JP7275792B2 - Fine particle dispersions and fine particle dispersions with excellent high-temperature stability - Google Patents

Description

The present invention provides a fine particle dispersion having excellent high-temperature stability in which fine particles are dispersed in a liquid medium (sometimes referred to as a "dispersion" in the present invention), and a fine particle dispersion in which fine particles are dispersed in a medium. (It may be described as "dispersion" in the present invention.).
Furthermore, the present invention relates to dispersions and dispersions containing functional fine particles (which may be referred to as "absorbing fine particles" in the present invention) that absorb electromagnetic waves represented by light and infrared rays.

While the reduction of carbon dioxide emissions is required on a global scale to curb global warming, high-rise buildings and automobiles are rapidly increasing in emerging countries. As a result, effective use and control of sunlight (which may be referred to as "sunlight" in the present invention), weight reduction of moving bodies such as automobiles, and prevention of high-altitude dropping and scattering of glass etc. Countermeasures are required.

In the field of effective utilization of sunlight, there are articles using photoelectric conversion and photothermal conversion, such as photovoltaic power generation and solar water heaters.
In the field of solar control, there are articles that block solar light containing visible light, such as curtains, blinds and smoke films. Furthermore, in recent years, reflective glasses and films that reflect most of the sunlight, such as mirror glass and mirror films, and reflective films, and absorption glasses and films in which functional fine particles that absorb light are dispersed have been developed. It is used as a window material for buildings such as houses and buildings and as a window material for automobiles.

Sunlight includes ultraviolet rays and infrared rays in addition to visible rays. Among the infrared rays contained in the sunlight, near-infrared rays with a wavelength of 800 to 2500 nm are called heat rays, and enter the interior of the room or vehicle through the openings of the above-mentioned buildings and automobiles, causing an increase in temperature. In order to eliminate the temperature rise, reflective glass, reflective film, absorbing glass, or absorbing film is used in the opening.

In the field of weight reduction, there is a demand for fusion of a transparent resin molded body such as polycarbonate resin used in conventional arcades, ceiling domes, carports, etc., with a heat ray shielding function. As a result, there is a rapid increase in the demand for a molded article having a heat ray shielding function that allows sufficient visible light to be taken in while shielding heat rays, and suppressing an internal temperature rise while maintaining brightness.

In the field of high-altitude drop and scattering prevention measures, there is concern about the risk of collision with the human body due to falling or scattering that occurs when high-rise buildings, window materials of vehicles, etc. are damaged. In order to solve this concern, a heat ray shielding function and a scattering prevention function are imparted to a transparent heat ray shielding film that shields heat rays while allowing sufficient visible light to suppress the temperature rise in the room while maintaining brightness. The spread of safety measures is progressing.

In response to the above-mentioned demands, many proposals have been made regarding molded articles having a heat ray shielding function and bonding thereof.
In the production of reflective glass, first, a reflective layer is formed on a transparent resin film such as polyethylene terephthalate resin (PET) by depositing a metal or a metal oxide to produce a transparent resin film with a reflective layer formed thereon. . Then, the transparent resin film on which the reflective layer is formed is laminated as an intermediate layer between two or more glass plates.
Of course, besides the method of forming a film having a reflective layer formed thereon and then attaching it to glass, there is also a method of directly forming a reflective layer on a glass plate by vapor deposition or the like.
There is also a method of using a transparent resin molding such as acrylic resin or polycarbonate resin instead of glass.

However, a highly transparent reflective layer that blocks a large amount of heat rays and at the same time transmits a large amount of visible light requires a multi-layer structure of several tens of layers, which itself is expensive. In addition, complicated processes such as adhesion for lamination may be required. As a result, in addition to further increasing the production cost, there are drawbacks such as peeling of the reflective layer from the glass over time.

On the other hand, the reflective film is formed by vapor-depositing a metal or metal oxide on a transparent resin film such as polyethylene terephthalate resin (PET) to form a reflective layer. be done. The reflective film is also commercially available as a roll or cut film.
Adhesion of the reflective film to transparent glass, etc. can be done by oneself, but there are problems such as the inclusion of air bubbles and the generation of fogging. often outsourced. The cost required for the construction, together with the cost of the reflective film, hinders the spread of the reflective film.

The absorbing glass is a transparent resin film such as polyethylene terephthalate resin (PET), and an absorbing layer formed by coating or kneading an organic near-infrared absorbing agent represented by a phthalocyanine-based compound or anthraquinone-based compound. It is produced by laminating as an intermediate layer in the same manner as the reflective glass.
However, in order for the absorbing glass to efficiently absorb heat rays and near-infrared rays, a large amount of organic near-infrared absorbing agent is required, and as a result, sufficient visible light transmission cannot be obtained. In addition, the organic near-infrared absorbent has poor weather resistance at high temperatures and for a long period of time.

Here, Patent Documents 1 and 2, for example, propose a method of using inorganic particles such as mica coated with titanium oxide instead of the above-described organic near-infrared absorbent. However, even in this method, it is necessary to add a large amount of the inorganic particles in order to absorb a large amount of heat rays and block the propagation of heat from the outside. Therefore, as with the organic near-infrared absorbing agent, it is difficult to obtain sufficient visible light transmission. At the same time, the impact strength, toughness, and ductility of the intermediate layer described above are lowered, and problems and limitations arise in terms of strength and workability.

The absorbing film is a transparent resin film such as polyethylene terephthalate resin (PET) described above, which contains an organic near-infrared absorbing agent and inorganic particles such as mica coated with titanium oxide, and is made into a film after forming an absorbing layer. , and used by adhering to existing transparent glass or the like. The absorbent film is also commercially available as a roll or cut film.
Adhesion of the absorbent film to transparent glass, etc. can be done by oneself, but there are problems such as inclusion of air bubbles and generation of fogging, so in order to obtain the desired performance, a specialized contractor with appropriate technology should perform the work. often outsourced. The cost required for the construction, together with the cost of the absorbent film, hinders the spread of the absorbent film.

Further, it is also possible to use a combination of the reflective glass/reflective film and the absorbing glass/absorbing film described above. However, any combination cannot avoid the manufacturing cost and the construction cost like the reflective glass and the absorbing film described above, which hinders its spread.

On the other hand, functional fine particles that absorb electromagnetic waves represented by light and infrared rays include indium-doped tin oxide (ITO), zinc-doped tin oxide (ATO), hexaboride, tungsten oxide, and composite tungsten oxide.
The applicant has disclosed as Patent Document 3 that among these functional fine particles, the composite tungsten oxide has high transparency in the visible light wavelength range and large light in other wide wavelength ranges, especially in the long infrared wavelength range. disclosed to have absorbent properties.

The applicant has disclosed as Patent Document 4, a laminated glass structure, various buildings, automobiles, trains, Disclosed is an article and means for suppressing a temperature rise in a room, a car, etc. due to sunlight incident through openings such as windows and doors provided in an aircraft while maintaining brightness.

In addition, the applicant has invented a light-absorbing resin composition for laser welding for industrial use, as described in Patent Document 5, utilizing the property that functional fine particles such as composite tungsten oxide absorb light and generate heat. A means for efficiently welding members has been disclosed.
In addition, as Patent Document 6, the applicant has disclosed that for consumer use, functional fine particles such as composite tungsten oxide that absorb infrared rays from sunlight etc. are mixed with acrylic resin, polyester resin, etc. to make a synthetic fiber that absorbs near infrared rays. A fiber and its application to heat generation and heat retention as a fiber product using the fiber were disclosed.

Furthermore, the applicant has disclosed in Patent Document 7, in response to the above-described demand for a molded article having a heat ray shielding function, a highly heat-resistant dispersant having a high thermal decomposition temperature, and the tungsten oxide fine particles and/or composite tungsten fine particles. Disclosed is a means for obtaining a heat ray shielding transparent resin molding by mixing and melting and kneading a dispersion liquid containing a thermoplastic resin.
Furthermore, the applicant has disclosed in Patent Document 8 that near-infrared rays are A near-infrared absorption filter for PDP is disclosed which does not reduce the shielding ability.
Further, Patent Document 9 discloses a near-infrared absorption filter for a PDP to which a metal deactivator different from that of Patent Document 8 is added.

JP-A-6-256541 JP-A-6-264050 International Publication No. 2005-037932 International Publication No. 2005-087680 JP 2008-127511 A International Publication No. 2006-049025 JP 2011-001551 A JP 2010-008818 A JP 2009-035615 A

In the examples of Patent Document 8 described above, a metal deactivator (sometimes referred to as a "metal deactivator") is maintained in an air atmosphere at 60 ° C., and the near-infrared shielding ability decreases and electromagnetic waves It is described that it is effective as means for suppressing deterioration of absorption properties.
In addition, in Patent Document 9, a metal deactivator suppresses oxidation of a (meth)acrylic resin adhesive due to the catalytic action of cesium/tungsten composite oxide fine particles, so that (meth) describes the effect of preventing an increase in transmittance in the near-infrared region of an acrylic resin, and describes the effect of heating at a high temperature of 80° C. or R.I. H. It is described that the effect is exhibited even in a high humidity environment of 95%.

However, as a result of investigations, the inventors of the present invention came to the conclusion that as the applications of heat ray shielding films and the like expand, stability at even higher temperatures such as 120° C. is required for the heat ray shielding films and the like.
The present invention has been made under the above circumstances, and the problem to be solved is to have excellent heat ray shielding properties (infrared absorption properties), and the excellent heat ray shielding properties can be maintained even in a high temperature environment. The object is to provide stable dispersions and dispersions.

The inventor of the present invention conducted intensive studies with the aim of solving the problems described above. As a result, dispersion liquids and dispersions to which a metal deactivator having a predetermined structure is added have excellent heat ray shielding properties, and the excellent heat ray shielding properties can be used in high temperature environments by conventional techniques (e.g., patent literature 8 and 9), the present invention was completed.

但し、前記構造式（１）においてＲ_１０は、炭素数１～２０のアルキレン基、炭素数５～１５の脂環族基、炭素数７～１３のアラルキレン基またはアリレン基のいずれかである。 That is, the first invention for solving the above problems is a fine particle dispersion liquid containing a liquid medium, absorbing fine particles dispersed in the medium, and a metal deactivator,
The absorbing fine particles are tungsten oxide fine particles represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≤ z/y ≤ 2.999), and the general formula MxWyOz (where M is H , He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, One or more elements selected from I and Yb, W for tungsten, O for oxygen, 0.001 ≤ x/y ≤ 1, 2.0 ≤ z/y ≤ 3.0) Tungsten oxide fine particles, one or more oxide fine particles selected from
The fine particle dispersion liquid, wherein the metal deactivator is a compound represented by the following structural formula (1).

However, in the structural formula (1), R ₁₀ is an alkylene group having 1 to 20 carbon atoms, an alicyclic group having 5 to 15 carbon atoms, an aralkylene group having 7 to 13 carbon atoms, or an arylene group.

The dispersion liquid and dispersion according to the present invention had heat ray shielding properties, and the excellent heat ray shielding properties were stable even in a high temperature environment.

Hereinafter, the dispersion and dispersion having excellent high-temperature stability according to the present invention will be described in detail.

The main components of the dispersion and the dispersion according to the present invention are absorbing fine particles, a medium for dispersing the absorbing fine particles (in the present invention, it may be referred to as a "medium"), an ultraviolet absorber, a plasticizer, and a surfactant. agents, antistatic agents, coupling agents, metal deactivators, and dispersants to properly disperse the absorbing particles in the medium.
As a medium for the dispersion, water, an organic solvent, a resin, or the like, which is liquid at room temperature, is used. On the other hand, as a medium for the dispersion, an inorganic substance, an organic substance, a thermosetting resin, an ultraviolet curable resin, or the like, which is solid or gel at room temperature, is used.
Furthermore, it is also possible to use a dispersing agent as an additive, if necessary, as a component of the dispersion and the dispersion.

Various forms such as film-like, plate-like, pellet-like and gel-like forms are appropriately selected for the dispersion according to the present invention.
For example, if it is in the form of a film, the dispersion may be coated on a convenient substrate to form a film. The coating may be formed by any method such as spin coating, bar coating, spray coating, dip coating, screen coating, roll coating, flow coating, etc., as long as the dispersion can be applied evenly and thinly. method is also acceptable. After the dispersion liquid is applied by the above method, the volatile components are volatilized by allowing it to stand in the air, in a vacuum, at room temperature, or in a heated state. For example, when the dispersion contains an ultraviolet curable resin, the film can be fixed on the base material by irradiating with ultraviolet rays, and when the dispersion contains a thermosetting resin, the film can be further fixed on the substrate by heating to obtain a dispersion. Furthermore, it may be in the form of a patterned film formed by application by an inkjet method or by a 3D printer or the like.

The dispersion is heated, melted, mixed, dispersed, and solidified together with an organic resin such as polycarbonate resin (PC resin) or polyethylene terephthalate resin (PET resin) in an extruder or calendar roll molding machine to produce pellets. Obtain dispersions by various methods, such as a method of obtaining a dispersion in the form of a film or plate, or a method of mixing, dispersing, and solidifying with an injection molding machine or compression molding machine to obtain a dispersion of a molded product of arbitrary shape. be able to.

Hereinafter, each component constituting the dispersion or the dispersion according to the present invention, the method for producing the dispersion or the dispersion, the dispersion or the dispersion, and the use thereof will be described with respect to [a] absorbing fine particles, [b] medium , [c] additive, [d] dispersant, [e] method for producing a dispersion according to the present invention, [f] method for producing a dispersion according to the present invention, [g] dispersion according to the present invention and its Application, [h] Dispersion according to the present invention and its application, and [i] Summary.

[a] Absorbing microparticles The absorbing microparticles according to the present invention are tungsten oxide microparticles represented by the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ≤ z/y ≤ 2.999). Formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag , Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re , Be, Hf, Os, Bi, I, and Yb, W is tungsten, O is oxygen, 0.001≦x/y≦1, 2.0≦z/y≦ 3.0) is one or more kinds of oxide fine particles selected from composite tungsten oxide fine particles represented by 3.0).
That is, the absorbing fine particles are either the above-described tungsten oxide fine particles or composite tungsten oxide fine particles, or oxide fine particles of both.

The composite tungsten oxide fine particles represented by the general formula MxWyOz described above are selected from hexagonal, tetragonal, and cubic crystals because they have excellent durability when they have a hexagonal, tetragonal, or cubic crystal structure. It preferably contains one or more crystal structures that are
In particular, among the elements of M, one or more elements selected from each element of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn that constitute a hexagonal crystal structure is preferred, and Cs, which has high electromagnetic wave absorption and excellent transmission in the visible light region with a wavelength of 400 nm to 780 nm, is preferred.

The addition amount x of the M element to be added is preferably 0.001 or more and 1 or less in the value of x/y, and further, the value of x/y calculated theoretically from the hexagonal crystal structure is around 0.33. is preferred.
On the other hand, the abundance Z of oxygen is preferably 2.0 or more and 3.0 or less as a value of z/y. Typical examples include _{Cs0.33WO3 , Rb0.33WO3 , K0.33WO3 , Ba0.33WO3 , Cs0.03Rb0.30WO3} and the _{like .} . However, if the values of x, y, and z fall within the above ranges, useful electromagnetic wave absorption characteristics can be obtained.

From the viewpoint of exhibiting excellent electromagnetic wave absorption characteristics, the crystallite size of the absorbing fine particles is preferably 1 nm or more and 200 nm or less, more preferably 1 nm or more and 100 nm or less, and still more preferably 10 nm or more and 70 nm or less. For the measurement of the crystallite size, X-ray diffraction pattern measurement by the powder X-ray diffraction method (θ-2θ method) and analysis by the Rietveld method are used. For the measurement of the X-ray diffraction pattern, for example, a powder X-ray diffractometer "X'Pert-PRO/MPD" manufactured by PANalytical, Spectris Co., Ltd. can be used.

Furthermore, it is also a preferable configuration that the surface of the absorbing fine particles is coated with a compound containing one or more elements selected from Si, Ti, Zr, and Al.

[b] Medium Regarding the liquid medium used for the dispersion according to the present invention and the solid or gel medium used for the dispersion, 1. liquid medium;2. A description will be given in the order of a solid medium and a gel medium.

1. Liquid medium The medium for the dispersion liquid according to the present invention includes water, organic solvents such as toluene and hexane, liquid organic resins such as epoxy resins and acrylic resins, oils and fats, and liquids for medium resins, which are liquid at room temperature. Plasticizers, polymer monomers, mixtures thereof, and the like are mentioned. The liquid medium is variously selected according to the dispersion produced using the dispersion according to the present invention, and is not particularly limited.

Here, as the organic solvent, alcohol-based, ketone-based, hydrocarbon-based, glycol-based, etc. can be selected. Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, diacetone alcohol,
ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone;
Ester solvents such as 3-methyl-methoxy-propionate,
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 methyl ether acetate, propylene glycol ethyl ether acetate;
amides such as formamide, N-methylformamide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone;
aromatic hydrocarbons such as toluene and xylene;
Ethylene chloride, chlorobenzene, etc. can be used.
Among these organic solvents, dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like are particularly preferred.

As fats and oils, vegetable fats and oils or plant-derived fats and oils are preferable. 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. A non-drying oil such as As the vegetable oil-derived compound, fatty acid monoesters, ethers, and the like obtained by directly esterifying fatty acids of vegetable oils and monoalcohols are used.
In addition, commercially available petroleum solvents can also be used as fats and oils, such as Isopar E, Exol Hexane, Exol Heptane, Exol E, Exol D30, Exol D40, Exol D60, Exol D80, Exol D95, Exol D110, Exol D130 (above, manufactured by ExxonMobil) and the like.

As the liquid plasticizer for the medium resin, known liquid plasticizers represented by organic acid esters and phosphate esters can be used.
This is because, in a dispersion used for producing a dispersion having plasticity, the plasticity of the dispersion can be improved by using the liquid plasticizer as a liquid medium. Then, the obtained dispersion having plasticity can be sandwiched between, for example, two or more transparent substrates that transmit at least visible light to form a laminated structure.

Examples of liquid plasticizers include plasticizers that are compounds of monohydric alcohols and organic acid esters, ester plasticizers such as polyhydric alcohol organic acid ester compounds, and organic phosphoric acid plasticizers. Phosphoric acid-based plasticizers can be mentioned, and those that are liquid at room temperature are preferred. Among them, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferable.

Ester compounds synthesized from polyhydric alcohols and fatty acids are not particularly limited. , n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), glycol-based ester compounds obtained by reaction with monobasic organic acids such as decylic acid. Also included are ester compounds of tetraethylene glycol, tripropylene glycol and the above monobasic organic compounds.
Among them, triethylene glycol fatty acid esters such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanate, and triethylene glycol di-2-ethylhexanonate are preferable. .

Further, the polymer monomer is a monomer that forms a polymer by polymerization or the like, and preferred polymer monomers used in the present invention include methyl methacrylate monomers, acrylate monomers and styrene resins. A monomer etc. are mentioned.

The liquid media described above can be used singly or in combination of two or more. Furthermore, if necessary, acid or alkali may be added to these liquid media to adjust the pH.

2. Solid or Gel Medium The medium used in the dispersion according to the present invention is a solid or gel medium at room temperature. Specifically, inorganic compounds such as glass, polymer organic compounds such as polycarbonate resins and PET resins, and the like can be selected from various materials.
However, when a phosphite-based compound is used as the "[c] additive" described later, the dispersion medium may be polycarbonate resin (PC resin) or acrylic resin that is highly compatible with the phosphite-based compound. (PMMA resin), polypropylene resin (PP resin), polyethylene resin (PE resin), polystyrene resin (PS resin), polyamide resin (PA resin), and polyethylene terephthalate resin (PET resin).

[c] Additive The additive according to the present invention is intended to improve the weather resistance of the dispersion and the dispersion according to the present invention, and to stably exhibit excellent heat ray shielding properties even at a high temperature of, for example, 120 ° C. is added.
Regarding the additive according to the present invention, 1. a metal deactivator having a given structure;2. A stabilizer having a structure different from that of the metal deactivator will be described in order.

1. Metal Deactivator Having Predetermined Structure The metal deactivator used in the present invention is a compound represented by the following structural formula (1), wherein R ₁₀ is an alkylene group having 1 to 20 carbon atoms and 5 to 15 carbon atoms. , an aralkylene group or an arylene group having 7 to 13 carbon atoms.

Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, i-butylene group, sec-butylene group, t-butylene group, t- Pentylene group, i-octylene group, t-octylene group, 2-ethylhexylene group, and the like.
Examples of alicyclic groups having 5 to 15 carbon atoms include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, 1-methylcyclopentylene, 1-methylcyclohexylene, 1-methyl- 4-i-propylcyclohexylene group and the like.

Examples of the aralkylene group having 7 to 13 carbon atoms include benzylene group, α-methylbenzylene group, α,α-dimethylbenzylene group and the like.
The arylene group having 7 to 13 carbon atoms includes, for example, phenylene group, naphthylene group, 2-methylphenylene group, 4-methylphenylene group, 2,4-dimethylphenylene group, 2,6-dimethylphenylene group and the like.

Among the metal deactivators represented by Structural Formula (1), it is particularly preferred that R ₁₀ is an alkylene group having 10 carbon atoms.

Preferred specific examples of the metal deactivator include decamethylene dicarboxylic acid disalicyloyl hydrazide (eg, commercially available as ADEKA STAB (registered trademark) CDA-6 (manufactured by ADEKA Corporation)) and the like.

The amount of the metal deactivator to be added is preferably 10 parts by weight or more and 10000 parts by weight or less, more preferably 50 parts by weight or more and 3000 parts by weight or less, and 100 parts by weight or more and 700 parts by weight or less with respect to 100 parts by weight of the absorbent fine particles. It is more preferably 130 parts by weight or more and 350 parts by weight or less.
When the amount of the metal deactivator added is 10 parts by weight or more with respect to 100 parts by weight of the absorbent fine particles, excellent heat ray shielding properties can be stably exhibited even at a high temperature of, for example, 120°C.
On the other hand, when the amount of the metal deactivator added is 10,000 parts by weight or less with respect to 100 parts by weight of the absorbent fine particles, there is no significant effect on the retention characteristics in an air atmosphere at a high temperature of 120 ° C., but the dispersion liquid It is possible to avoid the deterioration of workability and the decrease of visible light transmittance due to the viscosity increase etc.

2. A stabilizer having a structure different from that of the metal deactivator As the metal deactivator according to the present invention, in addition to the compounds described in "1. Metal deactivator", "1. Metal deactivator" It is also possible to add a stabilizer having a structure different from that of the compounds described in "Stabilizer". Examples of stabilizers having different structures include hindered phenol-based stabilizers, sulfide-based stabilizers, phosphorus-based stabilizers having phosphorus-based functional groups containing phosphites, trivalent and pentavalent phosphorus, and the like. can be used.
These stabilizers have the effect of scavenging radicals generated from the resin in a high-temperature holding environment and the effect of decomposing peroxides generated by radical reaction. Although the details of the mechanism by which these stabilizers exert their effects have not been elucidated, they act in combination with the metal deactivator to synergistically suppress the deterioration of the electromagnetic wave absorption characteristics of the absorbing fine particles. it is conceivable that.

Preferred examples of hindered phenolic stabilizers include compounds in which a large group such as a tert-butyl group is introduced at the first position of the phenolic OH group.
As an example of the sulfide-based stabilizer, a compound having divalent sulfur in the molecule, which is used as a sulfur-based anti-coloring agent, can be preferably mentioned. Specific examples include ADEKA STAB (registered trademark) AO-412S (manufactured by ADEKA Corporation) represented by structural formula (2) and ADEKA STAB (registered trademark) AO-503 (manufactured by ADEKA Corporation) represented by structural formula (3). is mentioned.

[d] Dispersant A dispersant can be used in the dispersion liquid or dispersion element according to the present invention in order to uniformly disperse the absorbent fine particles in the medium and/or the dispersion liquid.
A variety of dispersants can be selected according to the medium and dispersion liquid described above. The absorbent fine particles according to the present invention are tungsten oxide fine particles represented by the general formula WyOz and composite tungsten oxide fine particles represented by the general formula MxWyOz. A dispersant having a group, hydroxyl group, sulfo group, or the like is preferred. These functional groups have the effect of adsorbing to the surface of the absorbent fine particles, preventing aggregation of the absorbent fine particles, and uniformly dispersing the absorbent fine particles even in the dispersion medium or dispersion liquid.

Preferred specific examples of commercially available dispersants include SOLSPERSE (registered trademark) 3000, 9000, 11200, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC and 24000GR manufactured by Nippon Lubrizol Co., Ltd. ,26000,27000,28000,31845,32000,32500,32550,32600,33000,33500,34750,35100,35200,36600,37500,38500,39000,41000,41090,53095, 55000, 56000, 76500 etc.,
Disperbyk (registered trademark) manufactured by BYK Japan Co., Ltd.-101, 103, 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, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, Anti-Terra-U , Anti-Terra-203, Anti-Terra®-204, BYK®-P104, P104S, 220S, 6919, etc.
EFKA (registered trademark) 4008, 4046, 4047, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4500, 4510, 4530, 4550, 4560 manufactured by BASF Japan Ltd. , 4585, 4800, 5220, 6230, JONCRYL® 67, 678, 586, 611, 680, 682, 690, 819, -JDX5050, etc.,
Alfon (registered trademark) manufactured by Toagosei Co., Ltd. UC-3000, UF-5022, UG-4010, UG-4035, UG-4070, etc.
Ajinomoto Fine-Techno Co., Inc. Ajisper (registered trademark) PB-711, PB-821, PB-822, and the like.

Among them, acrylic-styrene copolymer dispersants having a carboxyl group as a functional group and acrylic dispersants having an amine-containing group as a functional group are more preferable examples. The dispersant having an amine-containing functional group preferably has a molecular weight Mw of 2,000 to 200,000 and an amine value of 5 to 100 mgKOH/g. Dispersants having carboxyl groups preferably have a molecular weight Mw of 2,000 to 200,000 and an acid value of 1 to 50 mgKOH/g.

The amount of the dispersing agent added varies depending on the type of the absorbing fine particles and the dispersing agent, but is preferably in the range of 10 parts by weight or more and 1000 parts by weight or less with respect to 100 parts by weight of the absorbing fine particles. When the particles are fine particles and the dispersion medium is, for example, polyvinyl acetal resin (PVA resin), the range is preferably 30 parts by weight or more and 400 parts by weight or less.
This is because when the amount of the dispersant added is within the above range, the absorbent fine particles are uniformly dispersed in the medium.

Further, when producing a dispersion by melt-mixing the absorbent fine particles and the resin, it is preferable to use a dispersant that does not change color even at the melt-mixing temperature.

[e] Method for producing a dispersion according to the present invention The dispersion according to the present invention is obtained by mixing and dispersing the absorbent fine particles according to the present invention in the liquid medium described above.
The method for dispersing the absorbing fine particles is not particularly limited as long as it is a method for uniformly dispersing the fine particles in the dispersion liquid. Further, a method capable of pulverizing the absorbing fine particles at the same time as dispersing is preferable because it is possible to disperse the absorbing fine particles while controlling the dispersed particle diameter to be the above-described preferable one.
Specific examples include pulverization/dispersion treatment methods for a predetermined time using devices such as bead mills, ball mills, sand mills, paint shakers, and ultrasonic homogenizers. Among them, pulverizing and dispersing with a medium stirring mill such as a bead mill, ball mill, sand mill, paint shaker, etc., which uses medium media such as beads, balls, and Ottawa sand, shortens the time required to obtain the desired dispersed particle size. Therefore, it is more preferable.

If emphasis is placed on reducing light scattering by the absorbing fine particles, the dispersed particle diameter of the absorbing fine particles should be 200 nm or less, preferably 100 nm or less. The reason for this is that if the dispersed particle size of the absorbing fine particles is small, the scattering of light in the visible light wavelength range of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. As a result of the reduced light scattering, it is possible to prevent the dispersion from becoming cloudy and failing to provide clear transparency.
This is because when the dispersed particle size of the absorbing fine particles is 800 nm or less, the geometric scattering or Mie scattering is reduced, resulting in a Rayleigh scattering region. In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter. Therefore, as the dispersed particle diameter is decreased, the scattering is reduced and the transparency is improved. Furthermore, when the dispersed particle diameter is 200 nm or less, the scattered light is extremely reduced, which is preferable, and when it is 100 nm or less, it is more preferable. From the viewpoint of avoiding light scattering, the smaller the dispersed particle size, the better. On the other hand, if the dispersed particle size is 10 nm or more, industrial production is easy.

The dispersed particle diameter can be confirmed by sampling the dispersion liquid and measuring it with various commercially available particle diameter measuring devices. As the particle size measuring device, for example, a known measuring device such as ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method can be used.

[f] Method for producing a dispersion according to the present invention After uniformly mixing the absorbent fine particles according to the present invention, medium resin granules or pellets, and, if necessary, other additives, A masterbatch can be obtained by kneading with a shaft extruder and processing into pellets by a general method of cutting melt-extruded strands. In this case, the shape of the masterbatch may be cylindrical or prismatic. It is also possible to employ a so-called hot cut method in which the molten extrudate is directly cut. In this case, the masterbatch generally has a nearly spherical shape. A masterbatch is an example of a dispersion according to the present invention.

In the manufacturing process of the masterbatch described above, it is preferable to remove the liquid medium contained in the dispersion to an allowable amount remaining in the masterbatch. It is also preferable to use absorbent fine particles obtained by removing a liquid medium from a dispersion liquid containing a dispersant, a liquid resin, etc., as the absorbent fine particles to be mixed with the medium resin in the production process of the masterbatch. Further, by removing the liquid medium from a dispersion containing a dispersing agent, a liquid resin, etc. while applying mechanical processing, it is also possible to use a powdery absorbing fine particle dispersed powder containing the solid content of the dispersion or the liquid resin. preferable. This is because the powder form facilitates mixing of the dispersed powder of the absorbing fine particles and the granular or pellet-shaped medium resin, thereby facilitating the adjustment of the concentration of the absorbing fine particles in the masterbatch with high accuracy. Incidentally, the absorbent fine particle dispersed powder is an example of the dispersion according to the present invention.
By adding the medium resin and kneading the obtained masterbatch, the dispersion concentration of the absorbent fine particles contained in the dispersion can be adjusted while maintaining the dispersed state.

On the other hand, medium resin monomers, oligomers, and uncured liquid medium resin precursors are mixed with absorbent fine particles to obtain a dispersion liquid, and then the monomers and the like are cured by chemical reactions such as condensation and polymerization. good too. For example, when an acrylic resin is used as the medium resin, an acrylic monomer or an acrylic ultraviolet curable resin is mixed with the absorbing fine particles to obtain a dispersion liquid. Then, by filling a predetermined mold or the like with the dispersion and performing radical polymerization, a dispersion using an acrylic resin can be obtained.
When a resin that cures by crosslinking, such as an ionomer resin, is used as the resin medium, a dispersion can be obtained by subjecting the dispersion to a crosslinking reaction, as in the case of using the acrylic resin described above.

Furthermore, a plasticizer dispersion can be obtained by mixing the absorbent fine particles and a liquid plasticizer. The resulting plasticizer dispersion is mixed with a medium resin, and a known heat treatment or the like is applied to remove the liquid medium to an allowable amount to remain in the dispersion, thereby obtaining a dispersion. When a liquid plasticizer is used as the liquid medium, the entire amount of the liquid plasticizer may remain in the dispersion.

Alternatively, any one of the absorbent fine particles, plasticizer dispersion, masterbatch, and absorbent fine particle dispersed powder, a thermoplastic resin, and, if desired, a plasticizer and other additives are kneaded to obtain a kneaded product. From the kneaded product, a sheet-like, board-like, or film-like dispersion molded into a flat or curved surface can be produced by a known extrusion molding method, injection molding method, or the like.

A known method can be used for forming a sheet-like, board-like or film-like dispersion. For example, a calendar roll method, an extrusion method, a casting method, an inflation method, or the like can be used.

[g] Dispersion liquid according to the present invention and use thereof The dispersion liquid according to the present invention is used in various applications utilizing photothermal conversion.
For example, a curable ink composition can be obtained by adding an uncured thermosetting resin after dispersing the absorbent fine particles according to the present invention in an appropriate medium. The curable ink composition is provided on a predetermined substrate and exhibits excellent adhesion to the substrate when cured by being irradiated with electromagnetic waves such as infrared rays.
In addition to the use as a conventional ink, the curable ink composition is applied in a predetermined amount, irradiated with electromagnetic waves such as infrared rays to cure and piled up, and then stereolithographically forming a three-dimensional object. It becomes the optimum curable ink composition for

Also, the dispersion liquid according to the present invention is mixed with a solid medium such as a resin or a polymer monomer to prepare a coating liquid. Using the coating solution to form a coating layer on a transparent substrate selected from a substrate film or a substrate glass by a known method to produce an electromagnetic wave absorbing film or electromagnetic wave absorbing glass in which the absorbing fine particles are dispersed in a solid medium. can be done. An electromagnetic wave absorbing film or electromagnetic wave absorbing glass is an example of a dispersion according to the present invention.

In addition, since the absorbent fine particles according to the present invention have absorption in the infrared region, they absorb a specific wavelength when an infrared laser is irradiated onto the printing surface containing the absorbent fine particles. Therefore, anti-counterfeiting printed matter printed on one side or both sides of a substrate to be printed with an anti-counterfeiting ink containing the absorbing fine particles is irradiated with infrared rays of a specific wavelength and the amount of reflection or transmission can be determined by reading the reflection or transmission. The authenticity of the printed matter can be determined from the difference between the two. An anti-counterfeit printed matter is an example of a dispersion according to the present invention.

Further, the dispersion liquid according to the present invention and a binder component are mixed to produce an ink, the ink is applied on a substrate, the applied ink is dried, and then the dried ink is cured by photothermal treatment. A conversion layer can be formed. The photothermal conversion layer can generate heat only at a desired location with high positional accuracy by irradiation with an electromagnetic wave laser such as infrared rays, and can be applied in a wide range of fields such as electronics, medicine, agriculture, and machinery. be. 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. A photothermal conversion layer is an example of a dispersion according to the present invention.

[h] Dispersion according to the present invention and uses thereof The dispersion according to the present invention can be applied to various uses by processing it into a sheet, board or film. A constituent member of an intermediate layer in which a sheet-shaped, board-shaped or film-shaped dispersion is sandwiched between two or more transparent substrates made of plate glass or plastic material and made of a transparent substrate that transmits at least visible light. By interposing as, it is possible to obtain an electromagnetic wave absorbing laminated structure having an electromagnetic wave absorbing function while transmitting visible light. The electromagnetic wave absorbing intermediate film is an example of the dispersion according to the present invention.

An electromagnetic wave absorbing fiber can be obtained by dispersing the absorbing fine particles according to the present invention in an appropriate medium and incorporating the dispersion on the surface and/or inside of the fiber. With this structure, the electromagnetic wave absorbing fiber efficiently absorbs near-infrared rays from sunlight, etc., due to the inclusion of the absorbing fine particles, and becomes an electromagnetic wave absorbing fiber with excellent heat retention, while at the same time transmitting light in the visible light range. Therefore, it becomes an electromagnetic wave absorbing fiber with excellent 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. An electromagnetic wave absorbing fiber is one example of a dispersion according to the present invention.

Moreover, the film-like or board-like dispersion according to the present invention can be applied to materials used for roofs, exterior walls, and the like of agricultural and horticultural greenhouses. And while ensuring light necessary for photosynthesis of plants in greenhouses for agriculture and horticulture by transmitting visible light, it efficiently absorbs other light such as near-infrared light contained in sunlight to provide heat insulation. It can be used as a heat insulating material for agricultural and horticultural facilities. A thermal insulation material for agricultural and horticultural facilities is an example of the dispersion according to the present invention.

[i] Summary As described above, according to the present invention, it is possible to obtain a resin molded article in which absorbing fine particles are dispersed that stably exhibits excellent heat ray shielding properties even at a high temperature of, for example, 120°C. . That is, it is possible to inexpensively manufacture transparent window materials, roof materials, and the like that can withstand long-term use even in high-temperature environments and exhibit excellent near-infrared absorption effects. In addition, when a molded body obtained by mixing and kneading the dispersion according to the present invention with a transparent resin is used without using glass as a member, impact resistance and weight reduction that cannot be obtained with glass can be achieved. In addition, it can have an excellent near-infrared absorbing effect. Furthermore, the dispersion produced using the dispersion according to the present invention is a method of dry blending the masterbatch produced from the dispersion at the time of molding, or an inexpensive production method such as adding the dispersion directly to the medium. Although it is transparent, it can convert light such as laser light and infrared light into heat, so it works effectively for joining members together.

As a result, members using the present invention can reduce energy consumption in a wide variety of applications, such as reduction in power required for air conditioning such as air conditioners, reduction in fuel consumption/electricity consumption due to weight reduction of moving bodies, and the like. Furthermore, in the past, even in applications such as antibacterial, sterilization, and sterilization, which used methods that are not favorable to the human body, such as the use of ultraviolet lamps, less energy or environmental light such as sunlight and lamp light is used. A zero-energy, transparent antibacterial medium can be realized.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples.
Incidentally, in the measurement of the crystallite size of the absorbing fine particles in the examples and comparative examples, the absorbing fine particles obtained by removing the liquid medium from the dispersion liquid were used. Then, the X-ray diffraction pattern of the absorbing fine particles is measured by a 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 crystallite size was calculated from the obtained X-ray diffraction pattern using the Rietveld method.
In addition, the optical properties of the infrared absorbing sheets according to Examples and Comparative Examples were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and the visible light transmittance and solar transmittance were calculated according to JISR3106. bottom.
The haze in Examples and Comparative Examples was measured according to JIS K7105 using a haze meter (HM-150, manufactured by Murakami Shiki Co., Ltd.).

[Example 1]
Cs/W (molar ratio) = 0.33 hexagonal cesium tungsten bronze powder CWO (YM-01 (registered trademark) manufactured by Sumitomo Metal Mining Co., Ltd.) 5% by mass, 5% by mass of polyacrylate dispersant, and 90% by mass of toluene %, and the resulting mixture was loaded into a paint shaker containing 0.3 mmφ ZrO ₂ beads and subjected to pulverization and dispersion treatment for 10 hours. Then, to 100 parts by weight of the hexagonal cesium tungsten bronze described above, 130 parts by weight of ADEKA STAB CDA-6 (registered trademark) (manufactured by ADEKA Co., Ltd.) represented by the structural formula (4) is added as a metal deactivator. , to obtain a dispersion liquid according to Example 1 by stirring and mixing. Here, when the crystallite size of the absorbing fine particles in the obtained dispersion was measured, it was 32 nm.

The liquid medium was evaporated from the dispersion of Example 1 by vacuum fluidized drying to obtain an absorbent fine particle dispersed powder of Example 1 (sometimes referred to as "dispersed powder" in the present invention). For the vacuum fluidized drying, an Ishikawa type stirring and crushing machine 24P manufactured by Ishikawa Factory Co., Ltd. was used. Moreover, the dispersed powder described above is an example of the dispersion according to the present invention.

The dispersed powder according to Example 1 and the polycarbonate resin were uniformly mixed in a blender so that the concentration of the absorbent fine particles was 0.05% by mass, and then kneaded at 290 ° C. using a twin-screw extruder, followed by a T die. It was then extruded and made into a sheet material having a thickness of 0.75 mm by a calender roll method to obtain an infrared absorbing sheet according to Example 1. Incidentally, the infrared absorbing sheet is an example of the dispersion according to the present invention.
When the optical properties of the obtained infrared absorbing sheet according to Example 1 were measured, the visible light transmittance was 79.6%, the solar transmittance was 48.6%, and the haze was 0.9%.

Subsequently, changes in visible light transmittance and solar transmittance were measured after the infrared absorbing sheet according to Example 1 was held in an air atmosphere at 120° C. for 30 days. The visible light transmittance change was +2.0%, and the solar transmittance change was +2.5%.
From this result, it was found that the infrared absorbing sheet according to Example 1 stably exhibits excellent heat ray shielding properties even at a high temperature of 120°C.
These results are listed in Table 1. Table 1 also shows the results obtained in Examples 2-9 and Comparative Examples 1-2.

[Examples 2 to 5]
Based on 100 parts by weight of hexagonal cesium tungsten bronze powder, 340 parts by weight (Example 2), 680 parts by weight (Example 3), 1020 parts by weight (Example 4), 1360 parts by weight (implementation Example 5) Dispersions and infrared absorbing sheets according to Examples 2 to 5 were obtained in the same manner as in Example 1, except that they were added.
The optical properties of the obtained dispersions and infrared absorbing sheets according to Examples 2 to 5 were evaluated in the same manner as in Example 1. Table 1 shows the production conditions and evaluation results for Examples 2 to 5.
From these results, it was found that the infrared absorbing sheets according to Examples 2 to 5 stably exhibited excellent heat ray shielding properties even at a high temperature of 120°C.

[Example 6]
The dispersion powder according to Example 1 and the polycarbonate resin were mixed so that the amount of the metal deactivator added to 100 parts by weight of the hexagonal cesium tungsten bronze powder was 10000 parts by weight, and the concentration of the absorbing fine particles was 0.05% by mass. After being uniformly mixed in a blender so as to obtain an absorbent fine particle-containing masterbatch, the mixture was melt-kneaded in a twin-screw extruder and the extruded strand was cut into pellets. Incidentally, the absorbing fine particle-containing masterbatch is an example of the dispersion according to the present invention.

10 parts by weight of the absorbing fine particle-containing masterbatch according to Example 6 and 90 parts by weight of polycarbonate resin pellets were dry-blended to form a plate material having a thickness of 10 mm using an injection molding machine. got a plate. Incidentally, the infrared absorbing plate is an example of the dispersion according to the present invention.
The optical properties of the obtained infrared absorption plate according to Example 6 were evaluated in the same manner as in Example 1. Table 1 shows the manufacturing conditions and evaluation results according to Example 6.
From these results, it was found that the infrared absorbing plate according to Example 6 stably exhibits excellent heat ray shielding properties even at a high temperature of 120°C.

[Example 7]
Cs/W (molar ratio) = 0.33 hexagonal cesium tungsten bronze powder (manufactured by Sumitomo Metal Mining Co., Ltd.) 5% by mass, 5% by mass of polyacrylate dispersant, and 90% by mass of toluene are mixed to obtain The resulting mixture was loaded into a paint shaker containing 0.3 mmφ ZrO ₂ beads and subjected to pulverization and dispersion treatment for 10 hours. Then, 340 parts by weight of Adekastab CDA-6 with respect to 100 parts by weight of the hexagonal cesium tungsten bronze described above, and IRGANOX1010 (registered trademark) (BASF SE) shown in the structural formula (5) as a hindered phenol antioxidant. Co., Ltd.) was added and mixed with stirring to obtain a dispersion liquid according to Example 7.

An infrared absorbing sheet according to Example 7 was obtained in the same manner as in Example 1 except that the dispersion according to Example 7 was used instead of the dispersion according to Example 1.
The crystallite size of the absorbing fine particles in the obtained dispersion liquid according to Example 7 and the optical properties of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. Table 1 shows the manufacturing conditions and evaluation results according to Example 7.
From these results, it was found that the infrared absorbing sheet according to Example 7 stably exhibits excellent heat ray shielding properties even at a high temperature of 120°C.

[Example 8]
Example 8 was prepared in the same manner as in Example 7, except that 150 parts by weight of ADEKA STAB 2112 (registered trademark) (manufactured by ADEKA Corporation) represented by the structural formula (6) was used as a phosphorus-based antioxidant instead of IRGANOX 1010. A dispersion liquid and an infrared absorbing sheet according to the above were obtained.
The crystallite size of the absorbing fine particles in the dispersion of Example 8 and the optical properties of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. Table 1 shows the manufacturing conditions and evaluation results according to Example 8.
From these results, it was found that the infrared absorbing sheet according to Example 8 stably exhibits excellent heat ray shielding properties even at a high temperature of 120°C.

[Example 9]
A dispersion liquid and an infrared absorbing sheet according to Example 9 were prepared in the same manner as in Example 2, except that Magneli phase W ₁₈ O ₄₉ was used instead of the hexagonal cesium tungsten bronze powder (manufactured by Sumitomo Metal Mining Co., Ltd.). got
The crystallite size of the absorbing fine particles in the obtained dispersion liquid according to Example 9 and the optical properties of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. Table 1 shows the manufacturing conditions and evaluation results according to Example 9.
From these results, it was found that the infrared absorbing sheet according to Example 9 stably exhibits excellent heat ray shielding properties even at a high temperature of 120°C.

[Comparative Example 1]
A dispersion liquid and an infrared absorbing sheet according to Comparative Example 1 were obtained in the same manner as in Example 1, except that nothing was added instead of Adekastab CDA-6.
In the same manner as in Example 1, the crystallite diameter of the absorbing fine particles in the dispersion and the optical properties of the infrared absorbing sheet obtained in Comparative Example 1 were measured and evaluated. Table 1 shows the manufacturing conditions and evaluation results according to Comparative Example 1.

[Comparative Example 2]
A dispersion liquid and an infrared absorbing sheet according to Comparative Example 2 were obtained in the same manner as in Example 9, except that nothing was added instead of Adekastab CDA-6.
The crystallite diameter of the absorbing fine particles in the dispersion liquid according to Comparative Example 2 and the optical properties of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. Table 1 shows the manufacturing conditions and evaluation results according to Comparative Example 2.

[summary]
The infrared absorbing sheets or infrared absorbing plates produced from the dispersions according to Examples 1 to 9 all have excellent heat ray shielding properties, and even at a high temperature of 120 ° C., the excellent heat ray shielding properties are stably maintained. It turned out to work.

Claims (13)

A particulate dispersion comprising a liquid medium, absorbent particulates dispersed in the medium, and a metal deactivator,
The absorbing fine particles are tungsten oxide fine particles represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≤ z/y ≤ 2.999), and the general formula MxWyOz (where M is H , He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, One or more elements selected from I and Yb, W for tungsten, O for oxygen, 0.001 ≤ x/y ≤ 1, 2.0 ≤ z/y ≤ 3.0) Tungsten oxide fine particles, one or more oxide fine particles selected from
The metal deactivator is a compound represented by the following structural formula (1),
The content of the metal deactivator is 130 parts by weight or more and 10000 parts by weight or less with respect to 100 parts by weight of the absorbent fine particles,
A fine particle dispersion, wherein the absorbent fine particle dispersed powder obtained by removing the liquid medium from the fine particle dispersion is dispersed in a polycarbonate resin .

However, in the structural formula (1), R ₁₀ is an alkylene group having 1 to 20 carbon atoms, an alicyclic group having 5 to 15 carbon atoms, an aralkylene group having 7 to 13 carbon atoms, or an arylene group. Furthermore, as a metal deactivator having a structure different from that of the compound represented by the structural formula (1), one or more stabilizers selected from phosphorus stabilizers, hindered phenol stabilizers, and sulfide stabilizers are added. 2. The fine particle dispersion of claim 1, comprising: The absorbing fine particles are composite tungsten oxide fine particles represented by the general formula MxWyOz, and the M is selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. 3. The fine particle dispersion liquid according to claim 1 or 2, wherein the fine particle dispersion is one or more kinds. 4. The fine particle dispersion liquid according to claim 1 , wherein said absorbing fine particles are composite tungsten oxide fine particles having a hexagonal crystal structure. 5. The fine particle dispersion liquid according to any one of claims 1 to 4, wherein the crystallite diameter of the absorbing fine particles is 1 nm or more and 200 nm or less. 6. The fine particle dispersion liquid according to any one of claims 1 to 5, wherein the surface of said absorbing fine particles is coated with a compound containing one or more elements selected from Si, Ti, Zr and Al. . 7. The fine particle dispersion liquid according to any one of claims 1 to 6, wherein the medium in which the absorbent fine particles are dispersed is a polymer monomer. A particulate dispersion comprising a medium, absorbent particulates dispersed in the medium, and a metal deactivator,
The absorbing fine particles are tungsten oxide fine particles represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≤ z/y ≤ 2.999), and the general formula MxWyOz (where M is H , He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, One or more elements selected from I and Yb, W for tungsten, O for oxygen, 0.001 ≤ x/y ≤ 1, 2.0 ≤ z/y ≤ 3.0) composed of one or more kinds of oxide fine particles selected from tungsten oxide fine particles,
The metal deactivator is a compound represented by the following structural formula (1),
The content of the metal deactivator is 130 parts by weight or more and 10000 parts by weight or less with respect to 100 parts by weight of the absorbent fine particles,
A fine particle dispersion , wherein the medium is a polycarbonate resin .

However, in the structural formula (1), R ₁₀ is an alkylene group having 1 to 20 carbon atoms, an alicyclic group having 5 to 15 carbon atoms, an aralkylene group having 7 to 13 carbon atoms, or an arylene group. Furthermore, as a metal deactivator having a structure different from that of the compound represented by the structural formula (1), one or more stabilizers selected from phosphorus stabilizers, hindered phenol stabilizers, and sulfide stabilizers. 9. The fine particle dispersion according to claim 8, comprising: The absorbing fine particles are composite tungsten oxide fine particles represented by the general formula MxWyOz, and M is selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. 10. The fine particle dispersion according to claim 8 or 9, characterized by being one or more kinds. 11. The fine particle dispersion according to any one of claims 8 to 10, wherein said absorbing fine particles are composite tungsten oxide fine particles having a hexagonal crystal structure. 12. The fine particle dispersion according to any one of claims 8 to 11, wherein the crystallite diameter of the absorbing fine particles is 1 nm or more and 200 nm or less. 13. The fine particle dispersion according to any one of claims 8 to 12, wherein the surface of said absorbing fine particles is coated with a compound containing one or more elements selected from Si, Ti, Zr and Al. .