Electromagnetic wave absorbing particles, electromagnetic wave absorbing particle dispersion, electromagnetic wave absorbing particle dispersion, electromagnetic wave absorbing laminate

Abstract

To provide novel electromagnetic wave absorbing particles.SOLUTION: Provided are electromagnetic wave absorbing particles containing a composite oxide, wherein: the composite oxide contains element A, which is one or more elements selected from rare earth elements, and element B, which is Ir; and when the mole number of the element A and the mole number of the element B contained in the composite oxide are denoted by x and y, respectively, the following relation is satisfied: 0.001≤x / y≤4.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to electromagnetic wave absorbing particles, an electromagnetic wave absorbing particle dispersion, an electromagnetic wave absorbing particle dispersion, and an electromagnetic wave absorbing laminate. [Background technology]

[0002] According to the 5th edition of the Physics and Chemistry Dictionary, "Electromagnetic waves with wavelengths in the range of approximately 1 nm to 1 mm are called light." This wavelength range includes the visible light region and the infrared region.

[0003] Near-infrared rays contained in sunlight penetrate windows and other materials, enter indoor spaces, and raise the surface temperatures of the walls and floors inside the rooms, thereby raising the indoor air temperature. In order to make the indoor thermal environment more comfortable, it has been conventional to use light-shielding materials in window materials and other materials to block the near-infrared rays that enter through the windows, thereby preventing the indoor air temperature from rising.

[0004] Patent Document 1 proposes a light-shielding film containing black fine powder including inorganic pigments such as carbon black and titanium black, and organic pigments such as aniline black, as a light-shielding material used in windows and the like.

[0005] Patent Document 2 discloses a thermal insulation sheet made of a woven fabric in which a belt-shaped film having infrared reflectivity and a belt-shaped film having infrared absorbing properties are used as warp and weft, respectively. It also discloses that the belt-shaped film having infrared reflectivity is made by depositing aluminum on a synthetic resin film and further laminating another synthetic resin film.

[0006] The present applicant has proposed in Patent Document 3 an infrared-shielding material microparticle dispersion in which infrared material microparticles are dispersed in a medium, the infrared material microparticles containing tungsten oxide microparticles and / or composite tungsten oxide microparticles, and the dispersed particle diameter of the infrared material microparticles being 1 nm or more and 800 nm or less. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2003-029314 A [Patent Document 2] Japanese Patent Application Publication No. 9-107815 [Patent Document 3] International Publication No. 2005 / 037932 Summary of the Invention [Problem to be solved by the invention]

[0008] Incidentally, in recent years, electromagnetic wave absorbing particles capable of absorbing electromagnetic waves such as infrared rays have come to be used for various purposes, and there is a demand for new electromagnetic wave absorbing particles so that the optimum material can be selected according to the application.

[0009] Therefore, an object of one aspect of the present invention is to provide novel electromagnetic wave absorbing particles. [Means for solving the problem]

[0010] In one aspect of the present invention, there is provided an electromagnetic wave absorbing particle containing a complex oxide, The composite oxide comprises an element A, which is one or more elements selected from rare earth elements; B element is Ir, When the amount of substance of the element A contained in the composite oxide is x and the amount of substance of the element B is y, the relationship of 0.001≦x / y≦4 is satisfied. death, The volume-based cumulative 50% particle size measured by a particle size distribution measuring device is 1 nm or more and 50 nm or less, and the cumulative 95% particle size is 5 nm or more and 100 nm or less, Absorbs near infrared rays The present invention provides electromagnetic wave absorbing particles. Effect of the Invention

[0011] In one aspect of the present invention, novel electromagnetic wave absorbing particles can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the electromagnetic wave absorbing particles will be described in detail in the following order: [1] electromagnetic wave absorbing particles, [2] a method for producing the electromagnetic wave absorbing particles, [3] electromagnetic wave absorbing particle dispersion, [4] electromagnetic wave absorbing particle dispersion, and [5] electromagnetic wave absorbing laminate.

[0013] [1] Electromagnetic wave absorbing particles The inventors of the present invention have conducted research into novel electromagnetic wave absorbing particles. The type of electromagnetic wave absorbed by the electromagnetic wave absorbing particles is not particularly limited, but as described above, electromagnetic wave absorbing particles that absorb infrared rays and near infrared rays are particularly desired. Therefore, the electromagnetic wave absorbing particles of this embodiment are preferably infrared absorbing particles that absorb infrared rays, and more preferably near infrared absorbing particles that absorb near infrared rays.

[0014] In examining new electromagnetic wave absorbing particles, the inventors of the present invention focused on iridium oxide. However, since there are no effective free electrons or holes in iridium oxide, it has little absorption and reflection characteristics in the infrared region and is not effective as an infrared absorbing material. However, when a composite oxide is made by adding an electropositive element to the above oxide, free electrons or holes are generated in the composite oxide, and absorption characteristics derived from the free electrons or holes are expressed in the infrared region. Therefore, it was found that it can be used as a new electromagnetic wave absorbing particle.

[0015] Furthermore, the inventors of the present invention have found that there is a specific range of the composition of the complex oxide that is particularly effective as an electromagnetic wave absorbing particle. Specifically, they have found that by setting the composition range of the complex oxide to a specific range, the complex oxide is transparent in the visible light region and absorbs in the infrared region, and have completed the present invention. (Composition of the composite oxide) The electromagnetic wave absorbing particles of this embodiment may contain a composite oxide. The composite oxide may contain an element A which is one or more elements selected from rare earth elements, and an element B which is Ir (iridium).

[0016] When the amount of substance of element A contained in the composite oxide is x and the amount of substance of element B contained in the composite oxide is y, it is preferable that the relationship 0.001≦x / y≦4 is satisfied.

[0017] The electromagnetic wave absorbing particles of this embodiment may be composed only of the composite oxide. However, even in this case, this does not exclude the case where the electromagnetic wave absorbing particles of this embodiment contain inevitable impurities that are mixed in during the manufacturing process, etc.

[0018] As described above, the electropositive element A is added to an oxide containing element B to form the above composite oxide, thereby enabling the exhibiting of electromagnetic wave absorbing properties. As described above, element A is preferably one or more elements selected from rare earth elements, more preferably one or more elements selected from Pr (praseodymium), Nd (neodymium), and Eu (europium), and further preferably Pr.

[0019] Also, the B element can be Ir as described above.

[0020] As for the value of x / y, which indicates the content ratio of the substance amount of the A element to the B element in the composite oxide, if it is 0.001 or more as described above, a sufficient amount of free electrons or holes are generated in the composite oxide, and the desired electromagnetic wave absorption effect can be obtained. The higher the content of the A element, the greater the supply of free electrons and the higher the electromagnetic wave absorption efficiency, but the effect saturates when the value of x / y is about 4. In addition, if the value of x / y is 4 or less, it is possible to avoid the generation of an impurity phase in the electromagnetic wave absorbing particle. For this reason, as described above, x / y is preferably 0.001≦x / y≦4, and from the viewpoint of enhancing the electromagnetic wave absorption effect, it is more preferable that 0.5≦x / y≦2, and even more preferable that 0.8≦x / y≦1.2, and most preferable that x / y=1.

[0021] The above composite oxide may be, for example, a compound represented by the general formula A x B y O zIn the general formula, A represents element A, B represents element B, and O represents oxygen, and the composite oxide is preferably composed of, for example, element A, element B, and oxygen, as shown in the general formula.

[0022] The range of z, which indicates the oxygen content, is not particularly limited, and may contain oxygen so as to be in a stoichiometric ratio, or may contain oxygen deficiencies, and z may be less than the stoichiometric ratio or more than the stoichiometric ratio.

[0023] The above general formula A x B y O z In the formula, x, y, and z preferably satisfy -2≦(3x+4y-2z) / y≦2, and more preferably satisfy -1≦(3x+4y-2z) / y≦1. The above formula (3x+4y-2z) / y indicates a guideline for the excess or deficiency of electrons per B element, and when the above range is satisfied, a particularly high electromagnetic wave absorption effect can be exhibited. (Crystal structure of complex oxide) According to the study by the inventors of the present invention, when a complex oxide has a cubic crystal structure, the transmittance of light in the visible light region is improved and the absorption of light in the infrared region is improved. However, in order to obtain the effect of improving the transmittance of light in the visible light region and improving the absorption of light in the infrared region, it is sufficient that the complex oxide contains a cubic crystal unit structure, and the complex oxide may partially contain amorphous or other structures. (Particle characteristics of electromagnetic wave absorbing particles) The particle characteristics such as particle diameter of the electromagnetic wave absorbing particles of this embodiment are not particularly limited, and can be selected arbitrarily depending on the required electromagnetic wave absorbing characteristics, etc.

[0024] The electromagnetic wave absorbing particles of this embodiment preferably have a volume-based cumulative 50% particle size of 1 nm or more and 50 nm or less, and a cumulative 95% particle size of 5 nm or more and 100 nm or less, as measured by a particle size distribution measuring device.

[0025] In general, it is known that materials containing free electrons or holes show a reflection / absorption response to electromagnetic waves around the solar radiation range of wavelengths from 200 nm to 2600 nm due to plasma oscillation. It is also known that when powder particles of such materials are made smaller than the wavelength of light, geometric scattering in the visible light range (wavelengths from 380 nm to 780 nm) is reduced, and transparency in the visible light range is obtained.

[0026] In this specification, the term "transparency" is used to mean "high transmittance with little scattering of light in the visible light region."

[0027] Therefore, when the electromagnetic wave absorbing particles of this embodiment are used in an application requiring transparency in the visible light region, it is preferable that the cumulative 95% particle diameter on a volume basis measured by a particle size distribution measuring device is 100 nm or less. This is because particles with a cumulative 95% particle diameter of 100 nm or less do not completely block light due to scattering, and can maintain visibility in the visible light region while efficiently maintaining transparency at the same time. In particular, when transparency in the visible light region is important, it is preferable to further consider scattering by the particles.

[0028] When further reduction in scattering by the electromagnetic wave absorbing particles is required, the cumulative 95% particle size is more preferably 70 nm or less, and even more preferably 60 nm or less. If the particle size of the electromagnetic wave absorbing particles is small, scattering of light in the visible light region with a wavelength of 400 nm or more and 780 nm or less due to geometric scattering or Mie scattering is reduced. Therefore, by setting the cumulative 95% particle size of the electromagnetic wave absorbing particles to the above range, for example, it is possible to more reliably prevent an electromagnetic wave absorbing particle dispersion using the electromagnetic wave absorbing particles from becoming like cloudy glass and not being able to obtain clear transparency. When the cumulative 95% particle size is 70 nm or less, the geometric scattering or Mie scattering is reduced, and the Rayleigh scattering region is reached. In the Rayleigh scattering region, scattered light is proportional to the sixth power of the particle size, so that scattering is reduced and transparency is improved as the particle size decreases.

[0029] Furthermore, if the cumulative 95% particle diameter is 60 nm or less, scattered light is very little, which is preferable. From the viewpoint of avoiding light scattering, the cumulative 95% particle diameter is preferably small, so the lower limit of the cumulative 95% particle diameter is not particularly limited, but the cumulative 95% particle diameter is preferably 5 nm or more. This is because industrial production is easy if the cumulative 95% particle diameter is 5 nm or more.

[0030] As explained above, by setting the cumulative 95% particle size to 100 nm or less, for example, the haze value of an electromagnetic wave absorbing particle dispersion in which the electromagnetic wave absorbing particles of this embodiment are dispersed in a solid medium can be set to 30% or less at a visible light transmittance of 85% or less. By setting the haze to 30% or less, particularly clear transparency can be obtained.

[0031] From the viewpoint of obtaining particularly excellent electromagnetic wave absorbing properties, the volume-based 50% cumulative particle size of the electromagnetic wave absorbing particles measured by a particle size distribution measuring device is preferably 1 nm or more. However, from the viewpoint of improving transparency in the visible light region, for the same reason as for the 95% cumulative particle size, the 50% cumulative particle size is preferably 50 nm or less.

[0032] The cumulative 50% particle size and cumulative 95% particle size of the electromagnetic wave absorbing particles can be measured using a particle size distribution measuring device (such as UPA-150 manufactured by Nikkiso Co., Ltd.) based on the dynamic light scattering method analyzed by frequency analysis.

[0033] Particle size distribution data is expressed as cumulative % or frequency % on a particle size scale, but conversely, it may be expressed as particle size on a cumulative % scale. For example, the particle size at the point where the distribution curve expressed as particle size on a cumulative % scale crosses the horizontal axis at 10% is called the cumulative 10% particle size, the particle size at the point where it crosses the horizontal axis at 50% is called the cumulative 50% particle size, and the particle size at the point where it crosses the horizontal axis at 95% is called the cumulative 95% particle size. It is not particularly fixed to 10%, 50%, or 95%, and any cumulative % is used as needed. The 50% particle size is also called the median size and is very commonly used. When comparing the particle size distribution of multiple samples, this median size is often used because it is necessary to represent the size of the measurement target with a single number. For this reason, the median size is often confused with the average particle size, but the definitions are different and the two sizes do not usually match. These two diameters coincide only if the particle size distribution is symmetric about the center (50% diameter). [2] Manufacturing method of electromagnetic wave absorbing particles Next, a method for producing the electromagnetic wave absorbing particles of this embodiment will be described. Since the electromagnetic wave absorbing particles already described can be produced by the method for producing the electromagnetic wave absorbing particles of this embodiment, some of the matters already described will not be described.

[0034] The electromagnetic wave absorbing particles of this embodiment can be produced by a solid-state reaction method. When synthesizing by the solid-state reaction method, a compound of element A and a compound of element B can be used as raw materials.

[0035] The method for producing the electromagnetic wave absorbing particles of this embodiment may include a mixed powder preparation step (first mixed powder preparation step) of preparing a mixed powder of an A element compound or an A element alone and a B element compound or an B element alone.

[0036] The source of element A can be an element A compound or a simple substance of element A. The compound of element A as a raw material is preferably at least one selected from oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, organic compounds, chlorides, and sulfides of element A.

[0037] Since the suitable A element has already been explained, the explanation will be omitted here.

[0038] The B element compound or element B as the B element source is preferably one or more selected from the group consisting of iridium oxide (IrO2), elemental metal (Ir), organic compounds, chlorides, and oxide hydrates obtained by dissolving the chloride in a liquid such as alcohol, adding water to hydrolyze the chloride, and evaporating the solvent.

[0039] In the mixed powder preparation step, the specific procedure for obtaining a mixed powder of an A element compound or an A element simple substance and a B element compound or an B element simple substance is not particularly limited. For example, the A element compound and the B element compound are dry-mixed in a powder state to obtain a mixed powder. Alternatively, the A element compound can be dissolved in water, wet-mixed with the B element compound, and then dried to obtain a mixed powder.

[0040] In the mixed powder preparation step, it is preferable to mix the A element and the B element so that the ratio of the substance amount in the resulting mixed powder is the ratio of the A element and the B element in the target composite oxide. That is, it is preferable to mix them so that the ratio of the substance amount (A) of the A element to the substance amount (B) of the B element in the composite oxide, A:B=x:y, is satisfied. As described above, x and y are preferably 0.001≦x / y≦4, more preferably 0.5≦x / y≦2, even more preferably 0.8≦x / y≦1.2, and most preferably x / y=1. For this reason, it is preferable to mix the A element compound and the B element compound so that they are in the above-mentioned preferred range.

[0041] The electromagnetic wave absorbing particles of this embodiment can be synthesized in multiple stages to obtain electromagnetic wave absorbing particles containing a composite oxide of a target composition. In this case, in the first mixed powder preparation step, the A element compound and the B element compound, etc. can be mixed to obtain the composition of the intermediate product.

[0042] The method for producing the electromagnetic wave absorbing particles of this embodiment may further include a firing step (first firing step) of firing the mixed powder obtained in the mixed powder preparation step.

[0043] The conditions for the firing step are not particularly limited. In the firing step, for example, the mixed powder can be fired under any atmosphere selected from an inert gas atmosphere, a reducing gas atmosphere, a vacuum atmosphere, a mixed gas atmosphere of an inert gas and a reducing gas, and an oxidizing atmosphere containing oxygen.

[0044] For example, in the case of a composite oxide, when oxygen vacancies are introduced and z / y in the general formula described above is made smaller than the stoichiometric ratio, the firing atmosphere is preferably a mixed gas atmosphere of an inert gas and a reducing gas. The reducing gas is not particularly limited, but is preferably, for example, hydrogen gas. In addition, when hydrogen gas is used as the reducing gas, the volume ratio of hydrogen gas is preferably 1% or more, and more preferably 3% or more. The upper limit of the volume ratio of hydrogen gas is not particularly limited, and since it can be reduced gas alone, it can be up to 100%.

[0045] The inert gas is not particularly limited, but one or more types selected from nitrogen gas, rare gases, and the like can be used.

[0046] The oxidizing atmosphere may be any atmosphere containing oxygen, for example, an atmosphere containing 18% to 100% oxygen by volume, for example, air atmosphere.

[0047] The firing temperature in the firing step is not particularly limited, but the firing temperature is preferably equal to or higher than the temperature at which the generated composite oxide starts to crystallize and equal to or lower than the melting point of the composite oxide. Specifically, the firing temperature is preferably set to, for example, 800° C. or higher and 1400° C. or lower.

[0048] The electromagnetic wave absorbing particles of this embodiment can be synthesized in multiple stages to obtain electromagnetic wave absorbing particles containing a complex oxide of a target composition. When synthesizing in multiple stages, a B element compound or a single B element can be further added and mixed with the intermediate product obtained in the above-mentioned firing step (first firing step) (second mixed powder preparation step). The B element compound used in this case is not particularly limited, but for example, the compound already described in the first mixed powder preparation step can be used. In the second mixed powder preparation step, it is preferable to mix the A element and the B element in the obtained mixed powder so that the ratio of the substance amount is the A element and the B element in the target complex oxide. That is, it is preferable to mix the A element and the B element in the complex oxide so that the ratio of the substance amount (A) of the A element and the substance amount (B) of the B element is satisfied, A:B=x:y. The mixing can be performed in the same manner as in the mixed powder preparation step, and therefore a description thereof will be omitted here.

[0049] The obtained mixed powder is then subjected to a firing step (second firing step) to prepare the electromagnetic wave absorbing particles of this embodiment. The conditions for the second firing step are not particularly limited, but the firing atmosphere and firing temperature can be similar to those described for the firing step (first firing step), and therefore will not be described here. The firing conditions for the first firing step and the second firing step may be the same or different.

[0050] By carrying out the steps described above, the electromagnetic wave absorbing particles of this embodiment can be obtained. After the firing step is completed, the obtained electromagnetic wave absorbing particles can be crushed, pulverized, sieved, or the like, as necessary, to obtain a desired particle size distribution. [3] Electromagnetic wave absorbing particle dispersion Next, the electromagnetic wave absorbing particle dispersion liquid of this embodiment will be described.

[0051] The electromagnetic wave absorbing particle dispersion liquid of this embodiment can contain a liquid medium and the above-mentioned electromagnetic wave absorbing particles contained in the liquid medium. The electromagnetic wave absorbing particles are preferably dispersed in the above-mentioned liquid medium.

[0052] The electromagnetic wave absorbing particle dispersion liquid of this embodiment can be obtained by using the electromagnetic wave absorbing particles already described, in other words, by using the electromagnetic wave absorbing particles obtained by the electromagnetic wave absorbing particle manufacturing method already described.

[0053] The electromagnetic wave absorbing particle dispersion may contain, in addition to the electromagnetic wave absorbing particles and the liquid medium, a dispersant and other additives as desired. The electromagnetic wave absorbing particle dispersion may be used as an intermediate product of the electromagnetic wave absorbing particle dispersion or as a coating liquid.

[0054] The liquid medium means a medium that is liquid at the temperature of use, and is preferably a medium that is liquid at room temperature (27° C.) in particular. The liquid medium is not particularly limited and can be arbitrarily selected depending on the application, etc., but the liquid medium is preferably one or more selected from water, organic solvents, liquid plasticizers, oils and fats, and compounds that are polymerized by curing.

[0055] The electromagnetic wave absorbing particle dispersion of this embodiment will be described below in the order of (1) the materials contained therein, (2) a method for producing the electromagnetic wave absorbing particle dispersion, and (3) a method for using the electromagnetic wave absorbing particle dispersion and an article using the same. (1) Materials contained (1-1) Electromagnetic wave absorbing particles The electromagnetic wave absorbing particle dispersion liquid of this embodiment can contain the electromagnetic wave absorbing particles described above. The electromagnetic wave absorbing particles have already been described, so a description thereof will be omitted here. (1-2)Liquid medium (1-2-1) Organic Solvent The organic solvent used as the liquid medium may be, for example, one or more selected from alcohols, ketones, esters, glycol derivatives, amides, aromatic hydrocarbons, and the like.

[0056] Specifically, alcohol-based materials such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, and diacetone alcohol; Ketone-based materials such as acetone, methyl ethyl ketone, dimethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; Ester-based materials such as 3-methyl-methoxy-propionate, n-butyl acetate; Glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone; Aromatic hydrocarbons such as toluene and xylene; The organic solvent may be one or more selected from ethylene chloride, chlorobenzene, and the like.

[0057] Among the above organic solvents, one or more selected from dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate, and the like can be more preferably used. (1-2-2)Oils and fats The oil or fat used as the liquid medium is not particularly limited, but vegetable oil or a compound derived from vegetable oil can be preferably used.

[0058] As the vegetable oil, one or more types selected from drying oils such as linseed oil, sunflower oil, tung oil, and perilla oil, semi-drying oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, and poppy oil, and non-drying oils such as olive oil, coconut oil, palm oil, and dehydrated castor oil can be preferably used.

[0059] As the compound derived from vegetable oil, one or more selected from fatty acid monoesters obtained by direct esterification of fatty acids of vegetable oil with monoalcohols, ethers, and the like can be preferably used.

[0060] Commercially available petroleum-based solvents can also be used as the oils and fats.

[0061] Commercially available petroleum-based solvents that can be used include Isopar (registered trademark) E, Exxor (registered trademark) (hereinafter the same), Hexane, Heptane, E, D30, D40, D60, D80, D95, D110, and D130 (all manufactured by ExxonMobil). (1-2-3) Liquid plasticizers Examples of the liquid plasticizer used as the liquid medium include one or more selected from the group consisting of plasticizers that are compounds of monohydric alcohols and organic acid esters, ester-based plasticizers such as polyhydric alcohol organic acid ester compounds, and phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers. Note that any of these plasticizers that are liquid at room temperature are preferred.

[0062] Among them, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid can be preferably used. The ester compound synthesized from the polyhydric alcohol and the fatty acid is not particularly limited, but for example, a glycol-based ester compound obtained by reacting a glycol with a monobasic organic acid can be preferably used. As the glycol, one or more selected from triethylene glycol, tetraethylene glycol, tripropylene glycol, etc. can be preferably used. In addition, as the monobasic organic acid, one or more selected from butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, pelargonic acid (n-nonylic acid), decyl acid, etc. can be preferably used.

[0063] Also, ester compounds of tetraethylene glycol, tripropylene glycol, and monobasic organic compounds can be preferably used. Among them, one or more selected from fatty acid esters of triethylene glycol, such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanate, and triethylene glycol di-2-ethylhexanoate, can be preferably used. Furthermore, fatty acid esters of triethylene glycol can also be preferably used. (1-2-4) Compounds that become polymerized by curing As the compound that is polymerized by curing and is used in the infrared absorbing particle dispersion liquid of this embodiment, a monomer or oligomer that forms a polymer by a polymerization reaction or the like caused by heat, light, or water can be suitably used.

[0064] Specific examples of compounds that can be polymerized by curing include methyl methacrylate monomers, acrylate monomers, and styrene resin monomers.

[0065] The liquid media described above may be used in combination of two or more kinds. Furthermore, if necessary, an acid or an alkali may be added to these liquid media to adjust the pH. (1-3) Dispersants In the electromagnetic wave absorbing particle dispersion liquid of this embodiment, in order to further improve the dispersion stability of the electromagnetic wave absorbing particles and to prevent the particle size from increasing due to re-aggregation, the electromagnetic wave absorbing particle dispersion liquid of this embodiment may also contain various dispersants, surfactants, coupling agents, etc.

[0066] The dispersant, coupling agent, and surfactant can be selected according to the application, but it is preferable that they are materials having one or more functional groups selected from an amine-containing group, a hydroxyl group, a carboxyl group, a phosphoric acid group, and an epoxy group. These functional groups adsorb to the surface of the electromagnetic wave absorbing particles to prevent aggregation and disperse them uniformly. Polymer dispersants having one or more functional groups selected from these functional groups in the molecule can be more preferably used as the dispersant.

[0067] Specific examples of commercially available dispersants include SOLSPERSE (registered trademark) 3000, 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, 24000GR, 26000, 27000, and 280 manufactured by Lubrizol Japan. 00, 31845, 32000, 32500, 32550, 32600, 33000, 33500, 34750, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 53095, 55000, 56000, 71000, 76500, J180, J200, M387, etc.; SOLPLUS (registered trademark) (hereinafter the same) D5 10, D520, D530, D540, DP310, K500, L300, L400, R700, etc.; Disperbyk (registered trademark) manufactured by BYK Japan (hereinafter the same) -101, 102, 103, 106, 107, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 154, 161, 162, 163, 164, 165, 16 6, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 191, 192, 2000, 2001, 2009, 2020, 2025, 2050, 2070, 2095, 2096, 2150, 2151, 2152, 2155, 2163, 2164, Anti-Terra (registered trademark) (hereinafter the same)-U, 203, 204, etc.;BYK (registered trademark) (hereinafter the same)-P104, P104S, P105, P9050, P9051, P9060, P9065, P9080, 051, 052, 053, 054, 055, 057, 063, 065, 066N, 067A, 077, 088, 141, 220S, 300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 345, 346, 347, 348, 350, 354, 355, 358N, 361N, 370, 375, 377, 378, 380N, 381, 392, 410, 425, 430, 1752, 4510, 6919, 9076, 9077, W909, W935, W940, W961, W966, W969, W972, W980, W985, W995, W996, W9010, D ynwet800, Cyclean3700, UV3500, UV3510, UV3570, etc.; EFKA Additives' EFKA (registered trademark) (hereinafter the same) 2020, 2025, 3030, 3031, 3236, 4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4310, 4320, 4330, 43 40, 4400, 4401, 4402, 4403, 4500, 5066, 5220, 6220, 6225, 6230, 6700, 6780, 6782, 7462, 8503, etc.; JONCRYL (registered trademark) manufactured by BASF Japan Ltd. (hereinafter the same); 67, 678, 586, 611, 680, 682, 690, 819, -JDX5050, etc.; TERPLUS (registered trademark) manufactured by Otsuka Chemical Co., Ltd. (hereinafter the same) MD1000, D 1180, D 1130, etc.; Ajisper (registered trademark) (hereinafter the same) PB-711, PB-821, PB-822, etc., manufactured by Ajinomoto Fine-Techno Co., Ltd.; Disparlon (registered trademark) (hereinafter the same) 1751N, 1831, 1850, 1860, 1934, DA-400N, DA-703-50, DA-325, DA-375, DA-550, DA-705, DA-725, DA-1401, DA-7301, DN-900, NS-5210, NVI-8514L, etc., manufactured by Kusumoto Chemicals Co., Ltd.;Examples of such products include Arphon (registered trademark) (hereinafter the same) UH-2170, UC-3000, UC-3910, UC-3920, UF-5022, UG-4010, UG-4035, UG-4040, and UG-4070, and Reseda (registered trademark) (hereinafter the same) GS-1015, GP-301, and GP-301S, manufactured by Toagosei Co., Ltd.; and Dianale (registered trademark) (hereinafter the same) BR-50, BR-52, BR-60, BR-73, BR-77, BR80, BR-83, BR-85, BR-87, BR-88, BR-90, BR-96, BR-102, BR-113, and BR-116, manufactured by Mitsubishi Chemical Corporation.

[0068] A liquid dispersant having a glass transition temperature lower than room temperature can be used instead of the liquid medium. That is, the electromagnetic wave absorbing particle dispersion of this embodiment can contain electromagnetic wave absorbing particles and a liquid dispersant, or can be composed of electromagnetic wave absorbing particles and a liquid dispersant. Preferable specific examples of commercially available liquid dispersants include SOLSPERSE (registered trademark) 20000 manufactured by Lubrizol Japan, and Disparlon (registered trademark) (hereinafter the same) DA234, DA325, DA375 manufactured by Kusumoto Chemicals. (1-4) Other additives The electromagnetic wave absorbing particle dispersion of this embodiment may contain additives such as various surfactants and resin components in order to control the coating property, leveling property, and drying property. When the additives are added, the electromagnetic wave absorbing particle dispersion preferably contains a small amount of the additive in the range of 5 mass % or less of the dispersion. Examples of the surfactant include anionic, cationic, nonionic, and amphoteric surfactants.

[0069] Furthermore, in order to impart flexibility to the electromagnetic wave absorbing particle dispersion obtained by using the electromagnetic wave absorbing particle dispersion, the dispersion may also contain one or more organic resins selected from silicone resins, acrylic resins, polyester resins, polyurethane resins, hydrophilic organic resins containing a polyoxyalkylene group, epoxy resins, etc. When such an organic resin is added, the electromagnetic wave absorbing particle dispersion preferably contains a small amount of the organic resin in the range of 5% by mass or less of the electromagnetic wave absorbing particle dispersion.

[0070] Furthermore, in order to impart crack prevention properties to the electromagnetic wave absorbing particle dispersion prepared using the electromagnetic wave absorbing particle dispersion, the electromagnetic wave absorbing particle dispersion may contain one or more resins selected from thermosetting resins, thermoplastic resins, ultraviolet curing resins, etc. When such a resin is added, the electromagnetic wave absorbing particle dispersion preferably contains the resin in an amount of 20 mass % or less of the dispersion. More specifically, examples of the resin include acrylic resins, epoxy resins, polyester resins, amino resins, urethane resins, furan resins, silicone resins, and modified products of these resins. (2) Method for producing electromagnetic wave absorbing particle dispersion The method for producing the electromagnetic wave absorbing particle dispersion of this embodiment is not particularly limited. The electromagnetic wave absorbing particle dispersion of this embodiment can be prepared, for example, by adding and dispersing the electromagnetic wave absorbing particles described above and, if necessary, a dispersant and other additives in the liquid medium described above. Note that, instead of the liquid medium as described above, a liquid dispersant can also be used.

[0071] The method for dispersing the electromagnetic wave absorbing particles and the like in the liquid medium is not particularly limited, and examples thereof include a grinding and dispersion treatment method using a device such as a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, etc. Among them, a media agitation mill such as a bead mill, a ball mill, a sand mill, a paint shaker, etc., which uses a medium such as beads, balls, Ottawa sand, etc., can be preferably used because it can give the electromagnetic wave absorbing particles a desired particle size in a short time.

[0072] By the pulverization-dispersion treatment using a media stirring mill, the electromagnetic wave absorbing particles are dispersed in the liquid medium, and at the same time, the electromagnetic wave absorbing particles are atomized due to collisions between the electromagnetic wave absorbing particles and between the medium and the electromagnetic wave absorbing particles, and the electromagnetic wave absorbing particles can be further atomized and dispersed. In other words, the pulverization-dispersion treatment is performed.

[0073] The dispersion concentration of the electromagnetic wave absorbing particles in the electromagnetic wave absorbing particle dispersion is preferably 0.01% by mass or more and 80% by mass or less. This is because a sufficient electromagnetic wave absorbing characteristic can be exhibited by making the content of the electromagnetic wave absorbing particles 0.01% by mass or more. Also, by making the content 80% by mass or less, the electromagnetic wave absorbing particles can be uniformly dispersed in the liquid medium. By selecting a combination of the liquid medium, dispersant, coupling agent, and surfactant, the electromagnetic wave absorbing particle dispersion of this embodiment can prevent gelation of the dispersion or sedimentation of the particles for more than six months even when placed in a thermostatic bath at a temperature of 40° C., and can suppress an increase in particle size. (3) Method of using the electromagnetic wave absorbing particle dispersion liquid, and article using the electromagnetic wave absorbing particle dispersion liquid The applications of the electromagnetic wave absorbing particle dispersion of the present embodiment are not particularly limited, and the dispersion can be used for various applications.

[0074] The electromagnetic wave absorbing particle dispersion of the present embodiment can be used as an electromagnetic wave absorbing substrate by, for example, applying it to the surface of a suitable substrate to form a dispersion film. The dispersion film is a type of electromagnetic wave absorbing particle dispersion and a type of dried solid of the electromagnetic wave absorbing particle dispersion.

[0075] The electromagnetic wave absorbing particle dispersion of this embodiment can also be dried and, if necessary, pulverized to form a powdered electromagnetic wave absorbing particle dispersion (sometimes referred to as "dispersed powder" in this specification). In other words, the dispersed powder is a type of electromagnetic wave absorbing particle dispersion, and is also a type of dried solidified electromagnetic wave absorbing particle dispersion. The dispersed powder is a powdered dispersion in which the electromagnetic wave absorbing particles are dispersed in a solid medium such as a dispersant. Since the dispersed powder contains a dispersant, the electromagnetic wave absorbing particles can be easily redispersed in the medium by mixing with an appropriate medium.

[0076] The dispersion powder can also be used as a raw material for adding the electromagnetic wave absorbing particles in a dispersed state to an electromagnetic wave absorbing product. That is, the dispersion powder in which the electromagnetic wave absorbing particles of this embodiment are dispersed in a solid medium may be dispersed again in a liquid medium and used as a dispersion liquid for an infrared absorbing product, or the dispersion powder may be kneaded into a resin and used as an electromagnetic wave absorbing particle dispersion, as described later.

[0077] The electromagnetic wave absorbing particle dispersion liquid of this embodiment can be used for various applications that utilize light-to-heat conversion.

[0078] For example, a curable ink composition can be prepared by adding an electromagnetic wave absorbing particle dispersion to an uncured thermosetting resin or by adding an uncured thermosetting resin to an electromagnetic wave absorbing particle dispersion. The curable ink composition contains the electromagnetic wave absorbing particles described above, which function as an assistant to increase the amount of heat generated by irradiation with electromagnetic waves such as infrared rays. Since the curable ink composition contains a thermosetting resin, the electromagnetic wave absorbing particles function as an assistant to increase the amount of heat generated by irradiating the curable ink composition with electromagnetic waves such as infrared rays, as described above, and the thermosetting resin can be cured. By providing the curable ink composition on, for example, a substrate, the adhesion between the cured product of the curable ink composition and the substrate can be increased when irradiated with electromagnetic waves such as infrared rays.

[0079] Therefore, in addition to its use as a conventional ink, the curable ink composition can be suitably used in applications such as photolithography, in which a three-dimensional object is formed by repeatedly applying a coating and curing it by irradiating it with electromagnetic waves such as infrared rays, and then building up the coating.

[0080] Alternatively, a thermoplastic resin-containing ink composition can be obtained by adding the electromagnetic wave absorbing particles of this embodiment to a thermoplastic resin that has been heated and melted, or by dispersing the electromagnetic wave absorbing particles of this embodiment in a suitable solvent and then adding a thermoplastic resin that is highly soluble in the solvent.

[0081] For example, by providing a thermoplastic resin-containing ink composition on a substrate and irradiating it with electromagnetic waves such as infrared rays, the solvent is removed and the resin is heat-fused, allowing the cured product of the thermoplastic resin-containing ink composition to adhere closely to the substrate. In this case, in the thermoplastic resin-containing ink composition, the electromagnetic wave absorbing particles function as an auxiliary agent that increases the amount of heat generated by irradiation with electromagnetic waves such as infrared rays, as in the case of the curable ink composition described above.

[0082] Therefore, in addition to its use as a conventional ink, the thermoplastic resin-containing ink composition can be suitably used in applications such as photolithography, in which a three-dimensional object is formed by repeatedly applying a coating, removing the solvent by irradiating with electromagnetic waves such as infrared rays, and heating and fusing the resin.

[0083] The curable ink composition and the thermoplastic resin-containing ink composition described above are also examples of the electromagnetic wave absorbing particle dispersion liquid of this embodiment. [4] Electromagnetic wave absorbing particle dispersion Next, the electromagnetic wave absorbing particle dispersion of this embodiment will be described.

[0084] The electromagnetic wave absorbing particle dispersion of this embodiment can contain a solid medium and the above-mentioned electromagnetic wave absorbing particles contained in the solid medium. The electromagnetic wave absorbing particles are preferably dispersed in the solid medium.

[0085] The solid medium means a medium that is solid at the temperature at which it is used, and is preferably a medium that is solid at room temperature (27° C.) As the solid medium, resin, glass, etc. can be used.

[0086] As the solid medium, a resin can be particularly preferably used from the viewpoint of ease of handling.

[0087] When a resin is used as the solid medium, the type of resin is not particularly limited, but the resin can be, for example, one type of resin selected from the group consisting of polyester resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene-vinyl acetate copolymer, polyvinyl acetal resin, and ultraviolet-curable resin, or a mixture of two or more types of resins selected from the above group of resins.

[0088] The content of the electromagnetic wave absorbing particles in the electromagnetic wave absorbing particle dispersion is not particularly limited, but the electromagnetic wave absorbing particle dispersion preferably contains the electromagnetic wave absorbing particles in a ratio of 0.001% by mass or more and 80% by mass or less. This is because the electromagnetic wave absorbing particles contain 0.001% by mass or more, and therefore sufficient infrared shielding function can be exhibited. Furthermore, by making the content of the electromagnetic wave absorbing particles 80% by mass or less, it is possible to suppress the granulation of the electromagnetic wave absorbing particles in the solid medium, and therefore particularly good transparency can be maintained. Furthermore, it is advantageous in terms of cost because the amount of the electromagnetic wave absorbing particles used can be suppressed. Furthermore, by making the content of the electromagnetic wave absorbing particles 80% by mass or less, the proportion of the solid medium contained in the electromagnetic wave absorbing particle dispersion can be increased, and the strength of the dispersion can be increased.

[0089] The shape etc. of the electromagnetic wave absorbing particle dispersion of this embodiment is not particularly limited and can be arbitrarily selected depending on the application etc. For example, the electromagnetic wave absorbing particle dispersion of this embodiment is preferably in the shape of a sheet, a board or a film.

[0090] The electromagnetic wave absorbing particle dispersion of this embodiment will be described in the following order: (1) a method for producing the electromagnetic wave absorbing particle dispersion, (2) an electromagnetic wave absorbing base material, and (3) a method for using the electromagnetic wave absorbing particle dispersion and an article using the same. (1) Method for producing electromagnetic wave absorbing particle dispersion The method for producing the electromagnetic wave absorbing particle dispersion is not particularly limited. The electromagnetic wave absorbing particle dispersion can be produced, for example, by kneading the above-mentioned electromagnetic wave absorbing particles into a solid medium such as a resin, and molding the mixture into a desired shape such as a film or a board.

[0091] The electromagnetic wave absorbing particle dispersion can also be produced by mixing the above-mentioned electromagnetic wave absorbing particle dispersion liquid with a solid medium such as a resin. It is also possible to produce an electromagnetic wave absorbing particle dispersion by adding a powder dispersion in which the electromagnetic wave absorbing particles are dispersed in a solid medium, i.e., the above-mentioned dispersed powder, to a liquid medium and mixing it with a solid medium such as a resin.

[0092] The shape of the electromagnetic wave absorbing particle dispersion of this embodiment is not particularly limited, but when a resin is used as the solid medium, it can be in the form of a sheet, board, or film having a thickness of 0.1 μm or more and 50 mm or less.

[0093] As described above, when the electromagnetic wave absorbing particles described above are kneaded into a solid medium such as a resin to prepare an electromagnetic wave absorbing particle dispersion, the electromagnetic wave absorbing particles and the solid medium are heated, mixed, and kneaded together at a temperature near the melting point of the solid medium, for example, the resin (for example, about 200°C or higher and 300°C or lower).

[0094] The material obtained by kneading the electromagnetic wave absorbing particles into a solid medium can be molded into a desired shape, but it is also possible to first pelletize the material and then mold the pellets into a desired shape such as a film or board using various methods.

[0095] The molding method is not particularly limited, and for example, extrusion molding, inflation molding, solution casting, casting, etc. can be used.

[0096] As described above, when the electromagnetic wave absorbing particle dispersion is in the form of a sheet, board or film, the thickness is not particularly limited and can be selected according to the application.

[0097] Furthermore, the amount of filler relative to the solid medium in the electromagnetic wave absorbing particle dispersion, i.e., the blending amount of the electromagnetic wave absorbing particles, can be selected as desired depending on the thickness of the electromagnetic wave absorbing particle dispersion and the optical properties and mechanical properties required of the electromagnetic wave absorbing particle dispersion, etc. For example, it is generally preferably 80 mass % or less relative to the resin.

[0098] If the amount of filler relative to the solid medium is 80% by mass or less, the electromagnetic wave absorbing particles in the solid medium can be prevented from granulating with each other, so that particularly good transparency can be maintained. In addition, the amount of electromagnetic wave absorbing particles used can be reduced, which is advantageous in terms of cost.

[0099] Although there is no particular lower limit to the amount of filler relative to the solid medium, it is preferably, for example, 0.001 mass % or more in order for the electromagnetic wave absorbing particle dispersion to exhibit a sufficient infrared shielding function.

[0100] The electromagnetic wave absorbing particle dispersion can also be used in a powder state by further pulverizing the electromagnetic wave absorbing particle dispersion in which the electromagnetic wave absorbing particles are dispersed in a solid medium. When this configuration is adopted, the electromagnetic wave absorbing particles are sufficiently dispersed in the solid medium in the powdered electromagnetic wave absorbing particle dispersion. Therefore, the powdered electromagnetic wave absorbing particle dispersion can be dissolved in an appropriate liquid medium as a so-called master batch, or kneaded with resin pellets or the like, to easily produce a liquid or solid electromagnetic wave absorbing particle dispersion.

[0101] The solid medium that becomes the matrix of the above-mentioned sheet, board, and film is not particularly limited and can be selected according to the application. As mentioned above, a resin can be suitably used from the viewpoint of handling. When a resin is used as the solid medium, one type of resin selected from the resin group consisting of polyester resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene-vinyl acetate copolymer, polyvinyl acetal resin, and ultraviolet curable resin, or a mixture of two or more types of resins selected from the above resin group can be suitably used. In particular, one or more types of resins selected from polyethylene terephthalate resin, acrylic resin, polyamide resin, vinyl chloride resin, polycarbonate resin, olefin resin, epoxy resin, polyimide resin, etc. can be suitably used as a resin that is low cost, highly transparent, and has a wide range of versatility. In addition, a fluororesin can also be used in consideration of weather resistance. (2) Electromagnetic wave absorbing substrate The electromagnetic wave absorbing particle dispersion of this embodiment also includes an electromagnetic wave absorbing substrate having a substrate and a dispersion film containing the above-mentioned electromagnetic wave absorbing particles disposed on the surface of the substrate.

[0102] Such an electromagnetic wave absorbing substrate can be produced, for example, by the following procedure.

[0103] The electromagnetic wave absorbing particles described above, a liquid medium such as an organic solvent such as alcohol or water, a resin binder, and optionally a dispersant are mixed to prepare an electromagnetic wave absorbing particle dispersion (dispersion preparation step).

[0104] Next, the electromagnetic wave absorbing particle dispersion is applied to a suitable substrate surface (application step).

[0105] The liquid medium is removed or cured to obtain an electromagnetic wave absorbing particle dispersion (dispersion preparation step).

[0106] By the above steps, an electromagnetic wave absorbing substrate is obtained in which the electromagnetic wave absorbing particle dispersion is directly laminated on the surface of the substrate.

[0107] The resin binder component can be selected according to the application, and examples thereof include ultraviolet curable resins, thermosetting resins, room temperature curable resins, thermoplastic resins, and the like.

[0108] Alternatively, an electromagnetic wave absorbing particle dispersion not containing a resin binder component may be applied to the surface of a substrate, and then the electromagnetic wave absorbing particle dispersion may be laminated on the surface of the substrate. Alternatively, after applying the electromagnetic wave absorbing particle dispersion not containing a resin binder component, a liquid medium containing a binder component may be applied onto the layer of the electromagnetic wave absorbing particle dispersion.

[0109] Specifically, for example, a liquid electromagnetic wave absorbing particle dispersion in which electromagnetic wave absorbing particles are dispersed in one or more liquid media selected from an organic solvent, an organic solvent in which a resin is dissolved, an organic solvent in which a resin is dispersed, and water is applied to the surface of a substrate, and the resulting coating film is solidified by an appropriate method to obtain an electromagnetic wave absorbing substrate.

[0110] Alternatively, an electromagnetic wave absorbing substrate can be obtained by applying a liquid electromagnetic wave absorbing particle dispersion containing a resin binder component to the surface of a substrate and then solidifying the resulting coating film by an appropriate method.

[0111] Furthermore, an electromagnetic wave absorbing substrate can also be obtained by applying a liquid electromagnetic wave absorbing particle dispersion, in which electromagnetic wave absorbing particles are dispersed in a powdered solid medium, to a specified medium, and then coating the surface of a substrate with the resulting coating film and solidifying it by an appropriate method.

[0112] Of course, it is also possible to prepare an electromagnetic wave absorbing substrate by applying a mixture of two or more of the above-mentioned liquid electromagnetic wave absorbing particle dispersions to the surface of a substrate and solidifying the resulting coating film by an appropriate method.

[0113] The material of the substrate used in the electromagnetic wave absorbing substrate is not particularly limited as long as it is transparent, but preferably one or more types selected from glass, a resin sheet, a resin board, a resin film, etc. Note that a transparent substrate is a material that transmits light in the visible light region, and the degree of transmission of light in the visible light region can be arbitrarily selected depending on the application of the electromagnetic wave absorbing substrate, etc.

[0114] Resins used for resin sheets, resin boards, and resin films are not particularly limited and can be selected according to the required properties such as the surface condition and durability of the sheet, board, or film. Examples of the resin include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate polymers, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene and acrylonitrile-styrene copolymers, olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers, vinyl chloride polymers, amide polymers such as aromatic polyamides, imide polymers, sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, and further transparent polymers such as various binary and ternary copolymers, graft copolymers, and blends thereof. In particular, polyester-based biaxially oriented films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate are preferred in terms of mechanical properties, optical properties, heat resistance, and economic efficiency. The polyester-based biaxially oriented film may be a copolymer polyester-based film. (3) Method of using the electromagnetic wave absorbing particle dispersion and articles using the same The electromagnetic wave absorbing particle dispersion and the electromagnetic wave absorbing substrate of the present embodiment described above can transmit light in the visible light region and block light in the infrared region. Therefore, for example, they can be used in window materials in various buildings and vehicles that allow sufficient visible light in while blocking light in the infrared region, and suppress the rise in temperature inside the room while maintaining brightness. They can also be suitably used in filters that block infrared rays emitted forward from a PDP (plasma display panel).

[0115] In addition, since the electromagnetic wave absorbing particles of this embodiment have absorption in the infrared region, when an infrared laser is irradiated onto a printed surface containing the electromagnetic wave absorbing particles, the infrared rays having a specific wavelength are absorbed. Therefore, the authenticity of an anti-counterfeiting printed matter obtained by printing the anti-counterfeiting ink containing the electromagnetic wave absorbing particles onto one or both sides of a printed substrate can be determined from the difference in the amount of reflection or transmission by irradiating the anti-counterfeiting printed matter with infrared rays having a specific wavelength and reading the reflection or transmission. The anti-counterfeiting printed matter is an example of the electromagnetic wave absorbing particle dispersion of this embodiment.

[0116] In addition, a light-to-heat conversion layer can be formed by applying an ink obtained by mixing the electromagnetic wave absorbing particle dispersion liquid and a binder component described above onto a substrate, drying the applied ink, and then curing the dried ink. The light-to-heat conversion layer generates heat at a location irradiated with an electromagnetic wave laser such as infrared light, and can heat adjacent materials. Therefore, the light-to-heat conversion layer can generate heat only at a desired location with high positional accuracy by irradiating an electromagnetic wave laser such as infrared light. Therefore, the light-to-heat conversion layer can be applied as a local heating medium in a wide range of fields such as electronics, medicine, agriculture, and machinery. For example, it can be suitably used as a donor sheet used when forming an organic electroluminescence element by a laser transfer method, thermal paper for a thermal printer, or an ink ribbon for a thermal transfer printer. The light-to-heat conversion layer is an example of the electromagnetic wave absorbing particle dispersion of this embodiment.

[0117] In addition, the above-mentioned electromagnetic wave absorbing particles are dispersed in a suitable medium, and the dispersion is contained in one or more places selected from the surface and the inside of the fiber, thereby making it possible to obtain an infrared absorbing fiber. Since the infrared absorbing fiber contains the electromagnetic wave absorbing particles, it efficiently absorbs near infrared rays from sunlight and the like, and becomes an infrared absorbing fiber with excellent heat retention. Since the infrared absorbing fiber transmits light in the visible light region, it becomes an infrared absorbing fiber with excellent design properties.

[0118] As a result, the infrared absorbing fiber can be used in various applications such as textile products that require heat retention, such as cold weather clothing, sports clothing, stockings, curtains, and other industrial textile products, etc. The infrared absorbing fiber is an example of the electromagnetic wave absorbing particle dispersion of this embodiment.

[0119] The electromagnetic wave absorbing particle dispersion of this embodiment can also be applied to materials such as roofs and exterior wall materials of agricultural and horticultural greenhouses. The electromagnetic wave absorbing particle dispersion of this embodiment transmits visible light, so light necessary for photosynthesis of plants in the agricultural and horticultural greenhouses can be secured. The electromagnetic wave absorbing particles of this embodiment can efficiently absorb light other than visible light, such as near-infrared light contained in sunlight, so they can be used as a heat insulating material for agricultural and horticultural facilities equipped with heat insulating properties. The heat insulating material for agricultural and horticultural facilities is an example of the electromagnetic wave absorbing particle dispersion of this embodiment. [5] Electromagnetic wave absorbing laminate The electromagnetic wave absorbing laminate of this embodiment can have a laminated structure including the electromagnetic wave absorbing particle dispersion and a transparent substrate. For example, the electromagnetic wave absorbing laminate can be formed by laminating two or more transparent substrates and the electromagnetic wave absorbing particle dispersion. In this case, the electromagnetic wave absorbing particle dispersion can be disposed between the transparent substrates and used as an intermediate film for absorbing electromagnetic waves.

[0120] In this case, the electromagnetic wave absorbing interlayer film preferably has any one of a sheet shape, a board shape, and a film shape.

[0121] The transparent substrate may be one or more selected from glass sheets, plastic sheets, plastic films, etc., which are transparent in the visible light region. The transparent substrate being transparent in the visible light region means that the substrate transmits light in the visible light region. The degree of transmission of light in the visible light region by the transparent substrate can be arbitrarily selected depending on the application of the electromagnetic wave absorbing laminate.

[0122] When plastic is used as the transparent substrate, the material of the plastic is not particularly limited and can be selected according to the application, and can be, for example, one or more types selected from polycarbonate resin, acrylic resin, polyester resin, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, ionomer resin, fluororesin, etc. As the polyester resin, polyethylene terephthalate resin can be preferably used.

[0123] The transparent substrate may contain particles having an electromagnetic wave absorbing function. As the particles having an electromagnetic wave absorbing function, for example, the above-mentioned electromagnetic wave absorbing particles can be used.

[0124] By using the electromagnetic wave absorbing particle dispersion described above as a constituent member of an intermediate layer sandwiched between multiple transparent substrates, a solar radiation-shielding laminated structure that is a type of electromagnetic wave absorbing laminate that transmits visible light and has electromagnetic wave absorbing properties can be obtained.

[0125] The electromagnetic wave absorbing laminate can also be obtained by bonding and integrating a plurality of transparent substrates facing each other with the electromagnetic wave absorbing particle dispersion therebetween by a known method.

[0126] When the above-mentioned electromagnetic wave absorbing particle dispersion is used as an electromagnetic wave absorbing intermediate film, the solid medium may be the same as that described for the electromagnetic wave absorbing particle dispersion. However, from the viewpoint of increasing the adhesive strength between the electromagnetic wave absorbing intermediate film and the transparent substrate, the solid medium is preferably a polyvinyl acetal resin.

[0127] The electromagnetic wave absorbing interlayer film can be produced by the above-mentioned method for producing an electromagnetic wave absorbing particle dispersion, and can be in the form of, for example, a sheet, board, or film.

[0128] In addition, when the electromagnetic wave absorbing interlayer does not have sufficient flexibility or adhesion to the transparent substrate, it is preferable to add a liquid plasticizer for the medium resin. For example, when the medium resin used in the electromagnetic wave absorbing interlayer is a polyvinyl acetal resin, the addition of a liquid plasticizer for polyacetal resin is beneficial for improving adhesion to the transparent substrate.

[0129] As the plasticizer, a substance that is used as a plasticizer for a medium resin can be used. For example, as the plasticizer used in the infrared shielding film made of polyvinyl acetal resin, there are a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, an ester-based plasticizer such as a polyhydric alcohol organic acid ester compound, and a phosphoric acid-based plasticizer such as an organic phosphoric acid-based plasticizer. It is preferable that any plasticizer is liquid at room temperature. Among them, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferable.

[0130] The electromagnetic wave absorbing interlayer film may also contain at least one selected from the group consisting of a silane coupling agent, a metal salt of a carboxylic acid, a metal hydroxide, and a metal carbonate. The metal constituting the metal salt of a carboxylic acid, the metal hydroxide, and the metal carbonate is not particularly limited, but is preferably at least one selected from sodium, potassium, magnesium, calcium, manganese, cesium, lithium, rubidium, and zinc. In the near-infrared absorbing interlayer film, the content of at least one selected from the group consisting of a metal salt of a carboxylic acid, a metal hydroxide, and a metal carbonate is preferably 1% by mass or more and 100% by mass or less relative to the electromagnetic wave absorbing particles.

[0131] Furthermore, the electromagnetic wave absorbing interlayer film may contain, in addition to the electromagnetic wave absorbing particles described above, at least one of oxide particles, composite oxide particles, and boride particles containing two or more elements selected from the group consisting of Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca. The electromagnetic wave absorbing interlayer film may contain such particles in a range of 5% by mass to 95% by mass, assuming that the total of such particles and the electromagnetic wave absorbing particles is 100% by mass.

[0132] The electromagnetic wave absorbing laminate may contain an ultraviolet absorbing agent in at least one layer of the intermediate film disposed between the transparent substrates. The ultraviolet absorbing agent may be one or more selected from a compound having a malonic acid ester structure, a compound having an oxalic acid anilide structure, a compound having a benzotriazole structure, a compound having a benzophenone structure, a compound having a triazine structure, a compound having a benzoate structure, a compound having a hindered amine structure, and the like.

[0133] Of course, the intermediate layer of the electromagnetic wave absorbing laminate may be composed of only the electromagnetic wave absorbing intermediate film.

[0134] The electromagnetic wave absorbing intermediate film described here is also an example of an electromagnetic wave absorbing particle dispersion. The electromagnetic wave absorbing laminate of this embodiment is not limited to the above-mentioned form in which an electromagnetic wave absorbing particle dispersion is disposed between transparent substrates, and may have any configuration as long as it has a laminate structure including an electromagnetic wave absorbing particle dispersion and a transparent substrate. EXAMPLES

[0135] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. (Evaluation method) First, the evaluation methods used in the following Examples and Reference Examples will be described. (Cumulative 50% particle size, cumulative 95% particle size) The particle size distribution of the electromagnetic wave absorbing particles in the examples and reference examples was measured using a particle size distribution measuring device (UPA-150 manufactured by Nikkiso Co., Ltd.) based on the principle of dynamic light scattering method analyzed by frequency analysis. The measurement conditions used were a particle refractive index of 1.81 and a non-spherical particle shape. The background was measured using methyl isobutyl ketone, and the solvent refractive index was 1.40. The cumulative 50% particle size and cumulative 95% particle size were then calculated from the obtained particle size distribution. (Crystal structure) The crystal structure of the composite oxide contained in the electromagnetic wave absorbing particles was measured using the electromagnetic wave absorbing particles obtained by removing the solvent from the electromagnetic wave absorbing particle dispersion liquid.

[0136] The X-ray diffraction pattern of the electromagnetic wave absorbing particles was measured by powder X-ray diffraction method (θ-2θ method) using a powder X-ray diffractometer (X'Pert-PRO / MPD manufactured by PANalytical, Spectris Co., Ltd.) The crystal structure contained in the particles was identified from the obtained X-ray diffraction pattern.

[0137] (Optical properties of dispersion) The optical properties of the electromagnetic wave absorbing particle dispersion in the examples and reference examples were measured as follows. First, the electromagnetic wave absorbing particle dispersion was diluted with methyl isobutyl ketone as a solvent in a glass cell for measuring a spectrophotometer. At this time, the dilution ratio was set so that the visible light transmittance after dilution was 70%. Next, a spectrophotometer (UH4150 manufactured by Hitachi High-Tech Science) was used to measure the transmitted light profile at intervals of 5 nm in the wavelength range of 200 nm to 2600 nm, and the visible light transmittance and solar transmittance were calculated in the wavelength range of 300 nm to 2100 nm based on JIS R 3106 (2019). At this time, in this measurement, the incident direction of the light of the spectrophotometer was set to a direction perpendicular to the glass cell for measuring. In addition, a blank liquid in which only the solvent methyl isobutyl ketone was put into the glass cell for measuring was used as the baseline of the light transmittance. (Optical properties of electromagnetic wave absorbing substrate) The optical properties of the electromagnetic wave absorbing substrate in the examples and reference examples were measured using a spectrophotometer (UH4150 manufactured by Hitachi High-Tech Science Corporation). The transmitted light profile was measured at intervals of 5 nm in the wavelength range of 200 nm to 2600 nm, and the visible light transmittance and solar radiation transmittance were calculated in the wavelength range of 300 nm to 2100 nm based on JIS R 3106 (2019). (Hayes) The haze value of the electromagnetic wave absorbing substrate was measured using a haze meter (HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd.) and calculated based on JIS K 7136 (2000). [Example 1] (Electromagnetic wave absorbing particles) Praseodymium oxide (PrO 11 0.351 g of Pr2Ir2O7 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%) and 0.462 g of iridium oxide (IrO2, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%) were thoroughly mixed to be homogeneous. The resulting mixed powder was placed in an alumina boat and fired at a temperature of 1000°C for 18 hours in an air atmosphere to obtain a powder of the composition formula Pr2Ir2O7 according to Example 1.

[0138] (Electromagnetic wave absorbing particle dispersion) A mixed liquid was prepared by mixing 72 mass% of Pr2Ir2O according to Example 1, 2 mass% of an acrylic polymer dispersant having an amine-containing functional group (an acrylic dispersant having an amine value of 48 mgKOH / g and a decomposition temperature of 250°C), and 94 mass% of methyl isobutyl ketone.

[0139] The obtained mixture (slurry) was placed in a glass bottle together with ZrO2 beads of φ0.3 mm, and then loaded into a paint shaker and subjected to a pulverization and dispersion treatment for 5 hours to obtain an electromagnetic wave absorbing particle dispersion liquid according to Example 1. At this time, the Pr2Ir2O7 particles become the electromagnetic wave absorbing particles.

[0140] When the particle size distribution of the electromagnetic wave absorbing particle dispersion liquid according to Example 1 was measured, the cumulative 50% particle size was 38 nm, and the cumulative 95% particle size was 58 nm.

[0141] Moreover, when the solvent (dispersion medium) was removed from the electromagnetic wave absorbing particle dispersion liquid and the powder X-ray diffraction pattern of Pr2Ir2O7 according to Example 1 was measured, a diffraction peak attributed to the cubic Pr2Ir2O7 crystal phase was confirmed.

[0142] The electromagnetic wave absorbing particle dispersion liquid according to Example 1 was diluted with a solvent, methyl isobutyl ketone, and the optical properties were measured, revealing that the visible light transmittance was 70% and the solar radiation transmittance was 44%. (Electromagnetic wave absorbing particle dispersion) The electromagnetic wave absorbing particle dispersion according to Example 1 and an ultraviolet curable resin (Aronix UV-3701, manufactured by Toagosei Co., Ltd.) were weighed out so that the mass ratio was 3:1, and mixed and stirred to prepare a dispersion for forming an electromagnetic wave absorbing base material. Then, using a bar coater with bar No. 10, the dispersion for forming an electromagnetic wave absorbing base material was applied onto a clear glass having a thickness of 3 mm, and then dried under conditions of 70°C for 1 minute and irradiated with a high-pressure mercury lamp to obtain an electromagnetic wave absorbing base material according to Example 1. The electromagnetic wave absorbing base material is an example of an electromagnetic wave absorbing particle dispersion.

[0143] The optical properties of the obtained electromagnetic wave absorbing substrate according to Example 1 were measured to find that the visible light transmittance was 69% and the solar radiation transmittance was 44%. Furthermore, the haze was measured to find that it was 0.4%.

[0144] The evaluation results are shown in Tables 1 and 2. [Examples 2 and 3] Instead of praseodymium oxide, neodymium oxide (Nd2O3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%) (Example 2) and europium oxide (Eu2O3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%) (Example 3) were used. Except for the above points, electromagnetic wave absorbing particles according to the composition formulas Nd2Ir2O7 (Example 2) and Eu2Ir2O7 (Example 3) were prepared in the same manner as in Example 1.

[0145] Moreover, except for using the electromagnetic wave absorbing particles, an electromagnetic wave absorbing particle dispersion and an electromagnetic wave absorbing base material were prepared in the same manner as in Example 1, and evaluations were carried out in the same manner as in Example 1. The evaluation results in Examples 2 and 3 are shown in Tables 1 and 2. [Reference example 1] A tin compound solution was prepared by dissolving 54.9 g of SnCl4·5H2O (Wako Pure Chemical Industries, Wako special grade, purity 98% or more) in 340 g of water at 25°C. 12.7 ml of a methanol solution (Yoneyama Chemical Industries, reagent special grade, purity 99.8% or more) in which 4.2 g of an antimony compound SbCl3 (Wako Pure Chemical Industries, JIS special grade, purity 98% or more) was dissolved, and an aqueous NH4OH solution (Wako Pure Chemical Industries, reagent special grade, concentration 30%) diluted to a concentration of 16% was dropped in parallel into the tin compound solution. Then, a hydroxide containing tin and antimony, which is a precursor of antimony-doped tin oxide (hereinafter abbreviated as ATO) electromagnetic wave absorbing particles, was generated and precipitated by the parallel dropping.

[0146] From the viewpoint of desired optical properties, the amount of antimony compound added to the tin compound solution was set to 9.5 parts by mass in terms of elemental antimony per 100 parts by mass of tin (IV) oxide. By adding this amount, ATO electromagnetic wave absorbing particles with about 68% by mass of Sn element and about 8% by mass of Sb element can be produced.

[0147] As described above, ammonia water was used as the alkaline solution used as the precipitant, and the alkaline concentration was 16%, which is 1.6 times the chemical equivalent required for the tin compound and the antimony compound to become hydroxides.

[0148] The parallel dropping time of the methanol solution and the alkaline solution was 25 minutes, and the parallel dropping was continued until the pH of the solution obtained by dropping reached 7.5. After the dropping was completed, the solution was stirred for 10 minutes to homogenize the system. The temperature of the solution at that time was the same as the temperature during the parallel dropping, 65°C.

[0149] Next, the precipitate was washed by repeatedly decanting until the conductivity of the supernatant of the washing solution in the decantation was 1 mS / cm or less, and then filtered.

[0150] Next, the washed precipitate was wetted with anhydrous ethyl alcohol solution (special grade reagent, purity 99.5% or more, manufactured by Wako Pure Chemical Industries, Ltd.). During the wet treatment, the mass ratio of [filtered precipitate:anhydrous ethyl alcohol solution] was set to 1:4 (corresponding to 80% alcohol), and the filtered precipitate and the anhydrous ethyl alcohol solution were stirred at room temperature for 1 hour to obtain a precursor. After completion of the wet treatment, the precursor was dried at 90°C for 10 hours to obtain a dried product.

[0151] The ATO electromagnetic-wave-absorbing particle precursor that had been subjected to the moistening treatment was heated to 700° C. in an air atmosphere and baked for 2 hours to produce the ATO electromagnetic-wave-absorbing particles of Reference Example 1.

[0152] Except for using the ATO electromagnetic wave absorbing particles according to Reference Example 1 instead of the Pr2Ir2O7 particles as the electromagnetic wave absorbing particles, an electromagnetic wave absorbing particle dispersion liquid and an electromagnetic wave absorbing base material according to Reference Example 1 were prepared in the same manner as in Example 1, and evaluations were carried out in the same manner as in Example 1. The evaluation results in Reference Example 1 are shown in Tables 1 and 2.

[0153] [Table 1]

[0154] [Table 2] According to the results shown in Tables 1 and 2, it was confirmed that the electromagnetic wave absorbing particle dispersion liquid and the electromagnetic wave absorbing particle dispersion using the electromagnetic wave absorbing particles obtained in Examples 1 to 3 had high visible light transmittance and were able to suppress solar radiation transmittance. In other words, it was confirmed that the transmittance in the visible light region was high and the transmittance in the infrared region was suppressed.

[0155] It was also confirmed that the visible light transmittance and solar radiation transmittance were similar to or superior to those of ATO, which has been conventionally used as an electromagnetic wave absorbing particle. Therefore, it was confirmed that the electromagnetic wave absorbing particles obtained in Examples 1 to 3 are novel electromagnetic wave absorbing particles that can be used in practical applications.

Claims

1. An electromagnetic wave absorbing particle containing a complex oxide, The composite oxide includes an element A, which is one or more elements selected from rare earth elements; and a B element which is Ir; When the amount of substance of the element A contained in the composite oxide is x and the amount of substance of the element B contained in the composite oxide is y, the relationship of 0.001≦x / y≦4 is satisfied, The volume-based cumulative 50% particle size measured by a particle size distribution measuring device is 1 nm or more and 50 nm or less, and the cumulative 95% particle size is 5 nm or more and 100 nm or less, Electromagnetic wave absorbing particles that absorb near infrared rays.

2. 2. The electromagnetic wave absorbing particle according to claim 1, wherein the element A is Pr.

3. 3. The electromagnetic wave absorbing particle according to claim 1, wherein 0.5≦x / y≦2 is satisfied.

4. A liquid medium; 4. An electromagnetic wave absorbing particle dispersion comprising: the electromagnetic wave absorbing particles according to claim 1 contained in the liquid medium.

5. 5. The electromagnetic wave absorbing particle dispersion liquid according to claim 4, wherein the liquid medium contains at least one selected from the group consisting of water, an organic solvent, a liquid plasticizer, an oil or fat, and a compound that is polymerized by curing.

6. A solid medium; An electromagnetic wave absorbing particle dispersion comprising: the electromagnetic wave absorbing particle according to claim 1 contained in the solid medium.

7. 7. The electromagnetic wave absorbing particle dispersion according to claim 6, wherein the solid medium is a resin.

8. 8. The electromagnetic wave absorbing particle dispersion according to claim 7, wherein the resin is one type of resin selected from the group consisting of polyester resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene-vinyl acetate copolymer, polyvinyl acetal resin, and ultraviolet curable resin, or a mixture of two or more types of resins selected from the group.

9. 9. The electromagnetic wave absorbing particle dispersion according to claim 6, which has a sheet, board or film shape.

10. An electromagnetic wave absorbing particle dispersion according to any one of claims 6 to 9, An electromagnetic wave absorbing laminate having a laminated structure including a transparent substrate.

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