JP6103283B2 - Composition for producing heat ray shielding film and method for producing the same, method for producing heat ray shielding film and method for producing heat ray shielding laminated transparent base material - Google Patents

Description

  The present invention relates to a heat ray shielding film having good visible light transmittance and an excellent heat ray shielding function, a heat ray shielding laminated transparent base material, and an automobile on which the heat ray shielding laminated transparent base material is mounted as a window material.

  As a safety glass used for window materials for automobiles and the like, a transparent base material is used in which a laminated glass is formed by sandwiching an intermediate layer containing a polyvinyl acetal resin or the like between a plurality of opposing (for example, two) sheet glasses. . Furthermore, a transparent base material has been proposed for the purpose of reducing the cooling load and the heat of human heat by blocking incident solar energy by providing the intermediate layer with a heat ray shielding function.

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

  Patent Document 2 discloses that Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, at least between two opposing glass plates. Metals such as Ta, W, V, and Mo, oxides of the metals, nitrides of the metals, sulfides of the metals, Sb and F dopants to the metals, and intermediate layers in which these composites are 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.

  Furthermore, in Patent Document 4, an intermediate layer composed of three layers is provided between at least two opposing transparent glass plates, and Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metal, metal oxide, metal nitride, metal sulfide, metal A laminated glass is disclosed in which a dope of Sb or F or a composite of these is dispersed and an intermediate layer of the first layer and the third layer is used as a resin layer.

  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.

  Furthermore, as a method for improving the heat ray shielding function of laminated glass, Patent Document 5 discloses that a metal oxide semiconductor, a near infrared absorber, and an ultraviolet absorber are mixed with a transparent synthetic resin and molded on a film. An ultraviolet and infrared shield is disclosed.

JP-A-8-217500 JP-A-8-259279 Japanese Patent Laid-Open No. 4-160041 Japanese Patent Laid-Open No. 10-297945 JP 2004-37768 A

However, as a result of further studies by the present inventors, the following problems have been found.
The first problem is that, in the laminated glass according to the conventional techniques described in Patent Documents 1 to 5, as described above, the heat ray shielding function when high visible light transmittance is required is not sufficient. is there.

  The present invention has been made paying attention to the above problems. The problem to be solved is a heat ray shielding film that exhibits excellent heat shielding properties while having a polyvinyl acetal resin as a main component, a heat ray shielding laminated transparent substrate using the heat ray shielding film, and the heat ray shielding laminated transparent It is to provide an automobile in which a base material is mounted as a window material.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research on a method for improving heat ray shielding characteristics while maintaining high visible light transmittance.

  The present inventors paid attention to the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106. Specifically, the wavelength distribution of the weight coefficient used for calculating the visible light transmittance and the solar radiation energy in the short wavelength region were studied in detail. And the knowledge that it was possible to reduce only the solar radiation transmittance | permeability was maintained, keeping visible light transmittance | permeability high by shielding the short wavelength area | region of visible light suitably.

  Specifically, in order to prevent the visible light transmittance from being lowered as much as possible, and to prevent the heat-shielding transparent substrate from being colored yellow, a conventional ultraviolet shielding agent that does not cut the visible light region as much as possible is used. In spite of the common sense of using it, a material that absorbs light in the vicinity of a wavelength of 450 nm strongly but does not absorb in the vicinity of a wavelength of 550 nm, which is a region that greatly contributes to the calculation of the visible light transmittance, is a compound having a heat ray shielding function. The present invention has been completed by conceiving the configuration of coexistence.

That is, the first invention for solving the above-described problem is
A heat ray shielding film comprising a compound having a heat ray shielding function, a selective wavelength absorbing material, a polyvinyl acetal resin, and a plasticizer, wherein the compound having the heat ray shielding function comprises indium tin oxide fine particles, antimony tin oxide The selected wavelength absorbing material has a transmission profile in which the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 40% or less. It is a heat ray shielding film characterized by having.

The second invention is
The heat ray shielding film according to the first aspect, wherein the indium tin oxide fine particles and the antimony tin oxide fine particles are fine particles having an average particle diameter of 40 nm or less.

The third invention is
The selective wavelength absorbing material is at least one selected from an isoindoline compound, an isoindolinone compound, a quinoxaline compound, a quinophthalone compound, a condensed diazo compound, a nickel azo compound, and a bismuth vanadate compound. It is a heat ray shielding film as described in the invention.

The fourth invention is:
The selective wavelength absorbing material has a transmission profile in which the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 15% or less. A heat ray shielding film according to any one of the inventions.

The fifth invention is:
The heat ray shielding film according to the first invention, wherein the selective wavelength absorbing material is at least one selected from a quinophthalone compound and a nickel azo compound.

The sixth invention is:
The weight ratio of the selective wavelength absorbing material and the indium tin oxide fine particles and / or antimony tin oxide fine particles oxide fine particles is [(indium tin oxide fine particles and / or antimony tin oxide fine particles) / selective wavelength absorbing material. ] = 99.9 / 0.1 to 97/3. The heat ray shielding film according to any one of the first to fifth inventions.

The seventh invention
The heat ray shielding film according to any one of the first to sixth inventions, wherein the heat ray shielding film further contains an infrared absorbing organic compound.

The eighth invention
The infrared absorbing organic compound is a phthalocyanine compound, naphthalocyanine compound, imonium compound, diimonium compound, polymethine compound, diphenylmethane compound, triphenylmethane compound, quinone compound, azo compound, pentadiene compound, azomethine compound, squarylium compound, organometallic complex The heat ray shielding film according to the seventh invention, wherein the heat ray shielding film is at least one selected from cyanine compounds.

The ninth invention
The infrared ray absorbing organic compound is at least one selected from a phthalocyanine compound and a diimonium compound, and is the heat ray shielding film according to the eighth invention.

The tenth invention is
The weight ratio of the infrared absorbing organic compound and the indium tin oxide fine particles and / or antimony tin oxide fine particles oxide fine particles is [(indium tin oxide fine particles and / or antimony tin oxide fine particles) / infrared absorptivity. Organic compound] = 99.5 / 0.5 to 95/5. The heat ray shielding film according to any one of the seventh to ninth inventions.

The eleventh invention is
A heat ray shielding laminated transparent substrate, wherein the heat ray shielding film according to any one of the first to tenth inventions is present between a plurality of transparent substrates.

The twelfth invention
The heat ray shielding combination according to the eleventh invention, wherein an infrared reflective film having a visible light transmittance of 88% or more and a solar reflectance of 21% or more is present between the plurality of transparent substrates. It is a transparent substrate.

The thirteenth invention
At least one of the transparent substrates is a heat ray shielding laminated transparent substrate according to the eleventh or twelfth invention, wherein at least one sheet is glass.

The fourteenth invention is
The visible ray transmittance calculated by JIS R 3106 is 70% or more, and the solar radiation transmittance is 35% or less. The heat ray shielding laminated transparent according to any one of the eleventh to thirteenth inventions, It is a substrate.

The fifteenth invention
A heat ray shielding laminated transparent substrate according to any one of the eleventh to fourteenth inventions is mounted as a window material.

  According to the present invention, a heat ray shielding film that exhibits excellent optical properties and high weather resistance by using a compound having a heat ray shielding function and a selective wavelength absorbing material together with a polyvinyl acetal resin as a main component. I was able to get. And the heat ray shielding laminated transparent base material which exhibits the outstanding optical characteristic, the high weather resistance, and the outstanding mechanical characteristic was able to be obtained by using a heat ray shielding film. Furthermore, by mounting the heat ray shielding laminated transparent base material on a car as a window material, it has become possible to suppress a rise in the temperature inside the car in summer.

It is a graph which shows the relationship between the visible light transmittance | permeability and the solar radiation transmittance | permeability in the heat ray shielding laminated transparent base material which concerns on Examples 1-16 and Comparative Examples 1-4, 6-9. It is a graph which shows the relationship between the visible light transmittance | permeability and the solar radiation transmittance | permeability in the heat ray shielding laminated transparent base material which concerns on Examples 17-28 and Comparative Examples 1-4. It is a graph which shows the relationship between the visible light transmittance | permeability and the solar radiation transmittance | permeability in the heat ray shielding laminated transparent base material which concerns on Examples 29-33 and Comparative Examples 1-4, 5. It is a graph which shows the relationship between the visible light transmittance | permeability in the heat ray shielding laminated transparent base material which concerns on Examples 5-8, 40-47, and Comparative Examples 1-4, and solar radiation transmittance | permeability.

Hereinafter, embodiments of the present invention will be described in detail.
The heat ray shielding film according to the present invention comprises a fine particle of a compound having a heat ray shielding function, a dispersant, a selective wavelength absorbing material, an infrared-absorbing organic compound, a polyvinyl acetal resin, a plasticizer, if desired, an adhesive strength adjusting agent, if desired, Contains other additives.

The heat ray shielding film according to the present invention is obtained by dispersing fine particles of a compound having a heat ray shielding function and a dispersant in a part of a plasticizer to be added to the polyvinyl acetal resin to obtain a fine particle dispersion of the compound having a heat ray shielding function. Produced by kneading the obtained dispersion, the selected wavelength absorbing material, the polyvinyl acetal resin, and the plasticizer, and then molding into a film by a known method such as an extrusion molding method or a calendar molding method. I can do it.
Further, the heat ray shielding film according to the present invention provides a dispersion in which fine particles of a compound having a heat ray shielding function and a dispersing agent are dispersed in a general organic solvent, and then the organic solvent is removed to disperse the solid. Obtaining a fine particle dispersion of a compound having a heat ray shielding function in a state where fine particles of a compound having a heat ray shielding function are dispersed in the agent, the obtained dispersion, a selective wavelength absorbing material, a polyvinyl acetal resin, and a plasticizer After kneading, it can also be produced by molding into a film by a known method such as extrusion molding or calendar molding.

Hereinafter, the components of the heat ray shielding film according to the present invention, the heat ray shielding film, and the heat ray shielding laminated transparent substrate using the heat ray shielding film will be described in detail.
The fine particles of the compound having a heat ray shielding function according to the present invention include indium tin oxide fine particles (may be referred to as ITO fine particles in the present invention), antimony tin oxide fine particles (in the present invention, ATO fine particles). Etc.) can be used.
In the present invention, ITO fine particles and ATO fine particles can be used and applied in the same manner. Therefore, in the following description, the case where ITO fine particles are used as the fine particles of the compound having a heat ray shielding function will be mainly described. However, when ATO fine particles are used, the case where ITO fine particles and ATO fine particles are mixed and used may be used. It is the same.

[1] Constituent Component of Heat Ray Shielding Film Regarding the heat ray shielding film according to the present invention, first, fine particles having a heat ray shielding function as a constituent thereof, a production method thereof, a dispersant, a selective wavelength absorbing material, an infrared absorbing organic compound, A polyvinyl acetal resin, a plasticizer, an adhesive force regulator, and other additives will be described.

(1) Fine particles having a heat ray shielding function A preferred example of the fine particles having a heat ray shielding function according to the present invention is ITO fine particles. Since the ITO fine particles largely absorb light in the near infrared region, particularly a wavelength of 1000 nm or more, the transmitted color tone often has a blue color tone.
As the ITO fine particles, commercially available ones can be used. There is no restriction | limiting in particular also about the addition amount of tin, Indium oxide which does not contain tin may be sufficient. The amount of tin added is preferably about 5 to 15 wt% as the amount of metal. As for the amount of oxygen, it is preferable that the amount of oxygen is smaller than the stoichiometric ratio because absorption in the near-infrared region is strengthened by having some oxygen defects.

  The particle diameter of the ITO fine particles can be appropriately selected depending on the purpose of use of the heat ray shielding film. For example, when the heat ray shielding film is used for applications requiring transparency, the ITO fine particles preferably have a dispersed particle diameter of 40 nm or less. If the ITO fine particles have a dispersed particle diameter smaller than 40 nm, light is not completely blocked by scattering, and visibility in the visible light region can be maintained, and at the same time, transparency can be efficiently maintained. Because you can.

  In the case where the heat ray shielding film or the heat ray shielding laminated transparent base material according to the present invention is applied to an application in which transparency in the visible light region is particularly important, such as an automobile windshield, further reduction of scattering due to ITO fine particles is considered. It is preferable to do. In consideration of the further reduction in scattering, the dispersed particle diameter of the ITO fine particles is 30 nm or less, preferably 25 nm or less.

  This is because if the dispersed particle diameter of the ITO fine particles is small, light scattering in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. By reducing the scattering of the light having the wavelength, it is possible to avoid a situation in which the heat ray shielding film has an appearance like a frosted glass when strong light is irradiated and the clear transparency is lost.

  This is because when the dispersed particle diameter of the ITO fine particles is 40 nm or less, the above-described geometrical scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is reduced. Furthermore, when the dispersed particle diameter of the ITO fine particles is 25 nm or less, the scattered light is preferably very small.

As described above, from the viewpoint of avoiding light scattering, it is preferable that the dispersed particle diameter of the ITO fine particles is small. On the other hand, if the dispersed particle diameter of the ITO fine particles is 1 nm or more, industrial production is easy.
As described above, when ATO fine particles are selected as the fine particles having a heat ray shielding function according to the present invention, the same applies when ITO fine particles and ATO fine particles are mixed and used.

(2) Dispersant The dispersant according to the present invention is used for uniformly dispersing the above-mentioned ITO fine particles in a polyvinyl acetal resin described later.
The dispersant according to the present invention has a thermal decomposition temperature of 200 ° C. or higher measured with a differential thermothermogravimetric simultaneous measurement apparatus (hereinafter sometimes referred to as TG-DTA), and has urethane, acrylic and styrene main chains. It is preferable that it is a dispersing agent which has. Here, the thermal decomposition temperature is a temperature at which weight loss due to thermal decomposition of the dispersant begins in the TG-DTA measurement.
This is because when the thermal decomposition temperature is 200 ° C. or higher, the dispersant does not decompose during kneading with the polyvinyl acetal resin. As a result, it is possible to avoid the browning of the heat ray shielding film for heat ray shielding laminated glass due to the decomposition of the dispersant, the reduction in visible light transmittance, and the inability to obtain the original optical characteristics.

  In addition, the dispersant is preferably a dispersant having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups are adsorbed on the surface of the ITO fine particles, prevent aggregation of the ITO fine particles, and have an effect of uniformly dispersing the fine particles even in the heat ray shielding film. Specific examples include acrylic-styrene copolymer dispersants having a carboxyl group as a functional group, and acrylic dispersants having an amine-containing group as a functional group. The dispersant having a functional group containing an amine is preferably one having a molecular weight Mw of 2,000 to 200,000 and an amine value of 5 to 100 mgKOH / g. Moreover, in the dispersing agent which has a carboxyl group, the thing of molecular weight Mw2000-200000 and an acid value of 1-50 mgKOH / g is preferable.

The addition amount of the dispersant is desirably in the range of 10 parts by weight to 1000 parts by weight, more preferably in the range of 30 parts by weight to 400 parts by weight with respect to 100 parts by weight of the ITO fine particles. This is because, if the added amount of the dispersant is in the above range, the ITO fine particles are uniformly dispersed in the polyvinyl acetal resin, and the physical properties of the obtained heat ray shielding film are not adversely affected.
As described above, when ATO fine particles are selected as the fine particles having a heat ray shielding function according to the present invention, the same applies when ITO fine particles and ATO fine particles are mixed and used.

(3) Selected Wavelength Absorbing Material The selected wavelength absorbing material according to the present invention is a material that selectively and strongly absorbs only light in a certain wavelength region.
As described above, the present inventors consider the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106, and the above ITO fine particles alone cannot sufficiently shield the light. The inventors have come up with a configuration in which a selective wavelength absorbing material that strongly absorbs light in the vicinity of a wavelength of 450 nm and does not absorb in the vicinity of a wavelength of 550 nm, which is a wavelength region that greatly contributes to the calculation of the visible light transmittance, is used in combination with ITO fine particles. And, by using a configuration in which the selective wavelength absorbing material that absorbs light in the vicinity of the wavelength of 450 nm and does not have absorption in the vicinity of the wavelength of 550 nm is used in combination with the ITO fine particles, compared to the case of using the ITO fine particles alone, A lower solar transmittance could be obtained.

In addition, for example, when a heat ray shielding laminated transparent base material is used as a member that requires high visibility, such as an automobile windshield, strong light such as direct sunlight, headlamps, etc. In some cases, the phenomenon that the contained fine particles such as ITO fine particles strongly scatter in the short wavelength region of visible light and the heat-shielding transparent transparent substrate becomes cloudy in blue and white.
Here, the present inventors suppress the occurrence of the bluish and cloudy by absorbing the scattered light in the short wavelength region of visible light generated by the selective wavelength absorbing material described above being scattered by the ITO fine particles, the present invention It was conceived that the effect of increasing the transparency of the heat ray shielding film according to the invention and the transparency of the heat ray shielding laminated transparent base material can also be exhibited.

As the optical characteristics of the selective wavelength absorbing material according to the present invention, the transmittance of light having a wavelength of 550 nm of the selective wavelength absorbing material itself excluding the absorption of the medium or the substrate is 90% or more, and the light having a wavelength of 450 nm is transmitted. The rate is preferably 40% or less. More preferably, the transmittance of light having a wavelength of 550 nm is 90% or more, and the transmittance of light having a wavelength of 450 nm is 15% or less.
If the light transmittance of the selected wavelength absorbing material is 90% or more with respect to light having a wavelength of 550 nm and 40% or less with respect to light having a wavelength of 450 nm, the selected wavelength absorbing material and ITO fine particles are used. Is used, the visible light transmittance does not decrease, and the absorption of light in the vicinity of a wavelength of 450 nm can be sufficiently obtained. As a result, compared with the case where the ITO fine particles are used alone, the solar radiation transmittance is lowered and the heat shielding characteristics are improved.

  Specific examples of the selective wavelength absorbing material used in the present invention include isoindoline compounds, isoindolinone compounds, quinoxaline compounds, quinophthalone compounds, condensed diazo compounds, nickel azo compounds, and bismuth vanadate compounds. In particular, in order to reduce the transmittance of light having a wavelength of 450 nm to 15% or less, it is preferable to use at least one selected from a quinophthalone compound and a nickel azo compound.

The mixing ratio of the selective wavelength absorbing material and the ITO fine particles and / or ATO fine particles is such that the weight ratio [(ITO fine particles and / or ATO fine particles)] / selected wavelength absorbing material is 99.9 / 0.1 to 97/3. A range is preferable. More preferably, it is 99.5 / 0.5-98 / 2, and it is still more preferable in it being 99 / 1-98 / 2. When the mixing ratio of the addition amount of the selective wavelength absorbing material is 97/3 or less in the above-described weight ratio, the visible wavelength region is not strongly absorbed by the selective wavelength absorbing material, and the visible light transmittance is maintained. As a result, the solar radiation transmittance is maintained as compared with the case where the ITO fine particles and / or the ATO fine particles are used alone, and the heat shielding characteristics are maintained.
Moreover, if the mixing ratio of the addition amount of the selective wavelength absorbing material is 99.9 / 0.1 or more in the above-described weight ratio, sufficient absorption of light in the vicinity of the wavelength of 450 nm is obtained, and the effect of addition is exhibited. It is.

As a method for adding the selective wavelength absorbing material to the heat ray shielding film, it is also possible to add the compound itself to the polyvinyl acetal resin and the plasticizer together with the ITO fine particle plasticizer dispersion described later or the ITO fine particle dispersion.
However, in consideration of the transparency of the obtained heat ray shielding film and the heat ray shielding laminated transparent base material using the heat ray shielding film, the selected wavelength absorbing material is dispersed in the plasticizer in the same manner as the ITO fine particles described above. It is also possible to add to the heat ray shielding film as a dispersion or a dispersion in which the selective wavelength absorbing material is dispersed in a solid dispersant.

  In any case, it is sufficient that the selective wavelength absorbing material is uniformly dispersed in the heat ray shielding film, and any method that does not impair the transparency of the obtained heat ray shielding film is preferably used.

(4) Infrared absorbing organic compound In the present invention, an infrared absorbing organic compound having a strong absorption in the near infrared region may be further added to the heat ray shielding film as desired.
Examples of infrared absorbing organic compounds used for this purpose include phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, azo compounds, pentadiene compounds, azomethine compounds, squarylium. Compounds, organometallic complexes, cyanine compounds and the like can be used.
As the infrared absorbing organic compound, it is preferable to select one that dissolves in the plasticizer constituting the heat ray shielding film described above, because the transparency of the obtained heat ray shielding film is not impaired.

The infrared-absorbing organic compound is more preferably a material that strongly absorbs light in the range from the visible long wavelength region to the near infrared region having a wavelength of 650 nm to 1000 nm. This has a large synergistic effect when the infrared absorbing organic compound having the optical characteristics and the ITO fine particles having strong absorption in the wavelength region of 800 nm or more are used in combination, and compared with the case where the ITO fine particles are used alone. This is because high heat shielding performance can be obtained.
From this point of view, as the infrared absorbing organic compound used in the present invention, a diimonium compound or a phthalocyanine compound is particularly preferable.

The weight ratio of the mixing ratio of the infrared absorbing organic compound and the ITO fine particles and / or ATO fine particles is [(ITO fine particles and / or ATO fine particles) / infrared absorbing organic compound] = 99.5 / 0.5- The range is preferably 95/5.
If the mixing ratio of the addition amount of the infrared absorbing organic compound is more than 95.5 / 0.5 in the above-mentioned weight ratio, the range from the visible light long wavelength region of the wavelength 650 nm to 1000 nm by the infrared absorbing organic compound to the near infrared region This is preferable because the effect of strongly absorbing the light is obtained and the effect of addition is obtained. Moreover, if the mixing ratio of the addition amount of the infrared absorbing organic compound is less than 95/5 in the above-mentioned weight ratio, the light near the wavelength of 550 nm, which is a wavelength region that greatly contributes to the calculation of the visible light transmittance by the infrared absorbing organic compound. Is not absorbed, and as a result, visible light transmittance is secured and heat shielding properties are secured, which is preferable.

(5) Polyvinyl acetal resin As the polyvinyl acetal resin used for the heat ray shielding film according to the present invention, a polyvinyl butyral resin is preferable. Further, in consideration of the physical properties of the heat ray shielding film, a plurality of types of polyvinyl acetal resins having different degrees of acetalization may be used in combination. Furthermore, a copolyvinyl acetal resin obtained by reacting a plurality of types of aldehydes in combination during acetalization can also be preferably used.
From this viewpoint, the preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 60%, and the upper limit is 75%.

The polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate. Generally, polyvinyl alcohol having a saponification degree of 80 to 99.8 mol% is used.
Moreover, the preferable minimum of the polymerization degree of the said polyvinyl alcohol is 200, and an upper limit is 3000. When the degree of polymerization is 200 or more, resistance to penetration of the manufactured heat ray shielding laminated transparent base material is maintained, and safety is maintained. On the other hand, if it is 3000 or less, the moldability of the resin film is maintained, the rigidity of the resin film is also maintained in a preferable range, and the workability is maintained.

  The aldehyde is not particularly limited, and generally, an aldehyde having 1 to 10 carbon atoms such as n-butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, acetaldehyde or the like is used. It is done. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and butyraldehyde having 4 carbon atoms is more preferable.

(6) Plasticizer The plasticizer used for the heat ray shielding film mainly composed of the polyvinyl acetal resin according to the present invention includes a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, and a polyhydric alcohol organic acid ester. Examples include ester plasticizers such as compounds, and phosphoric acid plasticizers such as organic phosphate plasticizers. Any plasticizer 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 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.
Of these, triethylene glycol fatty acid esters such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanoate, and triethylene glycol di-2-ethylhexanate are suitable. is there. 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.

  Note that the choice of plasticizer is low in hydrolyzability. From this viewpoint, triethylene glycol di-2-ethylhexanate, triethylene glycol di-2-ethylbutyrate, and tetraethylene glycol di-2-ethylhexanate are preferable.

(7) Adhesive strength adjusting agent It is also preferable to add an optional adhesive strength adjusting agent to the heat ray shielding film according to the present invention.
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 also has an effect as an original adhesive strength adjusting agent and an effect of improving the weather resistance of the ITO fine particles described above. be able to.

(8) Other additives The heat ray shielding film according to the present invention may further contain a general additive as desired. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc., which are generally used for coloring thermoplastic resins to give an arbitrary color tone as desired. It may be added. Particularly in the present invention, since the light on the short wavelength side of visible light is absorbed, the transmitted light color is yellowish. Therefore, it is preferable to adjust the color tone of the heat ray shielding film by adding a compound such as a dye or a pigment.
Furthermore, the selective wavelength absorbing material may have a high transmittance in the ultraviolet region, and when combined with an ultraviolet shielding agent, a higher heat ray shielding effect can be obtained. Examples of the ultraviolet screening agent include hydroxybenzophenone-based, salicylic acid-based, HALS-based, triazole-based, triazine-based organic ultraviolet absorbers, and inorganic ultraviolet absorbers such as zinc oxide, titanium oxide, and cerium oxide.
As other additives, a coupling agent, a surfactant, an antistatic agent, and the like can be added.

[2] Heat ray shielding film In order to produce the heat ray shielding film according to the present invention, the ITO fine particles and the dispersing agent described above are dispersed in a part of the plasticizer added to the polyvinyl acetal resin, and the ITO fine particle dispersion liquid is dispersed. Or after obtaining a dispersion in which ITO fine particles and a dispersant are dispersed in a general organic solvent, the organic solvent is removed so that the ITO fine particles are dispersed in the solid dispersant. An ITO fine particle dispersion is produced.
And the manufactured ITO fine particle plasticizer dispersion, or the manufactured ITO fine particle dispersion, the selective wavelength absorbing material, the polyvinyl acetal resin, the plasticizer, and other additives and adhesive strength adjusting agents as required. After mixing and kneading, they can be produced, for example, by forming into a film by a known method such as extrusion molding or calendering. Further, if an infrared absorbing organic compound is added to the heat ray shielding film as desired, higher heat ray shielding characteristics can be obtained.
As described above, when ATO fine particles are selected as the fine particles having a heat ray shielding function according to the present invention, the same applies when ITO fine particles and ATO fine particles are mixed and used.

  In the following description, a method for producing a plasticizer dispersion of ITO fine particles and a method for producing an ITO fine particle dispersion will be mainly described. When ATO fine particles are used, ITO fine particles and ATO fine particles are mixed and used. The same applies to the case.

(1) Production method of plasticizer dispersion of ITO fine particles ITO fine particles and a dispersant can be added to and mixed with a plasticizer, and a plasticizer dispersion of ITO fine particles can be obtained using a general dispersion method. Specifically, a dispersion method such as a bead mill, a ball mill, a sand mill, or ultrasonic dispersion can be used.

In addition, when the ITO fine particles are dispersed in the plasticizer, an organic solvent having a boiling point of 120 ° C. or lower may be added if desired.
As the organic solvent, those having a boiling point of 120 ° C. or less are preferably used. If the boiling point is 120 ° C. or lower, it is easy to remove by a drying step, which is a subsequent step, particularly by drying under reduced pressure. As a result, removal in the vacuum drying step proceeds rapidly, contributing to the productivity of the ITO fine particle-containing composition. Furthermore, since the vacuum drying process proceeds easily and sufficiently, it can be avoided that an excessive organic solvent remains in the ITO fine particle-containing composition according to the present invention. As a result, it is possible to avoid the occurrence of problems such as the generation of bubbles when forming the heat ray shielding film. Specific examples include toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, and ethanol, but any boiling point that is 120 ° C. or less and that can uniformly disperse ITO fine particles can be selected. .

  A method for uniformly dispersing ITO fine particles in an organic solvent can be arbitrarily selected from general methods. As specific examples, methods such as a bead mill, a ball mill, a sand mill, and ultrasonic dispersion can be used.

  Moreover, as a method for removing the organic solvent from the ITO fine particle-containing dispersion, a method of drying under reduced pressure is preferable. Specifically, the ITO fine particle-containing dispersion is dried under reduced pressure while stirring to separate the ITO fine particle-containing composition from the organic solvent component. Examples of the apparatus used for drying under reduced pressure include a vacuum stirring type dryer, but any apparatus having the above functions may be used, and the apparatus is not particularly limited. Moreover, the pressure of the pressure reduction of a drying process is selected suitably.

  The use of the reduced-pressure drying method is preferable because the removal efficiency of the solvent is improved and the ITO fine particle-containing composition is not exposed to high temperature for a long time, so that the dispersed fine particles do not aggregate. Furthermore, productivity is increased, and it is easy to collect the evaporated organic solvent, which is preferable from the environmental consideration.

(2) Production method of ITO fine particle dispersion Addition and mixing of plasticizer dispersion of ITO fine particles described above, or ITO fine particles, dispersant and plasticizer to organic solvent having a boiling point of 120 ° C. or lower, An ITO fine particle dispersion in which the concentration of ITO fine particles is 50% by mass or less is produced using a general dispersion method.

The concentration of the ITO fine particles in the plasticizer is preferably 50% by mass or less. If the concentration of the ITO fine particles in the plasticizer is 50% by mass or less, the fine particles are hardly aggregated, easily dispersed, a sudden increase in viscosity can be avoided, and handling is easy.
A method for uniformly dispersing the ITO fine particles in the plasticizer can be arbitrarily selected from general methods. As a specific example, after obtaining an ITO fine particle-containing dispersion, the organic solvent can be removed by a known method to obtain an ITO fine particle dispersion in which ITO fine particles are dispersed in a solid dispersant.

[3] Heat ray shielding laminated transparent base material The heat ray shielding laminated transparent base material using the heat ray shielding film according to the present invention has various forms.
For example, a heat ray shielding laminated inorganic glass using inorganic glass as a transparent substrate is obtained by laminating and integrating a plurality of opposing inorganic glasses that are sandwiched by the heat ray shielding film according to the present invention by a known method. can get. The obtained heat-shielding laminated inorganic glass can be used mainly as an inorganic glass for the front of an automobile or a window of a building.

Furthermore, the structure which uses the heat ray shielding film concerning this invention and the infrared rays reflective film mentioned later together as a heat ray shielding film, and makes it a heat ray shielding laminated transparent base material is also preferable. In the case of adopting this configuration, the infrared reflective film is sandwiched between a heat ray shielding film and a transparent PVB resin film to be integrated into a multilayer film. The obtained multilayer film is sandwiched between a plurality of opposing inorganic glasses and laminated and integrated by a known method to obtain a heat-shielding laminated inorganic glass.
Here, considering that the heat ray shielding laminated inorganic glass is used in an automobile, the structure in which the infrared reflection film is present outside the heat ray shielding film according to the present invention in consideration of the temperature rise suppressing effect in the automobile. preferable.

  In particular, when the heat ray shielding laminated transparent base material according to the present invention is used for a window material such as a windshield of an automobile, a high heat ray shielding ability is required while satisfying the transmittance of 70% or more stipulated by the Road Transport Vehicle Law. It is because it is said. Thereby, the power consumption of an air conditioner is suppressed compared with the case where the normal laminated glass is mounted. As a result, particularly in an automobile using a battery such as a hybrid car or an electric car, consumption of the battery can be suppressed, so that a significant effect is seen in extending the cruising distance. Therefore, it can be expected to contribute to improving the fuel efficiency of automobiles and reducing greenhouse gas emissions, and in the future, it is expected to become an essential member in the design of automobiles.

A transparent resin is used as a transparent substrate, and it is used in the same manner as the above inorganic glass, or in combination with the above inorganic glass, and a heat ray shielding film is sandwiched between opposing transparent substrates, so that the heat ray shielding transparent A substrate can be obtained. The application of the heat ray shielding laminated transparent base material is the same as that of the heat ray shielding laminated inorganic glass described above.
In addition, if desired, the heat ray shielding film according to the present invention can be used alone, or the heat ray shielding film according to the present invention can be used on one side or both sides of a transparent substrate such as inorganic glass or transparent resin. Is possible.

Here, the infrared reflective film used together with the heat ray shielding film according to the present invention described above will be described.
In consideration of optical characteristics when the infrared reflective film according to the present invention is used in combination with the heat ray shielding film according to the present invention, the visible light region hardly absorbs sunlight, specifically the near infrared region, specifically From the viewpoint of the heat ray shielding function, it is preferable to reflect only the wavelength range of 800 nm to 1200 nm.
Specifically, the optical properties of the infrared film are preferably a visible light transmittance of 85% or more and a solar reflectance of 18% or more, and a visible light transmittance of 88% or more and a solar reflectance of 21% or more. More preferred.
Furthermore, in consideration of the use of a heat ray shielding laminated transparent base material for automobile windshields and building windows, the infrared reflective film according to the present invention transmits electromagnetic waves in the wavelength region used for mobile phones and ETC. Those are preferred. Therefore, a film with a resin multilayer film that transmits electromagnetic waves is preferable to a film with metal film that has conductivity and does not transmit the electromagnetic waves.

[4] Summary As described in detail above, the ITO fine particle plasticizer dispersion according to the present invention, or the ITO fine particle dispersion according to the present invention, the selective wavelength absorbing material, the polyvinyl acetal resin, and the plasticizer. And further forming into a film shape by a known method, the heat ray shielding film according to the present invention can be produced.
And by presenting the heat ray shielding film according to the present invention so as to be sandwiched between a plurality of opposed transparent substrates, it exhibits a low solar transmittance while maintaining high transparency in the visible light region, The production of a heat-shielded transparent base material according to the present invention has become possible.
And by combining the ITO fine particles and a selective wavelength absorbing material having a transmission profile with a wavelength 550 nm transmittance of 90% or more and a wavelength 450 nm transmittance of 40% or less in a predetermined ratio, the ITO fine particles Compared with the case where it is used alone, it is possible to exhibit higher heat ray shielding characteristics.
As described above, when ATO fine particles are selected as the fine particles having a heat ray shielding function according to the present invention, the same applies when ITO fine particles and ATO fine particles are mixed and used.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
In addition, the light transmittance at a wavelength of 450 nm, the light transmittance at a wavelength of 550 nm, the visible light transmittance of the heat-shielded inorganic glass, and the solar transmittance of the selected wavelength absorbing material plasticizer dispersion liquid in each example are Hitachi Measurement was performed using a spectrophotometer U-4000 manufactured by Seisakusho. In addition, the said solar transmittance is an parameter | index which shows the heat ray shielding performance of a heat ray shielding matching transparent base material.
Moreover, the haze value was measured based on JISK7105 using HR-200 made by Murakami Color Research Laboratory Co., Ltd. In addition, the said haze value is a parameter | index which shows the transparency of a heat ray shielding laminated transparent base material.

[Example 1]
ITO fine particle a (Sumitomo Metal Mining Co., Ltd .: SUFP-HX) 20% by mass, acrylic dispersant (amine value 48 mgKOH / g, decomposition temperature 250 ° C.) having an amine-containing group as a functional group (Hereinafter abbreviated as “dispersant a”) 10% by mass and 70% by mass of triethylene glycol di-2-ethylhexanonate (hereinafter abbreviated as “plasticizer a”) were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of ITO fine particles (hereinafter abbreviated as “fine particle dispersion A”).
Here, the dispersion average particle diameter of the ITO fine particles in the fine particle dispersion A was measured with a Nikkiso Microtrac particle size distribution meter and found to be 26 nm.

On the other hand, 20% by mass of a quinophthalone compound manufactured by BASF Corporation, 10% by mass of a dispersant, and 70% by mass of a plasticizer a were weighed as selective wavelength absorbing materials. These are loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 3 hours to obtain a selective wavelength absorbing material plasticizer dispersion (hereinafter, abbreviated as a selective wavelength absorbing material dispersion α). It was.
The selected wavelength-absorbing material dispersion α was diluted with a plasticizer a to a predetermined concentration, and placed in a glass cell. The optical characteristics were measured. The transmittance was 92.8. Prior to the measurement, only the plasticizer a was added to the glass cell, and the baseline was measured.

A predetermined amount of the fine particle dispersion A and the selective wavelength absorbing material dispersion α are added to a mixture in which 30% by mass of the plasticizer a and 70% by mass of the polyvinyl butyral resin are mixed, and the concentration of the fine particles a in the mixture is 1.5. The composition A for manufacturing a heat ray shielding film was obtained by setting the mass concentration of the material of the selective wavelength absorbing material to 0.0079 mass%. As a result, the weight ratio of the selective wavelength absorbing material to the ITO fine particles in the composition A for producing a heat ray shielding film (ITO fine particles / selected wavelength absorbing material) is 1.5 / 0.0079 = 99.5 / 0. It became 5.
The composition A for producing the heat ray shielding film was kneaded at 200 ° C. with a twin-screw extruder, and the heat ray shielding film according to Example 1 was obtained as a sheet having a thickness of 0.7 mm by extrusion calendering from a T die. .

  The obtained heat ray shielding film according to Example 1 was sandwiched between two opposing inorganic glasses and bonded and integrated by a known method to obtain a heat ray shielding laminated transparent base material according to Example 1.

  As shown in Table 1, the optical properties of the heat-shielding transparent substrate were 43.5% when the visible light transmittance was 78.5%, and the haze value was 1.1%. The results are shown in Table 1.

[Examples 2-33]
Except for changing the concentration of the fine particles a in the composition A for producing a heat ray shielding film and the type and concentration of the selective wavelength absorbing material described in Example 1, the same manner as in Example 1 was repeated. A heat ray shielding laminated transparent base material according to No. 33 was obtained. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Examples 2-33 was measured similarly to Example 1. FIG. Table 1 shows the concentration of the fine particles a, the type of the selective wavelength absorbing material, and the concentration in Examples 2-33. Furthermore, the optical characteristic measurement result of the heat ray shielding laminated transparent base material concerning Examples 2-33 was shown in Table 1.
As the selective wavelength absorbing material, in Examples 2 to 16, the above-described quinophthalone compound was used, in Examples 17 to 28, a nickel azo compound was used, and in Example 29, an isoindoline compound was used. In Example 30, a quinoxaline compound was used, in Example 31, a condensed diazo compound was used, in Example 32, an isoindolinone compound was used, and in Example 33, a bismuth vanadate compound was used.

[Comparative Examples 1-4]
Comparative Examples 1 to 4 were carried out in the same manner as in Example 1 except that the concentration of the fine particles a in the composition A for producing a heat ray shielding film described in Example 1 was changed and the selective wavelength absorbing material was not added. Such a heat ray shielding laminated transparent base material was obtained. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Comparative Examples 1-4 was measured similarly to Example 1. FIG. Table 2 shows the concentration of the fine particles a in Comparative Examples 1 to 4. Furthermore, the optical characteristic measurement result of the heat ray shielding laminated transparent base material which concerns on Comparative Examples 1-4 was shown in Table 2.

[Comparative Examples 5 to 9]
Comparative Examples 5 to 9 were performed in the same manner as in Example 1 except that the concentration of fine particles a in the composition A for manufacturing a heat ray shielding film described in Example 1 and the type and concentration of the selective wavelength absorbing material were changed. Such a heat ray shielding laminated transparent base material was obtained. The results are shown in Table 2.
As the selective wavelength absorbing material, a benzimidazolone compound was used in Comparative Example 5, and the quinophthalone compound described above was used in Comparative Examples 6 to 9.

[Example 34]
20% by mass of ATO fine particles b (manufactured by Ishihara Sangyo Co., Ltd .: SN-100P), 10% by mass of dispersant a, and 70% by mass of plasticizer a were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of ATO fine particles (hereinafter abbreviated as “fine particle dispersion B”). Here, the dispersion average particle diameter of the ATO fine particles in the fine particle dispersion B was 29 nm as measured with a Nikkiso Microtrac particle size distribution meter.

  A predetermined amount of the fine particle dispersion B and the selective wavelength absorbing material dispersion α are added to a mixture obtained by mixing 30% by mass of the plasticizer a and 70% by mass of the polyvinyl butyral resin, and the concentration of the fine particles b in the mixture is 0.25%. %, The concentration of the selected wavelength absorbing material was 0.0278% by mass, and a composition B for producing a heat ray shielding film was obtained. As a result, the weight ratio of the selected wavelength absorbing material to the ATO fine particles in the composition B for producing a heat ray shielding film (ATO fine particles / selected wavelength absorbing material) was 2.5 / 0.0278 = 99/1. . The composition B for production of the heat ray shielding film was kneaded at 200 ° C. with a twin screw extruder, extruded from a T die, and a heat ray shielding film according to Example 34 was obtained as a 0.7 mm thick sheet by a calender roll method.

  The obtained heat ray shielding film was sandwiched between two opposing inorganic glasses and laminated together by a known method to obtain a heat ray shielding laminated transparent substrate according to Example 34. And the optical characteristic of the heat ray shielding laminated transparent base material concerning the said Example 34 was measured similarly to Example 1. FIG.

  As shown in Table 2, the solar light transmittance was 30.5% and the haze value was 1.3% when the visible light transmittance was 70.2%.

[Examples 35 to 39]
The heat-shielding laminated transparent base material according to Examples 35 to 39 in the same manner as in Example 34 except that the type of the selective wavelength absorbing material in the composition B for manufacturing a heat-ray shielding film described in Example 34 was changed. Got. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Examples 35-39 was measured similarly to Example 34. FIG. Table 2 shows the concentration of the fine particles b, the type and concentration of the selected wavelength absorbing material in Examples 35 to 39. Furthermore, the optical characteristic measurement result of the heat ray shielding laminated transparent base material which concerns on Examples 35-39 was shown in Table 2.
As the selective wavelength absorbing material, a nickel azo compound is used in Example 35, an isoindoline compound is used in Example 36, a quinoxaline compound is used in Example 37, and a condensed diazo compound is used in Example 38. In Example 39, an isoindolinone compound was used.

[Comparative Example 10]
A heat ray shielding laminated transparent base material according to Comparative Example 10 was obtained in the same manner as Example 34 except that the selective wavelength absorbing material was not added. The results are shown in Table 2.

[Example 40]
To the composition in which 30% by mass of the plasticizer a and 70% by mass of the polyvinyl butyral resin described in Example 1 were mixed, Nippon Carlit (as the infrared-absorbing organic compound with a predetermined amount of the fine particle dispersion A, the selective wavelength absorbing material dispersion α, and Co., Ltd. diimonium compound CIR-RL was added, the concentration of fine particles a in the mixture was 1.25% by mass, the material concentration of the selective wavelength absorbing material was 0.0126% by mass, and the infrared absorbing organic compound was 0.1% by mass. The composition C for production of a heat ray shielding film was obtained with 0126 mass%. As a result, the weight ratio of the selective wavelength absorbing material to the ITO fine particles in the composition C for producing a heat ray shielding film (ITO fine particles / selected wavelength absorbing material) was 1.25 / 0.0126 = 99/1. . The composition C for production of this heat ray shielding film was kneaded at 200 ° C. with a twin screw extruder, extruded from a T die, and a heat ray shielding film according to Example 40 was obtained as a sheet having a thickness of 0.7 mm by a calender roll method.

  The obtained heat ray shielding film was sandwiched between two opposing inorganic glasses and laminated together by a known method to obtain a heat ray shielding laminated transparent base material according to Example 40. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 40 was measured similarly to Example 1. FIG.

  As shown in Table 2, the optical characteristics of the heat-shielding laminated transparent base material were as follows. The solar radiation transmittance was 39.4% and the haze value was 1.3% when the visible light transmittance was 78.1%.

[Examples 41 to 51]
Implemented in the same manner as in Example 40 except that the type and concentration of the selective wavelength absorbing material, the type and concentration of the infrared-absorbing organic compound in the composition C for producing a heat ray shielding film described in Example 40 were changed. The heat ray shielding laminated transparent base material which concerns on Examples 41-51 was obtained. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Examples 41-51 was measured similarly to Example 40. FIG. Table 2 shows the concentration of the fine particles a, the type and concentration of the selected wavelength absorbing material, and the type and concentration of the infrared absorbing organic compound in Examples 41 to 51. Furthermore, the optical characteristic measurement result of the heat ray shielding laminated transparent base material which concerns on Examples 41-51 was shown in Table 2.

As the selective wavelength absorbing material, the above-described quinophthalone compound was used in Examples 41 to 43, 48, 50, and 51, and the nickel azo compound was used in Examples 44 to 47 and 49.
On the other hand, as the infrared absorbing organic compound, the above-described diimonium compound was used in Examples 41 to 47, 50, and 51, and the phthalocyanine-based compound was used in Examples 48 and 49.

[Example 52]
Infrared reflective film (Scotch Tint S90 manufactured by Sumitomo 3M Co., Ltd .: visible light transmittance 89%, solar reflectance 22%) is sandwiched between the heat ray shielding film obtained in Example 5 and a transparent PVB intermediate film, and two more sheets Were bonded together by a known method to obtain a heat ray shielding laminated transparent base material according to Example 52.
And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 52 was measured similarly to Example 1. FIG. During the measurement, optical characteristics were measured from the glass surface in contact with the transparent PVB intermediate film.
Table 3 shows the concentration of the fine particles a, the type and concentration of the selected wavelength absorbing material, and the type and concentration of the infrared absorbing organic compound in Example 52. Furthermore, Table 3 shows the measurement results of optical characteristics of the heat-shielding transparent substrate according to Example 52.

[Examples 53 to 55]
Using the infrared reflective film described in Example 52 and the heat ray shielding film obtained in Examples 6 to 8, the same operation as in Example 52 is performed, and the heat ray shielding laminated transparent base according to Examples 53 to 55 is performed. The material was obtained.
The optical characteristics of the heat ray shielding laminated transparent base materials according to Examples 53 to 55 were measured in the same manner as in Example 1. Table 3 shows the concentration of the fine particles a, the type and concentration of the selective wavelength absorbing material, and the type and concentration of the infrared absorbing organic compound in Examples 53 to 55. Furthermore, the optical characteristic measurement result of the heat ray shielding laminated transparent base material which concerns on Examples 53-55 was shown in Table 3.

[Evaluation of Examples 1 to 16 and Comparative Examples 1 to 4 and 6 to 9]
In Examples 1 to 16, a lower solar transmittance was obtained by using the selective wavelength absorbing material in combination with the ITO fine particles.
The result will be described with reference to FIG.
FIG. 1 is a graph in which the vertical axis represents solar transmittance and the horizontal axis represents visible light transmittance. And the data of Examples 1-4 whose weight ratio A of (ITO fine particle a / selection wavelength absorption material <quinophthalone compound>) is 99.5 / 0.5 is plotted by-(circle)-to the said graph, 99 / The data of Examples 5-8, which is 1, is plotted with-□-, the data of Examples 9-12, which is 98/2, is plotted with -Δ-, and the data of Examples 13-16, which is 97/3, are plotted. Is plotted with − ◇ −, data of Comparative Examples 1 to 4 being 100/0 is plotted with − × −, and data of Comparative Examples 6 to 9 being 96/4 is plotted with − + −. .

As shown in Examples 1 to 16, the weight ratio of the selective wavelength absorbing material to the ITO fine particles (ITO fine particles a / selective wavelength absorbing material <quinophthalone compound>) is 99.9 / 0.1 to 97 as shown in Examples 1 to 16. It was found that by setting the ratio to / 3, higher heat shielding performance can be obtained as compared with the case where ITO fine particles are used alone as shown in Comparative Examples 1 to 4.
On the other hand, as shown in Comparative Examples 6 to 9, when (ITO fine particles a / selective wavelength absorbing material <quinophthalone compound>) is 96/4 and out of the range of 99.9 / 0.1 to 97/3, the ITO fine particles It has been found that the heat shielding properties are lowered even when compared with the case where is used alone.

[Evaluation of Examples 17 to 28 and Comparative Examples 1 to 4]
Also in Examples 17 to 28, the lower solar transmittance can be obtained by using the selective wavelength absorbing material in combination with the ITO fine particles.
The result will be described with reference to FIG.
FIG. 2 is a graph similar to FIG. 1, and the data of Examples 17 to 20 in which the weight ratio A of (ITO fine particles a / selective wavelength absorbing material <nickel azo compound>) is 99.5 / 0.5 is − ◯ − The data of Examples 21-24, which are 99/1, are plotted with-□-, the data of Examples 25-28, which are 98/2, are plotted with -Δ-, and the comparison is 100/0. The data of Examples 1-4 are plotted by -x-.

  From FIG. 2, by setting the weight ratio of the selected wavelength absorbing material and the ITO fine particles (ITO fine particles a / selected wavelength absorbing material <nickel azo compound>) to a range of 99.9 / 0.1 to 97/3, As shown in Comparative Examples 1 to 4, it was found that higher heat shielding performance can be obtained as compared with the case where ITO fine particles are used alone.

[Evaluation of Examples 29 to 33 and Comparative Examples 1 to 4 and 5]
In Examples 29 to 33, the lower solar transmittance was obtained by using the selective wavelength absorbing material in combination with the ITO fine particles.
The result will be described with reference to FIG.
FIG. 3 is a graph similar to FIG. 1, in which the data of Example 29 in which the selected wavelength absorbing material is an isoindoline compound is plotted with − ◯ −, and the data of Example 30 with a quinoxaline compound is plotted with − □ −. The data of Example 31 which is a condensed diazo compound is plotted with -Δ-, the data of Example 32 which is an isoindolinone compound is -−, and the data of Example 33 which is a bismuth vanadate compound is -X-. The data of Comparative Example 5, which is a benzimidazolone compound, is plotted with-*-, and the data of Comparative Examples 1 to 4 to which these selective wavelength absorbing materials are not added are plotted with-++.

  FIG. 3 shows that the ITO fine particles are used in combination with a selective wavelength absorbing material having a transmission profile with a light transmittance of 90% or more at a wavelength of 550 nm and a light transmittance of 40% or less at a wavelength of 450 nm. Thus, it was found that higher heat shielding performance can be obtained as compared with the case where ITO fine particles are used alone.

  On the other hand, in Comparative Example 5, the transmission profile of the selected wavelength absorbing material used is such that the transmittance of light with a wavelength of 550 nm is 90% or less, and the transmittance of light with a wavelength of 450 nm is 40% or more, Since it is out of the range defined in the present invention, the heat shielding properties were lowered even when compared with the case where ITO fine particles were used alone.

[Evaluation of Examples 34 to 39 and Comparative Example 10]
In Examples 34 to 39, a lower solar transmittance was obtained by using the selected wavelength absorbing material in combination with the ATO fine particles. In addition, by using the selected wavelength absorbing material having a transmittance of 90% or more of light with a wavelength of 550 nm and a transmittance profile of 40% or less of light with a wavelength of 450 nm, together with the ATO fine particles, As compared with the case where the ATO fine particles described in Comparative Example 10 were used alone, it was found that higher heat shielding performance was obtained.

  It has also been found that ITO fine particles can be similarly applied as ATO fine particles as fine particles having a heat ray shielding function according to the present invention. Therefore, it is considered that the same is true when ITO fine particles and ATO fine particles are mixed and used.

[Evaluation of Examples 5 to 8, 40 to 47, and Comparative Examples 1 to 4]
In Examples 40 to 47, the lower solar transmittance was obtained by using the selected wavelength absorbing material and the infrared absorbing organic compound in combination with the ITO fine particles.
The result will be described with reference to FIG.
FIG. 4 is a graph similar to FIG. 1. The weight ratio A of (ITO fine particles / selective wavelength absorbing material <quinophthalone compound>) is 99/1, and (ITO fine particles / infrared absorbing organic compound <diimonium compound>) The data of Examples 40 to 43 in which the weight ratio B is 99/1 are plotted by -o-, and the weight ratio A of (ITO fine particles / selective wavelength absorbing material <nickel azo compound>) is 99/1. The data of Examples 44 to 47 in which the weight ratio B of ITO fine particles / infrared absorbing organic compound <diimonium compound> is 99/1 is plotted with-□-, and (ITO fine particles / selective wavelength absorbing material <quinophthalone compound>>), The data of Examples 5 to 8 in which the weight ratio A is 99/1 is plotted by-[Delta]-, and the data of Comparative Examples 1 to 4 in which 100/0 is plotted by -x-.

  From FIG. 4, it is compared with the case where the selected wavelength absorbing material and the infrared absorbing organic compound are used in combination with the ITO fine particles, when the ITO fine particles are used alone, or when the selected wavelength absorbing material and the ITO fine particles are used in combination. As a result, it was found that higher heat shielding performance can be obtained.

[Evaluation of Examples 48 to 51 and Comparative Examples 1 to 4]
In Examples 48 to 51, a selective wavelength absorbing material and an infrared absorbing organic compound were used in combination with ITO fine particles. In Examples 48 to 51, solar radiation transmittance lower than that of Comparative Examples 1 to 4 in which the combination was not performed was obtained by performing the combination. Further, it has been found that by using the selective wavelength absorbing material and the infrared absorbing organic compound in combination with the ITO fine particles, higher heat shielding performance can be obtained as compared with the case where the ITO fine particles are used alone.

  Here, in Example 48, the weight ratio A of (ITO fine particles / selective wavelength absorbing material <quinophthalone compound>) is 99/1 and the weight ratio B of (ITO fine particles / infrared absorbing organic compound <phthalocyanine compound>) is B / 1. Is 99/1, and the weight ratio B of (ITO fine particles / infrared absorbing organic compound <phthalocyanine compound>) is 99/1. In Example 49, (ITO fine particles / selective wavelength absorbing material <nickel azo compound>) The weight ratio A is 99/1, and the weight ratio B of (ITO fine particles / infrared absorbing organic compound <phthalocyanine compound>) is 99/1. In Example 50, (ITO fine particles / selective wavelength absorbing material <quinophthalone compound> >) And the weight ratio B of (ITO fine particles / infrared absorbing organic compound <diimonium compound>) is 99/1. In Example 51, the weight ratio A of (ITO fine particles / selective wavelength absorbing material <quinophthalone compound>) is 99/1, and the weight of (ITO fine particles / infrared absorbing organic compound <diimonium-based compound>). The ratio B was 99.5 / 0.5.

[Evaluation of Examples 52 to 55]
In Examples 52 to 55, the selective wavelength absorbing material and the infrared reflective film were used in combination with ITO fine particles. In Examples 52-55, the solar radiation transmittance lower than Comparative Examples 1-4 which are not performing the said combination was obtained by performing the said combined use. It has also been found that by using the selected wavelength absorbing material, the infrared reflective film, and the ITO fine particles in combination, higher heat shielding performance can be obtained as compared with the case where the ITO fine particles are used alone.

Claims (19)

A composition containing a compound having a heat ray shielding function, a dispersant, a selective wavelength absorbing material, a polyvinyl acetal resin, and a plasticizer,
The compound having the heat ray shielding function is at least one selected from indium tin oxide fine particles and antimony tin oxide fine particles, and the dispersant is at least one main chain selected from urethane, acrylic and styrene. Having a amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group, the selective wavelength absorbing material has a light transmittance of 90% or more at a wavelength of 550 nm, And the composition which has the transmittance | permeability profile whose light transmittance of wavelength 450nm is 40% or less.   The composition according to claim 1, wherein the indium tin oxide fine particles and the antimony tin oxide fine particles are fine particles having an average particle diameter of 40 nm or less.   2. The selective wavelength absorbing material is at least one selected from isoindoline compounds, isoindolinone compounds, quinoxaline compounds, quinophthalone compounds, condensed diazo compounds, nickel azo compounds, and bismuth vanadate compounds. A composition according to 1.   The selected wavelength absorbing material has a transmission profile in which the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 15% or less. A composition according to any one of the above.   The composition according to claim 1, wherein the selective wavelength absorbing material is at least one selected from a quinophthalone compound and a nickel azo compound.   The weight ratio of the selective wavelength absorbing material and the indium tin oxide fine particles and / or antimony tin oxide fine particles oxide fine particles is [(indium tin oxide fine particles and / or antimony tin oxide fine particles) / selective wavelength absorbing material. The composition according to claim 1, wherein the composition is in the range of 99.9 / 0.1 to 97/3.   The composition according to claim 1, wherein the heat ray shielding film further contains an infrared absorbing organic compound.   The infrared absorbing organic compound is a phthalocyanine compound, naphthalocyanine compound, imonium compound, diimonium compound, polymethine compound, diphenylmethane compound, triphenylmethane compound, quinone compound, azo compound, pentadiene compound, azomethine compound, squarylium compound, organometallic complex The composition according to claim 7, wherein the composition is at least one selected from cyanine compounds.   The composition according to claim 8, wherein the infrared absorbing organic compound is at least one selected from a phthalocyanine compound and a diimonium compound.   The weight ratio of the infrared absorbing organic compound and the indium tin oxide fine particles and / or antimony tin oxide fine particles oxide fine particles is [(indium tin oxide fine particles and / or antimony tin oxide fine particles) / infrared absorptivity. The composition according to any one of claims 7 to 9, wherein the organic compound is in a range of 99.5 / 0.5 to 95/5. A method for producing the composition according to any one of claims 1 to 10,
A compound having a heat ray shielding function selected from one or more types selected from indium tin oxide fine particles and antimony tin oxide fine particles, a dispersant, and a plasticizer are mixed and pulverized and dispersed. A dispersion step of a compound having a heat ray shielding function to be processed into a plasticizer dispersion;
A process of dispersing the selected wavelength absorbing material by mixing the selected wavelength absorbing material and the plasticizer and crushing and dispersing the selected wavelength absorbing material to obtain a plasticizer dispersion;
The manufacturing method of the composition characterized by including the mixing process which mixes the plasticizer dispersion liquid of the compound which has a heat ray shielding function, the plasticizer dispersion liquid of selective wavelength absorption material, a plasticizer, and a polyvinyl acetal resin.   In the dispersion step of the selective wavelength absorbing material, a dispersion step of further adding an organic solvent having a boiling point of 120 ° C. or less to pulverize and disperse the compound having a heat ray shielding function to obtain a plasticizer dispersion, and the organic solvent The method for producing a composition according to claim 11, further comprising a drying step of removing from the plasticizer dispersion. A method for producing the composition according to any one of claims 1 to 10,
A compound having a heat ray shielding function selected from one or more types selected from indium tin oxide fine particles and antimony tin oxide fine particles, a dispersant, and an organic solvent are mixed and pulverized and dispersed. A dispersion step of a compound having a heat ray shielding function to be processed into a dispersion;
A drying step of removing the organic solvent from the dispersion to obtain a dispersion;
A process for producing a plasticizer dispersion of a selected wavelength absorbing material, wherein the selected wavelength absorbing material and a plasticizer are mixed and the selected wavelength absorbing material is pulverized and dispersed;
The manufacturing method of the composition characterized by including the mixing process of mixing the dispersion of the compound which has a heat ray shielding function, the plasticizer dispersion liquid of a selective wavelength absorption material, a plasticizer, and a polyvinyl acetal resin.   The method for producing a composition according to claim 12 or 13, wherein the drying step is drying under reduced pressure.   The method for producing a composition according to any one of claims 11 to 14, wherein the pulverization / dispersion treatment is selected from a bead mill, a ball mill, a sand mill, and an ultrasonic dispersion.   A method for producing a heat ray shielding film, comprising kneading the composition obtained by the production method according to any one of claims 11 to 15 and forming the composition into a sheet shape.   The method for producing a heat ray shielding film according to claim 16, wherein the composition is kneaded by a twin screw extruder.   The method for producing a heat ray shielding film according to claim 16 or 17, wherein the composition is processed into a sheet by an extrusion calender roll method. The manufacturing method of the heat ray shielding laminated transparent base material characterized by sticking together the heat ray shielding film obtained by the manufacturing method in any one of Claim 16 to 18 with a plurality of transparent base materials.

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