JP5120661B2 - Laminated structure - Google Patents

Description

  The present invention relates to a laminated structure having a solar radiation shielding function and an ultraviolet shielding function, which is used for vehicles such as automobiles, for buildings, and for window materials for aircraft.

  Conventionally, as safety glass used for automobiles and the like, a laminated glass is formed by sandwiching a solar radiation shielding film between two sheets of glass, and the solar energy incident by the laminated glass is cut off, thereby cooling load and heat of people. The thing for the purpose of the reduction of a feeling is proposed.

  For example, Patent Document 1 discloses a laminated glass in which a soft resin layer containing a heat ray shielding metal oxide made of tin oxide or indium oxide having a fine particle diameter of 0.1 μm or less is interposed between a pair of plate glasses. It is disclosed.

  In Patent Document 2, Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, and Ta are provided between at least two plate glasses. Laminated glass formed by providing an intermediate layer in which a metal of W, V, Mo, an oxide, a nitride, a sulfide of the metal, a dope of Sb or F, or a composite thereof is dispersed. It is disclosed.

  In Patent Document 3, an intermediate layer composed of three layers is provided between at least two transparent glass plates, and the second intermediate layer of the intermediate layers is Sn, Ti, Si, Zn, Zr. , Fe, Al, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo, metal oxide, nitride, sulfide, or Sb or F doping In addition, a laminated glass in which a product or a composite thereof is dispersed and an intermediate layer between the first layer and the third layer is used as a resin layer has been proposed.

In addition, in the patent document 4, the applicant has disclosed an intermediate layer containing fine particles having solar radiation shielding function between two laminated plates selected from plate glass, resin board, and resin board containing fine particles having solar radiation shielding function. The laminated structure for solar radiation shielding, wherein the fine particles having the solar radiation shielding function have a general formula W _y O _z (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2. 999) and / or general formula M _x W _y O _z (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, T One or more elements selected from i, Nb, V, Mo, Ta, and Re, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3 .0), a solar radiation shielding laminated structure having an excellent solar radiation shielding effect, which is composed of fine particles of composite tungsten oxide represented by.

  Further, Patent Document 5 has at least one heat shielding layer and at least one ultraviolet shielding layer, the thermal shielding layer contains tin-doped indium oxide fine particles having an average particle size of 80 nm or less, and the ultraviolet shielding layer includes An interlayer film for laminated glass containing at least one of zinc oxide and / or titanium oxide and an organic ultraviolet absorber has been proposed.

JP-A-8-217500 (paragraph 0018) JP-A-8-259279 (paragraph 0012) JP-A-10-297945 (paragraph 0018) International Publication WO2005 / 087680 JP-A-2005-206453

However, according to studies by the present inventors, the conventional laminated glasses described in Patent Documents 1 to 3 have a problem that the solar radiation shielding function is not sufficient when high visible light transmittance is required. Was. Moreover, although the interlayer film for laminated glass described in Patent Document 5 also has an ultraviolet shielding function, it has not yet reached an ultraviolet shielding function while maintaining a high visible light transmittance.
The present invention has been made under such circumstances, and an object of the present invention is to provide a laminated structure having a high solar radiation shielding function and an ultraviolet shielding function and having a small haze value. .

In order to solve the above problems, the present inventors have conducted extensive research.
As a result, fine particles of tungsten oxide represented by the general formula W _y O _z (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999) / Or hexagonal crystal represented by the general formula M _x W _y O _z (W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0), The inventors have come up with fine particles of a complex oxide having one or more crystal structures of tetragonal, cubic and monoclinic.
On the other hand, as fine particles having ultraviolet shielding function, with crystallite diameter 15Nm～20nm, a specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19Nm～41nm, and X-ray diffraction (101) The inventors have conceived zinc oxide fine particles having a peak half-value width of 0.55 or less.
Then, by using the fine particles having the solar radiation shielding function and the fine particles having the ultraviolet radiation shielding function in combination, a laminated structure having a high solar radiation shielding function and an ultraviolet radiation shielding function and having a small haze value can be manufactured. As a result, the present invention has been completed.

That is, the first invention according to the present invention is:
An intermediate layer having a resin sheet and / or a resin film as an intermediate film, including fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function;
Solar radiation sandwiched between laminated plates selected from sheet glass, resin board not containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function, resin board containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function A laminated structure having a shielding function and an ultraviolet shielding function,
The fine particles having solar radiation shielding function are tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or 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 One or more elements selected from the above, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) , Cubic and monoclinic crystal structures with one or more crystal structures It is fine particles of Gusuten oxide,
Fine particles having the ultraviolet shielding function, crystallite diameter 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19nm~41nm, (101) in X-ray diffraction peaks of the half width Is a zinc oxide fine particle of 0.55 or less.
The second invention is
An intermediate layer having a resin sheet and / or a resin film as an intermediate film, including fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function,
A laminated board that is a resin board that does not have at least the intermediate layer, has a solar radiation shielding function including fine particles having a solar radiation shielding function, or has a ultraviolet radiation shielding function including fine particles having an ultraviolet radiation shielding function;
A laminated board selected from a sheet glass, a resin board not containing fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function, a resin board containing fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function,
A laminated structure having a solar radiation shielding function and an ultraviolet shielding function sandwiched therebetween,
The fine particles having solar radiation shielding function are tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or 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 One or more elements selected from the above, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) , Cubic and monoclinic crystal structures with one or more crystal structures It is fine particles of Gusuten oxide,
Fine particles having the ultraviolet shielding function, crystallite diameter 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19nm~41nm, (101) in X-ray diffraction peaks of the half width Is a zinc oxide fine particle of 0.55 or less.

The third invention is
A laminated board selected from a sheet glass, a resin board that does not contain fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function, and a resin board containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function. A board,
In the case where the one laminated plate is a resin board containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function, the other laminated plate is made of plate glass, fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function. A laminated board selected from a resin board not containing, a fine particle having a solar radiation shielding function and / or a resin board containing a fine particle having an ultraviolet shielding function,
In the case where the one laminated plate is a resin board containing fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function, the other laminated plate has at least the one laminated plate not having a solar radiation shielding function. A laminated board that is a resin board that includes a fine particle having a solar radiation shielding function or a fine particle having an ultraviolet shielding function and that has an ultraviolet shielding function;
In the case where the one laminated plate is a plate glass or a resin board that does not contain fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function, the other laminated plate includes the fine particles having a solar radiation shielding function and is shielded from sunlight. A laminated board that is a resin board having a function and containing a fine particle having an ultraviolet shielding function and having an ultraviolet shielding function;
Solar radiation shielding function in which an intermediate layer having a resin sheet and / or a resin film is sandwiched between the one laminated board and the other laminated board, which does not contain fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function. And a laminated structure having an ultraviolet shielding function,
The fine particles having solar radiation shielding function are tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or 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 One or more elements selected from the above, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) , Cubic and monoclinic crystal structures with one or more crystal structures It is fine particles of Gusuten oxide,
Fine particles having the ultraviolet shielding function, crystallite diameter 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19nm~41nm, (101) in X-ray diffraction peaks of the half width Is a zinc oxide fine particle of 0.55 or less.

The fourth invention is:
The laminated structure according to any one of the first to third inventions, wherein a particle diameter of the fine particles having the solar radiation shielding function is 1 nm or more and 800 nm or less.

The fifth invention is:
In the powder color according to the L * a * b * color system of the tungsten oxide fine particles and the composite tungsten oxide fine particles, L * is 25 to 80, a * is -10 to 10, and b * is -15. The laminated structure according to any one of the first to fourth inventions, which is within a range of 15.

The sixth invention is:
Fine particles having the solar radiation shielding function,
Fine particles of the tungsten oxide and / or fine particles of the composite tungsten oxide;
Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, At least one selected from oxide fine particles, composite oxide fine particles, or boride fine particles containing one or more elements selected from Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca. The laminated structure according to any one of the first to fifth inventions, wherein the laminated structure is a mixture with fine particles of seeds.

The seventh invention
The tungsten oxide fine particles and / or the composite tungsten oxide fine particles, and the Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, Including one or more elements selected from In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca A mixing ratio of at least one kind of fine particles selected from oxide fine particles, composite oxide fine particles or boride fine particles is in a range of 95: 5 to 5:95 by weight . The laminated structure according to the invention .

The eighth invention
The fine particles having an ultraviolet shielding function are zinc oxide fine particles surface-treated with a surface treatment agent containing one or more elements selected from Si, Al, Zr, and Ti . A laminated structure according to any one of the inventions .

The ninth invention
The laminated structure according to any one of the first to eighth inventions, wherein the fine particles having an ultraviolet shielding function contain one or more elements selected from Si, Al, Zr, and Ti. is there.

The tenth invention is
The first to ninth inventions, wherein the resin sheet and / or the resin film are a resin sheet and / or a resin film selected from a resin having a vinyl group, a polycarbonate resin, an acrylic resin, and a polyethylene terephthalate resin. The laminated structure according to any one of the above .

The eleventh invention is
The laminated structure according to the tenth invention, wherein the resin having a vinyl group is polyvinyl butyral or an ethylene-vinyl acetate copolymer.

The twelfth invention
The intermediate layer has one or two or more laminated intermediate films,
The laminated structure according to any one of the first and second inventions , wherein the fine particles having solar radiation shielding function and / or the fine particles having ultraviolet ray shielding function are dispersed in at least one layer of the intermediate film. It is.

The thirteenth invention
A shielding layer containing fine particles having the solar radiation shielding function and / or fine particles having an ultraviolet shielding function, which are formed on at least one inner surface of the laminated plate sandwiching the intermediate layer;
The laminated structure according to any one of the first to twelfth inventions , comprising an intermediate film laminated on the shielding layer.

The fourteenth invention is
In a ductile shielding resin film in which a shielding layer containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function is formed on one side of a resin film having ductility, or in the resin film having ductility, In either the first or second invention, the ductile resin film in which fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function are dispersed is sandwiched between laminated interlayer films. It is the alignment structure of description .

The fifteenth invention
The intermediate layer is
One or two or more laminated intermediate films, an adhesive layer, a shielding layer containing the fine particles having the solar radiation shielding function and / or the fine particles having an ultraviolet shielding function, and a release layer were laminated in order. Having a laminate,
The adhesive layer adheres to the inner surface of the one laminated plate,
The peeling layer is a laminated structure according to any one of the first and second inventions , wherein the peeling layer is in contact with the laminated intermediate film of one layer or two or more layers.

The sixteenth invention is
The interlayer according to the third invention is characterized in that the intermediate layer has an intermediate film which is laminated with one layer or two or more layers and which does not contain fine particles having solar radiation shielding function and fine particles having ultraviolet ray shielding function. It is a structure.

  The laminated structure according to the present invention having such a configuration has a high solar radiation shielding function and an ultraviolet shielding function, and has a small haze value, and is therefore optimal for vehicles such as automobiles, for construction, for aircraft window materials, etc. Yes, industrially useful.

(Α) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (α-1), and (β) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (β-1). (Α) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (α-2), and (β) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (β-2). (Α) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (α-3), and (β) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (β-3). (Α) is a schematic diagram of a cross-sectional view of a mating structure according to an embodiment (α-4), and (β) is a schematic diagram of a cross-sectional view of the mating structure according to an embodiment (β-4). (Α) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (α-5), and (β) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (β-5). (Α) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (α-6), and (β) is a schematic diagram of a cross-sectional view of the mating structure according to the embodiment (β-6). It is a schematic diagram of a sectional view of a mating structure according to an embodiment (β-7).

<1>. Sheet glass or laminated board of resin board not containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function (in the present invention, sometimes referred to as “laminated board <1>” not containing fine particles).
<2>. Resin board laminated plate containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function (in the present invention, sometimes referred to as “laminated plate <2>” containing fine particles).
<3>. Resin board laminated board containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function (in the present invention, sometimes referred to as “laminated board containing fine particles <3>”).
<5>. An intermediate layer according to embodiments (α-1) and (β-1) described later (in the present invention, it may be described as “intermediate layer <5>”).
<6>. An intermediate layer according to embodiments (α-2) and (β-2) described later (in the present invention, it may be described as “intermediate layer <6>”).
<7>. An intermediate layer according to embodiments (α-3) and (β-3) described later (in the present invention, it may be described as “intermediate layer <7>”).
<8>. An intermediate layer according to embodiments (α-4) and (β-4) described later (in the present invention, it may be described as “intermediate layer <8>”).
<9>. An intermediate layer according to embodiments (α-5) and (β-5) described later (in the present invention, it may be referred to as “intermediate layer <9>”).
<10>. An intermediate layer according to embodiments (α-6) and (β-6) described later (in the present invention, it may be described as “intermediate layer <10>”).
<11>. An intermediate layer according to an embodiment (β-7) described later (in the present invention, it may be referred to as “intermediate layer <11>”).
<A>. Resin sheet containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet ray shielding function (in the present invention, sometimes referred to as “resin sheet containing fine particles <A>”).
<A0>. Resin sheet containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function (in the present invention, sometimes referred to as “resin sheet containing fine particles <A0>”).
<A '>. Resin sheet containing fine particles having solar radiation shielding function (in the present invention, it may be referred to as “resin sheet <A ′> containing fine particles having solar radiation shielding function”).
<A ''>. Resin sheet containing fine particles having an ultraviolet shielding function (in the present invention, it may be referred to as “resin sheet containing fine particles having an ultraviolet shielding function <A ″>”).
<B>. Resin sheet not containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function (in the present invention, sometimes referred to as “resin sheet not containing fine particles <B>”).
<C>. Shielding layer containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function (in the present invention, sometimes referred to as “shielding layer containing fine particles <C>”).
<C0>. A shielding layer containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function (in the present invention, sometimes referred to as “shielding layer containing fine particles <C0>”).
<C ′>. A shielding layer containing fine particles having a solar radiation shielding function (in the present invention, sometimes referred to as “shielding layer having a solar radiation shielding function <C ′>”).
<C ''>. A shielding layer containing fine particles having an ultraviolet shielding function (in the present invention, it may be referred to as “shielding layer having an ultraviolet shielding function <C ″>”).
<D>. Ductile resin film (In the present invention, it may be referred to as “ductile resin film <D>”.)
<E>. Adhesive layer (In the present invention, it may be described as “adhesive layer <E>”)
<F>. Release layer (in the present invention, it may be described as “release layer <F>”)

  Hereinafter, with regard to the embodiment of the present invention, first, the fine particles having the solar radiation shielding function and the fine particles having the ultraviolet radiation shielding function and the manufacturing method thereof will be described, and then the fine particles having the solar radiation shielding function and the fine particles having the ultraviolet radiation shielding function. The used laminated structure will be described in detail.

[Fine particles with solar radiation shielding function and fine particles with ultraviolet shielding function]
(1) Fine particles having solar radiation shielding function The fine particles having the solar radiation shielding function according to the present invention have a general formula W _y O _z (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999). And / or general formula M _x W _y O _z (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, one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) hexagonal crystal, tetragonal crystal, cubic A nanoparticles of composite tungsten oxide having any one or more of the crystal structure of monoclinic.

The composition range of the tungsten and oxygen is such that the composition ratio of oxygen to tungsten is preferably 2.2 or more and 2.999 or less when the tungsten oxide fine particles that are the material having the solar radiation shielding function are described as W _y O _z. It is. If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a crystal phase of WO ₂ that is not intended in the material having the solar radiation shielding function, and the chemical stability as the material. Can be obtained. Therefore, the tungsten oxide fine particles can be applied as a material having an effective solar radiation shielding function. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated, and the material has an efficient solar radiation shielding function.

Further, when the tungsten oxide fine particles are represented by the general formula W _y O _z , the magnetic phase having a composition ratio represented by 2.45 ≦ z / y ≦ 2.99 is chemically stable, and the near infrared Since the region has good absorption characteristics, it is more preferable as a material having a solar radiation shielding function. For example, examples of the tungsten oxide include W ₁₈ O ₄₉ , W ₂₀ O ₅₈ , and W ₄ O ₁₁ .

  Further, to the tungsten oxide fine particles, element M (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) is added to form composite tungsten oxide fine particles, and free electrons are generated in the composite tungsten oxide fine particles. Absorption characteristics derived from free electrons are expressed in the infrared region, which is preferable because it is effective as a near-infrared absorbing material having a wavelength of around 1000 nm.

Moreover, a more efficient infrared shielding material can be obtained by using the composite tungsten oxide fine particles in combination with the above-described control of the amount of oxygen and addition of an element that generates free electrons. A general formula of a material having a solar radiation shielding function that combines the control of the amount of oxygen and the addition of an element that generates free electrons is expressed as M _x W _y O _z (where M is the M element, W is tungsten, O Is oxygen), any one of hexagonal, tetragonal, cubic, and monoclinic crystals satisfying the relationship of 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0 Composite tungsten oxide fine particles having the above crystal structure are preferred.

  First, the value of x / y indicating the amount of element M added will be described. If the value of x / y is larger than 0.001, a sufficient amount of free electrons is generated, and the intended infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding efficiency also increases, but the effect is saturated when the value of x / y is about 1. Moreover, if the value of x / y is 1 or less, it is preferable because an impurity phase can be avoided in the material having the solar radiation shielding function. From this viewpoint, the value of x / y is more preferably 0.01 to 0.5, and further preferably 0.1 to 0.4.

The element 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, and Re are preferably at least one selected from the group consisting of
Next, the value of z / y indicating the control of the oxygen amount will be described. Regarding the value of z / y, in the composite tungsten oxide material expressed by M _x W _y O _z , the same mechanism as that of the tungsten oxide material expressed by W _y O _z described above works, Even in the case of z / y ≦ 3.0, there is a supply of free electrons depending on the amount of the element M described above. Accordingly, the composition represented by preferably 2.2 ≦ z / y ≦ 3.0, more preferably 2.2 ≦ z / y ≦ 2.99, and still more preferably 2.45 ≦ z / y ≦ 2.99. Hexagonal crystals, tetragonal crystals, cubic crystals, and monoclinic crystals having a ratio are more preferable as an infrared shielding material because they are chemically stable and have good absorption characteristics in the near infrared region.

  Since the material having a solar radiation shielding function containing the tungsten oxide fine particles and / or the composite tungsten oxide fine particles according to the present invention absorbs a large amount of light in the near infrared region, particularly near the wavelength of 1000 nm, the transmitted color tone is blue. There are many things which become the color of the system. The particle size of the fine particles having the solar radiation shielding function can be appropriately selected depending on the purpose of use. First, when using for the application which maintained transparency, it is preferable to have a particle diameter of 800 nm or less. This is because particles smaller than 800 nm do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently maintain transparency.

In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles.
When importance is attached to the reduction of scattering by particles, the particle diameter is 200 nm or less, preferably 100 nm or less. The reason for this is that if the particle diameter of the particles is small, the scattering of light in the visible light range of 400 nm to 780 nm due to geometrical scattering or Mie scattering is reduced. This is because it is possible to avoid the loss of sex. That is, when the particle diameter is 200 nm or less, the geometric scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. This is because in the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the particle diameter is reduced. Furthermore, when the particle diameter is 100 nm or less, the scattered light is preferably extremely small. From the viewpoint of avoiding light scattering, a smaller particle diameter is preferable, and industrial production is easy if the particle diameter is 1 nm or more.

  By appropriately selecting the particle diameter within the above-mentioned range, the haze value of the solar shading material fine particle dispersion in which the solar shading material fine particles are dispersed in the medium has a visible light transmittance of 85% or less and a haze value of 30%. It can be as follows. When the haze value is 30% or less, it is possible to avoid the transparent substrate coated with the solar shading material fine particle dispersion from becoming cloudy glass, and clear transparency can be obtained.

  Moreover, it is preferable from a viewpoint of a weather resistance improvement that the surface of the fine particle which exhibits the solar radiation shielding function of this invention is coat | covered with the surface treating agent containing 1 or more types of elements of Si, Ti, Zr, and Al.

In order to obtain a desired laminated structure, the powder color of the tungsten oxide fine particles and composite tungsten oxide fine particles is an L ^* a ^* b ^* color system recommended by the International Commission on Illumination (CIE). In the powder color in (JIS Z 8729), it is desirable to satisfy the conditions that L ^* is 25 to 80, a ^* is -10 to 10, and b ^* is -15 to 15.

Here, the reason why the solar shading fine particles according to the present invention have the powder color and exhibit preferable optical characteristics will be briefly described. First, the interaction between general light and electrons in a substance will be explained. A substance has a specific plasma frequency, light having a longer wavelength than this frequency is reflected, and light having a shorter wavelength is transmitted. Are known. The plasma frequency ωp is expressed by equation (1).
ωp ² = nq ² / εm... Equation (1)
Here, n is the conduction electron density, q is the charge of the electron, ε is the dielectric constant, and m is the effective mass of the electron.

As is clear from the equation (1), the plasma frequency increases as the conduction electron density of the substance increases, so that even light on the shorter wavelength side is reflected. Since the conduction electron density is 1022 / cm ³ for metals, the reflectance is already high in the visible light region for metal, but in the case of tungsten oxide, visible light is transmitted and the absorption rate is increased from the near infrared region. Oxides can be used as solar shading materials.

On the other hand, when the tungsten oxide fine particles are treated with a reducing gas, the powder color changes from light yellow to yellowish green to dark blue to dark blue, and at the same time, the electrical resistance value of the green compact also decreases. This is presumably because oxygen vacancies were generated in the fine particles by treating the tungsten oxide fine particles with a reducing gas, thereby increasing free electrons in the fine particles. That is, it is considered that there is a close relationship between the powder color of the tungsten oxide fine particles, the conduction electron density, and the plasma frequency.

  Further, the tungsten oxide fine particles and / or the composite tungsten oxide fine particles, and Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, At least one selected from the group consisting of Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca At least one kind of fine particles selected from oxide fine particles, composite oxide fine particles, and boride fine particles composed of the above elements are mixed, and the mixing ratio is set in the range of 95: 5 to 5:95 by weight ratio. Are also preferred as fine particles having a solar radiation shielding function.

  If the mixing ratio is 95: 5 or less, the amount of tungsten oxide fine particles and / or composite tungsten oxide fine particles used can be reduced, and a cost reduction effect can be expected. On the other hand, if this mixing ratio is 5:95 or more, a sufficient solar radiation shielding function can be expected.

(2) fine particles having an ultraviolet shielding function according to the microparticles present invention having the ultraviolet shielding function, crystallite diameter 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter in 19nm~41nm And zinc oxide fine particles having a (101) peak half-value width of 0.55 or less in X-ray diffraction.

In the fine particles having an ultraviolet shielding function according to the present invention, the crystallite diameter, the specific surface area, the average particle diameter, and the half-value width of the X-ray peak are within the above ranges, thereby exhibiting transparency and an excellent ultraviolet shielding function. .
For example, when the average particle size is 19 nm or more, the ultraviolet ray shielding function is sufficiently secured, and it is avoided that the use amount of ultraviolet ray shielding fine particles necessary for exhibiting the desired ultraviolet ray shielding function is increased. It is preferable. On the other hand, when the particle diameter is 41 nm or less, the haze value when the laminated structure is obtained can be kept low.
The specific surface area of the fine particles having an ultraviolet shielding function according to the present invention was measured using a Macsorb manufactured by Mountec Co., and the average particle size was a value determined by the following equation (2).
d = 6 / ρ · S... Formula (2)
Here, d: particle diameter, ρ: true density, S: specific surface area.

  In addition, the ultraviolet shielding material fine particles used in the present invention contain at least one element of Si, Al, Zr, and Ti in order to suppress the photocatalytic activity and improve the dispersibility in the transparent resin. It is important that the surface treatment is performed with the contained surface treatment agent. Specifically, for example, an ultraviolet shielding material used in the present invention using at least one surface treatment agent selected from a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent. It is preferable to surface-treat the fine particles.

  As these surface treatment agents, those having an alkoxyl group having an affinity and forming a bond with the surface of the zinc oxide fine particles and an organic functional group having an affinity for the transparent resin are used. Examples of the alkoxyl group include a methoxy group, an ethoxy group, and an isopropoxyl group, but are not particularly limited as long as they can undergo hydrolysis and form a bond with the surface of the zinc oxide fine particles. Examples of the organic functional group include alkyl groups, vinyl groups, γ- (2-aminoethyl) aminopropyl groups, γ-glycidoxypropyl groups, γ-anilinopropyl groups, γ-mercaptopropyl groups, and γ-methacryloxy groups. However, it is not particularly limited as long as it has an affinity for the transparent resin.

  Further, for the purpose of improving the dispersibility of the zinc oxide fine particles in the transparent resin, it is possible to use an organic polymer dispersant in combination with the surface treatment agent.

  The blending ratio of the zinc oxide fine particles and the surface treatment agent in the present invention is preferably 0.05 ≦ X ≦ 10 (where X = weight of surface treatment agent added / weight of zinc oxide fine particles added). If the ratio of the said compounding ratio is 10 or less, the mechanical characteristic and weather resistance of the transparent resin molding obtained are preferable, and it is preferable. On the other hand, if the ratio of the blending ratio is larger than 0.05, the surface of the zinc oxide fine particles can be sufficiently treated, so that the dispersibility of the zinc oxide fine particles is ensured, and the transparency of the obtained transparent resin molded product is excellent. Preserved and preferred.

  The zinc oxide fine particles used in the present invention contain one or more elements selected from Si, Al, Zr and Ti in advance in order to suppress grain growth when the zinc oxide fine particle precursor is fired. Is also preferable. With this configuration, the zinc oxide fine particles used in the present invention can maintain the fine particle state even after firing. The raw material compounds as the Si source, Al source, Zr source and Ti source are not particularly limited.

The content of the zinc oxide fine particles in the present invention is preferably in the range of 0.01% by weight to 30% by weight, and more preferably in the range of 0.05% by weight to 10% by weight.
By making the content of zinc oxide fine particles 30% by weight or less, the zinc oxide fine particles do not aggregate with each other, and the transparency and mechanical properties of the transparent resin molded product obtained by sufficient dispersion in the resin are ensured. Is done. On the other hand, it is preferable that the content of the zinc oxide fine particles is 0.01% by weight or more because a desired ultraviolet shielding function is obtained.

  As described above in detail, desired optical characteristics can be obtained by applying tungsten oxide fine particles or composite tungsten oxide fine particles having the above general formula and zinc oxide fine particles to a laminated structure. Can do.

[Method of producing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function]
(3) Production method of fine particles having solar radiation shielding function Tungsten oxide fine particles represented by general formula W _y O _z , which are fine particles having solar radiation shielding function, and general formula M _x W _y O _z A method for producing tungsten oxide fine particles represented by M element cord, W for tungsten, O for acid cord, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) will be described. .

(A) the general formula _W y _O mentioned above the method of manufacturing the tungsten oxide fine particles expressed by _z, the general formula _W y _{O z} (where, W is tungsten, O is Sansaku, 2.2 ≦ z / y ≦ 2 .999), the tungsten oxide fine particles are hydrolyzed by adding water to tungsten hexachloride dissolved in tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, and alcohol. One or more tungsten compounds selected from evaporated tungsten hydrates are obtained by firing in an inert gas alone or a mixed gas atmosphere of an inert gas and a reducing gas. Here, tungstic acid (H ₂ WO ₄ ), ammonium tungstate, and tungsten hexachloride used as raw materials are not particularly limited.

However, selected from tungstic acid (H ₂ WO ₄ ), ammonium tungstate, or tungsten hexachloride, tungsten hydrate obtained by adding water to tungsten hexachloride dissolved in alcohol, hydrolyzing it, and evaporating the solvent. In the case of producing tungsten oxide fine particles by firing one or more kinds of tungsten compounds, the firing temperature is preferably 200 ° C. or higher and 1000 ° C. or lower from the viewpoint of desired fine particles and optical properties. When the firing temperature is in the range of 200 ° C. or higher and 1000 ° C. or lower, tungsten oxide fine particles having desired optical characteristics can be produced. The firing time may be appropriately selected according to the amount of treatment and the firing temperature, but 5 minutes to 10 hours is sufficient.

Next, the tungsten hydrate obtained by adding water to the tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, tungsten hexachloride dissolved in alcohol, hydrolyzing it, and evaporating the solvent. In order to generate oxygen vacancies in tungsten oxide fine particles prepared by firing one or more selected tungsten compounds, the tungsten oxide fine particles are mixed with an inert gas alone or with an inert gas and a reducing gas. Baking in a gas atmosphere. Here, a gas such as nitrogen, argon, or helium can be used as the inert gas, and a gas such as hydrogen or alcohol can be used as the reducing gas.

When the tungsten oxide fine particles are fired in a mixed gas atmosphere of an inert gas and a reducing gas, the concentration of the reducing gas in the inert gas is not particularly limited as long as it is appropriately selected according to the firing temperature. However, it is preferably 20 vol% or less, more preferably 10 vol% or less, and even more preferably 7 to 0.01 vol%. When the concentration of the reducing gas in the inert gas is 20 vol% or less, rapid reduction of the tungsten oxide fine particles can be avoided, and generation of WO ₂ having no solar radiation shielding function can be avoided.

The treatment temperature for generating oxygen vacancies in the tungsten oxide fine particles may be appropriately selected according to the atmosphere, but in the case of an inert gas alone, from the viewpoint of crystallinity and hiding power as the solar radiation shielding fine particles. It exceeds 500 ° C. and is 1200 ° C. or less, preferably 1100 ° C. or less, more preferably 1000 ° C. or less. On the other hand, in the case of a mixed gas of an inert gas and a reducing gas, a temperature at which WO ₂ is not generated may be appropriately selected according to the reducing gas concentration. Furthermore, in the case of a two-step reaction performed under both atmospheres of an inert gas alone and a mixed gas of an inert gas and a reducing gas, for example, a mixed gas atmosphere of an inert gas and a reducing gas at the first step. It is also preferable from the viewpoint of the solar radiation shielding function that baking is performed at 100 ° C. or more and 650 ° C. or less and baking at 650 ° C. and 1200 ° C. or less in an inert gas atmosphere in the second step. The firing treatment time at this time may be appropriately selected according to the treatment amount and temperature, but 5 minutes or more and 10 hours or less is sufficient.

Microparticles manufactured tungsten ^oxide in the powder colors in the L ^* a * ^{b *} color system, ^{L *} is 25 to 80, ^{a *} is -10 to 10, ^{b *} in the range of -15～15 It was in. Further, when X-ray diffraction measurement was performed on the tungsten oxide fine particles, a WO _3-x phase diffraction peak was observed, and the presence of so-called magnetic phases such as W ₂₀ O ₅₈ and W ₁₈ O ₄₉ was confirmed. According to the results of chemical analysis, it is determined that the phase is W _y O _z (where W is tungsten and O is oxygen 2.2 ≦ z / y ≦ 2.999).

(B) General formula M _x W _y O _z (where M is the M element, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) The above-described general formula M _x W _y O _z (where M is the M element, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2) .2 ≦ z / y ≦ 3.0), tungsten is added to tungsten hexachloride dissolved in tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, alcohol. Powder obtained by dry-mixing one or more tungsten compounds selected from hydrated tungsten hydrates that have been hydrolyzed and then evaporated, and M element oxide and / or hydroxide powders Inert gas alone or Baking in a mixed gas atmosphere of inert gas and reducing gas in one step, or baking in a mixed gas atmosphere of inert gas and reducing gas in the first step and further in an inert gas atmosphere in the second step It is obtained by performing two-stage firing called firing. Further, the tungsten oxide fine particles produced in (a) may be used in place of the tungsten compound.

As a different manufacturing method of the composite tungsten oxide fine particles, water is added to tungsten hexachloride dissolved in tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, and alcohol, and then the solvent is evaporated. A dry powder obtained by drying a mixture obtained by wet-mixing one or more tungsten compounds selected from the hydrates of tungsten and an aqueous solution containing the salt of the M element is used as an inert gas alone or insoluble. Baking in a mixed gas atmosphere of active gas and reducing gas in one step, or baking in a mixed gas atmosphere of inert gas and reducing gas in the first step, and further in an inert gas atmosphere in the second step It can also be obtained by performing a two-stage firing, ie, firing at a. Further, the tungsten oxide fine particles produced in (a) may be used in place of the tungsten compound.

  As described above, the element M to be added 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, One or more elements selected from Ta and Re are preferred. All of these elements can improve the solar radiation shielding function and weather resistance of the composite tungsten oxide fine particles, but from the viewpoint of improving the solar radiation shielding function, alkali metals, alkaline earth metals, and transition metals can be used. The element which belongs is preferable, and a 4B group element and a 5B group element are preferable from a viewpoint of improving a weather resistance.

Tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, tungsten hydrate obtained by adding water to tungsten hexachloride dissolved in alcohol, hydrolyzing it, and evaporating the solvent, tungsten oxide fine particles, As an M element compound, an oxide or a hydroxide is preferable when adding the M element to one or more selected from the above by using a dry mixing method.
Then, water is added to the M element oxide, hydroxide, tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, tungsten hexachloride dissolved in alcohol to hydrolyze, and then the solvent is evaporated. One or more selected from the hydrated tungsten hydrate and tungsten oxide fine particles are mixed. The dry mixing may be performed with a commercially available grinder, kneader, ball mill, sand mill, paint shaker, or the like.

In addition, as a mixing method different from the dry mixing method, water is added to tungsten hexachloride in which tungstic acid (H ₂ WO ₄ ), ammonium tungstate, and tungsten hexachloride are dissolved in alcohol, followed by water analysis, and then the solvent is evaporated. A mixture of the M element salt in an aqueous solution is mixed with one or more selected from hydrated tungsten hydrate and tungsten oxide fine particles by a wet mixing method, and then dried to obtain a dry powder. good. In this case, the salt of the M element is not particularly limited, and examples thereof include nitrates, sulfates, chlorides, and carbonates. The drying temperature and time after the wet mixing are not particularly limited.

Next, in order to generate oxygen vacancies in the composite tungsten oxide fine particles, firing is performed in an inert gas alone or in a mixed gas atmosphere of an inert gas and a reducing gas in one step, or inactive in the first step. A two-stage firing is performed in which firing is performed in a mixed gas atmosphere of a gas and a reducing gas, and further, firing is performed in an inert gas atmosphere in the second step. In the case of the inert gas used for the calcination treatment alone or in the case of a mixed gas of an inert gas and a reducing gas, the concentration of the reducing gas in the inert gas and the calcination treatment temperature are as described in (a) above. This is the same as the inert gas or reducing gas, the concentration of the reducing gas in the inert gas, and the firing temperature.
Microparticles of manufacturing composite tungsten ^oxide, L ^* a * ^{b *} in the powder colors in a color system, ^{L *} is 25 to 80, ^{a *} is -10 to 10, the range of ^{b *} is -15～15 It is preferable to be within.

(4) Method for Producing Zinc Oxide Fine Particles Having Ultraviolet Shielding Function A method for producing zinc oxide fine particles having an ultraviolet shielding function will be described.
The method for producing fine zinc oxide particles having an ultraviolet shielding function according to the present invention includes a step of dropping a solution of a zinc compound into an alkaline solution and stirring to obtain a precipitate;
The precipitate is subjected to decantation until the conductivity of the cleaning liquid after decantation is 1 mS / cm or less, and the precipitate after decantation is wet-treated with an alcohol solution to obtain a wet-processed product. And then drying the wet processed product to obtain a zinc oxide precursor;
The zinc oxide precursor is heat-treated at 350 ° C. or higher and 500 ° C. or lower in the atmosphere, in an inert gas, or in a mixed gas of an inert gas and a reducing gas to obtain zinc oxide fine particles. And a process.

Hereinafter, the step of obtaining a precipitate, the step of obtaining a zinc oxide precursor, and the step of obtaining zinc oxide fine particles by heat treatment will be described in this order.
First, the zinc compound solution is dropped into the alkaline solution, and the alkaline solution is continuously stirred to form a precipitate. By dropping the solution of the zinc compound into the alkaline solution, the supersaturation degree is instantaneously reached and a precipitate is generated, so that uniform fine particles having a relatively uniform particle size can be obtained. Even if the alkaline solution is dropped into the zinc compound solution, or the zinc compound solution and the alkaline solution are dropped in parallel, uniform fine particles having a relatively uniform particle size as in the present invention cannot be obtained.

  Here, the zinc compound applied in the present invention is not particularly limited, and examples thereof include zinc nitrate, zinc chloride, zinc acetate, zinc sulfate, and the like. Among them, nitrates are used for easy removal of impurities. Is preferred.

It does not specifically limit as an alkaline solution used as a precipitating agent, For example, each aqueous solution, such as ammonium hydrogencarbonate, ammonia water, sodium hydroxide, potassium hydroxide, is mentioned.
The alkali concentration is preferably at least the chemical equivalent required for each salt to become a hydroxide. Particularly preferred is an equivalent to 2.5-fold excess from the viewpoint of washing time due to residual alkali. The alkaline solution temperature at this time is not particularly limited, but is 50 ° C. or less, preferably room temperature. In particular, if the lower limit is too low, a cooling device or the like is newly required, and therefore it is preferable to set the temperature so that such a device is not required.

  The dropping time of the zinc compound solution is not particularly limited, but is 30 minutes or less, preferably 20 minutes or less, more preferably 10 minutes or less from the viewpoint of productivity. After completion, in order to make the system uniform, aging is carried out with continuous stirring, and the temperature at that time is preferably the same as the temperature at which precipitation is generated. The time for continuous stirring is not particularly limited, but 30 minutes or less, preferably 15 minutes or less is sufficient from the viewpoint of productivity.

  Next, the precipitate obtained by aging needs to be sufficiently washed by decantation until the conductivity of the washing liquid after decantation is 1 mS / cm or less. Impurities such as chloride ions, nitrate ions, sulfate ions, and acetate ions remaining in the fine particles cannot obtain a desired ultraviolet shielding function depending on their residual amounts. Therefore, the conductivity of the supernatant of the cleaning liquid is 1 mS / cm. It is preferable to perform sufficient cleaning until it becomes below (corresponding to a residual impurity amount of 1.5% or less).

Next, the washed precipitate is wet-treated with an alcohol solution to obtain a wet-processed product, and then the wet-processed product is dried to obtain a precursor of zinc oxide fine particles. At this time, the concentration of the alcohol solution is preferably 50% or more. If the concentration of the alcohol solution is 50% or more, it can be avoided that the zinc oxide fine particles become strong aggregates, and the haze value when the dispersion in the solvent proceeds efficiently to form a shielding body is excellent at 1% or less. This is because it exhibits high transparency.
Here, although the alcohol used for the said alcohol solution is not specifically limited, It is excellent in the solubility with respect to water, and alcohol with a boiling point of 100 degrees C or less is preferable. Examples include methanol, ethanol, propanol, and tert-butyl alcohol.

The wet treatment may be performed by adding the filtered and washed precipitate into the alcohol solution and stirring, and the time and stirring speed at this time may be appropriately selected according to the treatment amount.
The amount of the alcohol solution when the precipitate is put into the alcohol solution may be a liquid amount that can easily stir the precipitate and ensure fluidity. The agitation time and agitation speed are appropriately selected on the condition that a precipitate containing a part that has been partially aggregated during filtration and washing is uniformly mixed in the alcohol solution until there is no agglomerated part.
In addition, the temperature of the wet treatment may be normally performed at room temperature, but it is of course possible to perform the wet treatment while heating the alcohol so that the alcohol is not lost by evaporation. Preferably, by heating at a temperature lower than the boiling point of the alcohol, it can be avoided that the alcohol is evaporated and lost during the wet treatment, and the effect of the wet treatment is lost. After the alcohol is evaporated and lost during the wet treatment, and the wet treatment effect is lost, drying the wet treatment product results in strong agglomerates, which is not preferable.

After the wet treatment, the wet treated product is heat-dried while still wet with alcohol. The drying temperature and drying time of the wet processed product are not particularly limited. After the wet treatment, the wet treated product does not become a strong agglomerate even if it is dried. Therefore, the drying temperature and the drying time may be appropriately selected according to the conditions such as the treatment amount of the wet treated product and the treatment apparatus. .
By the drying treatment, a wet treated zinc oxide fine particle precursor is obtained. The precursor is composed of at least one of Zn ₅ (OH) ₆ (CO ₃ ) ₂ , ZnCO ₃ , and Zn ₄ CO ₃ (OH) 6 H ₂ O.

Here, before heat-treating the zinc oxide fine particle precursor, an alcohol containing at least 15% by weight of one or more elements selected from Si, Al, Zr, and Ti as required is converted into an oxide. After the solution is wet-treated, it may be dried. The wet treatment method and the alcohol solution used are the same as described above. Si, Al, Zr, and Ti exist independently in the vicinity of zinc oxide, and suppress the grain growth of zinc oxide during the heat treatment. The content of these elements in terms of oxide is preferably 15% by weight or less, so that the content ratio of zinc oxide is ensured and the ultraviolet shielding function and hiding power are ensured.

And it is important to heat-process about the dried zinc oxide precursor in order to improve an ultraviolet-ray shielding function and hiding power. It is important to perform the heat treatment in the atmosphere, in an inert gas such as nitrogen, argon, or helium, or in a mixed gas of the inert gas and a reducing gas such as hydrogen. It is important that the lower limit of the treatment temperature at this time is 350 ° C. or higher and the upper limit is 500 ° C. or lower from the viewpoint of a desired ultraviolet shielding function. The processing time at this time may be appropriately selected according to the processing amount of the precursor and the heat treatment temperature.
The method for producing ultraviolet shielding material fine particles of the present invention, the crystallite diameter is 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19Nm～41nm, X-ray diffraction (101) peak Zinc oxide fine particles having a half width of 0.55 or less can be obtained.

[Laminated structure using fine particles having solar radiation shielding function and ultraviolet shielding function]
(5) Intermediate layer and laminated plate used in laminated structure An intermediate layer is interposed between two laminated plates selected from plate glass and resin board, and at least one of the intermediate layer or resin board has a solar radiation shielding function The laminated structure having at least one of the ultraviolet shielding functions and having the solar radiation shielding function and the ultraviolet shielding function as the laminated structure will be described.
First, the laminated plate is a plate that sandwiches the intermediate layer from both sides, and plate glass or resin board that is transparent in the visible light region is used. At this time, the two laminated plates selected from the plate glass and the resin board include each configuration of the plate glass and the plate glass, the case of the plate glass and the resin board, and the case of the resin board and the resin board.

  In addition, when using a resin board for a laminated structure, the material of the said resin board is suitably selected according to the use of the said laminated structure, It does not specifically limit and can be selected according to a use. For example, when used in transportation equipment such as automobiles, a transparent resin such as polycarbonate resin, acrylic resin, polyester resin, or polyethylene terephthalate resin is preferable from the viewpoint of ensuring transparency of the driver or passenger of the transportation equipment. In addition, polyethylene terephthalate (PET) resin, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, and the like can be used.

  As an example of the embodiment of the laminated plate, a form using plate glass or the resin board as it is (referred to as “form α” for convenience in this specification), fine particles having a solar radiation shielding function on the resin board, and And / or a form used by containing fine particles having an ultraviolet shielding function (in the present specification, it is referred to as “form β” for convenience).

(6) Method for containing resin board with fine particles having solar radiation shielding function and / or fine particle having ultraviolet shielding function In form β, the resin board contains fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function The method of making it explain.
When kneading fine particles having a solar radiation shielding function and / or ultraviolet shielding fine particles into the raw material resin of the resin board, the resin is heated to a temperature near the melting point (around 200 to 300 ° C.) to obtain a fine particle having a solar radiation shielding function. And / or ultraviolet shielding particles. A mixture of the resin and fine particles having solar radiation shielding function and / or ultraviolet shielding fine particles can be pelletized and formed into a resin board, a resin film, a resin sheet, or the like by a desired method.
For example, it can be formed by an extrusion molding method, an inflation molding method, a solution casting method, a casting method, or the like. What is necessary is just to select suitably the thickness of the resin board at this time, a resin sheet, or a resin film according to the intended purpose.
The addition amount of the fine particles having solar radiation shielding function and / or ultraviolet shielding fine particles to the resin is variable depending on the thickness of the resin board, resin film or resin sheet, required optical characteristics, and mechanical characteristics. The amount is preferably 30% by weight or less based on the resin.

(7) Embodiment example of intermediate layer having intermediate film containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function (Mode 1)
An embodiment of an intermediate layer having an intermediate film containing fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function will be described.
As an example of an intermediate layer having an intermediate film containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function, an intermediate film containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function (In this specification, for convenience, it is described as “form 1”).

(Form 2)
Form consisting of two or more interlayer films, at least one of which includes a fine particle having a solar radiation shielding function and / or a fine particle having an ultraviolet light shielding function (in this specification, for convenience, “form 2”) It is described.)

(Form 3)
A solar radiation shielding and / or ultraviolet shielding layer containing fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet radiation shielding function is formed on the inner surface of at least one plate glass or resin board, and the solar radiation shielding and / or ultraviolet radiation shielding is performed. This is a mode in which an interlayer film is stacked on a layer (in this specification, it is described as “mode 3” for convenience).

(Form 4)
A ductile shielding resin film in which a solar radiation shielding and / or ultraviolet shielding layer is formed on one surface of a ductile resin film, or a particulate having a solar radiation shielding function in which the fine particles are dispersed in the resin film to form a shielding body and / or Alternatively, a form in which a resin shielding resin film containing fine particles having an ultraviolet shielding function is interposed between two or more laminated intermediate films (in this specification, for convenience, it is referred to as “form 4”). It is.

(Form 5)
A form in which a solar radiation shielding and / or ultraviolet shielding layer containing fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet radiation shielding function is formed on one surface of the interlayer film (in the present specification, “form 5” for convenience) .)

(Form 6)
Solar radiation in which an intermediate layer includes an adhesive layer, fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function on one inner surface of two laminated plates selected from the plate glass and the resin board The adhesive layer of the laminate laminated in the order of a shielding machine and / or an ultraviolet shielding layer and a release layer is adhered, and further, an intermediate film or two or more layers further laminated on the release layer side of the laminate And a laminated intermediate film (referred to as “form 6” for convenience in this specification).

(Form 7)
The intermediate layer has a form that does not have a layer containing fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function (referred to as “form 7” for convenience in this specification).

  Here, the material constituting the intermediate film is preferably a synthetic resin, and more preferably a vinyl resin, from the viewpoints of optical properties, mechanical properties, and material costs. Furthermore, from the same viewpoint, among the vinyl resins, polyvinyl butyral or ethylene-vinyl acetate copolymer is preferable.

  Hereinafter, while taking the case of using a vinyl-based resin as an intermediate film, for each form of “forms 1-7” combined with “forms α, β” of the laminated plate described above, with reference to FIGS. explain. 1 to 7 are schematic cross-sectional views of each form of “forms 1 to 7” combined with “forms α and β”.

(Form α-1)
Form α-1 is a laminated structure in which two laminated plates <1> that do not contain fine particles are used as the laminated plates, and the intermediate layer <5> is composed of a resin sheet <A0> that contains fine particles. (See FIG. 1 (α)).

Form α-1 is produced, for example, as follows.
An additive liquid in which fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function are dispersed in a plasticizer is added to the vinyl resin to produce a vinyl resin composition. This vinyl resin composition is formed into a sheet shape to obtain a resin sheet <A0> containing fine particles. A laminated structure is manufactured by sandwiching and bonding the resin sheet <A0> containing fine particles between two laminated plates <1> not containing fine particles.

The above production method is an example of a production method in which fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function are dispersed in a plasticizer. However, a dispersion method in which fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function are dispersed not in a plasticizer but in an appropriate solvent is added to a vinyl resin, and the plasticizer is added separately. A composition may be produced.
By both these production methods, it is possible to produce Form α-1, which is a laminated structure having a high solar shielding function and an ultraviolet shielding function and a small haze value. Furthermore, both the manufacturing methods can easily produce the laminated structure, and can produce the form α-1, which is a low-cost laminated structure.

(Form β-1)
Form β-1 is a resin sheet <A> in which the intermediate layer <5> contains fine particles, and as at least one laminated plate, at least the function of the interlayer film among the solar radiation shielding function and the ultraviolet shielding function A laminated structure having a configuration using a laminated board of resin boards containing fine particles having different functions (see FIG. 1 (β)). If the above conditions are satisfied, the laminated plates of both resin boards may contain fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function (not shown).
The laminated plate of both the resin boards may contain fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function, which will be described later in the forms β-2, β-3, It can be used similarly in β-4, β-5, β-6, and β-7 (not shown).

The laminated structure according to Form β-1 has at least one of the two laminated plates <1> that do not contain fine particles, and has a function different from at least the function of the intermediate film among the solar radiation shielding function and the ultraviolet shielding function. It can be produced in the same manner as in the form α-1, except that it is replaced with a laminated board of resin board containing fine particles. The interlayer film of the laminated structure of the above form and the laminated plate <2> containing fine particles are selected so as to contain at least one kind of fine particle having a solar radiation shielding function and one or more fine particles having an ultraviolet ray shielding function. It only has to be configured.

  The said form also has a high solar radiation shielding function and ultraviolet-ray shielding characteristic similarly to form (alpha) -1, and can manufacture the laminated structure with a small haze value. Further, this method also makes it possible to manufacture a laminated structure that is easy to produce a laminated structure and inexpensive to produce.

(Form α-2)
Form α-2 uses two laminated plates <1> that do not contain fine particles as laminated plates, and a resin sheet <A0> that contains fine particles as an intermediate layer <6>, and a resin sheet <B that does not contain fine particles>> Is a laminated structure using two or more resin sheets (see FIG. 2 (α)).

Form α-2 is produced, for example, as follows.
An additive liquid in which fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function are dispersed in a plasticizer is produced. The additive solution is added to a vinyl resin to prepare a vinyl resin composition, and the vinyl resin composition is molded into a sheet to obtain a resin sheet <A0> containing fine particles. On the other hand, a resin sheet <B> containing no fine particles is produced by a normal method.
The produced resin sheet <A0> containing fine particles is laminated with the resin sheet <B> containing no fine particles, or the resin sheet <A0> containing fine particles is a resin sheet <2 containing no fine particles>B> to obtain an intermediate layer <6>. The intermediate layer <6> obtained in this way is sandwiched between two laminated plates <1> that do not contain fine particles and bonded together to obtain a laminated structure.

Further, a plurality of resin sheets containing fine particles are used, at least one of which is a resin sheet <A '> containing fine particles having solar radiation shielding function, and at least one other sheet contains fine particles having ultraviolet shielding function. It is good also as a structure which laminates | stacks these as a resin sheet <A ''>.
In addition, as explained in the form α-1, instead of dispersing the fine particles having the solar radiation shielding function and the fine particles having the ultraviolet ray shielding function in the plasticizer, a dispersion liquid appropriately dispersed in a solvent is added to the vinyl resin. The vinyl resin composition may be produced by a method in which a plasticizer is added separately.

According to the manufacturing method, a laminated structure having a high solar radiation shielding function and an ultraviolet shielding function and a small haze value can be produced at a low production cost.
Furthermore, according to this method, the adhesiveness between the intermediate layer <6> and the two laminated plates <1> that do not contain fine particles can be increased, which is preferable because the strength of the laminated structure is increased.
In addition, for example, a PET film having an Al film or an Ag film formed on at least one surface by a sputtering method or the like is manufactured, and the PET film is interposed between the resin sheets to form an intermediate layer <6>. It is also preferable to add a configuration in which an appropriate additive is added to the resin sheet <B> not contained. Functions such as color tone adjustment can be performed by interposing a resin film on which an Al film, an Ag film or the like is formed, or by adding an additive.

(Form β-2)
Form β-2 is an intermediate film in which the intermediate layer <6> has two or more intermediate films, and at least one of them has a resin sheet <A> containing fine particles, and at least one of them The laminated structure is a laminated structure using a laminated board of resin board containing fine particles having at least a function different from the function of the intermediate film among the solar radiation shielding function and the ultraviolet shielding function (see FIG. 2 (β)). ).

The laminated structure according to Form β-2 has at least one of the two laminated plates <1> that do not contain fine particles, and has a function different from at least the function of the intermediate film among the solar radiation shielding function and the ultraviolet shielding function. It can be produced in the same manner as in the form α-2 except that it is replaced with a laminated board of resin board containing fine particles.
In the case of the laminated structure of the above embodiment, the laminated plate <2> containing the fine particles and the intermediate film are selected so that at least one fine particle having a solar radiation shielding function and fine particles having an ultraviolet shielding function are contained. It only has to be configured.

By this method, it is possible to produce a laminated structure having a high solar radiation shielding function and an ultraviolet shielding property and having a small haze value at a low production cost.
Also by this method, as with α-2, the adhesion between the resin sheet <B> containing no fine particles and two laminated plates selected from plate glass and plastic can be increased. The strength increases moderately, which is preferable.

(Form α-3)
With form α-3, the intermediate layer <7> is sandwiched between two laminated plates <1> that do not contain fine particles. And the said intermediate | middle layer <7> has the shielding layer <C0> containing the microparticles | fine-particles formed on the laminated board <1> which does not contain microparticles | fine-particles, and the laminated structure which has the resin sheet <B> which does not contain microparticles | fine-particles (See FIG. 3 (α)).

Form α-3 is produced, for example, as follows.
First, an additive liquid is produced in which fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function are dispersed in a plasticizer or an appropriate solvent. Then, an appropriate binder component (an inorganic binder such as silicate or an acrylic, vinyl or urethane organic binder) is blended with the additive liquid to produce a coating liquid.
The coating solution is applied to the inner surface of the laminated plate <1> that does not contain fine particles, which is at least one laminated plate, to form a shielding layer <C0> containing fine particles.
On the other hand, a resin composition <B> containing no fine particles is obtained by molding a resin composition not containing fine particles having solar radiation shielding function or fine particles having ultraviolet shielding function into a sheet shape. The resin sheet <B> containing no fine particles is placed between the shielding layer <C0> side containing fine particles on the laminated plate <1> containing no fine particles and the other laminated plate <1> containing no fine particles. The laminated structure is formed by sandwiching and bonding.

  On the other hand, in the production of Form α-3, instead of the shielding layer <C0> containing fine particles, the shielding layer <C ′> having a solar radiation shielding function on one side of the laminated plate <1> containing no fine particles is used. An intermediate layer <7> may be produced in the same manner by providing a shielding layer <C ″> having an ultraviolet shielding function.

According to the manufacturing method, the film thickness of the shielding layer <C0> containing fine particles on the laminated plate <1> can be set thin. Then, by setting the film thickness to be thin, the shielding layer <C0> containing fine particles exhibits a reflection effect in addition to an absorption effect, so that the solar radiation shielding function and the ultraviolet shielding function of the laminated structure can be improved. Can do. Accordingly, a laminated structure having a high solar radiation shielding function and an ultraviolet shielding function and a small haze value can be manufactured at a low production cost.
Furthermore, if the structure which adds an appropriate additive to resin sheet <B> which does not contain microparticles | fine-particles is taken, function addition, such as color tone adjustment, can be performed. This effect is obtained by providing the intermediate layer <7> with a shielding layer <C ′> having a solar radiation shielding function on the laminated plate <1> not containing fine particles and an ultraviolet shielding function on the laminated plate <1> not containing fine particles. The same applies when the shielding layer <C ″> is used.

(Form β-3)
Form β-3 uses a laminated plate <2> containing fine particles as at least one laminated plate, and the intermediate layer <7> contains fine particles formed on the inner surface of at least one plate glass or plastic. This is a laminated structure having the shielding layer <C> and the solar radiation shielding function and / or the intermediate film superimposed on the ultraviolet shielding layer (see FIG. 3 (β)).

  In the laminated structure according to Form β-3, at least one of the two laminated plates <1> containing no fine particles is used as a laminated plate of a resin board containing fine particles having a solar radiation shielding function and / or an ultraviolet shielding function. Except for the alternative, it can be produced in the same manner as in the form α-3. The intermediate layer <7> of the laminated structure of the above aspect and the laminated plate <2> containing fine particles contain at least one kind of fine particles having at least a solar radiation shielding function and fine particles having an ultraviolet shielding function, respectively. It suffices if it is configured to be selected.

Also by this method, similarly to α-3, the solar radiation shielding function and / or the film thickness of the ultraviolet shielding film in the laminated structure can be set thin. And by setting the film thickness to be thin, the solar radiation shielding function and the ultraviolet radiation shielding film exhibit a reflection effect in addition to the absorption effect, so that the solar radiation shielding function and the ultraviolet radiation shielding characteristic of the laminated structure can be improved. . Thereby, a laminated structure having a high solar radiation shielding function and an ultraviolet shielding property and a small haze value can be manufactured at a low production cost.
Furthermore, by adding an appropriate additive to the resin sheet <B> that does not contain fine particles, functions such as color tone adjustment can be added.

(Form α-4)
In form α-4, the intermediate layer <8> is sandwiched between two laminated plates <1> that do not contain fine particles. In the intermediate layer <8>, the ductile resin film <D> and the shielding layer <C0> containing fine particles formed thereon, or the fine particles having the solar radiation shielding function and the fine particles having the ultraviolet shielding function are used. This is a laminated structure in which the ductile resin film <D> contained is sandwiched between resin sheets <B> containing no fine particles (see FIG. 4 (α)).

As a production method of form α-4, two examples will be described below.
<Production Method 1 of Form α-4>
In the intermediate layer <8>, a description is given of the case of a laminated structure in which a ductile resin film <D> and a shielding layer <C0> containing fine particles thereon are sandwiched between resin sheets <B> containing no fine particles. To do.

  First, a coating liquid in which fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function are dispersed in a plasticizer or an appropriate solvent, or an appropriate binder component (an inorganic binder such as silicate or an acrylic type) is further added to the coating liquid. , Vinyl-based and urethane-based organic binders, etc.) are prepared. This coating solution is applied to one side of the ductile resin film <D> to form a shielding layer <C0> containing fine particles on the ductile resin film <D>. In addition, when forming the shielding layer <C0> containing fine particles on the ductile resin film <D>, for the purpose of improving the binding property with the resin binder on the surface of the ductile resin film <D>, in advance, Surface treatment such as corona treatment, plasma treatment, flame treatment, primer layer coating treatment may be performed.

On the other hand, a vinyl-based resin composition that does not contain fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function is molded into a sheet to obtain a resin sheet <B> that does not contain fine particles.
Then, the ductile resin film <D> and the shielding layer <C0> containing fine particles formed thereon are sandwiched between resin sheets <B> containing no fine particles to form an intermediate layer <8>.
By adopting this configuration, it is possible to avoid problems related to adhesiveness between the shielding layer <C0> containing fine particles on the ductile resin film <D> and the laminated plate <1> containing no fine particles. .

In the intermediate layer <8>, the shielding layer <C0> containing fine particles as one shielding layer is divided into a shielding layer <C ′> having a solar radiation shielding function and a shielding layer <C ″> having an ultraviolet shielding function. It may be divided into
Moreover, the structure which makes the resin sheet <B> which does not contain microparticles | fine-particles contain the appropriate additive which has effects, such as color tone adjustment, is also preferable.

<Production Method 2 of Form α-4>
In the case of a laminated structure in which a ductile resin film <D> in which fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function are dispersed is sandwiched between resin sheets <B> not containing fine particles in the intermediate layer <8> Will be described.

The ductile resin is heated at a temperature near its melting point (around 200 to 300 ° C.) and mixed with the fine particles having a solar radiation shielding function and the fine particles having an ultraviolet shielding function to obtain a mixture. Next, the mixture is pelletized, a resin film, a resin board, or the like is formed by a predetermined method to produce a ductile resin film <D> in which fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function are dispersed.
For example, it can be formed by an extrusion molding method, an inflation molding method, a solution casting method, a casting method, or the like.
What is necessary is just to select suitably the thickness of the resin film or board at the time of the said shaping | molding according to the intended purpose.
In addition, the amount of fine particles having solar radiation shielding function and the fine particle amount having ultraviolet shielding function added to the ductile resin is variable depending on the thickness of the substrate, required optical characteristics, and mechanical characteristics. In particular, it is preferably 50% by weight or less based on the weight of the resin.

On the other hand, a vinyl resin composition not containing fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function is molded into a sheet to obtain a resin sheet <B> containing no fine particles.
An intermediate layer <8> is manufactured by sandwiching a ductile resin film <D> in which fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function are dispersed between the two resin sheets <B> not containing fine particles. . This intermediate layer <8> is sandwiched and bonded between laminated plates <1> that do not contain fine particles, thereby producing a laminated structure.
Furthermore, if desired, it is also preferable to add an appropriate additive having an effect such as color tone adjustment to the resin sheet <B> containing no fine particles. With this configuration, a multi-functional laminated structure can be obtained.

  The shielding layer <C0> containing fine particles on the ductile resin film <D> or the shielding layer <C ′> having a solar radiation shielding function also according to <Manufacturing method 1 and 2 of form α-4> described above. The film thickness of the shielding layer <C ″> having an ultraviolet shielding function can be set thin. And by setting the film thickness to be thin, the solar radiation shielding functional layer and the ultraviolet shielding film exhibit a reflecting effect in addition to the infrared and ultraviolet absorbing effect, so that the infrared and ultraviolet shielding function can be improved. it can. As a result, a laminated structure having a high shielding function and a small haze value can be manufactured at a low production cost.

(Form β-4)
Form β-4 uses a laminated plate <2> containing fine particles as at least one laminated plate, and the intermediate layer <8> contains fine particles formed on one side of the ductile resin film <D>. The laminated structure having the shielding layer <C> and two or more laminated intermediate films, or the intermediate layer <8> has a solar radiation shielding function and / or an ultraviolet shielding function in the ductile resin film <D>. This is a laminated structure having a ductile resin film <D> in which fine particles are dispersed and having a shielding function, and an intermediate film in which two or more layers are laminated (see FIG. 4 (β)).

The laminated structure according to Form β-4 is the same as Form α-4 except that at least one of the two laminated boards <1> not containing fine particles is replaced with a laminated board <2> containing fine particles. Can be manufactured.
The intermediate layer <8> of the laminated structure of the above aspect and the laminated plate <2> containing fine particles contain at least one kind of fine particles having at least a solar radiation shielding function and fine particles having an ultraviolet shielding function, respectively. It suffices if it is configured to be selected.

Also by this method, similarly to α-4, the solar radiation shielding function and / or the thickness of the ultraviolet shielding film in the laminated structure can be set thin. By setting the film thickness to be thin, the solar radiation shielding function and / or the ultraviolet ray shielding film exhibits a reflection effect in addition to the infrared ray and / or ultraviolet ray absorption effect, so that the shielding property can be improved. Accordingly, a laminated structure having high shielding characteristics and a small haze value can be manufactured at a low production cost.
Furthermore, by adding an appropriate additive to the resin sheet <B> that does not contain fine particles, functions such as color tone adjustment can be added.

(Form α-5)
In form α-5, the intermediate layer <9> is sandwiched between two laminated plates <1> that do not contain fine particles.
The intermediate layer <9> is a laminated structure having a resin sheet <B> containing no fine particles and a shielding layer <C0> containing fine particles formed thereon (see FIG. 5 (α)). .

Form α-5 is produced, for example, as follows.
An additive solution is produced by dispersing fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function in a plasticizer or an appropriate solvent. Then, an appropriate binder component (an inorganic binder such as silicate or an acrylic, vinyl or urethane organic binder) is blended with the additive liquid to produce a coating liquid.
This coating solution is applied to one surface of the resin sheet <B> that does not contain fine particles to form a shielding layer <C0> that contains fine particles.
Next, the resin sheet <B> containing no fine particles and the shielding layer <C0> containing fine particles thereon are sandwiched and bonded between two laminated plates <1> containing no fine particles. Thus, a laminated structure is obtained.

  On the intermediate layer <9>, the shielding layer <C0> containing fine particles may be used as described above, but the shielding layer <C ′> having a solar radiation shielding function and the shielding layer <C ′ having an ultraviolet shielding function> ''> May be used.

  According to the manufacturing method, the shielding layer containing the fine particles having the solar radiation shielding function and the fine particles having the ultraviolet shielding function is formed on the surface of the resin sheet <B> not containing the fine particles. As a result, additives such as fillers can be added to the fine particles having the solar radiation shielding function and the fine particles having the ultraviolet ray shielding function as desired, and the shielding function can be improved. Accordingly, a laminated structure having a high shielding function and a small haze value can be manufactured at a low production cost.

(Form β-5)
Form β-5 uses a laminated plate <2> containing fine particles as at least one laminated plate, and the intermediate layer <9> has a shielding layer <C> containing fine particles on one surface of the intermediate film. This is a formed structure (see FIG. 5 (β)).

  The laminated structure according to Form β-5 is the same as Form α-5 except that at least one of the two laminated plates <1> not containing fine particles is replaced with a laminated plate <2> containing fine particles. Can be manufactured. The intermediate layer <9> of the laminated structure of the above embodiment and the laminated plate <2> containing fine particles contain at least one fine particle having a solar radiation shielding function and at least one fine particle having an ultraviolet shielding function. It suffices if it is configured to be selected.

  Also by this method, since the shielding layer <C> containing fine particles is formed on the surface of the resin sheet as the intermediate film, the fine particles having the solar radiation shielding function and / or the ultraviolet shielding function are further added to the filler and the like. Additives can be added as desired, and the shielding properties can be improved. Accordingly, a laminated structure having high shielding characteristics and a small haze value can be manufactured at a low production cost.

(Form α-6)
Form α-6 is a laminated structure in which an intermediate layer <10> is sandwiched between two laminated plates <1> that do not contain fine particles (see FIG. 6 (α)).
The intermediate layer <10> has an adhesive layer <E>, a shielding layer <C0> containing fine particles, a release layer <F>, and a resin sheet <B> containing no fine particles.
In form α-6, the laminate of the shielding layer <C0> containing fine particles and the release layer <F> is adhered to the laminated plate <1> containing no fine particles due to the effect of the adhesive layer <E>. . That is, the form α-6 is “a laminated sheet not containing one fine particle <1> —adhesive layer <E> —shielding layer containing fine particles <C0> —peeling layer <F> —resin sheet not containing fine particles. <B> —the other laminated plate <1> which does not contain fine particles ”.

Form α-6 is produced, for example, as follows.
First, on one side of a film sheet (for example, polyester, polypropylene, polyethylene, polyethylene terephthalate, polycarbonate, polyimide, fluorine resin film, paper, cellophane, etc.) A release layer <F> (for example, a wax layer, an acrylic resin layer, a polyvinyl acetal layer typified by polyvinyl butyral, etc.) is formed. On this release layer <F>, a shielding layer <C0> containing fine particles is formed, and further on the shielding layer <C0> containing the fine particles, an adhesive layer <E> (e.g., represented by polyvinyl butyral). Polyvinyl acetal layer, polyvinyl chloride layer, vinyl chloride-ethylene copolymer layer, vinyl chloride-ethylene-glycidyl methacrylate copolymer layer, vinyl chloride-ethylene-glycidyl acrylate copolymer layer, polyvinylidene chloride layer, vinylidene chloride -An acrylonitrile copolymer layer, a polyamide layer, a polymethacrylic acid ester layer, an acrylic acid ester copolymer layer, etc.) are formed into a laminate to obtain a transfer film.
After adhering the adhesive layer <E> of this transfer film to the inner surface of one of the laminated plates <1> not containing particles, when the film sheet is peeled off from the transfer film, the release layer <F From the presence of>, only the film sheet is peeled from the laminate. An intermediate layer <10> obtained by laminating a resin sheet <B> containing no fine particles thereon is sandwiched between two laminated plates <1> containing no fine particles to produce Form α-6. The

  Here, as an example of the laminated structure according to the form α-6 obtained, there is one in which the intermediate layer <10> is sandwiched between two laminated plates <1> not containing fine particles. And the said intermediate | middle layer <10> is comprised from resin sheet <B> which does not contain microparticles | fine-particles | peeling layer <F> -shielding layer <C0> which contains microparticles | fine-particles <E>. In this configuration, the shielding layer <C0> containing fine particles on the release layer <F> is combined with a shielding layer <C ′> having a solar radiation shielding function and a shielding layer <C ″> having an ultraviolet shielding function. It is good.

According to Form α-6, the shielding layer <C0> containing fine particles on the release layer <F>, or the shielding layer <C ′> having a solar radiation shielding function and the shielding layer <C ″ having an ultraviolet shielding function The thickness of> can be reduced.
Further, by adding an appropriate additive to the release layer <F> and the adhesive layer <E>, functions such as color tone adjustment can be added.

(Form β-6)
Form β-6 is a laminated plate <2> containing fine particles as at least one laminated plate, and the inner layer <10> is one inner side of two laminated plates selected from the above-mentioned plate glass and plastic. The adhesive layer <E> of the laminate laminated in the order of the adhesive layer <E>, the shielding layer <C> containing fine particles, and the release layer <F> is adhered to the surface of the laminate, and the laminate An intermediate film that overlaps the laminated body or two or more laminated intermediate films on the peeling layer <F> side of the laminated structure (that is, the laminated structure is “one laminated plate— Adhesive layer <E> -shielding layer <C> containing fine particles <-> release layer <F> -intermediate film or two or more laminated intermediate films-the other laminated plate ". (See FIG. 6 (β)).

  The laminated structure according to Form β-6 is the same as Form α-6 except that at least one of the two laminated plates <1> not containing fine particles is replaced with a laminated plate <2> containing fine particles. Can be manufactured. The intermediate layer of the laminated structure of the above embodiment and the laminated plate <2> containing fine particles contain at least one fine particle having a solar radiation shielding function and fine particles having an ultraviolet shielding function, each containing at least one or more kinds. What is necessary is just to be configured.

  Also by this method, a thin shielding layer can be easily manufactured, and further, by adding appropriate additives to the release layer <F> and the adhesive layer <E>, functions such as color tone adjustment Additions can be made.

(Form β-7)
Form β-7 is a laminated structure in which a laminated plate <3> containing fine particles is used as at least one laminated plate, and the intermediate layer <11> is composed of a resin sheet <B> not containing fine particles. Yes (see FIG. 7).

The laminated plate <3> containing fine particles in the laminated plate of the laminated structure according to the form β-7 contains at least one fine particle having a solar radiation shielding function and at least one fine particle having an ultraviolet shielding function. As long as it is selected and configured as described above.
For example, the solar radiation shielding laminated structure in which the intermediate layer <11> is constituted by the resin sheet <B> not containing fine particles containing a vinyl resin is manufactured as follows, for example.
A plasticizer is added to a vinyl resin to prepare a vinyl resin composition, and the vinyl resin composition is molded into a sheet to obtain an intermediate film sheet. A resin board containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function is used as at least one laminated plate of the interlayer sheet, and laminated plate <1> not containing fine particles is used as the other laminated plate. That's fine.

By this method, a laminated structure having high shielding properties and a small haze value can be produced. Furthermore, the method can easily produce a laminated structure, and can produce an inexpensive laminated structure.
Furthermore, by adding an appropriate additive to the intermediate film and / or the resin board of the other laminated plate, functions such as color tone adjustment can be added.

[Method of manufacturing laminated structure]
The method of dispersing the fine particles having solar radiation shielding function and / or the fine particles having ultraviolet ray shielding function in a plasticizer or an appropriate solvent is arbitrary as long as the fine particles can be uniformly dispersed in the plasticizer or an appropriate solvent. May be adopted. For example, methods such as bead mill, ball mill, sand mill, ultrasonic dispersion and the like can be mentioned. And the said addition liquid and coating liquid which are applied to manufacture of the laminated glass which concerns on this invention are manufactured by disperse | distributing the said microparticles | fine-particles uniformly to a plasticizer or a suitable solvent.

An appropriate solvent for dispersing the fine particles is not particularly limited. Therefore, the solvent can be appropriately selected in accordance with the conditions for forming the shielding film and the vinyl resin blended in preparing the vinyl resin composition. For example, alcohol such as water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol, ethers such as methyl ether, ethyl ether, propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isobutyl Various organic solvents such as ketones such as ketones can be used.
Moreover, it is also a preferable structure to adjust pH by adding an acid or alkali to the solvent as necessary. Furthermore, in order to further improve the dispersion stability of the fine particles in the coating solution, it is also preferable to add various surfactants, coupling agents and the like to the solvent.

  A plasticizer for adjusting the plasticity of the vinyl resin is not particularly limited. For example, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, adipic acid-di-2-ethylhexyl, diisodecyl adipate, epoxy fatty acid monoester, triethylene glycol-di-2-ethyl butyrate, triethylene glycol-di-2-ethyl Examples thereof include plasticizers such as hexoate, dibutyl sebacate, and dibutyl sebacate.

  Examples of the vinyl resin include polyvinyl acetal represented by polyvinyl butyral, polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-ethylene-glycidyl methacrylate copolymer, vinyl chloride-ethylene-glycidyl acrylate copolymer. , Vinyl chloride-glycidyl methacrylate copolymer, vinyl chloride-glycidyl acrylate copolymer, polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer, polyvinyl acetate ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, Examples thereof include a polyvinyl acetal-polyvinyl butyral mixture. However, from the viewpoints of adhesion to glass and plastic, transparency, safety, etc., polyvinyl acetal and ethylene-vinyl acetate copolymer represented by polyvinyl butyral are preferable.

In a method for forming a sheet for an interlayer film containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function, or resin sheet not containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function A known method can be used.
For example, a forming method such as a calendar roll method, an extrusion method, a casting method, or an inflation method can be used.

In particular, in the former resin sheet containing fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function and a vinyl resin composition, the vinyl resin composition includes, for example, fine particles having a solar radiation shielding function and / or An additive solution in which fine particles having an ultraviolet shielding function are dispersed in a plasticizer is added to a vinyl resin and kneaded to uniformly disperse the fine particles. The vinyl resin composition thus produced can be formed into a sheet shape.
When the vinyl resin composition is molded into a sheet shape, a heat stabilizer, an antioxidant, etc. are blended as necessary, and an adhesive strength modifier (for example, for controlling sheet penetration) It is also a preferable structure to mix a metal salt). However, the method for manufacturing a laminated structure according to the present invention is not particularly limited as long as it is a method capable of producing the above-described laminated structure.

[Method for producing dispersion for forming solar shield]
A method for producing a dispersion for forming a solar shading body that can be suitably applied to the laminated structure according to the present invention will be described.
The dispersion for forming a sunscreen according to the present invention is a dispersion for forming a sunscreen that contains a solvent and sunscreening fine particles, and the sunscreening fine particles are dispersed in the solvent. The solar shading fine particles include tungsten oxide fine particles represented by the general formula W _y O _z (where 2.2 ≦ z / y ≦ 2.999) and / or the general formula M _x W _y. It is composed of fine particles of composite tungsten oxide represented by O _z (where 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0). Also, the powder including the solar radiation-shielding fine particles, in the powder colors ^L * ^a * ^{b *} color system, ^{L *} is 25 to 80, ^{a *} is -10 to 10, ^{b *} is -15～15 These are tungsten oxide fine particles. The dispersed fine particle diameter of the tungsten oxide fine particles dispersed in the solvent is 800 nm or less. A solar radiation shielding body having a high solar radiation shielding function by applying a dispersion liquid for forming a solar radiation shielding body in which the dispersed fine particle diameter of tungsten oxide fine particles dispersed in the solvent is sufficiently fine up to 800 nm or less and uniformly dispersed. Can be obtained.

Here, the dispersed particle diameter of the tungsten oxide fine particles in the dispersion for forming a solar shield is briefly described.
The dispersed particle diameter of the tungsten oxide fine particles means the diameter of the aggregated particles produced by agglomeration of the tungsten oxide fine particles dispersed in the solvent, and is measured with various commercially available particle size distribution analyzers. can do. For example, a sample in a state where a simple substance or an aggregate of tungsten oxide fine particles exists is collected from the tungsten oxide fine particle dispersion, and the sample is ELS- manufactured by Otsuka Electronics Co., Ltd. based on the principle of dynamic light scattering. It can be determined by measuring at 8000.
In the solar shield-forming dispersion, it is desirable that the dispersed particle diameter of the tungsten oxide fine particles is 800 nm or less. When the dispersed particle size is 800 nm or less, the obtained solar shading body can be prevented from becoming a gray film or a molded body (plate, sheet, etc.) having a monotonous decrease in transmittance, and has a high solar shading function. It is because it shows. Further, if the dispersion for forming the solar radiation shielding body does not contain many aggregated coarse particles, these coarse particles become a light scattering source and cause haze, which causes a decrease in visible light transmittance. This is preferable because it can be avoided.

  The method for dispersing the tungsten oxide fine particles in the solvent is not particularly limited as long as it can be uniformly dispersed. For example, a pulverization / dispersion treatment using a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, or the like. A method is mentioned. By the dispersion treatment using these equipments, the tungsten oxide fine particles are dispersed in the solvent, and at the same time, the fine particles are formed by the collision of the tungsten oxide fine particles, so that the tungsten oxide particles can be further finely dispersed. (Ie, pulverized / dispersed).

Further, the Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb , Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, Ca, or a fine particle of an oxide containing one or more elements selected from general formula XB _m (where X is an alkali) Elements selected from earth metal elements or rare earth elements including yttrium (Y), B is boron, fine particles of boride represented by 4 ≦ m <6.3), or In ₄ Sn ₃ O ₁₂ It is also a preferred configuration that at least one kind of fine particles selected from fine particles of indium tin composite oxide is added to the dispersion for forming a solar radiation shield and dispersed in a solvent in the dispersion.

With the above-mentioned configuration, it is possible to obtain the effects of improving the solar shading function of the solar shading body, adjusting the color tone of the solar shading body, reducing the amount of added filler, etc., but from the viewpoint of improving the solar shading function, Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Fine particles of an oxide containing one or more elements selected from Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca and fine particles of an indium tin composite oxide are preferable. From the viewpoint of reducing the amount of filler, boride fine particles are preferred. Further, boride fine particles are preferable from the viewpoint of improving the shielding function against near infrared rays closer to visible light. In addition, what is necessary is just to select the addition ratio at this time suitably according to the desired solar radiation shielding function.

  In addition, the dispersion for forming a solar radiation shielding body may include an inorganic binder and / or a resin binder. The kind of inorganic binder or resin binder is not particularly limited. Examples of the inorganic binder include metal alkoxides of silicon, zirconium, titanium, or aluminum, partially hydrolyzed polycondensates thereof, or organosilazanes. Examples of the resin binder include thermoplastic resins such as acrylic resins, and epoxy. A thermosetting resin such as a resin can be used.

  In addition, in the dispersion for forming a solar shield, the solvent in which the tungsten oxide fine particles are dispersed is not particularly limited, and includes an application / kneading condition, an application / kneading environment, and an inorganic binder and a resin binder. What is necessary is just to select suitably according to a binder. Examples of the solvent include alcohols such as water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol and diacetone alcohol, ethers such as methyl ether, ethyl ether and propyl ether, esters, acetone, methyl ethyl alcohol. Various organic solvents such as tones, diethyl ketone, cyclohexanone, ketones such as inbutyl ketone can be used. Alternatively, the pH may be adjusted by adding an acid or alkali as necessary. Furthermore, in order to further improve the dispersion stability of the fine particles in the dispersion, various surfactants, coupling agents and the like can of course be added.

  Further, when a coating film is formed on a transparent substrate such as a plate glass, a resin board, a resin sheet, or a resin film using the dispersion for forming a solar shield, the conductivity of the film is determined by the contact of the tungsten oxide fine particles. It is obtained along a conductive path via a location. Therefore, for example, by adjusting the amount of the surfactant and the coupling agent in the dispersion for forming the solar shading body, the conductive path can be partially cut, and the surface electrical resistance of 106Ω / □ or more It is easy to reduce the conductivity of the film in terms of value. Further, the conductivity of the film can also be controlled by adjusting the content of the inorganic binder and / or the resin binder in the dispersion for forming a sunscreen.

  Next, when the solar shading body-forming dispersion is applied onto an appropriate transparent substrate such as a plate glass, a resin board, a resin sheet, or a resin film to form a film, the application method is not particularly limited. The coating method may be any method that can apply the dispersion liquid flatly and thinly and uniformly, such as spin coating, bar coating, spray coating, dip coating, screen printing, roll coating, and flow coating. The method may be used.

  Further, when the dispersion for forming the solar shading body contains a metal alkoxide of silicon, zirconium, titanium, or aluminum and a hydrolysis polymer thereof as an inorganic binder, the substrate heating temperature after application of the decomposition liquid is 100 ° C. By setting it as the above, the polymerization reaction of the alkoxide contained in a coating film or its hydrolysis polymer can be almost completed. By almost completing the polymerization reaction, it is possible to avoid water and organic solvents remaining in the film and causing a reduction in the visible light transmittance of the heated film, and therefore the heating temperature is preferably 100 ° C. or higher. More preferably, it is not less than the boiling point of the solvent in the dispersion.

  Moreover, what is necessary is just to harden | cure according to the hardening method of each resin binder, when using a resin binder in the said dispersion liquid for solar radiation shield formation. For example, if the resin binder is an ultraviolet curable resin, ultraviolet rays may be appropriately irradiated. If the resin binder is a room temperature curable resin, it may be left as it is after application.

  Moreover, when the dispersion for solar radiation shielding body contains no resin binder or inorganic binder, the film obtained on the transparent substrate has a film structure in which only the tungsten oxide fine particles are deposited. And even if the said film remains as it is, the solar radiation shielding effect is shown. However, on this film, a coating film is formed by further applying a coating solution containing an inorganic binder such as a metal alkoxide of silicon, zirconium, titanium, or aluminum or a partially hydrolyzed polycondensation polymer thereof, or a resin binder. A film is recommended. By adopting this configuration, the coating liquid component is formed by filling the gap where the first layer of tungsten oxide fine particles are deposited, so that the haze value of the film is reduced and the visible light transmittance is improved. The binding property of the fine particles to the base material is improved.

The solar radiation shielding body according to the present invention, which is formed of the transparent base material and the film formed thereon as described above, has tungsten oxide fine particles appropriately dispersed in the film. Therefore, the reflection in the visible light region is less than that of an oxide thin film formed by a physical film forming method having a mirror-like surface in which crystals are densely filled in the film, and it is possible to avoid a glare appearance. On the other hand, since it has a plasma frequency from the visible region to the near infrared region, the plasma reflection associated therewith becomes large in the near infrared region, and the solar radiation shielding property is excellent.
When it is desired to further suppress the reflection of the coating in the visible light region, a film having a low refractive index such as SiO ₂ or MgF ₂ is formed on the coating in which the tungsten oxide fine particles are dispersed. A multilayer film having a luminous reflectance of 1% or less can be easily obtained.
Moreover, in order to improve the visible light transmittance of the solar radiation shielding film, particles such as ATO, ITO, aluminum-added zinc oxide, and indium tin composite oxide may be further mixed.

[Method for producing dispersion for forming ultraviolet shielding material]
Meanwhile, fine particles having ultraviolet shielding function, as described above, in the crystallite diameter 15Nm～20nm, a specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter in 19Nm～41nm, X-ray diffraction (101) Zinc oxide fine particles having a half width of a peak of 0.55 or less and surface-treated with a surface treatment agent containing one or more elements selected from Si, Al, Zr, and Ti. Using the fine particles, a dispersion for forming an ultraviolet shielding material can be produced in the same manner as the dispersion for forming a solar radiation shielding body.

Examples of the present invention will be specifically described below together with comparative examples. However, the present invention is not limited to the following examples. In each example and comparative example, the solar radiation shielding laminated structure is abbreviated as a laminated structure.
In each example, powder colors of tungsten oxide fine particles and composite tungsten oxide fine particles (10 ° field of view, light source D65), and visible light transmittance and solar transmittance of the laminated structure are manufactured by Hitachi, Ltd. The spectrophotometer U-4000 was used. Moreover, the haze value was measured using HR-200 made by Murakami Color Research Laboratory Co., Ltd.

Example 1
19.5 g of Cs ₂ CO ₃ was dissolved in 49 g of water, and this was added to 90.7 g of H ₂ WO ₄ and sufficiently stirred, and then dried. The dried product was heated while supplying 1.6% H ₂ gas with N ₂ gas as a carrier, and calcined at a temperature of 800 ° C. for 20 minutes to obtain fine particles a. The powder color of the fine particles a is L ^* is 35.8916, a ^* is 0.2858, and b ^* is −4.1821, and as a result of identification of the crystal phase by powder X-ray diffraction, hexagonal Cs _0.33 It was a WO ₃ single phase.
Next, 8% by weight of the fine particles a, 84% by weight of methyl isobutyl ketone, polymer dispersant 8
A dispersion liquid (liquid A) was prepared by weighing out% by weight and crushing and dispersing for 6 hours in a paint shaker containing 0.3 mmφZrO ₂ beads. Here, when the dispersed particle diameter of the tungsten oxide fine particles in the dispersion liquid (liquid A) was measured, it was 80 nm.

On the other hand, 320 g of isopropyl alcohol, the crystallite diameter is 17.8 nm, the specific surface area is 54.5 m ² / g, the average particle diameter is 19.0 nm, and the half width of the X-ray diffraction (101) peak is 80 g of 10% SiO ₂ -containing zinc oxide fine particles (ZnO manufactured by Sumitomo Metal Mining Co., Ltd.) of 0.47 were mixed and stirred, and this was subjected to dispersion treatment with a medium stirring mill to disperse ZnO fine particles having an average dispersed particle size of 100 nm. A liquid was prepared (liquid B).
Next, 200 g of B liquid, silicone resin having an alkoxysilyl group (Si-OR) and / or silanol group (Si-OH) and having a methyl group as an organic substituent (Momentive Performance Materials Japan TSR127B) (Non-volatile content: 50%) 40 g, 158 g of isopropyl alcohol, and 2 g of catalyst (YC9103 manufactured by Momentive Performance Materials Japan) were mixed and stirred to obtain a mixed solution (C solution).
Next, this C liquid is vacuum-dried while being heated at 120 ° C. for 2 hours to evaporate the solvent to a dry solid, and the obtained dry solid is dry-pulverized to reduce the zinc oxide fine particles. Thus, surface-treated zinc oxide fine particles (fine particles b) coated with a silane compound of about 1/2 times the weight were obtained.
Dispersion liquid (liquid D) was obtained by mixing and stirring 52.8 g of the fine particles b, 41.25 g of a dispersant (acrylic polymer polymer dispersant) and 125.95 g of toluene, and further performing dispersion treatment with a medium stirring mill. Was prepared. Here, when the dispersed particle diameter of the fine particles b in the dispersion liquid (liquid D) was measured, it was 100 nm.

Next, the obtained dispersion (liquid A) is added to polyvinyl butyral, to which triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, and the concentration of fine particles a is 0.0366% by weight, A resin sheet composition was prepared so that the polyvinyl butyral concentration was 71.1% by weight. The prepared composition was kneaded with a roll and formed into a 0.76 mm thick sheet to prepare a resin sheet A. On the other hand, the above dispersion (liquid D) is added to polyvinyl butyral, to which triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, the concentration of fine particles b is 0.15 wt%, and the polyvinyl butyral concentration is A resin sheet composition was prepared so as to be 71.1% by weight. The prepared composition was kneaded with a roll and formed into a 0.76 mm thick sheet to prepare a resin sheet B. The produced resin sheets A and B are laminated, sandwiched between two 100 mm × 100 mm × 2.1 mm thick clear glass substrates, heated to 80 ° C. and temporarily bonded, and then 140 ° C. and 14 kg / cm ^2. This bonding was performed using an autoclave to prepare a laminated structure A.
As shown in Table 1, when the visible light transmittance of the laminated structure A is 80.0%, the solar transmittance is 47.5%, the ultraviolet transmittance is 0%, and the haze value is 0.3%. there were.

(Example 2)
Zinc oxide having a crystallite diameter of 19.6 nm, a specific surface area of 33.5 m ² / g, an average particle diameter of 30.9 nm, and an X-ray diffraction (101) peak half width of 0.43 Surface-treated zinc oxide fine particles (fine particles c) were obtained in the same manner as in Example 1 except that the fine particles (ZnO manufactured by Sumitomo Metal Mining Co., Ltd.) were used.
As shown in Table 1, when the visible light transmittance of the laminated structure B is 80.0%, the solar transmittance is 47.5%, the ultraviolet transmittance is 0%, and the haze value is 0.3%. there were.

(Comparative Example 1)
Zinc oxide having a crystallite diameter of 13.7 nm, a specific surface area of 75.4 m ² / g, an average particle diameter of 13.7 nm, and an X-ray diffraction (101) peak half width of 0.51 Surface-treated zinc oxide fine particles (fine particles d) were obtained in the same manner as in Example 1 except that the fine particles were used, and a laminated structure C was produced.
As shown in Table 1, the solar radiation transmittance was 49.2% when the visible light transmittance was 82.4%, the ultraviolet transmittance was 1.2%, and the haze value was 0.2%.

(Comparative Example 2)
Zinc oxide having a crystallite diameter of 48.3 nm, a specific surface area of 19.5 m ² / g, an average particle diameter of 53.1 nm, and an X-ray diffraction (101) peak half width of 0.28 Surface-treated zinc oxide fine particles (fine particles e) were obtained in the same manner as in Example 1 except that the fine particles were used, and a laminated structure D was produced.
As shown in Table 1, the solar radiation transmittance was 47.6% when the visible light transmittance was 79.5%, the ultraviolet transmittance was 0.9%, and the haze value was 2.3%.

(Example 3)
A laminated structure E according to Example 3 was produced in the same manner as in Example 1 except that one of the two clear glasses was replaced with polycarbonate.
As shown in Table 1, the solar radiation transmittance of the laminated structure E of Example 3 when the visible light transmittance is 79.5% is 47.8%, the ultraviolet transmittance is 0%, and the haze value is 0. 4%.

Example 4

10 g of H ₂ WO ₄ was put in a crucible, heated while supplying 3% H ₂ gas using N ₂ gas as a carrier, and fired at a temperature of 700 ° C. for 1 hour to obtain fine particles a. The fine particles a have a powder color of L ^* of 34.6894, a ^* of 2.3858, and b ^* of −5.0937. As a result of identification of a crystal phase by powder X-ray diffraction, W ₁₈ O ₄₉ single It was a phase.
Next, 5% by weight of the fine particles a, 5% by weight of a polymeric dispersant, and 90% by weight of methyl isobutyl ketone are weighed and pulverized and dispersed by a paint shaker containing 0.3 mmφZrO ₂ beads for 6 hours. (E solution) was prepared. Here, when the dispersed particle diameter of the tungsten oxide fine particles in the dispersion liquid (E liquid) was measured, it was 75 nm.
Next, the dispersion (liquid E) is added to polyvinyl butyral, to which triethylene glycol-di-2-ethylbutyrate is added as a plasticizer, the concentration of fine particles a is 0.0366% by weight, and polyvinyl butyral concentration The composition for resin sheets was prepared so that it might become 71.1 weight%. The prepared composition was kneaded with a roll and formed into a 0.76 mm thick sheet to prepare a resin sheet C. The resin sheet C and the resin sheet B produced in Example 1 were laminated and sandwiched between two clear glass substrates of 100 mm × 100 mm × about 2 mm thickness, heated to 80 ° C. and temporarily bonded, and then 140 ° C. , 14 g / cm ² autoclave was used for the main adhesion to produce a laminated structure F.
As shown in Table 1, the solar radiation transmittance was 53.5% when the visible light transmittance was 80.3%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 5)
The dispersion liquid (liquid A) of Example 1 was added to polycarbonate resin so that the CS _0.33 WO ₃ concentration was 0.0274% by weight, mixed uniformly with a blender, and melt-kneaded uniformly with a twin screw extruder. After that, extrusion molding was performed to a thickness of 2 mm using a T die to obtain a polycarbonate sheet in which CS _0.33 WO ₃ fine particles were uniformly dispersed throughout the resin. A laminated structure G was produced in the same manner as in Example 1 except that the resin sheet B produced in Example 1 was sandwiched between the sheet and the other clear glass substrate.
As shown in Table 1, the solar radiation transmittance was 50.4% when the visible light transmittance was 81.5%, and the haze value was 0.3%.

(Example 6)
In Example 5, except that PET resin was used in place of the polycarbonate resin, a PET sheet was formed by extrusion molding to a thickness of 2 mm in the same manner as in Example 5 and CS _0.33 WO ₃ fine particles were uniformly dispersed throughout the resin. Got. A laminated structure H was produced in the same manner as in Example 1 except that the resin sheet B produced in Example 1 was sandwiched between the sheet and the other clear glass substrate.
As shown in Table 1, the solar radiation transmittance was 50.2% when the visible light transmittance was 80.9%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 7)
In Example 1, except that an acrylic resin was used in place of the polycarbonate resin, an acrylic sheet in which CS _0.33 WO ₃ fine particles were uniformly dispersed throughout the resin was extruded to a thickness of 2 mm in the same manner as in Example 1. Got. A laminated structure I was produced in the same manner as in Example 1 except that the resin sheet B produced in Example 1 was sandwiched between the sheet and the other clear glass substrate.
As shown in Table 1, the solar radiation transmittance was 48.8% when the visible light transmittance was 80.7%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 8)
Except that a 0.76 mm thick resin sheet A and B produced in Example 1 were interposed with a polyvinyl butyral sheet not containing fine particles having solar radiation shielding function and ultraviolet shielding fine particles, as in Example 1. The laminated structure J according to Example 9 was manufactured by vitrification.
As shown in Table 1, the solar radiation transmittance was 47.5% when the visible light transmittance was 80.4%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

Example 9
The dispersion liquid (liquid A) of Example 1 was applied to a clear glass substrate of 100 mm × 100 mm × about 2 mm in thickness with a bar of count 24, and then baked at 180 ° C. for 1 hour to form a solar radiation shielding film.
Next, the clear glass substrate not containing fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function is opposed to the clear glass substrate on which the solar radiation shielding film is formed so that the solar radiation shielding film is on the inside. In addition, the 0.76 mm-thick resin sheet B produced in Example 1 was interposed between the pair of clear glass substrates, and after being temporarily bonded by heating to 80 ° C., an autoclave at 140 ° C. and 14 kg / cm ² was used. Bonding structure K according to Example 9 was manufactured by performing this bonding.
As shown in Table 1, the solar radiation transmittance was 47.8% when the visible light transmittance was 80.3%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 10)
Except that the methyl isobutyl ketone of the above dispersion (liquid A) prepared in Example 1 was replaced with toluene, a dispersion for forming a sunscreen (liquid F) was prepared in the same manner as in Example 1, and the dispersion (F liquid) was applied to one side of a ductile polyester film (thickness 50 μm) with a bar coater, dried, and irradiated with a high-pressure mercury lamp at 70 ° C. for 1 minute to form a solar radiation shielding layer. The solar radiation shielding layer is interposed between the 0.76 mm thick polyvinyl butyral sheet and the resin sheet B produced in Example 1, and this is sandwiched between two clear sheets of 100 mm × 100 mm × thickness of about 2 mm. After heating to 80 ° C. and temporarily bonding, main bonding was performed by an autoclave at 140 ° C. and 14 kg / cm ² to produce a laminated structure L according to Example 8.
As shown in Table 1, the solar radiation transmittance was 48.0% when the visible light transmittance was 80.5%, the ultraviolet transmittance was 0%, and the haze value was 0.4%.

(Example 11)
Example 1 except that ethylene-vinyl acetate copolymer was used instead of polyvinyl butyral
In the same manner as described above, a resin sheet C containing Cs _0.33 WO ₃ and a resin sheet D containing surface-treated zinc oxide were obtained, and a laminated structure M according to Example 11 was obtained.
As shown in Table 1, the solar radiation transmittance was 48.1% when the visible light transmittance was 80.6%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 12)
The dispersion liquid (liquid B) of Example 1 was added to PET resin so that the fine particle b concentration was 0.11% by weight, uniformly mixed with a blender, and uniformly melt-kneaded with a twin screw extruder, and then T Extrusion was performed to a thickness of 2 mm using a die to obtain a PET sheet in which fine particles b were uniformly dispersed throughout the resin. Clear glass / ethylene-acetic acid was interposed between the sheet and the clear-shielding layer side of the clear glass provided with the solar-shielding layer prepared in Example 9, with an ethylene-vinyl acetate copolymer sheet having a thickness of 0.76 mm interposed therebetween. A bilayer glass having the configuration of a vinyl copolymer sheet / PET film, heated to 80 ° C. and temporarily bonded, then subjected to main bonding by an autoclave at 140 ° C. and 14 kg / cm ² , and a laminated structure according to Example 12 Body N was obtained.
As shown in Table 1, the solar radiation transmittance was 48.0% when the visible light transmittance was 80.7%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Comparative Example 3)
In Example 1, instead of Cs _0.33 WO ₃ , commercially available WO3 (manufactured by Kanto Chemical Co., Inc., powder color L ^* is 92.5456, a ^* is -11.3853, b ^* is 34.5477) is used. A laminated structure O according to Comparative Example 1 was obtained in the same manner as Example 1 except that.
As shown in Table 1, the solar radiation transmittance was 64.0% when the visible light transmittance was 80.1%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Comparative Example 4)
A laminated structure P according to Comparative Example 4 was obtained in the same manner as in Example 1 except that the resin sheet A produced in Example 1 was interposed between two clear glasses.
As shown in Table 1, the solar radiation transmittance was 47.5% when the visible light transmittance was 80.2%, the ultraviolet transmittance was 63.0%, and the haze value was 0.3%.

(Example 13)
Using 10% SiO ₂ -containing zinc oxide fine particles (ZnO manufactured by Sumitomo Metal Mining Co., Ltd.) described in Example 1, the polycarbonate resin has a ZnO concentration of 0.14% by weight, and a silane coupling agent (SH 6040 manufactured by Toray Dow Corning) .14% by weight, mixed uniformly with a blender, melt-kneaded with a twin screw extruder and formed to a thickness of 2 mm to obtain a polycarbonate sheet in which zinc oxide fine particles were uniformly dispersed throughout . Between the sheet and the polycarbonate sheet in which the CS _0.33 WO ₃ fine particles produced in Example 5 are uniformly dispersed throughout the resin, no fine particles having solar radiation shielding function and / or fine particles having ultraviolet ray shielding function are contained. A laminated structure Q according to Example 13 was obtained by forming into a laminated glass in the same manner as in Example 1 except that a polyvinyl butyral sheet having a thickness of .76 mm was interposed.
As shown in Table 1, the solar radiation transmittance was 50.5% when the visible light transmittance was 82.1%, the ultraviolet transmittance was 0%, and the haze value was 0.4%.

(Example 14)
30% by weight of antimony-doped tin oxide (ATO) fine particles with a specific surface area of 65.3m ² / g, 65% by weight of methyl isobutyl ketone, and 5% by weight of a polymeric dispersant are mixed and filled into a container with 0.1 mmφ zirconia beads. After that, an ATO dispersion liquid (G liquid) was prepared by performing a bead mill dispersion treatment for 1.5 hours.
The dispersion (liquid A) and the ATO dispersion (liquid G) prepared in Example 1 were mixed well so that the weight ratio of the fine particles a to the ATO fine particles was 70:30, and the dispersion (liquid H) was obtained. Prepared. The obtained dispersion (Liquid H) had a fine particle a concentration of 1.80 wt%, an ATO fine particle concentration of 0.77 wt%, a normal temperature curable binder of 15 wt%, methyl isobutyl ketone of 70.63 wt% and a high A dispersion liquid (I liquid) composed of 11.8% by weight of a molecular dispersant was applied to the same clear glass substrate as in Example 1 by flow coating, and then baked at 180 ° C. for 1 hour to obtain a solar shading glass. . Except for interposing the resin sheet B similar to Example 1 containing fine particles having an ultraviolet shielding function between the other clear glass substrate so that the film surface of the solar radiation shielding glass is on the inside, Laminated glass was obtained in the same manner as in Example 1 to obtain a laminated structure R according to Example 14.
As shown in Table 1, the solar radiation transmittance was 54.0% when the visible light transmittance was 80.6%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 15)
Dispersion treatment of 20% by weight of lanthanum hexaboride (LaB ₆ ) particles having an average particle diameter of about 1 μm, 5% by weight of a polymeric dispersant and 75% by weight of toluene in a paint shaker containing 0.3 mmφZrO 2 beads for 24 hours. Thus, a LaB ₆ dispersion (liquid J) having an average dispersed particle diameter of 86 nm was prepared. The dispersion (liquid J) and the liquid dispersion (liquid A) prepared in Example 1 were mixed well so that the weight ratio of the fine particles a to LaB ₆ was 80:20, and the liquid dispersion (liquid K) was obtained. Prepared. The obtained dispersion (liquid K) was added to polyvinyl butyral, to which triethylene glycol-di-2-ethylbutyrate was added as a plasticizer, the concentration of fine particles a was 0.0293 wt%, and LaB ₆ fine particle concentration In the same manner as in Example 1 except that the resin sheet composition was prepared so that the polyvinyl butyral concentration was 71.1% by weight. S was obtained.
As shown in Table 1, the solar radiation transmittance was 52.0% when the visible light transmittance was 80.3%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 16)
The dispersion liquid (liquid A) and the liquid dispersion (liquid D) of Example 1 were added to polyvinyl butyral, to which triethylene glycol-di-2-ethylbutyrate was added as a plasticizer, and the concentration of fine particles a was 0.00. Except that the resin sheet composition was prepared such that the concentration of fine particles b was 0366% by weight, the concentration of fine particles b was 0.15% by weight, and the polyvinyl butyral concentration was 71.1% by weight, this was carried out by vitrification in the same manner as in Example 1. A laminated structure T according to Example 16 was obtained.
As shown in Table 1, the solar radiation transmittance was 47.6% when the visible light transmittance was 79.8%, the ultraviolet transmittance was 0%, and the haze value was 0.5%.

(Example 17)
Between the polycarbonate sheet of Example 5 and a clear glass substrate having a thickness of 100 mm × 100 mm × 2.1 mm, and between the resin sheet B having a thickness of 0.76 mm in Example 1 and containing solar radiation shielding function and ultraviolet shielding fine particles A laminated structure U according to Example 17 was obtained by forming into laminated glass in the same manner as in Example 1 except that the resin sheets not to be laminated were sandwiched.
As shown in Table 1, the solar radiation transmittance was 50.3% when the visible light transmittance was 81.6%, the ultraviolet transmittance was 0%, and the haze value was 0.3%.

(Example 18)
The dispersion (D liquid) prepared in Example 1 was applied to one side of a ductile polyester film (thickness 50 μm) with a bar coater, then dried and irradiated with a high-pressure mercury lamp at 70 ° C. for 1 minute. A solar shading layer was formed. The solar radiation shielding layer was interposed between two 0.76 mm thick polyvinyl butyral sheets, except that this solar radiation shielding layer was sandwiched between the polycarbonate sheet of Example 5 and a polycarbonate sheet containing no solar radiation shielding function and ultraviolet shielding fine particles. The laminated structure V according to Example 18 was obtained by vitrification in the same manner as in Example 1.
As shown in Table 1, the solar radiation transmittance was 48.3% when the visible light transmittance was 80.7%, the ultraviolet transmittance was 0%, and the haze value was 0.4%.

(Example 19)
The dispersion (A) prepared in Example 1 was applied to one side of a 0.76 mm thick polyvinyl butyral sheet with a bar coater, dried, and irradiated with a high-pressure mercury lamp at 70 ° C. for 1 minute. A solar shading layer was formed. The solar radiation shielding film was laminated with the 0.76 mm thick resin sheet B of Example 1, and was sandwiched between two 100 mm × 100 mm × 2.1 mm thick clear glass substrates, as in Example 1. Thus, a laminated structure W according to Example 19 was obtained.
As shown in Table 1, the solar radiation transmittance was 47.6% when the visible light transmittance was 79.8%, the ultraviolet transmittance was 0%, and the haze value was 0.4%.

(Example 20)
In Example 19, a polyvinyl butyral sheet having a thickness of 0.76 mm which does not contain solar radiation shielding function and ultraviolet shielding fine particles is used instead of the resin sheet B, and the polycarbonate sheet of Example 5 is used instead of one clear glass substrate. A laminated structure X according to Example 20 was obtained in the same manner as Example 1 except that it was used.
As shown in Table 1, the solar radiation transmittance was 47.5% when the visible light transmittance was 79.7%, the ultraviolet transmittance was 0%, and the haze value was 0.5%.

(Example 21)
After applying and drying a solution comprising 9% by weight of polyvinyl butyral resin and 91% by weight of isopropyl alcohol on one side of the polyester film, the dispersion liquid (A liquid) of Example 1 was applied and dried thereon to shield against solar radiation. A layer was formed. Furthermore, the solar radiation shielding layer is composed of 10% by weight of polyvinyl butyral resin, 3% by weight of polypropylene glycol dimethacrylate, 1% by weight of pentaerythritol hexaacrylate, 0.5% by weight of 9-phenylacridine, and 85.5% by weight of isopropyl alcohol. The coating solution was applied and dried. Next, a polypropylene film was laminated thereon to obtain a cover film.
Next, after this cover film was peeled off, the adhesive layer was adhered to a clear glass substrate having a thickness of 100 mm × 100 mm × 2.1 mm, and the adhesive layer was cured by UV irradiation.
Next, in the same manner as in Example 1, except that the resin sheet B described in Example 1 was interposed between the undercoat layer and another 100 mm × 100 mm × 2.1 mm thick clear glass substrate. A laminated structure Y according to Example 21 was obtained.
As shown in Table 1, the solar radiation transmittance was 51.7% when the visible light transmittance was 79.8%, the ultraviolet transmittance was 0%, and the haze value was 0.4%.

(Example 22)
In Example 21, instead of the resin sheet B, using a polyvinyl butyral sheet that does not contain solar radiation shielding function and ultraviolet shielding fine particles, and in addition to a clear glass substrate of 100 mm × 100 mm × 2.1 mm thickness to be pressure-bonded to the resin sheet, A laminated structure Z according to Example 22 was obtained in the same manner as in Example 21, except that the polycarbonate sheet containing 10% SiO 2 -containing zinc oxide fine particles described in Example 13 was used.
As shown in Table 1, the solar radiation transmittance was 51.8% when the visible light transmittance was 79.7%, the ultraviolet transmittance was 0%, and the haze value was 0.4%.

(Evaluation)
As shown in Table 1, the laminated structures according to Examples 1 to 22 have high visible light transmittance of 79.5% or higher, but the solar transmittance is 54% or less and the ultraviolet transmittance is 0%. The haze value was 0.5% or less and had excellent optical properties.
On the other hand, the solar transmittance of the laminated structures according to Comparative Examples 1, 2, and 4 is the same level as in Examples 1 to 22, but the ultraviolet transmittance is inferior from 0.9% to 63%. The haze value of the laminated structure according to Comparative Example 2 was 2.3%. Further, it was found that the ultraviolet transmittance of the laminated structure according to Comparative Example 3 was the same level as that of the laminated structure according to the example, but the solar radiation transmittance was inferior to 64%.

Claims (16)

An intermediate layer having a resin sheet and / or a resin film as an intermediate film, including fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function;
Solar radiation sandwiched between laminated plates selected from sheet glass, resin board not containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function, resin board containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function A laminated structure having a shielding function and an ultraviolet shielding function,
The fine particles having solar radiation shielding function are tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or 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 One or more elements selected from the above, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) , Cubic and monoclinic crystal structures with one or more crystal structures It is fine particles of Gusuten oxide,
Fine particles having the ultraviolet shielding function, crystallite diameter 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19nm~41nm, (101) in X-ray diffraction peaks of the half width Is a zinc oxide fine particle having a particle size of 0.55 or less. An intermediate layer having a resin sheet and / or a resin film as an intermediate film, including fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function,
A laminated board that is a resin board that does not have at least the intermediate layer, has a solar radiation shielding function including fine particles having a solar radiation shielding function, or has a ultraviolet radiation shielding function including fine particles having an ultraviolet radiation shielding function;
A laminated board selected from a sheet glass, a resin board not containing fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function, a resin board containing fine particles having a solar radiation shielding function and / or fine particles having an ultraviolet shielding function,
A laminated structure having a solar radiation shielding function and an ultraviolet shielding function sandwiched therebetween,
The fine particles having solar radiation shielding function are tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or 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 One or more elements selected from the above, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) , Cubic and monoclinic crystal structures with one or more crystal structures It is fine particles of Gusuten oxide,
Fine particles having the ultraviolet shielding function, crystallite diameter 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19nm~41nm, (101) in X-ray diffraction peaks of the half width Is a zinc oxide fine particle having a particle size of 0.55 or less. A laminated board selected from a sheet glass, a resin board that does not contain fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function, and a resin board containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function. A board,
In the case where the one laminated plate is a resin board containing fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function, the other laminated plate is made of plate glass, fine particles having solar radiation shielding function and fine particles having ultraviolet shielding function. A laminated board selected from a resin board not containing, a fine particle having a solar radiation shielding function and / or a resin board containing a fine particle having an ultraviolet shielding function,
In the case where the one laminated plate is a resin board containing fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function, the other laminated plate has at least the one laminated plate not having a solar radiation shielding function. A laminated board that is a resin board that includes a fine particle having a solar radiation shielding function or a fine particle having an ultraviolet shielding function and that has an ultraviolet shielding function;
In the case where the one laminated plate is a plate glass or a resin board that does not contain fine particles having a solar radiation shielding function or fine particles having an ultraviolet shielding function, the other laminated plate includes the fine particles having a solar radiation shielding function and is shielded from sunlight. A laminated board that is a resin board having a function and containing a fine particle having an ultraviolet shielding function and having an ultraviolet shielding function;
Solar radiation shielding function in which an intermediate layer having a resin sheet and / or a resin film is sandwiched between the one laminated board and the other laminated board, which does not contain fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function. And a laminated structure having an ultraviolet shielding function,
The fine particles having solar radiation shielding function are tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and / or 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 One or more elements selected from the above, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0) , Cubic and monoclinic crystal structures with one or more crystal structures It is fine particles of Gusuten oxide,
Fine particles having the ultraviolet shielding function, crystallite diameter 15Nm～20nm, specific surface area of ^{25m 2} / ^g~55m 2 / g, an average particle diameter of 19nm~41nm, (101) in X-ray diffraction peaks of the half width Is a zinc oxide fine particle having a particle size of 0.55 or less. The laminated structure according to any one of claims 1 to 3, wherein a particle diameter of the fine particles having the solar radiation shielding function is 1 nm or more and 800 nm or less. In the powder color according to the L * a * b * color system of the tungsten oxide fine particles and the composite tungsten oxide fine particles, L * is 25 to 80, a * is −10 to 10, and b * is −15.
It exists in the range of -15, The laminated structure in any one of Claims 1-4 characterized by the above-mentioned . Fine particles having the solar radiation shielding function,
Fine particles of the tungsten oxide and / or fine particles of the composite tungsten oxide;
Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, At least one selected from oxide fine particles, composite oxide fine particles, or boride fine particles containing one or more elements selected from Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca. The laminated structure according to any one of claims 1 to 5, which is a mixture with fine particles of seeds. The tungsten oxide fine particles and / or the composite tungsten oxide fine particles, and the Sb, V, Nb, Ta, W, Zr, F, Zn, Al, Ti, Pb, Ga, Re, Ru, P, Ge, Including one or more elements selected from In, Sn, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Tb, Lu, Sr, and Ca and at least one fine particle selected from the oxide fine particles or fine particles of composite oxide fine particles or boride, the mixing ratio, by weight ratio of 95: 5 to 5:95 claim 6, characterized in that in the range of 95 The laminated structure described . Claims 1 to 7, wherein the fine particles having an ultraviolet shielding function, and Si, Al, Zr, characterized in that the zinc oxide fine particles surface-treated with a surface treatment agent comprising one or more elements selected from Ti The laminated structure according to any one of the above . The laminated structure according to any one of claims 1 to 8, wherein the fine particles having an ultraviolet shielding function contain one or more elements selected from Si, Al, Zr, and Ti. The resin sheet and / or a resin film, a resin having a vinyl group, a polycarbonate resin, an acrylic resin, selected from polyethylene terephthalate resin, any of claims 1 to 9, characterized in that the resin sheet and / or a resin film The laminated structure according to crab . 11. The laminated structure according to claim 10, wherein the resin having a vinyl group is polyvinyl butyral or an ethylene-vinyl acetate copolymer. The intermediate layer has one or two or more laminated intermediate films,
3. The laminated structure according to claim 1 , wherein the fine particles having a solar radiation shielding function and / or the fine particles having an ultraviolet shielding function are dispersed in at least one layer of the intermediate film. A shielding layer containing fine particles having the solar radiation shielding function and / or fine particles having an ultraviolet shielding function, which are formed on at least one inner surface of the laminated plate sandwiching the intermediate layer;
It has an intermediate film laminated | stacked on the said shielding layer, The laminated structure in any one of Claims 1-12 characterized by the above-mentioned . In a ductile shielding resin film in which a shielding layer containing fine particles having solar radiation shielding function and / or fine particles having ultraviolet shielding function is formed on one side of a resin film having ductility, or in the resin film having ductility, resin film having ductility fine particles are dispersed with fine particles and / or ultraviolet light shielding function with a solar radiation shielding function, according to claim 1 or 2, characterized in that is sandwiched laminated interlayer film Laminated structure. The intermediate layer is
One or two or more laminated intermediate films, an adhesive layer, a shielding layer containing the fine particles having the solar radiation shielding function and / or the fine particles having an ultraviolet shielding function, and a release layer were laminated in order. Having a laminate,
The adhesive layer adheres to the inner surface of the one laminated plate,
The laminated structure according to claim 1 , wherein the release layer is in contact with the laminated intermediate film of one layer or two or more layers. 4. The laminated structure according to claim 3, wherein the intermediate layer includes an intermediate film that includes one layer or two or more layers and that does not include fine particles having a solar radiation shielding function and fine particles having an ultraviolet shielding function. body.

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