Composite material

Abstract

A composite material comprising: a material containing a nanofiber and / or a two-dimensional substance represented by the formula MQ a O b (wherein M is at least one element selected from the group consisting of Groups 3, 4, 5, 6, and 7, Q is at least one element selected from the group consisting of Groups 12, 13, 14, 15, and 16 (excluding O), a is 0 or more and 2 or less, and b is greater than 0 and 2 or less), and a resin having a negative zeta potential.

Description

Technical Field

[0001] This disclosure relates to composite materials. Background Technology

[0002] Previously, titanium dioxide, such as TiO2, has been known as a metal-containing oxide. For example, AEROXIDE (registered trademark) TiO2P-25 is a hydrophilic titanium dioxide with a particle size of 20-30 nm and a very high specific surface area. As shown in Non-Patent Literature 1, titanium dioxide is known to have various catalytic effects depending on the ratio of anatase to rutile crystal structures, and is particularly suitable for use as a photocatalyst. Based on the aforementioned photocatalytic effects, it can impart self-purification properties to inorganic compositions, for example.

[0003] Existing technical documents

[0004] Non-patent literature

[0005] Non-patent literature 1: Teruhisa Ohno, Koji Sarukawa, Kojiro Tokieda, MichioMatsumura, Morphology of a TiO2 Photocatalyst (Degussa, P-25) Consisting of Anatase and Rutile Crystalline Phases, Journal of Catalysis, Volume 203, Issue 1, 2001, Pages 82-86 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] TiO2 is known to be difficult to disperse in polymer aqueous solutions and tends to aggregate. Therefore, even when forming coatings using polymer aqueous solutions containing TiO2, it is difficult to obtain coatings with dispersed TiO2. Consequently, it is difficult to use such coatings as, for example, thermally conductive materials. It should be noted that dispersants are considered to improve the dispersibility of TiO2 in polymer aqueous solutions. However, the presence of dispersants may sometimes reduce desired properties, such as thermal conductivity. Furthermore, there is the problem of dispersant leakage.

[0008] This disclosure was made in view of the above circumstances, and its purpose is to provide novel composite materials such as films with high dispersibility and suitable for manufacturing desired properties.

[0009] Solution for solving the problem

[0010] According to one aspect of this disclosure, a composite material is provided, comprising:

[0011] Contains the formula MQ a O b Materials representing nanofibers and / or two-dimensional substances, and resins with a negative zeta potential.

[0012] (In the formula, M is at least one element selected from the group consisting of families 3, 4, 5, 6 and 7.)

[0013] Q is at least one element selected from the group consisting of families 12, 13, 14, 15, and 16 (excluding O).

[0014] a is 0 or higher and 2 or lower

[0015] (b is greater than 0 and less than 2).

[0016] The effects of the invention

[0017] According to this disclosure, a novel composite material is provided that comprises a specified material and a resin, wherein the specified material has high dispersibility. Attached Figure Description

[0018] Figure 1 This is an illustration of the failure of a polymer composite containing conventional TiO2 as a filler when subjected to tension.

[0019] Figure 2 This is an explanatory diagram regarding the destruction of a polymer composite containing MQO particles as a filler according to this embodiment.

[0020] Figure 3 This is a graph showing the Raman spectral analysis results of the material (TiCO) manufactured in the examples.

[0021] Figure 4 This is the XRD pattern of the material (TiCO) manufactured in the embodiment.

[0022] Figure 5 This is the XRD pattern of the material (TiCO / polyurethane composite) manufactured in the examples.

[0023] Figure 6 This is the above Figure 4 and the above Figure 5 An image showing the overlapping of XRD patterns.

[0024] Figure 7 This is the result of evaluating the dispersibility of the aqueous dispersion of titanium dioxide (TiO2) in the comparative example.

[0025] Figure 8 This is the result of evaluating the dispersibility of the polyurethane aqueous dispersion of titanium dioxide (TiO2) in the comparative example.

[0026] Figure 9 This is the result of evaluating the dispersibility of the poly(ethyleneimine) dispersion of the material (TiCO) manufactured in the comparative example.

[0027] Figure 10 This is the result of evaluating the dispersibility of the polyurethane aqueous dispersion of the material (TiCO) manufactured in the examples.

[0028] Figure 11 This is the result of evaluating the dispersibility of the acrylic resin aqueous dispersion of the material (TiCO) manufactured in the examples. Detailed Implementation

[0029] [Composite Materials]

[0030] This embodiment relates to composite materials comprising materials containing specified nanofibers and / or two-dimensional substances. In this disclosure, the term "material" refers to "material containing nanofibers and / or two-dimensional substances" (in other words, a material containing at least one of nanofibers and two-dimensional substances). In this embodiment, materials containing nanofibers and / or two-dimensional substances typically refer to materials that are solid components and do not contain binders or the like (e.g., polymers). In a narrower sense, materials containing nanofibers and / or two-dimensional substances can refer to materials substantially formed from at least one of nanofibers and two-dimensional substances (which may contain other objects, impurities, etc., that may inevitably be mixed in). However, materials containing nanofibers and / or two-dimensional substances are not limited to these.

[0031] (Including MQO materials)

[0032] The composite material in this embodiment contains nanofibers and / or two-dimensional materials of a specified material (substance). The specified material that can be used in this embodiment is represented by the following formula (1).

[0033] MQ a O b …(1)

[0034] (In the formula, M is at least one element selected from the group consisting of Groups 3, 4, 5, 6 and 7, and may include so-called early transition metals, such as at least one element selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and Mn, preferably at least one element selected from the group consisting of Ti, V, Cr, Mo and Mn.)

[0035] Q is selected from at least one element chosen from groups 12, 13, 14, 15, and 16 (excluding O), for example, it may include at least one element chosen from groups B, C, N, Si, P, and S.

[0036] a is 0 or higher and 2 or lower

[0037] (b is greater than 0 and less than 2)

[0038] Hereinafter, the materials specified above will also be referred to as "MQO". Examples of MQO include compounds represented by formulas such as TiO2, TiCO, TiCON, VO2, VCO, VCON, CrO2, CrCO, CrCON, MoO2, MoCO, MoCON, MnO2, MnCO, and MnCON. For example, in formula (1), M can be Ti and Q can be C. In addition, for example, in formula (1), a can be non-zero. That is, a can be greater than 0, for example, it can be 1 or more.

[0039] MQO has a crystal structure different from that of the hexagonal crystal system. This embodiment is not bound by any theory, but it is currently considered that the crystal structure of MQO is anatase, lepidocrocite, or a mixture thereof. For example, the crystal structure of MQO can be lepidocrocite.

[0040] For example, MQO can be manufactured using a first raw material and a second raw material as follows: the first raw material contains at least the above-described M, the second raw material contains at least the above-described Q, and the first and second raw materials can react in a protic solvent to generate MQO.

[0041] As the first raw material, the material shown in the following formula (2) can be used.

[0042] M c A 1 d …(2)

[0043] (where M is as described above,)

[0044] A 1 To select at least one element from the group consisting of groups 12, 13, 14, 15, and 16, for example, it may include at least one element selected from the group consisting of B, C, N, O, Si, P, and S.

[0045] c and d are each independently between 1 and 5.

[0046] The material represented by equation (2) needs to be different from the MQO of the product. The material represented by equation (2) is typically characterized by not having peaks in the X-ray diffraction (XRD) pattern in the range of diffraction angles 2θ above 2° and below 12°.

[0047] Examples of the first raw material shown in equation (2) include TiB2, TiB, TiC, TiN, TiO2, Ti5Si3, Ti2SbP, VO2, V2O4, NbC, Nb2O5, MoO2, MoO3, MoS2, MnO2, Mn3O4, MnCO3, etc. MnO2, which can be used as the first raw material, has a peak near 2θ = 13° in the XRD pattern, but no peak in the range where 2θ is above 2° and below 12°.

[0048] Alternatively, in addition to the above, as the first raw material, a material represented by the following formula (3) (hereinafter also referred to as "MAX phase" or "MAX raw material") may be used.

[0049] M m A 2 X n …(3)

[0050] (where M is as described above,)

[0051] X is at least one element selected from the group consisting of C and N.

[0052] n is 1 or more and 4 or less

[0053] m is greater than n and less than 5

[0054] A 2 The element selected is at least one element chosen from the group consisting of groups 12, 13, 14, 15, and 16, typically a group A element, representatively groups IIIA and IVA. More specifically, it may include at least one element chosen from the group consisting of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S, and Cd, preferably Al.

[0055] MAX phase has A 2 The atomic layer is located in the M m X n The MAX phase represents a crystal structure between two layers (which may have X atoms located within an octahedral array of M atoms). In the representative case of m=n+1, the MAX phase has layers with one layer of X atoms arranged between each of the n+1 layers of M atoms (also collectively referred to as "M"). m X n (layer), and configured with A 2 Atom layer (“A”) 2 The "atom layer" is the repeating unit of the layer below the M atom layer of the (n+1)th layer. However, the MAX phase is not limited to this.

[0056] Examples of the first raw material shown in formula (3) include Ti3AlC2, Ti3GaC2, Ti3SiC2, etc.

[0057] As the first raw material, the material shown in formula (2) and the material shown in formula (3) can be used together (e.g., as a mixture).

[0058] As a second raw material, ionic substances containing carbon groups can be used. Ionic substances containing carbon groups contain carbon (C). Examples of ionic substances include ammonium salts, phosphates, and sulfates.

[0059] More specifically, quaternary ammonium salts can be used as the second raw material. Examples of quaternary ammonium salts include: tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH or TBAOH), benzyltrimethylammonium hydroxide, tetrabutylammonium fluoride (TBAF), tetrabutylammonium chloride (TBACl), tetrabutylammonium bromide (TBAB), tetrabutylammonium iodide (TBAI), benzyltriethylammonium chloride (BTEAC), hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide (CTAB), benzylammonium chloride, benzalkonium chloride, and hexadecylpyridinium chloride (CPC), etc. Among these, TMAH and TBAOH are preferred.

[0060] Alternatively, in addition to the above, other ionic substances containing P and / or S can be used as a second raw material.

[0061] The protic solvent only needs to be able to dissolve the first and second raw materials at least partially, and is particularly suitable as an aqueous solvent. Water, alcohols (e.g., ethanol, 1-propanol, isopropanol), carboxylic acids (e.g., acetic acid, formic acid), etc., can be used as protic solvents. Aqueous solvents can consist of water and, depending on the circumstances, a liquid substance compatible with water (e.g., a protic solvent other than water), with water being preferred.

[0062] The first and second raw materials are reacted in a protic solvent. The second raw material may be added to the protic solvent beforehand. The ratio of the second raw material to the sum of the protic solvent and the second raw material may be, for example, 5% by mass or more, particularly 20% by mass or more, and / or, for example, 80% by mass or less, particularly 50% by mass or less. The first raw material may be further added to the protic solvent in which the second raw material is added and mixed. In this mixture, the reaction to generate MQO takes place. The temperature (reaction temperature) of the mixture (which may contain reaction products) may be, for example, 15°C or more, particularly 40°C or more, and / or, for example, 100°C or less, particularly 80°C or less. The mixing time (reaction time) may be, for example, 1 day or more, particularly 2 days or more, and / or, for example, 10 days or less, particularly 7 days or less. Mixing may be carried out, for example, by rotating and stirring the magnetic stir bar placed in the container while maintaining the reaction temperature using a heated plate stirrer and a warm water bath. However, the processing operations and conditions (temperature, time, etc.) that enable the reaction to proceed are not limited to those mentioned above, and can be appropriately selected based on the first raw material, the second raw material, and the protic solvent used.

[0063] Through the above reaction, MQO is generated, which can eventually grow into MQO nanofibers, and then into MQO nanosheets. While not limiting this disclosure, the obtained MQO nanofibers can be in the form of nanoribbons extending at the nanoscale width. Furthermore, multiple MQO nanofibers (e.g., nanoribbons) can also be combined and / or integrated to grow into nanosheets extending in a two-dimensional shape. Additionally, multiple MQO nanosheets can also overlap (e.g., via van der Waals forces) to form a laminate. This disclosure is not bound by any theory, but the generation and growth of MQO can be considered as based on a bottom-up synthetic reaction.

[0064] In this disclosure, the cross-sectional dimensions of MQO nanofibers refer to the shortest distance through the center of the cross-section traversing the long side of the MQO nanofiber. The shape of the cross-section of the MQO nanofiber is not particularly limited; for example, it can be approximated as rectangular (rectangle, square, etc.) or elliptical (flat circle, perfect circle, etc.). When the MQO nanofiber is in the form of nanoribbons, its cross-sectional shape can be approximated as rectangular, and its cross-sectional dimensions can be equivalent to the length of the short side of a rectangle. When the MQO nanofiber is in the form of nanofilaments, its cross-sectional shape can be approximated as a flat circle, and its cross-sectional dimensions can be equivalent to the length of the minor axis of a flat circle.

[0065] In this disclosure, MQO is a solid component. MQO can typically be granules (or powder).

[0066] The mixture after the reaction (also known as the reaction mixture) can be appropriately post-processed. Examples of such post-processing include washing, applying impact (including applying shear force), drying (e.g., freeze-drying, heat drying), pulverizing, etc.

[0067] Washing can be carried out using protic solvents. The same explanation applies to protic solvents as described above; for example, water or alcohol can be used for washing. After washing, separation operations (centrifugation and / or decantation) can be performed. Washing and separation operations can be repeated until the pH of the supernatant after centrifugation reaches, for example, below 8.

[0068] Depending on the circumstances, cleaning can be performed using an aqueous solution of a metal salt instead of the above-described cleaning method. The metal salt can be, for example, a halide (fluoride, chloride, bromide, iodide) of an alkali metal (Li, Na, K, etc.), typically LiCl, NaCl, KCl, etc. Specifically, cleaning can be performed using an aqueous solution of a metal salt with a concentration of 1 to 10 moles. After cleaning, separation operations (centrifugation and / or decantation) can be performed. In this case, the cleaning and separation operations can be repeated as needed until the pH of the supernatant after centrifugation reaches, for example, below 8.

[0069] During and / or after cleaning, impacts such as vibration and / or ultrasound can be applied. This promotes the dispersion of MQO particles (e.g., nanofibers / nanoflakes, hereinafter the same). In the case of MQO particle aggregation, it can be broken up. This effect is significantly obtained when impact is applied during cleaning with an aqueous solution of metal salt (it is believed that metal cations derived from the metal salt enter the gaps between the aggregates and can break them up). The impact can be applied using any one or more of the following: hand crank, automatic shaker, mechanical vibrator, vortex mixer, homogenizer, and ultrasonic bath.

[0070] Since MQO particles are solid, separation can be performed at any suitable time to remove unwanted liquid components, provided they are present. As a final separation operation, drying can be performed, typically freeze-drying or thermal drying. Freeze-drying can be performed, for example, by freezing a mixture containing MQO particles and liquid components at any suitable temperature (e.g., -40°C) and then drying it under reduced pressure. Thermal drying can be performed, for example, by drying a mixture containing MQO particles and liquid components at a temperature above 25°C (e.g., below 200°C) under normal or reduced pressure. Grinding is not particularly limited and can be performed, for example, using a combination of mortar and pestle, or an IKA grinder. Grinding can also be performed after drying.

[0071] It should be noted that, in order to obtain MQO-containing materials (defined nanofibers and / or two-dimensional materials, typically MQO particles, hereinafter sometimes referred to as "MQO-containing materials") with higher purity, it is preferable to repeat the washing and centrifugation process multiple times, and recover the supernatant after the final centrifugation. This supernatant can be prepared directly or appropriately diluted with a liquid medium, or mixed with a liquid medium after drying, to form a slurry containing MQO particles. This slurry can also be used to prepare membranes, thus creating the composite material of this embodiment.

[0072] Thus, MQO particles can be obtained as MQO-containing materials. MQO is represented by formula (1), but MQO-containing materials (typically MQO particles) do not need to be formed solely by the constituent elements of formula (1). Although not limited to this disclosure, MQO-containing materials may, depending on the circumstances, have at least one selected from the group consisting of hydroxyl, chlorine, oxygen, hydrogen, and nitrogen atoms as a modification or terminal T present on their surface. In addition, MQO-containing materials (typically MQO particles) may have two or more layers, between which at least one selected from the group consisting of ammonium ions (e.g., quaternary ammonium cations) and metal cations (e.g., alkali metal ions, alkaline earth metal ions) may be present.

[0073] The particle size of MQO can be, for example, greater than 0.01 nm, particularly greater than 0.1 nm, further greater than 1 nm, and / or, for example, less than 1000 nm, particularly less than 100 nm, further less than 50 nm. Such particles can also be referred to as nanoparticles.

[0074] The particles of MQO are in the form of nanofibers and / or two-dimensional materials. Two-dimensional materials include one or more of nanosheets and nanosheet stacks. In this embodiment, the two-dimensional materials are not limited to nanosheets and nanosheet stacks.

[0075] Nanofibers can also be called nanowires. In this disclosure, "nanofiber" refers to a solid material extending along its long side, with a cross-sectional dimension (cross-sectional dimension) perpendicular to the long side that is in the nanometer range (i.e., 1 nm or more and less than 1000 nm) or smaller in the sub-nanometer range (less than 1 nm, for example, 0.1 nm or more and less than 1 nm). The length of the nanofiber along its long side is not limited to the nanometer range (i.e., 1 nm or more and less than 1000 nm), but can also be in the micrometer range (1 μm or more and less than 1000 μm). The cross-sectional dimension of the nanofiber can be, for example, 0.1 nm or more, particularly 1 nm or more, for example, less than 100 nm, particularly less than 50 nm, and preferably less than 15 nm.

[0076] In this disclosure, "two-dimensional material" refers to a solid having a surface (also called a plane or two-dimensional sheet) with a two-dimensional extension, and a thickness relatively small relative to the maximum size of that surface (which may correspond to the "in-plane size" of a particle), with a thickness in the nanometer range (i.e., 1 nm or more and less than 1000 nm) or smaller in the sub-nanometer range (less than 1 nm, for example, 0.1 nm or more and less than 1 nm). The aforementioned in-plane size is not limited to the nanometer range (i.e., 1 nm or more and less than 1000 nm), but can also be in the micrometer range (1 μm or more and less than 1000 μm). As described above, two-dimensional materials include one or more of nanosheets and stacks of nanosheets. Nanosheets can also be called nanoplatelets or two-dimensional (nano)plates. The thickness of a single layer of a nanosheet can be, for example, 0.01 nm or more, particularly 0.8 nm or more, and for example, less than 20 nm, particularly less than 3 nm. The in-plane size of the nanosheet can be, for example, 0.1 μm or more, particularly 1 μm or more, and for example, less than 200 μm, particularly less than 40 μm. Nanosheets can be constructed by assembling nanofibers.

[0077] A stack of nanosheets can also be called a multilayer MQO. The distance (interlayer distance or void size) between two adjacent nanosheets (or two adjacent MQO layers) is not particularly limited.

[0078] It should be noted that the dimensions mentioned above (which may be processed by methods such as focused ion beam (FIB) if necessary) can be obtained as the number average size (at least 40) of photographs observed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), or atomic force microscopy (AFM), or as the distance in actual space calculated from the position of the (002) plane in reciprocal space determined by X-ray diffraction (XRD).

[0079] However, it should be noted that in this disclosure, MQO is not limited to the above-described form and can have any suitable form. Furthermore, it should be noted that the composite material of this embodiment only needs to contain MQO-containing material and a resin with a negative zeta potential, and can have any suitable form.

[0080] Materials containing MQO typically exhibit peaks in X-ray diffraction (XRD) patterns in the range of diffraction angles 2θ = 2° and below 12°. This disclosure is not bound by any theory, but it is assumed that the presence of peaks in XRD patterns in the range of 2θ = 2° and below 12° indicates that the MQO possesses a crystal structure different from that of known metal oxides.

[0081] It should be noted that in this disclosure, the XRD pattern is obtained by scanning along the θ-axis using an XRD analysis apparatus with CuKα rays (approximately 1.54 Å) as the characteristic X-rays. The vertical axis represents intensity, and the horizontal axis represents 2θ. This pattern can also be referred to as an "XRD pattern". Peaks in the XRD pattern can be identified visually or using software used with the XRD analysis apparatus.

[0082] This embodiment is not limited to this one. The material in this embodiment (more specifically, MQO) can, for example, achieve a Raman shift of at least 275 to 295 cm⁻¹ in the Raman spectrum of a laser with a wavelength of 514 nm. -1 435~455cm -1 and 665~745cm -1 The position has a peak.

[0083] While not limited to this embodiment, the material in this embodiment (more specifically MQO) may have a crystal structure of anatase or ferrimetallic type, or a mixture thereof. A ferrimetallic crystal structure is more preferred.

[0084] This embodiment is not limited to this one. The material (more specifically, MQO) in this embodiment can be, for example, such as in the Raman spectrum of a laser with a wavelength of 514 nm, having a Raman shift of at least 275~295 cm⁻¹. -1 435~455cm -1 and 665~745cm -1 The position has a peak, and when the intensity of each peak is set to X, Y, Z, X is the largest.

[0085] This embodiment is not limited to this one. Further preferred embodiments of this embodiment use materials (more specifically, MQO) that, in the Raman spectrum of a laser with a wavelength of 514 nm, have a Raman shift of at least 180-200 cm⁻¹. -1 275~295cm -1 375~395cm -1 435~455cm -1 and 665~745cm -1 The position has a peak, and when the intensity of each peak is set to V, X, Y, Z, W, X is the largest.

[0086] It should be noted that in this disclosure, the Raman spectrum is a spectrum measured using a 514 nm wavelength laser as the excitation source and a Raman spectroscopy analysis apparatus (the vertical axis represents intensity, and the horizontal axis represents Raman shift). Peaks in the Raman spectrum can be identified visually or using software used with the Raman spectroscopy analysis apparatus.

[0087] This embodiment is not limited to this one, but it is believed that the material in this embodiment (more specifically MQO) has anionic terminals such as O-terminals and OH-terminals on its surface, which are known to dissociate protons and countercations in solvents such as water and thus become negatively charged. The negative surface charge can be confirmed, for example, by obtaining a negative potential when measuring the Zeta potential of a liquid in which MQO is dispersed in water.

[0088] Furthermore, MQO-containing materials may contain unreacted first and / or second raw materials as impurities, and may also contain substances derived from the first, second, and / or protic solvents. For example, when using a quaternary ammonium salt as the second raw material, nitrogen (N) may exist (residual) in the MQO-containing material in any form. This embodiment is not limited, but the MQO-containing material may contain ammonium ions or tetramethylammonium ions. Additionally, for example, when using a MAX raw material as the first raw material, in this disclosure, the MQO-containing material may contain a small amount of residual atom, for example, 10% by mass or less relative to the original atom content. The residual amount of atom is preferably 8% by mass or less, more preferably 6% by mass or less. However, even if the residual amount of atom exceeds 10% by mass, it is sometimes not a problem depending on the usage conditions, etc.

[0089] The composite material of this embodiment comprises the aforementioned MQO-containing material and a resin with a negative zeta potential. By including the resin with a negative zeta potential, as described above, the dispersibility of both is maintained to a high degree due to the electrostatic repulsion between the negatively charged material of this embodiment (containing the MQO material) and the resin with a negative zeta potential. Furthermore, since the fluidity of the slurry is maintained, film formation can be performed, for example, by spraying.

[0090] Composite materials can be in the form of a fluid containing liquid or in the form of a solid.

[0091] When the composite material is a fluid material, it comprises an MQO-containing material (e.g., MQO particles), a resin with a negative zeta potential, and a liquid medium. The resin may be, for example, a water-soluble polymer. The composite material (fluid material) of this embodiment may be an aqueous dispersion, slurry, paste, etc., in which the MQO-containing material is dispersed in a mixed medium of the water-soluble polymer and the liquid medium. Regardless of the form of the fluid material, the MQO particles of this embodiment have high dispersibility and therefore do not aggregate in the mixed medium, thus dispersing well. For example, an aqueous polymer solution containing a water-soluble polymer in a proportion of more than 0% by mass and less than 20% by mass, preferably less than 10% by mass, relative to the sum of the water-soluble polymer and the liquid medium (e.g., water), can be used as the mixed medium. For the aforementioned water-soluble polymers, examples of polymers (resins) with a negative Zeta potential include alkyl polymers, polymers with amide bonds (-NHCO-) ​​(resins with amide bonds), polymers with urethane bonds (resins with urethane bonds), polymers with ester bonds, polymers with ether bonds, and acrylic polymers (acrylic resins). In this embodiment, these resins are known to have one or more anionic functional groups and anionic segments, which dissociate protons in solvents such as water, counteract cations, and are negatively charged. Since MQO is negatively charged, a composite material in which both are dispersed is obtained through electrostatic repulsion with the aforementioned negatively charged polymers. Examples of anionic functional groups include hydroxyl groups, hydroxyl salt groups, carboxyl groups, carboxyl salt groups, sulfonic acid groups, sulfonate groups, phosphate groups, phosphate groups, and thiol groups. Examples of the aforementioned polymers include polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylate, poly(vinylphosphonic acid), poly(vinylphosphonate), polymers containing an oxyacid, such as polyphosphoric acid, polyvinylsulfonic acid, and polyvinylsulfonate. Furthermore, the anionic functional groups and anionic segments in the aforementioned polymers can be 50 mol% or less, for example, self-emulsifying resins with amide or urethane bonds, or acrylic resins, that possess anionic functional groups and anionic segments. Examples of resins with amide or urethane bonds include polyamide-imide (PAI), polyacrylamide (PMA), nylon (polyamide resin), DNA (deoxyribonucleic acid), acetanilide, and acetaminophen. In addition, examples of acrylic resins include polymers made from monomers having acryloyl groups, such as monofunctional acrylates like methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, and 3-hydroxyethyl methacrylate, and difunctional acrylates like ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and butanediol di(meth)acrylate.Additionally, examples include alkyl polymers having at least one acryloyl group at the end, polymers having ether bonds, and polymers whose side chains have reactive functional groups such as hydroxyl, carboxyl, amino, epoxy, mercapto, and oxazoline groups. The resins described above are preferably one or more of resins having amide or urethane bonds and acrylic resins.

[0092] As the aforementioned liquid medium, organic media can also be used instead of water or as a mixing medium with water. Examples of organic media include acetonitrile, N,N-dimethylacetamide, N,N-dimethylformamide, DMSO, DMF, NMP, acetone, 2-methyl-2-propanol, isopropanol, ethanol, and methanol.

[0093] The proportion of the MQO-containing material in the fluid composite material can be appropriately set according to the application. For example, the proportion of the MQO-containing material in the fluid composite material can be more than 0.1% by mass or less than 99.9% by mass.

[0094] When the composite material is a solid material, examples of composite materials include those containing MQO material and resins (polymers) with a negative zeta potential. Examples of such polymers (resins) with a negative zeta potential include alkyl polymers, polymers with amide bonds (-NHCO-), polymers with urethane bonds, polymers with ester bonds, polymers with ether bonds, and acrylic polymers (acrylic resins). In this embodiment, these resins are known to have one or more anionic functional groups and anionic segments, dissociate protons in solvents such as water, counteract cations, and carry a negative charge. Since MQO is negatively charged, a composite material in which both are dispersed is obtained through electrostatic repulsion with the aforementioned negatively charged polymers. Examples of anionic functional groups include hydroxyl groups, hydroxyl salt groups, carboxyl groups, carboxyl salt groups, sulfonic acid groups, sulfonate groups, phosphate groups, phosphate groups, and thiol groups. Examples of the aforementioned polymers include polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylate, poly(vinylphosphonic acid), poly(vinylphosphonate), polymers containing an oxyacid, such as polyphosphoric acid, polyvinylsulfonic acid, and polyvinylsulfonate. Furthermore, the anionic functional groups and anionic segments in the aforementioned polymers can be 50 mol% or less, for example, self-emulsifying resins with amide or urethane bonds, or acrylic resins, that possess anionic functional groups and anionic segments. Examples of resins with amide or urethane bonds include polyamide-imide (PAI), polyacrylamide (PMA), nylon (polyamide resin), DNA (deoxyribonucleic acid), acetanilide, and acetaminophen. Furthermore, examples of acrylic resins include polymers polymerized from monofunctional acrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, and 3-hydroxyethyl methacrylate, and difunctional acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and butanediol di(meth)acrylate. Additionally, examples include alkyl polymers having at least one acryloyl group at the end, polymers having ether bonds, and polymers whose side chains have reactive functional groups such as hydroxyl, carboxyl, amino, epoxy, mercapto, and oxazoline groups. Preferably, the above-mentioned resins are one or more of resins having amide or urethane bonds and acrylic resins.

[0095] The proportion of the aforementioned polymer in the solid composite material can be determined based on the desired properties. For example, the proportion of the aforementioned polymer in the composite material can be set to 0.1% by mass or more and 99.9% by mass or less.

[0096] The proportion of the MQO-containing material in the solid composite material can be appropriately set according to the application. For example, the proportion of the MQO-containing material in the solid composite material can be more than 0.1% by mass or less than 99.9% by mass.

[0097] Because the MQO-containing material according to this embodiment has high dispersibility, the MQO-containing material and the above-mentioned polymer can be well mixed, and a polymer composite in which the MQO-containing material is well dispersed and does not aggregate can be obtained. The mixing of the MQO-containing material and the polymer can be carried out using a homogenizer, propeller mixer, thin-film rotary mixer, planetary mixer, mechanical vibrator, vortex mixer, high-pressure disperser, or other dispersion device.

[0098] When the composite material in this embodiment is in a solid state, it can be, for example, in the form of a film. The film-like composite material can be formed, for example, using a slurry, which is a mixture of the aforementioned MQO particles and a polymer, and is a fluid-like composite material as described above. Examples include coating the slurry of the aforementioned MQO particles and polymer onto a substrate (e.g., a substrate) to form a film-like composite material, but the coating method is not limited. Examples include spraying using nozzles such as single-fluid nozzles, two-fluid nozzles, or spray guns; slot coating using a benchtop coater, comma coater, or bar coater; screen printing; metal mask printing; and coating methods based on spin coating, dip coating, or drop coating. The above coating and drying can be repeated multiple times as needed until a film of the desired thickness is obtained. Drying and curing can be performed, for example, using an atmospheric pressure oven or a vacuum oven at a temperature of 400°C or below.

[0099] This disclosure is not bound by any theory, but it is believed that one reason for the high dispersibility of the MQO particles in this embodiment is the large absolute value of the Zeta (ζ) potential of the negatively charged MQO particles, resulting in strong electrostatic repulsion with the similarly negatively charged resin. When the Zeta potential of the MQO particles is measured by the following method, the absolute value of the Zeta potential of the MQO particles can be, for example, 1 or more, preferably 10 or more. In the above-described Zeta potential measurement, the dispersion medium is ion-exchanged water, and the MQO particles or the TiO2 particles used in the comparative example are adjusted to a range of 0.01 to 0.1% by mass. A dispersion treated by vortex mixing for 5 minutes is used. Using this dispersion, the Zeta potential is measured under atmospheric conditions using a Zeta potential measuring device (device name: Zetasizer Nano-ZS, Malvern Panalytical, Malvern, UK).

[0100] When the composite material in this embodiment is in the form of a film, a film with high film strength can be obtained. For example... Figure 1As illustrated, the polymer composite obtained by mixing TiO21 (previously used as a filler) and resin 3 without adding a dispersant and coating it onto a PET substrate 5 easily forms aggregates of TiO21, as shown in the dashed lines surrounding the aggregates 7. Figure 1 (Left). For the above polymer composite, for example, when stretching the film in the direction of the black arrow for film strength determination (tensile test), such as... Figure 1 As shown on the right, damage is easily caused starting from the aggregation point 7. In contrast, as... Figure 2 As illustrated, in a polymer composite obtained by mixing material 9, which contains specified nanofibers and / or two-dimensional materials, with resin 3 without the addition of a dispersant, and then coating it onto a PET substrate 5, the material 9 does not aggregate and can be dispersed. If a dispersant is added during mixing with the resin, the dispersant deteriorates, resulting in a short service life; in contrast, this problem does not occur in the composite material of this embodiment. As a result, for example, when the film is stretched in the direction of the black arrow for film strength testing (tensile test), it is not easily damaged, exhibiting high strength.

[0101] The composite material in one embodiment has been described in detail above, but various modifications can be made to this disclosure. It should be noted that the material of this disclosure can also be manufactured using methods different from those described in the above embodiments.

[0102] Example

[0103] The present invention will now be described in more detail with examples. The present invention is not limited to the examples described below; appropriate modifications may be made to implement it within the scope of the above and following descriptions, and all such modifications are included within the scope of protection of the present invention.

[0104] [Example 1: TiCO / polyurethane composite membrane]

[0105] [Preparation of TiCO-containing slurry]

[0106] First, 1 g of titanium diboride (TiB2, manufactured by Alfa Aesar) and 10 mL of a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) (manufactured by Alfa Aesar) were added to a container (100 mL wide-mouth bottle). A stir bar of approximately the same length as the inner diameter of the circular bottom of the container (35 mm) was placed inside. The mixture in the container was stirred with the stir bar while the container was kept in an oil bath at 80°C for 120 hours to carry out the reaction. Next, the reaction mixture in the container was transferred to a centrifuge tube. Centrifugation was performed at 3500 G for 5 minutes to allow the solid components to settle. (i) After centrifugation, the supernatant was discarded, (ii) 40 mL of ethanol (manufactured by Fisher Chemical) was added to the remaining sediment in the centrifuge tube, and dispersion was performed (re-slurrying) using a Vortex mixer for 5 minutes, (iii) centrifugation was performed under the same conditions as above. Repeat steps (i) through (iii) until the pH of the supernatant is below 8. After three repetitions, the pH of the supernatant is below 8; therefore, discard the supernatant and end the repetition. Add 40 mL of pure water to the remaining sediment in the centrifuge tube and agitate using a Vortex mixer for 5 minutes. Then, centrifuge at 3500 G for 30 minutes to recover the supernatant as a slurry containing TiCO as MQO.

[0107] [Analysis of the TiCO obtained above]

[0108] (SEM observation)

[0109] The shape of TiCO was observed using SEM. Specifically, the TiCO-containing slurry prepared above was diluted 1000 times and dropped onto an Al porous substrate. Pt / Pd vapor deposition was performed (40 mA, 30 s), and SEM observation confirmed the formation of nanofibers with a width of 20 nm.

[0110] (Measurement of Zeta potential)

[0111] The Zeta potential of the TiCO slurry was measured to be -80 mV, which is greater than the -0.5 mV of the previous titanium dioxide (P-25) slurry (aqueous dispersion). Next, the Zeta potential of the polymers was measured: polyurethane (manufactured by Daihatsu Seika Co., Ltd., Resamine D-4080 (polyether / carbonate based)) was -35.5 mV, acrylic resin material (Aron (registered trademark) NW-400, manufactured by Toa Gosei Co., Ltd.) was -30.5 mV, and poly(ethyleneimine) (manufactured by Sigma-Aldrich, poly(ethyleneimine) aqueous solution) was 10.5 mV.

[0112] (Raman spectroscopy analysis)

[0113] Using TiCO slurry, Raman spectra were obtained using a Renishaw Raman spectroscopy analyzer (product number: InVia) with a 514 nm laser as the excitation source. An example of the measurement results is shown below. Figure 3 .Depend on Figure 3 It can be seen that the Raman displacement is 275~295cm -1 435~455cm -1 and 665~745cm -1 The position of the peak indicates a fibrous, zeolite-type crystal structure. Furthermore, it is known that the Raman shift is at least 180–200 cm⁻¹. -1 275~295cm -1 375~395cm -1 435~455cm -1 and 665~745cm -1 The position has a peak, and when the intensity of each peak is set to V, X, Y, Z, W, X is the largest.

[0114] (Preparation of TiCO membrane)

[0115] To analyze the composition and structure of the TiCO3 obtained above, a TiCO3 membrane was prepared using a slurry containing the aforementioned TiCO3. 1 mL of the slurry containing the aforementioned TiCO3 was taken and mixed with 20 mL of pure water, then vortexed for 5 minutes. The resulting mixture was filtered overnight using a Buchner funnel. The filter used for filtration was a membrane filter (DURAPORE, 0.22 μm pore size, manufactured by Merck Co., Ltd.). After filtration, the precursor membrane on the filter was dried overnight in a vacuum oven at 80°C. The filter was then removed to obtain the membrane (self-supported membrane).

[0116] (X-ray photoelectron spectroscopy (XPS) analysis)

[0117] The obtained TiCO film (self-supporting film) was analyzed using X-ray photoelectron spectroscopy (XPS). The XPS spectra identified peaks corresponding to Ti 2p, C 1s, O 1s, and N 1s, thus confirming the presence of Ti, C, O, and N. N is considered a residual component of the TMAH from the raw material; therefore, the self-supporting film is believed to be composed of Ti, C, and O.

[0118] (Determination of XRD patterns)

[0119] The obtained film (self-supporting film) was subjected to XRD pattern determination using an XRD apparatus (Rigaku Corporation, MiniFlex) (characteristic X-rays: CuKα = 1.54 Å). The obtained XRD pattern is shown below. Figure 4 .Depend on Figure 4 It can be seen that the material has a peak on the (001) plane at 2θ=7.7° and a peak on the (002) plane at 2θ=15.4°. This indicates that the material has a periodic structure in the thickness direction.

[0120] [Preparation of resin slurry and mixing of resin slurry with TiCO-containing slurry]

[0121] Polyurethane (manufactured by Daihatsu Seika Co., Ltd., Resamine D-4080 (polyether / carbonate system)) and pure water were mixed in a ratio of 1:9 and stirred with a vortex mixer for 5 minutes to obtain a resin slurry.

[0122] To obtain a TiCO / polyurethane composite material with a polyurethane to TiCO ratio of 30% by mass (after film drying), the above resin slurry, pure water and TiCO-containing slurry were mixed and stirred with a vortex mixer for 5 minutes to obtain a mixed slurry of TiCO and resin.

[0123] [Preparation of TiCO / polyurethane composite membrane (1) Filtration]

[0124] The TiCO and resin mixture prepared above was filtered overnight using a Buchner funnel. The filter used for filtration was a membrane filter (DURAPORE, 0.22 μm pore size, manufactured by Merck Co., Ltd.). After filtration, the precursor membrane on the filter was dried overnight in a vacuum oven at 80°C. The filter was then removed to obtain a TiCO / polyurethane composite membrane (a self-supporting membrane, also known as a "TiCO / polyurethane composite membrane").

[0125] [Preparation of TiCO / polyurethane composite film (2) Spraying]

[0126] Using a spray gun with a spray nozzle, the prepared TiCO / resin mixture slurry was sprayed onto a PET substrate. The spraying and drying in a dryer were repeated until the TiCO / polyurethane composite film thickness reached 5 μm. After coating, the film was dried in an oven at 80°C for approximately 30 minutes to obtain the TiCO / polyurethane composite film (also known as "TiCO / polyurethane composite film").

[0127] [Example 2: TiCO / acrylic resin composite membrane]

[0128] The polyurethane in Example 1 was replaced with an acrylic resin material (Aron (registered trademark) NW-400, manufactured by Toa Synthetic Co., Ltd.). Otherwise, the same procedure as in Example 1 was followed to obtain a mixture of TiCO and resin, and a TiCO / acrylic resin composite film based on spraying.

[0129] [Comparative Example 1: TiO2 / polyurethane composite membrane]

[0130] The TiCO in Example 1 was replaced with TiO2, and the same procedure was followed as in Example 1 above to obtain a mixed slurry of TiO2 and resin, and a TiO2 / polyurethane composite film based on spraying.

[0131] [Comparative Example 2: TiCO / poly(ethyleneimine) composite membrane]

[0132] The polyurethane in Example 1 was replaced with poly(ethyleneimine) (aqueous poly(ethyleneimine) manufactured by Sigma-Aldrich). Otherwise, the same procedure as in Example 1 was followed to obtain a mixture of TiCO and resin, and a spray-applied TiCO / poly(ethyleneimine) composite film.

[0133] [evaluate]

[0134] The composite material membranes of the above-described embodiments and comparative examples were evaluated as follows.

[0135] [Determination of XRD pattern of TiCO / polyurethane composite film]

[0136] The TiCO / polyurethane composite membrane (self-supporting membrane) obtained through the above-described "Preparation of TiCO / polyurethane Composite Membrane (1) Filtration" was used to determine the XRD pattern (characteristic X-ray: CuKα = 1.54 Å) using an XRD apparatus (MiniFlex, manufactured by Rigaku Corporation). The obtained XRD pattern is shown below. Figure 5 In addition, this Figure 5 With the above Figure 4 The illustration of the XRD patterns overlapping is shown in the figure. Figure 6 .Depend on Figure 5 It can be seen that the TiCO / polyurethane composite material has a peak on the (001) plane at 2θ=7.7° and a peak on the (002) plane at 2θ=15.5°. For example... Figure 6 As shown, the position of the peak does not change significantly compared to the TiCO film alone, indicating that the TiCO mixed with the resin still has a periodic structure in the thickness direction.

[0137] [Evaluation of membrane strength]

[0138] Using the TiCO / polyurethane composite film obtained through the above-mentioned "Preparation of TiCO / polyurethane Composite Film (2) Spraying", the similarly obtained TiCO / acrylic resin composite film and the similarly obtained TiO2 / polyurethane composite film, a tape peel test was performed as shown below to determine the strength of each composite film. It should be noted that the TiCO / poly(ethyleneimine) composite film could not be sprayed due to gelation. This is believed to be because the negatively charged TiCO and the positively charged poly(ethyleneimine) aggregated due to electrostatic attraction, resulting in poor dispersion of TiCO in the composite film.

[0139] The details of the strength test of the composite film are as follows. An adhesive tape (3M, 6122MP Scotch Magic TAPE, 3 / 4 inch wide) was attached to a portion of the upper surface of the composite film formed on a PET substrate, and then peeled off. The presence or absence of cohesive failure of the composite film, i.e., intra-film separation caused by the transfer of a portion of the composite film to the adhesive surface of the tape, was visually confirmed.

[0140] As a result, cohesive failure could not be confirmed for TiCO / polyurethane composite membranes and TiCO / acrylic resin composite membranes. On the other hand, cohesive failure was confirmed for titanium dioxide / polyurethane composite membranes. This is attributed to the poor dispersibility of titanium dioxide (TiO2) in aqueous dispersions, which in turn resulted in poor dispersibility of titanium dioxide (TiO2) in composite membranes.

[0141] [Evaluation of thermal conductivity]

[0142] The specific heat capacity and thermal diffusivity of the TiCO / polyurethane composite membrane (self-supporting membrane) obtained through the above-mentioned "Preparation of TiCO / polyurethane Composite Membrane (1) Filtration" were determined using a benchtop xenon flash analyzer (device name: LFA 467 HyperFlash, NETZSCH) according to the laser flash method (ASTM E1461), and the thermal conductivity was calculated. Regarding the in-plane thermal diffusivity, the surface of the sample was pulsedly heated with a xenon lamp, and the thermal diffusivity in the thickness direction of the portion moving from the heated part in the in-plane direction was observed as the time change of the back surface temperature of the sample, thereby determining the in-plane thermal diffusivity of the flat sample.

[0143] As a result, the specific heat capacity (c ρ The thermal diffusivity (A) is 1.86 J / (g·K) and the thermal diffusivity (a) is 2.85 mm. 2The in-plane thermal conductivity (l) is 7.36 W / (m·K). It should be noted that, for reference, the in-plane thermal conductivity of the above-mentioned TiCO film was also measured, and the result was 8.67 W / (m·K). Therefore, it can be considered that the composite membrane of this embodiment, due to the good dispersion of TiCO, can suppress the decrease in thermal conductivity even when mixed with resin. On the other hand, filtration was performed using an aqueous dispersion of titanium dioxide (TiO2) using a membrane filter, but no membrane (self-supporting membrane) was obtained. This is believed to be due to the poor dispersion of titanium dioxide (TiO2) in the aqueous dispersion, and the result is caused by the shape of the nanoparticles. It can be considered that TiCO is a one-dimensional material (nanofibers) and / or a two-dimensional material, which is easy to form a film, while titanium dioxide is in particulate form, making it difficult to form a coating. Since a film containing titanium dioxide (TiO2) cannot be formed, the thermal conductivity of the film cannot be evaluated.

[0144] [Evaluation of Dispersion]

[0145] It should be noted that, in order to evaluate dispersibility, the inventors placed the following aqueous dispersions in glass containers: a titanium dioxide (TiO2) aqueous dispersion (titanium dioxide concentration of 1 wt%), a titanium dioxide (TiO2) polyurethane aqueous dispersion (titanium dioxide concentration of 1 wt% and polyurethane concentration of 1 wt%), a TiCO particle poly(ethyleneimine) aqueous dispersion (TiCO particle concentration of 1 wt% and poly(ethyleneimine) concentration of 1 wt%), a TiCO particle polyurethane aqueous dispersion of this embodiment (TiCO particle concentration of 1 wt% and polyurethane concentration of 1 wt%), and a TiCO particle acrylic resin aqueous dispersion of this embodiment (TiCO particle concentration of 1 wt% and acrylic resin concentration of 1 wt%), respectively. The bottom of the glass containers was then visually inspected after 4 days. Photographs of these dispersions are shown below. Figures 7-11 .exist Figure 7 In the center of the photo, a circular white deposit was identified. Figure 8 In the center, a circular white precipitate was identified. Figure 7 and Figure 8 The photos show that titanium dioxide precipitates at the bottom of the glass container.

[0146] in addition, Figure 9 This photograph shows a case where TiCO was not sufficiently dispersed in the poly(ethyleneimine) aqueous solution and gelled. In this gel-like sample, the viscosity was too high for spraying, thus confirming that even mixing a resin with a non-negative zeta potential with TiCO cannot provide a suitable composite material for the manufacture of films, etc. In contrast, as... Figure 10 As shown in the photograph, no precipitation of TiCO particles was observed in the polyurethane aqueous solution dispersion of TiCO(MQO) particles in this embodiment after 4 days (it should be noted that...). Figure 10 (The white area at the top of the photo is background material mixed in, not sediment). It is believed that the high dispersibility of the TiCO particles in this embodiment contributes to the excellent thermal conductivity of films containing these TiCO particles. Similarly, as... Figure 11 As shown in the photograph, no precipitation of TiCO particles was observed in the acrylic resin aqueous solution dispersion of TiCO(MQO) particles in this embodiment after 4 days, indicating high dispersibility.

[0147] This application claims priority to U.S. Application No. 63 / 609383, filed December 13, 2023, the entire contents of which are incorporated herein by reference.

[0148] Explanation of reference numerals in the attached figures

[0149] 1 TiO2 (filler)

[0150] 3. Resin

[0151] 5 PET substrate

[0152] 7. Gathering Section

[0153] 9. Materials containing specified nanofibers and / or two-dimensional substances

Claims

1. A composite material comprising: Contains the formula MQ a O b Materials representing nanofibers and / or two-dimensional substances, and resins with a negative zeta potential. MQ a O b In this context, M represents at least one element selected from groups 3, 4, 5, 6, and 7. Q is a selection of at least one element from groups 12, 13, 14, 15, and 16, where, Except for O, a is 0 or higher and 2 or lower b is greater than 0 and less than 2.

2. The composite material according to claim 1, wherein, In the X-ray diffraction pattern, there are peaks in the range where the diffraction angle 2θ is above 2° and below 12°.

3. The composite material according to claim 1 or 2, wherein, In Raman spectroscopy using a laser with a wavelength of 514 nm, the Raman shift is between 275 and 295 cm⁻¹. -1 435~455cm -1 and 665~745cm -1 The position has a peak.

4. The composite material according to any one of claims 1 to 3, having anatase or ferrimetallic crystal structures, or a mixture thereof.

5. The composite material according to any one of claims 1 to 4, wherein it has a ferrimagnesian crystal structure.

6. The composite material according to any one of claims 1 to 5, wherein, In Raman spectroscopy using a laser with a wavelength of 514 nm, the Raman shift is at least 180~200 cm⁻¹. -1 275~295cm -1 375~395cm -1 435~455cm -1 and 665~745cm -1 The position has a peak, and when the intensity of each peak is set to V, X, Y, Z, W, X is the largest.

7. The composite material according to any one of claims 1 to 6, wherein, The resin is one or more of resins having amide bonds or urethane bonds and acrylic resins.

8. The composite material according to any one of claims 1 to 7, wherein, The resin accounts for more than 5% by mass in the composite material.

9. The composite material according to any one of claims 1 to 8, wherein it is in the form of a film.

10. The composite material according to any one of claims 1 to 9, wherein it is a thermally conductive material.

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