JP2022118576A - Electromagnetic wave absorption particle, electromagnetic wave absorption particle fluid dispersion, electromagnetic wave absorption particle dispersing element, and electromagnetic wave absorption laminate - Google Patents

Abstract

To provide a novel electromagnetic wave absorption particle.SOLUTION: There is provided an electromagnetic wave absorption particle that contains complex oxide, and the complex oxide contains A elements being one or more types of elements selected from rare earth elements and B elements being one or more types of elements selected from Bi, Pb, and Sn. When an amount of substance of the A elements contained in the complex oxide is x and an amount of substance of the B elements is y, a relationship of 0.001≤x/y≤4 is satisfied.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to electromagnetic wave absorbing particles, electromagnetic wave absorbing particle dispersions, electromagnetic wave absorbing particle dispersions, and electromagnetic wave absorbing laminates.

According to the Rikagaku Jiten 5th Edition, "light is defined as an electromagnetic wave having a wavelength in the range of about 1 nm to 1 mm." This wavelength range includes the visible light region and the infrared region.

Near-infrared rays contained in sunlight pass through window materials, etc., enter a room, enter the room, raise the surface temperature of the walls and floors in the room, and also raise the room temperature. 2. Description of the Related Art Conventionally, in order to make the indoor thermal environment comfortable, a light shielding member is used as a window material or the like to block near-infrared rays entering through a window, thereby preventing the indoor temperature from rising.

As a light-shielding member used for window materials and the like, Patent Document 1 proposes a light-shielding film containing black fine powder containing inorganic pigments such as carbon black and titanium black, organic pigments such as aniline black, and the like. .

Further, Patent Document 2 discloses a heat insulating sheet formed by knitting and fabricating a band-shaped film having infrared reflectivity and a band-shaped film having infrared absorptivity as warp or weft, respectively. It also describes the use of a strip-shaped film having infrared reflectivity, which is obtained by subjecting a synthetic resin film to aluminum vapor deposition processing and further laminating a synthetic resin film.

The present applicant has disclosed in Patent Document 3 an infrared shielding material fine particle dispersion in which infrared material fine particles are dispersed in a medium, wherein the infrared material fine particles are tungsten oxide fine particles and/or composite tungsten oxide fine particles. The present inventors have proposed an infrared shielding material fine particle dispersion in which the dispersed particle diameter of the infrared material fine particles is 1 nm or more and 800 nm or less.

JP-A-2003-029314 JP-A-9-107815 WO2005/037932

By the way, in recent years, electromagnetic wave absorbing particles that can absorb electromagnetic waves such as infrared rays have come to be used in various applications, and new electromagnetic wave absorbing particles have been required so that the optimum material can be selected according to the application. there is

Accordingly, an object of one aspect of the present invention is to provide novel electromagnetic wave absorbing particles.

In one aspect of the present invention, electromagnetic wave absorbing particles containing a composite oxide,
The composite oxide includes an element A that is one or more elements selected from rare earth elements,
and a B element that is one or more elements selected from Bi, Pb, and Sn,
Provided is an electromagnetic wave absorbing particle that satisfies a relationship of 0.001≦x/y≦4, where x is the amount of the element A contained in the composite oxide and y is the amount of the element B contained in the composite oxide.

One aspect of the present invention can provide novel electromagnetic wave absorbing particles.

[1] Electromagnetic wave absorbing particles, [2] Electromagnetic wave absorbing particle production method, [3] Electromagnetic wave absorbing particle dispersion, [4] Electromagnetic wave absorbing particle dispersion, [5] Electromagnetic wave absorbing laminate, in this order. explain.

[1] Electromagnetic Wave Absorbing Particles The inventors of the present invention have studied novel electromagnetic wave absorbing particles. Although the type of electromagnetic waves absorbed by the electromagnetic wave absorbing particles is not particularly limited, as described above, electromagnetic wave absorbing particles that particularly absorb infrared rays and near-infrared rays are desired. Therefore, the electromagnetic-wave-absorbing particles of the present embodiment are preferably infrared-absorbing particles that absorb infrared rays, and more preferably near-infrared-absorbing particles that absorb near-infrared rays.

The inventors of the present invention focused on oxides of Bi (bismuth), Pb (lead), and Sn (tin) when studying new electromagnetic wave absorbing particles. However, since effective free electrons or positive holes (holes) do not exist in these oxides, they have little absorption/reflection characteristics in the infrared region and are not effective as infrared absorbing materials. However, when a composite oxide is formed by adding a positive element to the above oxide, free electrons or holes are generated in the composite oxide, so that absorption characteristics derived from free electrons or holes appear in the infrared region. . Therefore, the inventors have found that new electromagnetic wave absorbing particles can be obtained.

Furthermore, the inventors of the present invention have found that a specific part of the composition range of the composite oxide has a particularly effective range as electromagnetic wave absorbing particles. Specifically, by setting the composition range of the composite oxide to a predetermined range, the present inventors have found that the composite oxide is transparent in the visible light region and has absorption in the infrared region, and completed the present invention.
(Composition of composite oxide)
The electromagnetic wave absorbing particles of this embodiment can contain a composite oxide. The composite oxide can contain element A, which is one or more elements selected from rare earth elements, and element B, which is one or more elements selected from Bi, Pb, and Sn.

Then, where x is the substance amount of element A contained in the composite oxide and y is the substance quantity of element B contained in the composite oxide, the relationship 0.001≦x/y≦4 is satisfied. is preferred.

It should be noted that the electromagnetic wave absorbing particles of the present embodiment may be composed only of the composite oxide. However, even in this case, the case where the electromagnetic wave absorbing particles of the present embodiment contain unavoidable impurities mixed in the manufacturing process or the like is not excluded.

As described above, by adding the A element, which is a positive element, to the oxide containing the B element to form the composite oxide, electromagnetic wave absorption characteristics can be exhibited. The A element is preferably one or more elements selected from rare earth elements as described above, and one or more elements selected from La (lanthanum), Y (yttrium), and Nd (neodymium). is more preferred, and La is even more preferred.

Also, the B element is preferably one or more elements selected from Bi, Pb, and Sn as described above, and more preferably Bi.

Regarding 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, and the desired electromagnetic wave absorption effect can be obtained. As the content of element A increases, the amount of free electrons supplied increases and the electromagnetic wave absorption efficiency also increases. Also, if the value of x/y is 4 or less, it is possible to avoid the formation of an impurity phase in the electromagnetic wave absorbing particles. Therefore, as described above, x/y is preferably 0.001 ≤ x/y ≤ 4, more preferably 0.5 ≤ x/y ≤ 2 from the viewpoint of enhancing the electromagnetic wave absorption effect. It is more preferred that .8≤x/y≤1.2, and most preferably x/y=1.

The composite oxide can be represented by the general formula A _x B _y O _z , for example. In the general formula, A represents the A element, B represents the B element, and O represents oxygen. It is preferably composed of

The range of z indicating the oxygen content is not particularly limited, and oxygen may be contained in a stoichiometric ratio, for example. In addition, it is possible to include oxygen deficiency, etc., and z may be less than the stoichiometric ratio or may be more than the stoichiometric ratio.

x, y, and z in the general formula A _x B _y O _z preferably satisfy −2≦(3x+4y−2z)/y≦2, and −1≦(3x+4y−2z)/y≦1. is more preferable. This is because (3x+4y-2z)/y indicates an excess/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 composite oxide)
According to the studies of the inventors of the present invention, when the composite oxide has a cubic crystal structure, the transmission of light in the visible region is particularly improved, and the absorption of light in the infrared region is improved. However, in order to obtain the effect of improving light transmission in the visible light region and improving light absorption in the infrared region, it is sufficient that the composite oxide contains a cubic crystal unit structure. The object may be partially amorphous or contain other structures.
(Regarding particle characteristics of electromagnetic wave absorbing particles)

The particle characteristics such as the particle diameter of the electromagnetic wave absorbing particles of the present embodiment are not particularly limited, and can be arbitrarily selected according to the required electromagnetic wave absorbing characteristics and the like.

The electromagnetic wave-absorbing particles of the present embodiment preferably have a volume-based cumulative 50% particle diameter of 1 nm or more and 50 nm or less, and a volume-based cumulative 95% particle diameter of 5 nm or more and 100 nm or less, as measured by a particle size distribution analyzer.

In general, materials containing free electrons or holes are known to exhibit a reflection absorption response to electromagnetic waves in the vicinity of the solar ray region with wavelengths of 200 nm to 2600 nm due to plasma oscillation. It is known that when the powder particles of such a material are particles smaller than the wavelength of light, geometric scattering in the visible light region (wavelength of 380 nm or more and 780 nm or less) is reduced and transparency in the visible light region is obtained. ing.

In this specification, the term "transparency" is used in the sense of "having little scattering and high transmittance of light in the visible light region."

Therefore, when the electromagnetic wave-absorbing particles of the present embodiment are used in applications requiring transparency in the visible light region, the volume-based cumulative 95% particle diameter measured by a particle size distribution analyzer should be 100 nm or less. preferable. 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 and at the same time efficiently maintain transparency. be. In particular, when the transparency in the visible light region is emphasized, it is preferable to consider the scattering due to the particles.

When further reduction of scattering due to electromagnetic wave absorbing particles is required, the cumulative 95% particle size is more preferably 70 nm or less, even more preferably 60 nm or less. If the particle size of the electromagnetic wave absorbing particles is small, the 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 diameter of the electromagnetic wave-absorbing particles within the above range, for example, the electromagnetic wave-absorbing particle dispersion using the electromagnetic wave-absorbing particles becomes like frosted glass, and clear transparency cannot be obtained. can be more reliably avoided. When the cumulative 95% particle diameter is 70 nm or less, the above geometric scattering or Mie scattering is reduced, resulting in a Rayleigh scattering region. This is because, in the Rayleigh scattering region, scattered light is proportional to the sixth power of the particle diameter, so scattering decreases and transparency improves as the particle diameter decreases.

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

By setting the cumulative 95% particle diameter to 100 nm or less as described above, for example, the haze value of the electromagnetic wave absorbing particle dispersion obtained by dispersing the electromagnetic wave absorbing particles of the present embodiment in a solid medium can be reduced to a visible light transmittance of 85. % or less and 30% or less. By setting the haze to 30% or less, particularly clear transparency can be obtained.

From the viewpoint of obtaining particularly excellent electromagnetic wave absorption characteristics, the cumulative 50% particle size of the electromagnetic wave absorbing particles measured by a particle size distribution analyzer is preferably 1 nm or more. However, from the viewpoint of enhancing transparency in the visible light region, the cumulative 50% particle size is preferably 50 nm or less for the same reason as the cumulative 95% particle size.

The cumulative 50% particle size and cumulative 95% particle size of the electromagnetic wave absorbing particles are measured using a particle size distribution measuring device (for example, UPA-150 manufactured by Nikkiso Co., Ltd.) based on the dynamic light scattering method that analyzes by frequency analysis. can be measured.

Particle size distribution data is expressed as cumulative % or frequency % with respect to the particle diameter scale, but conversely, it may be expressed as particle diameter with respect to the cumulative % scale. The distribution curve expressed as the particle size on the cumulative % scale, for example, the particle size at the point where it intersects the horizontal axis of 10% is the cumulative 10% particle size, and the particle size at the point where it intersects the horizontal axis of 50% is the cumulative 50 % particle size, and the particle size at the point where it intersects the horizontal axis of 95% is called cumulative 95% particle size. 10%, 50%, and 95% are not particularly fixed, and arbitrary cumulative percentages are used as necessary. The 50% particle size is also called median size and is very commonly used. When comparing the sizes of the particle size distributions of a plurality of samples, the size of the object to be measured must be represented by a single numerical value, so the median diameter is often used. For this reason, the median diameter is often confused with the average particle diameter, but the definitions are different and the two diameters usually do not match. These two diameters match only if the particle size distribution is symmetrical about the center (50% diameter).
[2] Method for producing electromagnetic wave absorbing particles Next, a method for producing electromagnetic wave absorbing particles according to the present embodiment will be described. Since the electromagnetic wave absorbing particles described above can be manufactured by the method for manufacturing electromagnetic wave absorbing particles according to the present embodiment, the description of the already described items will be partially omitted.

The electromagnetic wave absorbing particles of this embodiment can be produced by a solid phase reaction method. When synthesizing by a solid phase reaction method, an A element compound and a B element compound can be used as raw materials.

The method for producing electromagnetic wave absorbing particles of the present embodiment includes a mixed powder preparation step (first mixed powder preparation step) of preparing a mixed powder of an A element compound or an element A alone and a B element compound or an element B alone. can have

As the A element source, an A element compound or an A element alone can be used. The A element compound used as a raw material is preferably one or more selected from oxides, hydroxides, carbonates, nitrates, sulfates, organic compounds, chlorides, and sulfides of the A element.

Since the preferred element A has already been explained, the explanation is omitted here.

Examples of B element compounds or B element simple substances that serve as B element sources include oxides, elemental metals, hydroxides, carbonates, oxycarbonates, nitrates, sulfates, organic compounds, ammonium salts, organic compounds, oxychlorides, Sulfides, chlorides, and hydrates of oxides obtained by dissolving chlorides in a liquid such as alcohol, adding water to hydrolyze the solution, and evaporating the solvent. is preferred. Since the preferred B element has already been explained, the explanation is omitted here.

In the mixed powder preparation step, the specific procedure for obtaining the mixed powder of the A element compound or A element alone and the B element compound or B element alone is not particularly limited. For example, there is a method of dry-mixing the A element compound and the like and the B element compound and the like in a powder state to obtain a mixed powder. Alternatively, the mixed powder can be obtained by dissolving the A element compound or the like in water, wet mixing it with the B element compound or the like, and then drying it.

In the mixed powder preparation step, mixing can be performed so that the ratio of the substance amounts of the A element and the B element in the mixed powder to be obtained becomes the ratio of the A element and the B element in the desired composite oxide. preferable. That is, it is preferable to mix so that A:B=x:y, which is the ratio of the substance amount (A) of the A element and the substance amount (B) of the B element in the composite oxide, is satisfied. As described above, x and y are preferably 0.001≦x/y≦4, more preferably 0.5≦x/y≦2, and 0.8≦ More preferably, x/y≦1.2, and most preferably, x/y=1. Therefore, it is preferable to mix the A element compound and the B element compound so that the above preferable range is obtained.

It should be noted that the electromagnetic wave absorbing particles of the present embodiment can also be synthesized in multiple stages in order to obtain electromagnetic wave absorbing particles containing a composite oxide having a desired composition. In this case, in the first mixed powder preparation step, the A element compound, the B element compound, and the like can be mixed so as to obtain the composition of the intermediate product.

Further, the method for producing electromagnetic wave absorbing particles of the present embodiment can have a firing step (first firing step) of firing the mixed powder obtained in the mixed powder preparing step.

Conditions for the firing step are not particularly limited. In the firing step, for example, the mixed powder is 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. It can be fired under any atmosphere.

For example, when oxygen deficiency is introduced into a composite oxide to make z/y in the general formula described above smaller than the stoichiometric ratio, the firing atmosphere is a mixed gas atmosphere of an inert gas and a reducing gas. is preferred. Although the reducing gas is not particularly limited, it is preferably hydrogen gas, for example. When hydrogen gas is used as the reducing gas, the volume ratio of hydrogen gas is preferably 1% or more, more preferably 3% or more. The upper limit of the volume ratio of the hydrogen gas is not particularly limited, and since the reducing gas can be used alone, the maximum can be 100%.

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

The oxidizing atmosphere may be an atmosphere containing oxygen, and for example, an atmosphere containing 18% or more and 100% or less of oxygen by volume can be used. For example, it can be an air atmosphere.

The firing temperature conditions in the firing step are not particularly limited, but the firing temperature is preferably higher than the temperature at which the produced composite oxide starts to crystallize and lower than the melting point of the composite oxide. Specifically, for example, it is preferable to set the firing temperature to 400° C. or higher and 1200° C. or lower.

In the firing process, when firing the mixed powder, a flux may be used as necessary. In this case, in order to remove the flux component after the firing process, washing with water, drying, etc. may be performed. Alkaline hydroxides such as NaOH and KOH can be used as suitable fluxing agents.

Since the electromagnetic wave absorbing particles of the present embodiment are electromagnetic wave absorbing particles containing a composite oxide having a target composition, they can be synthesized in multiple stages. When synthesis is performed in multiple steps, the intermediate product obtained in the firing step (first firing step) can be further added and mixed with a B element compound or a single element of B (second mixed powder preparation process). The B element compound or the like used at this time is not particularly limited, but for example, the compound described above in the first mixed powder preparation step can be used. In the second mixed powder preparation step, mixing is performed so that the ratio of the amounts of the A element and the B element in the mixed powder to be obtained becomes the ratio of the A element and the B element in the target composite oxide. is preferred. That is, it is preferable to mix so that A:B=x:y, which is the ratio of the substance amount (A) of the A element and the substance amount (B) of the B element in the composite oxide, is satisfied. Mixing can be carried out in the same manner as in the mixed powder preparation step, and thus the description is omitted here.

Then, the obtained mixed powder is subjected to a firing step (second firing step) to prepare the electromagnetic wave absorbing particles of the present embodiment. The conditions of the second firing step are not particularly limited, but the firing atmosphere and the firing temperature can be performed in the same manner as described in the firing step (first firing step), so the description is omitted here. . The firing conditions may be the same or different between the first firing step and the second firing step.

By performing the steps described above, the electromagnetic wave absorbing particles of the present embodiment can be obtained. After the firing step, the obtained electromagnetic wave absorbing particles can be crushed, pulverized, sieved, etc. as necessary to obtain a desired particle size distribution.
[3] Electromagnetic Wave Absorbing Particle Dispersion Next, the electromagnetic wave absorbing particle dispersion of the present embodiment will be described.

The electromagnetic wave absorbing particle dispersion of the present embodiment can contain a liquid medium and the electromagnetic wave absorbing particles contained in the liquid medium. The electromagnetic wave absorbing particles are preferably dispersed in the liquid medium.

The electromagnetic wave absorbing particle dispersion liquid of the present embodiment can be obtained using the electromagnetic wave absorbing particles described above, in other words, the electromagnetic wave absorbing particles obtained by the method for producing the electromagnetic wave absorbing particles described above. .

In addition to the electromagnetic wave absorbing particles and the liquid medium, the electromagnetic wave absorbing particle dispersion may optionally contain a dispersant and other additives. The electromagnetic wave absorbing particle dispersion can be used as an intermediate product of the electromagnetic wave absorbing particle dispersion or as a coating liquid.

A 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.). The liquid medium is not particularly limited and can be arbitrarily selected according to the application, etc., but the liquid medium is one or more selected from water, organic solvents, liquid plasticizers, oils and fats, and compounds that are polymerized by curing. can be preferably used.

Hereinafter, the electromagnetic wave absorbing particle dispersion liquid of the present embodiment will be described as follows: (1) Containing material; (2) Method for producing the electromagnetic wave absorbing particle dispersion liquid; (3) Method for using the electromagnetic wave absorbing particle dispersion liquid; will be explained in order.
(1) Materials Contained (1-1) Electromagnetic Wave Absorbing Particles The electromagnetic wave absorbing particle dispersion liquid of the present embodiment can contain the electromagnetic wave absorbing particles described above. Since the electromagnetic wave absorbing particles have already been explained, the explanation is omitted here.
(1-2) Liquid medium (1-2-1) Organic solvent The organic solvent used as the liquid medium is selected from, for example, alcohols, ketones, esters, glycol derivatives, amides, aromatic hydrocarbons, and the like. can be used.

Specifically, alcohol-based materials such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, diacetone alcohol;
Ketone-based materials such as acetone, methyl ethyl ketone, dimethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, 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, propylene glycol monoethyl ether acetate;
Amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone;
aromatic hydrocarbons such as toluene and xylene;
One or more selected from ethylene chloride, chlorobenzene, and the like can be used as the organic solvent.

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 used more preferably.
(1-2-2) Oils and Fats Fats and oils used as the liquid medium are not particularly limited, but vegetable oils or compounds derived from vegetable oils can be preferably used.

Vegetable oils include dry oils such as linseed oil, sunflower oil, tung oil, and perilla oil; semi-dry oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, and poppy oil; olive oil, coconut oil, palm oil, and dehydrated castor oil. One or more selected from non-drying oils such as oil can be preferably used.

As the vegetable oil-derived compound, one or more selected from fatty acid monoesters, ethers, and the like obtained by directly esterifying fatty acids of vegetable oils and monoalcohols can be preferably used.

In addition, commercially available petroleum-based solvents can also be used as fats and oils.

Commercially available petroleum solvents include Isopar (registered trademark) E, Exol (registered trademark) (hereinafter the same) Hexane, Heptane, E, D30, D40, D60, D80, D95, D110, D130 (manufactured by ExxonMobil), etc. can be used.
(1-2-3) Liquid plasticizers Liquid plasticizers used as liquid media include, for example, plasticizers that are compounds of monohydric alcohols and organic acid esters, and esters such as polyhydric alcohol organic acid ester compounds. One or more types selected from certain plasticizers, phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers, and the like. In addition, all of them are preferably liquid at room temperature.

Among them, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid can be preferably used. Although the ester compound synthesized from the polyhydric alcohol and fatty acid is not particularly limited, for example, a glycol-based ester compound obtained by reacting a glycol with a monobasic organic acid can be suitably used. As the glycol, one or more selected from triethylene glycol, tetraethylene glycol, tripropylene glycol and the like can be preferably used. In addition, the monobasic organic acids include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid, and the like. One or more selected types can be preferably used.

Ester compounds of tetraethylene glycol, tripropylene glycol, and monobasic organic compounds, etc. can also be suitably used. Among them, triethylene glycol fatty acid esters such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanate, triethylene glycol di-2-ethylhexanonate, etc. One or more selected types can be preferably used. Furthermore, fatty acid esters of triethylene glycol can also be preferably used.
(1-2-4) Compound polymerized by curing The compound polymerized by curing used in the infrared-absorbing particle dispersion of the present embodiment includes a polymerization reaction caused by heat, light, water, or the like. Monomers and oligomers that form polymers can be preferably used.

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

Two or more of the liquid media described above can be used in combination. Furthermore, if necessary, acid or alkali may be added to these liquid media to adjust the pH.
(1-3) Dispersant In the electromagnetic wave-absorbing particle dispersion liquid of the present embodiment, in order to further improve the dispersion stability of the electromagnetic wave-absorbing particles and avoid coarsening of the particle size due to reaggregation, the electromagnetic wave-absorbing agent of the present embodiment is used. The particle dispersion may also contain various dispersing agents, surfactants, coupling agents, and the like.

Dispersants, coupling agents, and surfactants can be selected according to the application, but have one or more functional groups selected from amine-containing groups, hydroxyl groups, carboxyl groups, phosphoric acid groups, and epoxy groups. Materials are preferred. These functional groups have the effect of being adsorbed on the surface of the electromagnetic wave absorbing particles to prevent aggregation and dispersing them uniformly. A polymeric dispersant having one or more selected from these functional groups in its molecule can be more preferably used as the dispersant.

Preferred specific examples of commercially available dispersants include SOLSPERSE (registered trademark) (hereinafter the same) manufactured by Nippon Lubrizol Co., Ltd. 3000, 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000 、２１０００、２４０００ＳＣ、２４０００ＧＲ、２６０００、２７０００、２８０００、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) D510, D520, D530, D540, DP310, K500, L300, L400, R700, etc.; Disperbyk (registered trademark) manufactured by BYK-Chemie Japan (same below) -101, 102, 103, 106, 107, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 154, 161, 162, 163, 164, 165, 166, 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® (same below)—U, 203, 204, etc.; BYK® (same below)—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, Dynwet800, Siclean3700, UV3500, UV3510, UV3570, etc.; 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4310, 4320, 4330, 4340, 4400, 4401, 4402, 4403, 4500, 5066, 5220, 6220, 6225, 6230, 6700, 6780, 6782, 7462, 8503, etc.; BASF Japan JONCRYL (registered trademark) (hereinafter the same) 67, 678, 586, 611, 680, 682, 690, 819, -JDX5050, etc.; Otsuka Chemical Co., Ltd. TERPLUS (registered trademark) (hereinafter the same) MD1000 , D 1180, D 1130, etc.; Ajinomoto Fine Techno Co., Ltd. Ajisper (registered trademark) (hereinafter the same) PB-711, PB-821, PB-822, etc.; Kusumoto Chemicals Co., Ltd. Disparon (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.; Alfon (registered trademark) manufactured by Toagosei Co., Ltd. (hereinafter the same) UH-2170, UC-3000, UC-3910, UC-3920, UF-5022, UG-4010, UG-4035, UG-4040, UG-4070, Reseda (registered trademark) (hereinafter the same) GS-1015, GP-301, GP-301S, etc.; Mitsubishi Chemical Corporation Dianal (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, BR- 116 and the like.

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 liquid of the present embodiment can contain the electromagnetic wave absorbing particles and the liquid dispersing agent, or can be composed of the electromagnetic wave absorbing particles and the liquid dispersing agent. Preferred specific examples of commercially available liquid dispersants include SOLSPERSE (registered trademark) 20000 manufactured by Nippon Lubrizol Co., Ltd., and Disparlon (registered trademark) manufactured by Kusumoto Kasei (hereinafter the same) DA234, DA325, DA375, and the like.
(1-4) Other Additives The electromagnetic wave-absorbing particle dispersion liquid of the present embodiment may contain additives such as various surfactants and resin components for control of coating properties, leveling properties, and drying properties. . When the additive is added, the electromagnetic wave absorbing particle dispersion liquid preferably contains a small amount of the additive in the range of 5% by mass or less of the dispersion liquid. Surfactants include anionic, cationic, nonionic, or amphoteric.

In order to impart flexibility to the electromagnetic wave absorbing particle dispersion obtained using the electromagnetic wave absorbing particle dispersion, the dispersion contains silicone resin, acrylic resin, polyester resin, polyurethane resin, and polyoxyalkylene group. It can also contain one or more organic resins selected from hydrophilic organic resins, epoxy resins, and the like. When the 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.

In addition, in order to impart anti-crack properties to the electromagnetic wave absorbing particle dispersion prepared using the electromagnetic wave absorbing particle dispersion, the electromagnetic wave absorbing particle dispersion may be a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, or the like. It can also contain one or more resins selected from When the resin is added, the electromagnetic wave absorbing particle dispersion liquid preferably contains the resin in an amount of 20% by mass or less of the dispersion liquid. More specifically, examples of the resin include acrylic resin, epoxy resin, polyester resin, amino resin, urethane resin, furan resin, silicone resin, 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 the present embodiment is not particularly limited. The electromagnetic wave absorbing particle dispersion liquid of the present 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 into the liquid medium described above. A liquid dispersant can be used instead of the liquid medium as described above.

The method of dispersing the electromagnetic wave absorbing particles in the liquid medium is not particularly limited, but examples thereof include pulverization/dispersion treatment methods using devices such as bead mills, ball mills, sand mills, paint shakers, and ultrasonic homogenizers. Among them, medium agitating mills such as bead mills, ball mills, sand mills, and paint shakers using medium media such as beads, balls, and Ottawa sand are suitable for electromagnetic wave-absorbing particles because they can be made to have a desired particle size in a short time. can be used for

By pulverizing and dispersing processing using a medium stirring mill, the electromagnetic wave absorbing particles are dispersed in the liquid medium, and at the same time, the electromagnetic wave absorbing particles collide with each other and the medium medium collides with the electromagnetic wave absorbing particles. Absorbing particles can be made finer and dispersed. That is, it is pulverized and dispersed.

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 sufficient electromagnetic wave absorbing properties can be exhibited by setting the content of the electromagnetic wave absorbing particles to 0.01% by mass or more. Also, by setting the content to 80% by mass or less, the electromagnetic wave absorbing particles can be uniformly dispersed in the liquid medium. By selecting a liquid medium, a combination of a dispersing agent, a coupling agent, and a surfactant, the electromagnetic wave absorbing particle dispersion of the present embodiment can be maintained for 6 months or more even when placed in a constant temperature bath at a temperature of 40° C., for example. Neither gelation nor sedimentation of particles occurs, and an increase in particle size can be suppressed.
(3) Method of Using Electromagnetic-Absorbing Particle Dispersion and Articles Using Electromagnetic-Absorbing Particle Dispersion The use of the electromagnetic-wave-absorbing particle dispersion of the present embodiment is not particularly limited, and it can be used for various purposes.

The electromagnetic wave absorbing particle dispersion liquid of the present embodiment can be used as an electromagnetic wave absorbing substrate by forming a dispersed film, for example, by coating it on the surface of an appropriate substrate. The dispersion film is also a kind of electromagnetic wave absorbing particle dispersion and a kind of dried and solidified electromagnetic wave absorbing particle dispersion liquid.

In addition, the electromagnetic wave absorbing particle dispersion liquid of the present embodiment is dried and, if necessary, pulverized to obtain a powdery electromagnetic wave absorbing particle dispersion (in this specification, sometimes referred to as "dispersed powder"). You can also In other words, the dispersed powder is also a kind of electromagnetic wave absorbing particle dispersion and a kind of dried and solidified electromagnetic wave absorbing particle dispersion liquid. The dispersed powder is a powdery dispersion in which electromagnetic wave absorbing particles are dispersed in a solid medium such as a dispersant. Since the dispersion powder contains a dispersing agent, it is possible to easily redisperse the electromagnetic wave absorbing particles in the medium by mixing it with an appropriate medium.

The dispersed powder can also be used as a raw material for adding electromagnetic wave absorbing particles in a dispersed state to electromagnetic wave absorbing products. That is, the dispersion powder obtained by dispersing the electromagnetic wave absorbing particles of the present embodiment in a solid medium may be dispersed again in a liquid medium and used as a dispersion liquid for infrared absorbing products. Dispersed powder may be kneaded into resin and used as an electromagnetic wave absorbing particle dispersion.

The electromagnetic wave absorbing particle dispersion liquid of the present embodiment can be used for various applications utilizing photothermal conversion.

For example, a curable ink composition can be obtained 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, and the electromagnetic wave absorbing particles function as an auxiliary agent for increasing the amount of heat generated by irradiation of electromagnetic waves such as infrared rays. Since the curable ink composition contains a thermosetting resin, by irradiating the curable ink composition with electromagnetic waves such as infrared rays, the electromagnetic wave absorbing particles function as an auxiliary agent for increasing the amount of heat generated as described above. Thermosetting resins can be cured. By providing the curable ink composition on, for example, a substrate, it is possible to increase the adhesion between the cured product of the curable ink composition and the substrate when irradiated with electromagnetic waves such as infrared rays.

Therefore, in addition to the use as a conventional ink, the curable ink composition can be used, for example, in a stereolithography method in which a three-dimensional object is formed by repeating application and curing by irradiation with electromagnetic waves such as infrared rays. It can be suitably used for

Alternatively, the electromagnetic wave absorbing particles of the present embodiment may be added to a heat-melted thermoplastic resin, or after dispersing the electromagnetic wave absorbing particles of the present embodiment in an appropriate solvent, a heat having high solubility in the solvent may be added. By adding a thermoplastic resin, a thermoplastic resin-containing ink composition is obtained.

A thermoplastic resin-containing ink composition is provided on a substrate, for example, and is irradiated with electromagnetic waves such as infrared rays to remove the solvent and heat-fuse the resin to form a cured product of the thermoplastic resin-containing ink composition. It can be adhered to the substrate. At this time, in such a thermoplastic resin-containing ink composition as well, the electromagnetic wave absorbing particles function as an auxiliary agent for increasing the amount of heat generated by irradiation of electromagnetic waves such as infrared rays, as in the case of the curable ink composition.

Therefore, the thermoplastic resin-containing ink composition can be used in addition to the conventional ink composition, for example, by repeatedly applying, removing the solvent by irradiation with electromagnetic waves such as infrared rays, and heating and fusing the resin. It can be suitably used for stereolithography for modeling a dimensional object.

The curable ink composition and the thermoplastic resin-containing ink composition described so far are also examples of the electromagnetic wave absorbing particle dispersion liquid of the present embodiment.
[4] Electromagnetic Wave Absorbing Particle Dispersion Next, the electromagnetic wave absorbing particle dispersion of the present embodiment will be described.

The electromagnetic wave-absorbing particle dispersion of the present embodiment can contain a solid medium and the electromagnetic wave-absorbing particles contained in the solid medium. The electromagnetic wave absorbing particles are preferably dispersed in the solid medium.

A solid medium means a medium that is solid at the temperature used, and is preferably a medium that is solid at room temperature (27° C.). A resin, glass, or the like can be used as the solid medium.

As the solid medium, a resin can be particularly suitably used from the viewpoint of ease of handling and the like.

When a resin is used as the solid medium, the type of resin is not particularly limited. One type of resin selected from the resin group consisting of polyimide resin, fluororesin, ethylene/vinyl acetate copolymer, polyvinyl acetal resin, and ultraviolet curable resin, or two or more types of resin selected from the above resin group. It can be a mixture.

Although the content ratio of the electromagnetic wave absorbing particles in the electromagnetic wave absorbing particle dispersion is not particularly limited, the electromagnetic wave absorbing particle dispersion preferably contains the electromagnetic wave absorbing particles at a rate of 0.001% by mass or more and 80% by mass or less. This is because a sufficient infrared shielding function can be exhibited by containing 0.001% by mass or more of the electromagnetic wave absorbing particles. Further, by setting the content ratio of the electromagnetic wave absorbing particles to 80% by mass or less, it is possible to suppress granulation of the electromagnetic wave absorbing particles in the solid medium, so that particularly good transparency can be maintained. In addition, since the amount of electromagnetic wave absorbing particles used can be suppressed, it is also advantageous in terms of cost. Furthermore, by setting the content ratio of the electromagnetic wave absorbing particles to 80% by mass or less, the ratio of the solid medium contained in the electromagnetic wave absorbing particle dispersion can be increased, and the strength of the dispersion can be increased.

The shape and the like of the electromagnetic wave absorbing particle dispersion of the present embodiment are not particularly limited, and can be arbitrarily selected according to the application. For example, the electromagnetic wave absorbing particle dispersion of the present embodiment preferably has a sheet shape, a board shape, or a film shape.

Regarding the electromagnetic wave absorbing particle dispersion of the present embodiment, (1) a method for producing the electromagnetic wave absorbing particle dispersion, (2) an electromagnetic wave absorbing substrate, and (3) a method for using the electromagnetic wave absorbing particle dispersion and an article using the same. I will explain in order.
(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 electromagnetic wave absorbing particles described above into a solid medium such as a resin and molding it into a desired shape such as a film or board.

The electromagnetic wave absorbing particle dispersion can also be produced by mixing the electromagnetic wave absorbing particle dispersion described above and a solid medium such as a resin. In addition, a powdery dispersion in which electromagnetic wave absorbing particles are dispersed in a solid medium, that is, the dispersion powder described above is added to a liquid medium and mixed with a solid medium such as a resin to produce an electromagnetic wave absorbing particle dispersion. It is also possible to

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

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

The material obtained by kneading the electromagnetic wave absorbing particles into a solid medium can be molded into a desired shape. However, once pelletized, the pellets are molded into a desired shape such as a film or board by various methods. is also possible.

The molding method is not particularly limited, and for example, an extrusion molding method, an inflation molding method, a solution casting method, a casting method, or the like can be used.

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

In addition, the amount of filler in the electromagnetic wave absorbing particle dispersion relative to the solid medium, that is, the blending amount of the electromagnetic wave absorbing particles, depends on the thickness of the electromagnetic wave absorbing particle dispersion and the optical properties, mechanical properties, etc. required for the electromagnetic wave absorbing particle dispersion. It can be selected arbitrarily. For example, 80% by mass or less is generally preferable with respect to the resin.

If the amount of filler in the solid medium is 80% by mass or less, granulation of the electromagnetic wave absorbing particles in the solid medium can be suppressed, so that particularly good transparency can be maintained. In addition, since the amount of electromagnetic wave absorbing particles used can be suppressed, it is also advantageous in terms of cost.

Although the lower limit of the amount of filler in the solid medium is not particularly limited, it is preferably 0.001% by mass or more, for example, from the viewpoint that the electromagnetic wave-absorbing particle dispersion exhibits a sufficient infrared shielding function.

The electromagnetic wave absorbing particle dispersion can also be used in a powdered state by further pulverizing the electromagnetic wave absorbing particle dispersion in which the electromagnetic wave absorbing particles are dispersed in a solid medium. When adopting this configuration, the electromagnetic wave absorbing particles are sufficiently dispersed in the solid medium in the powdery electromagnetic wave absorbing particle dispersion. Therefore, by dissolving the powdery electromagnetic wave absorbing particle dispersion as a so-called masterbatch in an appropriate liquid medium or kneading with resin pellets or the like, the liquid or solid electromagnetic wave absorbing particle dispersion can be easily obtained. can be manufactured.

The above-described sheet, board, or solid medium serving as the matrix of the film is not particularly limited and can be selected according to the application. As described above, a resin can be preferably used from the viewpoint of handleability. When a resin is used as the solid medium, polyester resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, ethylene/vinyl acetate copolymer, One type of resin selected from the group of resins consisting of polyvinyl acetal resins and UV-curable resins, or a mixture of two or more types of resins selected from the group of resins can be preferably used. In particular, as a low-cost, highly transparent and versatile resin, one or more 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. A fluororesin can also be used in consideration of weather resistance.
(2) Electromagnetic wave absorbing substrate The electromagnetic wave absorbing particle dispersion of the present embodiment also includes an electromagnetic wave absorbing substrate having a substrate and a dispersed film containing the above-described electromagnetic wave absorbing particles disposed on the surface of the substrate. include.

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

An electromagnetic wave absorbing particle dispersion liquid is prepared by mixing the electromagnetic wave absorbing particles described above, an organic solvent such as alcohol or a liquid medium such as water, a resin binder, and optionally a dispersant (dispersion liquid preparation step).

Next, the electromagnetic wave absorbing particle dispersion is applied to a suitable base material surface (coating step).

The liquid medium is removed or cured to obtain an electromagnetic wave absorbing particle dispersion (dispersion preparing step).

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

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

On the other hand, an electromagnetic wave absorbing particle dispersion containing no resin binder component may be applied, and the electromagnetic wave absorbing particle dispersion may be laminated on the substrate surface. Alternatively, after applying the electromagnetic wave absorbing particle dispersion containing no resin binder component, a liquid medium containing a binder component may be applied on the layer of the electromagnetic wave absorbing particle dispersion.

Specifically, liquid electromagnetic wave absorbing particles in which the electromagnetic wave absorbing particles are dispersed in one or more liquid media selected from, for example, an organic solvent, an organic solvent in which a resin is dissolved, an organic solvent in which a resin is dispersed, and water. The dispersion is applied to the substrate surface. Then, by solidifying the obtained coating film by an appropriate method, an electromagnetic wave absorbing base material can be obtained.

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

Furthermore, a liquid electromagnetic wave absorbing particle dispersion obtained by mixing an electromagnetic wave absorbing particle dispersion, in which electromagnetic wave absorbing particles are dispersed in a powdery solid medium, in a predetermined medium is applied to the surface of the base material to obtain a coating film. can be solidified by an appropriate method to obtain an electromagnetic wave absorbing base material.

Of course, among the liquid electromagnetic wave absorbing particle dispersions, an electromagnetic wave absorbing particle dispersion in which two or more types are mixed is applied to the substrate surface, and the resulting coating film is solidified by an appropriate method to form an electromagnetic wave absorbing substrate. You can also

The material of the base material used for the electromagnetic wave absorbing base material is not particularly limited as long as it is transparent, but one or more selected from glass, resin sheet, resin board, resin film and the like is preferably used. The transparent body 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 according to the use of the electromagnetic wave absorbing substrate.

The resin used for the resin sheet, resin board, and resin film is not particularly limited, and can be selected according to the required properties such as the surface state and durability of the sheet, board, and 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, polystyrene, and acrylonitrile/styrene. Styrene-based polymers such as polymers, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, olefin-based polymers such as ethylene/propylene copolymers, vinyl chloride-based polymers, amide-based polymers such as aromatic polyamides, imide-based polymers, Sulfone-based polymer, polyethersulfone-based polymer, polyetheretherketone-based polymer, polyphenylene sulfide-based polymer, vinyl alcohol-based polymer, vinylidene chloride-based polymer, vinyl butyral-based polymer, arylate-based polymer, polyoxymethylene-based polymer, epoxy-based polymer and one or more selected from transparent polymers such as these binary and ternary copolymers, graft copolymers, and blends. In particular, polyester-based biaxially oriented films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene-2,6-naphthalate are preferable from the viewpoint of mechanical properties, optical properties, heat resistance and economy. The polyester-based biaxially oriented film may be a copolyester-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 so far transmit light in the visible light range and light in the infrared range. can be shielded. For this reason, for example, in various buildings and vehicles, it is used as a window material for the purpose of suppressing the temperature rise in the room while maintaining the brightness by shielding the light in the infrared region while sufficiently taking in visible light. be able to. Moreover, it can be suitably used as a filter or the like for shielding infrared rays emitted forward from a PDP (Plasma Display Panel).

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

Further, the light-to-heat conversion layer can be formed by applying the ink obtained by mixing the electromagnetic wave absorbing particle dispersion described above and the binder component onto the substrate, drying the applied ink, and then curing the dried ink. . The photothermal conversion layer generates heat at a portion irradiated with an electromagnetic wave laser such as infrared rays, and can heat an adjacent material. Therefore, the photothermal conversion layer can generate heat only at desired locations with high positional accuracy by irradiation with an electromagnetic wave laser such as infrared rays. Therefore, the photothermal 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 photothermal conversion layer is an example of the electromagnetic wave absorbing particle dispersion of the present embodiment.

Also, by dispersing the electromagnetic wave absorbing particles described above in an appropriate medium and incorporating the dispersion in one or more locations selected from the surface and inside of the fiber, an infrared absorbing fiber can be obtained. Since the infrared-absorbing fiber contains electromagnetic wave-absorbing particles, it efficiently absorbs near-infrared rays from sunlight and the like, and becomes an infrared-absorbing fiber excellent in heat retention. Since the infrared absorbing fiber transmits light in the visible light region, it becomes an infrared absorbing fiber excellent in design.

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

Further, the electromagnetic wave absorbing particle dispersion of the present embodiment can also be applied to materials such as roofs and exterior wall materials of agricultural and horticultural greenhouses. Since the electromagnetic wave absorbing particle dispersion of the present embodiment transmits visible light, it is possible to ensure light necessary for photosynthesis of plants in a greenhouse for agriculture and horticulture. Since the electromagnetic wave absorbing particles of the present embodiment can efficiently absorb light such as near-infrared light contained in sunlight other than visible light, it can be used as a heat insulating material for agricultural and horticultural facilities having heat insulating properties. The thermal insulation material for agricultural and horticultural facilities is an example of the electromagnetic wave absorbing particle dispersion of the present embodiment.
[5] Electromagnetic-wave-absorbing laminate The electromagnetic-wave-absorbing laminate of the present embodiment can have a laminate structure including the electromagnetic-wave-absorbing particle dispersion described above and a transparent substrate. As an electromagnetic wave absorbing laminate, for example, there is an example in which two or more transparent substrates and the electromagnetic wave absorbing particle dispersion described above are laminated. In this case, the electromagnetic wave absorbing particle dispersion can be used as an electromagnetic wave absorbing intermediate film, for example, by placing it between transparent substrates.

In this case, the electromagnetic wave-absorbing intermediate film preferably has a sheet shape, a board shape, or a film shape.

As the transparent base material, one or more kinds selected from plate glass, plate-like plastic, film-like plastic, etc., which are transparent in the visible light region, can be preferably used. In addition, the fact that the transparent base material is transparent in the visible light region means that the base material transmits light in the visible light region. The degree of transmission of light in the visible region by the transparent base material can be arbitrarily selected according to the use of the electromagnetic wave absorbing laminate.

When a plastic is used as the transparent substrate, the material of the plastic is not particularly limited and can be selected according to the application. Examples include polycarbonate resin, acrylic resin, polyester resin, polyamide resin, vinyl chloride resin, and olefin resin. , epoxy resins, polyimide resins, ionomer resins, fluorine resins, and the like. As the polyester resin, polyethylene terephthalate resin can be preferably used.

The transparent base material may contain particles having an electromagnetic wave absorbing function. As the particles having an electromagnetic wave absorbing function, for example, the electromagnetic wave absorbing particles described above can be used.

1 of an electromagnetic wave absorbing laminate that transmits visible light and has an electromagnetic wave absorbing function by using the electromagnetic wave absorbing particle dispersion described above as a constituent member of an intermediate layer that is sandwiched between a plurality of transparent substrates. A seed solar shading laminated structure can be obtained.

The above-described 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 sandwiched therebetween by a known method.

When the electromagnetic wave-absorbing particle dispersion described above is used as an electromagnetic wave-absorbing intermediate film, as the solid medium, the one described for the electromagnetic wave-absorbing particle dispersion can be used. However, from the viewpoint of increasing the adhesion strength between the electromagnetic wave absorbing intermediate film and the transparent substrate, the solid medium is preferably polyvinyl acetal resin.

The electromagnetic wave-absorbing intermediate film can be produced by the method for producing the electromagnetic wave-absorbing particle dispersion described above. .

If the electromagnetic wave absorbing intermediate film does not have sufficient flexibility and adhesion to the transparent substrate, it is preferable to add a liquid plasticizer for the medium resin. For example, when the medium resin used for the electromagnetic wave absorbing intermediate film is polyvinyl acetal resin, the addition of a liquid plasticizer for polyacetal resin is beneficial for improving the adhesion to the transparent substrate.

As plasticizers, substances used as plasticizers for medium resins can be used. For example, plasticizers used for infrared shielding films made of polyvinyl acetal resin include plasticizers that are compounds of monohydric alcohols and organic acid esters, ester plasticizers such as polyhydric alcohol organic acid ester compounds, Phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers are included. Any plasticizer is preferably liquid at room temperature. Among them, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferable.

At least one selected from the group consisting of silane coupling agents, metal salts of carboxylic acids, metal hydroxides, and metal carbonates can also be added to the electromagnetic wave absorbing intermediate film. Metals constituting metal salts of carboxylic acids, metal hydroxides, and metal carbonates are not particularly limited, but at least one selected from sodium, potassium, magnesium, calcium, manganese, cesium, lithium, rubidium, and zinc. is preferably In the near-infrared absorbing intermediate film, the content of at least one selected from the group consisting of metal salts of carboxylic acids, metal hydroxides, and metal carbonates is 1% by mass or more with respect to the electromagnetic wave absorbing particles. % or less is preferable.

Furthermore, the electromagnetic wave absorbing intermediate film may contain Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru in addition to the electromagnetic wave absorbing particles described above, if necessary. , P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, Ca At least one kind of particles selected from oxide particles containing more than one kind of elements, composite oxide particles, and boride particles may be contained. The intermediate film for electromagnetic wave absorption can contain such particles in the range of 5% by mass or more and 95% by mass or less when the total of such particles and electromagnetic wave absorbing particles is 100% by mass.

The electromagnetic wave absorbing laminate may contain an ultraviolet absorber in at least one layer of the intermediate film arranged between the transparent substrates. Examples of UV absorbers include compounds having a malonic acid ester structure, compounds having an oxalic acid anilide structure, compounds having a benzotriazole structure, compounds having a benzophenone structure, compounds having a triazine structure, compounds having a benzoate structure, and hindered amine structures. one or more selected from compounds having

It goes without saying that the intermediate layer of the electromagnetic wave absorbing laminate may be composed only of the electromagnetic wave absorbing intermediate film.

The electromagnetic wave absorbing intermediate film described here is also an example of the electromagnetic wave absorbing particle dispersion. Further, the electromagnetic wave absorbing laminate of the present embodiment is not limited to the form in which the electromagnetic wave absorbing particle dispersion is arranged between the transparent substrates as described above, and the electromagnetic wave absorbing particle dispersion and the transparent substrate. Any configuration can be adopted as long as it has a laminated structure including

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.
(Evaluation method)
First, evaluation methods 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 by a particle size distribution analyzer (UPA-150 manufactured by Nikkiso Co., Ltd.) based on the dynamic light scattering method analyzed by the frequency analysis method. As measurement conditions, a particle refractive index of 1.81 and a non-spherical particle shape were used. Also, the background was measured with methyl isobutyl ketone, and the solvent refractive index was 1.40. Then, the cumulative 50% particle size and the cumulative 95% particle size were obtained from the obtained particle size distribution.
(Crystal structure)
Using the electromagnetic wave absorbing particles obtained by removing the solvent from the electromagnetic wave absorbing particle dispersion, the crystal structure of the composite oxide contained in the electromagnetic wave absorbing particles was measured.

For the measurement, the X-ray diffraction pattern of the electromagnetic wave absorbing particles was measured by the 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.

(Optical properties of dispersion liquid)
The optical properties of the electromagnetic wave absorbing particle dispersions in Examples and Reference Examples were measured as follows. First, an electromagnetic wave absorbing particle dispersion liquid was diluted with methyl isobutyl ketone as a solvent in a measurement glass cell of a spectrophotometer. At this time, the dilution ratio was set such that the visible light transmittance after dilution was 70%. Next, the transmitted light profile is measured at intervals of 5 nm in the wavelength range of 200 nm or more and 2600 nm or less with a spectrophotometer (UH4150 manufactured by Hitachi High-Tech Science), and the visible light transmittance and solar transmittance are measured according to JIS R 3106 (2019). Based on this, calculation was performed in the wavelength range of 300 nm or more and 2100 nm or less. At this time, in the measurement, the incident direction of the light of the spectrophotometer was the direction perpendicular to the measuring glass cell. In addition, a blank solution containing only methyl isobutyl ketone as a solvent in the glass cell for measurement was used as a baseline for light transmittance.
(Optical properties of electromagnetic wave absorbing base material)
The optical properties of the electromagnetic wave absorbing substrates in Examples and Reference Examples were measured with a spectrophotometer (UH4150 manufactured by Hitachi High-Tech Science Co., Ltd.). The transmitted light profile was measured at intervals of 5 nm in the wavelength range of 200 nm or more and 2600 nm or less, and the visible light transmittance and solar transmittance were calculated in the wavelength range of 300 nm or more and 2100 nm or less based on JIS R 3106 (2019).
(Haze)
The haze value of the electromagnetic wave absorbing substrate was measured using a haze meter (HM-150N manufactured by Murakami Color Research Laboratory) and calculated based on JIS K 7136 (2000).
[Example 1]
(Electromagnetic wave absorbing particles)
4.04 g of lanthanum oxide (La ₂ O ₃ , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.7%) and bismuth oxide (Bi ₂ O ₃ , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%) 5.77 g was mixed well to homogeneity. The obtained mixed powder was placed in an alumina crucible filled with 24.7 g of potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 85.0% or higher) as a fluxing agent, and an alumina lid fitted to the crucible was placed. Then, heat treatment was performed at a temperature of 450° C. for 9 hours in an air atmosphere. The obtained heat-treated product was washed with pure water by a vacuum filtration facility and dried in a vacuum atmosphere at room temperature for one day to obtain a powder of composition formula La ₂ Bi ₂ O ₇ according to Example 1. Here, circular quantitative filter paper No. 1 was used as the filter of the vacuum filtration equipment. 5C (manufactured by ADVANTEC) was used.

(Electromagnetic wave absorbing particle dispersion)
6% by mass of La ₂ Bi ₂ O ₇ according to Example 1 and 6 masses of an acrylic polymer dispersant having an amine-containing group as a functional group (an acrylic dispersant having an amine value of 48 mgKOH/g and a decomposition temperature of 250° C.) % and 88% by mass of methyl isobutyl ketone to prepare a mixture.

The resulting mixed solution (slurry) was placed in a glass bottle together with ZrO ₂ beads of φ0.3 mm, placed in a paint shaker, and pulverized and dispersed for 5 hours to obtain an electromagnetic wave absorbing particle dispersion liquid according to Example 1. . At this time, the La ₂ Bi ₂ O ₇ particles become electromagnetic wave absorbing particles.

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 56 nm.

Further, when the solvent (dispersion medium) was removed from the electromagnetic wave absorbing particle dispersion liquid and the powder X-ray diffraction pattern of La ₂ Bi ₂ O ₇ according to Example 1 was measured, cubic La ₂ Bi ₂ O ₇ crystals were obtained. Diffraction peaks attributed to phases were confirmed.

When the electromagnetic wave absorbing particle dispersion liquid according to Example 1 was diluted with methyl isobutyl ketone as a solvent and the optical properties were measured, the visible light transmittance was 70% and the solar radiation transmittance was 44%.
(Electromagnetic wave absorbing particle dispersion)
The electromagnetic wave absorbing particle dispersion liquid according to Example 1 and the ultraviolet curable resin (Aronix UV-3701 manufactured by Toagosei Co., Ltd.) are weighed so that the mass ratio is 1:1, mixed and stirred to form an electromagnetic wave absorbing base material. was prepared. And bar no. No. 10 bar coater was used to apply the dispersion liquid for forming an electromagnetic wave absorbing base material onto clear glass having a thickness of 3 mm, followed by drying at 70° C. for 1 minute and irradiating with a high-pressure mercury lamp. An electromagnetic wave absorbing substrate was obtained. The electromagnetic wave absorbing base material is an example of the electromagnetic wave absorbing particle dispersion.

When the optical properties of the obtained electromagnetic wave absorbing substrate according to Example 1 were measured, the visible light transmittance was 70% and the solar radiation transmittance was 45%. Moreover, when the haze was measured, it was 0.4%.

Evaluation results are shown in Tables 1 and 2.
[Example 2, Example 3]
Instead of lanthanum oxide, yttrium oxide (Y ₂ O ₃ , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.99%) (Example 2), neodymium oxide (Nd ₂ O ₃ , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) , purity 99.9%) (Example 3) was used. Electromagnetic-wave-absorbing particles according to the composition formulas Y ₂ Bi ₂ O ₇ (Example 2) and Nd ₂ Bi ₂ O ₇ (Example 3) were prepared in the same manner as in Example 1 except for the above points.

Further, an electromagnetic wave absorbing particle dispersion liquid and an electromagnetic wave absorbing substrate were prepared in the same manner as in Example 1 except that the electromagnetic wave absorbing particles were used, and the same evaluation as in Example 1 was performed. Tables 1 and 2 show the evaluation results in Examples 2 and 3.
[Example 4, Example 5]
Instead of bismuth oxide, tin oxide (SnO ₂ , manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99.99%) (Example 4), lead oxide (PbO ₂ , manufactured by Kojundo Chemical Laboratory Co., Ltd., purity 99%) ) (Example 5) was used. Electromagnetic-wave-absorbing particles according to the composition formulas La ₂ Sn ₂ O ₇ (Example 4) and La ₂ Pb ₂ O ₇ (Example 5) were prepared in the same manner as in Example 1 except for the above points.

Further, an electromagnetic wave absorbing particle dispersion liquid and an electromagnetic wave absorbing substrate were prepared in the same manner as in Example 1 except that the electromagnetic wave absorbing particles were used, and the same evaluation as in Example 1 was performed. The evaluation results in Examples 4 and 5 are shown in Tables 1 and 2.
[Reference example 1]
In 340 g of water at 25° C., 54.9 g of SnCl ₄ .5H ₂ O (manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade, purity of 98% or higher) was dissolved to prepare a tin compound solution. To the tin compound solution, 12.7 ml of a methanol solution (manufactured by Yoneyama Chemical Industries, reagent special grade, purity of 99.8% or more) in which 4.2 g of SbCl ₃ (manufactured by Wako Pure Chemical Industries, JIS special grade, purity of 98% or more), which is an antimony compound, is dissolved. and an aqueous NH ₄ OH solution (manufactured by Wako Pure Chemical Industries, special grade reagent, concentration 30%), which is an alkaline solution diluted to a concentration of 16%, were added dropwise in parallel. By the parallel dropping, 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.

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

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

The parallel dropping time of the methanol solution and the alkaline solution was set to 25 minutes, and parallel dropping was performed until the pH of the solution obtained by the dropping reached 7.5. Even after the dropwise addition, the solution was continuously stirred for 10 minutes in order to homogenize the system. The temperature of the solution at that time was set to 65° C., which was the same temperature as the temperature during parallel dropping.

Next, the precipitate was washed by repeated decantation. It was thoroughly washed until the conductivity of the supernatant liquid of the washing liquid in the decantation was 1 mS/cm or less, and filtered.

Next, the washed precipitate was wet-treated with an anhydrous ethyl alcohol solution (manufactured by Wako Pure Chemical Industries, special grade reagent, purity of 99.5% or more). During the wet treatment, the mass ratio of [filtered precipitate: anhydrous ethyl alcohol solution] is set to a ratio of 1:4 (alcohol proportion is 80%), and the filtered precipitate and anhydrous ethyl alcohol solution are mixed. was wet-treated by stirring 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 dry product.

Then, the wet-treated ATO electromagnetic wave-absorbing particle precursor was heated to 700° C. in an air atmosphere and baked for 2 hours to produce ATO electromagnetic wave-absorbing particles according to Reference Example 1.

The electromagnetic wave absorbing particle dispersion liquid according to Reference Example 1 was prepared in the same manner as in Example 1 except that the ATO electromagnetic wave absorbing particles according to Reference Example 1 were used instead of the La ₂ Bi ₂ O ₇ particles as the electromagnetic wave absorbing particles. An electromagnetic wave absorbing base material was prepared, and the same evaluation as in Example 1 was performed. Tables 1 and 2 show the evaluation results in Reference Example 1.

表１、表２に示した結果によると、実施例１～実施例５で得られた電磁波吸収粒子を用いた、電磁波吸収粒子分散液、電磁波吸収粒子分散体は、可視光透過率が高く、日射透過率を抑制できていることを確認できた。すなわち、可視光領域の透過率が高く、赤外線領域の透過率を抑制できていることを確認できた。

According to the results shown in Tables 1 and 2, 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 5 have high visible light transmittance, It was confirmed that the solar transmittance could be suppressed. That is, it was confirmed that the transmittance in the visible light region was high and the transmittance in the infrared region was suppressed.

It was also confirmed that the visible light transmittance and the solar radiation transmittance are the same as or better than ATO, which has been conventionally used as electromagnetic wave absorbing particles. Therefore, it was confirmed that the electromagnetic wave absorbing particles obtained in Examples 1 to 5 are practically novel electromagnetic wave absorbing particles.

Claims (11)

Electromagnetic wave absorbing particles containing a composite oxide,
The composite oxide includes an element A that is one or more elements selected from rare earth elements,
and a B element that is one or more elements selected from Bi, Pb, and Sn,
Electromagnetic-wave-absorbing particles satisfying a relationship of 0.001≦x/y≦4, where x is the amount of the element A contained in the composite oxide and y is the amount of the element B contained in the composite oxide. 2. The electromagnetic wave absorbing particles according to claim 1, having a volume-based cumulative 50% particle diameter of 1 nm or more and 50 nm or less and a volume-based cumulative 95% particle diameter of 5 nm or more and 100 nm or less, as measured by a particle size distribution analyzer. The A element is La,
3. The electromagnetic wave absorbing particles according to claim 1, wherein said B element is Bi. 4. The electromagnetic wave absorbing particles according to any one of claims 1 to 3, which satisfy 0.5≤x/y≤2. a liquid medium;
An electromagnetic wave absorbing particle dispersion liquid comprising the electromagnetic wave absorbing particles according to any one of claims 1 to 4 contained in the liquid medium. 6. The dispersion of electromagnetic wave absorbing particles according to claim 5, wherein the liquid medium contains one or more selected from water, organic solvents, liquid plasticizers, fats and oils, and compounds polymerized by curing. a solid medium;
An electromagnetic wave absorbing particle dispersion comprising the electromagnetic wave absorbing particles according to any one of claims 1 to 4 contained in the solid medium. 8. The electromagnetic wave absorbing particle dispersion according to claim 7, wherein said solid medium is resin. The resin is 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, 9. The electromagnetic wave-absorbing particle dispersion according to claim 8, which is a resin selected from the group of resins consisting of and UV-curable resins, or a mixture of two or more resins selected from the group of resins. 10. The electromagnetic wave absorbing particle dispersion according to any one of claims 7 to 9, having a sheet shape, board shape, or film shape. an electromagnetic wave absorbing particle dispersion according to any one of claims 7 to 10;
An electromagnetic wave absorbing laminate having a laminate structure including a transparent base material.