Graphene containing body and method for manufacturing graphene containing body

Abstract

To provide a new functional material.SOLUTION: A graphene containing body 10 includes: a matrix having a siloxane skeleton; graphene; and a metal element having an electronegativity of 1.60 or less. A method for manufacturing the graphene containing body 10 comprises: applying a mixed solution including at least one silicon containing raw material selected from a group consisting of silicon alkoxide and a silicon alkoxide hydrolysate, an organic solvent and metal element salt having an electronegativity of 1.60 or less on a base material; and heating the applied mixed solution at 200°C or more to deposit a film including the matrix having the siloxane skeleton, the graphene and the metal element. The graphene containing body 10 emits visible light by ultraviolet irradiation.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a graphene-containing body and a method for producing the graphene-containing body. [Background technology]

[0002] Films formed by the sol-gel method are widely used. Films formed by the sol-gel method using silicon-containing raw materials, such as silicon alkoxide, have a network structure of Si and O, in other words, a matrix with a siloxane skeleton. Patent Document 1 discloses the addition of copper ions to films formed by the sol-gel method. This film has antibacterial properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2022 / 092319 Summary of the Invention [Problem to be solved by the invention]

[0004] A coating having a matrix with a siloxane skeleton may be useful as a material that exhibits functions other than antibacterial properties. One of the objects of the present invention is to provide a novel functional material having a matrix with a siloxane skeleton. [Means for solving the problem]

[0005] The present invention provides A matrix having a siloxane skeleton, graphene, and a metal element having an electronegativity of 1.60 or less. A graphene-containing body is provided.

[0006] Also, from another aspect, the present invention provides: applying a mixed liquid containing at least one silicon-containing raw material selected from the group consisting of silicon alkoxides and silicon alkoxide hydrolysates, an organic solvent, and a salt of a metal element having an electronegativity of 1.60 or less onto a substrate; heating the applied mixed solution to 200°C or higher to form a film containing a matrix having a siloxane skeleton, graphene, and the metal element; Including, A method for producing a graphene-containing object is provided. [Effects of the Invention]

[0007] According to the present invention, a novel functional material is provided, and a method for producing the novel functional material is also provided. This functional material functions as at least a light emitter that emits visible light when irradiated with ultraviolet light. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic perspective view showing an example of a graphene inclusion. [Figure 2] FIG. 10 is a schematic perspective view showing another example of a graphene-containing body. [Figure 3A] 1 is a photograph of the solids according to the examples and comparative examples under room lighting. [Figure 3B] 1 is a photograph of solids according to Examples and Comparative Examples under black light irradiation. [Figure 4] 1 is an example of a 3D emission spectrum of a solid according to an example. [Figure 5] 1 is an example of a Raman spectrum of a solid according to an example. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, preferred embodiments of the present invention will be described, but the following description is not intended to limit the present invention to a specific embodiment. In this specification, the upper and lower limits of the numerical ranges described below can be arbitrarily combined both when the upper and lower limits are stated individually and when the upper and lower limits are stated as a range.

[0010] In this specification, when the expression "weight" appears, it may be read as "mass," which is a commonly used SI system unit for indicating weight. The same is true vice versa. The wavelength band of "ultraviolet light" is 10 nm or more and less than 380 nm, and the wavelength band of "visible light" is 380 nm or more and less than 780 nm. The term "metal" is used in the sense that it also includes "semimetals." "Semimetals" include B, Si, Ge, As, Sb, and Te.

[0011] In this specification, "electronegativity" refers to the value determined for each element according to Pauling's definition. This value is shown, for example, in JE Huheey, EA Keiter and RL Keiter: "Inorganic Chemistry" and is also listed in Table 2 of Surface Science, Vol. 22, No. 12, pp. 831-833, 2001. Strictly speaking, "graphene" refers to SP 2 It is a carbon allotrope (single-layer graphene) with a thickness of one atom that is bonded to each other by bonds, but in this specification, it is used to mean that it also includes multi-layer graphene and graphene oxide, which is graphene having oxygen atom-containing functional groups.

[0012] [Graphene-containing material] The present inventors have found that when a sol-gel process using a silicon-containing raw material is carried out in the presence of metal ions with low electronegativity and the process is heated at high temperatures, the resulting film turns black. Through further research, the present inventors have confirmed that the blackening of the film is due to the generation of graphene.

[0013] The graphene-containing material may be a film formed on a substrate, or may be peeled off from the substrate and used as a single material. In the latter case, the graphene-containing material is, for example, in the form of flakes.

[0014] The graphene-inclusive material according to this embodiment includes a matrix M having a siloxane skeleton, graphene G, and a metal element E1 having an electronegativity of 1.60 or less. The graphene-inclusive material according to this embodiment may be a light-emitting material that emits visible light when irradiated with ultraviolet light. However, the graphene-inclusive material is not limited to being a light-emitting material, and may be used in applications that utilize the properties of graphene, such as electrical conductivity and heat ray absorption.

[0015] The wavelength of the ultraviolet light irradiated onto the graphene-inclusive body is, for example, 300 nm or more, and may be 310 nm or more, 320 nm or more, 330 nm or more, 340 nm or more, or even 350 nm or more. The "ultraviolet light wavelength" refers to the wavelength with the highest intensity in the excitation spectrum of the graphene-inclusive body in the ultraviolet light wavelength band. The excitation spectrum can be obtained, for example, using a commercially available spectrofluorometer. The ultraviolet light wavelength may be less than 380 nm, 375 nm or less, or even 370 nm or less. An example of the ultraviolet light wavelength range is 350 nm or more and less than 380 nm, and a more specific example is 350 nm or more and 370 nm or less.

[0016] The wavelength of visible light emitted from the graphene-inclusive body is, for example, 390 nm or more, and may be 395 nm or more, or 400 nm or more. The "wavelength of visible light" refers to the wavelength with the highest intensity in the emission spectrum of the graphene-inclusive body in the visible light wavelength band. The emission spectrum can be obtained, for example, using a commercially available spectrofluorometer. The wavelength of visible light may be preferably less than 780 nm, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 500 nm or less, or even 450 nm or less. An example of the wavelength range of visible light is 390 nm or more and 500 nm or less, and a more specific example is 390 nm or more and 450 nm or less.

[0017] The components of the graphene-containing body will be described below.

[0018] (Matrix M) The graphene-containing material includes a matrix M having a siloxane skeleton. The matrix M typically has a network structure of Si-O bonds including SiO4 tetrahedra, each having an O atom at its vertices and an Si atom at its center. In the matrix M, the SiO4 tetrahedra may be bonded to each other by sharing an O atom. The matrix M may also include bonds other than the Si-O bond. An example of a bond other than the Si-O bond is an Si-R bond (R: organic group). R in the Si-R bond is preferably an alkyl group, and may be an alkyl group having 1 to 4 carbon atoms, or may further be an alkyl group having 1 to 2 carbon atoms.

[0019] In the matrix M, the SiO4 tetrahedra may be primarily formed of at least one type selected from the group consisting of three-membered rings, four-membered rings, five-membered rings, and six-membered rings. The SiO4 tetrahedra may be primarily formed of four-membered rings. Note that "primarily forming m-membered rings" means that, in a Raman spectrum obtained by Raman spectroscopy, the intensity is greatest at the wavenumber shift corresponding to the m-membered ring among the wavelength shifts caused by the ring structure of the Si-O bond. m is an integer from 3 to 6.

[0020] The matrix M may contain other atoms as long as it contains a network structure of Si atoms and O atoms that form a siloxane skeleton. For example, the matrix M may contain the above-mentioned R, or may contain metal atoms bonded to O atoms.

[0021] (Graphene G) The graphene-containing material contains graphene G. It is presumed that graphene G mainly plays a role in emitting visible light when irradiated with ultraviolet light. The presence of graphene G can be confirmed, for example, by Raman spectroscopy. As long as a peak characteristic of graphene G is confirmed by Raman spectroscopy, graphene G may be single-layer graphene or multi-layer graphene, or may be graphene oxide containing an oxygen atom-containing functional group. The oxygen atom-containing functional group is, for example, a hydroxyl group or a carboxyl group.

[0022] (Metal element E1 with electronegativity of 1.60 or less) The graphene-containing material includes a metal element E1 having an electronegativity of 1.60 or less. The metal element E1 having an electronegativity of 1.60 or less may be at least one element selected from the group consisting of Group 1 elements excluding H, Group 2 elements, Group 3 elements, Group 4 elements, and Group 5 elements excluding V and Nb. Here, the Group 3 elements include lanthanides and actinides in addition to Sc and Y. The metal element E1 may have an electronegativity of 1.5 or less, 1.4 or less, or even 1.35 or less. The metal element E1 may include at least one element selected from the group consisting of Group 1 elements excluding H, Group 2 elements excluding Be, and Group 3 elements, or may include at least one element selected from the group consisting of Group 1 elements excluding H and Group 2 elements excluding Be, or may include a Group 2 element excluding Be. The metal element E1 may contain at least one element selected from the group consisting of Ba (electronegativity 0.89), Sr (electronegativity 0.95), Ca (electronegativity 1.00), and Mg (electronegativity 1.31), or may contain at least one element selected from the group consisting of Ca and Mg. The metal element E1 may contain at least one element selected from the group consisting of Rb (electronegativity 0.89), K (electronegativity 0.82), Na (electronegativity 0.93), and Li (electronegativity 0.98).

[0023] The weight ratio of the metal element E1 to the Si element constituting the matrix M ((weight of the metal element E1) / (weight of the matrix M)×100(%)) is, for example, 0.1 to 10.0%, and may be 0.2 to 8.0%, or even 0.5 to 5.0%.

[0024] (Other components) The graphene-containing material may contain other components. The graphene-containing material may further contain at least one element E2 selected from the group consisting of B and P. The element E2 may be B. B and / or P may be contained in the graphene-containing material separately from the siloxane skeleton. B and / or P can be added to the raw materials for the sol-gel method as an acid containing these elements. The graphene-containing material may further contain alcohols such as alkyl alcohols (e.g., methanol, ethanol, etc.) and / or ethers such as dialkyl ethers (e.g., dimethyl ether, diethyl ether, etc.). The element E2, alcohols, and ethers may be components derived from an example of a method for producing a graphene-containing material (a production method using a sol-gel method) described below.

[0025] [Shape of graphene-containing material] 1, the graphene-containing material 10 may include a substrate 2 and a film 1a on the substrate 2. In this embodiment, the film 1a includes a matrix M, graphene G, and a metal element E1.

[0026] The length La of the film 1a in a direction perpendicular to the line segment that defines the maximum length La of the film 1a along the film surface and along the film surface is, for example, 100 times or more, 500 times or more, or even 1000 times or more the thickness Ta of the film 1a. The length La of the film 1a is, for example, 1.0 × 10 times the thickness Ta. 10 times less than 1.0 × 10 8 Less than twice, 1.0×10 6 It may be twice or less.

[0027] The thickness Ta of the film 1a is, for example, 500 μm or less, and may be 400 μm or less, 300 μm or less, 200 μm or less, or even 100 μm or less. The thickness Ta of the film 1a is, for example, 1 μm or more, 5 μm or more, 10 μm or more, or even 50 μm or more. The thickness Ta of the film 1a is preferably 5 μm or more and 500 μm or less, and more preferably 10 μm or more and 200 μm or less.

[0028] The substrate 2 is a transparent substrate, and the material of the transparent substrate serving as the substrate 2 is, for example, glass or resin.

[0029] When the material of the substrate 2 is glass, the substrate 2 is made of, for example, soda-lime glass, borosilicate glass, aluminosilicate glass, or alkali-free glass.

[0030] When the material of the substrate 2 is a resin, the substrate 2 is composed of, for example, polyolefin resins such as polyethylene (PE) and polypropylene (PP); acrylic resins such as polymethyl methacrylate (PMMA); polyester resins such as polyethylene terephthalate (PET); polyamide resins such as nylon and aramid; polyimide resins such as aromatic polyimide; polycarbonate resin; cellulose resins such as polyacetyl cellulose; polyvinyl chloride (PVC) resin; polyvinyl acetal (PVA) resin; polyvinyl butyral (PVB) resin; silicone resin, etc.

[0031] The thickness T2 of the substrate 2 can be changed as appropriate depending on the application of the graphene-containing material 10. The thickness Ta of the film 1a is, for example, 5.0 mm or less, and may be 4.0 mm or less, 3.0 mm or less, 2.5 mm or less, 2.0 mm or less, 1.5 mm or less, or even 1.0 mm or less. The thickness Ta of the film 1a is, for example, 0.1 mm or more, and may be 0.2 mm or more, 0.3 mm or more, 0.4 mm or more, or even 0.5 mm or more. The thickness T2 of the substrate 2 may be 0.3 mm or more and 3.0 mm or less, or 0.5 mm or more and 2.5 mm or less.

[0032] The thickness T2 of the substrate 2 is preferably greater than the thickness Ta of the film 1a.

[0033] When the graphene inclusion is a single luminescent material, the graphene inclusion 20 has, for example, the shape of a flake-like body 1b. The length Lb in the direction along the main surface of the flake-like body 1b, which is perpendicular to the line segment defining the maximum length Lbm of the flake-like body 1b, and which is along the main surface, is, for example, 100 times or more, 500 times or more, or even 1000 times or more the thickness Tb of the flake-like body 1b. The length Lb of the flake-like body 1b is, for example, 1.0 × 10 times the thickness Tb. 10 times less than 1.0 × 10 8 Less than twice, 1.0×10 6 It may be twice or less.

[0034] The thickness Tb of the flake-shaped bodies 1b is, for example, 500 μm or less, and may be 400 μm or less, 300 μm or less, 200 μm or less, or even 100 μm or less. The thickness Tb of the flake-shaped bodies 1b is, for example, 1 μm or more, 5 μm or more, 10 μm or more, or even 50 μm or more. The thickness Tb of the flake-shaped bodies 1b is preferably 5 μm or more and 500 μm or less, and more preferably 10 μm or more and 200 μm or less.

[0035] [Method of manufacturing graphene-containing material] The graphene-containing material of this embodiment can be produced by a sol-gel method. The production method of this embodiment includes, for example, the following steps P1 and P2.

[0036] (Process P1) First, a mixed solution L containing at least one silicon-containing raw material A selected from the group consisting of silicon alkoxides and silicon alkoxide hydrolysates, an organic solvent S, and a salt of a metal element E1 having an electronegativity of 1.60 or less is applied onto a substrate (step P1). The mixed solution L may further contain water.

[0037] Silicon alkoxides that can constitute silicon-containing raw material A are silicon compounds containing an alkoxy group. Silicon alkoxides are, for example, silicon compounds represented by formula (1). R 2 n Si(OR 1 ) 4-n (1) In formula (1), R 1 and R 2 is an organic group, and n is an integer of 0 to 3.

[0038] In formula (1), R 1 is preferably an alkyl group, and may be an alkyl group having 1 to 4 carbon atoms, or may further be an alkyl group having 1 to 2 carbon atoms. 2 R may be an aliphatic or aromatic group and may contain heteroatoms. 2 is preferably an alkyl group, and may be an alkyl group having 1 to 10 carbon atoms, or may further be an alkyl group having 1 to 4 carbon atoms. n is preferably an integer of 0 to 2, and may be an integer of 0 to 1, or may further be 0.

[0039] Two or more silicon alkoxides may be combined. Such a combination includes, for example, tetraalkoxysilane (in formula (1), n ​​is 0 and Si(OR 1 ) 4) and alkyltrialkoxysilane (in formula (1), n ​​is 1 and R 2 is an alkyl group, and R 2 Si(OR 1 )3) is used in combination with

[0040] The silicon alkoxide may include at least one selected from the group consisting of tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS).

[0041] The silicon alkoxide may constitute the silicon-containing raw material A as a hydrolyzate. The hydrolyzate may be a partial hydrolyzate in which hydrolysis has progressed partially. The silicon-containing raw material A may be a metal alkoxide or a hydrolyzate thereof.

[0042] The organic solvent S can be selected from known organic solvents that are miscible with silicon alkoxide and water, and may be an alcohol having 1 to 4 carbon atoms, such as ethanol.

[0043] The salt of the metal element E1 is, for example, an inorganic acid salt such as hydrochloride, nitrate, or sulfate, or an organic acid salt such as trichloroacetate, trifluoroacetate, methanesulfonate, or paratoluenesulfonate.

[0044] The weight ratio of the salt of the metal element E1 to the Si element ((weight of the salt of the metal element E1) / (weight of the Si element)×100(%)) is, for example, 1% or more, and may be 2% or more, 3% or more, 4% or more, 5% or more, 6% or more, 7% or more, 8% or more, 9% or more, or even 10% or more. The weight ratio of the salt of the metal element E1 to the Si element is, for example, 25% or less, and may be 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, or even 10% or less. A preferred example of the weight ratio of the salt of the metal element E1 to the Si element is 5.0% or more and 20.0% or less. If the Si element is too little, it is difficult to ensure the mechanical strength of the graphene-containing body. If the metal element E1 is too little, it is difficult to produce graphene G.

[0045] The mixed liquid L may further contain a raw material containing at least one element selected from the group consisting of B and P. This raw material may be an oxide or an acid. The oxide containing B may be boron oxide, and the oxide containing P may be phosphorus oxide. The acid containing B is, for example, boric acid, and the raw material containing P is, for example, phosphoric acid. The mixed liquid L may contain, for example, at least one selected from the group consisting of boric acid (B(OH)3) and phosphoric acid (H3PO4).

[0046] A raw material containing B and / or P can promote the diffusion of the metal element E1 within the matrix. For example, boric acid binds to the matrix M when the matrix M is formed in the mixed liquid L. However, as heating proceeds, a portion of the boric acid is esterified and volatilized. As the boric acid volatilizes, the metal element E1 replaces B and is incorporated into the matrix M.

[0047] The weight ratio of the raw material containing B and / or P to the metal element E1 ((weight of the raw material containing B and / or P) / (weight of the metal element E1)×100(%)) is, for example, 50% or more, and may be 60% or more, 70% or more, 80% or more, 90% or more, or even 100% or more. The weight ratio of the raw material containing B and / or P to the metal element E1 is, for example, 250% or less, and may be 240% or less, 230% or less, 220% or less, 210% or less, 200% or less, 190% or less, 180% or less, 170% or less, 160% or less, or even 150% or less. A preferred example of the weight ratio of the raw material containing B and / or P to the metal element E1 is 100% or more and 250% or less. The mixed liquid L does not necessarily contain a raw material containing B and / or P.

[0048] The mixed solution L may further contain a hydrolysis catalyst. The hydrolysis catalyst is, for example, an acid catalyst, preferably a strong acid (an acid dissociation constant: pKa<0). The strong acid is, for example, an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, or an organic acid such as trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, or paratoluenesulfonic acid. From the viewpoint of preventing a decrease in the hardness of the matrix M, the acid catalyst is preferably an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, and from the viewpoint of preventing the acid from remaining in the matrix M, hydrochloric acid is more preferred because of its high volatility.

[0049] The method for applying the mixed liquid L onto the substrate is not particularly limited, and methods such as flow coating, spray coating, and spin coating can be used.

[0050] A reaction promotion period for promoting the hydrolysis reaction and the polycondensation reaction may be provided between step P1 and step P2. The reaction promotion period is, for example, 100 hours or less, 80 hours or less, or 60 hours or less, or 1 hour or more, 2 hours or more, or 10 hours or more. During the reaction promotion period, the mixed liquid L is left under conditions such as a thermostatic bath at 20°C.

[0051] (Process P2) Next, the mixed solution L applied to the substrate is heated to 200°C or higher to form a film containing a matrix M having a siloxane skeleton, graphene G, and a metal element E1 from the silicon-containing raw material (step P2). In step P2, the matrix M and graphene G are produced. Carbon atoms, which are the raw materials for graphene G, are supplied from an alcohol, which is a by-product of the hydrolysis reaction of the silicon-containing raw material A, and an organic solvent.

[0052] The heating temperature of the mixed liquid L in step P2 is preferably 200°C or higher, and may be 210°C or higher, 220°C or higher, 230°C or higher, 240°C or higher, 250°C or higher, 260°C or higher, 270°C or higher, 280°C or higher, 290°C or higher, or even 300°C or higher. The heating temperature of the mixed liquid L in step P2 is preferably 600°C or lower, and may be 590°C or lower, 580°C or lower, 570°C or lower, 560°C or lower, 550°C or lower, 540°C or lower, 530°C or lower, 520°C or lower, 510°C or lower, or even 500°C or lower. A preferred example of the heating temperature of the mixed liquid L is 200°C or higher and 500°C or lower. At such a heating temperature, graphene G can be produced from the mixed liquid L. When the mixed liquid L contains a salt of the metal element E1, graphene G can be produced from the mixed liquid L at a lower temperature than when the mixed liquid L does not contain a salt of the metal element E1. For example, when the mixed liquid L contains a salt of the metal element E1, graphene G can be produced even if the mixed liquid L is heated to a temperature of 400° C. or lower.

[0053] Through the above steps A and B, a graphene-containing material that emits visible light when irradiated with ultraviolet light is obtained.

[0054] As described above, the present embodiment provides the following techniques.

[0055] (Technology 1) A matrix having a siloxane skeleton, graphene, and a metal element having an electronegativity of 1.60 or less. Graphene inclusions.

[0056] (Technology 2) The graphene-containing material according to Art. 1, which emits visible light when irradiated with ultraviolet light.

[0057] (Technology 3) a substrate and a film on the substrate, the film includes the matrix, the graphene, and the metal element; 3. The graphene-containing material according to claim 1 or 2.

[0058] (Technology 4) 4. The graphene inclusion according to claim 3, wherein a length La in a direction along the film surface, perpendicular to a line segment that defines a maximum length of the film, and along the film surface, is 100 times or more a thickness Ta of the film.

[0059] (Technology 5) 5. The graphene-containing material according to claim 3, wherein the thickness Ta of the film is 5 μm or more and 500 μm or less.

[0060] (Technology 6) 6. The graphene-containing material according to any one of techniques 3 to 5, wherein the substrate is a transparent substrate.

[0061] (Technology 7) It has a flake shape, a length Lb of the flake-shaped body in a direction perpendicular to a line segment that defines the maximum length of the flake-shaped body along the main surface and along the main surface, the length Lb being 100 times or more the thickness Tb of the flake-shaped body; 3. The graphene-containing material according to claim 1 or 2.

[0062] (Technology 8) 8. The graphene-containing material according to claim 7, wherein the thickness Tb of the flake-shaped material is 5 μm or more and 500 μm or less.

[0063] (Technology 9) 9. The graphene-containing material according to any one of techniques 1 to 8, wherein the metal element includes a Group 2 element excluding Be.

[0064] (Technology 10) 10. The graphene-containing material according to claim 9, wherein the metal element includes at least one element selected from the group consisting of Ca and Mg.

[0065] (Technology 11) 11. The graphene-containing material according to any one of claims 1 to 10, further comprising at least one element selected from the group consisting of B and P.

[0066] (Technology 12) 12. The graphene-containing material according to any one of claims 1 to 11, wherein in the siloxane skeleton, SiO 4 tetrahedra mainly form four-membered rings.

[0067] (Technology 13) applying a mixed liquid containing at least one silicon-containing raw material selected from the group consisting of silicon alkoxides and silicon alkoxide hydrolysates, an organic solvent, and a salt of a metal element having an electronegativity of 1.60 or less onto a substrate; heating the applied mixed solution to 200°C or higher to form a film containing a matrix having a siloxane skeleton, graphene, and the metal element; Including, A method for producing a graphene-containing object.

[0068] (Technology 14) 14. The method for producing a graphene-containing material according to claim 13, wherein the metal element includes a Group 2 element excluding Be.

[0069] (Technology 15) 15. The method for producing a graphene-containing material according to claim 13, wherein the mixed solution further contains a raw material containing at least one element selected from the group consisting of B and P. [Example]

[0070] (Preparation of Mixture 1) Calcium chloride (CaCl2) was added to ethanol ("Neoethanol P-7" manufactured by Taishin Chemical Co., Ltd.), and then tetraethoxysilane (TEOS) as a silicon alkoxide, concentrated hydrochloric acid as a hydrolysis catalyst, and water were added to prepare mixed solution R. The weight ratios of each component in mixed solution 1 are shown in Table 1.

[0071] (Preparation of Mixture 2) Mixture 2 was prepared in the same manner as Mixture 1, except that magnesium chloride (MgCl) was added to ethanol in advance instead of calcium chloride (CaCl), and the weight ratio of each component was changed. The weight ratio of each component in Mixture 2 is shown in Table 1.

[0072] (Preparation of Mixture 3) Mixture 3 was prepared in the same manner as Mixture 1, except that boric acid (B(OH)3) was further added and the weight ratio of each component was changed. The weight ratio of each component in Mixture 3 is shown in Table 1.

[0073] (Preparation of Mixture 4) Mixture 4 was prepared in the same manner as Mixture 2, except that boric acid (B(OH)3) was further added and the weight ratio of each component was changed. The weight ratio of each component in Mixture 4 is shown in Table 1.

[0074] (Preparation of Mixtures 5 to 8) Except for changing the weight ratio of each component, Mixtures 5 to 8 were prepared in the same manner as Mixture 3. The weight ratios of each component in Mixtures 5 to 8 are shown in Table 1.

[0075] (Preparation of Mixture C) Mixture C was prepared in the same manner as Mixture 3, except that copper chloride (CuCl) was added in advance to ethanol ("Neoethanol P-7" manufactured by Taishin Chemical Co., Ltd.) instead of calcium chloride (CaCl), and the weight ratio of each component was changed. The weight ratio of each component in Mixture C is shown in Table 1.

[0076] [Table 1]

[0077] Examples 1A to 1E After leaving the mixture in a constant temperature bath at 20°C for 48 hours, the resulting mixture 1, in which tetraethoxysilane had been hydrolyzed, was poured into a polystyrene petri dish and heated on a hot plate heated to 45°C for approximately 1 hour. As a result, the gel film formed from mixture 1 was almost completely peeled off from the petri dish due to film shrinkage caused by hardening. The gel film had a curled, flaky shape, with the side in contact with the bottom of the petri dish being concave and the side in contact with the air being convex. Five gel films were prepared.

[0078] The five gel films were each transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 1A), 350°C (Example 1B), 400°C (Example 1C), 450°C (Example 1D), and 500°C (Example 1E). This resulted in the solids of Examples 1A to 1E, respectively. The thickness of the solids of Examples 1A to 1E was approximately 100 μm.

[0079] The solids of Examples 1A to 1E were irradiated with ultraviolet light (dominant wavelength: 351 nm, energy density: 1 mW / cm) using a black light (UVL-56 manufactured by Funakoshi Co., Ltd.). 2 The luminescent states of the solids of Examples 1A to 1E under irradiation with ultraviolet light from the black light are shown in Table 2.

[0080] Examples 2A to 2E Five gel films were prepared using Mixture 2 in the same manner as for the solids of Examples 1A to 1E. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 2A), 350°C (Example 2B), 400°C (Example 2C), 450°C (Example 2D), and 500°C (Example 2E). This resulted in the solids of Examples 2A to 2E, each with a thickness of approximately 100 μm. The luminescence states of the solids of Examples 2A to 2E under ultraviolet irradiation using the black light are shown in Table 2.

[0081] Examples 3A to 3E Five gel films were prepared using Mixture 3 in the same manner as for the solids of Examples 1A to 1E. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 3A), 350°C (Example 3B), 400°C (Example 3C), 450°C (Example 3D), and 500°C (Example 3E). This resulted in the solids of Examples 3A to 3E, each with a thickness of approximately 100 μm. The luminescence states of the solids of Examples 3A to 3E under ultraviolet irradiation using the black light are shown in Table 2.

[0082] Examples 4A to 4E Five gel films were prepared using Mixture 4 in the same manner as for the solids of Examples 1A to 1E. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 4A), 350°C (Example 4B), 400°C (Example 4C), 450°C (Example 4D), and 500°C (Example 4E). This resulted in the solids of Examples 4A to 4E, each with a thickness of approximately 100 μm. The luminescence states of the solids of Examples 4A to 4E under ultraviolet irradiation using the black light are shown in Table 2.

[0083] Examples 5A to 5E Five gel films were prepared using Mixture 5. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 5A), 350°C (Example 5B), 400°C (Example 5C), 450°C (Example 5D), and 500°C (Example 5E). This resulted in solids of Examples 5A to 5E, each with a thickness of approximately 100 μm. The luminescence states of the solids of Examples 5A to 5E under ultraviolet irradiation using the black light are shown in Table 2.

[0084] (Examples 5X to 5Z) Three gel films were prepared using Mixture 5 in the same manner as the solids of Examples 1A to 1E, except that instead of leaving the solids in a 20°C thermostatic chamber for 48 hours, they were left in a 20°C thermostatic chamber for 65 hours (hereinafter, this leaving period is referred to as the "reaction acceleration period"). The petri dish was heated on a hot plate heated to 45°C for approximately one hour. As a result, the gel film formed from Mixture 1 was approximately 100% peeled off from the petri dish due to film shrinkage associated with curing. The three gel films were transferred to aluminum cups and heated at temperatures of 220°C (Example 5X), 230°C (Example 5Y), and 240°C (Example 5Z) for 48 hours. This resulted in solids of Examples 5X to 5Z, each with a thickness of approximately 100 μm. Table 2 shows the luminescence state of the solids of Examples 5X to 5Z under ultraviolet irradiation using the black light.

[0085] Examples 6A to 6E Five gel films were prepared using Mixture 6 in the same manner as for the solids of Examples 1A to 1E. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 6A), 350°C (Example 6B), 400°C (Example 6C), 450°C (Example 6D), and 500°C (Example 6E). This resulted in solids of Examples 6A to 6E, each with a thickness of approximately 100 μm. The luminescence states of the solids of Examples 6A to 6E under ultraviolet irradiation using the black light are shown in Table 2.

[0086] (Examples 6X to 6Z) Using the same method as in Examples 5X to 5Z, three gel films were prepared using Mixture 6 after the reaction promotion period. The three gel films were transferred to aluminum cups and heated at temperatures of 220°C (Example 6X), 230°C (Example 6Y), and 240°C (Example 6Z) for 48 hours. This resulted in solids of Examples 6X to 6Z, each with a thickness of approximately 100 μm. The luminescence state of the solids of Examples 6X to 6Z under ultraviolet irradiation using the black light is shown in Table 2.

[0087] (Examples 7A to 7E) Five gel films were prepared using Mixture 7 in the same manner as for the solids of Examples 1A to 1E. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 7A), 350°C (Example 7B), 400°C (Example 7C), 450°C (Example 7D), and 500°C (Example 7E). This resulted in the solids of Examples 7A to 7E, each with a thickness of approximately 100 μm. The luminescence states of the solids of Examples 7A to 7E under ultraviolet irradiation using the black light are shown in Table 2.

[0088] (Examples 7X to 7Z) Using the same method as in Examples 5X to 5Z, three gel films were prepared using Mixture 7 after the reaction promotion period. The three gel films were transferred to aluminum cups and heated at temperatures of 220°C (Example 7X), 230°C (Example 7Y), and 240°C (Example 7Z) for 48 hours. This resulted in solids of Examples 7X to 7Z, each with a thickness of approximately 100 μm. The luminescence state of the solids of Examples 7X to 7Z under ultraviolet irradiation using the black light is shown in Table 2.

[0089] Examples 8A to 8E Five gel films were prepared using Mixture 8 in the same manner as for the solids of Examples 1A to 1E. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Example 8A), 350°C (Example 8B), 400°C (Example 8C), 450°C (Example 8D), and 500°C (Example 8E). This resulted in solids of Examples 8A to 8E, each with a thickness of approximately 100 μm. The luminescence states of the solids of Examples 8A to 8E under ultraviolet irradiation using the black light are shown in Table 2.

[0090] (Examples 8X to 8Z) Using the same method as in Examples 5X to 5Z, three gel films were prepared using Mixture 8 after the reaction promotion period. The three gel films were transferred to aluminum cups and heated at temperatures of 220°C (Example 8X), 230°C (Example 8Y), and 240°C (Example 8Z) for 48 hours. This resulted in solids of Examples 8X to 8Z, each with a thickness of approximately 100 μm. The luminescence state of the solids of Examples 8X to 8Z under ultraviolet irradiation using the black light is shown in Table 2.

[0091] (Comparative examples CA~CE) Five gel films were prepared using Mixture C in the same manner as for the solids of Examples 1A to 1E. Each of the five gel films was transferred to an aluminum cup and heated for 48 hours at temperatures of 300°C (Comparative Example CA), 350°C (Comparative Example CB), 400°C (Comparative Example CC), 450°C (Comparative Example CD), and 500°C (Comparative Example CE). This resulted in solids of Comparative Examples CA to CE, each with a thickness of approximately 100 μm. The luminescence state of the solids of Comparative Examples CA to CE under ultraviolet irradiation by the black light is shown in Table 2.

[0092] Although not shown in Table 2, mixed solution R was prepared by adding tetraethoxysilane (TEOS), concentrated hydrochloric acid, and water to ethanol without adding calcium chloride (CaCl2) and / or magnesium chloride (MgCl2) in advance. In this case, no visible luminescence was observed in the solid obtained from mixed solution R after heating at 400°C for 48 hours.

[0093] [Table 2]

[0094] The symbols in Table 2 indicate the following luminescent states when the solids of the Examples and Comparative Examples were irradiated with ultraviolet light using the black light. "◎": The light (purple light) is clearly visible. "Good": The luminescence (purple light) can be seen. "△": Light emission (purple light) is slightly visible. "▲": Immediately after production, luminescence (purple light) was visible, and then the luminescence disappeared after about three months. "X": No visible light.

[0095] Figure 3A is a photograph of the solids of the Examples and Comparative Examples under room lighting, and Figure 3B is a photograph of the solids of the Examples and Comparative Examples under the black light irradiation. The left column of Figures 3A and 3B shows, from top to bottom, the solids of Example 3A, Example 3B, Example 3C, Example 3D, and Example 3E. The right column of Figures 3A and 3B shows, from top to bottom, the solids of Comparative Examples CA, CB, CC, CD, and CE.

[0096] As shown in FIG. 3B, under the black light irradiation, the solid of the example emits light, while the solid of the comparative example does not emit light.

[0097] FIG. 4 shows an example of a 3D emission spectrum of the solid of the example. The 3D emission spectrum of FIG. 4 was measured for the solid of Example 3C using an FP-8300 manufactured by JASCO Corporation. As shown in FIG. 4, it can be seen that the solid of Example 3C emits strong purple light in the vicinity of 400 nm when excited by ultraviolet light in the vicinity of 350 nm. The solids of the other examples also had the emission characteristic of emitting strong purple light in the vicinity of 400 nm when excited by ultraviolet light in the vicinity of 350 nm.

[0098] FIG. 5 shows an example of a Raman spectrum of a solid of an example. The Raman spectrum of FIG. 5 was measured for the solid of Example 3C using a LabRAM Odyssey manufactured by HORIBA France SAS. As shown in FIG. 5, the Raman spectrum of the solid of Example 3C has an intensity peak at the wavelength shift amount due to the C-C bond of graphene. The Raman spectra of the solids of the other examples also had intensity peaks at the wavelength shift amount due to the C-C bond of graphene. This indicates that the solids of the examples contain graphene.

[0099] As shown in Figure 5, the Raman spectrum of the solid of Example 3C shows that, among the wavelength shifts due to the ring structure of the Si-O bond, the wavenumber shift corresponding to the four-membered ring has the highest peak intensity. The Raman spectra of the solids of the other Examples also show the highest peak intensity at the wavenumber shift corresponding to the four-membered ring. This indicates that the solids of the Examples have a siloxane skeleton mainly formed from four-membered rings. [Industrial Applicability]

[0100] The graphene-inclusive material of the present invention can be used, for example, for conductive material applications, heat ray absorption material applications, etc. In particular, since the graphene-inclusive material of the present invention can emit visible light when irradiated with ultraviolet rays, it can be used for ultraviolet detection applications, lighting equipment applications, display equipment applications, etc. [Explanation of symbols]

[0101] 1a Membrane (luminous material) 1b Flake-like object (luminous object) 2 Base material 10,20 Graphene inclusions La: Length in the direction perpendicular to the line that defines the maximum length of the film Lam: Maximum length of the membrane along the membrane surface Lb: Length in the direction of the main surface perpendicular to the line that defines the maximum length of the flake-like body Lbm: Maximum length of flakes along the main surface of the flakes

Claims

1. A matrix having a siloxane skeleton, graphene, and a metal element having an electronegativity of 1.60 or less. Graphene inclusions.

2. The graphene-containing material according to claim 1 , which emits visible light when irradiated with ultraviolet light.

3. a substrate and a film on the substrate, the film includes the matrix, the graphene, and the metal element; The graphene-containing material according to claim 1 .

4. 4. The graphene inclusion according to claim 3, wherein a length La in a direction along a film surface of the film, perpendicular to a line segment that defines a maximum length of the film, and along the film surface, is 100 times or more a thickness Ta of the film.

5. The graphene-containing material according to claim 3 , wherein the film has a thickness Ta of 5 μm or more and 500 μm or less.

6. The graphene-containing material according to claim 3 , wherein the substrate is a transparent substrate.

7. It has a flake shape, a length Lb of the flake-shaped body in a direction perpendicular to a line segment defining the maximum length of the flake-shaped body along the main surface and along the main surface is 100 times or more the thickness Tb of the flake-shaped body; The graphene-containing material according to claim 1 .

8. The graphene-containing material according to claim 7 , wherein the flake-shaped material has a thickness Tb of 5 μm or more and 500 μm or less.

9. The graphene-containing material according to claim 1 , wherein the metal element comprises a Group 2 element excluding Be.

10. The graphene-containing material according to claim 9 , wherein the metal element includes at least one element selected from the group consisting of Ca and Mg.

11. The graphene-containing material according to claim 1 , further comprising at least one element selected from the group consisting of B and P.

12. In the siloxane skeleton, SiO 4 2. The graphene-containing material according to claim 1, wherein the tetrahedra mainly form four-membered rings.

13. applying a mixed liquid containing at least one silicon-containing raw material selected from the group consisting of silicon alkoxides and silicon alkoxide hydrolysates, an organic solvent, and a salt of a metal element having an electronegativity of 1.60 or less onto a substrate; heating the applied mixed solution to 200°C or higher to form a film containing a matrix having a siloxane skeleton, graphene, and the metal element; Including, A method for producing a graphene-containing object.

14. The method for producing a graphene-containing body according to claim 13 , wherein the metal element includes a Group 2 element excluding Be.

15. The method for producing a graphene-containing material according to claim 13 , wherein the mixed solution further contains a raw material containing at least one element selected from the group consisting of B and P.

Images