JP2018124363A - Infrared shielding material fine particle dispersion, infrared shielding adhesive liquid containing the same, base material with infrared shielding layer, base material with infrared shielding adhesive layer, and infrared shielding optical member produced using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine particle dispersion of an infrared shielding material having excellent infrared shielding performance and visible light transmission performance and capable of suppressing deterioration of infrared shielding characteristics over time. An infrared shielding material fine particle dispersion containing an infrared shielding material fine particle and a dispersant in a solvent, the infrared shielding material fine particle having a general formula WyOz (2.2 ≦ (z / y) ≦ 2 .999) and a general formula MxWyOz (M is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, etc., 0.001) ≦ (x / y) ≦ 1, 2.2 ≦ (z / y) ≦ 3) composed of one or more oxide fine particles selected from composite tungsten oxide fine particles, and the dispersant has a main chain. An acrylic ester copolymer, which is a polymer compound having a phosphate group as a side chain, and the phosphate group of the dispersant is adsorbed on the surface of the infrared shielding material fine particles. [Selection figure] None

Description

  The present invention relates to an infrared shielding material fine particle dispersion in which infrared shielding material fine particles and a dispersant are dispersed in a solvent, and the dispersion is dispersed in an adhesive having good compatibility with the dispersant. The present invention relates to an infrared shielding adhesive liquid, and a base material with an infrared shielding layer, a base material with an infrared shielding adhesive layer, and an infrared shielding optical member which are prepared using these dispersions or adhesive liquids.

Conventionally, in order to prevent the temperature of the interior space of buildings, vehicles, telephone boxes, etc. from rising too much, as a method of removing and reducing the heat component from sunlight that has passed through the window glass and entered, It has been practiced to form a heat ray reflective glass by forming a thin film that reflects visible and infrared wavelengths on the surface. As the material of the thin film used here, metal oxides such as FeO _X , CoO _X , CrO _X , and TiO _X and metal materials having a large amount of free electrons such as Ag, Au, Cu, Ni, and Al are selected. There were many cases. These materials can reflect near-infrared rays that make a significant contribution to the thermal effect among solar rays, but also have the property of reflecting or absorbing light in the visible light region at the same time, resulting in a reduction in visible light transmittance. I had a problem.

  Therefore, when using these materials for the transparent base material in the above building materials, vehicles, telephone boxes, etc., it was necessary to make the film thickness very thin in order to ensure high light transmittance in the visible light region. . Therefore, an extremely thin thin film having a thickness of about 10 nm has been formed by using a physical film forming method such as spray baking, CVD method, sputtering method or vacuum deposition method. However, these film formation methods require a large-scale apparatus and vacuum equipment, and are difficult to cope with improvement in productivity and increase in area, resulting in high film formation costs.

  In addition, when a film is formed on a glass such as a building using these materials, if the visible light transmittance is increased, the solar shading property is lowered, and conversely, if the solar shading property is increased, the visible light transmittance is lowered. For this reason, there was a problem that the internal space of the building and the like was darkened. In addition, the films using these materials tend to increase the reflectivity in the visible light region at the same time, and have a glaring appearance like a mirror, which may impair the aesthetic appearance of buildings and the like. . In addition, many films using these materials have high electrical conductivity, and in this case, the radio waves received by mobile phones and TVs may be reflected and reception may be disabled, or radio interference may be caused in the surrounding area. was there.

  In order to solve the various problems described above, the light transmittance in the visible light region is high, the light transmittance in the near infrared region is low, the light reflectance in the visible light region is low, and the light in the near infrared region is low. Therefore, it is necessary to form a film having a high reflectivity and a film conductivity having a surface resistivity of approximately 106 Ω / □ or more.

  Antimony-containing tin oxide (ATO), tin-containing indium oxide (ITO), and aluminum-containing zinc oxide (AZO) are known as materials having a high visible light transmittance and a heat ray shielding function. These materials have a relatively low visible light reflectance and do not have a glaring appearance, but the plasma wavelength is on the relatively long wavelength side, and the reflection and absorption effects of these films in the near infrared region close to visible light. Was not enough. Further, when these films are formed by a physical film forming method, the conductivity of the films is increased, and there is a possibility that the above-described interference of radio waves is caused.

  In the above reflection / absorption characteristics, light in the visible light region (wavelength region, about 380 to 780 nm) is sufficiently transmitted, and near infrared light in the wavelength region 800 to 1100 nm is shielded, and a film containing a material that absorbs this near infrared light Organic compounds such as organic dyes and metal complexes are used as near-infrared absorbing materials that satisfy the characteristics of low turbidity (hereinafter sometimes referred to as haze). When forming an infrared shielding film containing a near-infrared absorbing material such as an organic compound or a metal complex, a method of dissolving the organic compound or the metal complex in a solvent and coating the substrate is generally performed. .

  Near-infrared absorbing materials such as the above organic compounds and metal complexes include diimonium compounds, aminium compounds, phthalocyanine compounds, organometallic complexes, cyanine compounds, azo compounds, polymethine compounds, quinone compounds, diphenylmethane compounds , Triphenylmethane compounds, etc., but these have low resistance to heat and light and easily deteriorate over time. Therefore, when these organic compounds and metal complexes are used alone, they are used for a long time. It was difficult to maintain the performance. In addition, when an infrared shielding film is formed using an organic compound or a metal complex, it is easily affected by the external environment because of its low resistance to heat and light, and other layers are provided on the infrared shielding film to shield the infrared radiation. It was necessary to supplement the durability of the membrane.

Under such a technical background, Patent Document 1 discloses a near-infrared absorbing material (infrared shielding material) instead of an organic compound or a metal complex having low resistance to heat or light, having a general formula W _y O _z. (W is tungsten, O is oxygen, 2.2 ≦ (z / y) ≦ 2.999) and / or general formula M _x W _y O _z (where M is , H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, One or more elements selected from the group consisting of Bi and I, W is tongue And O are oxygen, composed of composite tungsten oxide fine particles represented by 0.001 ≦ (x / y) ≦ 1, 2.2 ≦ (z / y) ≦ 3), and the infrared shielding material fine particles An infrared shielding material fine particle dispersion having a particle diameter of 1 nm or more and 800 nm or less, and optical characteristics, conductivity, manufacturing method, and the like of the infrared shielding material fine particle dispersion are disclosed.

Patent Document 2 discloses an infrared shielding film using the tungsten oxide fine particles represented by the general formula W _y O _z and / or the composite tungsten oxide fine particles represented by the general formula M _x W _y O _z. A multilayer filter (laminate) for PDP is disclosed. Furthermore, Patent Document 3 discloses infrared shielding material fine particles composed of tungsten oxide fine particles represented by the general formula W _y O _z and / or composite tungsten oxide fine particles represented by the general formula M _x W _y O _z. Is applied to the surface of the base material after further adding an adhesive to the dispersion of the infrared shielding material fine particles contained in the solvent together with the metal salt, and then the solvent is evaporated from the coating film. Thus, it is disclosed that an infrared shielding film in which the infrared shielding properties hardly deteriorate with time can be obtained.

  As described above, the infrared shielding film on which the infrared shielding film is formed has a high light transmittance in the visible light region, a low light transmittance in the near infrared region, and a low light reflectance in the visible light region. Infrared shielding material to which pressure sensitive adhesive is added as described above, although it is required that the reflectance of light in the near infrared region is high, the conductivity of the film is low, and that the infrared shielding properties are not easily deteriorated over time. In the case where the fine particle dispersion is applied to the surface of the substrate to form a coating film, and the coating film is bonded to another substrate as an adhesive layer, it is desirable that the bonding and peeling be further easier.

  However, the conventional technology can provide an infrared shielding film that has excellent infrared shielding performance and suppresses the deterioration of infrared shielding properties over time due to ultraviolet rays or the like, but is capable of shielding infrared rays in adhesives or adhesives. Dispersion of the material fine particles is difficult, and even if it can be dispersed to some extent, the aggregation of the infrared shielding material fine particles becomes intense and the haze increases, so that it is difficult to obtain an infrared shielding film that maintains the transmission performance.

International Publication No. WO2005 / 037932 JP 2006-154516 A JP 2009-197146 A

  The present invention has been made paying attention to such problems, and the problem is that an infrared shielding layer in which an infrared shielding layer formed from a fine particle dispersion of an infrared shielding material is formed on the surface of a substrate is used. With an infrared shielding adhesive layer formed on the surface of the base material, an infrared shielding adhesive layer formed from an infrared shielding adhesive solution containing a dispersion of an infrared shielding material fine particle dispersion in an adhesive in a base material with a layer In the base material, the infrared shielding material fine particles can be sufficiently dispersed without agglomerating in the infrared shielding layer or the infrared shielding adhesive layer, and in addition to excellent infrared shielding performance, it is excellent in suppressing an increase in haze. It is another object of the present invention to provide an infrared shielding layer or an infrared shielding adhesive layer in which visible light transmission performance can be exhibited, and further, the deterioration of infrared shielding properties due to ultraviolet rays or the like is suppressed over time.

  In order to solve the above problems, the present inventors conducted extensive research on an infrared shielding material fine particle dispersion containing infrared shielding material fine particles and a dispersant in a solvent. As a result, the infrared shielding material fine particles were converted to tungsten oxide. By using an oxide fine particle selected from fine particles and composite tungsten oxide fine particles, and using the polymer compound having a phosphate group as a side chain, the main chain of which is an acrylic ester copolymer as the dispersant, An infrared shielding material fine particle dispersion in which the phosphoric acid group of the dispersing agent is adsorbed on the surface of the infrared shielding material fine particles is obtained, thereby significantly increasing the dispersibility of the infrared shielding material fine particles in the infrared shielding material fine particle dispersion. In addition, the infrared shielding material fine particle dispersion can be dispersed in an adhesive and formed from the infrared shielding adhesive obtained thereby. It found that can significantly enhance the dispersibility of the infrared shielding material microparticle in serial infrared shielding adhesive layer, thereby completing the present invention.

That is, the infrared shielding material fine particle dispersion of the present invention is an infrared shielding material fine particle dispersion containing an infrared shielding material fine particle and a dispersant in a solvent, and the infrared shielding material fine particle has the general formula W _y O _z. (W is tungsten, O is oxygen, 2.2 ≦ (z / y) ≦ 2.999), and a general formula M _x W _y O _z (where M is H , He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, And at least one selected from the group consisting of I and I Element, W is tungsten, O is oxygen, one or more selected from composite tungsten oxide fine particles represented by 0.001 ≦ (x / y) ≦ 1, 2.2 ≦ (z / y) ≦ 3) The dispersant is a polymer compound having a main chain of an acrylate ester copolymer and a phosphate group as a side chain, and the dispersing agent phosphor on the surface of the infrared shielding material fine particles. It is characterized by adsorbing acid groups.

  According to the present invention, in an infrared shielding material fine particle dispersion, in an infrared shielding layer using the dispersion, or in an infrared shielding adhesive layer using an infrared shielding adhesive in which the dispersion is dispersed in an adhesive Since the dispersibility of the infrared shielding material fine particles in the substrate can be improved, the base material with an infrared shielding layer having an infrared shielding layer formed from the infrared shielding material fine particle dispersion on the substrate surface, or the infrared shielding adhesive liquid is used. In the base material with the infrared shielding adhesive layer having the infrared shielding adhesive layer on the surface of the base material, excellent infrared shielding performance can be obtained, and since an increase in haze can be suppressed, excellent visible light transmission performance can be obtained. Furthermore, it is possible to suppress the deterioration of the infrared shielding characteristics over time due to ultraviolet rays or the like.

It is a schematic diagram of the crystal structure of composite tungsten oxide fine particles having hexagonal crystals applicable to the infrared shielding material fine particle dispersion of the present invention. It is typical sectional drawing of the base material with an infrared shielding adhesive layer which concerns on embodiment of this invention. It is typical sectional drawing of the base material with an infrared shielding adhesive layer which concerns on other embodiment of this invention. It is typical sectional drawing of the base material with the infrared shielding adhesive layer of one specific example of this invention produced as an infrared shielding optical member. It is typical sectional drawing of the base material with the infrared shielding adhesive layer of the other specific example of this invention produced as an infrared shielding optical member.

Hereinafter, embodiments of an infrared shielding material fine particle dispersion according to the present invention will be described in detail. The infrared shielding material fine particle dispersion of the embodiment of the present invention is a solution in which infrared shielding material fine particles and a dispersant are contained in a solvent, and the infrared shielding material fine particles have a general formula W _y O _z (wherein W is tungsten, O is oxygen, tungsten oxide fine particles represented by 2.2 ≦ (z / y) ≦ 2.999), and general formula M _x W _y O _z (where M is H, He, Alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In , Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I One or more elements selected from the group consisting of W And O is oxygen, and is one or more oxide fine particles selected from composite tungsten oxide fine particles represented by 0.001 ≦ (x / y) ≦ 1, 2.2 ≦ (z / y) ≦ 3). The dispersant is a high molecular compound having an acrylic ester copolymer as a main chain and a phosphate group as a side chain. And the phosphate group of this dispersing agent is adsorb | sucking to the surface of the said infrared shielding material microparticles | fine-particles.

  Hereinafter, the elements constituting the infrared shielding material fine particle dispersion will be described in the order of “1. Dispersant”, “2. Infrared shielding material fine particles”, and “3. Solvent”, and then the dispersion is contained in the adhesive. “4. Infrared shielding adhesive” and “5. Adhesive” present in a dispersed state are further described, and “6. Substrate with infrared shielding layer” formed using the dispersion, and the adhesive “7. Substrate with infrared shielding adhesive layer” formed using the liquid will be described, and finally “8. Infrared shielding optical member” using the substrate with infrared shielding adhesive layer will be described.

1. Dispersant The dispersant used in the infrared shielding material fine particle dispersion of the embodiment of the present invention is a polymer compound having a main chain of an acrylate copolymer and a phosphate group as a side chain. And the phosphate group of this dispersing agent is adsorb | sucking to the surface of the infrared shielding material microparticles | fine-particles which are contained together in the infrared shielding material microparticle dispersion liquid. That is, the phosphate group present in the side chain has a strong affinity with the infrared shielding material fine particles of the embodiment of the present invention, and can therefore be adsorbed very strongly to the infrared shielding material fine particles. As a result, a space is secured in the surface layer portion of the infrared shielding material fine particles due to steric hindrance due to the phosphate groups adsorbed on the surface of the infrared shielding material fine particles, and aggregation of the fine particles can be suppressed.

  Other functional groups such as carboxylic acids and amines, which are generally said to have a strong affinity for fine particles, do not have sufficient adsorptive power to the infrared shielding material fine particles of the embodiment of the present invention and have high dispersion. Sex cannot be obtained. On the other hand, the dispersant used in the embodiment of the present invention absorbs the surface of the infrared shielding material fine particles so that the acrylic ester copolymer constituting the main chain is dispersed from the surface side of the infrared shielding material fine particles. This is characterized in that it is highly compatible with the solvent. Furthermore, since this acrylate copolymer is very compatible with the resin polymer constituting the adhesive described later, it is not only in the above-mentioned infrared shielding material fine particle dispersion, Good dispersibility can be maintained even in the adhesive resin polymer after applying and drying the infrared shielding adhesive liquid in which the shielding material fine particle dispersion is dispersed in the adhesive.

  Examples of the dispersant for the polymer compound in which the main chain is an acrylate copolymer and the side chain has a phosphate group include, for example, a copolymer of a phosphate group-containing monomer and an acrylate ester. (Polyphosmer MHB-10 of DAP Corporation, BYK-W903 (BYK is a registered trademark) manufactured by Big Chemie Japan Co., Ltd.) and the like.

  In the embodiment of the present invention, the content of the dispersant is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the infrared shielding material fine particles. When the content is less than 10 parts by mass, the amount of the dispersant with respect to the infrared shielding material fine particles becomes insufficient, and it becomes difficult to improve the dispersion stability of the infrared shielding material fine particles. On the other hand, when the amount exceeds 100 parts by mass, the dispersing agent may be adsorbed across a plurality of infrared shielding material fine particles, or adsorption or aggregation of excess dispersants may easily occur, and as a result, the infrared shielding material fine particles are excellent. It becomes difficult to disperse in As a result, in an infrared shielding layer formed by applying an infrared shielding material fine particle dispersion or an infrared shielding adhesive layer formed from an infrared shielding adhesive liquid in which an infrared shielding material fine particle dispersion is dispersed in an adhesive, There is a possibility that it is difficult to obtain the effect of dispersing the fine particles of the infrared shielding material and the effect of suppressing the temporal degradation of the infrared shielding properties due to ultraviolet rays or the like.

2. Infrared shielding material fine particles 1) Tungsten oxide fine particles and composite tungsten oxide fine particles In general, materials containing free electrons are known to exhibit a reflection absorption response to electromagnetic waves such as solar rays having a wavelength of 200 to 2600 nm by plasma vibration. It has been. It is known that when the powder of such a material is a fine particle having a wavelength smaller than the wavelength of light, geometrical scattering in the visible light region (wavelength 380 to 780 nm) is reduced, and transparency in the visible light region can be obtained. In the present specification, the term “transparency” is used in the sense that there is little scattering and high transparency with respect to light in the visible light region.

Since there are no effective free electrons in tungsten trioxide WO ₃ , WO ₃ has little absorption and reflection characteristics in the near infrared region, and is not effective as an infrared shielding material. On the other hand, tungsten trioxide having oxygen vacancies and so-called tungsten bronzes obtained by adding a positive element such as Na to tungsten trioxide are known to be conductive materials having free electrons. Analysis of crystals and the like suggests the response of free electrons to light in the infrared region. In addition, there is a particularly effective range as an infrared shielding material within the composition range of the compound of tungsten and oxygen, from which tungsten oxide fine particles and composite tungsten oxide that are transparent in the visible light region and have absorption in the near infrared region. In the above-mentioned Patent Document 1, an infrared shielding material fine particle dispersion in which the tungsten oxide fine particles and / or composite tungsten oxide fine particles are dispersed in a medium such as a resin or glass, and the infrared shielding material fine particles. An infrared shielding body manufactured from a dispersion has been proposed.

Also in the infrared shielding material fine particle dispersion of the embodiment of the present invention, the infrared shielding material fine particles contained in the solvent have a general formula W _y O _z (W is tungsten, O is oxygen, 2.2 ≦ (z / y) Tungsten oxide fine particles represented by ≦ 2.999) and a general formula M _x W _y O _z (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, One or more elements selected from the group consisting of F, P, S, Se, 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 It is comprised by 1 or more types of oxide microparticles | fine-particles chosen from the composite tungsten oxide microparticles | fine-particles represented by 0.2 <(z / y) <= 3).

As described above, in the tungsten oxide fine particles represented by the general formula W _y O _z (W is tungsten and O is oxygen), the composition ratio of oxygen to tungsten, that is, z / y is smaller than 3, It is 2.2 or more and 2.999 or less. If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a WO ₂ crystal phase other than the target compound 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, the required amount of free electrons is generated, and an efficient infrared shielding material is obtained.

On the other hand, in the case of composite tungsten oxide fine particles, element M (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe with respect to W _y O _z 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 one or more elements selected from the group consisting of I), Including the case of z / y = 3.0, free electrons are generated in the W _y O _z , and free electron-derived absorption characteristics are expressed in the near-infrared region, which is effective as a near-infrared absorbing material near a wavelength of 1000 nm. Therefore, it is preferable.

In this way, a more efficient infrared shielding material can be obtained by combining the control of the amount of oxygen and the addition of an element that generates free electrons with respect to W _y O _z . In this case, when the general formula of the infrared shielding material is expressed as M _x W _y O _z (where M is the M element, W is tungsten, and O is oxygen), 0.001 ≦ (x / y as described above) ) ≦ 1, 2.2 ≦ (z / y) ≦ 3.

  Regarding the reason, first, the value of x / y indicating the amount of the element M added will be described. If the value of x / y is 0.001 or more, a sufficient amount of free electrons is generated, and the intended infrared shielding effect can be obtained. As the additive amount of the element M is increased, the supply amount of free electrons is increased and the infrared shielding efficiency is increased. However, when the value of x / y is about 1, the effect is almost saturated. Conversely, if the value of x / y is 1 or less, it is preferable because an impurity phase can be avoided in the infrared shielding material.

  The element M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be , Hf, Os, Bi, and I are one or more selected from the group consisting of I and H.

Among these, from the viewpoint of stability in the M _x W _y O _z to which the element M is added, the element M is an alkali metal, an alkaline earth metal, a 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, One or more elements selected from the group consisting of Se, Br, Te, Ti, Nb, V, Mo, Ta, and Re are preferable. Furthermore, from the viewpoint of improving optical characteristics and weather resistance as an infrared shielding material, the element M is more preferably an element belonging to an alkali metal, alkaline earth metal element, transition metal element, group 4B element, or group 5B element.

Next, the value of z / y indicating the control of the oxygen amount will be described. Regarding the value of z / y, the same mechanism as that of the infrared shielding material of tungsten oxide fine particles represented by W _y O _z described above also works in the infrared shielding material represented by M _x W _y O _z. In addition, even when z / y = 3.0, since there is free electron supply due to the addition amount of the element M described above, the relationship of 2.2 ≦ (z / y) ≦ 3 is satisfied as described above. Preferably 2.45 ≦ (z / y) ≦ 3.

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. The hexagonal crystal structure will be described with reference to the plan view of FIG. In FIG. 1, _six octahedrons formed of WO ₆ units indicated by reference numeral 1 are gathered in an annular shape to form hexagonal voids inside thereof, and an element M indicated by reference numeral 2 is arranged in the voids. Constitutes one unit. A large number of these one units are assembled to form a hexagonal crystal structure.

In the present invention improves the transmission of visible light region, and in order to obtain the effect of improving the absorption of near-infrared region, forming the composite tungsten oxide fine particles, a unit structure (WO ₆ units described in FIG. 1 The hexagonal voids are formed by assembling six octahedrons and a structure in which the element M is arranged in the voids is included, and the composite tungsten oxide fine particles are crystalline. It may be amorphous. When the cation of the element M added to the hexagonal void is present, the transmittance in the visible light region is improved and the absorptivity in the near infrared region is improved. Here, generally, when an element M having a large ionic radius, specifically, Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn is added, a hexagonal crystal is formed. Cheap. Of course, it is not necessarily limited to these elements, and other elements M may be present in hexagonal voids formed of WO ₆ units.

  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 0.33 is More preferred. When the value of x / y becomes 0.33, it is considered that the additive element M is arranged in all the hexagonal voids.

  In addition to hexagonal crystals, tetragonal and cubic tungsten bronzes are also effective as infrared shielding materials. Thus, when the crystal structures are different, the absorption position in the near infrared region tends to change, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Further, the accompanying absorption in the visible light region is small in the order of hexagonal crystal <tetragonal crystal <cubic crystal. Therefore, it is preferable to use hexagonal tungsten bronze for applications that transmit light in the visible region and shield light in the infrared region. However, the tendency of the optical characteristics described here is merely a rough tendency, and changes depending on the type of additive element, the amount of addition, and the amount of oxygen. Therefore, the present invention is limited to the above crystal structure. is not.

  One or more types of oxide fine particles selected from the group consisting of tungsten oxide fine particles and composite tungsten oxide fine particles according to an embodiment of the present invention greatly absorb light in the near infrared region, particularly in the vicinity of a wavelength of 1000 nm. Many of them are blue to green. Further, the dispersed particle diameter of the infrared shielding material fine particles can be selected according to the purpose of use. First, when used for applications requiring transparency, it is preferable to have a dispersed particle size of 2000 nm or less. If the dispersed particle size is 2000 nm or less, the difference between the peak of transmittance and the bottom of absorption in the near infrared region becomes large, and the effect as a near infrared absorbing material having transparency in the visible light region is exhibited. This is because that. Furthermore, fine particles having a dispersed particle diameter smaller than 2000 nm do not completely block light by scattering, maintain visibility in the visible light region, and at the same time efficiently ensure transparency.

  When the transparency in the visible light region is particularly important, it is preferable to further consider scattering by particles. When importance is attached to the reduction of scattering by the particles, the dispersed particle diameter is 200 nm or less, preferably 100 nm or less. The reason for this is that if the dispersed particle size of the particles is small, the scattering of light in the visible light region having a wavelength of 400 to 780 nm due to geometric scattering or Mie scattering is reduced, and as a result, the infrared shielding film becomes like frosted glass. This is because it is possible to avoid the loss of clear transparency.

  That is, when the dispersed particle diameter is 200 nm or less, the geometric scattering or Mie scattering is reduced, and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, since the scattering intensity is proportional to the sixth power of the dispersed particle diameter, the scattering is reduced as the dispersed particle diameter is reduced, and the transparency is improved. Furthermore, when the dispersed particle diameter is 100 nm or less, the scattered light becomes very small, which is more preferable. Thus, from the viewpoint of avoiding light scattering, a smaller dispersed particle size is preferable. If the particle diameter is 1 nm or more, industrial production is easy.

  By setting the dispersed particle diameter to 800 nm or less, the haze value of the infrared shielding material fine particle dispersion (infrared shielding film) in which the infrared shielding material fine particles are dispersed in a medium such as a resin, the visible light transmittance is 85% or less. 30% or less. When this haze value is larger than 30%, it becomes like frosted glass, and clear transparency cannot be obtained.

  Here, the dispersed particle size of one or more oxide fine particles selected from the group consisting of the tungsten oxide fine particles and the composite tungsten oxide fine particles in the infrared shielding material fine particle dispersion is dispersed in the solvent. This means a so-called secondary particle size in the form of aggregated particles formed by aggregation of the oxide fine particles, and can be measured by various commercially available particle size distribution analyzers. For example, a sample in a state where the simple particles or aggregates of the oxide fine particles are present from the infrared shielding material fine particle dispersion, and the sample is ELS manufactured by Otsuka Electronics Co., Ltd. based on the dynamic light scattering method. It can be determined by measuring at -8000.

Further, the surface of the fine particles of the infrared shielding material according to the present invention is coated with an oxide containing one or more of Si, Ti, Zr, and Al, which improves the weather resistance of the infrared shielding material. It is preferable from the viewpoint. In addition, in one or more kinds of oxide fine particles selected from the group consisting of tungsten oxide fine particles and composite tungsten oxide fine particles, when expressed as W _y O _z , 2.45 ≦ (z / y) ≦ 2.999. A so-called “magnet phase” having a composition ratio represented by the formula is preferable as an infrared shielding material because it is chemically stable and has good absorption characteristics in the near infrared region.

2) Method for producing tungsten oxide fine particles and composite tungsten oxide fine particles Tungsten oxide fine particles represented by general formula W _y O _z and composite tungsten oxide fine particles represented by M _x W _y O _z are tungsten compounds. The starting material can be obtained by heat treatment in an inert gas atmosphere or a reducing gas atmosphere.

The tungsten compound starting material for tungsten oxide fine particles represented by the former general formula W _y O _{z includes} tungsten trioxide powder, tungsten oxide hydrate powder, tungsten hexachloride powder, ammonium tungstate powder, hexachloride. Tungsten oxide hydrate powder obtained by dissolving tungsten in alcohol and drying, tungsten oxide obtained by dissolving tungsten hexachloride in alcohol, adding water, and precipitating it It is preferable that it is at least one selected from the group consisting of a hydrate powder of a product, a tungsten compound powder obtained by drying an aqueous ammonium tungstate solution, and a metal tungsten powder.

On the other hand, the tungsten compound starting material of the composite tungsten oxide fine particles represented by the latter general formula M _x W _y O _z is the tungsten compound starting material for the tungsten oxide fine particles represented by the general formula W _y O _z. In addition to the above, a tungsten compound containing the element M in the form of a single element 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. For example, tungstate, chloride, nitrate, sulfate, oxalate, oxide and the like containing the element M can be mentioned, but not limited thereto as long as it becomes a solution.

  Among these, when producing tungsten oxide fine particles, tungsten oxide hydrate powder or tungsten compound powder obtained by drying an aqueous solution of ammonium tungstate is used from the viewpoint of ease of production process. More preferably, when producing composite tungsten oxide fine particles, it is more preferable to use an ammonium tungstate aqueous solution or a tungsten hexachloride solution because each element can be easily and uniformly mixed if the starting material is a solution. By heat-treating these raw materials in an inert gas atmosphere or a reducing gas atmosphere, tungsten oxide fine particles and composite tungsten oxide fine particles having the above-described particle diameter can be obtained.

Here, as a heat treatment condition in an inert atmosphere, it is preferable that the heat treatment temperature is 650 ° C. or higher. The starting material heat-treated at a heat treatment temperature of 650 ° C. or higher has sufficient coloring power and is efficient as infrared shielding material fine particles. Ar or N ₂ is preferably used as the inert gas. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated in a reducing gas atmosphere at a temperature of 100 ° C. to 650 ° C., and then in an inert gas atmosphere at a temperature of 650 ° C. to 1200 ° C. Heat treatment is preferred. The reducing gas at this time is not particularly limited, but H ₂ is preferable. If H ₂ is used as the reducing gas, the composition of the reducing atmosphere, preferably not less than 0.1% with H ₂ volume basis, more than 2% is more preferable. This is because if H ₂ 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 material fine particles in this state. However, since hydrogen contained in tungsten oxide is unstable, the use may be limited in terms of weather resistance. Therefore, by further heat-treating the tungsten oxide compound containing hydrogen at a heat treatment temperature of 650 ° C. or higher in an inert atmosphere, more stable infrared shielding material fine particles can be obtained. The atmosphere gas at the time of 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 magnetic phase is obtained in the infrared shielding material fine particles, and the weather resistance is improved.

  As described above, the surface of the obtained infrared shielding material fine particles may be coated with an oxide containing one or more metals of Si, Ti, Zr, and Al from the viewpoint of improving weather resistance. The coating method in that case is not particularly limited. For example, the metal alkoxide may be added to a solution in which the infrared shielding material fine particles are dispersed. Thereby, the surface of infrared shielding material microparticles | fine-particles can be coat | covered favorably.

3. Solvent The solvent used in the infrared shielding material fine particle dispersion of the embodiment of the present invention is not particularly limited, and a general organic solvent can be used. For example, alcohol solvents such as methanol (MA), ethanol (EA), 1-propanol (NPA), isopropanol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol, acetone, methyl ethyl ketone (MEK), methylpropyl Ketone solvents such as ketone, methyl isobutyl ketone (MIBK), cyclohexanone, isophorone, ester solvents such as 3-methyl-methoxy-propionate (MMP), ethylene glycol monomethyl ether (MCS), ethylene glycol monoethyl ether (ECS) , Ethylene glycol isopropyl ether (IPC), propylene glycol methyl ether (PGM), propylene glycol ethyl ether (PE), propylene glycol methyl ether Glycol derivatives such as teracetate (PGMEA), propylene glycol ethyl ether acetate (PE-AC), formamide (FA), N-methylformamide, dimethylformamide (DMF), dimethylacetamide, N-methyl-2-pyrrolidone ( Amides such as NMP), aromatic hydrocarbons such as toluene and xylene, and halogenated hydrocarbons such as ethylene chloride and chlorobenzene. Among these, organic solvents with low polarity are preferable, and in particular, high hydrophobicity such as ketones such as MIBK and MEK, aromatic hydrocarbons such as toluene and xylene, glycol ether acetates such as PGMEA and PE-AC, etc. Those are more preferred. These solvents may be used alone or in combination of two or more.

4. Infrared shielding adhesive liquid In the infrared shielding adhesive liquid according to the embodiment of the present invention, the above-described infrared shielding material fine particle dispersion is dispersed in an adhesive having good compatibility with the dispersant used in the dispersion. Exists in a state. As this adhesive, a heat-sensitive adhesive or a pressure-sensitive adhesive is used as will be described later.

5. Adhesive A heat-sensitive adhesive or a pressure-sensitive adhesive is used as the adhesive used in the infrared shielding adhesive. As the pressure-sensitive adhesive, general materials such as acrylic, rubber, polyvinyl ether, and silicone can be used. For example, an acrylic pressure-sensitive adhesive is a copolymer of a (meth) acrylic acid ester containing an alkyl group and a polymerizable unsaturated carboxylic acid or a hydroxyl group-containing ethylenically unsaturated monomer, or further copolymerizable with this mixture. It is obtained by copolymerizing a vinyl monomer added in an organic solvent. As described above, many types of pressure-sensitive adhesives are marketed under various trade names, and can be appropriately selected and used according to the application.

  A heat-sensitive adhesive is an adhesive that exhibits no adhesiveness at room temperature but exhibits adhesiveness when heated, and is also referred to as a hot-melt adhesive or a heat sealant. These are all thermoplastic resins. For example, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid copolymer, polyamide resin, polyester resin, polyamide resin, rubber styrene / isoprene / butadiene / styrene copolymer Examples thereof include those having a rubber-based styrene / isoprene / styrene copolymer as a base polymer. As described above, various heat-sensitive adhesives are marketed under various trade names, and can be appropriately selected and used according to the application.

6. Substrate with an infrared shielding layer The substrate with an infrared shielding layer according to an embodiment of the present invention includes a substrate and an infrared shielding layer formed on the surface of the substrate, and the infrared shielding layer includes the infrared shielding material fine particles. It is possible to form a film by applying an infrared shielding layer forming coating solution in which a binder component is added to an infrared shielding material fine particle dispersion containing the above and a dispersant in a solvent.

  If necessary, an ultraviolet absorber or a diluting solvent may be added to and mixed with the coating liquid for forming an infrared shielding layer obtained using the above-described infrared shielding material fine particle dispersion. As described above, the phosphate group of the dispersant composed of a polymer compound having a main chain of an acrylate ester copolymer and a phosphate group as a side chain is adsorbed on the surface of the infrared shielding material fine particles. In the above-described coating liquid for forming an infrared shielding layer, the dispersion is maintained well.

  The blending amount of the infrared shielding material fine particles in the infrared shielding material fine particle dispersion is desirably adjusted to, for example, 40 parts by mass or more with respect to 6 parts by mass of the infrared shielding material fine particles. This is because if the amount of the solvent is less than the above value, the amount of fine particles is excessively increased, and there is a possibility that the stirring / dispersing treatment performed after the mixing may not be performed normally. In addition, the blending amount of the dispersant in the infrared shielding material fine particle dispersion is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more with respect to 1 part by mass of the infrared shielding material fine particles. This is because if the amount of the dispersing agent is less than the above value, there is a high possibility that the fine particles of the infrared shielding material cannot be suitably dispersed.

  Further, the amount of the binder component added to the infrared shielding material fine particle dispersion containing the infrared shielding material fine particles and the dispersant in a solvent is appropriately set according to the required performance of the infrared shielding layer to be formed. The binder component is preferably adjusted to 1 part by mass or more with respect to 1 part by mass of the infrared shielding material fine particles in the infrared shielding material fine particle dispersion. By suitably selecting the amount of the binder component, the surface hardness of the formed infrared shielding layer can be sufficiently ensured, and the viscosity of the coating solution can be avoided from being excessively high, so that uniform coating is easily performed. be able to.

  In addition to the binder component, the infrared shielding material fine particle dispersion may further contain an ultraviolet absorber, a diluting solvent and the like as required. What is necessary is just to adjust suitably the compounding quantity of additive materials, such as the said ultraviolet absorber and a dilution solvent, according to desired performance. By adjusting the blending amount of the ultraviolet absorber, the ultraviolet shielding ability of the formed infrared shielding layer can be sufficiently secured, and a good film appearance can be secured. Further, if a curing catalyst is blended in the infrared shielding layer forming coating liquid in which the binder component is added to the infrared shielding material fine particle dispersion, an effect of promoting the curing of the formed infrared shielding layer can be obtained. By adjusting the amount, the leveling property of the liquid at the time of application can be secured, and the mixed application liquid can be prevented from curing before application.

  When the curing catalyst is added to the coating solution for forming the infrared shielding layer, the binder component starts to be cured. Therefore, the curing catalyst is preferably added immediately before the coating solution for forming the infrared shielding layer. Further, the curing catalyst includes alcohols such as methanol, ethanol and isobutyl alcohol, ether alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, esters such as methyl acetate and ethyl acetate, ketones such as methyl ethyl ketone and cyclohexanone. It is preferable to dissolve in advance in various solvents such as This is because, in the form of a solution, it can be easily added and can be made uniform immediately.

  The above infrared shielding layer-forming coating solution is applied to one or both sides of a predetermined substrate such as a glass substrate, a plastic plate, a transparent film and the like, and cured at room temperature, thereby increasing the surface hardness. In addition, an infrared shielding layer having an infrared shielding ability can be formed on the surface of the transparent substrate, whereby a substrate with an infrared shielding layer can be obtained. As the transparent film used in the embodiment of the present invention, for example, any transparent film such as a polyethylene film, a polypropylene film, a polyester film, a polycarbonate film, a polyvinyl chloride film, a polystyrene film, and a polyamide film can be used. The size of these transparent films is not particularly limited. Although it changes with uses about the thickness of a transparent film, it has a film or sheet | seat form about 6-200 micrometers in thickness normally.

  There is no particular limitation on the coating method of the infrared shielding layer forming coating solution, and the processing solution is thin, flat and uniform, such as spin coating method, spray coating method, dip coating method, screen printing method, coating method using cloth or brush. Any method can be used as long as it can be applied. By using these coating methods, the infrared shielding layer can be produced with high productivity.

  The obtained infrared shielding layer has a high infrared shielding function while having high surface hardness and excellent transparency. Furthermore, the base material with an infrared shielding layer in which the infrared shielding layer is formed on one side or both sides has high mechanical durability and excellent transparency, and also has high infrared shielding performance. Furthermore, when the said infrared shielding layer contains a ultraviolet absorber, an ultraviolet-ray shielding capability is exhibited and it can also suppress that a base material itself deteriorates with an ultraviolet-ray.

7. Substrate with infrared shielding adhesive layer The substrate with infrared shielding adhesive layer of the embodiment of the present invention has two aspects, and the first aspect is the application of the heat ray shielding adhesive liquid described above on the surface of the substrate. Thus, an infrared shielding adhesive layer is formed. Moreover, the 2nd aspect has the structure where the infrared shielding adhesive layer formed from the above-mentioned infrared shielding adhesive liquid was laminated | stacked with the functional multilayer film on the surface of the base material. In the second aspect, the infrared shielding adhesive layer is 1) between the base material and the functional multilayer film, or 2) between the functional films constituting the functional multilayer film provided on the surface of the base material. It is formed in either.

  In the base material with an infrared shielding adhesive layer of the embodiment of the present invention, the adhesive and the infrared shielding material fine particle dispersion are blended so that an appropriate adhesive performance can be obtained according to the use. The blending amount is appropriately set in accordance with the required performance of the infrared shielding adhesive layer to be formed. The amount of the adhesive is 1 part by mass or more with respect to 1 part by mass of the infrared shielding material fine particles in the infrared shielding material fine particle dispersion. It is preferable to adjust. After mixing at the above ratio, sufficiently agitate, and apply the obtained infrared shielding adhesive liquid to the surface of the base material to a predetermined thickness by an appropriate coating method to form an infrared shielding adhesive layer on the substrate surface The base material with the infrared shielding adhesive layer of embodiment of this invention which was made can be produced.

  As an application means suitable for application to the base material of the infrared shielding adhesive liquid, for example, a general coating machine such as a knife over roll coater, a roll coater, a reverse coater, a gravure coat, etc. can be used. After that, you may perform a drying process as needed. When the adhesive is a pressure-sensitive adhesive, a release sheet such as a resin film or paper coated with a release silicone may be pasted on the surface of the adhesive layer in consideration of handleability. preferable.

  As the substrate for forming the adhesive layer, a substrate such as a transparent substrate such as a glass substrate, a plastic plate, or a transparent film can be used in the same manner as the substrate used for the substrate with an infrared shielding layer. . For example, as the transparent film, any transparent film such as a polyethylene film, a polypropylene film, a polyester film, a polycarbonate film, a polyvinyl chloride film, a polystyrene film, and a polyamide film can be used. The size of these transparent films is not particularly limited. Although it changes with uses about the thickness of a transparent film, it has the form of the film or sheet | seat about 6-200 micrometers in thickness normally.

  Of the substrate with an infrared shielding adhesive layer according to an embodiment of the present invention, a specific example of the second aspect of the structure in which the infrared shielding adhesive layer formed from the above-described infrared shielding adhesive liquid is laminated together with the functional multilayer film on the substrate surface A typical configuration will be exemplified below.

1) When the infrared shielding adhesive layer is formed between the base material and the functional multilayer film In FIGS. 2A to 2C, the infrared shielding adhesive layer is provided between the base material and the functional multilayer film. The manufacturing method of the base material with the infrared shielding adhesive layer of the laminated body structure currently formed is shown with typical sectional drawing. First, as shown in FIG. 2A, a transfer film 10 having a laminate structure is prepared. This transfer film 10 has a release layer 12 (for example, wax, a resin film such as polyester, polypropylene, polyethylene, polyethylene terephthalate, polycarbonate, polyimide, etc., paper, cellophane, etc.) on one side of a film sheet 11. Acrylic resin, polyvinyl acetal typified by polyvinyl butyral, etc.) is formed, and an infrared shielding layer 13 containing infrared shielding material fine particles 13a is formed on the release layer 12, and this infrared shielding layer 13 is formed. The infrared shielding adhesive layer 14 of the embodiment of the present invention is formed on the substrate.

  After the infrared shielding adhesive layer 14 side of the transfer film 10 is bonded to the inner surface of the plate glass or plastic plate 15 under pressure, the film sheet 11 is peeled from the bonded transfer film 10. In this case, only the film sheet 11 is peeled from the transfer film 10 having a laminate structure due to the effect of the peeling layer 12. The state after this peeling is shown in FIG.

  After the film sheet 11 is peeled off, it is bonded under pressure to an inner surface of a separately prepared plate glass or plastic plate 15 through an adhesive layer 16 containing no functional material on the peeling side. Thereby, a base material with an infrared shielding adhesive layer as shown in FIG. 2C is obtained.

  The base material with an infrared shielding adhesive layer of one specific example of the present invention produced by the above manufacturing method has a structure in which an intermediate layer is sandwiched between two laminated base materials 15 as shown in FIG. In this intermediate layer, an adhesive layer 16 containing no functional material, a release layer 12, an infrared shielding layer 13 containing infrared shielding material fine particles 13a, and an infrared shielding adhesive layer 14 according to an embodiment of the present invention are laminated in this order. It has a structure.

  According to the above manufacturing method, a thin infrared shielding layer can be easily manufactured, and the infrared shielding layer 13 containing the infrared shielding material fine particles 13a can be replaced with a thin film layer having other functions. Functions such as ultraviolet shielding and color tone adjustment can be added by appropriately adding additives having other functions to the adhesive layer 16 and the release layer 12 that do not contain a functional material.

2) In the case where an infrared shielding adhesive layer is formed between the functional films constituting the functional multilayer film provided on the substrate surface. FIG. 3 shows the functional multilayer film provided on the substrate surface. An optical filter as a specific example of a base material with an infrared shielding adhesive layer having a structure in which an infrared shielding adhesive layer is formed between each functional film is shown in a schematic sectional view. This optical filter includes a transparent substrate 20, an electromagnetic wave shielding layer 21 provided on one surface thereof, an infrared shielding adhesive layer 22 formed so as to fill a gap between the electromagnetic wave shielding layer 21 and cover the surface. The external force absorbing layer 23 attached by the infrared shielding adhesive layer 22 and the antireflection layer 24 provided on the external force absorbing layer 23. An adhesive layer 25 is provided on the other surface of the transparent substrate 20 and is adhered to the glass surface of the electronic display device main body via the adhesive layer 25. As shown in FIG. 3, although the infrared shielding material fine particles 22a are contained in the dispersed state in the infrared shielding adhesive layer 22, the infrared shielding material fine particles are contained in the other adhesive layer 25 or the external force absorbing layer 23 or both of them. You may make it contain by dispersion.

  As described above, the infrared ray shielding adhesive layer of the embodiment of the present invention is formed on the surface of the functional film formed on the base material, and the transfer film configuration separately prepared on the infrared ray shielding adhesive layer By adhering the other functional films, it is possible to obtain a substrate with an infrared shielding adhesive layer in which two different functional films are adhered via an infrared shielding adhesive layer.

8. Infrared shielding optical member The infrared shielding optical member of the present invention is an optical member formed by bonding the above-mentioned base material with an infrared shielding adhesive layer to another base material. A schematic cross-sectional view of a specific example of the infrared shielding optical member of the present invention is shown in FIG. The infrared shielding optical member shown in FIG. 4 is a base material with an infrared shielding adhesive layer in which an infrared shielding adhesive layer 31 is formed on the surface of a transparent film 30, and in the pressure-sensitive adhesive constituting the infrared shielding adhesive layer. In addition, the infrared shielding material fine particles 31a are present in a dispersed state. Since this pressure-sensitive adhesive exhibits adhesiveness at room temperature, a film sheet 33 having a release layer 32 on one surface is attached to the surface of the adhesive layer 31 from the release layer 32 side for the purpose of eliminating the disadvantages. Are combined. With this configuration, the base material with an infrared shielding adhesive layer is bonded to, for example, a glass window of an automobile after the surface film sheet 33 is peeled off or peeled off when used as an infrared shielding optical member.

  FIG. 5 shows a schematic cross-sectional view of another specific example of the infrared shielding optical member of the present invention. The infrared shielding optical member shown in FIG. 5 is an example in which an infrared shielding adhesive layer 31 in which infrared shielding material fine particles 31 a are present in a dispersed state is interposed between two transparent films 30. When the infrared shielding adhesive layer 31 is formed by a heat sealing method, the infrared shielding heat-sensitive adhesive is applied and dried on one surface of one transparent film 30 to form the infrared shielding adhesive layer 31, and then The other transparent film 30 is bonded by a laminator such as a hot roll. In this base material with an infrared shielding adhesive layer, a film sheet 33 having a release layer 32 on one surface is bonded to the outer surface of one of the two transparent films 30 from the release layer 32 side. With this configuration, the base material with an infrared shielding adhesive layer can be used, for example, in a glass of an automobile while peeling or peeling the surface film sheet 33 when used as an infrared shielding optical member, as in FIG. Laminate on the window.

  Thus, the infrared shielding optical member produced using the inorganic infrared shielding material fine particle dispersion of the embodiment of the present invention is excellent in sharpness, transparency, light resistance, stability, etc., and such an optical member. Can be provided at low cost, it is excellent as a laminated solar control film for automobiles and architectural windows.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. In addition, the measurement of the following visible light transmittance and solar radiation transmittance was performed based on JISR3106. The haze value was measured according to JIS K7105.

[Example 1]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material and 30 methyl isobutyl ketone as a solvent. .80 g, 1.20 g of a dispersant (BYK-W903 manufactured by BYK Japan Japan Co., Ltd.) whose main chain is an acrylate copolymer and has a phosphate group as a side chain, and mixed them Thus, 40 g of a raw material liquid was prepared. Further, 140 g of zirconia beads having a diameter of 0.3 mm (manufactured by Toray Industries, Inc.) was added to the raw material liquid, and then the glass container was sealed.

Next, the sealed the glass container, a paint shaker (Asada Iron Works Co., Ltd., frequency 640Rpm) was stirred for 15 h by, Cs _0.33 according to Example 1, Cs _0.33 WO ₃ fine particles are dispersed A WO ₃ dispersion (liquid A) was prepared. Next, 85.0 parts by mass of a heat-sensitive adhesive (solid content: 40 parts by mass) made of a polyester resin is added to 15.0 parts by mass of this Cs _0.33 WO ₃ dispersion (liquid A). These were sufficiently mixed to obtain an infrared shielding adhesive liquid according to Example 1 containing Cs _0.33 WO ₃ fine particles. The obtained infrared shielding adhesive liquid is applied onto a PET film having a thickness of 50 μm using an applicator to form a coating film having a thickness of 150 μm, and this coating film is dried at a heat treatment temperature of 80 ° C. for 180 seconds. The solvent was evaporated to obtain a film with an infrared shielding adhesive layer according to Example 1.

  The visible light transmittance, solar transmittance, and haze value of the obtained film with an infrared shielding adhesive layer were measured. As a result, the visible light transmittance was 69.7% and the solar radiation transmittance was 36.5%, and it was confirmed that the light in the infrared region was shielded while sufficiently transmitting the light in the visible light region. It was also confirmed that the haze value was 0.9% and the transparency was extremely high.

[Example 2]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. Infrared shielding adhesive layer according to Example 2 in the same manner as in Example 1 except that 0.000 g and 4.00 g of the same dispersant as in Example 1 were added and mixed to prepare a 40 g raw material solution. An attached film was obtained.

  With respect to the obtained film with an infrared shielding adhesive layer according to Example 2, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 70.3% and the solar radiation transmittance was 37.2%, and the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. Further, the haze value was 0.9%, and it was confirmed that the transparency was extremely high.

[Example 3]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 24 methyl isobutyl ketone as a solvent. Infrared shielding adhesive layer according to Example 3 in the same manner as in Example 1 except that .80 g and 7.20 g of the same dispersant as in Example 1 were added and mixed to prepare a 40 g raw material solution. An attached film was obtained.

  With respect to the obtained film with infrared shielding adhesive layer according to Example 3, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 68.2% and the solar radiation transmittance was 35.1%, and the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. Further, the haze value was 0.9%, and it was confirmed that the transparency was extremely high.

[Comparative Example 1]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 4.00 g of a dispersant (A-30SL, manufactured by Toa Gosei Co., Ltd.) having a main chain of an acrylic ester copolymer and an ammonium base as a side chain, and mixing them. A film with an infrared shielding adhesive layer according to Comparative Example 1 was obtained in the same manner as in Example 1 except that 40 g of the raw material liquid was prepared.

  With respect to the obtained film with infrared shielding adhesive layer according to Comparative Example 1, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 70.8% and the solar radiation transmittance was 38.5%, and the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 10.2%, and it was confirmed that the transparency was extremely poor.

[Comparative Example 2]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 0.000 g, 4.00 g of a dispersant (UC-3000 manufactured by Toagosei Co., Ltd.) having a carboxylic acid group as a side chain and having a carboxylic acid group as a side chain, and mixing them Then, a film with an infrared shielding adhesive layer according to Comparative Example 2 was obtained in the same manner as in Example 1 except that 40 g of the raw material liquid was prepared.

  With respect to the obtained film with an infrared shielding adhesive layer according to Comparative Example 2, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 71.1% and the solar radiation transmittance was 38.8%, and the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 12.6%, and it was confirmed that the transparency was extremely poor.

[Comparative Example 3]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 0.000 g, 4.00 g of a dispersant (Disperbyk-142 manufactured by Big Chemie Japan Co., Ltd.) having a main chain of urethane copolymer and having a phosphate group as a side chain, and mixing them. A film with an infrared shielding adhesive layer according to Comparative Example 3 was obtained in the same manner as in Example 1 except that 40 g of the raw material solution was prepared.

  With respect to the obtained film with infrared shielding adhesive layer according to Comparative Example 3, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 70.8% and the solar radiation transmittance was 38.5%, and the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 20.5%, and it was confirmed that the transparency was extremely poor.

[Comparative Example 4]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 0.000 g, 4.00 g of a dispersant having a carboxylic acid group as a side chain (ANTI-TERRA-204 manufactured by Big Chemie Japan Co., Ltd.) as a side chain, and A film with an infrared shielding adhesive layer according to Comparative Example 4 was obtained in the same manner as in Example 1 except that 40 g of the raw material liquid was prepared.

  With respect to the obtained film with an infrared shielding adhesive layer according to Comparative Example 4, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, the visible light transmittance was 70.1% and the solar radiation transmittance was 37.9%. It was confirmed that the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 15.8%, and it was confirmed that the transparency was extremely poor.

[Comparative Example 5]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 4.00 g of a dispersant (Disperbyk-108 manufactured by Big Chemie Japan Co., Ltd.) having a main chain of a carboxylic acid ester copolymer and having a hydroxyl group as a side chain, and mixing them. A film with an infrared shielding adhesive layer according to Comparative Example 5 was obtained in the same manner as in Example 1 except that 40 g of the raw material liquid was prepared.

  With respect to the obtained film with an infrared shielding adhesive layer according to Comparative Example 5, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, the visible light transmittance was 72.4% and the solar radiation transmittance was 39.6%. It was confirmed that the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 11.6%, and it was confirmed that the transparency was extremely poor.

[Comparative Example 6]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 4.00 g of a dispersant (A-6114 manufactured by Toa Gosei Co., Ltd.) having an ammonium group as a side chain and a main chain of a carboxylic acid ester copolymer was added to each, and these were mixed. A film with an infrared shielding adhesive layer according to Comparative Example 6 was obtained in the same manner as in Example 1 except that 40 g of the raw material liquid was prepared.

  With respect to the obtained film with an infrared shielding adhesive layer according to Comparative Example 6, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 71.5% and the solar radiation transmittance was 39.3%, and the light in the visible region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 18.6%, and it was confirmed that the transparency was extremely poor.

[Comparative Example 7]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 4.00 g of a dispersant (11-408 manufactured by DIC Corporation) having a main chain of a polyester copolymer and having a carboxylic acid as a side chain, and mixing them, 40 g of raw material A film with an infrared shielding adhesive layer according to Comparative Example 7 was obtained in the same manner as in Example 1 except that the liquid was prepared.

  With respect to the obtained film with an infrared shielding adhesive layer according to Comparative Example 7, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 70.4% and the solar radiation transmittance was 38.2%, and the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 23.6%, and it was confirmed that the transparency was extremely poor.

[Comparative Example 8]
In a 70 ml glass container, 8.00 g of Cs _0.33 WO ₃ powder having a particle size distribution of 1.2 μm at 50% diameter and 4.8 μm at 95% diameter as an infrared shielding material, and 28 methyl isobutyl ketone as a solvent. 0.000 g, 4.00 g of a dispersant (B4103 manufactured by Tokyo Chemical Industry Co., Ltd.) whose main chain is a boric acid ester copolymer were added and mixed to prepare a 40 g raw material solution. In the same manner as in Example 1, a film with an infrared shielding adhesive layer according to Comparative Example 8 was obtained.

With respect to the obtained film with an infrared shielding adhesive layer according to Comparative Example 8, the visible light transmittance, solar transmittance, and haze value were measured in the same manner as in Example 1. As a result, it was confirmed that the visible light transmittance was 72.2% and the solar radiation transmittance was 39.4%, and that the light in the visible light region was sufficiently transmitted while the light in the infrared region was shielded. However, the haze value was 17.2%, and it was confirmed that the transparency was extremely poor. Tables 1 and 2 below show the dispersants, dispersant content (parts by mass), visible light transmittance (%), solar transmittance (%), and haze (%) according to the above Examples and Comparative Examples. Here, the numerical value of the dispersant content (parts by mass) indicates parts by mass with respect to 100 parts by mass of Cs _0.33 WO ₃ fine particles.

  As can be seen from the “Haze” column in Table 1 above, in Examples 1 to 3, a dispersant having an acrylate copolymer as a main chain and a phosphate as a side chain is applied. Therefore, the transparency of the manufactured film with an infrared shielding adhesive layer is extremely high at 0.9%.

  On the other hand, as can be seen from the “Haze” column in Table 2, Comparative Examples 1 to 8 contain a heat-sensitive adhesive composed of the polyester resin, and have an acrylate copolymer as the main chain. In addition, since a film with an infrared shielding adhesive layer is manufactured by applying an infrared shielding material fine particle dispersion not containing a dispersant having a phosphate as a side chain, the haze is as high as 10.2 to 23.6%. The transparency of the manufactured film with an infrared shielding adhesive layer is extremely deteriorated.

1 WO ₆ units 2 Element M
DESCRIPTION OF SYMBOLS 10 Transfer film 11 Film sheet 12 Release layer 13 Infrared shielding layer 13a, 22a, 31a, 14a Infrared shielding material fine particles 14, 22, 31 Infrared shielding adhesive layer 15 Plate glass or plastic plate 16 Adhesive layer containing no functional material 20 Transparent group Material 21 Electromagnetic wave shielding layer 23 External force absorbing layer 24 Antireflection layer 25 Adhesive layer 30 Transparent film 32 Peeling layer 33 Film sheet

Claims (11)

An infrared shielding material fine particle dispersion containing an infrared shielding material fine particle and a dispersant in a solvent, wherein the infrared shielding material fine particle has a general formula W _y O _z (W is tungsten, O is oxygen, 2. 2 ≦ (z / y) ≦ 2.999), and a general formula M _x W _y O _z (where M is H, He, alkali metal, alkaline earth metal, rare earth element) Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb , Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, one type selected from the group The above elements, W is tungsten, O is oxygen, 0.001 ≦ ( x / y) ≦ 1, 2.2 ≦ (z / y) ≦ 3) composed of one or more oxide fine particles selected from composite tungsten oxide fine particles, wherein the dispersant has an acrylic main chain. An infrared shielding material comprising an acid ester-based copolymer having a phosphate group as a side chain, wherein the phosphoric acid group of the dispersant is adsorbed on the surface of the infrared shielding material fine particles Fine particle dispersion.   2. The infrared shielding material fine particle dispersion according to claim 1, wherein a content of the dispersant is 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the infrared shielding material fine particles. One or more oxide fine particles selected from the tungsten oxide fine particles and the composite tungsten oxide fine particles have a general formula W _y O _z (W is tungsten, O is oxygen, 2.45 ≦ (z / y) The infrared shielding material fine particle dispersion according to claim 1, comprising a magnetic phase having a composition ratio represented by ≦ 2.999).   The composite tungsten oxide fine particles include one or more of composite tungsten oxide fine particles having a hexagonal, tetragonal, or cubic crystal structure, according to any one of claims 1 to 3. Infrared shielding material fine particle dispersion as described.   In the composite tungsten oxide fine particles, the M element includes one or more members selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn, and hexagonal crystal The infrared shielding material fine particle dispersion according to claim 4, which has a crystal structure of:   An infrared shielding adhesive liquid, wherein the infrared shielding material fine particle dispersion according to any one of claims 1 to 5 is dispersed in an adhesive.   The infrared shielding adhesive liquid according to claim 6, wherein the adhesive is a heat-sensitive adhesive or a pressure-sensitive adhesive.   The base material with an infrared shielding layer in which the infrared shielding layer obtained using the infrared shielding material fine particle dispersion liquid of any one of Claims 1-5 is formed in the base-material surface.   The base material with an infrared shielding adhesive layer in which the infrared shielding adhesive layer obtained using the infrared shielding adhesive liquid of Claim 6 or 7 is formed in the base-material surface.   A base material with an infrared shielding adhesive layer in which a functional multilayer film and an infrared shielding adhesive layer using the heat ray shielding adhesive liquid according to claim 6 or 7 are laminated on the surface of the substrate, wherein the infrared ray A shielding adhesive layer is formed between the base material and the functional multilayer film, or is formed between the functional films constituting the functional multilayer film provided on the base material surface. A substrate with an infrared shielding adhesive layer, characterized in that.   The infrared shielding optical member formed by adhere | attaching the base material with an infrared shielding adhesive layer of Claim 9 or 10 to another base material.

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