JP2009062409A - Near infrared-shielding material, laminate and optical filter for display using the same and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate suitable for laminated glass etc., having excellent heat ray-cutting properties, transparency and weather resistance and to provide an optical filter for display having excellent near infrared-shielding properties and excellent transparency and weather resistance. <P>SOLUTION: The laminate is obtained by sandwiching an interlayer between two substrates and bonding and integrating the whole. In the laminate, a heat ray-cutting layer and the interlayer or the heat ray-cutting layer, a plastic film and the interlayer are provided between the interlayer and the substrates. The heat ray-cutting layer comprises a tungsten oxide and/or a composite tungsten oxide and a weather-resistant resin. The optical filter for the display comprises a near infrared-shielding layer. In the optical filter for the display, the near infrared-shielding layer comprises the tungsten oxide and/or the composite tungsten oxide and the weather-resistant resin. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention is a near-infrared shield having a near-infrared shielding function, a laminated glass excellent in impact resistance, penetration resistance, crime prevention, etc. used in automobiles, railway vehicles, buildings, showcases and the like using the same, The present invention relates to a laminate used for safety glass such as film tempered glass (eg, bilayer, window film), an optical filter for display, and a display provided with the optical filter, particularly a plasma display panel (PDP).

  Generally, laminated glass having a structure in which a transparent adhesive layer (intermediate film) is sandwiched between glass plates is used for glass used for automobiles, particularly windshields. The transparent adhesive layer is formed of, for example, a PVB film, an EVA film, or the like, and the presence of the transparent adhesive layer improves the penetration resistance of the laminated glass. In addition, broken glass fragments remain attached to the transparent adhesive layer in response to an impact from the outside, thus preventing scattering. For this reason, for example, even if a laminated glass of an automobile is broken for the purpose of theft or intrusion, the window cannot be opened freely, so that it is useful as a security glass.

  On the other hand, for example, automobile door glass and fitted glass are generally less likely to be destroyed in an accident, and therefore do not require the penetration resistance or the like as in the case of the front glass. A board is used. However, when only such a single glass plate is used, there are the following drawbacks. That is, (1) Inferior to laminated glass in terms of impact resistance, penetration resistance, etc. (2) When broken for the purpose of theft or intrusion, it breaks into many pieces and opens the window freely And so on. For this reason, it is also considered to use glass having characteristics such as laminated glass for the door glass and the fitted glass. As glass suitable for such applications, film tempered glass in which a glass plate and a plastic film are bonded via a transparent adhesive layer is described in Patent Documents 1 and 2, for example.

  The transparent adhesive layer that bonds the two glass plates of laminated glass or the glass plate of the film tempered glass and the plastic film is required to have excellent adhesion and penetration resistance as described above. .

  The laminated glass generally has excellent adhesion and penetration resistance and is excellent in safety, but does not take into account heat ray blocking properties. As glass having a heat ray blocking function, for example, heat ray cut glass is commercially available. This heat ray cut glass is obtained by applying a metal / metal oxide multi-layer coating on the surface of a glass plate by vapor deposition of metal or the like and sputtering processing for the purpose of directly blocking sunlight. This multilayer coating is vulnerable to external scratches and has poor chemical resistance. Such glass is generally used as laminated glass by laminating an intermediate film made of EVA or the like.

  Moreover, since the said heat ray cut glass uses a metal, there exists a problem that transparency falls, obstructs permeation | transmission of electromagnetic waves, and exerts a bad influence on communication functions, such as a mobile telephone and a car navigation system. Furthermore, since the above-mentioned heat ray cut glass uses a multilayer coating, there is a problem that it becomes expensive.

  Patent Document 3 proposes the use of a film containing a hydrophilic resin such as PVA and inorganic fine particles such as silica, antimony oxide, titania, alumina, zirconia, or tungsten oxide as an intermediate film of laminated glass. Patent Document 4 proposes to use a plasticized polyvinyl butyral film containing a metal oxide as an intermediate film of laminated glass.

JP 2002-046217 A JP 2002-068785 A Japanese Patent Laid-Open No. 6-144891 JP 2001-302288 A

  In the laminated glass having the interlayer film described in Patent Documents 3 and 4, various metal oxides are used as described above for the heat ray cut. However, the laminated glass obtained by improving the heat ray cut function is transparent. Tend to decrease. Further, according to the study of the present inventor, the use of tungsten oxide ensures both the heat ray cutting function and transparency, but there is a problem that the transparency after long-term use is insufficient.

  On the other hand, optical filters used for displays, especially PDPs (plasma display panels), have the property of blocking near-infrared rays and maintain transparency to prevent malfunctions in surrounding electronic equipment. It is requested to do. When the above tungsten oxide is used as a near-infrared absorber, it is extremely effective for blocking near-infrared rays, but there is a problem that the transparency is lowered after long-term use as described above.

  An object of this invention is to provide the near-infrared shielding body excellent in heat ray cutting property and transparency.

  Moreover, an object of this invention is to provide the near-infrared shielding body excellent in heat ray cut property, transparency, and a weather resistance.

  An object of this invention is to provide the laminated body suitable for the laminated glass etc. which were excellent in heat ray cut property, transparency, and a weather resistance.

  Another object of the present invention is to provide a laminate suitable for laminated glass and the like which is excellent in heat ray cutting property, transparency and weather resistance, and also excellent in penetration resistance and impact resistance.

  Furthermore, the objective of this invention is providing the optical filter for displays which has the outstanding near-infrared shielding property, and was excellent also in transparency and a weather resistance.

  Another object of the present invention is to provide a plasma display panel with an optical filter for display having the above characteristics.

  Furthermore, the objective of this invention is also providing the plasma display panel with the optical filter for plasma display panels provided with said characteristic.

  Tungsten oxide and / or composite tungsten oxide has strong absorption in the near infrared and is excellent in the shielding effect of near infrared, but when an infrared shielding filter using this is used as, for example, laminated glass In some cases, a transmittance change accompanying blue discoloration may be observed in the laminated glass. This is considered because the laminated glass is exposed to sunlight for a long time when used outdoors for a long time. Regarding this point, it is known that cesium tungsten oxide is colored by the formation of pentavalent tungsten in the oxide due to such long-time exposure to sunlight. The reason is that the resin in which cesium tungsten oxide is dispersed is exposed to light, particularly ultraviolet rays, to generate radicals, which affect tungsten and change it to pentavalent tungsten. The present invention has been conceived from this idea. And it turned out that long-term transparency is securable by using the weather resistant resin considered that it is hard to generate | occur | produce a radical.

Therefore, the present invention
A near-infrared shield comprising tungsten oxide and / or composite tungsten oxide and weathering resin;
It is in.

  The weather resistant resin in the present invention is a resin generally containing a bond having a bond energy of 80 kcal / mol or more, preferably a bond having a bond energy of 100 kcal / mol or more. For example, Si—O is 108 kcal / mol, and C—F is 116 kcal / mol.

Preferred embodiments of the near-infrared shield of the present invention are as follows.
(1) The weather resistant resin is at least one resin selected from a fluororesin, a silicone resin, an olefin resin, and an acrylic resin. Blue discoloration after long-term use of the filter can be suppressed. In particular, a fluororesin or a silicone resin is preferable. The blue discoloration after long-term use of the filter can be remarkably suppressed. (2) The tungsten oxide and / or the composite tungsten oxide is a composite tungsten oxide.
(3) The tungsten oxide and / or the composite tungsten oxide is in the form of fine particles. The average particle size of the fine particles is preferably 400 nm or less.
(4) The tungsten oxide is represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is represented by the general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, One or more elements selected from Os, Bi, and I, W represents tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3) expressed.
(5) Tungsten oxide and / or composite tungsten oxide is treated with a silane coupling agent.

The present invention
An intermediate film is sandwiched between two substrates and these are bonded and integrated,
A heat ray cut layer and an intermediate film, or a heat ray cut layer, a plastic film and an intermediate film are provided between the intermediate film and the substrate, and the heat ray cut layer contains tungsten oxide and / or composite tungsten oxide and a weather resistant resin. A laminate characterized by:
It is in.

Preferred embodiments of the laminate of the present invention are as follows.
(1) The suitable aspect ((1)-(5)) of the said near-infrared shielding body is applicable also to this laminated body.
(2) The two substrates are both glass plates.
(3) The intermediate film is a layer (PVB layer) of a composition containing polyvinyl butyral and / or a layer (EVA layer) of a composition containing an ethylene / vinyl acetate copolymer.
(4) The intermediate film is a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide.
(5) The heat ray cut layer is a layer in which the composite tungsten oxide is dispersed in the weather resistant resin.
(6) A laminate that is a laminated glass.

The present invention
A laminated body in which an intermediate film is sandwiched between two substrates and bonded and integrated,
One of the two substrates is a glass plate, the other is a plastic film provided with a hard coat layer on the surface opposite to the intermediate film, and a heat ray cut layer is further provided between the intermediate film and the plastic film, And the heat ray-cut layer includes a tungsten oxide and / or a composite tungsten oxide and a weather-resistant resin;
It is in.

Preferred embodiments of the laminate of the present invention are as follows.
(1) The suitable aspect ((1)-(5)) of the said near-infrared shielding body is applicable also to this laminated body.
(2) The intermediate film is a layer (PVB layer) of a composition containing polyvinyl butyral and / or a layer (EVA layer) of a composition containing an ethylene / vinyl acetate copolymer.
(3) The intermediate film is a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide.
(4) The intermediate film is an adhesive layer. The pressure-sensitive adhesive layer is a resin layer that can be re-peeled in the present invention.
(5) The heat ray cut layer is a layer in which the composite tungsten oxide is dispersed in the weather resistant resin.
(6) A laminate that is a bilayer (film tempered glass).
(7) A laminate that is a window film.

The present invention also provides:
An optical filter for display comprising a near-infrared shielding layer, wherein the near-infrared shielding layer comprises tungsten oxide and / or composite tungsten oxide and a weather resistant resin; and an antireflection layer And an optical filter for display comprising a near-infrared shielding layer, wherein the near-infrared shielding layer comprises tungsten oxide and / or composite tungsten oxide and a weather resistant resin;
It is in.

Preferred embodiments of the optical filter for display according to the present invention are as follows.
(1) The suitable aspect ((1)-(5)) of the said near-infrared shielding body is applicable also to this laminated body.
(2) A conductive layer is further included.
(3) Furthermore, an adhesive layer is included.
(4) A display optical filter in which a conductive layer and an antireflection layer are provided in this order on one surface of a substrate (generally a transparent substrate), and a near-infrared shielding layer is provided on the other surface of the substrate. An adhesive layer may be provided on the near infrared shielding layer. Moreover, the near-infrared shielding layer may have adhesiveness.
(5) A substrate having an antireflection layer on the front surface and a near infrared shielding layer on the back surface, and another substrate having a conductive layer on the front surface and an adhesive layer on the back surface, the near infrared shielding layer and the conductive layer face each other. A near-infrared shielding optical filter comprising a laminate bonded in a state.
(6) Any of the above layers (generally a layer having a near infrared shielding function, a pressure-sensitive adhesive layer) has a neon cut function.
(7) The conductive layer is a mesh-like metal conductive layer. The aperture ratio is preferably 50% or more.
(8) The substrate is generally a transparent film (particularly a transparent plastic film).
(9) A plasma display panel filter.
(10) A display optical filter having a display optical filter attached to a glass substrate.

Furthermore, the present invention provides
A display comprising the display optical filter; and a plasma display panel comprising the display optical filter.

  The near-infrared shield (film) suitable for the optical filter for display or the laminated glass of the present invention contains tungsten oxide and / or composite tungsten oxide that efficiently cuts near infrared rays, and oxidizes the tank tank of oxide. Contains a weather-resistant resin that does not occur. A laminated body such as laminated glass having such a near-infrared shielding film can efficiently cut heat rays and maintain excellent transparency over a long period of time. Therefore, when such a laminated glass is used in an automobile, the interior of the automobile is comfortable to reach a high temperature, and the transparency of the window is maintained for a long time, so that safe driving is guaranteed. In addition, the display optical filter having such a near-infrared shielding film is particularly good when used as a PDP optical filter because the near-infrared rays are effectively cut in the obtained display image of the PDP. Since transparency is maintained over a long period of time, a good display image can be ensured over a long period of time.

  In addition, the near-infrared shielding body has excellent near-infrared shielding properties and can ensure transparency over a long period of time, so it is useful for applications other than laminated glass and display, window glass, showcases, and the like.

  The near-infrared shield of the present invention generally has a film containing tungsten oxide and / or composite tungsten oxide and a weather resistant resin.

  A laminate suitable for safety glass such as laminated glass and film-reinforced glass (eg, bilayer, window film) of the present invention has a basic structure in which an intermediate film is sandwiched between substrates. The intermediate film or other layer provided as necessary contains tungsten oxide and / or composite tungsten oxide and weather resistant resin, and corresponds to the near-infrared shield of the present invention.

  A laminate suitable for the laminated glass of the present invention will be described in detail below with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a laminate (laminated glass) of the present invention. In the laminate 10 of FIG. 1, on the glass plate 11A, the intermediate film 12A, the plastic film 13, the tungsten oxide and / or the composite tungsten oxide fine particles W, and the heat ray cut layer 14 containing a weather resistant resin, the intermediate film 12B, and The glass plates 11B are laminated and integrated in order. In general, the laminate 10 is bonded and integrated by sandwiching a plastic film 13 having a heat ray cut layer 14 on the surface between two glass plates 11A and 11B via intermediate films 12A and 12B. It is a thing. The heat ray cut layer 14 is generally a layer in which a composite tungsten oxide is dispersed in a weather resistant resin. The interlayer film 12 is a layer of a composition containing polyvinyl butyral (PVB layer) or a layer of a composition containing an ethylene / vinyl acetate copolymer (EVA layer). These laminates may be used. The EVA layer is preferably a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide. The positions of the plastic film 13 and the heat ray cut layer 14 may be reversed.

  The fine particles W of the tungsten oxide and / or the composite tungsten oxide contained in the heat ray cut layer 14 hardly block visible light, and are excellent in blocking function of near infrared rays (particularly near infrared rays in the vicinity of 850 to 1150 nm), Excellent heat ray cut. Near infrared rays of 850 to 1150 nm are infrared rays that are difficult to cut with ITO and AZO, which are conventional heat ray cutting agents, despite the large amount of radiation from sunlight. Therefore, the laminate of the present invention has heat ray cut characteristics. However, this is a significant improvement over the previous model.

  The heat ray cut layer 14 contains the fine particles W of tungsten oxide and / or composite tungsten oxide as described above, and as a result, the weather resistant resin that effectively cuts the heat ray and disperses it is generally used. Since it is a resin that does not easily generate radicals upon receiving light, radicals are not supplied to tungsten that is easily oxidized by radicals, and oxidation of tungsten from trivalent to pentavalent hardly occurs. For this reason, the heat ray cut layer hardly causes blue discoloration even when used for a long time.

  The fine particles W of tungsten oxide and / or composite tungsten oxide may be included in the intermediate films 12A and 12B, the glass plates 11A and 11B, and the plastic film 13. Further, only the heat ray cut layer 14 may be provided without using the plastic film 13.

  If a glass plate can be bonded to the heat ray cut layer 14 (if it has an intermediate film function), it is also possible to produce a laminated glass by bonding the two glass plates 11A and 11B with the heat ray cut layer 14. .

  However, by using the plastic film 13 provided with the heat ray cut layer 14 on the surface, there is an advantage that the conventional intermediate film can be used as it is.

  FIG. 2 is a schematic cross-sectional view showing an example of an embodiment of a laminate (film reinforced glass such as bilayer and window film) of the present invention. In the laminated body 20 of FIG. 2, an intermediate film 22, a heat ray cut layer 24 containing fine particles W of tungsten oxide and / or composite tungsten oxide and a weather resistant resin, a plastic film 23 and a hard coat layer 25 are formed on a glass plate 21. Are sequentially laminated and integrated. In general, the laminate 20 is obtained by bonding and integrating a glass plate 21 and a plastic film 23 having a heat ray cut layer 24 and a hard coat layer 25 on the front and back sides with an intermediate film 22.

  Instead of using the heat ray cut layer 24, the hard coat layer 25 may be a heat ray cut layer containing fine particles W of tungsten oxide and / or composite tungsten oxide and a weather-resistant resin, and may further be provided with a hard coat function. That is, it is obtained by imparting the function of the weather-resistant resin to the resin used for the hard coat layer (for example, use of a fluororesin having a polymerizable double bond, or blending of a fluororesin and an ultraviolet curable resin). In this case, the composite tungsten oxide fine particles may be dispersed and coated in the hard coat layer forming composition, and mixing of the composite tungsten oxide fine particles is extremely simple.

  Moreover, if the heat ray cut layer 24 can adhere a glass plate and a plastic film, it is also possible to produce a laminate by adhering them with the heat ray cut layer 14.

  For example, when the laminate is a bilayer used for a side glass of an automobile, the intermediate film 22 needs to be an adhesive layer. In this case, the intermediate film 22 includes polyvinyl butyral as described above. It is a layer of composition (PVB layer) or a layer of composition containing an ethylene / vinyl acetate copolymer (EVA layer). These laminates may be used. The EVA layer is preferably a crosslinked layer of a composition containing an ethylene / vinyl acetate copolymer containing an organic peroxide.

  Moreover, when a laminated body is used for a window film etc., generally an intermediate film is an adhesive layer. The pressure-sensitive adhesive layer is a resin layer that can be re-peeled in the present invention. For example, an acrylic adhesive.

The fine particles W of tungsten oxide and / or composite tungsten oxide are generally contained in the heat ray cut layer, but may be mixed in any layer or a plurality of layers such as an intermediate film, a heat ray cut layer, and a hard coat layer. Since it is good, since the thickness of the layer differs depending on which mode is adopted, the amount of addition to the layer varies. Therefore, by defining the amount of the composite tungsten oxide fine particles W contained per 1 m ^{2 of} the laminated body, the present invention can be applied to any case. In the present invention, the amount of fine particles W of tungsten oxide and / or composite tungsten oxide contained per 1 m ² of the laminate is generally preferably 0.1 to 50 g, 0.5 to 20 g, and more preferably 0.1 to 10 g. preferable. By including the composite tungsten oxide fine particles in such a range, it is possible to achieve both the heat ray cut characteristics and transparency of the obtained laminate.

  When one of the glass plates is a plastic film (film tempered glass), the laminated glass of the present invention can also be designed to have appropriate performance in impact resistance, penetration resistance, transparency, and the like. For example, it can be used for glass such as window glass provided in various vehicle bodies and buildings, or glass such as showcases and show windows. In particular, a window glass provided in a building or the like is called a window film, and an adhesive layer is generally used as an intermediate film. Both glass plates can be designed to exhibit particularly excellent impact resistance and improved penetration resistance, and can be used for various applications including laminated glass.

  The tungsten oxide used in the present invention is an oxide represented by the general formula WyOz (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and is a composite tungsten oxide. Is an 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, Be, Hf, Os, Bi, and I). As a result, free electrons are generated in WyOz, including the case of z / y = 3.0, and free electron-derived absorption characteristics are expressed in the near infrared region, which is effective as a near infrared absorbing material near 1000 nm. . In the present invention, composite tungsten oxide is preferable.

In the tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), the preferable composition range of tungsten and oxygen is When the composition ratio of oxygen is less than 3 and the infrared shielding material is described as WyOz, 2.2 ≦ z / y ≦ 2.999. 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 which is not intended in the infrared shielding material and to obtain chemical stability as a material. Therefore, it can be applied as an effective infrared shielding material. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated and an efficient infrared shielding material can be obtained.

  From the viewpoint of stability, the composite tungsten oxide fine particles are generally 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, One or more elements selected from Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, (0.001 ≦ x / Y ≦ 1, 2.2 ≦ z / y ≦ 3) The alkali metal is a group 1 element of the periodic table excluding hydrogen, and the alkaline earth metal is the second element of the periodic table. Group elements and rare earth elements are Sc, Y and lanthanoid elements.

  In particular, from the viewpoint of improving optical characteristics and weather resistance as an infrared shielding material, the M element is one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Some are preferred. The composite tungsten oxide is preferably treated with a silane coupling agent. Excellent dispersibility is obtained, and an excellent infrared cut function and transparency are obtained.

  If the value of x / y indicating the added amount of the element M is larger than 0.001, a sufficient amount of free electrons is generated, and a sufficient 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 effect also increases, but the value of x / y is saturated at about 1. Moreover, if the value of x / y is smaller than 1, it is preferable because an impurity phase can be prevented from being generated in the fine particle-containing layer.

  Regarding the value of z / y indicating the control of the amount of oxygen, in the composite tungsten oxide represented by MxWyOz, the same mechanism as that of the infrared shielding material represented by WyOz described above works, and z / y = Even in 3.0, since there is a supply of free electrons due to the addition amount of the element M described above, 2.2 ≦ z / y ≦ 3.0 is preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable. It is.

  Further, when the composite tungsten oxide fine particles have a hexagonal crystal structure, the transmission of the fine particles in the visible light region is improved and the absorption in the near infrared region is improved.

When the cation of the element M is added to the hexagonal void, the transmission in the visible light region is improved and the absorption in the near infrared region is improved. Here, generally, when the element M having a large ionic radius is added, the hexagonal crystal is formed. Specifically, Cs, K, Rb, Tl, In, Ba, Sn, Li, Ca, Sr, When Fe is added, hexagonal crystals are easily formed. Of course, other elements may be added as long as the additive element M exists in the hexagonal void formed by the WO ₆ unit, and is not limited to the above elements.

  When the composite tungsten oxide fine particles having a hexagonal crystal structure have a uniform crystal structure, the addition amount of the additive element M is preferably 0.2 or more and 0.5 or less in terms of x / y, and more preferably 0. .33. When the value of x / y is 0.33, it is considered that the additive element M is arranged in all of the hexagonal voids.

  Besides hexagonal crystals, tetragonal and cubic tungsten bronzes also have an infrared shielding effect. These crystal structures tend to change the absorption position in the near infrared region, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Further, it is in the order of hexagonal crystal <tetragonal crystal <cubic crystal that has little absorption in the visible light region. For this reason, it is preferable to use hexagonal tungsten bronze for applications that transmit light in the visible light region and shield light in the infrared region.

  The particle diameter of the composite tungsten oxide fine particles used in the present invention is preferably 800 nm or less (average particle diameter), particularly 400 nm or less from the viewpoint of maintaining transparency. This is because particles smaller than 800 nm do not completely block light due to scattering, can maintain visibility in the visible light region, and at the same time can 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 the particles, the particle size is 200 nm or less, preferably 100 nm or less.

  Moreover, it is preferable from the viewpoint of improving weather resistance that the surface of the composite tungsten oxide fine particles of the present invention is coated with an oxide containing one or more of Si, Ti, Zr, and Al.

  The composite tungsten oxide fine particles of the present invention are produced, for example, as follows.

  The tungsten oxide fine particles represented by the general formula WyOz and / or the composite tungsten oxide fine particles represented by MxWyOz are obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. Can do.

  The tungsten compound starting material is obtained by dissolving tungsten trioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride in alcohol and then drying. Tungsten oxide hydrate powder, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying it, or ammonium tungstate It is preferable that it is at least one selected from a tungsten compound powder obtained by drying an aqueous solution and a metal tungsten powder.

  Here, when producing tungsten oxide fine particles, it is preferable to use tungsten oxide hydrate powder or tungsten compound powder obtained by drying an ammonium tungstate aqueous solution from the viewpoint of the ease of the production process. More preferably, when producing the composite tungsten oxide fine particles, an ammonium tungstate aqueous solution or a tungsten hexachloride solution is further used from the viewpoint that each element can be easily and uniformly mixed when the starting material is a solution. preferable. These raw materials are used and heat-treated in an inert gas atmosphere or a reducing gas atmosphere to obtain tungsten oxide fine particles and / or composite tungsten oxide fine particles having the above-mentioned particle diameter.

  The composite tungsten oxide fine particles represented by the general formula MxWyOz containing the element M are the same as the tungsten compound starting material of the tungsten oxide fine particles represented by the general formula WyOz described above. A tungsten compound contained in the form of a simple substance or a compound is used as a starting material. Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material with a solution, and the tungsten compound starting material containing the element M is dissolved in a solvent such as water or an organic solvent. Preferably it is possible. Examples thereof include tungstate, chloride, nitrate, sulfate, oxalate, oxide, and the like containing element M, but are not limited to these and are preferably in the form of a solution.

Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has sufficient coloring power and is efficient as infrared shielding fine particles. As the inert gas, an inert gas such as Ar or N ₂ is preferably used. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated at 100 to 650 ° C. in a reducing gas atmosphere, and then heat-treated at a temperature of 650 to 1200 ° C. in an inert gas atmosphere. . The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the volume ratio of H ₂ is preferably 0.1% or more, more preferably 2% or more, as the composition of the reducing atmosphere. If it is 0.1% or more, the reduction can proceed efficiently.

The raw material powder reduced with hydrogen contains a magnetic phase, exhibits good infrared shielding properties, and can be used as infrared shielding particles in this state. However, since hydrogen contained in tungsten oxide is unstable, application may be limited in terms of weather resistance. Therefore, a more stable infrared shielding fine particle can be obtained by heat-treating the tungsten oxide compound containing hydrogen at 650 ° C. or higher in an inert atmosphere. The atmosphere during the heat treatment at 650 ° C. or higher is not particularly limited, but N ₂ and Ar are preferable from an industrial viewpoint. By the heat treatment at 650 ° C. or higher, a Magneli phase is obtained in the infrared shielding fine particles, and the weather resistance is improved.

  The composite tungsten oxide fine particles of the present invention are preferably surface-treated with a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. Silane coupling agents are preferred. Thereby, affinity with binders, such as an intermediate | middle layer, a hard-coat layer, and a heat ray cut layer, becomes favorable, and various physical properties improve other than transparency and heat ray cut property.

  Examples of silane coupling agents include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β -(Aminoethyl) -γ-aminopropyltrimethoxysilane and trimethoxyacrylsilane can be mentioned. Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and trimethoxyacrylsilane are preferred. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable to use 5-20 mass parts of content of the said compound with respect to 100 mass parts of microparticles | fine-particles.

  The heat ray cut layer of the present invention or the near-infrared shielding layer described later is a layer in which fine particles of the above tungsten oxide and / or composite tungsten oxide are dispersed in a weather resistant resin.

  The weather resistant resin in the present invention is a resin containing a bond having a bond energy of 80 kcal / mol or more, preferably 100 kcal / mol or more. For example, Si—O is 108 kcal / mol, and C—F is 116 kcal / mol.

  Examples of such weather resistant resins include fluororesins, silicone resins, olefin resins, acrylic resins and the like, with fluororesins and silicone resins being preferred.

  Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ), Polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), fluoroethylene vinyl ether (FEVE) and ethylene chlorotrifluoroethylene copolymer (ECTFE), the following structure:

(N = 10 to 1000)
The polymer A which has this can be mentioned. Among these, the polymer A and fluoroethylene vinyl ether (FEVE) are preferable. These (co) polymers further have functional groups (eg, alkoxysilyl groups, hydroxyl groups, amino groups, imino groups, (meth) acryloyloxy groups, epoxy groups, carboxyl groups, sulfonyl groups, acrylate type isocyanurate groups, sulfuric acid groups. Base). Preferred examples of commercially available fluororesins include CYTOP (Asahi Glass Co., Ltd.), Zeffle (Daikin Chemical Co., Ltd.), and OPTOOL (Daikin Chemical Co., Ltd.). These are thermoplastic, thermosetting, or light (generally UV) curable resins. When curing, it is preferable to use a curing agent and a crosslinking agent as appropriate. For example, when ultraviolet curing is performed, it is preferable to use various polymerizable monomers and initiators used in the formation of the hard coat layer.

  Examples of silicone resins include straight silicone varnish and modified silicone varnish. Straight silicone varnish is usually produced by hydrolysis polymerization of phenyltrichlorosilane, diphenyldichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane (when used, it is generally cured at 100 ° C. or higher after application). The modified silicone varnish is obtained by reacting a silicone varnish with a resin such as alkyd, polyester, acrylic, or epoxy. Preferable examples of commercially available silicone resins include silicone varnish KR series (manufactured by Shin-Etsu Chemical Co., Ltd.).

  Examples of the olefin resin include polyethylene, polypropylene, and chlorinated polyethylene.

  Examples of the acrylic resin include thermoplastic acrylic resins such as acrylonitrile ethylene propylene rubber styrene copolymer (AES) and acrylonitrile styrene acrylate (ASA), or thermosetting acrylic resins (self-curing type, polyisocyanate, amino resin, polyester). Or, a cross-linking type with an epoxy resin).

  The heat ray cut layer or near-infrared shielding layer of the present invention is obtained by applying a coating solution in which fine particles of the above tungsten oxide and / or composite tungsten oxide are dispersed together with a weather-resistant resin and, if necessary, an organic solvent, onto a plastic film or the like. It is obtained by coating and drying. When the (composite) tungsten oxide fine particles are mixed in the weather resistant resin, the resin composition containing the (composite) tungsten oxide fine particles is generally kneaded in advance using a roll mill, a sand mill, an attritor or the like. It is preferable to disperse oxide fine particles.

  Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and alcohols such as isopropyl alcohol.

  The heat ray cut layer preferably contains 10 to 500 parts by mass, more preferably 20 to 500 parts by mass, and particularly preferably 30 to 300 parts by mass of the (composite) tungsten oxide with respect to 100 parts by mass of the binder resin. The thickness of the heat ray cut layer is generally 0.1 to 50 μm, preferably 0.1 to 10 μm, and particularly preferably 0.1 to 5 μm.

  The glass plate used in the present invention is usually silicate glass. In the case of film tempered glass, the glass plate thickness varies depending on the place where it is installed. For example, when it is used for a side glass and a fitted glass of an automobile, it is not necessary to make it thick like a windshield, generally 0.1 to 10 mm, and preferably 0.3 to 5 mm. The one glass plate 1 is reinforced chemically or thermally.

  In the case of a laminated glass that is both a glass plate suitable for an automobile windshield or the like, the thickness of the glass plate is generally 0.5 to 10 mm, and preferably 1 to 8 mm.

  In the case of an adhesive layer, the intermediate film used in the laminate of the present invention is generally an EVA layer or a PVB layer, or a laminate film thereof.

  The PVB resin composition constituting the PVB layer generally contains a PVB resin, a plasticizer, an ultraviolet absorber, and the like. As the PVB resin, those having a polyvinyl acetal unit of 70 to 95% by weight, a polyvinyl acetate unit of 1 to 15% by weight and an average degree of polymerization of 200 to 3000, particularly 300 to 2500 are preferred.

  Examples of the plasticizer for the PVB resin composition include organic plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers.

  Monobasic acid esters include organic acids such as butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid), decylic acid, and tris. Esters obtained by reaction with ethylene glycol are preferred, in particular triethylene-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, triethylene glycol-di-capronate, triethylene glycol- Di-n-octoate is preferred. An ester of the above organic acid with tetraethylene glycol or tripropylene glycol can also be used.

  As the polybasic acid ester plasticizer, for example, an ester of an organic acid such as adipic acid, sebacic acid or azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms is preferable. Kate, dioctyl azelate and dibutyl carbitol adipate are preferred.

  As the phosphoric acid plasticizer, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like are preferable.

  In the PVB resin composition, if the amount of the plasticizer is small, the film formability is deteriorated, and if it is too large, the durability during heat resistance is impaired. Therefore, the plasticizer is generally added in an amount of 5 to 50 with respect to 100 parts by mass of the polyvinyl butyral resin. It is preferable to include 10 parts by mass, particularly 10 to 40 parts by mass.

  In the PVB resin composition of the present invention, a benzophenone compound, a triazine compound, a benzoate compound, a hindered amine compound, or the like can be used as an ultraviolet absorber (UV absorber). Benzophenone compounds are preferred because yellowing is suppressed.

  Preferred examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, particularly 2-hydroxy-4-n-octylbenzophenone, 2,2'-dihydroxy- 4,4′-dimethoxybenzophenone is preferred.

  In a PVB layer, it is preferable to use the said ultraviolet absorber 0.05-1.0 mass part (especially 0.1-0.2 mass part) with respect to 100 mass parts of PVB.

  Furthermore, the PVB resin composition may contain an alkali or alkaline earth metal salt of a fatty acid (generally used as an adhesion modifier).

  Examples of alkaline earth metal salts of the above fatty acids include magnesium formate, magnesium acetate, magnesium lactate, magnesium stearate, magnesium octylate, calcium formate, calcium acetate, calcium lactate, calcium stearate, calcium octylate, barium formate, acetic acid Barium, barium lactate, barium stearate, barium octylate, etc .; examples of alkali metal salts of fatty acids include potassium formate, potassium acetate, potassium lactate, potassium stearate, potassium octylate, sodium formate, sodium acetate, sodium lactate , Sodium stearate, sodium octylate and the like.

  Additives such as stabilizers and antioxidants may be added to the PVB resin composition to further prevent deterioration.

  EVA used for the EVA resin composition constituting the EVA layer generally has a vinyl acetate content of 23 to 38% by mass, more preferably 23 to 38% by mass, and particularly preferably 23 to 28% by mass. When the vinyl acetate content is less than 23% by mass, the transparency of the resin obtained when crosslinked and cured at a high temperature is not sufficient. Conversely, when the vinyl acetate content exceeds 38% by mass, the impact resistance when a security glass is obtained. The penetration resistance tends to be insufficient. Moreover, it is preferable that the melt flow index (MFR) of EVA is 4.0-30.0 g / 10min, especially 8.0-18.0g / 10min. Pre-crimping becomes easy.

  The EVA resin composition contains an organic peroxide and an ultraviolet absorber in the EVA, and may further contain various additives such as a crosslinking aid, an adhesion improver, and a plasticizer as necessary. it can.

  Examples of the ultraviolet absorber include benzophenone compounds, triazine compounds, benzoate compounds, and hindered amine compounds. From the viewpoint of suppressing yellowing, benzophenone compounds are preferred.

  In the EVA layer, it is preferable to use 0.05 to 1.0 parts by mass (particularly 0.1 to 0.2 parts by mass) of the ultraviolet absorber with respect to 100 parts by mass of EVA.

  In the present invention, any organic peroxide can be used in combination as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.

  Examples of this organic peroxide include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di- t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α′-bis (t-butylperoxy) Isopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone pero Oxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide Oxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic acid peroxide, acetyl peroxide, m-toluoyl peroxide, t-butyl peroxyisobutylene and 2,4-dichlorobenzoyl peroxide Can be mentioned.

  The EVA layer is used to improve or adjust various physical properties of the film (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.), and in particular to improve mechanical strength. It preferably contains a group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound.

  The acryloxy group-containing compound and methacryloxy group-containing compound to be used are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group. Group, 3-chloro-2-hydroxypropyl group. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used.

  Examples of amides include diacetone acrylamide.

  Examples of polyfunctional compounds (crosslinking aids) include esters obtained by esterifying a plurality of acrylic acid or methacrylic acid with glycerin, trimethylolpropane, pentaerythritol, and the like, and the aforementioned triallyl cyanurate and triallyl isocyanurate. it can.

Examples of epoxy-containing compounds include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and phenol. (Ethyleneoxy) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether can be mentioned.

  In the present invention, a silane coupling agent can be added as an adhesion improver in order to further enhance the adhesive force between the EVA layer and the glass plate or transparent plastic film.

  Examples of this silane coupling agent include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltri Methoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- Mention may be made of β- (aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable that content of the said compound is 5 mass parts or less with respect to 100 mass parts of EVA.

  The plasticizer is not particularly limited, but polybasic acid esters and polyhydric alcohol esters are generally used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate. One type of plasticizer may be used, or two or more types may be used in combination. The content of the plasticizer is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of EVA.

  When the intermediate film used in the laminate of the present invention is a pressure-sensitive adhesive layer, a layer of a thermosetting resin is generally used in addition to the EVA layer or the PVB layer. In the case of the EVA layer or the PVB layer, it is necessary to set the composition of the layer so as to have tackiness so that, for example, a plastic film can be peeled again from the window film, unlike the adhesive layer. For example, in the case of an EVA layer, it is considered to use a material having a high vinyl acetate content and suppress the amount of the crosslinking agent (organic peroxide) used. As other thermosetting resins, acrylic resins, polyurethane resins, epoxy resins, and the like can be used.

  The EVA layer of the present invention is produced, for example, by a method of obtaining a layered product by molding a composition containing the above-mentioned EVA, organic peroxide, ultraviolet absorber, etc. by ordinary extrusion molding, calendar molding (calendering) or the like. can do. In the same manner as described above, the PVB layer of the present invention is formed by, for example, a method of obtaining a layered product by molding a composition containing PVB, an ultraviolet absorber, etc. by ordinary extrusion molding, calendar molding (calendering), or the like. Can be manufactured. When the (composite) tungsten oxide fine particles are mixed in the intermediate film, the molding may be performed by adding the fine particles to the composition. When the fine particles need to be sufficiently dispersed, they may be dispersed in advance using a roll mill, a sand mill, an attritor or the like.

  Alternatively, a layered product can be obtained by dissolving the above composition in a solvent and coating the solution on a suitable support with a suitable coating machine (coater) and drying to form a coating film. When a composition containing fine particles of (composite) tungsten oxide is applied as described above, it is generally preferable to disperse in advance using a roll mill, a sand mill, an attritor or the like.

  The PVB layer and the EVA layer may be formed by using a resin film, or a PVB / EVA composite resin film formed by two-layer extrusion molding of a PVB resin and an EVA resin. Moreover, the other resin composition is applied to any one of the resin films, and for example, the EVA resin composition is applied to a previously formed PVB resin film to form a two-layer laminated film. You may do it. A three-layer laminated film for bonding can be formed in the same manner.

  In order to produce a laminated glass as the laminate of the present invention, first, a plastic film having a heat ray cut layer is prepared. This can be obtained by applying a coating liquid in which fine particles of (composite) tungsten oxide are dispersed in a weather-resistant resin on a plastic film and drying (by further curing with light or the like if necessary). In order to disperse the (composite) tungsten oxide fine particles in the weather resistant resin, generally, a roll mill, a sand mill, an attritor or the like is used in advance.

  As a laminated body of the present invention, for example, a laminated glass is manufactured by first forming an EVA resin film as described above, and a plastic in which the heat ray cut layer is formed between the glass plates via the EVA resin film. After sandwiching the film and degassing the laminate, it may be bonded and integrated by pressing under heating. Such a laminate can be obtained, for example, by a vacuum bag method or a nip roll method. Such lamination can be performed by pressure bonding by a nip roll method because the EVA layer is soft, and the production of the laminate becomes easy. It is preferable that the temperature of a nip roll is 80-140 degreeC.

  When the laminate (laminated glass) is produced, the EVA layer is generally crosslinked at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. Such cross-linking is carried out at the temperature of 80 to 120 ° C., for example, at 100 to 150 ° C. (especially around 130 ° C.) after degassing while being sandwiched between the glass plates when the laminate is produced. The heat treatment is performed for 10 minutes to 1 hour. Cooling after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

  As described above, one glass plate of the laminate of the present invention may be a film reinforced glass as a plastic film, and as the plastic film used at that time, a polyethylene terephthalate (PET) film or a polyethylene aphthalate (PEN) film is used. And polyethylene butyrate film, and PET film is preferred.

  When the hard coat layer is formed on the surface of the plastic film, an ultraviolet curable resin or a thermosetting resin is used as the resin used for that purpose. The hard coat layer generally has a thickness of 1 to 50 μm, preferably 3 to 20 μm.

  As the ultraviolet curable resin, a known ultraviolet curable resin can be used, and any other low molecular weight and multifunctional resin suitable for hard coat treatment is not particularly limited. In general, an ultraviolet curable resin used in a hard coat layer for an optical filter described later can be used. Particularly preferred ultraviolet curable resins include, for example, urethane oligomers having a plurality of ethylenic double bonds, oligomers such as polyester oligomers or epoxy oligomers, pentaerythritol tetraacrylate (PETA), pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate (DPEHA). The monofunctional or polyfunctional oligomer such as) is generally composed of a reactive diluent and a photopolymerization initiator. Furthermore, various additives can be contained. As the reactive diluent, the acryloxy group-containing compound, methacryloxy group-containing compound and / or epoxy group-containing compound used in the transparent adhesive layer can be used, and the transparent adhesive layer can also be used as a photopolymerization initiator. The compounds used in can be used.

  One kind of each of the oligomer, the reactive diluent and the initiator may be used, or two or more kinds thereof may be used in combination. As for content of a reactive diluent, 0.1-10 mass parts is common with respect to 100 mass parts of ultraviolet curable resin, and 0.5-5 mass parts is preferable. The content of the photopolymerization initiator is preferably 5 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable resin.

  As the thermosetting resin, a reactive acrylic resin, a melamine resin, an epoxy resin, or the like can be used. The ultraviolet curable resin can also be used.

  When a hard coat layer is formed using an ultraviolet curable resin, the ultraviolet curable resin is diluted as it is or with an organic solvent to an appropriate concentration, and the resulting solution is applied to an appropriate film with an appropriate coating machine (coater). After coating on top and drying as necessary, a hard coat layer can be formed by irradiating with UV light for several seconds to several minutes directly or through a release sheet (after vacuum degassing) with a UV lamp. As the UV lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or the like can be used. When the (composite) tungsten oxide fine particles are dispersed and mixed in the hard coat layer, the hard coat layer forming composition or the ultraviolet curable resin containing the composite tungsten oxide fine particles is generally prepared in advance by a roll mill, a sand mill or an attritor. It is preferable to disperse the fine particles of the composite tungsten oxide by kneading using a method such as the like.

  When a hard coat layer is formed using a thermosetting resin, an organic solvent solution of the thermosetting resin is applied onto an appropriate film with an appropriate coating machine (coater), and a release sheet is provided if necessary, a laminator, etc. After degassing, heat curing and thermocompression bonding are performed. In the case where the release sheet is not used, it is preferable to dry for 60 seconds before heating and pressure bonding to evaporate the solvent of the coating layer and to prevent the surface from sticking. Even when a release sheet is used, it is preferable that the release sheet is provided after slightly drying.

  In order to produce a film tempered glass as the laminate of the present invention, for example, first, the hard coat layer and / or the heat ray cut layer is provided on the plastic film by coating as described above, and then laminated. Is placed on a glass plate through an EVA resin film obtained by film formation, and after degassing the laminate, it may be bonded and integrated by pressing under heating. Such a laminate can be obtained, for example, by a vacuum bag method or a nip roll method. Such lamination can be performed by pressure bonding by a nip roll method because the EVA layer is soft, and the production of the laminate becomes easy. It is preferable that the temperature of a nip roll is 80-140 degreeC.

  When the laminate (laminated glass) is produced, the EVA layer is generally crosslinked at 100 to 150 ° C. (particularly around 130 ° C.) for 10 minutes to 1 hour. Such cross-linking is carried out at the temperature of 80 to 120 ° C., for example, at 100 to 150 ° C. (especially around 130 ° C.) after degassing while being sandwiched between the glass plates when the laminate is produced. The heat treatment is performed for 10 minutes to 1 hour. Cooling after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

  You may provide the transparent conductive layer which consists of a metal and / or a metal oxide in the surface of the glass plate of the laminated body obtained by this invention.

  A barrier layer may be formed on the side surface of the laminate obtained as described above. In general, the thickness of the barrier layer is preferably 0.1 to 20 μm and 1 to 10 μm.

  The laminate thus obtained can be used for the following applications. In other words, glass fitted in automobiles, side glass and rear glass, railway vehicles such as ordinary vehicles, express vehicles, express vehicles and sleeper vehicles, door windows for opening and closing doors for passengers, window glasses and indoor door glasses, windows in buildings such as buildings Glass and indoor door glass, indoor display showcases and show windows. Preferably, it is useful for automobile side or rear glass, railcar window glass, especially automobile door glass.

  Next, the display optical filter of the present invention will be described with reference to the drawings.

  FIG. 3 is a schematic cross-sectional view of an example of an embodiment of the optical filter of the present invention.

  The optical filter of the present invention has a configuration in which a transparent film 31, an antireflection layer 36 formed on one surface of the transparent film 31, and a near-infrared shielding layer 34 formed on the other surface of the transparent film 31 are provided. Have. In the case of such a filter, in the present invention, the near-infrared shielding layer 34 includes fine particles W of tungsten oxide and / or composite tungsten oxide and weather resistant resin.

  Alternatively, the near-infrared shielding layer 34 may be made sticky and used to adhere to another optical film or the display surface. Alternatively, an adhesive layer may be provided on the near infrared shielding layer 33. Depending on the application, the antireflection layer 36 may be omitted.

  Such a display optical filter having a near-infrared shielding film is particularly good when used as a PDP optical filter, because the display image of the obtained PDP is effectively cut off from near-infrared rays. Therefore, a good display image can be maintained for a long time.

  FIG. 4 shows a schematic sectional view of an example of a preferred embodiment of the optical filter of the present invention. This optical filter is a laminate (front) provided with a transparent film 41A, an antireflection layer 46 formed on one surface of the transparent film 41A, and a near-infrared shielding layer 44 formed on the other surface of the transparent film 41A. 3 and the transparent film 41B, a mesh-like conductive layer 47 formed on one surface of the transparent film 41B, and an adhesive layer 48 containing a neon cut pigment formed on the other surface of the transparent film 41B. And a laminated body provided with a near-infrared shielding layer (when sticking) 44. When the near-infrared shielding layer 44 does not have adhesiveness, it is necessary to provide an adhesive layer between the near-infrared shielding layer (adhesive layer) 44 and the mesh-like conductive layer 47.

  In the case of such a filter, in the present invention, the near-infrared shielding layer 44 contains tungsten oxide and / or composite tungsten oxide and weathering resin, and the adhesive layer 48 removes the orange color derived from neon light emission. It is preferable to contain a neon cut dye. A display provided with such an optical filter, particularly a PDP, exhibits excellent display characteristics.

  Such an optical filter is generally adhered to the display surface via an adhesive layer 48, or is adhered to a glass plate via the adhesive layer 48 and disposed on the front surface of the PDP.

  An example of another preferred embodiment of the optical filter of the present invention is shown in FIG. A mesh-like conductive layer (electromagnetic wave shielding layer) 54 is provided on one surface of the transparent film 51, an antireflection layer 56 is provided on the conductive layer 54, and a near-infrared shielding layer is provided on the other surface of the transparent film 51. 54 is provided, and an adhesive layer 55 containing a neon cut pigment is further provided thereon. Therefore, only one transparent film 51 is used as a substrate, and a thin film can be obtained as compared with the optical filter of FIG. In this optical filter, the near-infrared shielding layer 54 contains tungsten oxide and / or composite tungsten oxide fine particles and a weather resistant resin.

  The optical filter of the present invention may have any configuration as long as it contains fine particles of tungsten oxide and / or composite tungsten oxide and a weather resistant resin, and configurations other than those shown in FIGS. For example, the position of the layer shown above may be changed as appropriate.

  In the present invention, generally, the antireflection layer 36 or the like is a hard coat layer; whether it comprises a hard coat layer and a low refractive index layer having a lower refractive index than the hard coat layer (in this case, the hard coat layer is a metal conductive layer). Or a high refractive index layer having a higher refractive index than that of the hard coat layer and a low refractive index layer having a lower refractive index than that of the hard coat layer (in this case, the hard coat layer is in contact with the metal conductive layer). ing). The more layers, the better antireflection properties are obtained. Alternatively, it is also preferable that the antireflection layer 36 or the like is composed of an antiglare layer or an antiglare layer and a low refractive index layer having a lower refractive index than the antiglare layer (the antiglare layer is in contact with the metal conductive layer). The antiglare layer is a so-called antiglare layer, generally has an excellent antireflection effect, and it is often unnecessary to provide an antireflection layer such as a low refractive index layer.

  4 and 5 show examples of the near-infrared shielding layer and the adhesive layer, but a near-infrared shielding layer, a neon cut layer, and an adhesive layer may be used. Or it consists of the transparent adhesive layer which has a near-infrared absorption function and a neon cut function, or consists of the near-infrared shielding layer which has a neon cut function, and an adhesive layer (it is provided on the transparent film in this order). Or you may consist of a near-infrared shielding layer, a neon cut layer, and an adhesive layer (it is provided on the transparent film in this order).

  The conductive layer 47 or the like is, for example, a mesh-like metal layer or metal-containing layer, a metal oxide layer (dielectric layer), or an alternately laminated film of metal oxide layers and metal layers. The mesh-like metal layer or metal-containing layer is generally formed by etching or printing, or is a metal fiber layer. This makes it easy to obtain low resistance. In general, the voids of the mesh of the mesh-like metal layer or metal-containing layer are filled with the hard coat layer or the antiglare layer as described above. This improves transparency. When it is not filled with a hard coat layer or the like, it is preferably filled with another layer, for example, a near-infrared shielding layer or the like, or a dedicated transparent resin layer.

  The near infrared shielding layer 34 and the like have a function of blocking unnecessary light from the PDP. Generally, it is a layer containing the tungsten oxide and / or composite tungsten oxide of the present invention and a weather resistant resin. The adhesive layer 48 or the like generally contains a neon cut pigment and is provided for easy mounting on a display. A release sheet may be provided on the pressure-sensitive adhesive layer 48 or the like.

  The optical filter for display according to the present invention is formed, for example, by forming a mesh-like metal conductive layer over the entire surface of the transparent film and then forming an antireflection layer over the entire mesh-like metal conductive layer. It is obtained by forming a near-infrared shielding layer on the back surface and a transparent pressure-sensitive adhesive layer thereon. Alternatively, using two transparent films, for example, on the conductive layer of a transparent film having a mesh-like conductive layer (generally having a pressure-sensitive adhesive layer or the like on the back surface), an antireflection layer on the front surface and an adhesive near-infrared surface on the back surface It can also be obtained by laminating and adhering a transparent film having a shielding layer via a near infrared shielding layer. Alternatively, an antireflection layer such as a mesh-like metal conductive layer, an antiglare layer and a low refractive index layer is provided in this order on the surface of the transparent film, and a near infrared shielding layer and an upper layer are provided on the surface of another transparent film. A transparent pressure-sensitive adhesive layer is provided on the surface, and two transparent film layers are not provided, and the surfaces are adhered to each other. In this case, the former laminate is produced by the method of the present invention.

  The material used for the optical filter for display of this invention is demonstrated below.

  The film is generally a transparent film, in particular a transparent plastic film. The material is not particularly limited as long as it is transparent (meaning “transparent to visible light”). Examples of plastic films include polyester {eg, polyethylene terephthalate (PET), polybutylene terephthalate}, polymethyl methacrylate (PMMA), acrylic resin, polycarbonate (PC), polystyrene, triacetate resin, polyvinyl alcohol, polyvinyl chloride, poly Examples thereof include vinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, polyvinyl butyral, metal ion crosslinked ethylene-methacrylic acid copolymer, polyurethane, cellophane and the like. Among these, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), etc. are highly resistant to loads during processing (heat, solvent, bending, etc.) and particularly highly transparent. preferable. In particular, PET is preferable because it has excellent processability. Further, the organic dyes contained in the second functional layer are likely to be deteriorated in durability by receiving ultraviolet rays, but polyesters such as PET are preferable because they tend to absorb such ultraviolet rays.

  The thickness of the transparent film varies depending on the use of the optical filter, but is generally 1 μm to 10 mm, 1 μm to 5 mm, and particularly preferably 25 to 250 μm.

  The metal conductive layer of the present invention is set so that the surface resistance value of the obtained optical filter is generally 10Ω / □ or less, preferably in the range of 0.001 to 5Ω / □, particularly 0.005 to 5Ω / □. Is done. A mesh-like conductive layer is also preferable. Alternatively, the conductive layer may be a layer obtained by a vapor deposition method (a transparent conductive thin film of metal oxide (ITO or the like)). Further, it may be an alternate laminate of a metal oxide dielectric film such as ITO and a metal layer such as Ag (eg, ITO / silver / ITO / silver / ITO laminate).

  The mesh-like metal conductive layer is made of metal fibers and metal-covered organic fibers made of a mesh, the copper foil on the transparent film is etched into a mesh and the openings are provided, on the transparent film Examples thereof include a conductive ink printed in a mesh shape.

  In the case of a mesh-shaped metal conductive layer, the mesh preferably has a wire diameter of 1 μm to 1 mm made of metal fibers and / or metal-coated organic fibers and an aperture ratio of 50% or more. A more preferable wire diameter is 10 to 500 μm, and an aperture ratio is 50 to 95%. When the wire diameter exceeds 1 mm in the mesh-like conductive layer, the electromagnetic wave shielding property is improved, but the aperture ratio is lowered and cannot be made compatible. If it is less than 1 μm, the strength as a mesh is lowered and handling becomes difficult. Further, if the aperture ratio exceeds 95%, it is difficult to maintain the shape as a mesh. If the aperture ratio is less than 50%, the light transmittance decreases and the light amount from the display also decreases.

  The opening ratio of the conductive mesh refers to the area ratio occupied by the opening portion in the projected area of the conductive mesh.

  The metal fibers constituting the mesh-like conductive layer and the metal of the metal-coated organic fiber include copper, stainless steel, aluminum, nickel, titanium, tungsten, tin, lead, iron, silver, carbon or alloys thereof, preferably copper, Stainless steel and nickel are used.

  As the organic material for the metal-coated organic fiber, polyester, nylon, vinylidene chloride, aramid, vinylon, cellulose and the like are used.

  When a conductive foil such as a metal foil is subjected to pattern etching, copper, stainless steel, aluminum, nickel, iron, brass, or an alloy thereof, preferably copper, stainless steel, or aluminum is used as the metal of the metal foil.

  If the thickness of the metal foil is too thin, it is not preferable in terms of handleability and workability of pattern etching, and if it is too thick, it affects the thickness of the film obtained, and the time required for the etching process becomes long. The thickness is preferably about 1 to 200 μm.

  The shape of the etching pattern is not particularly limited, and examples thereof include a grid-like metal foil in which square holes are formed, and a punching metal-like metal foil in which circular, hexagonal, triangular or elliptical holes are formed. It is done. Further, the holes are not limited to those regularly arranged, and may be a random pattern. It is preferable that the area ratio of the opening part in the projection surface of this metal foil is 20 to 95%. Further, those having an aperture ratio of 50% or more are preferable, and particularly 50% or more and 95% or less. The line width is preferably 10 to 500 μm.

  In addition to the above, as a mesh-shaped metal conductive layer, dots are formed on the film surface by a material soluble in a solvent, and a conductive material layer made of a conductive material insoluble in a solvent is formed on the film surface. A mesh-like metal conductive layer obtained by removing the dots and the conductive material layer on the dots by bringing the film surface into contact with a solvent may be used.

  A metal plating layer may be further provided on the metal conductive layer in order to improve the conductivity (particularly in the case of forming a dot with a material soluble in the solvent). The metal plating layer can be formed by a known electrolytic plating method or electroless plating method. As the metal used for plating, generally, copper, copper alloy, nickel, aluminum, silver, gold, zinc, tin or the like can be used, preferably copper, copper alloy, silver, or nickel, In particular, it is preferable to use copper or a copper alloy from the viewpoint of economy and conductivity.

  Moreover, you may give anti-glare performance. When this anti-glare treatment is performed, a blackening treatment may be performed on the surface of the (mesh) conductive layer. For example, oxidation treatment of a metal film, black plating such as chromium alloy, application of black or dark ink, and the like can be performed.

  The antireflection layer of the present invention is generally a composite film of a hard coat layer having a refractive index lower than that of a transparent film as a substrate and a low refractive index layer having a refractive index lower than that of the hard coat layer provided thereon, or This is a composite film in which a high refractive index layer is further provided between the hard coat layer and the low refractive index layer. The antireflection film is effective even if it is only a hard coat layer having a refractive index lower than that of the substrate. However, when the refractive index of the substrate is low, a composite film of a hard coat layer having a higher refractive index than the transparent film and a low refractive index layer provided thereon, or a higher refractive index layer is provided on the low refractive index layer. A composite film obtained may be used.

  The hard coat layer is a layer mainly composed of a synthetic resin such as an acrylic resin layer, an epoxy resin layer, a urethane resin layer, or a silicon resin layer. The thickness is usually 1 to 50 μm, preferably 1 to 10 μm. The synthetic resin is generally a thermosetting resin or an ultraviolet curable resin, and an ultraviolet curable resin is preferable. The ultraviolet curable resin is preferable because it can be cured in a short time and has excellent productivity.

  Examples of the thermosetting resin include phenol resin, resorcinol resin, urea resin, melamine resin, epoxy resin, acrylic resin, urethane resin, furan resin, and silicon resin.

  The hard coat layer is preferably a cured layer of a layer mainly composed of an ultraviolet curable resin composition (consisting of an ultraviolet curable resin, a photopolymerization initiator, etc.), and usually has a thickness of 1 to 50 μm, preferably 1 10 μm.

  Examples of the ultraviolet curable resin (monomer, oligomer) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-ethylhexyl polyethoxy (meth) acrylate. , Benzyl (meth) acrylate, isobornyl (meth) acrylate, phenyloxyethyl (meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, acryloylmorpholine , N-vinylcaprolactam, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, neopentylglyce Di (meth) acrylate, neopentyl glycol dipropoxy di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, tricyclodecane dimethylol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane (Meth) acrylate monomers such as tetra (meth) acrylate; polyol compounds (for example, ethylene glycol, propylene glycol, neopentyl glycol, , 6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, trimethylolpropane, diethylene glycol, dipropylene glycol, polypropylene Polyols such as glycol, 1,4-dimethylolcyclohexane, bisphenol A polyethoxydiol, polytetramethylene glycol, the polyols and succinic acid, maleic acid, itaconic acid, adipic acid, hydrogenated dimer acid, phthalic acid, isophthalic acid Polyester polyols which are reaction products of polybasic acids such as acid and terephthalic acid or acid anhydrides thereof, polycaprolactone polyols which are reaction products of the polyols and ε-caprolactone, the polyols and the above, Polybasic acid or this Reaction products of these acid anhydrides with ε-caprolactone, polycarbonate polyols, polymer polyols, etc.) and organic polyisocyanates (for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, diisocyanate) Cyclopentanyl diisocyanate, hexamethylene diisocyanate, 2,4,4′-trimethylhexamethylene diisocyanate, 2,2′-4-trimethylhexamethylene diisocyanate, etc.) and a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylic Rate, cyclohexane-1,4-dimethylol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin di (meth) acrylate, etc.) (Meth) such as bisphenol type epoxy (meth) acrylate, which is a reaction product of bisphenol type epoxy resin such as polyurethane (meth) acrylate, bisphenol A type epoxy resin, bisphenol F type epoxy resin and (meth) acrylic acid which is a reaction product Examples include acrylate oligomers. These compounds can be used alone or in combination. These ultraviolet curable resins may be used as a thermosetting resin together with a thermal polymerization initiator.

  For the hard coat layer, among the above-mentioned ultraviolet curable resins (monomers and oligomers), hard materials such as pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are used. It is preferable to mainly use polyfunctional monomers.

  Any compound suitable for the properties of the ultraviolet curable resin can be used as the photopolymerization initiator for the ultraviolet curable resin. For example, acetophenone such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 Benzoin series such as benzyldimethyl ketal, benzophenone, 4-phenylbenzophenone, benzophenone series such as hydroxybenzophenone, thioxanthone series such as isopropylthioxanthone, 2-4-diethylthioxanthone, and other special ones include methylphenyl glyoxylate Etc. can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone. These photopolymerization initiators may be optionally selected from one or more known photopolymerization accelerators such as benzoic acid type or tertiary amine type such as 4-dimethylaminobenzoic acid. It can be used by mixing at a ratio. Moreover, it can be used by 1 type, or 2 or more types of mixture of only a photoinitiator. Particularly preferred is 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals).

  Generally the quantity of a photoinitiator is 0.1-10 mass% with respect to a resin composition, Preferably it is 0.1-5 mass%.

  Further, the hard coat layer may contain a small amount of an ultraviolet absorber, an infrared absorber, an anti-aging agent, a paint processing aid, a colorant and the like. In particular, it is preferable to contain an ultraviolet absorber (for example, a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber), whereby yellowing of the filter can be efficiently prevented. The amount thereof is generally 0.1 to 10% by mass, preferably 0.1 to 5% by mass, based on the resin composition.

  The hard coat layer preferably has a refractive index lower than that of the transparent film. By using the ultraviolet curable resin, a refractive index lower than that of the substrate is generally easily obtained. Therefore, it is preferable to use a material having a high refractive index such as PET as the transparent substrate. Therefore, the hard coat layer preferably has a refractive index of 1.60 or less. The film thickness is as described above.

The high refractive index layer is made of a polymer (preferably UV curable resin), ITO, ATO, Sb ₂ O ₃ , SbO ₂ , In ₂ O ₃ , SnO ₂ , ZnO, Al-doped ZnO, TiO ₂ , oxidation A layer (cured layer) in which conductive metal oxide fine particles (inorganic compound) such as cesium tungsten are dispersed is preferable. The metal oxide fine particles preferably have an average particle size of 10 to 10,000 nm, preferably 10 to 50 nm. In particular, ITO (especially having an average particle diameter of 10 to 50 nm) is preferable. Those having a refractive index of 1.64 or more are suitable. The film thickness is generally in the range of 10 to 500 nm, preferably 20 to 200 nm.

  When the high refractive index layer is a conductive layer, the minimum reflectance of the surface reflectance of the antireflection film is set within 1.5% by setting the refractive index of the high refractive index layer 2 to 1.64 or more. The minimum reflectance of the surface reflectance of the antireflection film can be made to be within 1.0% by setting it to 1.69 or more, preferably 1.69 to 1.82.

  The low refractive index layer is a layer (cured) in which fine particles such as silica and fluororesin, preferably 10 to 40% by weight (preferably 10 to 30% by mass) of hollow silica are dispersed in a polymer (preferably UV curable resin). Layer). The refractive index of the low refractive index layer is preferably 1.45 or less. When the refractive index is more than 1.45, the antireflection characteristic of the antireflection film is deteriorated. The film thickness is generally in the range of 10 to 500 nm, preferably 20 to 200 nm.

  As the hollow silica, those having an average particle diameter of 10 to 100 nm, preferably 10 to 50 nm, and a specific gravity of 0.5 to 1.0, preferably 0.8 to 0.9 are preferable.

  The hard coat layer preferably has a visible light transmittance of 70% or more. Both the visible light transmittance of the high refractive index layer and the low refractive index layer are preferably 85% or more.

  When the antireflection layer is composed of the hard coat layer and the above two layers, for example, the thickness of the hard coat layer is 2 to 20 μm, the thickness of the high refractive index layer is 75 to 90 nm, and the thickness of the low refractive index layer is It is preferable that it is 85-110 nm.

  In order to form each layer of the antireflection layer, for example, as described above, the above-mentioned fine particles are blended with a polymer (preferably an ultraviolet curable resin) as necessary, and the obtained coating liquid is mixed with the rectangular transparent After coating on the substrate surface and then drying, it may be cured by irradiation with ultraviolet rays. In this case, each layer may be applied and cured one by one, or all the layers may be applied and then cured together.

  As a specific method of coating, a method of coating a coating solution in which an ultraviolet curable resin containing an acrylic monomer or the like is made into a solution with a solvent such as toluene is coated with a gravure coater, and then dried, and then cured by ultraviolet rays. Can be mentioned. This wet coating method has the advantage that the film can be uniformly formed at high speed at low cost. After this coating, for example, by irradiating and curing with ultraviolet rays, the effect of improving the adhesion and increasing the hardness of the film can be obtained. The conductive layer can be formed similarly.

  In the case of ultraviolet curing, many light sources that emit light in the ultraviolet to visible range can be used as the light source, such as ultra-high pressure, high pressure, low pressure mercury lamp, chemical lamp, xenon lamp, halogen lamp, mercury lamp, carbon arc lamp, incandescent lamp. And laser light. The irradiation time cannot be determined unconditionally depending on the type of lamp and the intensity of the light source, but is about several seconds to several minutes. Moreover, in order to accelerate curing, the laminate may be preheated to 40 to 120 ° C. and irradiated with ultraviolet rays.

  It is also preferable to provide an antiglare layer instead of the hard coat layer as described above. What has a large antireflection effect is easily obtained. As the antiglare layer, for example, an antiglare layer obtained by applying and drying a liquid in which a transparent filler (preferably an average particle diameter of 1 to 10 μm) such as polymer fine particles (eg, acrylic beads) is dispersed in a binder, Or the anti-glare layer which has the hard-coat function which apply | coated and hardened the liquid which added the transparent filler (polymer fine particle; for example, acrylic beads) to the above-mentioned hard-coat layer formation material can be mentioned, and is preferable. The layer thickness of the antiglare layer is generally in the range of 0.01 to 20 μm.

  As described above, the optical filter of the present invention contains tungsten oxide and / or composite tungsten oxide that efficiently cuts near infrared rays. The layer containing tungsten oxide and / or composite tungsten oxide is generally a near-infrared shielding layer, and may be contained in the hard coat layer or the pressure-sensitive adhesive layer.

  The near-infrared shielding layer can be formed in the same manner as the heat ray cut layer.

  The near-infrared shielding layer is coated with a coating solution containing, for example, the above (composite) tungsten oxide and the above weather resistant resin (thermoplastic resin, ultraviolet curable or electron beam curable resin, or thermosetting resin). Obtained by drying and, if necessary, curing.

  In addition to the (composite) tungsten oxide, a dye may be used if necessary. The dye generally has an absorption maximum at a wavelength of 800 to 1200 nm. Examples include phthalocyanine dyes, metal complex dyes, nickel dithiolene complex dyes, cyanine dyes, squarylium dyes, polymethine dyes, Examples thereof include azomethine dyes, azo dyes, polyazo dyes, diimonium dyes, aminium dyes, and anthraquinone dyes, and cyanine dyes, phthalocyanine dyes, and diimonium dyes are particularly preferable. These dyes can be used alone or in combination. The near-infrared shielding layer may be a pressure-sensitive adhesive layer. In that case, it is necessary to use a thermoplastic resin having adhesiveness such as an acrylic resin as the weather-resistant resin or in combination with the weather-resistant resin. is there.

  The near-infrared shielding layer preferably contains 0.1 to 20 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass of the (composite) tungsten oxide with respect to 100 parts by mass of the binder resin. The thickness of the near infrared shielding layer is generally 1 to 50 μm, preferably 5 to 50 μm, and particularly preferably 10 to 50 μm.

  In the present invention, the near-infrared shielding layer may be provided with a function of adjusting the color tone by providing an absorption function of neon light emission. For this purpose, a neon-emission absorbing layer may be provided, but the near-infrared shielding layer may contain a neon-emission selective absorption dye. It is preferable to provide a pressure-sensitive adhesive layer having a function of absorbing neon light emission.

  Neon luminescent selective absorption dyes include cyanine dyes, squarylium dyes, anthraquinone dyes, phthalocyanine dyes, polymethine dyes, polyazo dyes, azurenium dyes, diphenylmethane dyes, and triphenylmethane dyes. it can. Such a selective absorption dye is required to have a selective absorption of neon emission near 585 nm and a small absorption at other visible light wavelengths, so that the absorption maximum wavelength is 575 to 595 nm and the absorption spectrum half width is What is 40 nm or less is preferable.

  Further, as long as the optical properties are not greatly affected, coloring pigments, ultraviolet absorbers, antioxidants and the like may be further added.

  The above-mentioned or normal pressure-sensitive adhesive layer is mainly a layer for adhering the optical film of the present invention to a display, and any resin having an adhesive function can be used. For example, acrylic adhesives, rubber adhesives, thermoplastic elastomers (TPE) such as SEBS (styrene / ethylene / butylene / styrene) and SBS (styrene / butadiene / styrene), which are formed from butyl acrylate, are the main components. TPE-based pressure-sensitive adhesives and adhesives can also be used.

  The layer thickness is generally in the range of 5 to 500 μm, particularly 10 to 100 μm. In general, the optical filter can be equipped by pressing the pressure-sensitive adhesive layer on a glass plate of a display.

  As a near-infrared absorption characteristic of the optical filter of the present invention, it is preferable that the transmittance at 850 to 1000 nm is 20% or less, and further 15%. Moreover, as selective absorptivity, it is preferable that the transmittance | permeability of 585 nm is 50% or less.

  In the optical filter of the present invention, it is preferable that the minimum value of transmittance in the near infrared ray in the wavelength range of 800 to 1100 nm is 30% or less, particularly 20% or less in the wavelength range. As a result, there is an effect of reducing the transmittance in a wavelength region where malfunction of a remote controller or the like of a peripheral device is pointed out. In particular, the minimum value of the transmittance in the visible light in the wavelength range of 560 to 610 nm is the wavelength range. In addition to the above effects, the orange color having a peak at 575 to 595 nm is a cause of deteriorating the color reproducibility, so that the orange wavelength is absorbed. There is an effect, and this improves the redness and improves the color reproducibility.

It is preferable for the light transmitted through the optical filter L ^* a ^* b ^* display system of b ^* is -15 or more.

  When two transparent films are used in the present invention, these adhesions (adhesive layer) include, for example, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, acrylic resin (eg, ethylene- ( (Meth) acrylic acid copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, metal ion crosslinked ethylene- (meth) acrylic acid copolymer), partially saponified ethylene -Ethylene copolymers such as vinyl acetate copolymer, carboxylated ethylene-vinyl acetate copolymer, ethylene- (meth) acryl-maleic anhydride copolymer, ethylene-vinyl acetate- (meth) acrylate copolymer ("(Meth) acryl" indicates "acryl or methacryl"). In addition, polyvinyl butyral (PVB) resin, epoxy resin, phenol resin, silicon resin, polyester resin, urethane resin, rubber adhesive, thermoplastic elastomer such as SEBS and SBS can be used, but good adhesion Acrylic resin adhesives and epoxy resins are easily obtained.

  The layer thickness is generally 10 to 50 μm, preferably 20 to 30 μm. In general, the optical filter can be equipped by heat-pressing the pressure-sensitive adhesive layer to a glass plate of a display.

  When EVA is also used as the material for the pressure-sensitive adhesive layer, the material used for the interlayer film in the laminate can be used.

  As the material of the release sheet provided on the pressure-sensitive adhesive layer, a transparent polymer having a glass transition temperature of 50 ° C. or higher is preferable. Examples of such a material include polyesters such as polyethylene terephthalate, polycyclohexylene terephthalate, and polyethylene naphthalate. In addition to resins, nylon 46, modified nylon 6T, nylon MXD6, polyamide resins such as polyphthalamide, ketone resins such as polyphenylene sulfide and polythioether sulfone, and sulfone resins such as polysulfone and polyether sulfone. Mainly composed of polymers such as ether nitrile, polyarylate, polyetherimide, polyamideimide, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polystyrene, polyvinyl chloride It can be used fat. Of these, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polystyrene, and polyethylene terephthalate can be suitably used. The thickness is preferably 10 to 200 μm, particularly preferably 30 to 100 μm.

  FIG. 6 shows an example of a state where the optical filter of the present invention is affixed to the image display surface of a plasma display panel, which is a kind of display. An optical filter is bonded to the surface of the display surface of the display panel 70 via an adhesive layer 68. That is, a mesh-like conductive layer 67, a hard coat layer 66A, and a low refractive index layer 66B are provided in this order on one surface of the transparent film 61, and a near-infrared shielding layer 64 and a transparent layer are provided on the other surface of the transparent film 61. An optical filter provided with an adhesive layer 68 is provided on the display surface. The mesh-like conductive layer 67 'is exposed at the edge (side edge) of the filter (for example, obtained by removing each layer at the end with a laser). The exposed mesh-like conductive layer 67 'is brought into contact with a metal cover 69B provided around the plasma display panel 70 via a shield finger (plate spring-like metal part) 69A. A conductive gasket or the like may be used instead of the shield finger (plate spring-like metal part). As a result, the optical filter and the metal cover 69 </ b> B are electrically connected to achieve grounding. The metal cover 69B may be a metal frame or a frame. As is clear from FIG. 6, the mesh-like conductive layer 67 faces the viewer side.

  Since the PDP display of the present invention generally uses a plastic film as a transparent substrate, the optical filter of the present invention can be directly bonded to the surface of the glass plate as described above. When one sheet is used, the PDP itself can contribute to weight reduction, thickness reduction, and cost reduction. Compared with the case where a front plate made of a transparent molded body is installed on the front side of the PDP, an air layer having a low refractive index can be eliminated between the PDP and the PDP filter, so that visible light reflection due to interface reflection can be achieved. Problems such as an increase in rate and double reflection can be solved, and the visibility of the PDP can be further improved.

The near-infrared shield of the present invention is useful for the laminate and the optical filter of the present invention, but it is obvious that any one can be used as long as the above-described effects can be used. Further, the near-infrared shield of the present invention may be in any form as long as it contains tungsten oxide and / or composite tungsten oxide and a weather resistant resin (for example, a film containing both components, a separate film). Included).

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example.

[Example 1]
(Preparation of interlayer film)
An EVA sheet having a thickness of 0.7 mm was obtained as an intermediate film (transparent adhesive layer) by a calendar molding method using the following composition as a raw material. The kneading of the blend was carried out at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.

(Combination)
EVA (vinyl acetate content 25% by mass,
Product name: Ultrasen 635, manufactured by Tosoh Corporation): 100 parts by mass Cross-linking agent (Perbutyl E; manufactured by Nippon Oil & Fats Co., Ltd. t-butylperoxy-2-ethylhexyl monocarbonate): 2.2 parts by mass Silane Coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0 part by mass Ultraviolet absorber (Ubinal 3049; manufactured by BASF Japan Ltd.): 0.1 part by mass

(Preparation of PET film with heat ray cut layer)
On the PET film (200 μm), the following coating solution for forming a heat ray cut layer was applied by a bar coater and dried at 80 ° C. for 30 seconds to form a heat ray cut layer having a thickness of 1 μm.

(Combination)
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass,
Optool AR-110 (polymer A), manufactured by Daikin Industries, Ltd., 100 parts by mass Cesium tungsten oxide (Cs _0.33 WO ₃ ,
Solid content 20% by mass, MIBK 80% by mass) 100 parts by mass

(Production of laminate)
The PET film with a heat ray cut layer obtained above was laminated on both sides with a glass plate via an EVA sheet, placed in a rubber bag, vacuum degassed, and pre-pressed at a temperature of 110 ° C. Next, this pre-press-bonded glass was put in an oven and pressurized for 30 minutes under the condition of a temperature of 130 ° C. to produce a laminated glass (glass plate / EVA / film with heat ray cut layer / EVA / glass plate). .

[Example 2]
In Example 1, a laminated glass was produced in the same manner except that a PET film with a heat ray cut layer was produced as follows.

(Preparation of PET film with heat ray cut layer)
The following coating solution for forming a heat ray cut layer is applied on a PET film (200 μm) with a bar coater, dried at 80 ° C. for 30 seconds, and irradiated with ultraviolet rays (1000 mJ / cm ² irradiation using a high-pressure mercury lamp). A heat ray cut layer having a thickness of 1 μm was formed.

(Combination)
Functional group-containing fluororesin (solid content 15% by mass, MIBK 85% by mass,
Optool AR-110 (polymer A), manufactured by Daikin Industries, Ltd. 100 parts by mass Cesium tungsten oxide (Cs _0.33 WO ₃ ,
Solid content 20% by mass, MIBK 80% by mass) 100 parts by mass Irgacure 184 (manufactured by Ciba Specialty Chemicals) 2 parts by mass

[Example 3]
In Example 1, a laminated glass was produced in the same manner except that a PET film with a heat ray cut layer was produced as follows.

(Preparation of PET film with heat ray cut layer)
The following coating solution for forming a heat ray cut layer was applied on a PET film (200 μm) with a bar coater and dried at 120 ° C. for 2 minutes to form a heat ray cut layer having a thickness of 1 μm.

(Combination)
Silicone resin (solid content 20% by mass, toluene 80% by mass,
KR-251 manufactured by Shin-Etsu Chemical Co., Ltd.) 75 parts by mass Cesium tungsten oxide (Cs _0.33 WO ₃ ,
Solid content 20% by mass, MIBK 80% by mass) 100 parts by mass

[Comparative Example 1]
In Example 1, a laminated glass was produced in the same manner except that a PET film with a heat ray cut layer was produced as follows.

(Preparation of PET film with heat ray cut layer)
The following coating solution for forming a heat ray cut layer was applied on a PET film (200 μm) with a bar coater and dried at 120 ° C. for 2 minutes to form a heat ray cut layer having a thickness of 1 μm.

(Combination)
Unsaturated polyester resin resin (solid content 15% by mass) 100 parts by mass Cesium tungsten oxide (Cs _0.33 WO ₃ ,
Solid content 20% by mass, MIBK 80% by mass) 100 parts by mass

[Evaluation of laminate]
(1) Initial luminous transmittance (Y in 2 ° visual field XYZ color system)
Using the transmission spectrum of the filter measured by a spectrophotometer UV3100PC (trade name) manufactured by Shimadzu Corporation, Y of the tristimulus value of the XYZ color system was calculated and used as luminous transmittance (Y). The calculation method was based on JIS Z8722-2000.
(2) Luminous transmittance after weather resistance test After performing a super UV test (Super UV tester SUV-F11, manufactured by Iwasaki Electric Co., Ltd.) for 250 hours, the luminous transmittance of (1) above was measured.

  The measurement results are shown below.

  As is clear from the above results, it is understood that the laminated glasses obtained in Examples 1 to 3 according to the present invention are excellent in visible light permeability and weather resistance.

It is a schematic sectional drawing of one example of embodiment of the laminated body of this invention. It is a schematic sectional drawing of another example of embodiment of the laminated body of this invention. It is a schematic sectional drawing of one example of embodiment of the optical filter for displays of this invention. It is a schematic sectional drawing of another example of embodiment of the optical filter for displays of this invention. It is a schematic sectional drawing of another example of embodiment of the optical filter for displays of this invention. It is a schematic sectional drawing of an example of the state where the optical filter of this invention was affixed on the image display surface of the plasma display panel which is 1 type of a display.

Explanation of symbols

10, 20 Laminate 11A, 11B, 21 Glass plate 12A, 12B, 22 Intermediate film 13, 23 Plastic film 14, 24 Heat ray cut layer 25 Hard coat layer 31, 41A, 41B, 51, 61 Transparent film 36, 46, 56 Antireflection layer 34, 44, 54 Near-infrared shielding layer 47, 57 Conductive layer 48, 58 Adhesive layer

Claims (21)

  A near-infrared shield including tungsten oxide and / or composite tungsten oxide and a weather-resistant resin.   The near-infrared shielding body according to claim 1, wherein the weather-resistant resin is at least one resin selected from a fluororesin, a silicone resin, an olefin resin, and an acrylic resin.   The near-infrared shielding body according to claim 1 or 2, wherein the weather-resistant resin is a fluororesin or a silicone resin.   The near-infrared shielding body according to claim 1, wherein the tungsten oxide and / or the composite tungsten oxide is in the form of fine particles.   The near-infrared shielding body according to claim 4, wherein the average particle diameter of the fine particles is 400 nm or less.   The tungsten oxide is represented by the general formula WyOz (where W is tungsten, O is oxygen, and 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is represented by the general formula MxWyOz ( Where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, One or more elements selected from Hf, Os, Bi, and I, W represents tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3 The near-infrared shielding of any one of Claims 1-5 represented by this body.   The near-infrared shielding body according to any one of claims 1 to 6, wherein the tungsten oxide and / or the composite tungsten oxide is treated with a silane coupling agent. An intermediate film is sandwiched between two substrates and these are bonded and integrated,
A heat ray cut layer and an intermediate film, or a heat ray cut layer, a plastic film and an intermediate film are provided between the intermediate film and the substrate, and the heat ray cut layer contains tungsten oxide and / or composite tungsten oxide and a weather resistant resin. A laminate characterized by the above.   The laminate according to claim 8, wherein the two substrates are both glass plates.   The laminate according to claim 8 or 9, wherein the interlayer film is a layer of a composition containing polyvinyl butyral (PVB layer) or a layer of a composition containing an ethylene / vinyl acetate copolymer (EVA layer).   The laminate according to any one of claims 8 to 10, wherein the intermediate film is a crosslinked layer of a composition comprising an ethylene / vinyl acetate copolymer containing an organic peroxide.   It is a laminated glass, The laminated body of any one of Claims 8-11. A laminated body in which an intermediate film is sandwiched between two substrates and bonded and integrated,
One of the two substrates is a glass plate, the other is a plastic film provided with a hard coat layer on the surface opposite to the intermediate film, and a heat ray cut layer is further provided between the intermediate film and the plastic film, The heat ray cut layer includes a tungsten oxide and / or a composite tungsten oxide and a weather resistant resin.   An optical filter for display comprising a near-infrared shielding layer, wherein the near-infrared shielding layer contains tungsten oxide and / or composite tungsten oxide and a weather resistant resin.   An optical filter for a display comprising an antireflection layer and a near-infrared shielding layer, wherein the near-infrared shielding layer contains tungsten oxide and / or a composite tungsten oxide and a weather resistant resin.   The optical filter for display according to claim 14 or 15, further comprising a conductive layer.   Furthermore, the optical filter for displays of any one of Claims 14-16 containing an adhesive layer.   The optical filter for display according to any one of claims 14 to 17, which is a filter for a plasma display panel.   An optical filter for display, wherein the optical filter for display according to any one of claims 14 to 17 is attached to a glass substrate.   A display comprising the display optical filter according to any one of claims 14 to 17.   A plasma display panel comprising the optical filter for display according to any one of claims 14 to 17.

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