by volume, preferably 23.00% or more, more preferably 25.00% or more, further preferably 27.00% or more, and preferably 34.00% or less, more preferably 32.00% or less, and further preferably 30.00% or less. In condition (2), if the total proportion of the main conductive filler (A) and the carbon-based conductive filler (C) is less than 21.00% by volume, the conductivity of the resin composition is impaired; if it is more than 38.00% by volume, the thickening of the resin composition cannot be suppressed.

[0106] -Condition (3)-

[0107] The resin composition that meets condition (3) satisfies all of the following items [3-1] to [3-3].

[0108] [3-1] The resin composition contains carbon-based conductive filler (B) but does not contain carbon-based conductive filler (C).

[0109] [3-2] When the total volume of the resin composition is set to 100% by volume, the content of carbon-based conductive filler (B) is 0.10% by volume or more and less than 2.50% by volume.

[0110] [3-3] When the total volume of the resin composition is set to 100% by volume, the combined content of the main conductive filler (A) and the carbon-based conductive filler (B) exceeds 20.20% by volume and is less than 36.00% by volume.

[0111] In condition (3), the content ratio of the carbon-based conductive filler (B) specified in item [3-2] above, based on the total volume of the resin composition as 100% by volume, is as described above, preferably 0.10% by volume or more and less than 2.50% by volume, more preferably 0.20% by volume or more, more preferably 0.25% by volume or more, and preferably 2.00% by volume or less, more preferably 1.00% by volume or less, further preferably 0.70% by volume or less, and particularly preferably 0.50% by volume or less. In condition (3), if the content ratio of the carbon-based conductive filler (B) is less than 0.10% by volume, filler sedimentation in the resin composition cannot be suppressed, and the conductivity of the resin composition is impaired. In addition, the adhesiveness of the resin composition is reduced. On the other hand, if the content ratio of the carbon-based conductive filler (B) is 2.50% by volume or more, thickening of the resin composition cannot be suppressed.

[0112] Furthermore, in condition (3), the total proportion of the main conductive filler (A) and the carbon-based conductive filler (B) specified in the above item [3-3], based on the total volume of the resin composition as 100% by volume, shall, as described above, exceed 20.20% by volume and be less than 36.00% by volume, preferably 20.30% by volume or more, and more preferably 35.50% by volume or less. In condition (3), if the total proportion of the main conductive filler (A) and the carbon-based conductive filler (B) is less than 20.20% by volume, the conductivity of the resin composition is impaired; if it is more than 36.00% by volume, the thickening of the resin composition cannot be suppressed.

[0113] Furthermore, the resin composition of the present invention only needs to satisfy any one of the above conditions (1) to (3), but from the viewpoint of further suppressing filler sedimentation and thickening of the resin composition while further improving conductivity and enabling the resin composition to exhibit excellent adhesion, it is preferable to satisfy condition (1) or (2), and more preferably to satisfy condition (1).

[0114] Furthermore, if the resin composition of the present invention satisfies condition (1), it has the advantage that even when the resin composition and the cured product are exposed to high temperature and high humidity conditions for a long time, they can still maintain their good conductivity.

[0115] <Any ingredient>

[0116] The resin composition of the present invention may contain any of the following components, other than the matrix resin, the main conductive filler (A), and the carbon-based conductive fillers (B) and (C), without particular limitation, and may be selected appropriately according to the intended use and desired properties of the resin composition. An example of any component that may be used is described below. Furthermore, sometimes embodiments using silicone resin as the matrix resin are specifically used as examples to illustrate any component, but the present invention is not limited thereto.

[0117] <<Reinforcing Fillers>>

[0118] The resin composition of the present invention may optionally contain reinforcing fillers. Reinforcing fillers can impart mechanical strength to the cured product obtained by curing the resin composition of the present invention, thereby improving its performance as a protective agent or adhesive. Furthermore, reinforcing fillers are generally non-conductive. Additionally, in this specification, fillers equivalent to the main conductive filler (A) and carbon-based conductive fillers (B) and (C) described above, even if they can impart mechanical strength like the reinforcing fillers described above, are not classified as reinforcing fillers.

[0119] Inorganic fillers are preferred as reinforcing fillers, such as fumed silica micro powder, precipitated silica micro powder, calcined silica micro powder, fumed titanium dioxide micro powder, quartz micro powder, calcium carbonate micro powder, diatomaceous earth micro powder, alumina micro powder, aluminum hydroxide micro powder, zinc oxide micro powder, and zinc carbonate micro powder. Furthermore, a single reinforcing filler can be used alone, or two or more can be combined in any proportion.

[0120] In addition, the reinforcing filler can be surface-treated with surface-treatment agents such as siloxane oligomers. Examples of siloxane oligomers that can be used as surface-treatment agents include organoalkoxysilanes such as methyltrimethoxysilane; organohalosilanes such as trimethylchlorosilane; organosilazanes such as hexamethyldisilazane; α,ω-silanol-terminated dimethylsiloxane oligomers; α,ω-silanol-terminated methylphenylsiloxane oligomers; and α,ω-silanol-terminated methylvinylsiloxane oligomers. Furthermore, a single surface-treatment agent can be used, or two or more can be combined in any proportion.

[0121] The volume average particle size (primary average particle size) of the reinforcing filler is not particularly limited, for example, it can be in the range of 0.005 μm or more and 1000 μm or less.

[0122] Furthermore, the proportion of reinforcing filler in the resin composition of the present invention is not particularly limited, and can be, for example, 0.10% or more and 5.00% or less, based on the total volume of the resin composition as 100% by volume.

[0123] <<Catalyst Solidification>>

[0124] When the resin composition of the present invention is curable, it may optionally contain a curing catalyst. The type of curing catalyst is not particularly limited as long as it can cure the matrix resin, and can be appropriately selected according to the matrix resin and the type of curing reaction. Here, the curing reaction of the matrix resin is not particularly limited; examples include addition reactions such as hydrosilylation; condensation reactions; ring-opening reactions; and combinations thereof. For example, when the resin composition of the present invention contains an organosilicon resin as the matrix resin, hydrosilylation and condensation reactions are preferably used as the curing reactions, and combinations thereof are more preferred. Hereinafter, the catalyst for the hydrosilylation reaction (hereinafter referred to as "catalyst for hydrosilylation reaction") and the catalyst for the condensation reaction (hereinafter referred to as "catalyst for condensation reaction") will be described in detail.

[0125] Catalyst for hydrosilylation reaction-

[0126] The catalyst used in the hydrosilylation reaction can promote the hydrosilylation reaction between the alkenyl group and the hydrogen atom directly bonded to the silicon atom (hereinafter referred to as "silicon atom bonded hydrogen atom"), thereby curing the resin composition.

[0127] Examples of catalysts for hydrosilylation reactions include platinum-based catalysts such as platinum black, platinum-loaded activated carbon, platinum-loaded silica micropowder, chloroplatinic acid, alcoholic solutions of chloroplatinic acid, platinum olefin complexes, and platinum vinylsiloxane complexes; palladium-based catalysts such as tetra(triphenylphosphine)palladium; rhodium-based catalysts; iron-based catalysts; ruthenium-based catalysts; and iron / cobalt-based catalysts. Furthermore, from the viewpoint of improving operability and the pot life of the resin composition, these hydrosilylation catalysts can be in the form of particulates dispersed or encapsulated in thermoplastic resins.

[0128] Furthermore, the catalyst for the hydrosilylation reaction can be a single type or a combination of two or more types in any proportion. Platinum-based catalysts are preferred for the hydrosilylation reaction.

[0129] The content of the catalyst for the hydrosilylation reaction in the resin composition of the present invention is not particularly limited as long as it is an amount that can fully exert the function of the curing catalyst (hereinafter referred to as "catalytic amount"). It can be appropriately selected according to the desired curing conditions, but for example, it can be more than 1 ppm by mass and less than 1000 ppm by mass relative to the organosilicon resin used as the matrix resin.

[0130] Catalyst for condensation reaction-

[0131] The catalyst for the condensation reaction can promote the de-alcoholization condensation reaction between alkoxysilyl groups, thereby curing the resin composition. By using the catalyst for the condensation reaction in conjunction with the above-mentioned catalyst for the hydrosilylation reaction, the curing properties of the resin composition containing the silicone resin under heating conditions of room temperature to 50°C or below can be improved, and the resin composition can further exhibit excellent adhesive properties.

[0132] Examples of tin compounds used as catalysts for condensation reactions include dimethyltin dinedecanoate and stannous octoate; titanium compounds such as tetra(isopropoxy)titanium, tetra(n-butoxy)titanium, tetra(tert-butoxy)titanium, di(isopropoxy)bis(ethyl acetoacetate)titanium, di(isopropoxy)bis(methyl acetoacetate)titanium, tetraacetylacetone titanium, and di(isopropoxy)bis(acetylacetone)titanium; aluminum compounds such as aluminum triacetylacetone, aluminum triacetylacetone, and tri(sec-butoxy)aluminum; nickel compounds such as nickel diacetylacetone; cobalt compounds such as cobalt triacetylacetone; zinc compounds such as zinc diacetylacetone; and zirconium compounds such as zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetraacetylacetone, zirconium tributoxymonoacetylacetone, zirconium monobutoxyacetylacetone, zirconium dibutoxybis(ethyl acetoacetate), zirconium tetraacetylacetone, and zirconium tributoxymonostearate.

[0133] Furthermore, the catalyst for the condensation reaction can be a single type or a combination of two or more types in any proportion. Moreover, titanium compounds are preferred as catalysts for the condensation reaction.

[0134] The content of the catalyst for the condensation reaction in the resin composition of the present invention is not particularly limited as long as it is the catalytic amount, and can be appropriately selected according to the desired curing conditions. However, for example, it can be 0.01 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the above-mentioned matrix resin.

[0135] <<Crossing Agents>>

[0136] The resin composition of the present invention may optionally contain a crosslinking agent. Preferably, the crosslinking agent is a substance having three or more alkenyl (vinyl, etc.) or silicon-to-hydrogen atom crosslinking reaction sites, and capable of reacting with the matrix resin or the like to form a three-dimensional crosslinked structure during the curing reaction carried out by the aforementioned curing catalyst. Examples of such crosslinking agents include Si-H crosslinking agents having three or more silicon-to-hydrogen atom bonds per molecule, and vinyl crosslinking agents having three or more vinyl groups per molecule. Furthermore, a single crosslinking agent may be used, or two or more may be used in any proportion.

[0137] -Si-H crosslinking agent-

[0138] If the resin composition contains a Si-H crosslinking agent, the Si-H crosslinking agent can undergo a hydrosilylation reaction with alkenyl groups, such as those found in silicone resins, to form a three-dimensional high-density crosslinked structure. As a result, the resin composition exhibits excellent adhesive properties and the strength of the cured product formed from the resin composition is improved.

[0139] Here, as a Si-H crosslinking agent, a chain-like organopolysiloxane having three or more silicon atoms bonded to hydrogen atoms in one molecule is preferably used. Examples of the organic groups bonded to silicon atoms in this chain-like organopolysiloxane include monovalent hydrocarbon groups without aliphatic unsaturated bonds, such as alkyl, cycloalkyl, aryl, aralkyl, and haloalkyl groups; alkyl and aryl groups are preferred, and methyl and phenyl groups are particularly preferred.

[0140] Furthermore, the chain structure of the above-mentioned chain organopolysiloxane can be exemplified as a straight chain, a straight chain with partial branches, or a branched chain, preferably a straight chain.

[0141] Furthermore, the viscosity of the aforementioned chain-like organopolysiloxanes and other Si-H crosslinking agents is not particularly limited, but is preferably 1 mPa·s or more and 10,000 mPa·s or less. The viscosity of the Si-H crosslinking agent can be measured using the same method as that used for the "matrix resin" described above.

[0142] Examples of chain-like organopolysiloxanes having three or more silicon atoms bonded to hydrogen atoms in one molecule include methyl-hydrogen polysiloxanes whose molecular chains are capped at both ends by trimethylsiloxy groups, methyl-hydrogen siloxane-dimethylsiloxane copolymers whose molecular chains are capped at both ends by trimethylsiloxy groups, and methyl-hydrogen siloxane-dimethylsiloxane copolymers whose molecular chains are capped at both ends by dimethylsiloxy groups. These chain-like organopolysiloxanes can be used alone or in combination of two or more in any proportion. Furthermore, from the viewpoint of enabling the resin composition to exhibit excellent adhesive properties, methyl-hydrogen siloxane-dimethylsiloxane copolymers whose molecular chains are capped at both ends by trimethylsiloxy groups are preferred.

[0143] Furthermore, the proportion of Si-H crosslinking agent contained in the resin composition is not particularly limited, but from the viewpoint of enabling the resin composition to exhibit excellent adhesion, it is preferably 0.10% by mass or more, more preferably 0.40% by mass or more, and more preferably 1.50% by mass or less, more preferably 1.20% by mass or less, based on the total mass of the resin composition of 100% by mass.

[0144] -Vinyl crosslinker-

[0145] If the resin composition contains a vinyl crosslinking agent, the vinyl crosslinking agent will also react during, for example, a hydrosilylation reaction occurring between the silicon atoms bonded to hydrogen atoms in the Si-H crosslinking agent and the alkenyl groups in the silicone resin. Furthermore, the formation of a three-dimensional high-density crosslinked structure through this vinyl crosslinking agent enables the resin composition to exhibit excellent adhesion and improves the strength of the cured product formed from the resin composition.

[0146] As a vinyl crosslinking agent, a silicon-containing compound having three or more vinyl groups in one molecule is preferred. Examples of such silicon-containing compounds include tetra(vinyldimethylsiloxy)silane, tris(vinyldimethylsiloxy)methylsilane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, and dimethyl-methylvinylsiloxane oligomers. Among these silicon-containing compounds, tetra(vinyldimethylsiloxy)silane is more preferred from the viewpoint of enabling the resin composition to exhibit excellent adhesive properties.

[0147] Furthermore, the proportion of the vinyl crosslinking agent contained in the resin composition is not particularly limited, but from the viewpoint of enabling the resin composition to exhibit excellent adhesion, it is preferably 0.10% by mass or more, more preferably 0.30% by mass or more, and more preferably 1.20% by mass or less, and more preferably 1.00% by mass or less, based on the total mass of the resin composition of 100% by mass.

[0148] <<Siloxanes Containing Si-H and Trialkoxy Groups>>

[0149] In one aspect of the present invention, when using an organosilicon resin as the matrix resin, the resin composition of the present invention preferably contains a siloxane containing a trialkoxysilyl group (referred to in this specification as "siloxane containing Si-H and trialkoxy group") having only one silicon atom bonded to a hydrogen atom in one molecule and having at least one trialkoxysilyl group.

[0150] Because siloxanes containing Si-H and trialkoxy groups have silicon atoms bonded to hydrogen atoms, they react with alkenyl-based silicone resins or vinyl crosslinking agents during curing via hydrosilylation, thereby being incorporated into the cured product. Furthermore, because siloxanes containing Si-H and trialkoxy groups possess highly reactive trialkoxysilyl groups, they can improve the adhesiveness of the resin composition while participating in curing via condensation reactions.

[0151] Here, the trialkoxysilyl group contained in the siloxane containing Si-H and trialkoxy groups is preferably trimethoxysilyl or triethoxysilyl. Furthermore, the groups in the siloxane containing Si-H and trialkoxy groups, other than the silicon atom bonded to the hydrogen atom and the trialkoxysilyl group, are preferably non-reactive functional groups, more preferably alkyl or aryl groups.

[0152] As siloxanes containing Si-H and trialkoxy groups, compounds having the following structures are preferred examples.

[0153] [Chemical Formula 1]

[0154]

[0155] In the above formula, R 1 It is a monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, and multiple R groups exist. 1 They can be the same or different. Furthermore, in the above formula, R... 2 It is an alkyl group, R 3 It is an alkylene group, and p is an integer greater than 1 and less than 50.

[0156] As a component of R 1 The monovalent hydrocarbon group without aliphatic unsaturated bonds includes, for example, chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and octadecyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and haloalkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl. Alkyl and aryl groups are preferred, and methyl and phenyl groups are more preferred.

[0157] As a component of R 2Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, are examples. Among them, methyl and ethyl are preferred.

[0158] As a component of R 3 The alkylene group is preferably an alkylene group with 2 or more but less than 10 carbon atoms, and more preferably ethylene or propyleneene.

[0159] Furthermore, p is an integer greater than or equal to 1 and less than 50, as described above, preferably an integer greater than or equal to 1 and less than 10, and more preferably an integer greater than or equal to 1 and less than 5.

[0160] Furthermore, the proportion of siloxanes containing Si-H and trialkoxy groups contained in the resin composition is not particularly limited, but from the viewpoint of enabling the resin composition to exhibit excellent adhesive properties, it is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and more preferably 1.50% by mass or less, more preferably 1.00% by mass or less, based on 100% by mass of the total weight of the resin composition.

[0161] <<Other arbitrary ingredients>>

[0162] Other than the components mentioned above, such as adhesion promoters, curing inhibitors, chain extenders, and hollow fillers are also possible components.

[0163] If the resin composition contains an adhesion promoter, the resin composition can exhibit excellent adhesive properties. There are no particular limitations on the adhesion promoter; for example, substances described in International Publication No. 2018 / 043270 can be used. Furthermore, an adhesion promoter can be used alone or in combination of two or more in any proportion. From the viewpoint of enabling the resin composition to exhibit excellent adhesive properties, examples of adhesion promoters preferably include 3-glycidyl etheroxypropyltrimethoxysilane, 3-glycidyl etheroxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and 1,6-bis(triethoxysilyl)hexane. Alkane, 1,4-bis(trimethoxysilyl)hexane, 1,5-bis(trimethoxysilyl)hexane, 2,5-bis(trimethoxysilyl)hexane, 1-methyldimethoxysilyl-6-trimethoxysilylhexane, 1-phenyldiethoxysilyl-6-triethoxysilylhexane, 1,6-bis(methyldimethoxysilyl)hexane, 3-methacryloyloxypropyltrimethoxysilane, tetraethoxysilane, etc. Among these, from the viewpoint of further enhancing the adhesive properties of the resin composition, 3-glycidyloxypropyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, 3-methacryloyloxypropyltrimethoxysilane, and tetraethoxysilane are preferred.

[0164] In some embodiments, from the viewpoint of rapidly exhibiting good adhesion after the resin composition has cured, the resin composition may contain both 3-methacryloxypropyltrimethoxysilane and tetraethoxysilane as adhesion promoters. In this case, the ratio of 3-methacryloxypropyltrimethoxysilane to tetraethoxysilane is not particularly limited. For example, the mass ratio of 3-methacryloxypropyltrimethoxysilane to tetraethoxysilane (3-methacryloxypropyltrimethoxysilane:tetraethoxysilane) may be in the range of 1:1 to 1:10, or 1:1 to 1:7, or 1:1 to 1:5, or 1:1 to 1:4, or 1:2 to 1:10, or 1:2 to 1:7, or 1:2 to 1:5, or 1:2 to 1:4.

[0165] Furthermore, the proportion of the adhesive accelerator contained in the resin composition is not particularly limited, but from the viewpoint of enabling the resin composition to exhibit excellent adhesive properties, it is preferably 0.50% by mass or more, more preferably 1.00% by mass or more, even more preferably 1.50% by mass or more, and preferably 5.00% by mass or less, more preferably 4.00% by mass or less, and even more preferably 3.00% by mass or less, based on the total mass of the resin composition as 100% by mass.

[0166] Curing inhibitors are components used to appropriately control the curing rate of a resin composition. If the resin composition contains a curing inhibitor, its storage stability and workability are improved. There are no particular limitations on the curing inhibitor; for example, substances described in International Publication No. 2018 / 043270 can be used. Furthermore, a single curing inhibitor can be used alone, or two or more can be used in any proportion. Examples of preferred curing inhibitors include 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynylcyclohexanol. Among these, 2-phenyl-3-butyn-2-ol is preferred.

[0167] Furthermore, the proportion of curing inhibitor contained in the resin composition is not particularly limited, but it is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, and preferably 4.00% by mass or less, more preferably 3.00% by mass or less, based on 100% by mass of the total weight of the resin composition.

[0168] Chain extenders are components used in the hydrogenation silylation reaction to improve the elongation and flexibility of the cured product. There are no particular limitations on the type of chain extender; for example, linear siloxanes with silicon atoms bonded to hydrogen atoms only at the two ends of the molecular chain, as described in International Publication No. 2020 / 121939, can be used. Furthermore, a single chain extender can be used, or two or more can be combined in any proportion. 1,1,5,5-Tetramethyl-3,3-diphenyltrisiloxane is preferred as a chain extender.

[0169] Furthermore, the proportion of the chain extender contained in the resin composition, based on the total mass of the resin composition as 100% by mass, is preferably 0.10% by mass or more, more preferably 0.30% by mass or more, and preferably 4.00% by mass or less, more preferably 2.00% by mass or less.

[0170] Hollow fillers are components used to reduce the specific gravity of resin compositions and / or cured products. There are no particular limitations on hollow fillers; known fillers with internal voids and composed of glass and / or resin can be used. Furthermore, a single hollow filler can be used alone, or two or more can be combined in any proportion. Additionally, in this specification, fillers equivalent to the aforementioned main conductive filler (A) and carbon-based conductive fillers (B) and (C), even those with internal spaces like the aforementioned hollow fillers that contribute to weight reduction, are not classified as hollow fillers.

[0171] Furthermore, the proportion of hollow filler contained in the resin composition, for example, based on the total mass of the resin composition as 100% by mass, can be more than 0.01% by mass and less than 5.00% by mass.

[0172] <Method for manufacturing resin composition>

[0173] The resin composition of the present invention can be manufactured by mixing the above-mentioned components. The mixing method is not particularly limited; for example, known mixing apparatus can be used. Examples of known mixing apparatus include, for instance, a single-shaft or bi-shaft continuous mixer, a two-roll mill, a three-roll mill, a Ross mixer, a Hobart mixer, a dental mixer, a planetary mixer, a kneader, and a Henschel mixer.

[0174] Properties of the Resin Composition

[0175] In one aspect of the invention, the resin composition may be a curable resin composition or a room temperature curable resin composition.

[0176] Furthermore, in this specification, the term "room temperature curing property" of a resin composition means that the resin composition can be cured at a temperature range of 10°C to 40°C.

[0177] Here, in the case where the resin composition of the present invention is a curable resin composition, although it can be used as a one-component type resin composition, in order to uniformly cure both the surface layer and the interior without relying on moisture and water in the atmosphere, it is preferably a multi-component type, and particularly preferably a two-liquid type resin composition.

[0178] In one embodiment of the present invention, when the resin composition is a two-liquid type, the liquid I component and the liquid II component can be as described below.

[0179] <<Liquid I Component>>

[0180] It contains at least a silicone resin, a main conductive filler (A), a carbon-based conductive filler (B) and / or a carbon-based conductive filler (C), a catalyst for hydrosilylation reaction, and a catalyst for condensation reaction, and does not contain a siloxane containing Si-H and trialkoxy and a Si-H crosslinking agent. In addition, the liquid I component can optionally contain a vinyl crosslinking agent.

[0181] <<Liquid II Component>>

[0182] It contains at least a silicone resin, a main conductive filler (A), a carbon-based conductive filler (B) and / or a carbon-based conductive filler (C), a siloxane containing Si-H and trialkoxy, and a Si-H crosslinking agent, and does not contain a catalyst for hydrosilylation reaction and a catalyst for condensation reaction. In addition, the liquid II component can optionally contain a vinyl crosslinking agent.

[0183] The above liquid I component and liquid II component can be sealed in a closed container under moisture-proof conditions for long-term storage. And, after mixing the liquid I component and the liquid II component, it cures rapidly at room temperature or under heating at 50 °C or below to form a cured product.

[0184] In addition, in one embodiment of the present invention, from the viewpoint of enabling the resin composition to exhibit excellent adhesiveness, the ratio of the number of moles of hydrogen atoms bonded to silicon atoms in the resin composition to the number of moles of vinyl can be 0.70 or more, can be 1.05 or more, can be 1.20 or more, and at the same time can be 1.80 or less, can be 1.60 or less.

[0185] (Cured Product)

[0186] The cured product of the present invention is obtained by curing the above resin composition. The curing method and curing conditions are not particularly limited and can be appropriately selected according to the type of matrix resin, etc. As described above, the filler sedimentation and thickening of the resin composition of the present invention are suppressed. Therefore, in the cured product formed using this resin composition, the main conductive filler (A) and the carbon-based conductive fillers (B) and (C) are arranged without deviation, and excellent conductivity can be exhibited.

[0187] (Uses of resin compositions and cured products)

[0188] The uses of the resin composition and cured product of the present invention are not particularly limited, but are preferably used in the field of electronic devices or electronic components. Specifically, they are preferably used for internal or external electrodes of chip-type electronic components; for various components (electrodes, wiring, etc.) such as RFID, electromagnetic wave shielding, oscillator bonding, membrane switches, touch panels, or electroluminescence; and for the manufacture of various constituent components (electrodes, battery cells, modules, etc.) of batteries (secondary batteries, solar cells, etc.). In one aspect of the present invention, the electronic device comprises at least one of the resin composition and the cured product of the present invention. Furthermore, in another aspect of the present invention, the electronic component comprises at least one of the resin composition and the cured product of the present invention.

[0189] Example

[0190] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0191] -Experiment 1-

[0192] (Assessment and Measurement Methods)

[0193] In Examples 1-18 and Comparative Examples 1-9, the following methods were used for various evaluation and measurement methods.

[0194] <Viscosity (Thickening Inhibition)>

[0195] The viscosities (Pa·s) of the prepared liquid I and liquid II components, as well as the freshly mixed resin composition obtained by mixing the liquid I and liquid II components, were measured at 25°C using a viscometer (Anton Paar Rheocompass MCR302). Furthermore, the geometry was measured using parallel plates with a diameter of 20 mm and a gap of 0.5 mm at a shear rate of 10 s. -1 The lower the viscosity of the resin composition, the more inhibited the thickening of the resin composition is.

[0196] <Electrical conductivity>

[0197] The resin composition obtained by mixing component I and component II was compressed at 100°C for 15 minutes to cure it, resulting in a cured sheet (i.e., a sheet-like cured material). After standing at room temperature for 1 hour, the volume resistivity of the surface and back of the cured sheet was measured using a volume resistivity measuring device (four-probe, Nittoseiko Analytech "Loresta-GP MCP-T610"). The lower the volume resistivity, the better the conductivity of the cured material.

[0198] <Conductivity after high temperature and high humidity test (Example 17 and Comparative Example 5 only)>

[0199] Cured sheets were prepared in the same manner as those used in the "Conductivity" assessment (different from the cured sheets used in the "Conductivity" assessment). The volume resistivity of the resulting cured sheets was measured after standing at room temperature for 1 hour (time elapsed: 0 days), in the same manner as for the "Conductivity" assessment. Next, the cured sheets were degraded under high temperature and high humidity conditions of 85°C and 85%RH for a certain period (14 days, 21 days, 24 days, and 30 days; furthermore, 21 days was only performed for Comparative Example 5, and 24 days was only performed for Example 17). After degradation, the volume resistivity was measured after standing at room temperature for 1 hour, in the same manner as for the "Conductivity" assessment. Furthermore, the "volume resistivity" disclosed in Table 7 below is the average value for both the surface and back surfaces.

[0200] <Adhesion>

[0201] A resin composition obtained by mixing liquid I and liquid II was sandwiched between two aluminum plates (the materials to be bonded) using a spacer made of Teflon (registered trademark), with a thickness of 0.25 mm. The mixture was then allowed to stand at 25±2℃ and 50±5% humidity to cure, resulting in a bonded test specimen.

[0202] For the obtained bonded test specimens, the tensile shear bond strength (MPa) was determined after 168 hours and 336 hours of curing. Furthermore, the tensile shear bond strength was determined according to the method specified in JIS K 6850:1999 "Adhesives—Test method for tensile shear bond strength of rigid bonded materials", and at a tensile speed of 5 mm / min.

[0203] <Packing Settling>

[0204] For the prepared liquid I and liquid II components, as well as the freshly mixed resin composition obtained by mixing the liquid I and liquid II components, the presence or absence of filler sedimentation is visually confirmed, and the following criteria are used for evaluation.

[0205] N: Unfilled settling.

[0206] Y: There is packing material settling.

[0207] Furthermore, in this invention, even if filler sedimentation is confirmed in at least one of the I-component and II-component, as long as filler sedimentation is not confirmed in the resin composition obtained by mixing them, it can be said that the task of suppressing filler sedimentation has been achieved.

[0208] (Material)

[0209] In Examples 1-18 and Comparative Examples 1-9, the following materials were used for various purposes.

[0210] <Masterbatch>

[0211] • A mixture of the following two components

[0212] Dimethyl polysiloxane with dimethyl vinylsiloxy groups at both ends of its molecular chain (viscosity: 2,000 mPa·s, vinyl content (Vi content): 0.23% by mass): 74.0% by mass

[0213] Fumed silica micro powder: 26.0% by mass

[0214] <Matrix resin (1)>

[0215] • Dimethyl polysiloxane with dimethyl vinylsiloxy groups at both ends of the molecular chain (viscosity: 2,000 mPa·s, Vi content: 0.23% by mass)

[0216] <Matrix resin (2)>

[0217] • A mixture of the following two components

[0218] Dimethyl polysiloxane with dimethyl vinylsiloxy groups at both ends of the molecular chain (viscosity: 2,000 mPa·s, Vi content: 0.23% by mass): 68.0% by mass

[0219] From the formula: (CH2=CH(CH3)2SiO) 0.5 )4((CH3)3SiO 0.5 ) 40 (SiO) 2.0 ) 56 The indicated vinyl-containing siloxane resin (weight average molecular weight: 20,000, Vi content: 1.6% by mass): 32.0% by mass

[0220] <Main conductive filler (A)>

[0221] • Nickel-plated graphite (manufactured by Metco, “E-FiLL (registered trademark) #2701”, graphite with nickel coating, plate-like, volume average particle size: 100μm)

[0222] <Carbon-based conductive filler (B)>

[0223] ・Carbon nanostructure (manufactured by CABOT Corporation, "ATHLOS (registered trademark) SR1200 CNS", branched nanotubes, aspect ratio: 50 or more)

[0224] ・Carbon nanotubes (manufactured by OCSiAl, "TUBALL (registered trademark) 602", aspect ratio: 3000 or more)

[0225] <Carbon-based conductive filler (C)>

[0226] ・Carbon black (manufactured by Orion Engineered Carbon, "Printex (registered trademark) XE2B", specific surface area: 1,000 m 2 / g, aspect ratio: less than 50)

[0227] <Catalyst for hydrosilylation reaction>

[0228] ・1,3-Divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (platinum-based catalyst)

[0229] <Catalyst for condensation reaction>

[0230] ・Mixture of the following 3 components

[0231] Titanium bis(isopropoxy)bis(ethyl acetoacetate): 78.4% by mass

[0232] Methyltrimethoxysilane: 20.0% by mass

[0233] Isopropanol: 1.6% by mass [[ID=**39**]]

[0234] <Vinyl crosslinker>

[0235] ・Tetrakis(ethenyldimethylsilyloxy)silane

[0236] <Si-H crosslinker>

[0237] ・Methylhydrogen siloxane-dimethylsiloxane copolymer capped with trimethylsilyloxy at both ends of the molecular chain

[0238] <Siloxane containing Si-H and trialkoxy>

[0239] ・Compound having the following structure:

[0240] [Chemical formula 2]

[0241]

[0242] <Adhesion Promoter>

[0243] ・ Adhesion Promoter (1): 1,6 - bis(trimethoxysilyl)hexane

[0244] ・ Adhesion Promoter (2): 3 - glycidoxypropyltrimethoxysilane

[0245] <Curing Inhibitor>

[0246] ・ 2 - phenyl - 3 - butyn - 2 - ol

[0247] <Chain Extender>

[0248] ・ 1,1,5,5 - tetramethyl - 3,3 - diphenyltrisiloxane

[0249] (Example 1)

[0250] <Preparation of Component I Liquid>

[0251] 3.06 parts by mass of masterbatch, 33.87 parts by mass of main conductive filler (A), 0.72 parts by mass of carbon - based conductive filler (C), 11.40 parts by mass of matrix resin (1), and 0.50 parts by mass of vinyl cross - linker were premixed to obtain a premix. 0.20 parts by mass of hydrosilylation reaction catalyst and 0.25 parts by mass of condensation reaction catalyst were added to the obtained premix, and after sufficient stirring, defoaming was carried out to prepare 50.00 parts by mass of Component I Liquid. For the obtained Component I Liquid, viscosity (thickening inhibition) and filler sedimentation were evaluated. The results are shown in Table 4.

[0252] <Preparation of Component II Liquid>

[0253] 3.06 parts by mass of masterbatch, 33.69 parts by mass of main conductive filler (A), 0.72 parts by mass of carbon - based conductive filler (C), 7.13 parts by mass of matrix resin (1), 1.20 parts by mass of Adhesion Promoter (1), and 1.20 parts by mass of Adhesion Promoter (2) were premixed to obtain a premix. In the obtained premix, 0.30 parts by mass of siloxane containing Si - H and trialkoxy, 0.60 parts by mass of Si - H cross - linker, and 0.60 parts by mass of chain extender were added, and after sufficient stirring, defoaming was carried out to prepare 50.00 parts by mass of Component II Liquid. For the obtained Component II Liquid, viscosity (thickening inhibition) and filler sedimentation were evaluated. The results are shown in Table 4.

[0254] <Mixing of Component I Liquid and Component II Liquid>

[0255] The prepared liquid I and liquid II components were respectively filled into a plastic duplex mixing cartridge manufactured by MIX-PAC, and a static mixing tube (17 segments) was installed at the front end of the cartridge. Liquid I and liquid II components were mixed and extruded using a glue gun, and the viscosity (thickening inhibition) and filler settling of the mixture were rapidly evaluated. Additionally, adhesion and conductivity were evaluated. The results are shown in Table 4. Furthermore, the molar ratio of silicon atoms bonded to hydrogen atoms to vinyl groups in the resin composition (Si-H / Vi) is shown in Table 1. Further, the content ratio (volume %) of various fillers in the resin composition is shown in Table 4.

[0256] (Examples 2-18, Comparative Examples 1-8)

[0257] In preparing liquid component I and liquid component II, resin compositions consisting of liquid component I and liquid component II were prepared in the same manner as in Example 1, except that the materials used were changed as shown in Tables 1-3. The two components were then mixed and various evaluations were performed. The results are shown in Tables 4-6. Furthermore, when carbon-based conductive filler (B) was used in the preparation of liquid component I and / or liquid component II, it was included in the premix in the same manner as the carbon-based conductive filler (C) in Example 1. Additionally, when matrix resin (2) was used in the preparation of liquid component I and / or liquid component II, it was included in the premix in the same manner as the matrix resin (1) in Example 1.

[0258] Furthermore, the conductivity after high temperature and high humidity tests was also evaluated for Example 17 and Comparative Example 5. The results are shown in Table 7.

[0259] (Comparative Example 9)

[0260] Apart from changing the materials used as shown in Table 3, the preparation of liquid component I and liquid component II was attempted in the same manner as in Example 1. However, both liquid component I and liquid component II were excessively thickened and clearly unworkable. Therefore, no evaluations were conducted.

[0261] Furthermore, in Tables 1 to 7 shown below,

[0262] "Filling (A)" refers to the main conductive filler (A).

[0263] "Fill (B)" refers to carbon-based conductive filler (B).

[0264] "Fill (C)" refers to carbon-based conductive filler (C).

[0265] "CNS" refers to carbon nanostructures (branched nanotubes).

[0266] "CNT" refers to carbon nanotubes.

[0267] "SiH+TAS siloxane" refers to siloxanes containing Si-H and trialkoxy groups.

[0268] "Hydrosilane catalyst" refers to the catalyst used in the hydrosilane reaction.

[0269] "Condensation catalyst" refers to a catalyst used in condensation reactions.

[0270] "Liquid I" refers to the components of Liquid I.

[0271] "II liquid" refers to the components of II liquid.

[0272] "Si-H / Vi" refers to the ratio of the molar number of hydrogen atoms bonded to silicon atoms to the molar number of vinyl groups in the resin composition.

[0273] "OVLD" means that the volume resistivity is outside the measurement range (exceeding the upper limit).

[0274] "(B)+(C)" refers to the total (volume %) of the content of carbon-based conductive filler (B) and carbon-based conductive filler (C).

[0275] "(A)+(B)+(C)" refers to the total (volume %) of the content of the main conductive filler (A), carbon-based conductive filler (B), and carbon-based conductive filler (C).

[0276] "(C) / (B)" refers to the ratio (times) of the volumetric content of carbon-based conductive filler (C) to the volumetric content of carbon-based conductive filler (B).

[0277] [Table 1]

[0278]

[0279] [Table 2]

[0280]

[0281] [Table 3]

[0282]

[0283] [Table 4]

[0284]

[0285] [Table 5]

[0286]

[0287] [Table 6]

[0288]

[0289] [Table 7]

[0290]

[0291] As shown in Tables 4 and 5, the resin compositions of Examples 2, 4, 5, 16, 17 and 18, which contain a matrix resin and a specified proportion of main conductive filler (A) and satisfy condition (1), exhibit suppressed filler sedimentation and sufficiently low viscosity, thereby suppressing thickening. Furthermore, the cured products formed from these resin compositions possess excellent conductivity and adhesion.

[0292] As shown in Tables 4 and 5, the resin compositions of Examples 1, 7-9, and 12, which contain a matrix resin and a specified proportion of main conductive filler (A) and satisfy condition (2), exhibit suppressed filler sedimentation and sufficiently low viscosity, thereby suppressing thickening. Furthermore, the cured product formed from this resin composition possesses excellent conductivity and adhesion.

[0293] As shown in Tables 4 and 5, the resin compositions of Examples 3, 6, 10, 11 and 13-15, which contain a matrix resin and a specified proportion of main conductive filler (A) and satisfy condition (3), exhibit suppressed filler sedimentation and sufficiently low viscosity, thereby suppressing thickening. Furthermore, the cured product formed from this resin composition possesses excellent conductivity and adhesion.

[0294] As shown in Table 6, the resin compositions of Comparative Examples 1, 3 and 5, which do not contain carbon-based conductive fillers (B) and (C), cannot suppress filler sedimentation.

[0295] As shown in Table 6, the resin compositions of Comparative Examples 2 and 4, which contain both carbon-based conductive fillers (B) and (C), but whose total content of main conductive filler (A) and carbon-based conductive fillers (B) and (C) is 36.50% by volume or more, exhibit increased viscosity and thickening was not inhibited.

[0296] As shown in Table 6, in Comparative Example 6, which uses a resin composition containing both carbon-based conductive fillers (B) and (C), but where the carbon-based conductive filler (B) is 0.10% by volume or less, and the total content of the main conductive filler (A) and the carbon-based conductive fillers (B) and (C) is 20.60% by volume or less, the volume resistivity of the cured product increases and the conductivity decreases.

[0297] As shown in Table 6, the resin composition of Comparative Example 7, which contains carbon-based conductive filler (C) but whose content of carbon-based conductive filler (C) is less than 1.00% by volume, failed to suppress filler sedimentation.

[0298] As shown in Table 6, the resin composition of Comparative Example 8, which contains carbon-based conductive filler (C) but has a carbon-based conductive filler (C) content of 6.00% by volume or more, exhibits increased viscosity and thickening that is not suppressed.

[0299] Furthermore, Comparative Example 9 described in Table 6 was not evaluated as mentioned above.

[0300] Furthermore, as shown in Table 7, the cured product of Example 17, formed from a resin composition comprising a matrix resin and a specified proportion of main conductive filler (A) and satisfying condition (1), can maintain conductivity relatively well even when exposed to high temperature and high humidity conditions for a long time.

[0301] Experiment 2

[0302] (Assessment and Measurement Methods)

[0303] In Examples 19–28, the various evaluation and measurement methods used were the same as those used in Experiment 1.

[0304] In addition, the assessment of "adhesion" included the determination of shear bond strength (MPa) after 168 hours and 336 hours of curing, as well as the determination of shear bond strength (MPa) after 6 hours of curing.

[0305] (Material)

[0306] In Examples 19-28, the following materials were used for various purposes.

[0307] <Main conductive filler (A)>

[0308] • Nickel-plated graphite (manufactured by Metco, “E-FiLL (registered trademark) #2701”, graphite with nickel coating, plate-like, volume average particle size: 100μm)

[0309] <Main conductive filler (A2)>

[0310] • Nickel-plated graphite (Weber Corporation "VNCG-085", graphite with nickel coating, plate-like, volume average particle size: 85μm)

[0311] <Carbon-based conductive filler (B)>

[0312] • Carbon nanostructures (CABOT Corporation "ATHLOS (registered trademark) SR1200 CNS", branched nanotubes, aspect ratio: 50 or higher)

[0313] <Carbon-based conductive filler (C)>

[0314] • Carbon black (manufactured by Orion Engineered Carbon, "Printex XE2B" (registered trademark), specific surface area: 1,000 m²) 2 / g, Aspect ratio: less than 50)

[0315] <Matrix resin (2)>

[0316] • A mixture of the following two components

[0317] Dimethyl polysiloxane with dimethyl vinylsiloxy groups at both ends of the molecular chain (viscosity: 2,000 mPa·s, Vi content: 0.23% by mass): 68.0% by mass

[0318] From the formula: (CH2=CH(CH3)2SiO) 0.5 )4((CH3)3SiO 0.5 ) 40 (SiO) 2.0 ) 56 The indicated vinyl-containing siloxane resin (weight average molecular weight: 20,000, Vi content: 1.6% by mass): 32.0% by mass

[0319] Vinyl crosslinking agent

[0320] Tetra(vinyldimethylsiloxy)silane

[0321] Catalysts for Hydrosilylation Reactions

[0322] • 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (platinum-based catalyst)

[0323] Catalysts for condensation reactions

[0324] • A mixture of the following three components

[0325] Di(isopropoxy)bis(ethyl acetoacetate)titanium: 78.4% by mass

[0326] Methyltrimethoxysilane: 20.0% by mass

[0327] Isopropanol: 1.6% by mass

[0328] <Catalysts for Condensation Reactions (2)>

[0329] Tetra-(tert-butoxy)titanium

[0330] <Masterbatch (2)>

[0331] • A mixture of the following three components

[0332] Aluminum triacetylacetonate: 20.0% by mass (catalyst for condensation reaction)

[0333] Vinyl-containing siloxane resin represented by the formula: (CH2=CH(CH3)2SiO 0.5 )4((CH3)3SiO 0.5 ) 40 (SiO 2.0 ) 56 : 22.0% by mass (weight-average molecular weight: 20,000, Vi content: 1.6% by mass)

[0334] Dimethylpolysiloxane capped at both ends of the molecular chain with dimethylethenylsilanyloxy groups: 58.0% by mass (viscosity: 2,000 mPa・s, Vi content: 0.23% by mass)

[0335] [Adhesion promoter]<

[0336] ・ Adhesion promoter (1): 1,6-bis(trimethoxysilyl)hexane

[0337] ・ Adhesion promoter (2): 3-glycidoxypropyltrimethoxysilane

[0338] ・ Adhesion promoter (3): 3-methacryloxypropyltrimethoxysilane

[0339] ・ Adhesion promoter (4): tetraethoxysilane

[0340] [Curing inhibitor]<

[0341] ・ 2-phenyl-3-butyn-2-ol

[0342] [Siloxane containing Si-H and trialkoxy]<

[0343] ・ Compound having the following structure:

[0344] [Chemical formula 3]

[0345]

[0346] [Si-H crosslinking agent]<

[0347] ・ Methylhydrogen siloxane-dimethylsiloxane copolymer capped at both ends of the molecular chain with trimethylsilanyloxy groups

[0348] [Si-H crosslinking agent (2)]<

[0349] ・ Methylhydrogen polysiloxane capped at both ends of the molecular chain with trimethylsilanyloxy groups (MD H 10 M)

[0350] [Si-H crosslinking agent (3)]<

[0351] • Methyl hydrogen-containing polysiloxanes (MD) with trimethylsiloxy groups at both ends of their molecular chains H 50 M)

[0352] Chain extension agent

[0353] • 1,1,5,5-Tetramethyl-3,3-diphenyltrisiloxane

[0354] (Examples 19-28)

[0355] In preparing the I and II components, except for changing the materials used as shown in Tables 8-9, resin compositions consisting of the I and II components were prepared in the same manner as in Experiment 1. The two components were then mixed, and various evaluations were performed in the same way as in Experiment 1. The results are shown in Tables 8-9.

[0356] Furthermore, in Tables 8-9 shown below,

[0357] "Filling (A)" refers to the main conductive filler (A).

[0358] "Filling (A2)" refers to the main conductive filler (A2).

[0359] "Fill (B)" refers to carbon-based conductive filler (B).

[0360] "Fill (C)" refers to carbon-based conductive filler (C).

[0361] "CNS" refers to carbon nanostructures (branched nanotubes).

[0362] "SiH+TAS siloxane" refers to siloxanes containing Si-H and trialkoxy groups.

[0363] "Hydrosilane catalyst" refers to the catalyst used in the hydrosilane reaction.

[0364] "Condensation catalyst" refers to a catalyst used in condensation reactions.

[0365] "Liquid I" refers to the components of Liquid I.

[0366] "II liquid" refers to the components of II liquid.

[0367] "Si-H / Vi" refers to the ratio of the molar number of hydrogen atoms bonded to silicon atoms to the molar number of vinyl groups in the resin composition.

[0368] "(B)+(C)" refers to the total (volume %) of the content of carbon-based conductive filler (B) and carbon-based conductive filler (C).

[0369] "(A)+(B)+(C)" refers to the total (volume %) of the content of the main conductive filler (A), carbon-based conductive filler (B), and carbon-based conductive filler (C).

[0370] "(C) / (B)" refers to the ratio (times) of the volumetric content of carbon-based conductive filler (C) to the volumetric content of carbon-based conductive filler (B).

[0371] [Table 8]

[0372]

[0373] [Table 9]

[0374]

[0375] [Table 10]

[0376]

[0377] [Table 11]

[0378]

[0379] As shown in Tables 10 and 11, the resin compositions of Examples 19 to 28, which contain a matrix resin and a specified proportion of main conductive filler (A) and satisfy condition (1), exhibit suppressed filler sedimentation and sufficiently low viscosity, thereby suppressing thickening. Furthermore, the cured product formed from this resin composition possesses excellent conductivity and adhesion.

[0380] Experiment 3

[0381] (Assessment and Measurement Methods)

[0382] In Examples 29-30, the following methods were used for various evaluation and measurement methods.

[0383] <Viscosity (Thickening Inhibition)>

[0384] The viscosity (Pa·s) of the freshly mixed resin composition obtained by mixing component I and component II was measured at 25°C using a viscometer (Anton Paar Rheocompass MCR302). Furthermore, the geometry was measured using parallel plates with a diameter of 20 mm and a gap of 0.5 mm at a shear rate of 10 s. -1 The lower the viscosity of the resin composition, the more inhibited the thickening of the resin composition is.

[0385] <Conductivity (lap shear resistance value)>

[0386] A resin composition obtained by mixing liquid I and liquid II was sandwiched between two aluminum plates (the materials to be bonded) using a spacer, with a thickness of 0.25 mm. The mixture was then allowed to cure at 25±2℃ and 50±5% humidity to obtain the test specimen. The lap shear resistance (Ω) of the obtained test specimen was measured using a HIOKI ohmmeter (RM3544). A lower lap shear resistance indicates better conductivity of the cured material.

[0387] <Adhesion>

[0388] A resin composition obtained by mixing liquid I and liquid II was sandwiched between two aluminum plates (materials to be bonded) using a spacer, with a thickness of 0.25 mm. The mixture was then allowed to cure at a temperature of 25±2℃ and a humidity of 50±5%, resulting in a bonded test specimen.

[0389] For the obtained bonded test specimens, the tensile shear bond strength (MPa) was determined 168 hours after curing. Furthermore, the tensile shear bond strength was determined according to the method specified in JIS K 6850:1999 "Adhesives—Test method for tensile shear bond strength of rigid bonded materials", and was performed at a tensile speed of 5 mm / min.

[0390] <Packing Settling>

[0391] For the freshly mixed resin composition obtained by mixing component I and component II, visually confirm the presence or absence of filler sedimentation and evaluate it according to the following criteria.

[0392] N: Unfilled settling.

[0393] Y: There is packing material settling.

[0394] (Material)

[0395] In the following Examples 29-30, the following materials were used for various purposes.

[0396] <Epoxy Resin (Matrix Resin)>

[0397] • Bisphenol A type epoxy resin (manufactured by Olin Corporation "DER331", epoxy equivalent: 182-192, viscosity: 11,000-14,000 mPa·s)

[0398] • Long-chain polydiol-type bifunctional liquid epoxy resin (manufactured by Olin Corporation, “DER732”, epoxy equivalent: 310-330, viscosity: 60-70 mPa·s)

[0399] <Curing agent (crosslinking agent)>

[0400] - Curing agent (1): Pentaethylenehexamine (manufactured by Sigma-Aldrich)

[0401] - Curing agent (2): 4’,4’-Methylenebis(2-methylcyclohexylamine), isomer mixture (manufactured by Sigma-Aldrich)

[0402] <Adhesion promoter>

[0403] - Adhesion promoter (5): 3-(Trimethoxysilyl)-1-propanamine

[0404] - Adhesion promoter (6): “EP0409” manufactured by Hybrid Plastics (hydrolysate of trimethoxy[3-(oxiran-2-ylmethoxy)propyl]silane)

[0405] <Conductive filler (A)>

[0406] - Nickel-plated graphite (“E-FiLL (registered trademark) #2701” manufactured by Metco, graphite with nickel-coated surface, plate-like, volume average particle size: 100 μm)

[0407] <Carbon-based conductive filler (B)>

[0408] - Carbon nanostructure (“ATHLOS (registered trademark) SR1200 CNS” manufactured by CABOT, branched nanotubes, aspect ratio: 50 or more)

[0409] <Carbon-based conductive filler (C)>

[0410] - Carbon black (“Printex (registered trademark) XE2B” manufactured by Orion Engineered Carbon, specific surface area: 1,000 m 2 / g, aspect ratio: less than 50)

[0411] (Example 29)

[0412] <Preparation of Component I>

[0413] 24.50 parts by mass of bisphenol A type epoxy resin, 8.35 parts by mass of long-chain polyglycol type bifunctional liquid epoxy resin, 0.10 part by mass of adhesion promoter (6), 2.00 parts by mass of carbon-based conductive filler (C), and 54.65 parts by mass of conductive filler (A) were mixed and stirred well to obtain 89.60 parts by mass of Component I.

[0414] <Preparation of Component II>

[0415] 6.14 parts by mass of curing agent (1), 2.58 parts by mass of curing agent (2), and 1.69 parts by mass of adhesion promoter (5) were mixed and stirred thoroughly to obtain 10.41 parts by mass of Component II liquid.

[0416] <Mixing of Component I liquid and Component II liquid>

[0417] The above-prepared Component I liquid and Component II liquid were mixed in a plastic container and stirred using a rotation-revolution mixer manufactured by THINKY Corporation. After stirring, the viscosity (thickening inhibition) of the mixed liquid and the filler sedimentation were quickly evaluated. In addition, the adhesiveness and conductivity were evaluated. The results are shown in Table 12.

[0418] (Example 30)

[0419] <Preparation of Component I liquid>

[0420] 26.14 parts by mass of bisphenol A epoxy resin, 0.50 parts by mass of carbon-based conductive filler (C), 0.02 parts by mass of carbon-based conductive filler (B), and 19.97 parts by mass of main conductive filler (A) were mixed and stirred thoroughly to obtain 46.63 parts by mass of Component I liquid.

[0421] <Preparation of Component II liquid>

[0422] 13.99 parts by mass of curing agent (2), 3.12 parts by mass of adhesion promoter (5), 1.30 parts by mass of carbon-based conductive filler (C), and 34.95 parts by mass of main conductive filler (A) were mixed and stirred thoroughly to obtain 53.36 parts by mass of Component II liquid.

[0423] <Mixing of Component I liquid and Component II liquid>

[0424] The above-prepared Component I liquid and Component II liquid were mixed in a plastic container and stirred using a rotation-revolution mixer manufactured by THINKY Corporation. After stirring, the viscosity (thickening inhibition) of the mixed liquid and the filler sedimentation were quickly evaluated. In addition, the adhesiveness and conductivity were evaluated. The results are shown in Table 12.

[0425] [Table 12]

[0426]

[0427] As can be seen from Table 12, for the resin composition of Example 29 containing a matrix resin and a specified proportion of main conductive filler (A) and satisfying condition (2), the filler sedimentation was inhibited, and the viscosity was sufficiently low so that thickening was inhibited. Further, it can be seen that the cured product formed from this resin composition has excellent conductivity and adhesiveness.

[0428] As shown in Table 12, the resin composition of Example 30, which contains a matrix resin and a specified proportion of main conductive filler (A) and satisfies condition (1), exhibits suppressed filler sedimentation and sufficiently low viscosity, thereby suppressing thickening. Furthermore, the cured product formed from this resin composition demonstrates excellent conductivity and adhesion.

[0429] Experiment 4

[0430] (Assessment and Measurement Methods)

[0431] In Examples 31 and 32, the following methods were used for various evaluation and measurement methods.

[0432] <Viscosity (Thickening Inhibition)>

[0433] The viscosity (Pa·s) of the freshly mixed resin composition was measured at 25°C using a viscometer (Anton Paar Rheocompass MCR302). Furthermore, the geometry was measured using parallel plates with a diameter of 20 mm and a gap of 0.5 mm at a shear rate of 10 s. -1 The lower the viscosity of the resin composition, the more inhibited the thickening of the resin composition is.

[0434] <Conductivity (lap shear resistance value)>

[0435] The resin composition obtained by mixing all components was sandwiched between two aluminum plates (the materials to be bonded) using a spacer, with a thickness of 0.25 mm. The mixture was then allowed to cure at a temperature of 25±2℃ and a humidity of 50±5%, resulting in a test specimen. The lap shear resistance (Ω) of the obtained test specimen was measured using a HIOKI ohmmeter (RM3544). A lower lap shear resistance indicates better conductivity of the cured material.

[0436] <Adhesion>

[0437] The resin composition obtained by mixing all the components was sandwiched between two aluminum plates (the materials to be bonded) using a spacer, with a thickness of 0.25 mm. Then, it was left to stand for 7 days at a temperature of 25±2℃ and a humidity of 50±5% to allow the resin composition to cure, thus obtaining the bonding test specimen.

[0438] For the obtained bonded test specimens, the tensile shear bond strength (MPa) was determined. Furthermore, the tensile shear bond strength was determined according to the method specified in JIS K 6850:1999 "Adhesives—Test method for tensile shear bond strength of rigid bonded materials", and was performed at a tensile speed of 50 mm / min.

[0439] <Packing Settling>

[0440] For the freshly mixed resin composition obtained by mixing all the components, visually confirm the presence or absence of filler sedimentation and evaluate it according to the following criteria.

[0441] N: Unfilled settling.

[0442] Y: There is packing material settling.

[0443] (Material)

[0444] In the following Examples 31-32, the following materials were used for various purposes.

[0445] <Polyols>

[0446] • Polyol T-3000 (polyether triol with a molecular weight of 3000)

[0447] <Polyisocyanates>

[0448] • PAPI (registered trademark) Polymeric MDI (polymethylene phenyl isocyanate)

[0449] <Catalyst Solidification>

[0450] • Tin(II) 2-Ethylhexanoate

[0451] <Main conductive filler (A)>

[0452] • Nickel-plated graphite (Weber Corporation "VNCG-085", graphite with nickel coating, plate-like, volume average particle size: 85μm)

[0453] <Carbon-based conductive filler (B)>

[0454] • Carbon nanostructures (CABOT Corporation "ATHLOS (registered trademark) SR1200 CNS", branched nanotubes, aspect ratio: 50 or higher)

[0455] <Carbon-based conductive filler (C)>

[0456] • Carbon black (manufactured by Orion Engineered Carbon, "Printex XE2B" (registered trademark), specific surface area: 1,000 m²) 2 / g, Aspect ratio: less than 50)

[0457] (Example 31)

[0458] <Preparation of Resin Compositions>

[0459] 19.87 parts by weight of polyol and 54.00 parts by weight of main conductive filler (A) were mixed and stirred. To the resulting mixture, 2.13 parts by weight of carbon-based conductive filler (C) were added and mixed and stirred, followed by 23.95 parts by weight of polyisocyanate and further 0.05 parts by weight of curing catalyst. Finally, the mixture was stirred using a mixer. After stirring, the viscosity (thickening inhibition) and filler sedimentation of the composition were rapidly evaluated. Additionally, adhesion and conductivity were evaluated. The results are shown in Table 13.

[0460] (Example 32)

[0461] <Preparation of Resin Compositions>

[0462] 19.86 parts by weight of polyol, 54.00 parts by weight of main conductive filler (A), and 0.02 parts by weight of carbon-based conductive filler (B) were mixed and stirred. To the resulting mixture, 2.13 parts by weight of carbon-based conductive filler (C) were added and mixed and stirred, followed by 23.93 parts by weight of polyisocyanate and further mixing. 0.05 parts by weight of curing catalyst was then added, and finally, the mixture was stirred using a mixer. After stirring, the viscosity (thickening inhibition) and filler sedimentation of the composition were rapidly evaluated. Additionally, adhesion and conductivity were evaluated. The results are shown in Table 13.

[0463] [Table 13]

[0464]

[0465] As shown in Table 13, the resin composition of Example 31, which contains a matrix resin and a specified proportion of main conductive filler (A) and satisfies condition (2), exhibits suppressed filler sedimentation and sufficiently low viscosity, thereby suppressing thickening. Furthermore, the cured product formed from this resin composition possesses excellent conductivity and adhesion.

[0466] As shown in Table 13, the resin composition of Example 32, which contains a matrix resin and a specified proportion of main conductive filler (A) and satisfies condition (1), exhibits suppressed filler sedimentation and sufficiently low viscosity, thereby suppressing thickening. Furthermore, the cured product formed from this resin composition demonstrates excellent conductivity and adhesion.

[0467] Furthermore, in Examples 31 and 32, the viscosity values ​​of the resin compositions were greater than those of the resin compositions containing silicone resin or epoxy resin (Experiments 1-3). However, as compositions containing polyurethane resin, the viscosity of the resin compositions in Examples 31 and 32 was such that thickening could be sufficiently suppressed, and they could be easily compressed in practical applications.

[0468] Industrial availability

[0469] According to the present invention, a resin composition capable of suppressing filler sedimentation and excessive thickening and exhibiting excellent electrical conductivity is provided, as well as a cured product formed by curing the resin composition.

Claims

1. A resin composition comprising a matrix resin and a primary conductive filler (A) having a metallic component at least in a portion of its surface, wherein... When the total volume of the resin composition is set to 100% by volume, the content of the main conductive filler (A) is 19.80% by volume or more and 35.20% by volume or less, and, The following conditions (1), (2), or (3) must be met: Condition (1): The resin composition comprises a carbon-based conductive filler (B) with an aspect ratio of 50 or greater and a specific surface area of ​​10 m². 2 Both of these are carbon-based conductive fillers (C) with a content of / g or more, and When the total volume of the resin composition is set to 100% by volume... The carbon-based conductive filler (B) is present in a concentration of 0.01% by volume or more but less than 1.00% by volume. The carbon-based conductive filler (C) is present in a proportion exceeding 0.10% by volume and less than 2.00% by volume. The total content of the main conductive filler (A), the carbon-based conductive filler (B), and the carbon-based conductive filler (C) exceeds 20.60% by volume and is less than 36.50% by volume. Condition (2): The resin composition contains a specific surface area of ​​10 m². 2 Carbon-based conductive fillers (C) with a length-to-diameter ratio of 50 or higher, excluding carbon-based conductive fillers (B) with a length-to-diameter ratio of 50 or higher, and When the total volume of the resin composition is set to 100% by volume... The carbon-based conductive filler (C) is present in a proportion exceeding 1.00% by volume and less than 6.00% by volume. The combined content of the main conductive filler (A) and the carbon-based conductive filler (C) exceeds 21.00% by volume and is less than 38.00% by volume. Condition (3): The resin composition contains a carbon-based conductive filler (B) with an aspect ratio of 50 or more, but does not contain a specific surface area of ​​10 m². 2 / g or more of carbon-based conductive filler (C), and When the total volume of the resin composition is set to 100% by volume... The carbon-based conductive filler (B) is present in a concentration of 0.10% by volume or more and less than 2.50% by volume. The combined content of the main conductive filler (A) and the carbon-based conductive filler (B) exceeds 20.20% by volume and is less than 36.00% by volume.

2. The resin composition according to claim 1, wherein, The main conductive filler (A) comprises nickel-plated graphite.

3. The resin composition according to claim 1, wherein, The carbon-based conductive filler (B) contains carbon nanostructures.

4. The resin composition according to claim 1, wherein, The carbon-based conductive filler (C) contains carbon black.

5. The resin composition according to claim 1, wherein, The matrix resin comprises at least one selected from the group consisting of silicone resin, epoxy resin, acrylic resin, polyolefin oxide resin and polyurethane resin.

6. The resin composition according to claim 1, wherein, The matrix resin comprises at least one selected from the group consisting of silicone resins, epoxy resins, and polyurethane resins.

7. The resin composition according to claim 1, further comprising a curing catalyst capable of curing the matrix resin.

8. The resin composition according to claim 1, further comprising a reinforcing filler.

9. The resin composition according to claim 1, further comprising an adhesion promoter comprising both 3-methacryloyloxypropyltrimethoxysilane and tetraethoxysilane.

10. The resin composition according to claim 1, wherein the condition (1) or (2) is satisfied.

11. The resin composition according to claim 1, wherein the condition (1) is satisfied.

12. The resin composition according to claim 1, wherein it is a two-component type.

13. The resin composition according to any one of claims 1 to 12, wherein it has curable properties.

14. The resin composition according to any one of claims 1 to 12, wherein it has room temperature curing properties.

15. A cured product formed by curing the resin composition of claim 13.

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