JP6201127B2 - Heat ray shielding film having weather resistance, heat ray shielding sheet or film having weather resistance, heat ray shielding fine particle dispersion, and heat ray shielding fine particle dispersion powder - Google Patents

Description

The present invention relates to a heat ray shielding laminated structure used as a window material for vehicles such as automobiles and buildings.

Sun rays are roughly divided into three types: near infrared light (heat rays), visible light, and ultraviolet light. Near-infrared light (heat rays) is a wavelength region that is perceived by the human body as thermal energy, and causes a rise in indoor temperature in summer. In addition, it has been pointed out that ultraviolet light adversely affects the human body such as sunburn and skin cancer. By controlling the transmittance of visible light, a transparent substrate such as a window glass can have a privacy protection function.
In recent years, in order to shield near-infrared rays as heat rays and to impart heat retention and heat insulation performance, it has been required to impart near-infrared absorbing ability to transparent substrates such as glass, polycarbonate resin, and acrylic resin.

On the other hand, as safety glass used for automobiles or the like, a laminated glass is used in which an intermediate layer containing a polyvinyl acetal resin or the like is sandwiched between a plurality of (for example, two) opposing glass plates. And the thing for the purpose of the reduction | decrease of a cooling load and a human heat feeling is interrupted | blocked by the laminated glass which gave the heat ray shielding function to the said intermediate | middle layer, and interrupted the solar energy which injected into a vehicle interior.

For example, in Patent Document 1, a soft resin layer containing a heat ray shielding metal oxide made of tin oxide or indium oxide having a fine particle size of 0.1 μm or less is sandwiched between two opposing plate glasses. Glass is disclosed.
Patent Document 2 discloses that Sn, Ti, Si between at least two opposing plate glasses.
Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn,
An intermediate layer in which a metal of Ta, W, V, or Mo, an oxide of the metal, a nitride of the metal, a sulfide of the metal, a Sb or F dopant to the metal, or a composite thereof is dispersed. A laminated glass sandwiching a glass is disclosed.
In Patent Document 3, fine particles made of TiO ₂ , ZrO ₂ , SnO ₂ , and In ₂ O ₃ and a glass component made of organic silicon or an organic silicon compound are sandwiched between opposing transparent plate-like members. An automotive window glass is disclosed. Further, in Patent Document 4, an intermediate layer composed of three layers is provided between at least two opposing transparent glass plates, and Sn is formed on the second layer of the intermediate layer. Ti, Si, Zn, Zr, Fe, Al
, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo, metal oxide, metal nitride, metal sulfide, Sb to the metal Further, a laminated glass in which a dope of F or F or a composite thereof is dispersed and an intermediate layer of the first layer and the third layer is used as a resin layer is disclosed.
However, each of the conventional laminated glasses disclosed in Patent Documents 1 to 4 has a problem that the heat ray shielding function is not sufficient when high visible light transmittance is required.

The applicant consists of an intermediate layer having a heat ray shielding function between two sheet glasses, and this intermediate layer is composed of hexaboride fine particles alone, or hexaboride fine particles and ITO fine particles and / or ATO fine particles, A heat ray shielding laminated glass comprising a heat ray shielding film containing a vinyl-based resin, or a heat ray shielding film containing the fine particles, wherein the intermediate layer is formed on a surface facing the inside of at least one plate glass. Patent Document 5 discloses a heat-shielding laminated glass composed of a heat-ray shielding film containing a vinyl resin interposed between the two plate glasses.
As described in Patent Document 5, hexaboride fine particles alone, or hexaboride fine particles and I
The optical characteristics of heat-shielding laminated glass to which TO fine particles and / or ATO fine particles are applied have a maximum transmittance in the visible light region and a strong absorption in the near infrared region, thereby minimizing the transmittance. Have. As a result, the heat-shielding laminated glass is improved until the solar radiation transmittance is in the 50% range when the visible light transmittance is 70% or more, as compared with the conventional laminated glasses described in Patent Documents 1 to 4. It was.

On the other hand, as the fine particles having a shielding function in the near infrared region, the above-mentioned ITO fine particles, ATO
In addition to fine particles and hexaboride fine particles, composite tungsten oxide fine particles are known. The applicant has disclosed, in Patent Document 6, a laminated glass for heat ray shielding, in which a polyvinyl acetal resin is replaced with an ultraviolet curable resin, and a heat ray shielding film containing a composite tungsten compound and hexaboride in the ultraviolet curable resin is used as an intermediate layer. Disclosure.

JP-A-8-217500 JP-A-8-259279 Japanese Patent Laid-Open No. 4-160041 Japanese Patent Laid-Open No. 10-297945 JP 2001-89202 A JP 2010-202495 A

However, as a result of further studies by the present inventors, the following problems have been found.
That is, in the laminated glass which concerns on the prior art described in patent documents 1-4, as above-mentioned, as for all, the heat ray shielding function when high visible light transmittance is calculated | required is not enough. Further, the haze value indicating the degree of fogging of the transparent base material needs to be 1% or less for vehicle window materials and 3% or less for building window materials, for example, the heat ray shielding described in Patent Document 5 The laminated glass still has room for improvement.
In addition, the heat-shielding laminated glass and the like according to the prior art are all insufficient in weather resistance when used for a long period of time, and a decrease (deterioration) in visible light transmittance has been found over time.

The present invention has been made paying attention to the above problems. The problem to be solved is to provide a laminated structure for heat ray shielding that uses composite tungsten oxide fine particles having excellent heat ray shielding properties and exhibits excellent optical properties and high weather resistance.

In order to achieve the above-mentioned object, the present inventors mixed composite tungsten oxide fine particles, which are near-infrared absorbing materials, with a resin binder, and further mixed with a metal carbonate or carbonate hydroxide to produce visible light. It has been found that it has maximum transmittance in the region, strong absorption in the near infrared region, low haze value, and excellent weather resistance. The present invention has been completed based on such technical knowledge.

That is, the first invention for solving the above-described problem is
Including fine particles having a heat ray shielding function, metal carbonate or carbonate hydroxide,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
A heat ray shielding film having weather resistance, wherein the metal carbonate or carbonate hydroxide is contained in an amount of 1 part by weight or more and 100 parts by weight or less based on 100 parts by weight of the composite tungsten oxide fine particles. It is.
The second invention is
The heat-ray shielding film is a heat-ray shielding film having weather resistance according to the first invention, which further comprising a binder.
The third invention is
The heat-shielding film having weather resistance according to the second invention, wherein the binder is an inorganic binder or an organic binder.
The fourth invention is:
Fine particles having a heat ray shielding function and metal carbonate or carbonate hydroxide are contained in the plastic,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
The heat-shielding sheet having weather resistance, wherein the metal carbonate or carbonate hydroxide is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. Or a film.
The fifth invention is:
The plastic is a polycarbonate resin, an acrylic resin, or a polyethylene terephthalate resin. The heat-shielding sheet or film having weather resistance according to the fourth aspect of the invention.
The sixth invention is:
A heat ray shielding film having weather resistance according to any one of the first to third inventions, or a heat ray for producing a heat ray shielding sheet or film having weather resistance according to the fourth or fifth inventions. A shielding fine particle dispersion,
Including fine particles having a heat ray shielding function, metal carbonate or carbonate hydroxide, and a solvent,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
The heat-shielding fine particle dispersion is characterized in that the metal carbonate or carbonate hydroxide is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles.
The seventh invention
The heat ray shielding fine particle dispersion according to the sixth aspect, wherein the heat ray shielding fine particle dispersion further contains a binder.
The eighth invention
A heat ray shielding film having weather resistance according to any one of the first to third inventions, or a heat ray for producing a heat ray shielding sheet or film having weather resistance according to the fourth or fifth inventions. A shielding fine particle dispersion,
Including fine particles having a heat ray shielding function, metal carbonate or carbonate hydroxide,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
The heat ray shielding fine particle dispersed powder, wherein the metal carbonate or carbonate hydroxide is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles.

The laminated structure for heat ray shielding according to the present invention contains a composite tungsten oxide represented by the general formula M _Y WO _Z and a metal carbonate or carbonate hydroxide having a function of preventing its deterioration. It exhibited excellent optical properties and excellent weather resistance.

Sectional drawing of an example of the laminated structure for heat ray shielding which concerns on (form A-1) is shown. Sectional drawing of an example of the laminated structure for heat ray shielding which concerns on (form A-2) is shown. Sectional drawing of an example of the laminated structure for heat ray shielding which concerns on (form A-3) is shown. Sectional drawing of an example of the laminated structure for heat ray shielding which concerns on (form A-4 (I)) is shown. Sectional drawing of an example of the laminated structure for heat ray shielding which concerns on (form A-4 (b)) is shown. Sectional drawing in the manufacturing process of an example of the laminated structure for heat ray shielding which concerns on (form A-6) is shown. Sectional drawing of an example of the laminated structure for heat ray shielding which concerns on (form B-7) is shown.

The present invention has been made by the inventors paying attention to the following problems of the prior art.
That is, none of the laminated structures for heat ray shielding such as laminated glass according to the prior art has a sufficient heat ray shielding function when high visible light transmittance is required. Further, the haze value indicating the degree of fogging of the transparent base material is required to be 1% or less for vehicle window materials and 3% or less for building window materials, whereas, for example, the heat ray described in Patent Document 5 The laminated glass for shielding still has room for improvement. In addition, the heat ray shielding laminated structures such as the laminated glass for heat ray shielding according to the prior art are insufficient in weather resistance when used for a long period of time, and the visible light transmittance decreases (deteriorates) over time. It was found that the near-infrared absorption function decreased, the color tone changed, and the haze value increased.

Furthermore, the present inventors paid attention to the following problems.
That is, in addition to optical characteristics, mechanical characteristics are also required for laminated glass for heat ray shielding used for various window materials. Specifically, laminated glass such as safety glass is required to have resistance to penetration. Conventionally, in order to impart penetration resistance to laminated glass or the like, a vinyl resin such as a polyvinyl acetal resin has been used for the intermediate layer. However, it has been found that when composite tungsten oxide fine particles are contained in a vinyl resin such as a polyvinyl acetal resin, the optical properties are lowered. Therefore, as a second best measure, for example, as described in Patent Document 6, a polyvinyl acetal resin is replaced with an ultraviolet curable resin, and a heat ray shielding film containing a composite tungsten compound and hexaboride in the ultraviolet curable resin is disclosed. did. However, from the viewpoint of satisfying the mechanical strength of safety glass or the like, it is considered that vinyl resins such as polyvinyl acetal resin are preferable as the resin for the intermediate layer.

The present invention has been made paying attention to the above problems. The problem to be solved is to provide a composite structure for heat ray shielding that uses composite tungsten oxide fine particles having excellent heat ray shielding properties and exhibits excellent optical properties and excellent weather resistance. .
Further, the problem to be solved by the present invention is that even when a vinyl resin such as polyvinyl acetal resin is used as the main component of the intermediate film in the laminated structure for heat ray shielding of the present invention, excellent optical characteristics and excellent Another object of the present invention is to provide a heat ray shielding laminated structure that exhibits excellent weather resistance.

The laminated structure for heat ray shielding according to the present invention for solving the above-described problems has composite tungsten oxide fine particles and metal carbonate or carbonate hydroxide.
Hereinafter, regarding the heat ray shielding laminated structure according to the present invention, 1. Fine particles having a heat ray shielding function; 2. metal carbonate or carbonate hydroxide; 3. Method for producing fine particles having a heat ray shielding function to which metal carbonate or carbonate hydroxide is added; 4. Heat-shielding laminated structure; 5. Form example of laminated structure for heat ray shielding, 6. manufacturing method of heat ray shielding laminated structure, and Details will be described in the order of summary.

1. (Fine particles with heat ray shielding function)
In general, a material containing free electrons has a wavelength of 200 nm to 2600 n by plasma oscillation.
It is known to show a reflection / absorption response to electromagnetic waves around the area of m solar rays. When the powder of such a substance is a fine particle smaller than the wavelength of light, geometric scattering in the visible light region (wavelength 380 nm to 780 nm) is reduced, and transparency in the visible light region is obtained.

In general, there is no effective free electron in tungsten trioxide (WO ₃ ).
No. 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 or so-called tungsten bronze obtained by adding a positive element such as Na to tungsten trioxide is a conductive material and a material having free electrons.
Furthermore, the analysis of single crystals of these materials suggests the response of free electrons to light in the infrared region.

The present inventors have found that the composition range of tungsten and oxygen is particularly effective as a near-infrared shielding material when the composition range is in a specific range. Specifically, the fine particle having a heat ray shielding function is represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0) and has a hexagonal crystal structure. Composite tungsten oxide fine particles having The composite tungsten oxide fine particles function effectively as a heat ray absorbing component when applied to a heat ray shielding laminated structure.
Examples of the composite tungsten oxide fine particles represented by the above general formula M _Y WO _Z (0.01 ≦ Y ≦ 0.5, 2.45 ≦ Z ≦ 3.0) and having a hexagonal crystal structure include, for example, M Element is C
Examples thereof include composite tungsten oxide fine particles containing one or more of s, Rb, K, and Tl. The addition amount of the additive element M is preferably 0.1 or more and 0.5 or less, more preferably 0.
. The vicinity of 33 is preferable. This is because the value theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. Typical examples include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Tl _0.33 WO _{3 and the} like, but Y and Z fall within the above ranges. If it is a thing, a useful heat ray absorption characteristic can be acquired.

Furthermore, considering design properties, it is required to efficiently shield near infrared rays while maintaining transparency. Since the heat ray absorbing component containing the composite tungsten oxide fine particles according to the present invention absorbs a large amount of light in the near infrared region, particularly in the vicinity of a wavelength of 900 to 2200 nm, the transmitted color tone often changes from blue to green.

When the particle diameter of the fine particles is smaller than 800 nm, light is not shielded, and near infrared rays can be shielded efficiently while maintaining transparency in the visible light region. In particular, when importance is attached to transparency in the visible light region, the particle diameter is preferably 200 nm or less, and preferably 100 nm or less.
When the particle diameter of the fine particles is large, the wavelength is 400 to 780 n due to geometric scattering or diffraction scattering.
This is because light in the visible light region of m is scattered and becomes like frosted glass, and clear transparency is impossible. When the particle diameter is 200 nm or less, the scattering is reduced and a Mie scattering or Rayleigh scattering region is obtained. In particular, when the particle size is reduced to the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the dispersed particle size, so that scattering is reduced and transparency is improved as the particle size is reduced.
Further, when the particle size is 100 nm or less, the scattered light is preferably very small. From the viewpoint of avoiding light scattering, a smaller particle diameter is preferable, and industrial production is easy if the particle diameter is 1 nm or more.

In addition, the heat ray absorption capacity per unit weight of the composite tungsten oxide fine particles is very high,
Compared with ITO and ATO, the effect is exhibited with a usage amount of about 4 to 1/10. The amount of the composite tungsten oxide fine particles contained in the heat ray shielding laminated structure is about 0.00 per unit area.
2g ^{/ m 2} ~2.5g ^/ m 2 is desirable. When the content is 0.2 g / m ² or more, expected heat ray shielding characteristics can be obtained. Moreover, if content is 2.5 g / m < ² > or less, the transparency of the laminated structure for heat ray shielding and the physical property of resin are not impaired, and it is preferable.

2. (Metal carbonate or carbonate hydroxide)
In the present invention, the addition of metal carbonate or carbonate hydroxide to the composite tungsten oxide fine particles is intended to improve the weather resistance of the laminated structure for heat ray shielding and to suppress changes in optical characteristics over time. Is added.
According to the knowledge of the present inventors, the metal carbonate or carbonate hydroxide has an effect of suppressing deterioration with time of the composite tungsten oxide fine particles. Although the specific mechanism for suppressing the deterioration over time has not yet been elucidated, the specific effect of the addition of metal carbonate or carbonate hydroxide is It is possible to suppress a decrease (deterioration) in visible light transmittance after the initial period of the shielding laminated structure and after a predetermined period of use. On the other hand, when the metal carbonate or carbonate hydroxide is not added to the composite tungsten oxide fine particles, the visible light transmittance is reduced (deteriorated) after the predetermined period of use of the heat ray shielding laminated structure. It was confirmed.

As a result of the study by the present inventors, as a metal constituting the carbonate or carbonate hydroxide of the metal, alkali metals such as lithium, sodium, potassium, rubidium and cesium, alkaline earth metals such as magnesium, calcium and strontium, manganese By using transition metals such as cobalt, nickel, copper, and zinc, the effect of suppressing deterioration in visible light transmittance has been confirmed.
In particular, when sodium, potassium, magnesium, manganese, cesium, lithium, or rubidium was used, a remarkable effect was found in suppressing deterioration of visible light transmittance. Specifically, the remarkable effect that the rate of change is suppressed to half or less of the initial visible light transmittance was found.
Further, by adding a carbonate or carbonate hydroxide using the above-mentioned metals, particularly sodium, potassium, magnesium, manganese, cesium, lithium, rubidium, to the composite tungsten oxide fine particles, for heat ray shielding using these It was also confirmed that the laminated structure had a deterioration suppressing effect that an increase in haze value was suppressed.

The addition amount of the metal carbonate or carbonate hydroxide is such that the composite tungsten oxide fine particles 10
The range is preferably 1 part by weight or more and 100 parts by weight or less with respect to 0 part by weight, and more preferably 3 parts by weight or more and 50 parts by weight or less. If the added amount of the metal carbonate or carbonate hydroxide is within the above range, the composite tungsten oxide fine particles have an effect of improving the weather resistance and may adversely affect the physical properties of the obtained heat ray shielding laminated structure. Because there is no.

3. (Production method of fine particles having heat ray shielding function to which metal carbonate or carbonate hydroxide is added)
Mixing a predetermined amount of fine particles having a heat ray shielding function, a predetermined amount of metal carbonate or carbonate hydroxide, an appropriate organic solvent, and a predetermined amount of a dispersing agent for dispersing fine particles, a medium stirring mill, an ultrasonic wave Dispersion treatment is performed using a homogenizer or the like, and a dispersion of fine particles having a heat ray shielding function to which a metal carbonate or carbonate hydroxide is added can be produced.
Fine particles having a heat ray shielding function to which a metal carbonate or carbonate hydroxide is added and the organic solvent is removed from the dispersion of fine particles having a heat ray shielding function to which the metal carbonate or carbonate hydroxide is added. Can also be produced.

In the description of the “heat ray shielding laminated structure” described below, “fine particles having a heat ray shielding function to which a metal carbonate or carbonate hydroxide is added” is simply referred to as “fine particles having a heat ray shielding function”. May be described.

4). (Matching structure for heat ray shielding)
In the laminated structure for heat ray shielding according to the present invention, an intermediate layer is interposed between two laminated plates selected from plate glass and plastic, and at least one of the intermediate layer and plastic has a heat ray shielding function. A structure comprising fine particles. About the heat ray shielding laminated structure according to the present invention, i. Laminated board, ii. A method of containing fine particles having a heat ray shielding function in the plastic constituting the laminated plate, iii. The intermediate layer will be described in this order.
i. <Laminated plate>
The laminated plate is a plate that sandwiches the intermediate layer from both sides, and is made of plate glass or plate-like plastic that is transparent in the visible light region. At this time, the two laminated plates selected from plate glass and plate-shaped plastic include each configuration of plate glass and plate glass, plate glass and plastic, and plastic and plastic.

When plastic is used for the laminated plate, the material of the plastic is appropriately selected according to the use of the heat ray shielding laminated structure, and is not particularly limited and can be selected according to the use. For example, when used for transportation equipment such as automobiles, from the viewpoint of ensuring the transparency of the driver and passenger of the transportation equipment, a transparent resin such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin is preferable. PET resin, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, and the like can be used.

As an example of the form of the laminated plate, a form in which plate glass or the plastic is used as it is (referred to as “form A” for convenience in this specification) and a fine particle having a heat ray shielding function contained in the plastic are used. Form (referred to as “form B” for convenience in this specification).

ii. <Method of incorporating fine particles having a heat ray shielding function into the plastic constituting the laminated plate>
Hereinafter, a method of incorporating fine particles having a heat ray shielding function into the plastic constituting the laminated plate in the form B will be described.
When the fine particles having the heat ray shielding function are kneaded into the plastic, the plastic is heated to a temperature near the melting point (around 200 to 300 ° C.), and the fine particles having the heat ray shielding function are mixed. Then, it is possible to pelletize a mixture of plastic and fine particles having a heat ray shielding function, and form the mixture into a film or a sheet by a desired method. For example, it can be formed by an extrusion molding method, an inflation molding method, a solution casting method, a casting method, or the like. The thickness of the film or board at this time may be appropriately selected according to the purpose of use. The addition amount of the fine particles having a heat ray shielding function for the plastic is variable depending on the thickness of the film or sheet material, required optical characteristics, and mechanical characteristics, but generally 50% of the resin.
The mass% or less is preferable.

iii. <Intermediate layer>
As an example of the form of the intermediate layer having a heat ray shielding function, there is a form constituted by an intermediate film containing fine particles having a heat ray shielding function (hereinafter referred to as “form 1” for convenience).
In addition, there is a mode of being composed of two or more intermediate films, and at least one of them includes a fine particle having a heat ray shielding function (in this specification, it is described as “mode 2” for convenience). In addition, a heat ray shielding film containing fine particles having a heat ray shielding function is formed on at least one plate glass or plastic inner surface, and an intermediate film not containing fine particles having a heat ray shielding function is overlaid on the heat ray shielding film (this book) In the specification, it is described as “form 3” for convenience.) Also, a heat ray shielding film substrate in which a heat ray shielding film containing fine particles having a heat ray shielding function is formed on one or both sides of a resin film substrate, or a heat ray shielding film substrate containing fine particles having a heat ray shielding function therein, and 2 There is a form (in the present specification, described as “form 4” for the sake of convenience) composed of an intermediate film that does not contain fine particles having a heat ray shielding function that is laminated more than one layer. Further, a form in which a heat ray shielding film containing fine particles having a heat ray shielding function is formed on one surface of an intermediate film not containing fine particles having a heat ray shielding function (in the present specification, for convenience, it is described as “form 5”). .) Further, the intermediate layer not containing fine particles having a heat ray shielding function includes an adhesive layer and fine particles having the heat ray shielding function on one inner surface of two laminated plates selected from the plate glass and plastic. An intermediate film that does not contain fine particles having a heat ray shielding function that adheres the adhesive layer of the laminate laminated in the order of the heat ray shielding film and the release layer, and further overlaps the laminate to the release layer side of the laminate. And an intermediate film that does not include fine particles having a heat ray shielding function that is laminated in two or more layers (in the present specification, it is referred to as “form 6” for convenience). Furthermore, there is a form in which the intermediate layer does not contain fine particles having a heat ray shielding function (in this specification, it is described as “form 7” for convenience).
In addition, in the “forms 3 to 7” described above, the intermediate film that does not include the fine particles having the heat ray shielding function may be replaced with an intermediate film that includes the fine particles having the thermal integrity shielding function.

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

5. (Example of heat-shielding laminated structure)
Hereinafter, while taking as an example the case of using a vinyl-based resin as the intermediate film, the above-described embodiments A and B of the laminated plate, and the embodiments 1 to 7 of the intermediate layer having a heat ray shielding function, The form of the combined structure for heat ray shielding combined will be described with reference to FIGS. 1-7 is typical sectional drawing of the laminated structure for heat ray shielding which concerns on this invention.

<Form A-1>
The laminated structure for heat ray shielding, which uses a sheet glass or plastic not containing fine particles having a heat ray shielding function as a laminated plate, and the intermediate layer is composed of an intermediate film in which fine particles having a heat ray shielding function are dispersed, is, for example, It is manufactured as follows.
An additive solution in which fine particles having a heat ray shielding function are dispersed in a plasticizer is added to a vinyl resin to prepare a vinyl resin composition, and the vinyl resin composition is molded into a sheet to form a sheet of an intermediate film And a method of forming a laminated structure for heat ray shielding by sandwiching and bonding the sheet of the interlayer film between two laminated plates selected from plate glass and plastic.
In the above description, an example in which fine particles having a heat ray shielding function are dispersed in a plasticizer has been described. However, a dispersion liquid in which fine particles having a heat ray shielding function are appropriately dispersed in a solvent that is not a plasticizer is added to a vinyl resin, You may prepare a vinyl-type resin composition by the method of adding a plasticizer separately.

Accordingly, a heat ray shielding laminated structure having high heat ray shielding characteristics and a low haze value can be produced. Furthermore, the method can easily produce a heat ray shielding laminated structure, and can produce a heat ray shielding laminated structure at a low production cost.
In FIG. 1, sectional drawing of an example of the laminated structure for heat ray shielding which concerns on the said (form A-1) is shown. As shown in FIG. 1, the heat ray shielding laminated structure has an intermediate layer 2 sandwiched between two laminated plates 1. The intermediate layer 2 includes an intermediate film 1 containing fine particles 11 having a heat ray shielding function dispersed therein.
It is comprised by 2.

<Form B-1>
The laminated structure for heat ray shielding, which uses a plastic containing fine particles having a heat ray shielding function as at least one laminated plate and the intermediate layer is composed of an intermediate film in which fine particles having a heat ray shielding function are dispersed, is heat ray shielding. It can be produced in the same manner as in (Embodiment A-1) except that at least one of two sheets of glass and plastic not containing fine particles having a function is replaced with a plastic containing fine particles having a heat ray shielding function.

The (form B-1) has a high heat ray shielding property as in the (form A-1), and can produce a heat ray shielding laminated structure having a low haze value. Further, in (Form B-1), it is easy to manufacture the heat ray shielding laminated structure, and it is possible to produce a heat ray shielding laminated structure at a low production cost.

<Form A-2>
Use a glass that does not contain plate glass or fine particles having a heat ray shielding function as the laminated plate, the intermediate layer has two or more intermediate films, and at least one of them contains fine particles having a heat ray shielding function dispersed therein The laminated structure for heat ray shielding constituted by the intermediate film is manufactured as follows, for example.
An additive liquid in which fine particles having a heat ray shielding function are dispersed in a plasticizer is added to a vinyl resin to prepare a vinyl resin composition, and the vinyl resin composition is molded into a sheet to form an intermediate film sheet. The intermediate film sheet is laminated with another intermediate film sheet not containing fine particles having a heat ray shielding function, or interposed between two sheets of intermediate film sheets not containing fine particles having a heat ray shielding function. A method of forming a laminated structure for heat ray shielding by sandwiching and bonding between two laminated plates selected from plate glass and plastic is mentioned.
In the same manner as in (Form 1), instead of dispersing fine particles having a heat ray shielding function in a plasticizer, a dispersion liquid appropriately dispersed in a solvent is added to a vinyl resin, and a plasticizer is added separately. A vinyl resin composition may be prepared. Accordingly, a heat ray shielding laminated structure having high heat ray shielding characteristics and a low haze value can be manufactured at a low production cost.

According to the method, the adhesiveness between the interlayer film sheet having no heat ray shielding function and containing no fine particles and two laminated plates selected from plate glass and plastic can be improved. The strength of is moderately increased, which is preferable.

Further, for example, P in which an Al film or an Ag film is formed on at least one surface by sputtering or the like.
An ET (polyethylene terephthalate) film is prepared, and the PET film is interposed between the intermediate films to form an intermediate layer, or appropriate additives are added to the intermediate film sheet that does not contain fine particles having a heat ray shielding function. It is also good to do. Functions such as UV cut and color tone adjustment can be performed by interposing a film or adding an additive.
In FIG. 2, sectional drawing of an example of the laminated structure for heat ray shielding which concerns on (form A-2) is shown. As shown in FIG. 2, in the heat ray shielding laminated structure, the intermediate layer 2 is sandwiched between two laminated plates 1. The intermediate layer 2 is configured such that an intermediate film containing dispersed fine particles 11 having a heat ray shielding function is sandwiched between intermediate films 12 not containing fine particles having a heat ray shielding function.

<Form B-2>
A plastic containing fine particles having a heat ray shielding function is used as at least one laminated plate, the intermediate layer has two or more intermediate films, and at least one of them contains fine particles having a heat ray shielding function. This is a heat ray shielding laminated structure constituted by an intermediate film. The laminated structure for heat ray shielding includes two plate glasses not containing fine particles having a heat ray shielding function,
It can be produced in the same manner as in (Form A-2) except that at least one plastic is replaced with a plastic containing fine particles having a heat ray shielding function.

Accordingly, a heat ray shielding laminated structure having high heat ray shielding characteristics and a low haze value can be manufactured at a low production cost.

Also by the said method, the adhesiveness of the sheet | seat for intermediate films which does not contain the microparticles | fine-particles which have a heat ray shielding function, and the two laminated plates chosen from plate glass and a plastics can be improved like (Form A-2). Since it can do, the intensity | strength of the laminated structure for heat ray shielding increases moderately, and it is preferable.

<Form A-3>
A heat ray shielding film containing fine particles having a heat ray shielding function, which is formed on at least one plate glass or a plastic inner surface, using a sheet glass or plastic not containing fine particles having a heat ray shielding function as a laminated plate The heat ray shielding laminated structure having the intermediate film not containing fine particles having the heat ray shielding function, which is superimposed on the heat ray shielding film, is produced, for example, as follows.
A coating liquid containing an appropriate binder component (an inorganic binder such as silicate or an acrylic, vinyl or urethane organic binder) mixed with an additive liquid in which fine particles having a heat ray shielding function are dispersed in a plasticizer or an appropriate solvent. To prepare. Using this prepared coating solution, a heat ray shielding film is formed on a surface located on the inner side of at least one plate glass or plastic. Next, a resin composition that does not contain fine particles having a heat ray shielding function is formed into a sheet to obtain an intermediate film sheet, and this intermediate film sheet is formed from at least one plate glass or plastic on which the heat ray shielding film is formed. A method of forming a laminated structure for heat ray shielding by sandwiching and bonding between the inner surface side and another plate glass or plastic on which no heat ray shielding film is formed.
Furthermore, by adding an appropriate additive to the intermediate film sheet that does not contain fine particles having a heat ray shielding function, functions such as UV cut and color tone adjustment can be added.

In FIG. 3, sectional drawing of an example of the laminated structure for heat ray shielding which concerns on the said (form A-3) is shown. As shown in FIG. 3, the laminated structure for heat ray shielding includes a laminated plate 1 on which a heat ray shielding film 13 including fine particles 11 having a heat ray shielding function is formed, and a laminated plate 1 on which no heat ray shielding film 13 is formed. The intermediate film 12 not containing fine particles having a heat ray shielding function is sandwiched. The intermediate layer 2 is composed of an intermediate film 12 containing no fine particles having a heat ray shielding function and a heat ray shielding film 13 containing fine particles 11 having a heat ray shielding function formed on a laminated plate.

<Form B-3>
A plastic containing fine particles having a heat ray shielding function as at least one laminated plate, and a heat ray shielding film containing fine particles having a heat ray shielding function formed on an inner surface of at least one plate glass or plastic The laminated structure for heat ray shielding having the intermediate film not containing fine particles having the heat ray shielding function superimposed on the heat ray shielding film is composed of at least one sheet glass or plastic that does not contain the fine particles having the heat ray shielding function. (Form A-3) except that the above is replaced with a plastic containing fine particles having a heat ray shielding function.
).
Furthermore, by adding an appropriate additive to the intermediate film sheet that does not contain fine particles having a heat ray shielding function, functions such as UV cut and color tone adjustment can be added.

<Form A-4>
A plastic that does not contain a glass plate or fine particles having a heat ray shielding function was used as a laminated plate, and a heat ray shielding film containing fine particles having a heat ray shielding function was formed on one or both surfaces of a resin film substrate as an intermediate layer. A heat ray shielding laminated structure comprising a heat ray shielding film substrate, or a heat ray shielding film substrate containing fine particles having a heat ray shielding function therein, and an intermediate film not containing fine particles having a heat ray shielding function laminated in two or more layers, For example, it is manufactured as follows.
(A) The intermediate layer has a heat ray shielding function in which a heat ray shielding film containing fine particles having a heat ray shielding function formed on one surface of a resin film substrate is formed, and two or more layers are laminated. A case of having an intermediate film not containing fine particles will be described.
For example, a coating liquid in which fine particles having a heat ray shielding function are dispersed in a plasticizer or an appropriate solvent,
Alternatively, a heat ray shielding film is formed on one surface of the resin film using a coating liquid prepared by appropriately blending the additive liquid with a binder component (such as an inorganic binder such as silicate or an acrylic, vinyl or urethane organic binder). To do. Here, the resin film to be used is not particularly limited as long as it is transparent. For example, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate, polyimide, aramid, polyphenylene sulfide, polyamideimide, polyether ether ketone, polyether sulfone and the like can be mentioned. When forming a heat ray shielding film on one surface of the resin film substrate, the resin film surface is previously subjected to corona treatment, plasma treatment, flame treatment, primer layer coating treatment, etc. for the purpose of improving the binding property with the resin binder. A surface treatment may be applied. Next, a vinyl resin composition not containing fine particles having a heat ray shielding function is formed into a sheet shape to obtain an intermediate film sheet. It is preferable that two sheets of the intermediate film are used and the heat ray shielding resin film substrate having the heat ray shielding film formed on one side is disposed between the sheets of the intermediate film to form an intermediate layer. By adopting the configuration, a resin film substrate in which a heat ray shielding film is formed on the one surface;
It is because it can avoid that the problem regarding adhesiveness generate | occur | produces between a laminated board. Here, in one of the intermediate films not including fine particles having a heat ray shielding function, which are laminated in two or more layers, fine particles having a heat ray shielding function and appropriate additives having effects such as UV cut and color tone adjustment Of course, it may be included.

(B) The case where the intermediate layer has a heat ray shielding film substrate in which fine particles having a heat ray shielding function are contained inside the film substrate, and an intermediate film not containing fine particles having a heat ray shielding function laminated in two or more layers is described. To do.
A heat ray shielding film substrate in which fine particles having a heat ray shielding function are contained inside the film substrate can be produced by the following method. The resin is heated to a temperature around its melting point (200-300 ° C.
And mixed with fine particles having a heat ray shielding function. Furthermore, a mixture of the resin and fine particles having a heat ray shielding function is pelletized, and a film, a board, or the like is formed by a predetermined method. For example, it can be formed by an extrusion molding method, an inflation molding method, a solution casting method, a casting method, or the like. The thickness of the film or board at this time may be appropriately selected according to the purpose of use. The amount of fine particles having a heat ray shielding function added to the resin can vary depending on the thickness of the base material, required optical characteristics, and mechanical characteristics, but is generally preferably 50% by weight or less based on the resin. Next, a vinyl resin composition not containing fine particles having a heat ray shielding function is formed into a sheet shape to obtain an intermediate film sheet. The resin film containing fine particles having the heat ray shielding function is disposed between the two sheets of the intermediate film to form an intermediate layer. A method of forming a laminated structure for heat ray shielding by sandwiching and bonding the intermediate layer between two laminated plates selected from plate glass and plastic is mentioned. Here, it is needless to say that fine particles having a heat ray shielding function may be contained in one layer of the intermediate film not including fine particles having a heat ray shielding function, which are laminated in two or more layers.
Furthermore, if necessary, an appropriate additive having effects such as UV cut, color tone adjustment, etc. can be freely and easily added to the intermediate film containing no fine particles having the heat ray shielding function. A shielding laminated structure can be obtained.
Furthermore, by adding an appropriate additive to the sheet of the intermediate film that does not contain fine particles having a heat ray shielding function, functions such as UV cut and color tone adjustment can be added.

In FIG. 4, sectional drawing of an example of the laminated structure for heat ray shielding which concerns on the said (form A-4 (I)) is shown. As shown in FIG. 4, the heat ray shielding laminated structure includes an intermediate layer 2 formed by two laminated plates 1.
Is sandwiched. In the intermediate layer 2, a heat ray shielding film 13 including fine particles 11 having a heat ray shielding function is formed on a resin film 14, and the laminate of the resin film and the heat ray shielding film does not contain fine particles having a heat ray shielding function. It is configured to be sandwiched between films 12.
In FIG. 5, sectional drawing of an example of the laminated structure for heat ray shielding which concerns on the said (form A-4 (b)) is shown. As shown in FIG. 5, the laminated structure for heat ray shielding includes an intermediate layer 2 formed by two laminated plates 1.
Is sandwiched. The intermediate layer 2 is configured such that a resin film 15 containing fine particles 11 having a heat ray shielding function is sandwiched between intermediate films 12 not containing fine particles having a heat ray shielding function.

<Form B-4>
A heat ray in which a plastic containing fine particles having a heat ray shielding function is used as at least one laminated plate and an intermediate layer is formed on one surface of a resin film substrate and a heat ray shielding film containing fine particles having a heat ray shielding function is formed. A heat-ray shielding film having a shielding film substrate and an intermediate film not containing fine particles having a heat ray shielding function, which is laminated in two or more layers, or the intermediate layer contains fine particles having a heat ray shielding function inside the film substrate A laminated structure for heat ray shielding having a substrate and an intermediate film not containing fine particles having a heat ray shielding function, which is laminated in two or more layers, is at least one sheet glass or plastic containing no fine particles having a heat ray shielding function Is replaced with a plastic containing fine particles having a heat ray shielding function in the same manner as in (Form A-4). Can.
Furthermore, by adding an appropriate additive to the sheet of the intermediate film that does not contain fine particles having a heat ray shielding function, functions such as UV cut and color tone adjustment can be added.

<Form A-5>
A heat ray shielding film in which a glass that does not contain fine particles having a heat ray shielding function is used as a laminated plate and the intermediate layer contains fine particles having a heat ray shielding function on one surface of an intermediate film that does not contain fine particles having a heat ray shielding function The heat ray shielding laminated structure in which is formed is manufactured as follows, for example.
A binder component (for example, an inorganic binder such as silicate, acrylic, vinyl, or the like) is appropriately added to an additive liquid in which fine particles having a heat ray shielding function are dispersed in a plasticizer or an appropriate solvent.
Urethane organic binder. ) To prepare a coating solution. This coating solution is applied to one surface of an intermediate film sheet obtained by forming a resin composition containing no fine particles having a heat ray shielding function into a sheet shape to form a heat ray shielding film. Next, a method of forming a heat ray shielding laminated structure by sandwiching and bonding the intermediate film on which the heat ray shielding film is formed between two laminated plates selected from plate glass and plastic can be mentioned.

According to the method, since the film containing the fine particles having the heat ray shielding function is formed on the surface of the sheet of the intermediate film not containing the fine particles having the heat ray shielding function, the filler is further added to the fine particles having the heat ray shielding function. Additives such as can be added as desired, and the heat ray shielding characteristics can be improved. Accordingly, a heat ray shielding laminated structure having high heat ray shielding characteristics and a low haze value can be manufactured at a low production cost.

<Form B-5>
A heat ray in which a plastic containing fine particles having a heat ray shielding function is used as at least one laminated plate, and the intermediate layer contains fine particles having a heat ray shielding function on at least one surface of an intermediate film not containing the fine particles having a heat ray shielding function The laminated structure for heat ray shielding, in which a shielding film is formed, replaces at least one of two sheet glass and plastic not containing fine particles having a heat ray shielding function with plastic containing fine particles having a heat ray shielding function. Except for this, it can be produced in the same manner as (Form A-5).

Also by this method, the film containing the fine particles having the heat ray shielding function is formed on the surface of the sheet of the intermediate film not containing the fine particles having the heat ray shielding function. These additives can be added as desired, and the heat ray shielding characteristics can be improved. As a result, a heat ray shielding quick alignment structure having high heat ray shielding characteristics and a low haze value can be produced at a low production cost.

<Form A-6>
The laminated plate is made of plastic that does not contain a glass plate or fine particles having a heat ray shielding function, and an intermediate layer is formed on one inner surface of the two laminated plates selected from the plate glass and the plastic layer, and the heat ray shielding layer. A heat ray shielding film containing fine particles having a function, and the adhesive layer of the laminate laminated in the order of the release layer are adhered, and further, the laminate has a heat ray shielding function overlapping the laminate on the release layer side. An intermediate film that does not contain fine particles or an intermediate film that does not contain fine particles having a heat ray shielding function that is laminated in two or more layers (that is, the heat ray shielding laminated structure includes: Structure of "one laminated plate / adhesive layer / heat ray shielding film containing fine particles having heat ray shielding function / release layer / intermediate film or two or more laminated intermediate films / the other laminated plate" Has.), For example, it is produced as follows. This process will be described with reference to FIGS. 6 (A) to 6 (C) show (form A
Sectional drawing in a manufacturing process of an example of the laminated structure for heat ray shielding which concerns on -6) is shown.
First, as shown in FIG. 6A, a film sheet 17 (for example, polyester, polypropylene, polyethylene, polyethylene terephthalate, polycarbonate, polyimide,
Examples thereof include synthetic resin films such as fluorine, paper, and cellophane. ) Is formed on one surface of the release layer 16 (for example, wax, acrylic resin, polyvinyl acetal typified by polyvinyl butyral, etc.), and a heat ray shielding film containing fine particles 11 having a heat ray shielding function on the release layer. 13 and an adhesive layer 18 (for example, polyvinyl acetal represented by polyvinyl butyral, polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-ethylene-glycidyl methacrylate copolymer, A vinyl chloride-ethylene-glycidyl acrylate copolymer, a polyvinylidene chloride, a vinylidene chloride-acrylonitrile copolymer, a polyamide, a polymethacrylic acid ester, an acrylic acid ester copolymer, etc.). Film 19 is obtained.
After the adhesive layer 18 of the transfer film 19 is adhered to the inner surface of one plate glass or plastic laminated plate 1 under pressure, the film sheet 17 is peeled from the transfer film. Then, only the film sheet 17 is peeled from the laminate due to the effect of the peeling layer 16. This state is shown in FIG.
After the film sheet 17 is peeled off, the other sheet glass or the intermediate film 12 not containing fine particles having the heat ray shielding function described above or the intermediate film not containing fine particles having the heat ray shielding function laminated in two or more layers is used. A method of forming a laminated structure for heat ray shielding shown in FIG. 6C by adhering to the inner surface of the plastic laminated plate 1 under pressure is exemplified.
As a result, an example of the heat ray shielding laminated structure according to (Form A-6) obtained is shown in FIG.
), The intermediate layer 2 is sandwiched between the two laminated plates 1. The intermediate layer 2 includes an intermediate film 12 that does not contain fine particles having a heat ray shielding function, a release layer 16, a heat ray shielding film 13 that contains fine particles 11 that have a heat ray shielding function, and an adhesive layer 18.

According to this method, a thin heat ray shielding film can be easily produced, and an appropriate additive is added to the intermediate film, release layer, and adhesive layer not containing fine particles having a heat ray shielding function. Thus, functions such as UV cut and color tone adjustment can be added.

<Form B-6>
A plastic containing fine particles having a heat ray shielding function is used as at least one laminated plate, and an intermediate layer is formed on the inner surface of one of the two laminated plates selected from the plate glass and plastic. A heat ray shielding film containing fine particles having a shielding function, and the adhesive layer of the laminate laminated in the order of the release layer; and a heat ray shielding function of overlapping the laminate on the release layer side of the laminate. An intermediate film that does not contain fine particles or an intermediate film that does not contain fine particles that have two or more layers of heat ray shielding functions (that is, the heat ray shielding laminated structure includes: “One laminated plate / adhesive layer / heat ray shielding film containing fine particles having a heat ray shielding function / release layer / intermediate film or two or more laminated interlayer films / the other laminated plate” Has a structure.), Except that at least one of two sheets of glass and plastic not containing fine particles having a heat ray shielding function is replaced with a plastic containing fine particles having a heat ray shielding function. 6 can be produced.

Also by this method, a heat ray shielding film having a thin film thickness can be easily produced, and an appropriate additive is added to the intermediate film, release layer and adhesive layer not containing fine particles having a heat ray shielding function. Thus, functions such as UV cut and color tone adjustment can be added.

<Form B-7>
A plastic containing fine particles having a heat ray shielding function is used as at least one of the laminated plates, and the intermediate layer does not contain fine particles having a heat ray shielding function, for example, a heat ray shielding laminate comprising an intermediate film containing a vinyl resin. The structure is manufactured as follows, for example. A plasticizer is added to the vinyl resin to prepare a vinyl resin composition, and the vinyl resin composition is molded into a sheet to obtain an intermediate film sheet. A plastic containing fine particles having a heat ray shielding function may be used as at least one laminated plate of the intermediate film, and a glass plate or plastic may be used as the other laminated plate.

By this method, it is possible to produce a heat ray shielding laminated structure having high heat ray shielding characteristics and a low haze value. Furthermore, the method can easily produce a heat ray shielding laminated structure, and can produce a heat ray shielding laminated structure at a low production cost.
Furthermore, by adding an appropriate additive to the intermediate film not containing fine particles having a heat ray shielding function and / or the plastic of the other laminated plate, functions such as UV cut and color tone adjustment can be added.
In FIG. 7, sectional drawing of an example of the laminated structure for heat ray shielding which concerns on the said (form B-7) is shown. As shown in FIG. 7, in the laminated structure for heat ray shielding, the intermediate layer 2 is sandwiched between a laminated plate 20 containing fine particles 11 having a heat ray shielding function and a laminated plate 1 not containing the fine particles. The intermediate layer 2 is formed on the intermediate film 12 that does not contain fine particles having a heat ray shielding function.

6). (Method for manufacturing laminated structure for heat ray shielding)
About the manufacturing method of the laminated structure for heat ray shielding, i. An additive solution or coating solution applied to the production of a heat ray shielding laminated structure; ii. Plasticizers used in laminated structures for heat ray shielding, iii
. An interlayer sheet used in the laminated structure for heat ray shielding, iv. Method for forming interlayer sheet, v. Other additives, and vi. It demonstrates in detail in order of the manufacturing method of the addition liquid or coating liquid applied to manufacture of the laminated structure for heat ray shielding.

i. <Additive solution or coating solution applied to manufacture of heat ray shielding laminated structure>
A method for dispersing the fine particles having a heat ray shielding function in a plasticizer or an appropriate solvent is arbitrary as long as the fine particles can be uniformly dispersed in the plasticizer or an appropriate solvent. For example, methods such as a bead mill, a ball mill, a sand mill, and an ultrasonic dispersion can be mentioned. The fine particles are uniformly dispersed in a plasticizer or an appropriate solvent and applied to the production of the heat ray shielding laminated structure of the present invention. The additive solution or coating solution is prepared.

The solvent for dispersing the fine particles having a heat ray shielding function is not particularly limited, and may be appropriately selected according to the conditions for forming the heat ray shielding film and the vinyl resin compounded when preparing the vinyl resin composition. It is possible to select. For example, water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, diacetone alcohol and other alcohols, ethers such as methyl ether, ethyl ether, propyl ether, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isobutyl Various organic solvents such as ketones such as ketones can be used. Moreover, you may adjust pH by adding an acid and an alkali as needed. Furthermore, various surfactants, coupling agents, and the like may be added in order to further improve the dispersion stability of the fine particles in the coating solution.

ii. <Plasticizer used in heat ray shielding laminated structure>
The plasticizer used in the heat ray shielding laminated structure mainly composed of the vinyl resin according to the present invention is a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, a polyhydric alcohol organic acid ester compound, or the like. Examples thereof include phosphoric acid plasticizers such as ester plasticizers and organic phosphoric acid plasticizers. Any of them is preferably liquid at room temperature. In particular, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferred.

The ester compound synthesized from the polyhydric alcohol and the fatty acid is not particularly limited. For example, glycol such as triethylene glycol, tetraethylene glycol, tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl Examples thereof include glycol ester compounds obtained by reaction with monobasic organic acids such as acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonyl acid), and decyl acid. In addition, ester compounds of tetraethylene glycol, tripropylene glycol, and the above-mentioned monobasic organic are also included.
Among them, triethylene glycol dihexanate, triethylene glycol di-2-
Preference is given to fatty acid esters of triethylene glycol such as ethyl butyrate, triethylene glycol di-octanoate, triethylene glycol di-2-ethyl hexanonate. The fatty acid ester of triethylene glycol has various properties such as compatibility with polyvinyl acetal and cold resistance in a well-balanced manner, and is excellent in processability and economy.
When selecting a plasticizer, pay attention to hydrolyzability. From this viewpoint, triethylene glycol di-2-ethylhexanate, triethylene glycol di-2-ethylbutyrate, and tetraethylene glycol di-2-ethylhexanate are preferable.

iii. <Intermediate film sheet used in heat ray shielding laminated structure>
Examples of the vinyl resin used in the interlayer film sheet used in the laminated structure for heat ray shielding according to the present invention include, for example, polyvinyl acetal represented by polyvinyl butyral, polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride- Ethylene-glycidyl methacrylate copolymer, vinyl chloride-ethylene-glycidyl acrylate copolymer, vinyl chloride
Glycidyl methacrylate copolymer, vinyl chloride-glycidyl acrylate copolymer, polyvinylidene chloride, vinylidene chloride-acrylonitrile copolymer, polyvinyl acetate ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyvinyl acetal-polyvinyl Examples include butyral mixtures. Polyvinyl acetal and ethylene-vinyl acetate copolymer represented by polyvinyl butyral are particularly preferred from the viewpoints of adhesion to glass and plastic, transparency and safety.

iv. <Method for forming sheet for interlayer film>
A known method is used as a method for forming the interlayer film containing fine particles having the heat ray shielding function or the intermediate film sheet not containing fine particles having the heat ray shielding function. For example,
A calendar roll method, an extrusion method, a casting method, an inflation method, or the like can be used. In particular, in the former sheet for an intermediate film containing fine particles having a heat ray shielding function and a vinyl resin composition, the vinyl resin composition is prepared by, for example, adding an additive liquid in which fine particles having a heat ray shielding function are dispersed in a plasticizer. The resin is added to a resin and kneaded to uniformly disperse the fine particles. The vinyl resin composition thus prepared can be formed into a sheet. In addition, when shape | molding a vinyl-type resin composition in a sheet form, you may mix | blend a heat stabilizer, antioxidant, a ultraviolet-ray shielding material, etc. as needed.

Moreover, you may mix | blend an adhesive force regulator for sheet | seat penetration control. Although the said adhesive force regulator is not specifically limited, An alkali metal salt and / or an alkaline-earth metal salt are used suitably. The acid which comprises the said metal salt is not specifically limited, For example, inorganic acids, such as carboxylic acids, such as octyl acid, hexyl acid, butyric acid, acetic acid, formic acid, or hydrochloric acid, nitric acid, are mentioned. Among the alkali metal salts and / or alkaline earth metal salts, a carboxylic acid magnesium salt having 2 to 16 carbon atoms and a carboxylic acid potassium salt having 2 to 16 carbon atoms are preferable.
The carboxylic acid magnesium salt and potassium salt of the organic acid having 2 to 16 carbon atoms are not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, and 2-ethylbutane. Potassium acid, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like are preferably used.
These adhesive strength modifiers may be used alone or in combination of two or more.
In addition, when sodium, potassium, magnesium, calcium, or cerium carboxylate is used as an adhesive strength adjusting agent, it acts as an original adhesive strength adjusting agent and improves the weather resistance of the composite tungsten oxide fine particles. Can be combined.
Moreover, the manufacturing method of the laminated structure of this invention will not be limited if it is a method of taking the structure of the laminated structure mentioned above.

v. <Other additives>
If desired, the laminated structure for heat ray shielding according to the present invention may further contain a general additive. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black and the like, which are generally used for coloring thermoplastic resins, are added to give an arbitrary color tone as desired. May be.
In addition, as a UV absorber, stabilizers such as hindered phenols and phosphorus, mold release agents, hydroxybenzophenone, salicylic acid, HALS, triazole, and triazine organic UV, zinc oxide, titanium oxide, cerium oxide, etc. Inorganic ultraviolet absorbers such as may be added.
Further, coupling agents, surfactants, antistatic agents, stabilizers, antioxidants and the like can be used as additives.

vi. <Manufacturing method of additive solution or coating solution applied to manufacture of laminated structure for heat ray shielding>
The manufacturing method of the dispersion liquid for heat ray shielding body used for the addition liquid or coating liquid applied to manufacture of the laminated structure for heat ray shielding is demonstrated.
The dispersion for forming a heat ray shield according to the present invention is a dispersion for forming a heat ray shield containing a solvent and fine particles having a heat ray shielding function, and the fine particles having the heat ray shielding function are dispersed in the solvent. is there. The method for dispersing the fine particles in a solvent is not particularly limited as long as it is a method capable of uniformly dispersing, and examples thereof include a grinding / dispersing treatment method using a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, and the like. By dispersion treatment using these equipment, fine particles are formed by collision of fine particles simultaneously with dispersion of fine particles in a solvent, and particles can be made finer and dispersed (that is, pulverized / dispersed). )

Moreover, the dispersion for forming a heat ray shield can be configured to contain an inorganic binder and / or a resin binder. The kind of inorganic binder or resin binder is not particularly limited. For example, as the inorganic binder, silicon, zirconium, titanium, or
Examples thereof include metal alkoxides of aluminum, partially hydrolyzed polycondensates thereof, or organosilazanes, and thermoplastic resins such as acrylic resins and thermosetting resins such as epoxy resins can be used as the resin binder. Moreover, in the dispersion for forming a heat ray shield, the solvent in which the fine particles are dispersed is not particularly limited. When the coating / kneading conditions, the coating / kneading environment, and an inorganic binder or a resin binder are contained, May be appropriately selected according to the binder.
Examples of the solvent include alcohols such as water, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol and diacetone alcohol, ethers such as methyl ether, ethyl ether and propyl ether, esters, acetone, methyl ethyl alcohol. Various organic solvents such as tones, diethyl ketone, cyclohexanone, ketones such as inbutyl ketone can be used. Alternatively, the pH may be adjusted by adding an acid or alkali as necessary. Furthermore, in order to further improve the dispersion stability of the fine particles in the dispersion, various surfactants, coupling agents and the like can of course be added.
In addition, a material in which fine particles are directly dispersed in a resin binder is preferable from the environmental and industrial viewpoints because it is not necessary to evaporate the solvent after coating on the medium surface.

The coating method on the substrate surface is not particularly limited as long as it can be uniformly coated. For example, bar coating method, gravure coating method, spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, screen printing. Method, blade coating method and the like can be used. The layer containing the composite tungsten oxide fine particles and the ultraviolet absorbing oxide fine particles formed by these coating methods is a dry method such as sputtering, vapor deposition, ion plating, and chemical vapor deposition (CVD), Compared with the case where it is manufactured by the spray method, it is possible to efficiently absorb light in the ultraviolet region and near infrared region and transmit light in the visible light region at the same time without using the light interference effect.

As the resin used for the medium or the substrate, for example, an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, a thermoplastic resin, or the like can be selected according to the purpose.
In addition, as an inorganic binder in the dispersion for forming a heat ray shield, silicon, zirconium,
When containing titanium or aluminum metal alkoxide and its hydrolysis polymer,
By setting the substrate heating temperature after application of the dispersion to 100 ° C. or higher, the polymerization reaction of the alkoxide or its hydrolysis polymer contained in the coating film can be almost completed. By almost completing the polymerization reaction, it is possible to avoid water and organic solvents remaining in the film and causing a reduction in the visible light transmittance of the heated film, and therefore the heating temperature is preferably 100 ° C. or higher. More preferably, it is not less than the boiling point of the solvent in the dispersion.

When the dispersion for forming a heat ray shield does not contain a resin binder or an inorganic binder, the film obtained on the transparent substrate has a film structure in which only the fine particles of the tungsten oxide are deposited. And even if the said film remains as it is, it shows a heat ray shielding characteristic. However, on this film, a coating film is formed by further applying a coating solution containing an inorganic binder such as a metal alkoxide of silicon, zirconium, titanium, or aluminum or a partially hydrolyzed polycondensation polymer thereof, or a resin binder. A film is recommended. By adopting this configuration, the coating liquid component is formed to fill the gap where the first layer of tungsten oxide particles are deposited, so that the haze of the film is reduced and the visible light transmittance is improved. The binding property of the fine particles to the base material is improved.

7). (Summary)
As described above in detail, the heat ray shielding laminated structure according to the present invention is capable of absorbing near infrared rays in sunlight by adding metal carbonate or carbonate hydroxide to the composite tungsten oxide fine particles. And can be manufactured at a low cost by a simple method. And the general formula _MY WO
_The composite tungsten oxide represented by _Z and the metal carbonate or carbonate hydroxide, which is a deterioration preventing agent, contain visible light transmittance over time even when used for a long time. Reduction (deterioration), decrease in near-infrared absorption function, change in color tone, and increase in haze value can be suppressed, and excellent optical properties and excellent weather resistance were exhibited.
Furthermore, even when a vinyl resin such as polyvinyl acetal resin was used as the main component of the interlayer film in the laminated structure for heat ray shielding of the present invention, excellent optical characteristics and excellent weather resistance were exhibited.
As a result, the laminated structure for heat ray shielding according to the present invention includes automotive window glass, side glass and rear glass, railroad vehicle door glass, window glass and indoor door glass, vehicle window materials, window glass in buildings and the like, and It can be used for various purposes such as indoor window glass, architectural window materials such as indoor display showcases and show windows.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples.
In this example, the visible light transmittance and the solar radiation transmittance were measured according to the transmittance of light having a wavelength of 200 to 2500 nm using a spectrophotometer manufactured by Hitachi, Ltd., and calculated according to JIS R 3106. In addition, the said solar transmittance is an parameter | index which shows the heat ray shielding characteristic of the laminated structure for heat ray shielding.
The haze value of the film is determined using JIS K 710 using HM-150 manufactured by Murakami Color Research Laboratory.
Measurement based on 5 was performed.
The evaluation of the change in optical characteristics when the laminated structure for heat ray shielding was used for a long time was performed by using an ultraviolet irradiation device (SUV-W131 manufactured by Iwasaki Electric Co., Ltd.). / Cm ² was irradiated with ultraviolet rays for 2 hours to make an acceleration test, and the change rate of visible light transmittance and the change of haze value before and after the acceleration test were measured.

Example 1
20 parts by weight of Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g), 2 parts by weight of sodium carbonate, 58 parts by weight of 4-methyl-2-pentanone, and 20 parts by weight of a dispersant for dispersing fine particles were mixed. , Cs _0.33 WO with average dispersion particle diameter of 80 nm
A dispersion of ₃ fine particles and sodium carbonate was prepared (A liquid).
The solution A, a thermosetting resin (100% solid content) and 4-methyl-2-pentanone were sufficiently mixed to prepare a coating solution. This coating solution was applied and formed on a polyethylene terephthalate film (PET) using a bar coater, and this film was heated and cured at 130 ° C. for 30 minutes to obtain a heat ray shielding film substrate on which a heat ray shielding film was formed. .
The heat ray shielding film substrate on which the heat ray shielding film is formed is disposed between two sheets of an ethylene-vinyl acetate copolymer sheet for intermediate film that does not contain fine particles having a heat ray shielding function, and these are opposed to two opposing inorganic films. The laminated structure 1 for heat ray shielding which concerns on Example 1 was obtained by inserting | pinching with glass and bonding and integrating by a well-known method (form A-4). Table 1 shows the optical characteristics of the manufactured structure 1.
The manufactured structure 1 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 2)
20 parts by weight of Rb _0.33 WO ₃ fine particles (specific surface area 20 m ² / g), 2 parts by weight of sodium carbonate, 58 parts by weight of 4-methyl-2-pentanone, and 20 parts by weight of a dispersant for dispersing fine particles were mixed. , Rb _0.33 WO with an average dispersed particle size of 80 nm after carrying out dispersion treatment with a medium stirring mill
A dispersion of _three fine particles and sodium carbonate was prepared (B solution).
This B liquid, thermosetting resin (solid content: 100%) and 4-methyl-2-pentanone were sufficiently mixed to obtain a coating liquid. This coating solution was applied onto a polyethylene terephthalate film (PET) using a bar coater, formed into a film, and heated and cured at 130 ° C. for 30 minutes to obtain a heat ray shielding film substrate on which a heat ray shielding film was formed.
The heat ray shielding film substrate on which the heat ray shielding film is formed is disposed between two sheets of an ethylene-vinyl acetate copolymer sheet for intermediate film that does not contain fine particles having a heat ray shielding function, and these are opposed to two opposing inorganic films. The laminated structure 2 for heat ray shielding which concerns on Example 2 was obtained by inserting | pinching with glass and sticking together by the well-known method (form A-4). Table 1 shows the optical characteristics of the manufactured structure 2.
Using the produced structure 2 as a test sample, a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 3)
K _0.33 WO ₃ fine particles (specific surface area 20 m ² / g) 20 parts by weight, sodium carbonate 4
Part by weight, 56 parts by weight of 4-methyl-2-pentanone, and 20 parts by weight of a fine particle dispersing agent are mixed and dispersed with a medium stirring mill to obtain K _0.33 WO ₃ fine particles having an average dispersed particle diameter of 80 nm and A dispersion of sodium carbonate was prepared (C solution).
This liquid C, a thermoplastic resin (solid content 100%) and 4-methyl-2-pentanone were sufficiently mixed to obtain a coating solution. This coating solution was applied and formed on a polyethylene terephthalate film (PET) using a bar coater, and baked at 120 ° C. for 30 minutes to obtain a heat ray shielding film substrate on which a heat ray shielding film was formed.
The heat ray shielding film substrate on which the heat ray shielding film is formed is disposed between two sheets of the ethylene-vinyl acetate copolymer sheet for an intermediate film not containing fine particles having a two heat ray shielding function, and the two inorganic sheets are opposed to each other. The laminated structure 3 for heat ray shielding which concerns on Example 3 was obtained by inserting | pinching between glass and sticking and integrating by the well-known method (form A-4). Table 1 shows the optical characteristics of the manufactured structure 3.
The produced structure 3 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

Example 4
20 parts by weight of Tl _0.33 WO ₃ fine particles (specific surface area 20 m ² / g), 0.6 parts by weight of sodium carbonate, 59.4 parts by weight of 4-methyl-2-pentanone, dispersant 20 for dispersing fine particles
A part by weight is mixed and subjected to a dispersion treatment with a medium stirring mill, and Tl of an average dispersed particle diameter of 80 nm is obtained _.
A dispersion of ₃₃ WO ₃ fine particles and sodium carbonate was prepared (D liquid).
This D solution, an ultraviolet curable resin for hard coat (100% solid content) and 4-methyl-2-pentanone were mixed sufficiently to obtain a coating solution. This coating solution is applied and formed on a polyethylene terephthalate film (PET) using a bar coater, this film is dried at 70 ° C. for 2 minutes to evaporate the solvent, and then cured with a high-pressure mercury lamp to block heat rays. A heat ray shielding film substrate on which a film was formed was obtained.
The heat ray shielding film substrate on which the heat ray shielding film is formed is disposed between two sheets of the ethylene-vinyl acetate copolymer sheet for intermediate film which does not contain fine particles having the heat ray shielding function.
Sandwiched between two opposing inorganic glasses and bonded together by a known method (form A-4)
Thus, a heat ray shielding laminated structure 4 according to Example 4 was obtained. Table 1 shows the optical characteristics of the manufactured structure 4.
The manufactured structure 4 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 5)
A heat ray shielding laminated structure 5 according to Example 5 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with manganese carbonate as the metal carbonate. Table 1 shows the optical characteristics of the manufactured structure 5.
The manufactured structure 5 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 6)
A heat ray shielding laminated structure 6 according to Example 6 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with lithium carbonate as the metal carbonate. The optical characteristics of the manufactured structure 6 are shown in Table 1.
The manufactured structure 6 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 7)
A heat ray shielding laminated structure 7 according to Example 7 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with rubidium carbonate as the metal carbonate. Table 1 shows the optical characteristics of the manufactured structure 7.
The manufactured structure 7 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 8)
A heat ray shielding laminated structure 8 according to Example 8 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with magnesium carbonate hydroxide as the metal carbonate hydroxide. The optical characteristics of the manufactured structure 8 are shown in Table 1.
The manufactured structure 8 was used as a test sample, and a change in visible light transmittance and a change in haze value after irradiation with ultraviolet rays for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

Example 9
Heat-shielding laminated structure according to Example 9 in the same manner as in Example 1 except that 1 part by weight of sodium carbonate was added to 20 parts by weight of Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g). Body 9 was obtained. Table 1 shows the optical characteristics of the manufactured structure 9.
The produced structure 9 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 10)
For heat ray shielding according to Example 10, except that 0.2 part by weight of sodium carbonate is added to 20 parts by weight of Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g). A laminated structure 10 was obtained. Table 1 shows the optical characteristics of the manufactured structure 10.
The manufactured structure 10 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 11)
Heat-shielding laminated structure according to Example 11, except that 10 parts by weight of sodium carbonate is added to 20 parts by weight of Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g). Body 11 was obtained. Table 2 shows optical characteristics of the manufactured structure 11.
The manufactured structure 11 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

Example 12
Heat-shielding laminated structure according to Example 12, except that 20 parts by weight of sodium carbonate is added to 20 parts by weight of Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g). Body 12 was obtained. Table 2 shows the optical characteristics of the manufactured structure 12.
The manufactured structure 12 was used as a test sample, and the change in visible light transmittance and the change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 13)
A heat ray shielding laminated structure 13 according to Example 13 is obtained in the same manner as in Example 1 except that the vinyl-based resin is replaced with the intermediate film ethylene-vinyl acetate copolymer sheet by an interlayer film polyvinyl butyral sheet. It was. Table 2 shows the optical characteristics of the manufactured structure 13.
The manufactured structure 13 was used as a test sample, and a change in visible light transmittance and a change in haze value after irradiation with ultraviolet rays for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 1.

(Example 14)
Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g) 20 parts by weight, sodium carbonate 2 parts by weight, triethylene glycol di-2-ethylhexanoate (hereinafter abbreviated as plasticizer a) 58 Part by weight and 20 parts by weight of a fine particle dispersing agent were mixed and dispersed with a medium stirring mill to prepare a dispersion of Cs _0.33 WO ₃ fine particles having an average dispersed particle size of 80 nm and sodium carbonate (solution E). .
A predetermined amount of solution E is added to a composition in which 30 parts by weight of plasticizer a and 70 parts by weight of polyvinyl butyral resin are mixed, and the concentration of Cs _0.33 WO ₃ fine particles in the composition is set to _0.00 .
It was 15% by weight. This composition was kneaded at 200 ° C. using a twin-screw extruder, extruded from a T die, and an intermediate film containing heat ray shielding fine particles was obtained as a sheet having a thickness of 0.7 mm by a calender roll method.
The obtained intermediate film containing the heat ray shielding fine particles is sandwiched between two opposing inorganic glasses and bonded and integrated by a known method (form A-1) to obtain a heat ray shielding laminated structure 14 according to Example 14. It was. Table 2 shows the optical characteristics of the manufactured structure 14.
The fabricated structure 14 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 15)
A heat ray shielding laminated structure 15 according to Example 15 was obtained in the same manner as Example 14 except that polyvinyl butyral resin was replaced with ethylene-vinyl acetate copolymer as the vinyl resin. Table 2 shows the optical characteristics of the manufactured structure 15.
The manufactured structure 15 was used as a test sample, and a change in visible light transmittance and a change in haze value after irradiation with ultraviolet rays for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 16)
A heat ray shielding laminated structure 16 according to Example 16 was obtained in the same manner as Example 15 except that one of the two inorganic glasses was replaced with a polycarbonate plate. Table 2 shows the optical characteristics of the manufactured structure 16.
The manufactured structure 16 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 17)
Liquid A prepared in Example 1, thermosetting resin (solid content: 100%), and 4-methyl-2-pentanone were sufficiently mixed to obtain a coating solution. This coating solution was applied and formed on inorganic glass using a bar coater, and this film was heated and cured at 130 ° C. for 30 minutes to obtain a heat ray shielding film.
Next, the inorganic glass on which the heat ray shielding film is not formed and the inorganic glass on which the heat ray shielding film is formed are opposed so that the heat ray shielding film is on the inside, and the fine particles having a heat ray shielding function between these inorganic glasses A polyvinyl butyral sheet for interlayer film that does not contain bismuth and is laminated and integrated by a known method (form A-3), and heat ray shielding laminated structure 17 according to example 17
Got. Table 2 shows the optical characteristics of the manufactured structure 17.
The manufactured structure 17 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 18)
An intermediate film ethylene-vinyl acetate copolymer sheet containing no fine particles having a heat ray shielding function, the heat ray shielding film side of the inorganic glass on which the heat ray shielding film produced in Example 17 was formed, and a polyethylene terephthalate film (PET) And laminated together by a known method to obtain a heat ray shielding laminated structure 18 according to Example 18. Table 2 shows the optical characteristics of the manufactured structure 18.
The produced structure 18 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 19)
The intermediate film containing the heat ray shielding fine particles produced in Example 15 is sandwiched between two polyvinyl butyral sheets for an intermediate film that do not contain heat ray shielding fine particles, and is further sandwiched between two opposing inorganic glasses. Bonding and integration (Form A-2) were carried out to obtain a heat ray shielding laminated structure 19 according to Example 19. Table 2 shows the optical characteristics of the manufactured structure 19.
The manufactured structure 19 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 20)
The liquid A produced in Example 1 was added to and mixed with the polycarbonate resin so that the concentration of Cs _0.33 WO ₃ fine particles was 0.07 wt%, and the mixture was kneaded with a twin-screw extruder and extruded from a T-die. A heat ray shielding film substrate on which a heat ray shielding film was formed as a 2 mm thick sheet was obtained.
The heat ray shielding film substrate on which the heat ray shielding film is formed is used as one laminated plate, and a polyvinyl butyral sheet is sandwiched between the inorganic glass as the other laminated plate as an intermediate film that does not contain fine particles having a heat ray shielding function. And pasting and integrating by a known method (form B
-7) A heat ray shielding laminated structure 20 according to Example 20 was obtained. Table 2 shows the optical characteristics of the manufactured structure 20.
The produced structure 20 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 21)
The liquid A produced in Example 1 was added and mixed with polyethylene terephthalate resin so that the concentration of Cs _0.33 WO ₃ fine particles was 0.07 wt%, and the mixture was kneaded with a twin-screw extruder, and the T-die Further, a heat ray shielding film substrate on which a heat ray shielding film was formed as a sheet having a thickness of 2 mm was obtained.
The heat ray shielding film substrate on which the heat ray shielding film is formed is used as one laminated plate, and ethylene-vinyl acetate is used as an intermediate film that does not contain fine particles having a heat ray shielding function between the other laminated plate and inorganic glass. The polymer sheet was sandwiched and bonded and integrated by a known method (Form B-7) to obtain a heat ray shielding laminated structure 21 according to Example 21. Table 2 shows the optical characteristics of the manufactured structure 21.
The manufactured structure 21 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 22)
The intermediate film containing the heat ray shielding fine particles produced in Example 15 is sandwiched between the heat ray shielding film substrate on which the heat ray shielding film produced in Example 20 is formed as a laminated plate and the other laminated plate, inorganic glass, Lamination and integration were performed by a known method (Form B-1) to obtain a heat ray shielding laminated structure 22 according to Example 22. Table 2 shows the optical characteristics of the manufactured structure 22.
Using the produced structure 22 as a test sample, a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 23)
Liquid A prepared in Example 1, thermosetting resin (solid content: 100%), and 4-methyl-2-pentanone were sufficiently mixed to obtain a coating solution. This coating solution was applied and formed on an ethylene-vinyl acetate copolymer sheet for intermediate film containing no heat ray shielding fine particles using a bar coater. This film was heat-cured at 130 ° C. for 30 minutes to obtain an intermediate film free of fine particles having a heat ray shielding function and having a heat ray shielding film. An intermediate film ethylene-vinyl acetate copolymer sheet that does not contain heat ray shielding fine particles is disposed on the coating film side of the intermediate film on which the heat ray shielding film is formed, and is further sandwiched between two opposing inorganic glasses. Were joined together (Form A-5) to obtain a heat ray shielding laminated structure 23 according to Example 23. Table 3 shows the optical characteristics of the manufactured structure 23.
The manufactured structure 23 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 24)
Liquid A prepared in Example 1, thermosetting resin (solid content: 100%), and 4-methyl-2-pentanone were sufficiently mixed to obtain a coating solution. A polyvinyl butyral sheet was formed as a release layer on one surface of the polyester film sheet, and a coating solution was applied and formed on the release layer using a bar coater. This film was heat-cured at 130 ° C./30 minutes to obtain a heat ray shielding film. On this heat ray shielding film, a polyvinyl butyral sheet for an intermediate film not containing fine particles having a heat ray shielding function was formed as an adhesive layer to obtain a transfer film 19 as a laminate.
The adhesive layer of the transfer film 19 is adhered to the inner surface of one inorganic glass laminated plate by a known method, and the polyester film sheet is peeled off from the transfer film. A polyvinyl butyral sheet for an interlayer film that does not contain heat ray shielding fine particles is placed on the surface of the release layer from which the sheet has been peeled off, and is laminated and integrated with the inner surface of the other laminated sheet of inorganic glass by a known method (form A-6) Thus, a heat ray shielding laminated structure 24 according to Example 24 was obtained. Produced structure 2
Table 3 shows the optical characteristics of No. 4.
The produced structure 24 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 25)
A heat ray shielding laminated structure 25 according to Example 25 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with cesium carbonate as the metal carbonate. Table 3 shows the optical characteristics of the manufactured structure 25.
Using the manufactured structure 25 as a test sample, a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 2.

(Example 26)
A heat ray shielding laminated structure 26 according to Example 26 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with potassium carbonate as the metal carbonate. Table 3 shows the optical characteristics of the manufactured structure 26.
The produced structure 26 was used as a test sample, and a change in visible light transmittance and a change in haze value after irradiation with ultraviolet rays for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Example 27)
A heat ray shielding laminated structure 27 according to Example 27 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with calcium carbonate as the metal carbonate. Fabricated structure 27
Table 3 shows the optical characteristics.
Using the manufactured structure 27 as a test sample, a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Example 28)
Example 1 except that sodium carbonate was replaced with strontium carbonate as the metal carbonate.
In the same manner as described above, a heat ray shielding laminated structure 28 according to Example 28 was obtained. Table 3 shows the optical characteristics of the manufactured structure 28.
The manufactured structure 28 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Example 29)
A heat ray shielding laminated structure 29 according to Example 29 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with nickel carbonate as the metal carbonate. Table 3 shows the optical characteristics of the manufactured structure 29.
The produced structure 29 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Example 30)
A heat ray shielding laminated structure 30 according to Example 30 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with cobalt carbonate as the metal carbonate. Table 3 shows the optical characteristics of the manufactured structure 30.
The produced structure 30 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Example 31)
A heat ray shielding laminated structure 31 according to Example 31 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with copper carbonate (II) as the metal carbonate. Table 3 shows the optical characteristics of the manufactured structure 31.
The manufactured structure 31 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Example 32)
A heat ray shielding laminated structure 32 according to Example 32 was obtained in the same manner as in Example 1 except that sodium carbonate was replaced with zinc carbonate as the metal carbonate. Table 3 shows the optical characteristics of the manufactured structure 32.
The manufactured structure 32 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Comparative Example 1)
A heat ray shielding dispersion liquid (hereinafter abbreviated as “K liquid”) according to Comparative Example 1 was produced in the same manner as in Example 1 except that sodium carbonate was not added.
A heat ray shielding laminated structure 33 according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the A liquid was replaced with the K liquid. Table 3 shows the optical characteristics of the manufactured structure 33.
The manufactured structure 33 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Comparative Example 2)
For heat ray shielding according to Comparative Example 2, except that 0.1 part by weight of sodium carbonate was added to 20 parts by weight of Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g). A laminated structure 34 was obtained. Table 3 shows the optical characteristics of the manufactured structure 34.
The manufactured structure 34 was used as a test sample, and a change in visible light transmittance and a change in haze value after irradiation with ultraviolet rays for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

(Comparative Example 3)
Heat ray shielding dispersion liquid according to Comparative Example 3 (excluding addition of 40 parts by weight of sodium carbonate to 20 parts by weight of Cs _0.33 WO ₃ fine particles (specific surface area 20 m ² / g) ( Hereinafter, it was abbreviated as L liquid).
Comparative Example 3 was performed in the same manner as in Example 15 except that the liquid dispersion used in Example 15 was replaced with liquid L.
The heat ray shielding laminated structure 35 according to the above was obtained. Table 3 shows the optical characteristics of the manufactured structure 35.
However, since the addition amount of the metal carbonate is too large, the structure 35 has insufficient adhesion between the inorganic glass and the intermediate film containing the heat ray shielding fine particles, and the intermediate film containing the inorganic glass and the heat ray shielding fine particles is not present. There was a problem that it was easily peeled off.
Therefore, the acceleration test was not performed.

(Comparative Example 4)
A heat ray shielding dispersion liquid (hereinafter, abbreviated as “M liquid”) according to Comparative Example 4 was prepared in the same manner as in Example 14 except that sodium carbonate was not added.
A heat ray shielding laminated structure 36 according to Comparative Example 4 was obtained in the same manner as in Example 14 except that the E liquid was replaced with the M liquid. Table 3 shows the optical characteristics of the manufactured structure 36.
The produced structure 36 was used as a test sample, and a change in visible light transmittance and a change in haze value after ultraviolet irradiation for 2 hours were measured using an ultraviolet irradiation device. The results are shown in Table 3.

[Evaluation]
From the results of Tables 1 to 3, in Examples 1 to 32, to the composite tungsten oxide fine particles,
By adding an appropriate amount of metal carbonate or carbonate hydroxide, heat ray shielding laminated structure 1 having high visible light transmittance and high heat ray shielding properties, low haze value and excellent transparency. ~ 32
was gotten.
Among them, in the heat ray shielding laminated structures 1 to 26 according to Examples 1 to 26 to which appropriate amounts of sodium, potassium, magnesium, manganese, cesium, lithium, rubidium carbonate or carbonate hydroxide are added, ultraviolet rays are used. In the accelerated test irradiated for 2 hours, the remarkable effect that the rate of change was suppressed to half or less of the initial visible light transmittance was found.
Moreover, in the heat ray shielding laminated structures 1 to 26 according to Examples 1 to 26, it was found that the increase in the haze value was 0.5% or less in the acceleration test in which ultraviolet rays were irradiated for 2 hours.
On the other hand, in Comparative Examples 1, 2, and 4, the change in visible light transmittance increased in the accelerated test because the metal carbonate or carbonate hydroxide was not added or the addition amount was too small. In Comparative Example 3, since the amount of carbonate added was too large, adhesion to inorganic glass, which is an important physical property of the laminated structure, was impaired.

1. Laminated plate Intermediate layer 11. 11. Fine particles having a heat ray shielding function Interlayer film 13. Heat ray shielding film 14. Resin film 15. Resin film containing fine particles having heat ray shielding function 16. Release layer 17. Film sheet 18. Adhesive layer 20. Laminated plate containing fine particles having a heat ray shielding function

Claims (8)

Including fine particles having a heat ray shielding function, metal carbonate or carbonate hydroxide,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
A heat ray shielding film having weather resistance, wherein the metal carbonate or carbonate hydroxide is contained in an amount of 1 part by weight or more and 100 parts by weight or less based on 100 parts by weight of the composite tungsten oxide fine particles. . The heat ray shielding film having weather resistance according to claim 1, wherein the heat ray shielding film further contains a binder. The heat-shielding film having weather resistance according to claim 2, wherein the binder is an inorganic binder or an organic binder. Fine particles having a heat ray shielding function and metal carbonate or carbonate hydroxide are contained in the plastic,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
The heat-shielding sheet having weather resistance, wherein the metal carbonate or carbonate hydroxide is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. Or film. The heat-shielding sheet or film having weather resistance according to claim 4, wherein the plastic is any one of polycarbonate resin, acrylic resin, and polyethylene terephthalate resin. The heat ray shielding film having weather resistance according to any one of claims 1 to 3, or the heat ray shielding fine particle dispersion powder for producing the heat ray shielding sheet or film having weather resistance according to claim 4 or 5. Because
Including fine particles having a heat ray shielding function, metal carbonate or carbonate hydroxide, and a solvent,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
The heat-ray shielding fine particle dispersion, wherein the metal carbonate or carbonate hydroxide is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles.   The heat ray shielding fine particle dispersion according to claim 6, wherein the heat ray shielding fine particle dispersion further contains a binder. The heat ray shielding film having weather resistance according to any one of claims 1 to 3, or the heat ray shielding fine particle dispersion powder for producing the heat ray shielding sheet or film having weather resistance according to claim 4 or 5. Because
Including fine particles having a heat ray shielding function, metal carbonate or carbonate hydroxide,
The fine particles having the heat ray shielding function are represented by a general formula M _Y WO _Z (0.001 ≦ Y ≦ 1.0, 2.2 ≦ Z ≦ 3.0), and M element is Cs, Rb, K, Tl. Composite tungsten oxide fine particles having a hexagonal crystal structure and a particle diameter of 1 nm or more and 800 nm or less.
The metal is one of alkali metal, alkaline earth metal, manganese, cobalt, nickel, copper, and zinc,
1. A heat ray shielding fine particle dispersed powder, wherein the metal carbonate or carbonate hydroxide is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles.

Images