JP2020172407A - Fine particle dispersing liquid excellent in high temperature stability and fine particle dispersion - Google Patents

Abstract

To provide a dispersion having excellent heat ray shielding characteristics and exhibiting high-temperature stability, and a dispersing liquid for producing the dispersion.SOLUTION: A fine particle dispersing liquid comprises a liquid medium, absorbing fine particles dispersed in the medium, and a metal deactivator, in which the absorbing fine particles are one or more oxide fine particles selected from tungsten oxide fine particles represented by general formula WxOy and composite tungsten oxide fine particles represented by general formula MxWxOy, and the metal deactivator is a metal deactivator having a predetermined structure.SELECTED DRAWING: None

Description

The present invention is a fine particle dispersion liquid in which fine particles are dispersed in a liquid medium (sometimes referred to as "dispersion liquid" in the present invention), which is excellent in high temperature stability, and a fine particle dispersion in which fine particles are dispersed in the medium. (In the present invention, it may be referred to as "dispersion").
Furthermore, the present invention relates to a dispersion liquid and a dispersion containing functional fine particles (sometimes referred to as "absorbent fine particles" in the present invention) that absorb electromagnetic waves typified by light and infrared rays.

While carbon dioxide emissions control is required on a global scale to curb global warming, skyscrapers and automobiles are rapidly increasing in emerging countries. As a result, effective use and control of solar light (sometimes referred to as "sunlight" in the present invention), weight reduction of moving objects such as automobiles, and prevention of falling and scattering of glass and the like at high places. Measures are required.

In the field of effective use of solar light, there are articles using photovoltaic power generation, photoelectric conversion such as solar water heaters, and photothermal conversion.
In the field of solar light control, there are articles such as curtains, blinds and smoke films that block sunlight containing visible light. Furthermore, in recent years, reflective glass such as mirror glass and mirror film that reflects most of the sunlight and transmits a part of it, a reflective film, and an absorbent glass and an absorbent film in which functional fine particles that absorb light are dispersed have been introduced. , Used for window materials of buildings such as houses and buildings, and window materials of automobiles.

In addition to visible light, solar light includes ultraviolet rays and infrared rays. Of the infrared rays contained in this solar radiation, near-infrared rays having a wavelength of 800 to 2500 nm are called heat rays, which cause the temperature to rise by entering the interior or the interior of the vehicle through the above-mentioned opening portion of a building or an automobile. In order to eliminate the temperature rise, a reflective glass, a reflective film, an absorbent glass, and an absorbent film are used for the opening portion.

In the field of weight reduction, it is required to integrate a transparent resin molded body such as polycarbonate resin used for arcades, ceiling domes, carports, etc., which have been conventionally used, with a heat ray shielding function. As a result, there is a rapid increase in demand for a molded product having a heat ray shielding function that shields heat rays while sufficiently taking in visible light and suppresses an internal temperature rise while maintaining brightness.

In the field of measures to prevent falling to high places and scattering, 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 added to a transparent heat ray shielding film that shields heat rays while sufficiently taking in visible light and suppresses the temperature rise in the room while maintaining brightness. Safety measures are becoming more widespread.

Then, in response to the above-mentioned demand, many proposals have been made regarding a molded product having a heat ray shielding function and its joining.
In the production of reflective glass, first, a reflective layer is formed by depositing a metal or metal oxide on a transparent resin film such as polyethylene terephthalate resin (PET) to produce a transparent resin film on which the reflective layer is formed. .. Then, the transparent resin film on which the reflective layer is formed is laminated as an intermediate layer between two or more glass plates.
However, in addition to the method of attaching the film on which the reflective layer is formed to the glass after the formation, there is also a method of forming the reflective layer directly on the glass plate by vapor deposition or the like.
There is also a method of using a transparent resin molded product such as acrylic resin or polycarbonate resin instead of glass.

However, a highly transparent reflective layer that shields a large amount of heat rays and at the same time transmits a large amount of visible light needs to be a multi-layered body of several tens of layers, which itself is expensive. In addition, a complicated process such as adhesion for laminating may be required. As a result, in addition to further increasing the manufacturing cost, there are drawbacks such as peeling of the reflective layer from the glass due to aging.

On the other hand, the reflective film is a transparent resin film such as polyethylene terephthalate resin (PET) that is vapor-deposited with metal or metal oxide to form a reflective layer and then formed into a film, which is used by adhering to existing transparent glass or the like. 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 mixing of air bubbles and generation of fogging, so in order to obtain the desired performance, the construction should be done by a specialized contractor who has the appropriate technology. Often outsourced. The cost required for the construction, together with the cost of the reflective film, hinders the spread of the reflective film.

The absorbent glass is an absorbent layer formed by applying or kneading an organic near-infrared absorber typified by a phthalocyanine compound or an anthraquinone compound onto a transparent resin film such as polyethylene terephthalate resin (PET). 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 the heat rays and near infrared rays, a large amount of an organic near infrared ray absorber is required, and as a result, sufficient transmission of visible light cannot be obtained. In addition, the organic near-infrared absorber is inferior in weather resistance under high temperature and for a long period of time, and when added in a large amount, deterioration such as discoloration and cracks in the intermediate layer occurs.

Here, a method of using inorganic particles such as mica coated with titanium oxide instead of the above-mentioned organic near-infrared absorber has been proposed in Patent Documents 1 and 2, for example. 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 shield the heat propagation from the outside. Therefore, as with the organic near-infrared absorber, it is difficult to obtain sufficient transmission of visible light. At the same time, the impact resistance, toughness, and ductility of the above-mentioned intermediate layer are lowered, and problems and restrictions are caused in the strength and workability.

The absorbent film is a transparent resin film such as polyethylene terephthalate resin (PET) described above, which contains an organic near-infrared absorber and inorganic particles such as mica coated with titanium oxide, and is formed into a film after forming an absorbent layer. , 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 air bubbles and fogging, so in order to obtain the desired performance, the construction should be done by a specialized contractor who has the appropriate technology. 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 the above-mentioned reflective glass / reflective film in combination with the absorbent glass / absorbent film. However, in any combination, like the above-mentioned reflective glass and absorbent film, the manufacturing cost and the construction cost cannot be avoided, which hinders the spread.

On the other hand, functional fine particles that absorb electromagnetic waves typified by light and infrared rays include indium-doped tin oxide (ITO), zinc-doped tin oxide (ATO), hexaboride, tungsten oxide, and composite tungsten oxide.
According to Patent Document 3, the applicant states that among these functional fine particles, the composite tungsten oxide has high transparency in the visible light wavelength range, and large light in a wide wavelength range other than that, particularly a long wavelength infrared wavelength range. It has been disclosed that it has absorption characteristics.

Then, as Patent Document 4, the applicant describes a laminated glass structure in which an intermediate layer or a film containing the fine particles is provided between at least two opposing transparent glass plate-like bodies, various buildings, automobiles, trains, and the like. Disclosed are articles and means for suppressing a temperature rise in a room, a car, etc. due to sunlight incident from openings such as windows and doors provided in an aircraft, etc. while maintaining brightness.

Further, as Patent Document 5, the applicant invented a laser welding light absorbing resin composition for industrial use by 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.
Further, as Patent Document 6, the applicant has described near-infrared absorption as synthetic fibers by mixing functional fine particles such as composite tungsten oxide that absorbs infrared rays from sunlight and the like with acrylic resin, polyester resin and the like for consumer use. The application of fibers and textile products using them for heat generation and heat retention was disclosed.

Further, as Patent Document 7, in response to the above-mentioned request for a molded product having a heat ray shielding function, the applicant has provided a highly heat-resistant dispersant having a high thermal decomposition temperature and the tungsten oxide fine particles and / or composite tungsten fine particles. A means for obtaining a heat ray-shielding transparent resin molded product by mixing, melting and kneading the containing dispersion with a thermoplastic resin has been disclosed.
Further, as Patent Document 8, the applicant has added a metal inactivating agent that captures metal ions to the pressure-sensitive adhesive resin layer containing the tungsten oxide fine particles and / or composite tungsten fine particles, so that the near infrared rays can be used even after long-term use. We have disclosed a near-infrared absorbing filter for PDP that does not reduce the shielding ability.
Further, Patent Document 9 discloses a near-infrared absorbing filter for PDP to which a metal inactivating agent different from Patent Document 8 is added.

Japanese Unexamined Patent Publication No. 6-256541 Japanese Unexamined Patent Publication No. 6-264050 International Publication No. 2005-037932 International Publication No. 2005-0876880 Japanese Unexamined Patent Publication No. 2008-127511 International Publication No. 2006-049025 Japanese Unexamined Patent Publication No. 2011-001551 Japanese Unexamined Patent Publication No. 2010-008818 Japanese Unexamined Patent Publication No. 2009-035615

In the above-mentioned Examples of Patent Document 8, the metal inactivating agent (sometimes referred to as “metal inactivating agent”) has a reduced near-infrared shielding ability and electromagnetic waves in a holding environment at 60 ° C. in an air atmosphere. It is described that it is effective as a means for suppressing deterioration of absorption characteristics.
Further, in Patent Document 9, the metal inactivating agent suppresses the oxidation of the (meth) acrylic resin pressure-sensitive adhesive by the catalytic action of the cesium-tungsten composite oxide fine particles, thereby suppressing the oxidation of the (meth) acrylic resin pressure-sensitive adhesive in a high-temperature and high-humidity environment (meth). The effect of preventing an increase in the transmittance of the acrylic resin in the near infrared region is described, and the effect is described at a high temperature of 80 ° C. or R.I. H. It is stated that the effect is exhibited even in a high humidity environment of 95%.

However, as a result of studies, the present inventors have come up with the idea that as the use of the heat ray-shielding film and the like expands, the heat ray-shielding film and the like are required to have stability at a higher temperature, for example, 120 ° C.
The present invention has been made under the above-mentioned circumstances, and the problem to be solved is that it has excellent heat ray shielding characteristics (infrared absorption characteristics), and the excellent heat ray shielding characteristics are even in a high temperature environment. It is to provide a stable dispersion and dispersion.

The present inventor has conducted diligent studies for the purpose of solving the above-mentioned problems. As a result, the dispersion liquid and the dispersion to which the metal inactivating agent having a predetermined structure is added have excellent heat ray-shielding characteristics, and the excellent heat ray-shielding characteristics are exhibited in the prior art (for example, patent documents) in a high temperature environment. It was found that it was more stable than 8 and 9), and the present invention was completed.

That is, the first invention for solving the above-mentioned problems is a fine particle dispersion liquid containing a liquid medium, absorption fine particles dispersed in the medium, and a metal inactivating agent.
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 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, One or more elements selected from I and Yb, W is tungsten, O is oxygen, and a composite represented by 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) One or more oxide fine particles selected from tungsten oxide fine particles,
The metal inactivating agent is a fine particle dispersion liquid characterized by being a compound represented by the following structural formula (1).
However, in the structural formula (1), R ₁₀ is any one of an alkylene group having 1 to 20 carbon atoms, an alicyclic group having 5 to 15 carbon atoms, and an aralkylene group or an arylene group having 7 to 13 carbon atoms.

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

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

The main components of the dispersion liquid and the dispersion according to the present invention are absorbent fine particles, a medium for dispersing the absorbent fine particles (sometimes referred to as "medium" in the present invention), an ultraviolet absorber, a plasticizer, and a surfactant. Additives such as agents, antistatic agents, coupling agents, and metal inactivating agents, and dispersants for appropriately dispersing absorbed fine particles in a medium.
As the medium of the dispersion liquid, water, an organic solvent, a resin or the like which is liquid at room temperature is used. On the other hand, as the medium of the dispersion, a solid or gel-like inorganic substance, an organic substance, a thermosetting resin, an ultraviolet curable resin or the like is used at room temperature.
Further, as a component of the dispersion liquid and the dispersion, a dispersant can be used as an additive, if necessary.

As the dispersion according to the present invention, various forms such as a film, a plate, a pellet, and a gel are timely selected.
For example, if it is in the form of a film, the dispersion may be applied onto a convenient base material to form a film. The coating method may be any method such as spin coating method, bar coating method, spray coating method, dip coating method, screen coating method, roll coating method, sink coating, etc., as long as the dispersion can be applied flatly, thinly and uniformly. The method of is also acceptable. After applying the dispersion by the above method, the volatile components are volatilized by allowing the dispersion to stand in the air, vacuum, room temperature or heated. When the dispersion liquid contains, for example, an ultraviolet curable resin, the film can be fixed on the substrate by irradiation with ultraviolet rays, and when the thermosetting resin is contained, the film can be further fixed on the substrate to obtain a dispersion. Further, it may be in the form of a patterned film by a coating method by an inkjet method or a 3D printer device.

The dispersion is heated, melted, mixed, dispersed, solidified and pelletized in an extrusion molding machine or a calendar roll molding machine together with an organic resin such as a polycarbonate resin (PC resin) or a polyethylene terephthalate resin (PET resin). Dispersions are obtained by various methods such as a method of obtaining a shape-like or film-like / plate-like dispersion, a method of mixing, dispersing, and solidifying with an injection molding machine or a compression molding machine to obtain a dispersion of a molded product having an arbitrary shape. be able to.

Hereinafter, [a] absorbing fine particles and [b] medium will be described with respect to each component constituting the dispersion or dispersion according to the present invention, the method for producing the dispersion or dispersion, the dispersion or dispersion and its use. , [C] Additive, [d] Dispersant, [e] Method for producing dispersion according to the present invention, [f] Method for producing dispersion according to the present invention, [g] Dispersant according to the present invention and the same. Applications, [h] the dispersion according to the present invention and its applications, and [i] summary will be described in this order.

[A] Absorbing fine particles The absorbing fine particles according to the present invention are tungsten oxide fine particles represented by the general formula WyOz (where W is tungsten and O is oxygen, 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, Yb, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ It is one or more kinds of oxide fine particles selected from the composite tungsten oxide fine particles represented by 3.0).
That is, the absorption fine particles are oxide fine particles of either or both of the above-mentioned tungsten oxide fine particles and composite tungsten oxide fine particles.

The fine particles of the composite tungsten oxide represented by the general formula MxWyOz described above are excellent in durability when they have a hexagonal, tetragonal, or cubic crystal structure, and therefore are selected from the hexagonal, tetragonal, and cubic crystals. It is preferable to include one or more crystal structures.
In particular, one or more elements selected from the Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn elements constituting the hexagonal crystal structure among the elements of M. Fine particles of the composite tungsten oxide containing the above are preferable, and Cs having excellent high electromagnetic wave absorption and excellent transmission in the visible light region having a wavelength of 400 nm to 780 nm is preferable.

The amount x of the M element to be added is preferably 0.001 or more and 1 or less in terms of x / y, and further, the value of x / y theoretically calculated from the hexagonal crystal structure is around 0.33. Is preferable.
On the other hand, the oxygen abundance Z is preferably 2.2 or more and 3.0 or less in terms of z / y. Typical examples include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ , Cs _0.03 Rb _0.30 WO _3. .. However, if the values of x, y, and z fall within the above range, useful electromagnetic wave absorption characteristics can be obtained.

Further, from the viewpoint of exhibiting excellent electromagnetic wave absorption characteristics, the crystallite diameter 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 further preferably 10 nm or more and 70 nm or less. The crystallite diameter is measured by measuring the X-ray diffraction pattern by the powder X-ray diffraction method (θ-2θ method) and analyzing by the Rietveld method. For the measurement of the X-ray diffraction pattern, for example, a powder X-ray diffractometer "X'Pert-PRO / MPD" manufactured by PANalytical Co., Ltd. of Spectris Co., Ltd. can be used.

Further, it is also preferable that the surface of the absorbing fine particles is coated with a compound containing at least one element of Si, Ti, Zr and Al.

[B] Medium Regarding the liquid medium used for the dispersion liquid according to the present invention and the solid or gel medium used for the dispersion, 1. Liquid medium, 2. The solid and gel-like media will be described in this order.

1. 1. Liquid medium The medium of the dispersion according to the present invention is liquid at room temperature, for example, water, an organic solvent such as toluene or hexane, a liquid organic resin such as an epoxy resin or an acrylic resin, a fat or oil, or a liquid for a medium resin. Examples thereof include plasticizers, polymer monomers, and mixtures thereof. The liquid medium is variously selected depending on the dispersion produced by using the dispersion liquid according to the present invention, and is not particularly limited.

Here, as the organic solvent, various solvents such as alcohol-based, ketone-based, hydrocarbon-based, and glycol-based solvents can be selected. Specifically, alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol, and diacetone alcohol,
Ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, etc.
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, and 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 preferable.

As the fats and oils, vegetable fats and oils or plant-derived fats and oils are preferable. Vegetable oils include drying oils such as flaxseed oil, sunflower oil, tung oil, and eno oil, semi-drying oils such as sesame oil, cottonseed oil, rapeseed oil, soybean oil, rice bran oil, and poppy oil, olive oil, palm oil, palm oil, and dehydrated sunflower oil. Non-drying oil such as is used. As the compound derived from vegetable oil, fatty acid monoester, ethers and the like obtained by directly transesterifying the fatty acid of vegetable oil with monoalcohol are used.
In addition, commercially available petroleum-based solvents can also be used as fats and oils. Exxon Mobile Co., Ltd.) and the like.

As the liquid plasticizer for the medium resin, a known liquid plasticizer typified by an organic acid ester type or a phosphoric acid ester type can be used.
This is because, in the dispersion liquid 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.

Here, examples of the liquid plasticizer include plasticizers that are compounds of monovalent alcohols and organic acid esters, ester-based plasticizers such as polyhydric alcohol organic acid ester compounds, and organic phosphoric acid-based plasticizers. Examples thereof include phosphoric acid-based plasticizers, all of which are preferably liquid at room temperature. Of these, a plasticizer, which is an ester compound synthesized from a polyhydric alcohol and a fatty acid, is preferable.

The ester compound synthesized from the polyhydric alcohol and the fatty acid is not particularly limited, and for example, glycols such as triethylene glycol, tetraethylene glycol and tripropylene glycol, and butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid and heptylic acid are used. , N-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonyl acid), decylic acid and other monobasic organic acids obtained by reaction with glycol-based ester compounds. Further, an ester compound of tetraethylene glycol or tripropylene glycol and the above-mentioned monobasic organic substance can also be mentioned.
Of these, fatty acid esters of triethylene glycol such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanate, and triethylene glycol di-2-ethylhexanoate are preferable. ..

The polymer monomer is a monomer that forms a polymer by polymerization or the like, and preferred polymer monomers used in the present invention are methyl methacrylate monomer, accrete monomer, and styrene resin. Examples include monomers.

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

2. Solid or gel-like medium The medium used for the dispersion according to the present invention is a solid or gel-like medium at room temperature. Specifically, various kinds of inorganic compounds such as glass, polymer organic compounds such as polycarbonate resin and PET resin, and the like can be selected.
However, when a styrene ester compound is used as the "[c] additive" described later, the dispersion medium is a polycarbonate resin (PC resin) or acrylic resin having high compatibility with the styrene compound. Polymers such as (PMMA resin), polypropylene resin (PP resin), polyethylene resin (PE resin), polystyrene resin (PS resin), polyamide resin (PA resin), and polyethylene terephthalate resin (PET resin) are preferable.

[C] Additive The purpose of the additive according to the present invention is to improve the weather resistance of the dispersion liquid and the dispersion according to the present invention, and to stably exhibit excellent heat ray shielding characteristics even at a high temperature of, for example, 120 ° C. It is added in.
Regarding the additives according to the present invention, 1. 2. A metal inactivating agent having a predetermined structure. Stabilizers having a structure different from that of the metal inactivating agent will be described in this order.

1. 1. Metal inactivating agent having a predetermined structure The metal inactivating agent used in the present invention is a compound represented by the following structural formula (1), in which R ₁₀ has an alkylene group having 1 to 20 carbon atoms and 5 to 15 carbon atoms. It has an alicyclic group, an aralkylene group having 7 to 13 carbon atoms, or an arylene group.

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 and t-. Examples thereof include a pentylene group, an i-octylene group, a t-octylene group and a 2-ethylhexylene group.
Examples of the alicyclic group having 5 to 15 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a 1-methylcyclopentylene group, a 1-methylcyclohexylene group and a 1-methyl-. Examples thereof include a 4-i-propylcyclohexylene group.

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

Among the metal inactivating agents represented by the structural formula (1), it is particularly preferable that R ₁₀ is an alkylene group having 10 carbon atoms.

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

The amount of the metal inactivating agent added is preferably 10 parts by weight or more and 10,000 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 absorbed fine particles. More preferably, it is 130 parts by weight or more and 350 parts by weight or less.
When the amount of the metal inactivating agent added is 10 parts by weight or more with respect to 100 parts by weight of the absorbed fine particles, excellent heat ray shielding characteristics can be stably exhibited even at a high temperature of, for example, 120 ° C.
On the other hand, when the amount of the metal inactivating agent added is 10,000 parts by weight or less with respect to 100 parts by weight of the absorbed fine particles, the retention characteristics in a high temperature air atmosphere of 120 ° C. are not significantly affected, but the dispersion liquid. It is possible to avoid deterioration of workability and decrease in visible light transmittance due to an increase in viscosity of the particles.

2. Stabilizer having a structure different from that of the metal inactivating agent As the metal inactivating agent according to the present invention, in addition to the compound described in "1. Metal inactivating agent", "1. Metal inactivating agent". A stabilizer having a structure different from that of the compound described in "Agent" can also be added. Examples of the stabilizer having a different structure include hindered phenol-based stabilizers, sulfide-based stabilizers, phosphite esters, and phosphorus-based stabilizers having a phosphorus-based functional group containing trivalent or pentavalent phosphorus. Can be used.
These stabilizers have an effect of capturing radicals generated from a resin in a high temperature holding environment and an effect of decomposing peroxides generated by a 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 inactivating agent to synergistically suppress the deterioration of the electromagnetic wave absorption characteristics of the absorbing fine particles. it is conceivable that.

As an example of the hindered phenolic stabilizer, a compound in which a large group such as a tertiary butyl group is introduced into one position of the phenolic OH group can be preferably mentioned.
As an example of the sulfide-based stabilizer, a compound having divalent sulfur in the molecule used as a sulfur-based colorant inhibitor can be preferably mentioned. Specific examples include ADEKA STAB (registered trademark) AO-412S (manufactured by ADEKA Corporation) shown in the structural formula (2), ADEKA STAB (registered trademark) AO-503 (manufactured by ADEKA Corporation) shown in the structural formula (3), and the like. Can be mentioned.

[D] Dispersant In the dispersion or dispersion according to the present invention, a dispersant can be used in order to uniformly disperse the absorbed fine particles in the medium and / or the dispersion.
Various dispersants can be selected depending on the medium and the dispersion liquid described above. Since the absorbent fine particles described in 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, the functional groups include amino groups, epoxy groups, and carboxyls. It is preferably a dispersant having a group, a hydroxyl group, a sulfo group and the like. These functional groups have the effect of adsorbing on the surface of the absorbed fine particles, preventing the agglomeration of the absorbed fine particles, and uniformly dispersing the absorbed fine particles even in the medium of the dispersion or the dispersion liquid.

As a preferable specific example of the commercially available dispersant, SOLSPERSE (registered trademark) 3000, 9000, 11200, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000SC, 24000GR manufactured by Japan 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®-101, 103, 107, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 154, 161, 162, 163, 164, 165 manufactured by Big Chemie Japan Co., Ltd. , 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.
BASF Japan Ltd. EFKA (registered trademark) 4008, 4046, 4047, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4500, 4510, 4530, 4550, 4560 , 4585, 4800, 5220, 6230, JONCRYL® 67, 678, 586, 611, 680, 682, 690, 819, -JDX5050, etc.
Toagosei Co., Ltd. Alfon (registered trademark) UC-3000, UF-5022, UG-4010, UG-4035, UG-4070, etc.
Ajinomoto Fine-Techno Co., Ltd. Ajispar (registered trademark) PB-711, PB-821, PB-822, and the like can be mentioned.

Among them, an acrylic-styrene copolymer system dispersant having a carboxyl group as a functional group and an acrylic dispersant having an amine-containing group as a functional group are more preferable examples. The dispersant having a group containing an amine as a functional group preferably has a molecular weight of Mw 2000 to 200,000 and an amine value of 5 to 100 mgKOH / g. The dispersant having a carboxyl group preferably has a molecular weight of Mw 2000 to 200,000 and an acid value of 1 to 50 mgKOH / g.

The amount of the dispersant added varies depending on the type of the absorbent fine particles and the dispersant, 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 absorbed fine particles, and the absorbed fine particles are composite tungsten oxide. When the particles are fine particles and the dispersion medium is, for example, a 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 if the amount of the dispersant added is within the above range, the absorbing fine particles are uniformly dispersed in the medium.

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

[E] Method for producing a dispersion liquid according to the present invention The dispersion liquid according to the present invention is obtained by mixing and dispersing the absorbent fine particles according to the present invention in the above-mentioned liquid medium.
The method for dispersing the absorbed 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 absorbed fine particles at the same time as the dispersion is preferable because the absorbed fine particles can be dispersed while being controlled to the above-mentioned preferable dispersed particle size.
Specific examples thereof include a pulverization / dispersion treatment method for a predetermined time using an apparatus such as a bead mill, a ball mill, a sand mill, a paint shaker, and an ultrasonic homogenizer. Among them, pulverizing and dispersing with a medium stirring mill such as a bead mill, a ball mill, a sand mill, and a paint shaker using a medium medium such as beads, balls, and Otawa sand requires a short time to obtain a desired dispersed particle size. Therefore, it is more preferable.

If the reduction of light scattering by the absorbing fine particles is important, the dispersed particle size of the absorbing fine particles is preferably 200 nm or less, preferably 100 nm or less. The reason is that if the dispersed particle size of the absorbed 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 reducing the scattering of the light, it is possible to prevent the dispersion liquid from becoming like frosted glass and losing clear transparency.
This is because when the dispersed particle size of the absorbed fine particles is 800 nm or less, geometric scattering or Mie scattering is reduced and a Rayleigh scattering region is formed. Then, in the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle size, so that the scattering is reduced and the transparency is improved as the dispersed particle size is reduced. Further, when the dispersed particle diameter is 200 nm or less, the scattered light is very small, which is preferable, and when it is 100 nm or less, it is more preferable. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size is small. On the other hand, if the dispersed particle size is 10 nm or more, industrial production is easy.

The dispersed particle size can be confirmed by sampling the dispersion liquid and measuring it with various commercially available particle size 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 Dispersion According to the Present Invention After uniformly mixing the absorbent fine particles according to the present invention, powders or pellets of a medium resin, and other additives as necessary, a vent type uniaxial or two. 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 adopt a so-called hot cut method in which the melt extruded product is directly cut. In this case, the masterbatch generally has a shape close to a spherical shape. The masterbatch is an example of the dispersion according to the present invention.

In the above-mentioned master batch manufacturing process, it is a preferable configuration to remove the liquid medium contained in the dispersion liquid to an amount that allows residue in the master batch. Further, in the master batch manufacturing process, it is also preferable to use the absorbing fine particles obtained by removing the liquid medium from the dispersion liquid containing the dispersant, the liquid resin and the like as the absorbing fine particles to be mixed with the medium resin. It is also possible to use a powdery absorbent fine particle dispersion powder containing the solid content of the dispersion liquid or the liquid resin by removing the liquid medium from the dispersion liquid containing the dispersant or the liquid resin while applying mechanical processing. preferable. This is because the powdery state makes it easier to mix the absorbed fine particle-dispersed powder with the powder or pellet-shaped medium resin, and makes it easier to adjust the concentration of the absorbed fine particles in the masterbatch with high accuracy. The absorbent fine particle dispersion powder is an example of the dispersion according to the present invention.
By adding a medium resin and kneading the obtained masterbatch, the dispersion concentration of the absorbed fine particles contained in the dispersion can be adjusted while maintaining the dispersed state.

On the other hand, the monomer, oligomer, uncured and liquid medium resin precursor of the medium resin and the absorbing fine particles are mixed to obtain a dispersion liquid, and then the monomer or the like is cured by a chemical reaction such as condensation or polymerization. May be good. 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 the dispersion liquid in a predetermined mold or the like and performing radical polymerization, a dispersion using an acrylic resin can be obtained.
When a resin that is cured by cross-linking, such as an ionomer resin, is used as the resin medium, a dispersion can be obtained by subjecting the dispersion to a cross-linking reaction in the same manner as when the acrylic resin described above is used.

Further, a plasticizer dispersion can be obtained by mixing the absorbent fine particles and the liquid plasticizer. A dispersion can be obtained by mixing the obtained plasticizer dispersion with a medium resin and removing the liquid medium to an amount that allows residue in the dispersion by a known heat treatment or the like. When a liquid plasticizer is used as the liquid medium, the entire amount of the liquid plasticizer may remain in the dispersion.

Further, any one of the absorbent fine particles, the plasticizer dispersion liquid, the master batch, and the absorbent fine particle dispersion powder, the thermoplastic resin, and the plasticizer and other additives as desired are kneaded to obtain a kneaded product. From the kneaded product, a sheet-like, board-like or film-like dispersion formed into, for example, a flat surface or a curved surface can be produced by a known extrusion molding method, injection molding method or the like.

A known method can be used as a method for forming the sheet-shaped, board-shaped or film-shaped dispersion. For example, a calender 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 Its Use The dispersion liquid according to the present invention is used for various purposes using photothermal conversion.
For example, a curable ink composition can be obtained by dispersing the absorbent fine particles according to the present invention in an appropriate medium and then adding an uncured thermosetting resin. The curable ink composition is provided on a predetermined base material and has excellent adhesion to the base material when cured by being irradiated with an electromagnetic wave such as infrared rays.
Then, in addition to the conventional use as an ink, the curable ink composition is coated with a predetermined amount, irradiated with electromagnetic waves such as infrared rays to cure the ink composition, and then stacked, and then a stereolithography method for forming a three-dimensional object. It becomes the most suitable curable ink composition.

Further, 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. When a coating layer is formed on a transparent substrate selected from a substrate film or substrate glass by a known method using the coating liquid, an electromagnetic wave absorbing film or electromagnetic wave absorbing glass in which absorbent fine particles are dispersed in a solid medium can be produced. Can be done. The electromagnetic wave absorbing film or the electromagnetic wave absorbing glass is an example of the dispersion according to the present invention.

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

Further, an ink is produced by mixing the dispersion liquid according to the present invention and a binder component, the ink is applied onto a base material, the applied ink is dried, and then the dried ink is cured to generate photothermal heat. A conversion layer can be formed. The photothermal conversion layer can generate heat only at a desired location with high accuracy by irradiating an electromagnetic wave laser such as infrared rays, and can be applied in a wide range of fields such as electronics, medical care, agriculture, and machinery. is there. For example, it can be suitably used as a donor sheet used when forming an organic electroluminescence element by a laser transfer method, a thermal paper for a thermal printer, or an ink ribbon for a thermal transfer printer. The photothermal conversion layer is an example of the dispersion according to the present invention.

[H] Dispersion according to the present invention and its use The dispersion according to the present invention can be applied to various uses by processing it into a sheet shape, a board shape or a film shape. A component of an intermediate layer in which a sheet-shaped, board-shaped or film-shaped dispersion is sandwiched between a plurality of transparent base materials made of a plate glass or plastic material of at least two or more transparent base materials that transmit visible light. It is possible to obtain an electromagnetic wave absorption combined structure having an electromagnetic wave absorption function while transmitting visible light. The electromagnetic wave absorbing interlayer film is an example of the dispersion according to the present invention.

Further, the electromagnetic wave absorbing fiber can be obtained by dispersing the absorbing fine particles according to the present invention in an appropriate medium and containing the dispersion on the surface and / or inside of the fiber. By having this structure, the electromagnetic wave absorbing fiber efficiently absorbs near infrared rays and the like from sunlight and the like by containing the absorbing fine particles, and becomes an electromagnetic wave absorbing fiber having excellent heat retention, and at the same time transmits light in the visible light region. Therefore, it becomes an infrared absorbing fiber with excellent design. As a result, it can be used for various purposes such as winter clothing, sports clothing, stockings, textile products such as curtains, and other industrial textile products that require heat retention. The electromagnetic wave absorbing fiber is an example of the dispersion according to the present invention.

Further, the film-shaped or board-shaped dispersion according to the present invention can be applied to materials used for roofs and outer wall materials of agricultural and horticultural greenhouses. Insulation is achieved by efficiently absorbing other light such as near-infrared light contained in sunlight while ensuring the light required for photosynthesis of plants in the agricultural and horticultural house by transmitting visible light. It can be used as a heat insulating material for agricultural and horticultural facilities. The heat insulating 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 product in which absorbent fine particles that stably exhibit excellent heat ray shielding characteristics are dispersed even at a high temperature of, for example, 120 ° C. .. That is, it is possible to inexpensively manufacture transparent window materials, roofing materials, and the like that can withstand long-term use even in a high temperature environment and exhibit an excellent near-infrared absorption effect. In addition, when a molded product obtained by mixing and kneading the dispersion liquid according to the present invention with a transparent resin without using glass as a member is used, impact resistance and weight reduction that cannot be obtained with glass are obtained. In addition, it can also have an excellent near-infrared absorption effect. Further, the dispersion produced by using the dispersion liquid according to the present invention is a method of dry blending a master batch prepared from the dispersion liquid at the time of molding, or an inexpensive production method such as adding the dispersion liquid directly to a medium. Although it is transparent, it can convert light such as laser light and infrared light into heat, so it also works effectively for joining members.

As a result, the member using the present invention brings about energy reduction in various applications such as reduction of electric power required for air conditioning of an air conditioner and the like, reduction of fuel consumption / electric cost by reducing the weight of a moving body. Furthermore, even in applications such as antibacterial, sterilization, and sterilization, which used to be unfavorable to the human body, such as the use of ultraviolet lamps, less energy or ambient light such as solar light or lamp light is used. It is possible to realize a transparent antibacterial medium with zero energy.

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the following examples.
In the measurement of the crystallite diameter of the absorbed fine particles in Examples and Comparative Examples, the absorbed fine particles obtained by removing the liquid medium from the dispersion liquid were used. Then, the X-ray diffraction pattern of the absorbed 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 Co., Ltd.), and obtained. The crystallite diameter was calculated from the X-ray diffraction pattern obtained by using the Rietveld method.
Further, the optical characteristics of the infrared absorbing sheet according to the examples and the comparative examples were measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.), and the visible light transmittance and the solar radiation transmittance were calculated according to JIS R3106. did.
The haze in Examples and Comparative Examples was measured according to JIS K7105 using a haze meter (HM-150 manufactured by Murakami Color Co., Ltd.).

[Example 1]
Hexagonal cesium tungsten bronze powder CWO (YM-01 (registered trademark) manufactured by Sumitomo Metal Mining Co., Ltd.) with Cs / W (molar ratio) = 0.33 5% by mass, polyacrylate-based dispersant 5% by mass, and toluene 90% by mass. % Was mixed, and the obtained mixed solution was loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 10 hours. Then, 130 parts by weight of ADEKA STAB CDA-6 (registered trademark) (manufactured by ADEKA Corporation) represented by the structural formula (4) is added to 100 parts by weight of the above-mentioned hexagonal cesium tungsten bronze as a metal inactivating agent. , The dispersion according to Example 1 was obtained by stirring and mixing. Here, the crystallite diameter of the absorbed fine particles in the obtained dispersion was measured and found to be 32 nm.

A liquid medium was evaporated from the dispersion liquid according to Example 1 by vacuum flow drying to obtain an absorbent fine particle dispersion powder according to Example 1 (may be referred to as “dispersion powder” in the present invention). For vacuum flow drying, an Ishikawa-type stirring and grinding machine 24P manufactured by Ishikawa Factory Co., Ltd. was used, the atmosphere inside the device was vacuum, the temperature was set to 50 ° C., and the rotation speed of the milk rod was 40 rpm. The above-mentioned dispersion powder is an example of the dispersion according to the present invention.

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

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

[Examples 2 to 5]
With respect to 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) of Adecaster CDA-6. Example 5) A dispersion liquid and an infrared absorbing sheet according to Examples 2 to 5 were obtained in the same manner as in Example 1 except that they were added.
The optical characteristics of the obtained dispersion liquid and infrared absorbing sheet according to Examples 2 to 5 were evaluated in the same manner as in Example 1. The production conditions and evaluation results according to Examples 2 to 5 are shown in Table 1.
From this result, it was found that the infrared absorbing sheets according to Examples 2 to 5 stably exhibited excellent heat ray shielding characteristics even at a high temperature of 120 ° C.

[Example 6]
With respect to the dispersed powder and the polycarbonate resin according to Example 1, the amount of the metal inactivating agent added to 100 parts by weight of the hexagonal cesium tungsten bronze powder was 10,000 parts by weight, and the concentration of the absorbing fine particles was 0.05% by mass. After uniformly mixing with a blender, the mixture was melt-kneaded with a twin-screw extruder, and the extruded strands were cut into pellets to obtain a masterbatch containing absorbent fine particles. The masterbatch containing absorbent particles is an example of the dispersion according to the present invention.

10 parts by weight of the obtained masterbatch containing absorbent particles according to Example 6 and 90 parts by weight of polycarbonate resin pellets were dry-blended to obtain a plate material having a thickness of 10 mm using an injection molding machine, and infrared absorption according to Example 6. I got a plate. The infrared absorbing plate is an example of the dispersion according to the present invention.
The optical characteristics of the obtained infrared absorbing plate according to Example 6 were evaluated in the same manner as in Example 1. The production conditions and evaluation results according to Example 6 are shown in Table 1.
From this result, it was found that the infrared absorbing plate according to Example 6 stably exhibited excellent heat ray shielding characteristics even at a high temperature of 120 ° C.

[Example 7]
Obtained by mixing 5% by mass of hexagonal cesium tungsten bronze powder (manufactured by Sumitomo Metal Mining Co., Ltd.) with Cs / W (molar ratio) = 0.33, 5% by mass of polyacrylate-based dispersant, and 90% by mass of toluene. The mixed solution was loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 10 hours. Then, with respect to 100 parts by weight of the hexagonal cesium tungsten bronze described above, 340 parts by weight of Adecastab CDA-6 and IRGANOX 1010 (registered trademark) (BASF SE) represented by the structural formula (5) as a hindered phenolic antioxidant. The dispersion liquid according to Example 7 was obtained by adding 150 parts by weight of (manufactured by the same company) and stirring and mixing.

An infrared absorbing sheet according to Example 7 was obtained in the same manner as in Example 1 except that the dispersion liquid according to Example 7 was used instead of the dispersion liquid according to Example 1.
The crystallite diameter of the absorbed fine particles in the dispersion liquid according to Example 7 and the optical characteristics of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. Table 1 shows the production conditions and the evaluation results according to the seventh embodiment.
From this result, it was found that the infrared absorbing sheet according to Example 7 stably exhibited excellent heat ray shielding characteristics even at a high temperature of 120 ° C.

[Example 8]
Examples were the same as in Example 7 except that 150 parts by weight of ADEKA STAB 2112 (registered trademark) (manufactured by ADEKA Corporation) shown in structural formula (6) was used as a phosphite-based antioxidant instead of IRGANOX1010. A dispersion liquid according to No. 8 and an infrared absorbing sheet were obtained.
The crystallite diameter of the absorbed fine particles in the obtained dispersion liquid according to Example 8 and the optical characteristics of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. The manufacturing conditions and evaluation results according to Example 8 are shown in Table 1.
From this result, it was found that the infrared absorbing sheet according to Example 8 stably exhibited excellent heat ray shielding characteristics even at a high temperature of 120 ° C.

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

[Comparative Example 1]
The dispersion liquid and the infrared absorbing sheet according to Comparative Example 1 were obtained in the same manner as in Example 1 except that nothing was added in place of Adecaster CDA-6.
The crystallite diameter of the absorbed fine particles in the dispersion liquid according to Comparative Example 1 and the optical characteristics of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. Table 1 shows the production conditions and the 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 in place of Adecaster CDA-6.
The crystallite diameter of the absorbed fine particles in the dispersion liquid according to Comparative Example 2 and the optical characteristics of the infrared absorbing sheet were measured and evaluated in the same manner as in Example 1. Table 1 shows the production conditions and the evaluation results according to Comparative Example 2.

[Summary]
The infrared absorbing sheet or the infrared absorbing plate produced from the dispersion liquid according to Examples 1 to 9 all have excellent heat ray shielding characteristics, and the excellent heat ray shielding characteristics can be stably maintained even at a high temperature of 120 ° C. It turned out to work.

Claims (17)

A fine particle dispersion containing a liquid medium, absorbent fine particles dispersed in the medium, and a metal inactivating agent.
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 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, One or more elements selected from I and Yb, W is tungsten, O is oxygen, and a composite represented by 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) One or more oxide fine particles selected from tungsten oxide fine particles,
The metal inactivating agent is a fine particle dispersion liquid characterized by being a compound represented by the following structural formula (1).
However, in the structural formula (1), R ₁₀ is any one of an alkylene group having 1 to 20 carbon atoms, an alicyclic group having 5 to 15 carbon atoms, and an aralkylene group or an arylene group having 7 to 13 carbon atoms. The fine particle dispersion according to claim 1, wherein the content of the metal inactivating agent is 10 parts by weight or more and 10000 parts by weight or less with respect to 100 parts by weight of the absorbed fine particles. Further, as a metal inactivating agent having a structure different from that of the compound represented by the structural formula (1), one or more kinds of stabilizers selected from phosphorus-based stabilizers, hindered phenol-based stabilizers, and sulfide-based stabilizers are used. The fine particle dispersion according to any one of claims 1 or 2, which comprises. 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. The fine particle dispersion liquid according to any one of claims 1 to 3, wherein the number of the fine particle dispersion liquid is one or more. The fine particle dispersion liquid according to any one of claims 1 to 4, wherein the absorbing fine particles are composite tungsten oxide fine particles having a hexagonal crystal structure. The fine particle dispersion liquid according to any one of claims 1 to 5, wherein the crystallite diameter of the absorbed fine particles is 1 nm or more and 200 nm or less. The fine particle dispersion according to any one of claims 1 to 6, wherein the surface of the absorbing fine particles is coated with a compound containing at least one element of Si, Ti, Zr, and Al. .. The fine particle dispersion liquid according to any one of claims 1 to 7, wherein the medium for dispersing the absorbed fine particles is a polymer monomer. A fine particle dispersion containing a medium, absorption fine particles dispersed in the medium, and a metal inactivating agent.
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 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, One or more elements selected from I and Yb, W is tungsten, O is oxygen, and a composite represented by 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) Consists of one or more oxide fine particles selected from tungsten oxide fine particles,
The metal inactivating agent is a fine particle dispersion characterized by being a compound represented by the following structural formula (1).
However, in the structural formula (1), R ₁₀ is any one of an alkylene group having 1 to 20 carbon atoms, an alicyclic group having 5 to 15 carbon atoms, and an arylene or arylene group having 7 to 13 carbon atoms. The fine particle dispersion according to claim 9, wherein the content of the metal inactivating agent is 10 parts by weight or more and 10000 parts by weight or less with respect to 100 parts by weight of the absorbed fine particles. Further, as a metal inactivating agent having a structure different from that of the compound represented by the structural formula (1), one or more kinds of stabilizers selected from phosphorus-based stabilizers, hindered phenol-based stabilizers, and sulfide-based stabilizers. The fine particle dispersion according to any one of claims 9 or 10, wherein the fine particle dispersion comprises. 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. The fine particle dispersion according to any one of claims 9 to 11, characterized in that there is one or more types. The fine particle dispersion according to any one of claims 9 to 12, wherein the absorbing fine particles are composite tungsten oxide fine particles having a hexagonal crystal structure. The fine particle dispersion according to any one of claims 9 to 13, wherein the crystallite diameter of the absorbed fine particles is 1 nm or more and 200 nm or less. The fine particle dispersion according to any one of claims 9 to 14, wherein the surface of the absorbing fine particles is coated with a compound containing at least one element of Si, Ti, Zr, and Al. .. The fine particle dispersion according to any one of claims 9 to 15, wherein the medium is a polymer. The fine particle dispersion according to any one of claims 9 to 16, wherein the medium is a polycarbonate resin.