JP2005179121A - Solar radiation shielding particulate and solar radiation shielding resin material dispersed with the particulate in resin component, and solar radiation shielding particulate dispersing element used for manufacturing solar radiation shielding resin material, and solar radiation shielding resin base material and solar radiation shielding composite base material obtained by using solar radiation shielding resin material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide solar radiation shielding particulates having transmission performance of a high solar radiation shielding function and a high visible light region and having a color tone of blue, a solar radiation shielding resin material dispersed with the particulates in the resin component, and a solar radiation shielding particulate dispersing element used for manufacturing the solar radiation shielding resin material, and a solar radiation shielding resin base material and solar radiation shielding composite base material obtained by using the solar radiation shielding resin material. <P>SOLUTION: The solar radiation shielding particulates are composed of titanium nitride particulates which have a crystal structure of a face-centered cubic crystal of ≥0.423 nm in lattice constant, is ≤250 nm in average grain size, and is L*=35 to 60, a*=-0.1 to 10.0, and b*=-0.5 to 15.0 in powder color due to diffused reflected light in an L*a*b* color system. Also, the solar radiation shielding resin material is prepared by dispersing the solar radiation shielding particulates into the resin component. The solar radiation shielding resin base material and the solar radiation shielding composite base material are obtained by molding the solar radiation shielding resin material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to solar shading fine particles and solar shading resin materials applied to vehicles, buildings, general housing window materials, and arcades, dome roof materials, etc., and in particular, has a high solar shading function and a visible light region. Solar radiation-shielding fine particles having high transmission performance and blue color tone, solar radiation-shielding resin material in which these fine particles are dispersed in a resin component, and solar radiation-shielding fine particle dispersion used in the production of solar radiation shielding resin materials The present invention relates to a solar radiation shielding resin base material and a solar radiation shielding composite base material obtained by using a body and a solar radiation shielding resin material.

  Conventionally, so-called openings such as roofs of various buildings and windows of vehicles are made of a transparent glass plate or resin plate for taking in sunlight. However, the sun rays include ultraviolet rays and infrared rays in addition to visible rays. In particular, near infrared rays of 800 to 2500 nm out of infrared rays are called heat rays, and cause the indoor temperature to rise by entering from the opening. Become.

  Therefore, in recent years, heat ray shielding materials have been studied as window materials for various buildings and vehicles, etc., which sufficiently absorb visible light and shield the heat rays to maintain the brightness while simultaneously suppressing the temperature rise in the room. Proposed. In addition, from the viewpoint of design properties, there is an increasing demand for a heat ray shielding material having a blue color tone, a high solar shading function, a visible light region transmission performance, and a high weather resistance.

  For example, Patent Document 1 and Patent Document 2 propose a heat ray shielding plate formed by kneading mica coated with titanium oxide as heat ray reflective particles (sunlight shielding fine particles) in a transparent resin such as an acrylic resin or a polycarbonate resin. Has been. However, in this method, it is necessary to add a large amount of heat ray reflective particles in order to improve the heat ray reflectivity. For this reason, when the addition amount of the heat ray reflective particles is increased, the visible light transmittance is lowered. On the other hand, if the addition amount of the heat ray reflective particles is reduced, it is difficult to satisfy both the heat ray shielding property and the visible light transmittance at the same time. Further, when a large amount of heat ray reflective particles are blended, there is a drawback in strength that the physical properties of the transparent resin as a base material, particularly impact resistance and toughness, are lowered.

  Therefore, Patent Document 3 proposes a heat ray reflective glass in which various metals and metal oxide materials such as nitrides such as TiN and metal oxides are sputtered onto the glass. However, this method requires large-scale equipment and vacuum equipment, and there are problems in productivity, large area, production cost, etc., and in this heat ray reflective glass, light in the visible light region other than near infrared rays is reflected or reflected simultaneously. It has the property of absorbing and has the disadvantage of giving a glimmering appearance like a mirror and detracting from aesthetics. Furthermore, this method often has high film conductivity, and if the film conductivity is high, there is a problem that radio waves from mobile phones, TVs, radios, etc. are reflected to cause radio interference.

  Patent Document 4 discloses a heat ray reflective glass formed by forming a titanium nitride film on a colored glass by a vacuum deposition method, a sputtering method, or the like, and forming a metal oxide film on the titanium nitride film. Proposed. That is, in this heat ray reflective glass, the visible light reflectance when viewed from the surface side where the glass plate coating is not formed is 25% or less, and the reflection color viewed from the side where the glass plate coating is not formed. It exhibits green and blue color tones, and the drawbacks such as reflected light damage in Patent Document 3 are improved. However, this method also requires a large-scale device and vacuum equipment, and still has problems in productivity, area increase, production cost, etc., as in Patent Document 3.

On the other hand, methods have been developed in which the above-described Patent Documents 3 to 4 are free from adverse effects such as productivity, area increase, and production cost. For example, Patent Document 5 discloses a heat ray shielding film in which at least one of titanium nitride fine particles, zirconium nitride fine particles, hafnium fine particles, vanadium nitride fine particles, niobium nitride fine particles, and tantalum nitride fine particles having an average particle diameter of 100 nm or less is dispersed. The light transmittance in the visible light region is high and the reflectance is low, the light transmittance in the near infrared region is low and the reflectance is high, and the conductivity of the film is about 10 A heat ray shielding film (sunlight shielding film) that can be controlled to ⁶ Ω / □ or more is disclosed. However, Patent Document 5 does not elucidate the optimization of the physical properties of the material used (sunlight shielding fine particles), and even if the dispersion of the sunscreening fine particles in the heat ray shielding film (sunlight shielding film) is advanced, a bright blue color is achieved. The color tone of was not developed. Further, the invention described in Patent Document 5 is limited to the coating film formed on the transparent substrate, and has not been studied at all for the method of kneading the solar shielding fine particles into the resin component.

Similarly, in Patent Document 6, as the deeply colored component, inorganic fine particles having a particle diameter of 200 nm or less composed of any one or more of titanium nitride oxide, titanium nitride, carbon black, and iron oxide, and, if necessary, a solar radiation shielding component , An antimony-added tin oxide (ATO) and / or tin-added indium oxide (ITO) inorganic fine particles having a particle diameter of 200 nm or less, and a deeply colored ink for obtaining a film capable of simultaneously providing privacy protection and solar shading function Etc. have been proposed. However, as in the above-mentioned Patent Document 5, the optimization of the physical properties of inorganic fine particles as a dark coloring component has not been elucidated, and it has not yet been possible to express a vivid blue color tone as a characteristic of the obtained film. It was.
JP-A-5-78544 JP-A-2-173060 JP-A-6-345489 JP 2000-233946 A Japanese Patent Laid-Open No. 11-263639 JP 2001-262016 A

  The present invention has been made paying attention to such problems, and the problem is that the solar shading fine particles having a high solar shading function and a high transmission performance in the visible light region and having a blue color tone. A solar shading resin material in which the fine particles are dispersed in a resin component, and a solar shading resin base material obtained by using the solar shading fine particle dispersion and the solar shading resin material used in the production of the solar shading resin material. It is to provide a shielding composite substrate.

  Therefore, in order to obtain a solar shading fine particle having a high solar shading function and a high transmission performance in the visible light region and having a blue color tone, the present inventors have nitrided a large amount of free electrons as a characteristic of the material itself. Various studies were conducted focusing on titanium. As a result, titanium nitride fine particles with specific conditions have a maximum transmittance in the visible light region and a strong plasma reflection in the near infrared region close to the visible light region so that the transmittance has a minimum. In addition, the inventors have discovered the fact that this transmitted color exhibits a beautiful blue color tone. In addition, the surface of the titanium nitride fine particles having specific conditions may be coated with a compound containing any element selected from the group of Si, Al, Zr, and Ti, thereby providing high weather resistance. I came to find that it would be possible. The present invention has been completed based on such technical findings.

That is, the invention according to claim 1
Assuming solar shielding particles that transmit visible light and shield heat rays,
It has a face-centered cubic crystal structure with a lattice constant of 0.423 nm or more, an average particle size of 250 nm or less, and the powder color by diffuse reflection in the L ^* a ^* b ^* color system is L ^* = 35 to 60, a ^* = − 0.1 to 10.0, and b ^* = − 0.5 to 15.0.

The invention according to claim 2
On the premise of solar radiation shielding fine particles according to the invention of claim 1,
The above-mentioned maximum is obtained when the transmittance of the diluting liquid in which the solar shielding fine particles are dispersed has a maximum value at a wavelength of 400 to 600 nm, a minimum value at a wavelength of 700 to 1100 nm, and a visible light transmittance of 20% or more and less than 80%. The difference between the value and the minimum value is 15 points or more in percentage,
The invention according to claim 3
On the premise of the solar radiation shielding fine particles according to the invention of claim 1 or 2,
It is characterized by being coated with a compound containing any element selected from the group of Si, Al, Zr and Ti.

Next, the invention according to claim 4 is:
Assuming a solar radiation shielding resin material containing a resin component and solar radiation shielding fine particles dispersed in the resin component,
The solar shading fine particles dispersed in the resin component is composed of the solar shading fine particles according to any one of claims 1 to 3,
The invention according to claim 5
Based on the solar radiation shielding resin material according to the invention of claim 4,
The resin component is any one of a polycarbonate resin, an acrylic resin, a fluorine resin, a polyester resin, a polyvinyl acetal resin, a polyvinyl butyral resin, and an ethylene-vinyl acetate copolymer resin.

The invention according to claim 6
Assuming a sunscreen resin base material,
The solar radiation shielding resin material according to claim 4 or 5 is formed into a flat or three-dimensional shape,
The invention according to claim 7 provides:
Assuming a solar-shielding composite substrate,
It is comprised by the solar radiation shielding resin base material which shape | molded the solar radiation shielding resin material of Claim 4 or 5 in the sheet form, and a pair of plate-like glass bonded together on both surfaces of this solar radiation shielding resin base material, or Claim 4 Or it is comprised by the solar radiation shielding resin base material which shape | molded the solar radiation shielding resin material of 5 in the sheet form, and one or more other resin plates bonded together by this solar radiation shielding resin base material.

Next, the invention according to claim 8 is:
Premise of the solar shading fine particle dispersion used for producing the solar shading resin material according to claim 4 or 5,
An organic solvent and / or a plasticizer, the solar shading fine particles according to any one of claims 1 to 3, and a polymer-based dispersant for dispersing the solar shading fine particles as main components, and for sun shading The mixing ratio of the fine particles and the polymer dispersant is 0.3 parts by weight or more and less than 10 parts by weight of the polymer dispersant with respect to 1 part by weight of the solar radiation shielding particles,
The invention according to claim 9 is
Premise of the solar shading fine particle dispersion used for producing the solar shading resin material according to claim 4 or 5,
The solar radiation shielding fine particles according to any one of claims 1 to 3 and a polymer dispersing agent that disperses the solar radiation shielding fine particles, and the mixing ratio of the solar radiation shielding fine particles and the polymer dispersing agent is The amount of the polymer dispersant is not less than 0.3 parts by weight and less than 10 parts by weight with respect to 1 part by weight of the solar radiation shielding fine particles, and is substantially free of solution components.

The solar radiation shielding fine particles according to the present invention have a face-centered cubic crystal structure with a lattice constant of 0.423 nm or more, an average particle size of 250 nm or less, and an L ^* a ^* b ^* color system. The powder color by diffuse reflected light in is composed of titanium nitride fine particles having L ^* = 35-60, a ^* = − 0.1 to 10.0, and b ^* = − 0.5 to 15.0.

  Therefore, the transmittance of the diluted liquid in which the titanium nitride fine particles are dispersed has a maximum value at a wavelength of 400 to 600 nm, a minimum value at a wavelength of 700 to 1100 nm, and a visible light transmittance of 20% or more and less than 80%. The difference between the maximum value and the minimum value is 15 points or more as a percentage, and the color tone of blue is exhibited. Therefore, the solar radiation shielding function is high, the transmission performance in the visible light region is high, and the color tone of blue is provided. It is possible to obtain solar radiation shielding fine particles.

  Further, according to the solar shading resin material according to the present invention in which the solar shading fine particles are dispersed in the resin component, the window having a high solar shading function and a high transmission performance in the visible light region and having a blue color tone. It becomes possible to obtain a solar radiation shielding resin base material such as a material or a solar radiation shielding composite base material.

  Furthermore, according to the liquid or powdery solar shading fine particle dispersion according to the present invention in which the solar shading fine particles are dispersed, the solar shading resin material in which the solar shading fine particles are dispersed in the resin component can be simply and It becomes possible to manufacture at low cost.

  Hereinafter, the present invention will be described in detail.

First, the solar shading fine particles according to the present invention have a face-centered cubic crystal structure with a lattice constant of 0.423 nm or more, an average particle size of 250 nm or less, and specified by the International Commission on Illumination (CIE). Powder color by diffuse reflection in the L ^* a ^* b ^* color system (JIS Z 8729) is L ^* = 35-60, a ^* = − 0.1 to 10.0, b ^* = − 0. The titanium nitride fine particles are characterized by being composed of 5 to 15.0 titanium nitride fine particles. The titanium nitride fine particles have both excellent solar radiation shielding characteristics and beautiful blue tone.

  By the way, industrialized titanium nitride (TiN) is a typical material that forms interstitial compounds, and is known to have a face-centered cubic crystal structure and a lattice constant of 0.424 nm. Titanium nitride (TiN) has a B1 type (NaCl type) crystal structure and can be expressed as TiNx, with N entering the Ti lattice as a penetrating solid solution. At this time, the composition region is broadly set as 0.8 <x <1.16. obtain. It is known that when x is changed within this composition region, the lattice constant of TiN changes within the range of 0.423 to 0.425. By the way, there is a powder having a lattice constant of less than 0.423 nm as commonly obtained titanium nitride (TiN). However, a powder having a lattice constant of less than 0.423 nm as a result of research by the present inventors is not desirable for reasons such as a deviation in the equivalent ratio of nitrogen to titanium in titanium nitride or the influence of oxidation. It has been found that the optical characteristics to be obtained cannot be obtained.

Also, the powder color by diffuse reflection in the L ^* a ^* b ^* color system is L ^* = 35-60, a ^* = − 0.1 to 10.0, b ^* = − 0.5 to 15.0 In the case of titanium nitride fine particles outside the above range, the desired solar radiation shielding characteristics cannot be obtained due to excessive oxidation of the titanium nitride surface of the raw material, and vivid blue does not appear even if the dispersion is advanced This has also been confirmed by experiments by the inventors. The surface of the titanium nitride fine particles is preferably not oxidized, but usually the surface is often slightly oxidized, and surface oxidation is inevitable to some extent during the fine particle dispersion step. However, even in such a case, if the above-described powder color condition is satisfied, the effectiveness of exhibiting the solar radiation shielding effect is not changed, and the same applies to the case where a part thereof is changed to oxynitride.

  Visible light transmission occurs when the particle diameter of the titanium nitride fine particles is sufficiently smaller than the visible light wavelength and is uniformly dispersed in the transparent medium. Even in this state, the infrared light shielding property can be kept sufficiently strong. The reason for this has not been elucidated in detail, but since the amount of free electrons in the fine particles is large and the plasma frequency of free electron plasmons inside and on the surface of the particles is just in the vicinity of visible to near infrared, this wavelength region It is thought that the heat rays of are selectively reflected and absorbed. That is, the titanium nitride fine particles used in the present invention are sufficiently finely pulverized, and the liquid transmission profile obtained by diluting and dispersing the fine particles has a maximum transmittance at a wavelength of 400 to 600 nm and a minimum at a wavelength of 700 to 1100 nm. It was confirmed that when the difference between the maximum value and the minimum value of the transmittance was 20% or more and less than 80%, the percentage was 15 points or more. Considering that the visible light region is 380 to 780 nm and the visibility is a bell-shaped peak having a peak at around 550 nm, it has the transmittance profile as described above, so that visible light is effectively transmitted, It can be understood that it has an optical characteristic of effectively reflecting and absorbing heat rays other than the above.

  The solar shading fine particles according to the present invention are required to have an average particle size of 250 nm or less. When the average particle diameter exceeds 250 nm, the above-described specific transmittance profile, that is, the transmittance has a maximum value at a wavelength of 400 to 600 nm and a minimum value at a wavelength of 700 to 1100 nm, and the above-mentioned maximum of transmittance. When the difference between the minimum value and the minimum value is 20% or more and less than 80%, a profile with a percentage of 15 points or more cannot be obtained, and the transmission color is monotonously reduced from black to gray. . Moreover, when the average particle diameter exceeds 250 nm, the tendency of the fine particles to aggregate becomes strong when dispersed in the resin, causing the fine particles to settle. Further, fine particles exceeding 250 nm or coarse particles obtained by agglomerating them become a light scattering source and cause clouding (haze), or cause a decrease in visible light transmittance.

  Such titanium nitride fine particles can be produced by a dry process such as a thermal plasma method or a solid phase reaction method in a reducing atmosphere. Even if the average particle size of the fine particles in the raw material stage is larger than 250 nm, there is no particular problem as long as a pulverization step is introduced and the final particle size can be reduced to 250 nm or less.

  Next, the surface treatment of the titanium nitride fine particles is preferable because it can improve the weather resistance of the fine particles and can be easily and uniformly introduced into the resin component. The surface treatment method is not particularly limited. For example, in the step of pulverizing the fine particles, it is usual to use an alkoxide based on Si, Al, Zr, Ti, a coupling agent, a surfactant, etc. together with a general organic solvent. The compound containing Si, Al, Zr, and Ti elements is uniformly coated on the surface of the fine particles by performing a pulverization process and, if necessary, a hydrolysis process, a polycondensation process, a sintering process, etc. be able to. The pulverization method is not particularly limited, and methods such as a ball mill, a sand mill, ultrasonic dispersion, and a bead mill can be used. At this time, various dispersants may be added as necessary. By performing these surface coating treatments, the surface state of the titanium nitride fine particles becomes more stable, and the weather resistance is improved as compared with the untreated titanium nitride fine particles.

Further, fine particles of titanium nitride having the above-mentioned crystal structure, average particle diameter, and powder color requirements by diffuse reflected light in the L ^* a ^* b ^* color system, or titanium nitride subjected to surface coating treatment The solar radiation shielding resin material described below is constituted by dispersing fine particles in a resin component. When this solar radiation shielding resin material is produced, a solar radiation shielding fine particle dispersion is applied. That is, liquid solar radiation shielding mainly composed of an organic solvent and / or a plasticizer, titanium nitride fine particles having the above-mentioned requirements, or titanium nitride fine particles subjected to surface coating treatment, and a polymer dispersant. A solar shading resin material in which titanium nitride fine particles are dispersed in a resin component using a fine particle dispersion for heat treatment or a powdery solar shading fine particle dispersion obtained by heating and removing a solution component by a known method can do. Incidentally, the powdery solar shielding fine particle dispersion obtained by heating and removing the solution component by a known method does not require any special equipment or treatment when introduced into an organic solvent, a plasticizer, or a resin. Fine particles can be uniformly dispersed by simple stirring. At this time, if the polymer dispersant is less than 0.3 part by weight with respect to 1 part by weight of the solar shading fine particles, aggregation or the like may occur when it is introduced into the organic solvent, plasticizer or resin. This causes haze in the material. On the other hand, if the amount is 10 parts by weight or more, the polymer dispersant in the solar shading resin material becomes excessive, which may adversely affect the weather resistance of the solar shading resin material. Therefore, it is desirable that the mixing ratio of the solar shielding fine particles and the polymer dispersant is 0.3 part by weight or more and less than 10 parts by weight of the polymer dispersant with respect to 1 part by weight of the solar radiation shielding particles.

  In addition, the above-mentioned solar shading fine particle dispersion is in a liquid form that does not remove the solution components added in the pulverization and surface treatment steps as described above, in addition to the powder obtained by heating and removing the solution components by a known method. Alternatively, it may be a material dispersed in a raw material or a plasticizer according to the resin used for the solar shading resin material. The organic solvent and plasticizer used here are not particularly limited, and can be selected according to the conditions for forming the resin to be blended, and general organic solvents and plasticizers can be used. Moreover, you may adjust pH by adding an acid and an alkali as needed. Examples of the polymer dispersant include polyacrylate dispersants, polyurethane dispersants, polyether dispersants, polyester dispersants, polyester urethane dispersants, and the like. SAN NOPKO (SAN NOPKO) brand name SN thickener A-850, SN thickener A-815, EFKA ADDITIVES BV brand name EFKA4500, EFKA4530, BYK-Chemie company The product name Disperbyk-116 and the like manufactured by Efka Additives Co., Ltd. are trade names of EFKA4046, EFKA4047, EFKA4520, Cognis, TEXAPHOR P60, TEXAPHOR P63, and TEXAPHOR P610. Etc., and as a polyether-based dispersant, trade names of SN Nopco Corporation SN thickener A-801, SN thickener A-802, SN thickener A -803, SN thickener A-804, SN thickener A-806, trade names manufactured by Enomoto Kasei Co., Ltd. DISPARLON DA234, DISPARLON DA325, etc. are exemplified. As polyester-based dispersants, trade names manufactured by Avecia, Solsperse 22000, Solsperse 24000SC , Solsperse24000GR, Solsperse26000, Solsperse27000, Solsperse28000, Solsperse36000, Solsperse36600, Solsperse38500, trade names made by Enomoto Kasei Co., Ltd. DISPARLON DA70350, DISPARLON DA705, DISPARLON DA725, DISPARLON DA860, DISPARLON DA873N, etc. In addition, the state of the polymer dispersant at normal temperature can be used in any of liquid, solid, and gel.

  And, in order to produce a solar shading resin material using the above-mentioned liquid or powdery solar shading fine particle dispersion, any method can be used as long as the solar shading fine particles can be uniformly dispersed in the resin used for the solar shading resin material. good. It is also possible to use a method of uniformly melt-mixing with a kneader such as a general ribbon blender, tumbler, nauter mixer, Henschel mixer, etc., and a Banbury mixer, kneader, roll, single screw extruder, twin screw extruder, etc. Is possible.

  For example, when the resin used for the solar shading resin material is a polycarbonate resin, a powdery solar shading fine particle dispersion is added to a dihydric phenol used as a raw material of the resin, melt-mixed, and exemplified by phosgene. By reacting with the carbonate precursor, a mixture (sunlight shielding resin material) in which fine particles are uniformly dispersed in the resin can be prepared. Further, when the resin used for the solar shading resin material is an acrylic resin, a liquid solar shading fine particle dispersion is added to methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate or the like that is a raw material of the acrylic resin, By mixing uniformly by a method and polymerizing by a known method such as suspension polymerization or soul polymerization, a mixture (sunlight shielding resin material) in which fine particles are uniformly dispersed in an acrylic resin can be prepared. Further, when the resin used for the solar shading resin material is a polyvinyl butyral resin, the powdery solar shading fine particle dispersion is made of triethylene glycol di-2 ethyl butyrate (3GH) or triethylene glycol di-2 ethyl. Mixing and kneading with a general plasticizer such as hexanoate (3GO) and mixing and kneading it with a polyvinyl butyral resin by a known method, a mixture (sunlight shielding resin material) in which fine particles are uniformly dispersed in the resin Can be prepared.

  Next, the mixture (sunlight shielding resin material) thus obtained is molded into a planar shape or a curved surface shape (that is, a planar or three-dimensional shape) by a known molding method such as injection molding, extrusion molding, or compression molding. Thus, it is possible to produce a solar radiation shielding resin substrate. Also, a mixture (sunlight shielding resin material) in which fine particles for solar shading are uniformly dispersed in the resin is once pelletized by a granulator, and the pellet is added and mixed in the resin, and the solar shading is performed by the same molding method as above. A resin base material can also be manufactured. In addition, the thickness of a solar radiation shielding resin base material can be arbitrarily adjusted as needed from a plate shape to a thin film shape.

  Further, it is also possible to use a solar radiation shielding resin base material formed into a sheet shape as a solar radiation shielding composite base material by laminating it with two plate glasses or one or more other resin plates. For example, a polycarbonate resin base material and a glass plate formed into a sheet shape are bonded together using an adhesive and used as a solar radiation shielding composite base material, or a polyvinyl butyral resin base material formed into a sheet shape is used as an intermediate film And this can be used as a solar radiation shielding composite base material sandwiched between two glass plates and pressure-bonded by an autoclave.

  A heat ray shielding film or an ultraviolet absorbing film may be further formed on the surfaces of the solar radiation shielding resin base material and the solar radiation shielding composite base material. For example, it is possible to apply a coating solution in which ITO fine particles or ATO fine particles are dispersed in various binders on a solar radiation shielding resin substrate, and further form a heat ray shielding film on the surface. In addition, an ultraviolet absorbing film can be formed by applying a coating solution prepared by dissolving a benzotriazole-based or benzophenone-based ultraviolet absorber in various binders on the solar radiation shielding resin substrate and curing it. By forming this ultraviolet absorbing film, it is possible to further improve the weather resistance of the resin substrate.

  The resin material for the solar shading resin base material is not particularly limited as long as it is a transparent and lightly transparent, colorless and transparent resin. Polycarbonate resin, acrylic resin, fluororesin, polyester resin, polyvinyl acetal resin, polyvinyl butyral In addition to resins and ethylene-vinyl acetate copolymer resins, polyolefin resins, vinyl chloride resins, vinyl fluoride resins, and the like can be used as appropriate.

  The polycarbonate resin is obtained by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Representative examples include phenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. Further, a preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane series, and those having bisphenol A as a main component are particularly preferred.

  As acrylic resins, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate are used as main raw materials, and acrylic acid esters having 1 to 8 carbon atoms, vinyl acetate, styrene, acrylonitrile, methacryloyl as necessary. A polymer or copolymer using nitrile or the like as a copolymerization component is used. Furthermore, an acrylic resin polymerized in multiple stages can also be used.

  Further, as the fluororesin, any resin containing fluorine in the molecular structure may be used, and examples thereof include tetrafluoroethylene resin, trifluoride ethylene resin, difluoroethylene resin, monofluoroethylene resin, and the like. A mixture thereof may be used.

  As the polyester resin, a linear saturated polyester resin obtained by polycondensation of an acid component and a diol component, specifically, polyethylene terephthalate, polyethylene naphthalate, or the like can be used as appropriate. Here, the acid component may be one or more of saturated dibasic acids such as phthalic acid, phthalic anhydride, sebacic acid and azelaic acid, and dimer acid, and the diol component may be ethylene glycol, propylene glycol, decane. One kind or two or more kinds such as diol, dodecanediol, hexadecanediol, bisphenol compound and ethylene oxide or propylene oxide adduct thereof can be used.

  The polyvinyl acetal resin is particularly preferably a polyvinyl butyral resin obtained by acetalizing polyvinyl alcohol with an aldehyde having about 4 to 8 carbon atoms when used as an adhesive resin constituting a laminated glass sandwiched between two plate glasses. . The degree of butyralization of this polyvinyl butyral resin is not particularly limited, but about 60 to 75% is particularly preferable from the viewpoint of transparency and adhesion.

  The ethylene-vinyl acetate copolymer-based resin is not particularly limited as long as it is an ethylene-vinyl acetate random copolymer containing ethylene as a main component, and the content of vinyl acetate units is preferably about 10 to 45% by weight. .

  In this way, titanium nitride fine particles having the above-mentioned characteristics are used as solar shielding fine particles, and are uniformly dispersed in the resin component and formed into a sheet shape without using a high-cost physical film forming method or a complicated bonding process. In addition, it is possible to provide a solar radiation shielding resin base material or a solar radiation shielding composite base material that has a solar radiation shielding function and has high transparency in the visible light range and exhibits a blue color tone.

  In addition, since the titanium nitride fine particles having the above-described characteristics have a high hiding power compared to a general organic blue pigment and can exhibit an effect when added in a small amount, it is possible to reduce the material cost.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to the following examples. The visible light transmittance VLT (wavelength 380 to 780 nm) of the obtained sample, the transmission profile of the diluted solution, and the powder color (standard light source D65, 10 ° field of view) by diffuse reflected light are spectroscopic products manufactured by Hitachi, Ltd. It measured using the photometer U-4000.

  The VLT was calculated according to JIS R3106, and the powder color was calculated according to JIS Z8729. Moreover, the powder color by diffuse reflected light was measured using a powder cell for Hitachi U4000 type spectrophotometer (Part No. 139-0647, 22 mm diameter × 10 mm thickness).

  Further, haze was measured using HR-200 manufactured by Murakami Coloring Co., Ltd. In addition, in the weather resistance test, the produced solar shading resin base material or solar shading composite base material was placed in a sunshine weatherometer (Ci4000 manufactured by ATLAS) operating according to the test cycle of ISO 4892-2 for 500 hours. Evaluation was made by measuring the difference in visible light transmittance (ΔVLT).

  200 g of TiN powder having an initial particle diameter of 1500 nm, 700 g of ethylene glycol, and an appropriate amount of a polymeric dispersant were mixed, and dispersion treatment was performed by ball mill mixing and grinding for 200 hours using zirconia balls having a diameter of 5 mm. The average particle diameter of the TiN powder in this dispersion (liquid A) was 145 nm.

Next, after the ethylene glycol was dried using a vacuum dryer for a part of the dispersion liquid (liquid A), the characteristics of the obtained powder were evaluated. As a result, the lattice constant was 0.4245 nm. The powder color by diffuse reflected light was L ^* = 46.68, a ^* = 4.74, b ^* = 1.11.99. Further, this powder was diluted with ethanol so that the TiN concentration was 0.003% by weight, and the permeation profile of this liquid was put into a 10 mm square cell made of PYREX (registered trademark), and the transmission profile was measured. As a result, the maximum value of transmittance was 49.48% at a wavelength of 440 nm, the minimum value was 31.48% at a wavelength of 945 nm, and the difference between the transmittances of the maximum value and the minimum value was 18.0%. The VLT of the diluted solution at the time of measurement was 43.5%.

  Next, the dispersion (liquid A) is diluted with ethylene glycol so that the TiN concentration is 0.2% by weight to obtain a liquid solar shading fine particle dispersion. Terephthalic acid is mixed with 30% by weight of the former and 70% by weight of the latter, and esterification and polycondensation are performed in a high-temperature vacuum mixing tank to prepare a solar-shielding polyethylene terephthalate resin (solar-shielding resin material). did.

  This solar shading resin material is melted and mixed uniformly with a blender and a twin screw extruder, and then extruded using a T-die to a thickness of 50 μm. The solar shading polyethylene in which the solar shading fine particles are uniformly dispersed throughout. A terephthalate molded body (sunlight shielding resin base material) was produced.

  The transmission profile of the obtained sample (sunlight shielding resin substrate) is shown in FIG. It is confirmed that the transmittance maximum is at a wavelength of 440 nm, the minimum is at a wavelength of 945 nm, the transmittance is high in the visible light region, and the transmittance is small in the near infrared region, and the solar radiation shielding characteristics are excellent.

  Further, the transmitted color of this sample (sunlight shielding resin base material) was a beautiful blue color.

  Table 1 below shows the visible light transmittance, maximum, minimum transmittance, haze, weather resistance test result (ΔVLT), and the like of this sample (sunlight shielding resin base material).

  After adding 500 g of tetramethoxysilane and 400 g of water to the liquid A obtained in Example 1 and stirring sufficiently, the ethylene glycol was evaporated using a vacuum dryer, and this was baked at 300 ° C. to obtain a Si compound. TiN powder coated on the surface was obtained.

  Next, the polymer dispersant is added to the TiN powder coated with the Si compound so that the polymer dispersant is 3 parts by weight with respect to 1 part by weight of TiN, and an appropriate amount of ethanol is further added and stirred. Mixed. The ethanol in the dispersion was evaporated using a vacuum dryer to obtain a powdery solar shading fine particle dispersion (dispersion B).

  Next, after adding powdery solar shading fine particle dispersion (dispersion B) to polycarbonate resin so that the TiN concentration is 0.001% by weight, the mixture is uniformly melt-mixed by a blender and a twin screw extruder. The sheet was extruded to a thickness of 3 mm using a T-die to produce a sheet-shaped solar-shielding polycarbonate molded body (solar-shielding resin base material) in which the solar-shielding fine particles were uniformly dispersed throughout.

  The transmission profile of the obtained sample (sunlight shielding resin base material) has a maximum transmittance of 430 nm, a minimum of 860 nm, a high transmittance in the visible light region, and a low transmittance in the near infrared region. It is confirmed that it has excellent solar shading characteristics.

  Further, the transmitted color of this sample (sunlight shielding resin base material) was a beautiful blue color.

  Table 1 below shows the visible light transmittance, maximum, minimum transmittance, haze, weather resistance test result (ΔVLT), and the like of this sample (sunlight shielding resin base material).

  200 g of TiN powder having an initial particle size of 220 nm, 700 g of ethanol, and an appropriate amount of a polymeric dispersant were mixed, and ball mill mixing was performed for 100 hours using zirconia balls having a diameter of 5 mm to obtain a dispersion (solution C). The average particle diameter of TiN in this dispersion (liquid C) was 110 nm.

Next, ethanol was evaporated from a part of the dispersion liquid (liquid C), and the characteristics of the obtained powder were evaluated. As a result, the lattice constant was 0.4239 nm with a face-centered cubic crystal, and the powder color by diffuse reflected light was L ^* = 36.61, a ^* = 0.27, b ^* = 1.50. Further, this powder was diluted with ethanol so that the TiN concentration was 0.003% by weight, and the permeation profile of this liquid was put into a 10 mm square cell made of PYREX (registered trademark), and the transmission profile was measured. As a result, the maximum value of the transmittance was 45.7% at a wavelength of 420 nm, the minimum value was 26.8% at a wavelength of 750 nm, and the difference between the transmittances of the maximum value and the minimum value was 18.9%. . The VLT of the diluted solution at the time of measurement was 35.14%.

  Next, the polymer dispersant was added to the dispersion (liquid C) so that the polymer dispersant was 3 parts by weight with respect to 1 part by weight of TiN, and the mixture was stirred and mixed. The ethanol in the dispersion was evaporated using a vacuum dryer to obtain a powdery solar shielding fine particle dispersion (dispersion C).

  Next, after adding powdery solar shading fine particle dispersion (dispersion C) to polycarbonate resin so that the TiN concentration is 0.001% by weight, the mixture is uniformly melt-mixed by a blender and a twin screw extruder. The sheet was extruded to a thickness of 3 mm using a T-die to produce a sheet-shaped solar-shielding polycarbonate molded body (solar-shielding resin base material) in which the solar-shielding fine particles were uniformly dispersed throughout.

  The transmission profile of the obtained sample (sunlight shielding resin substrate) is shown in FIG. It is confirmed that the transmittance maximum is 420 nm, the minimum is 720 nm, the transmittance is high in the visible light region, and the transmittance is small at the wavelength close to the near infrared region, and the solar radiation shielding characteristics are excellent. .

  Moreover, the transmitted color of this sample (sunlight shielding resin base material) was a beautiful deep blue.

  Table 1 below shows the visible light transmittance, maximum, minimum transmittance, haze, weather resistance test result (ΔVLT), and the like of this sample (sunlight shielding resin base material).

  After adding 500 g of titanium isopropoxide and 400 g of water to the dispersion (liquid C) obtained in Example 3 and stirring sufficiently, ethanol was evaporated using a vacuum dryer, and this was baked at 250 ° C. Thus, TiN powder (D powder) coated with a Ti compound was obtained.

  Next, the TiN powder (D powder) coated with the Ti compound is mixed with triethylene glycol di-2 ethyl butyrate (3GH) so that the TiN concentration is 4% by weight, and an appropriate amount of polymer system is mixed. A dispersing agent was added, and the dispersion treatment was performed by ball mill mixing for 20 hours using zirconia balls having a diameter of 5 mm. The obtained liquid solar shading fine particle dispersion was mixed with polyvinyl butyral resin so that the TiN concentration was 0.004 wt%, and kneaded and mixed at about 70 ° C. with a three-roll mixer. The obtained resin (sunlight shielding resin material) was extruded into a 0.8 mm thick sheet using a mold extruder to obtain a sheet-like resin (sunlight shielding resin substrate).

  Next, two pieces of blue plate glass having a size of about 300 × 300 mm and a thickness of about 2.1 mm are prepared, and after cutting the sheet-like resin (sunlight shielding resin base material) into the same size as this blue plate glass, 2 A laminate was obtained by sandwiching between a pair of blue plate glasses.

Next, this laminate is put into a rubber vacuum bag, the inside of the bag is decompressed and held at about 100 ° C. for 30 minutes, then cooled to room temperature, and the laminate taken out of the bag is put into an autoclave apparatus, and the pressure is about 12 kg / A laminated glass substrate was prepared by applying pressure and heating at cm ² and a temperature of about 120 ° C. for 30 minutes to perform vitrification.

  The transmission profile of the obtained sample (sunlight shielding composite substrate) is shown in FIG. It is confirmed that the transmittance maximum is 420 nm, the minimum is 720 nm, the transmittance is high in the visible light region, and the transmittance is small at the wavelength close to the near infrared region, and the solar radiation shielding characteristics are excellent. .

  Further, the transmitted color of this sample (sunlight shielding composite base material) was a beautiful deep blue color.

  Table 1 below shows the visible light transmittance, maximum, minimum transmittance, haze, weather resistance test result (ΔVLT), and the like of this sample (sunlight shielding composite base material).

  Appropriate amounts of ethylene glycol and a polymeric dispersant were added to the TiN powder (D powder) coated with the Ti compound obtained in Example 4, and the mixture was liquid-mixed by ball milling for 3 hours using 5 mm zirconia balls. A sunscreen fine particle dispersion (dispersion D) was prepared.

  Next, using the dispersion D, a sheet-shaped solar-shielding polyethylene terephthalate molded body (solar-shielding resin base material) in which the solar-shielding fine particles were uniformly dispersed throughout was produced in the same manner as in Example 1.

  The transmission profile of the obtained sample (sunlight shielding resin base material) has a transmittance maximum at a wavelength of 430 nm, a minimum at a wavelength of 740 nm, a high transmittance in the visible light region, and a transmittance at a wavelength close to the near infrared region. It is confirmed that it has a small profile and excellent solar shading characteristics.

  Moreover, the transmitted color of this sample (sunlight shielding resin base material) was a beautiful deep blue.

  Table 1 below shows the visible light transmittance, maximum, minimum transmittance, haze, weather resistance test result (ΔVLT), and the like of this sample (sunlight shielding resin base material).

  The sheet-shaped solar-shielded polyethylene terephthalate molded body (solar-shielding resin base material) produced in Example 5 was subjected to UV shielding ink [benzotriazole-based UV absorber (“Tinubin 384” manufactured by Ciba Specialty Co., Ltd.)] by a dip coating method. 2 wt%, acrylic resin 10 wt%, toluene 88 wt%] was applied and dried in an electric furnace at 80 ° C. for 30 minutes to produce a solar shading resin base material on which an ultraviolet absorbing film was formed.

Table 1 below shows the visible light transmittance, maximum value, minimum transmittance, haze, weather resistance test result (ΔVLT), and the like of the obtained solar shading resin base material.
(Comparative Example 1)
200 g of TiN powder having an initial particle size of 300 nm, 700 g of ethylene glycol, and an appropriate amount of a polymer dispersant were mixed, and dispersion treatment was performed by ball mill mixing and grinding for 100 hours using zirconia balls having a diameter of 5 mm. The average particle size of this dispersion (liquid E) was 135 nm.

Next, when the ethylene glycol in the dispersion (liquid E) was evaporated using a vacuum dryer and the TiN powder was evaluated, it was face-centered cubic and the lattice constant was 0.4225 nm. Is lower than the condition “0.423 nm” required for the fine particles for use, and the powder color by diffuse reflected light is L ^* = 34.73, a ^* = − 0.12, and b ^* = − 0.74. The value was below the conditions required for the solar shading fine particles of the present invention.

  Moreover, when this powder was diluted with ethanol so that the TiN concentration was 0.012% by weight, and the diluted liquid was put in a 10 mm square cell made of PYREX (registered trademark), the transmission profile was measured. The maximum value is 47.1% at a wavelength of 580 nm, the minimum value is 44.91% at a wavelength of 805 nm, the difference between the transmittances of the maximum value and the minimum value is 2.2%, and a difference in transmittance of 15% or more is obtained. There wasn't. The VLT of the diluted solution at the time of measurement was 46.89%.

  Next, it carried out similarly to Example 1 except having used the dispersion liquid (E liquid) instead of A liquid obtained in Example 1, and produced the sheet-like solar radiation shielding polyethylene terephthalate molded object.

  The transmission profile of the obtained molded body is shown in FIG. The maximum value of transmittance is 43.35% at a wavelength of 540 nm, the minimum value is 41.59% at a wavelength of 945 nm, and the difference in transmittance between the maximum value and the minimum value is 1.76%, thereby obtaining a solar radiation shielding function. I couldn't.

  Moreover, the transmission color of this sample (sheet-like solar-shielded polyethylene terephthalate molded product) did not exhibit blue, but was black to gray.

The visible light transmittance, maximum, minimum transmittance, haze, weather resistance test result (ΔVLT), etc. of this sample are shown in Table 1 below.
(Comparative Example 2)
A sheet-like solar shading polycarbonate molded body was produced in the same manner as in Example 3 except that the above dispersion (Liquid E) was used instead of the dispersion (Liquid C) obtained in Example 3.

  The transmission color of the obtained solar shading polycarbonate molded article was not blue but black to gray.

The visible light transmittance, maximum, minimum transmittance, haze, weather resistance test result (ΔVLT), etc. of this sample are shown in Table 1 below.
(Comparative Example 3)
Dispersion treatment was performed by mixing 200 g of TiN powder having an initial particle diameter of 1500 nm and 700 g of ethylene glycol, and ball mill mixing for 20 hours using zirconia balls having a diameter of 5 mm. The average particle diameter of the TiN powder in this dispersion (F liquid) was 350 nm, and the fine particles did not satisfy the condition “250 nm or less” required for the solar radiation shielding fine particles of the present invention.

Next, after the ethylene glycol was dried and vaporized by using a vacuum dryer for a part of the dispersion liquid (F liquid), the characteristics of the powder were evaluated. As a result, the lattice constant was 0.4242 with a face-centered cubic crystal. The powder color by reflected light is L ^* = 43.58, a ^* = 3.73, b ^* = 10.98, and satisfies the conditions required for the solar shading fine particles of the present invention except for the average particle diameter. It was.

  Next, this powder was diluted with ethanol so that the TiN concentration was 0.003% by weight, and when this diluted solution was put in a 10 mm square cell made of PYREX (registered trademark), the transmission profile was measured. The maximum value is 51.9% at a wavelength of 435 nm, the minimum value is 43.0% at a wavelength of 800 nm, and the difference in transmittance between the maximum value and the minimum value is 8.9%, and a difference in transmittance of 15% or more cannot be obtained. It was. The VLT of the diluted solution at the time of measurement was 46.89%.

  Next, it carried out similarly to Example 2 except having used the said dispersion liquid (F liquid) instead of A liquid obtained in Example 1, and produced the sheet-like solar radiation shielding polycarbonate molding.

  The transmission profile of the obtained molded body is shown in FIG. Moreover, the transmission color of this molded object did not exhibit blue, and was blue black.

  The visible light transmittance, maximum value, minimum transmittance, haze, weather resistance test result (ΔVLT) and the like of this molded body are shown in Table 1 below.

［評 価］
１．表１に示されたデータから明らかなように各実施例に係る試料においては日射遮蔽機能が高く、可視光領域の高い透過性能を有し、しかも青色の色調を備えていることが確認される。
２．他方、各比較例に係る試料においてはその全てが青色の色調を備えておらず、かつ、日射遮蔽機能と可視光領域の透過性能についても劣っていることが確認される。特に、比較例３においては、ヘイズ値が１３．９と他の試料に較べて極端に劣っていることも確認される。

[Evaluation]
1. As is clear from the data shown in Table 1, it is confirmed that the samples according to each Example have a high solar shading function, a high transmission performance in the visible light region, and a blue color tone. .
2. On the other hand, it is confirmed that all the samples according to the comparative examples do not have a blue color tone, and that the solar radiation shielding function and the transmission performance in the visible light region are inferior. In particular, in Comparative Example 3, it is also confirmed that the haze value is 13.9, which is extremely inferior compared to other samples.

The graph which shows the permeation | transmission profile of the sample concerning an Example and a comparative example.

Claims (9)

In solar radiation shielding particles that transmit visible light and shield heat rays,
It has a face-centered cubic crystal structure with a lattice constant of 0.423 nm or more, an average particle size of 250 nm or less, and the powder color by diffuse reflection in the L ^* a ^* b ^* color system is L ^* = 35. A solar shading fine particle comprising 35 to 60, titanium nitride fine particles having a ^* = − 0.1 to 10.0 and b ^* = − 0.5 to 15.0.   The above-mentioned maximum is obtained when the transmittance of the diluting liquid in which the solar shielding fine particles are dispersed has a maximum value at a wavelength of 400 to 600 nm, a minimum value at a wavelength of 700 to 1100 nm, and a visible light transmittance of 20% or more and less than 80%. The fine particle for solar radiation shielding according to claim 1, wherein the difference between the value and the minimum value is 15 points or more in percentage.   3. The solar radiation shielding fine particles according to claim 1, which are coated with a compound containing any element selected from the group consisting of Si, Al, Zr and Ti. In the solar radiation shielding resin material containing the resin component and the solar radiation shielding fine particles dispersed in the resin component,
The solar radiation shielding resin material, wherein the solar radiation shielding fine particles dispersed in the resin component are composed of the solar radiation shielding fine particles according to any one of claims 1 to 3.   5. The solar radiation shielding according to claim 4, wherein the resin component is one of polycarbonate resin, acrylic resin, fluororesin, polyester resin, polyvinyl acetal resin, polyvinyl butyral resin, and ethylene-vinyl acetate copolymer resin. Resin material.   A solar radiation shielding resin base material, comprising the solar radiation shielding resin material according to claim 4 or 5 molded into a flat or three-dimensional shape.   It is comprised by the solar radiation shielding resin base material which shape | molded the solar radiation shielding resin material of Claim 4 or 5 in the sheet form, and a pair of plate-like glass bonded together on both surfaces of this solar radiation shielding resin base material, or Claim 4 Or a solar radiation shielding composite comprising a solar radiation shielding resin base material obtained by molding the solar radiation shielding resin material according to 5 into a sheet and one or more other resin plates bonded to the solar radiation shielding resin base material. Base material. In the solar shading fine particle dispersion used for producing the solar shading resin material according to claim 4 or 5,
An organic solvent and / or a plasticizer, the solar shading fine particles according to any one of claims 1 to 3, and a polymer-based dispersant for dispersing the solar shading fine particles as main components, and for sun shading A fine particle dispersion for solar radiation shielding, wherein the mixing ratio of the fine particles and the polymer dispersant is 0.3 part by weight or more and less than 10 parts by weight of the polymer dispersant with respect to 1 part by weight of the solar radiation shielding fine particles. In the solar shading fine particle dispersion used for producing the solar shading resin material according to claim 4 or 5,
The solar radiation shielding fine particles according to any one of claims 1 to 3 and a polymer dispersing agent that disperses the solar radiation shielding fine particles, and the mixing ratio of the solar radiation shielding fine particles and the polymer dispersing agent is A fine particle dispersion for solar shading, characterized in that the amount is not less than 0.3 part by weight and less than 10 parts by weight of a polymer-based dispersant with respect to 1 part by weight of the solar shading fine particles, and does not substantially contain a solution component.

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