CN108473324B - Infrared shielding transparent substrate, optical member, particle dispersion, interlayer transparent substrate, particle dispersion powder, and master batch - Google Patents
Infrared shielding transparent substrate, optical member, particle dispersion, interlayer transparent substrate, particle dispersion powder, and master batch Download PDFInfo
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- CN108473324B CN108473324B CN201680077498.9A CN201680077498A CN108473324B CN 108473324 B CN108473324 B CN 108473324B CN 201680077498 A CN201680077498 A CN 201680077498A CN 108473324 B CN108473324 B CN 108473324B
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- infrared shielding
- particles
- particle dispersion
- boride
- transparent substrate
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Abstract
The invention provides boride particles, which are represented by the general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, and m is a number indicating the boron content in the general formula), and wherein the carbon content contained in the boride particles when measured by the combustion infrared absorption method is 0.2 mass% or less.
Description
Technical Field
The present invention relates to boride particles, boride particle dispersion liquid, infrared shielding transparent substrate, infrared shielding optical member, infrared shielding particle dispersion, infrared shielding interlayer transparent substrate, infrared shielding particle dispersion powder, and master batch.
Background
Conventionally, boride particles of rare earth elements such as La are produced by synthesizing by a solid phase reaction method and then pulverizing by a dry pulverizing method, and particularly, a method of pulverizing particles by collision with each other by a high-speed air flow such as a jet mill is common. For example, lanthanum hexaboride among boride particles of a rare earth element is obtained by heating lanthanum oxide and boron oxide to a high temperature in the presence of carbon, and then pulverizing the particles by a dry pulverizing device. For example, patent document 1 discloses a method for pulverizing a powder using a jet mill.
These boride particles have been conventionally used for thick film resistor pastes and the like, and when they are made into fine particles, they can be used as an optical material for solar shading. In other words, since the film dispersing boride particles transmits visible light and can effectively shield near infrared rays acting as thermal energy, it is known that it is preferable as a solar shielding material for a house, an automobile window, or the like (for example, see patent documents 2, 3).
However, since boride of rare earth element such as La is hard, it is difficult to pulverize into fine particles by a dry pulverizing method using a jet mill or the like, and only large particles of about 1 μm to 3 μm can be obtained. In addition, it is difficult to suppress reagglomeration of boride particles obtained by the dry pulverizing method.
In the following studies, it was found that the average dispersion particle diameter of boride particles can be made 200nm or less by treatment with a medium stirring mill (for example, see patent document 4). Thus, boride particles having an average dispersion particle diameter of about 200nm can be economically obtained. If boride particles having an average dispersion particle diameter of 200nm or less are used, geometric scattering or Mie scattering caused when the particle diameter is larger than 200nm can be reduced. Therefore, it is possible to prevent the phenomenon that light in the visible light range of 400nm to 780nm is scattered and becomes frosted glass, and it is possible to obtain an optical member in which transparency is important.
However, as the infrared shielding particles, a phenomenon (hereinafter, this phenomenon may be referred to as "blue haze") in which the infrared shielding optical member in which the boride particles are dispersed changes color to blue-white when strong light such as sunlight or a spotlight is irradiated may occur. If this blue fog occurs, there is a problem that the appearance of the infrared shielding optical member may be impaired.
It is known that if the average dispersion particle diameter of boride particles is 200nm or less, geometric scattering or mie scattering is reduced, and the scattering coefficient of most of the scattering follows rayleigh scattering defined by the following formula (1).
S＝[16π 5 r 6 /3λ 4 ]·[(m 2 －1)/(m 2 +2)] 2 ·[m] (1)
[ wherein in the above formula (1), S is a scattering coefficient, λ is a wavelength, r is a particle size, and m=n 1 /n 0 ，n 0 Is the refractive index of the substrate, and n 1 Refractive index of the dispersed substance]
The Rayleigh scattering is scattering of light due to particles having a size smaller than the wavelength of light. According to the above formula (1), since rayleigh scattering is inversely proportional to the fourth power of the wavelength (λ), blue light having a relatively short wavelength is considered to be scattered and discolored to bluish-white.
In the rayleigh scattering region, according to the above formula (1), since scattered light is proportional to the sixth power of the particle diameter (r), it is considered that the particle diameter is reduced, thereby reducing rayleigh scattering and suppressing the occurrence of blue fog.
Further, for example, patent document 5 discloses an example in which generation of blue fog can be suppressed by setting the average dispersion particle diameter to 85nm or less.
< prior art document >
< patent document >
Patent document 1: japanese patent application laid-open No. 2001-314776
Patent document 2: japanese patent laid-open No. 2000-096034
Patent document 3: japanese patent application laid-open No. 11-181336
Patent document 4: japanese patent application laid-open No. 2004-237250
Patent document 5: japanese patent application laid-open No. 2009-150979
< non-patent literature >
Non-patent document 1: V.Domnich et al, J.Am.Ceram.Soc., (2011) vol.94, issue 11, pp.3605-3628
Non-patent document 2: X.H.Zhao et al, app.Mech.Mater, vol.55-57, pp.1436-1440 (2011)
Disclosure of Invention
< problem to be solved by the invention >
However, when conventionally used boride particles are crushed to an average dispersion particle diameter of 85nm or less by the crushing method using a medium stirring mill disclosed in patent document 4, the slurry viscosity may become high and crushing treatment may be difficult.
Therefore, there are problems that the average dispersion particle diameter is further reduced and blue fog is suppressed in order to continue the pulverization treatment, the concentration of boride particles in the slurry needs to be extremely reduced to lower the viscosity, and the pulverization efficiency is poor and uneconomical.
Accordingly, in view of the problems in the prior art described above, an object of an aspect of the present invention is to provide boride particles that can be easily subjected to micronization.
< means for solving the problems >
In order to solve the above problems, according to one embodiment of the present invention, there is provided boride particles represented by the general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number representing the boron content in the general formula), and the carbon content contained in the boride particles when measured by combustion infrared absorption methodThe amount is 0.2 mass% or less.
< Effect of the invention >
According to one embodiment of the present invention, boride particles that can be easily subjected to micro-pulverization can be provided.
Drawings
Fig. 1 is an explanatory diagram (first) showing a principle of measuring a diffuse transmission curve of an infrared shielding particle dispersion or the like according to an embodiment of the present invention.
Fig. 2 is an explanatory diagram showing a principle of measurement of a diffuse transmission curve of an infrared shielding particle dispersion or the like according to an embodiment of the present invention (second example).
Detailed Description
The embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to the following embodiments, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.
(boride particles)
In this embodiment, first, a description will be given of a structural example of boride particles.
The boride particles of the present embodiment are represented by the general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, and m is a number indicating the boron content in the general formula). The carbon content of the boride particles when measured by the infrared absorption by combustion method may be set to 0.2 mass% or less.
The inventors of the present invention have conducted intensive studies on boride particles that can be easily subjected to fine pulverization, that is, can be pulverized into fine particles. Further, it has been found that boride particles which are easily subjected to fine grinding can be obtained by setting the carbon content (carbon concentration) in boride particles to a predetermined value or less, and the present invention has been completed.
The boride particles of the present embodiment may be represented by the general formula XB as described above m Particles of boride are shown.
In the general formula XB m In the boride particles of the present embodiment, m, which is the element ratio (molar ratio) of boron (B) to metal element X (B/X), is not particularly limited, and is preferably 3.0 to 20.0.
Is formed by a general formula XB m Examples of the boride particles include XB 4 、XB 6 、XB 12 Etc. However, from the viewpoint of selectively and effectively reducing the transmittance of light in the near infrared region around the wavelength of 1000nm, the boride particles of the present embodiment are preferably XB 4 Or XB (XB) 6 Can be a main body and can partially contain XB 12 。
Thus, for the above general formula XB m M, which is the element ratio (B/X) of boron (B) to metal element (X), is more preferably 4.0 to 6.2.
When the above (B/X) is 4.0 or more, XB or XB can be suppressed 2 Etc., although the cause is not clear, the solar shading characteristics can be improved. In addition, when the above (B/X) is 6.2 or less, the content ratio of hexaboride excellent in solar shielding property can be particularly increased, and it is preferable to improve the solar shielding property.
Particularly, since the boride has high near infrared absorption ability, the boride particles of the present embodiment are preferably XB 6 Is a main body.
Thus, in the above general formula XB m In the boride particles represented, m, which is the element ratio (B/X) of boron (B) to metal element (X), is more preferably 5.8 to 6.2.
In the production of boride particles, the resulting powder containing boride particles may be particles containing boride having a plurality of compositions, not only particles of boride having a single composition. Specifically, for example, XB can be used 4 、XB 6 、XB 12 Particles of a mixture of such borides.
Therefore, when measuring X-ray diffraction for particles of hexaboride, which is a typical boride particle, for example, even if the X-ray diffraction is single-phase in analysis, it is considered that other phases are actually contained in a trace amount.
Therefore, the boride particles of the present embodiment have the general formula XB m For example, m may be an atomic ratio of boron (B) to 1 atom of the X element when the powder containing the boride particles obtained is chemically analyzed by ICP emission spectrometry (high frequency inductively coupled ion emission spectrometry) or the like.
The metal element (X) of the boride particles of the present embodiment is not particularly limited as shown in the above general formula, and may be, for example, one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca.
However, since the near infrared ray absorption ability of lanthanum hexaboride, which is a hexaboride of lanthanum, is particularly high, the boride particles of the present embodiment preferably include lanthanum hexaboride particles.
As described above, according to the study of the inventors of the present invention, boride particles that can be easily micronized can be obtained by setting the carbon content (carbon concentration) in boride particles to a predetermined value or less. The reason for this will be described below.
According to the studies of the inventors of the present invention, carbon contained in boride particles and components of boride particles may form a carbon compound, or a carbon compound contained in a raw material may remain.
Examples of such carbon compounds include LaB 2 C 2 、LaB 2 C 4 、B 4 C、B 4.5 C、B 5.6 C、B 6.5 C、B 7.7 C、B 9 C, etc.
According to non-patent document 1, B is a carbon compound of the above carbon compounds 4 C、B 4.5 C、B 5.6 C、B 6.5 C、B 7.7 C、B 9 C is a high-hardness carbon compound having Young's moduli of 472GPa, 463GPa, 462GPa, 446GPa, 352GPa, 348GPa as the hardness index.
On the other hand, non-patent document 2 reports that, for example, lanthanum hexaboride has a young's modulus of 194GPa. In addition, it is estimated that other boride particles have a young's modulus of the same degree.
In this way, the young's modulus of the carbon compound mixed as an impurity may be higher than that of the boride particle as a target. Therefore, in order to obtain boride particles that can be easily pulverized, it is demanded to suppress the mixing of these carbon compounds.
Further, since the mixing amount (content) of these carbon compounds is related to the carbon content in the boride particles, as described above, it is considered that the boride particles can be obtained by setting the carbon content in the boride particles to a predetermined value or less, and thus can be easily micro-pulverized.
The carbon content contained in the boride particles of the present embodiment can be measured by the infrared absorption by combustion. The carbon content of the boride particles of the present embodiment is preferably 0.2 mass% or less, more preferably 0.1 mass% or less, as measured by the combustion infrared absorption method.
In addition, B is contained in the above carbon compound in boride particles 4 Since C (boron carbide) is particularly easily produced, the boride particles of the present embodiment are preferably used for B contained therein 4 The amount of C is also suppressed. For example, B of boride particles of the present embodiment 4 The content (content ratio) of C is preferably 1.0 mass% or less.
By making B contained in the boride particles of the present embodiment 4 The amount of C, i.e. B 4 The content ratio of C is preferably 1.0 mass% or less, since the content of other carbon compounds can be suppressed, boride particles which can be particularly easily pulverized can be obtained.
B contained in boride particles of the present embodiment 4 The amount of C can be determined by ICP analysis by performing pretreatment of nitric acid dissolution and filtration separation.
Known B 4 C is hardly soluble in nitric acid. On the other hand, boride particles are known to dissolve in nitric acid.
Thus, when B in boride particles 4 When evaluating the C content, the nitric acid is addedAdding boride particles, dissolving the boride particles, and filtering to separate undissolved residues to extract only B in the boride particles 4 And C particles. And, by using sodium carbonate, separating B 4 C particles were dissolved and the boron concentration was measured by ICP analysis, whereby B was calculated 4 C concentration.
In this case, in order to confirm that the undissolved residue obtained after the filtration separation was B 4 C, it is desirable to prepare reagents which have undergone the same treatment as the filtration separation in parallel, and XRD measurement of undissolved residues of the reagents obtained after the filtration separation is performed to confirm B 4 C single phase.
On the other hand, although boride particles such as hexaboride particles are powder colored in dark bluish violet or the like, when the particles are pulverized to a particle size sufficiently smaller than the wavelength of visible light and dispersed in a film, visible light transmittance is generated to the film. At the same time, an infrared shielding function was found.
The reason for this is not yet clarified in detail, but it is considered that these boride materials have a large number of free electrons, and there is an inter-band migration between 4f and 5d in the near infrared region or absorption due to electron-electron and electron-phonon interactions.
From experiments, it was confirmed that, in the film in which these boride particles were sufficiently finely and uniformly dispersed, the transmittance of the film had a maximum value in a region of a wavelength of 400nm to 700nm, and a minimum value in a region of a wavelength of 700nm to 1800 nm. When the visible light wavelength is 380nm to 780nm, and the photosensitivity is bell-shaped with a peak around 550nm, it can be understood that the film transmits visible light efficiently and absorbs and reflects sunlight other than visible light efficiently.
The average dispersion particle diameter of the boride particles of the present embodiment is preferably 100nm or less, more preferably 85nm or less. The average dispersed particle diameter may be measured by a particle diameter measuring apparatus using a dynamic light scattering method.
The lower limit of the average particle diameter of boride particles is not particularly limited, but is preferably, for example, 1nm or more. This is because it is industrially difficult to form boride particles to have an average particle diameter of less than 1nm.
Since the boride particles of the present embodiment have a carbon content of a predetermined value or less, the boride particles can be easily finely pulverized so that the average dispersion particle diameter is 100nm or less, particularly 85nm or less, for example. Therefore, the infrared shielding optical member in which boride particles of the present embodiment are dispersed can suppress the occurrence of blue fog even when strong light such as sunlight or a spotlight is irradiated.
(method for producing boride particles)
Next, a configuration example of the method for producing boride particles according to the present embodiment will be described.
As a method for producing boride particles of the present embodiment, the resulting boride particles are represented by general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, and m is a number indicating the boron content in the general formula), and the carbon content (carbon concentration) contained in the boride particles when the boride particles are measured by the infrared absorption by combustion is not particularly limited, if the carbon content is 0.2 mass% or less.
As an example of a constitution of the method for producing boride particles of the present embodiment, a solid phase reaction method using carbon or boron carbide as a reducing agent is given. The case of producing boride particles using lanthanum as a metal element will be described below as an example.
For example, boride particles using lanthanum as a metal element can be produced by firing a mixture of a boron source, a reducing agent, and a lanthanum source.
Specifically, when producing lanthanum boride particles using, for example, boron carbide as a boron source and a reducing agent, and lanthanum oxide as a lanthanum source, a raw material mixture of boron carbide and lanthanum oxide is first prepared. Then, the raw material mixture is fired at a temperature of 1500 ℃ or higher in an inert atmosphere, whereby the lanthanum oxide is reduced with carbon in the boron carbide to produce carbon monoxide and carbon dioxide, and carbon is removed. Lanthanum boride is then obtained from the remainder of lanthanum and boron.
Carbon derived from boron carbide is not completely removed as carbon monoxide and carbon dioxide, but a part thereof remains in lanthanum boride particles as impurity carbon. Therefore, if the ratio of boron carbide in the raw material increases, the impurity carbon concentration in the obtained lanthanum boride particles increases.
As described above, the resulting powder comprising boride particles is not composed of boride particles of a single composition only, but is LaB 4 、LaB 6 、LaB 12 Particles of a mixture of the same, etc. Therefore, when the powder containing boride particles is measured by X-ray diffraction, even if the boride is single-phase in X-ray diffraction analysis, it is considered that the boride actually contains a small amount of other phases.
In this case, in the case of producing boride particles using lanthanum as a metal element, the element ratio B/La of boron in the boron source and lanthanum in the lanthanum source of the raw material is not particularly limited, and is preferably 3.0 to 20.0.
In particular, when the element ratio B/La of boron in the boron source and lanthanum in the lanthanum source of the raw material is 4.0 or more, laB and LaB can be suppressed 2 And the like. In addition, although the reason is not clear, the solar shading characteristics can be improved.
On the other hand, when the elemental ratio B/La of boron in the boron source and lanthanum in the lanthanum source of the raw material is 6.2 or less, the formation of boron oxide other than boride particles is suppressed. Since the boron oxide particles have hygroscopicity, if the boron oxide particles are mixed into the powder containing the boride particles, the moisture resistance of the powder containing the boride particles decreases, and the deterioration of the solar radiation shielding property with time increases.
Therefore, it is preferable to suppress the generation of boron oxide particles by setting the elemental ratio B/La of boron in the boron source and lanthanum in the lanthanum source of the raw material to 6.2 or less. In addition, when the element ratio B/La is 6.2 or less, the content ratio of hexaboride excellent in solar shielding property can be particularly increased, and it is preferable to improve solar shielding property.
In order to further reduce the impurity carbon concentration, it is effective to reduce the ratio of boron carbide in the raw material as much as possible. Therefore, for example, particles of lanthanum boride are produced by setting B/La to 6.2 or less, whereby a powder containing particles of lanthanum boride having an impurity carbon concentration of 0.2 mass% or less can be more reliably obtained.
As described above, when boride particles using lanthanum as a metal element are produced, the element ratio (molar ratio) B/La of boron in the boron source and lanthanum in the lanthanum source is preferably 4.0 to 6.2. By setting the composition of the raw materials to the above range, the impurity carbon concentration in the obtained powder containing lanthanum boride particles can be kept low, and a powder containing lanthanum boride particles exhibiting high solar shielding properties can be obtained.
In addition, it is particularly preferred that the particles of lanthanum boride obtained are in the form of LaB 6 Is a main body. This is due to LaB 6 The near infrared ray absorption ability of (2) is particularly high.
Therefore, it is more preferable that the elemental ratio B/La of boron in the boron source and lanthanum in the lanthanum source of the raw material is 5.8 to 6.2.
Here, the case where boron carbide is used as the boron source and the reducing agent, and lanthanum oxide is used as the lanthanum source to produce lanthanum boride particles has been described as an example, but the present invention is not limited to this embodiment. For example, boron or boron oxide may be used as the boron source, carbon may be used as the reducing agent, and lanthanum oxide may be used as the lanthanum source. In this case, it is preferable to perform preliminary experiments or the like so that no residual carbon or oxygen remains in the product, and to select the mixing ratio of each component.
For example, a compound containing a metal element X may be used instead of lanthanum oxide, depending on the metal element X contained in the boride particles to be produced. Examples of the compound containing the metal element X include 1 or more compounds selected from the group consisting of hydroxides of the metal element X, hydrates of the metal element X, and oxides of the metal element X. The method for producing the compound containing the metal element X is not particularly limited, and for example, a solution containing the compound containing the metal element X and an alkaline solution may be stirred and reacted to form a precipitate, and the precipitate may be obtained from the precipitate.
As described above, even when a compound containing the metal element X is used instead of lanthanum oxide, it is preferable to perform preliminary experiments or the like so that no residual carbon or oxygen remains in the product, and to select the mixing ratio of each component. For example, the elemental ratio of boron in the boron source and the elemental ratio of the elemental X in the elemental X source may be the same as the elemental ratio of boron in the boron source and the elemental ratio of lanthanum in the elemental X source.
The boride particles thus obtained are subjected to wet grinding or the like, for example, whereby boride particles having a desired average dispersed particle diameter can be obtained.
(boride particle Dispersion)
Next, a description will be given of one configuration example of the boride particle dispersion liquid of the present embodiment.
The boride particle dispersion liquid of the present embodiment may include the boride particles described above, and a liquid medium. The boride particles are preferably dispersed in a liquid medium, for example.
The liquid medium for boride particle dispersion may include one or more liquid mediums selected from water, organic solvents, oils, liquid resins, plasticizers.
The organic solvent preferably has a function for maintaining dispersibility of boride particles and a function for not generating coating defects when coating the dispersion liquid. Examples of the organic solvent include alcohol solvents such as Methanol (MA), ethanol (EA), 1-propanol (NPA), isopropyl alcohol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol, etc., ketone solvents such as acetone, methyl Ethyl Ketone (MEK), methyl propyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, isophorone, etc., ester solvents such as 3-methyl-methoxy-propionate (MMP), ethylene glycol monomethyl ether (MCS), ethylene glycol monoether (ECS), ethylene glycol isopropyl ether (IPC), propylene glycol methyl ether (PGM), propylene glycol diethyl ether (PE), propylene Glycol Methyl Ether Acetate (PGMEA), propylene glycol diethyl ether acetate (PE-AC), etc., amides such as Formamide (FA), N-methylformamide (DMF), dimethylacetamide, N-methyl-2-pyrrolidone (NMP), etc., aromatic hydrocarbons such as toluene, xylene, etc., chlorinated ethylene, halogenated hydrocarbons such as chlorobenzene, etc., and the above may be used in combination.
Among the above, ketones such as MIBK and MEK, aromatic hydrocarbons such as toluene and xylene, and glycol ether acetates such as PGMEA and PE-AC are more preferable as the organic solvent. Therefore, one or two or more selected from the above may be used in combination.
Examples of the oils and fats include one or more oils and fats selected from the group consisting of drying oils such as linseed oil, sunflower oil, tung oil, sesame oil, cottonseed oil, rapeseed oil, soybean oil, and semi-drying oils such as rice bran oil, olive oil, coconut oil, palm oil, and dehydrated castor oil, fatty acid monoesters obtained by directly esterifying fatty acids of vegetable oils with a monohydric alcohol, ethers, isopar E, exxsol Hexane, exxsol Heptane, exxsol E, exxsol D30, exxsol D40, exxsol D60, exxsol D80, exxsol D95, exxsol D110, and Exxsol D130 (the above are manufactured by Exxon meiu corporation).
As the liquid resin, for example, one or more kinds selected from the group consisting of a liquid acrylic resin, a liquid epoxy resin, a liquid polyester resin, and a liquid urethane resin can be used.
As the plasticizer, for example, a liquid plastic plasticizer can be used. As the plasticizer for liquid plastics, for example, one or more selected from phthalic acid plasticizers such as DEHP and DINP, adipic acid plasticizers such as DINA and DOA, phosphoric acid plasticizers, epoxy plasticizers and polyester plasticizers can be used.
The liquid medium used in the boride particle dispersion liquid of the present embodiment may contain, for example, a dispersing agent, a coupling agent, a surfactant, and the like, in addition to the above-described components. The dispersant, the coupling agent, and the surfactant may be selected according to the purpose, and those having an amine group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group are preferable. These functional groups can adsorb on the surface of boride particles and prevent aggregation of boride particles, and for example, in boride particle dispersions produced using boride particle dispersions, the effect of uniformly dispersing boride particles is exhibited.
As the dispersant, coupling agent, and surfactant, for example, a phosphate compound, a polymer-based dispersant, a silane-based coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, and the like can be preferably used, but the present invention is not limited thereto. Examples of the polymer-based dispersant include an acrylic polymer-based dispersant, a polyurethane polymer-based dispersant, an acrylic-block copolymer polymer-based dispersant, a polyether-based dispersant, and a polyester-based polymer-based dispersant.
The amount of one or more materials selected from the group consisting of dispersants, coupling agents, and surfactants to be added to the boride particle dispersion is preferably in the range of 10 parts by weight to 1000 parts by weight, more preferably in the range of 20 parts by weight to 200 parts by weight, based on 100 parts by weight of boride particles. If the amount of the dispersant or the like is within the above range, aggregation of boride particles in the dispersion liquid can be suppressed, and dispersion stability can be maintained at a high level, which is preferable.
The method for dispersing boride particles in a liquid medium is not particularly limited. For example, a method of dispersing a raw material mixture of boride particle dispersion liquid using a wet medium mill such as a bead mill, a ball mill, or a sand mill is mentioned. In particular, the boride particle dispersion liquid of the present embodiment preferably has boride particles having an average dispersion particle diameter of 100nm or less dispersed in a liquid medium, and more preferably has an average dispersion particle diameter of 85nm or less. Therefore, it is preferable to disperse boride particles by wet grinding using a medium stirring mill such as a bead mill to prepare a dispersion liquid.
When preparing a boride particle dispersion in which boride particles are dispersed in a dispersion medium (liquid medium), there is a method in which boride particles, a dispersant, or the like as a raw material are added to water, an organic solvent, an oil, a liquid resin, a plasticizer, or the like as a liquid medium, and dispersion treatment is performed by a medium stirring mill or the like, as described above.
The boride particle dispersion may be prepared by the following steps. Here, a case of preparing a boride particle plasticizer dispersion will be described as an example.
Specifically, first, a boride particle dispersion liquid in which boride particles are dispersed in an organic solvent is prepared in advance using the above-described organic solvent as a liquid medium. Then, a plasticizer is added to the boride particle dispersion liquid, and the organic solvent is removed, whereby a boride particle plasticizer dispersion liquid can be obtained.
The method for removing the organic solvent includes, for example, a method of drying the boride particle dispersion under reduced pressure.
Specifically, the organic solvent component is separated by drying under reduced pressure while stirring a boride particle dispersion liquid containing an organic solvent as a liquid medium to which a plasticizer is added. The apparatus for the reduced pressure drying is not particularly limited, and may be any apparatus having the above-described functions. In addition, the pressure value at the time of depressurization is appropriately selected.
By using this reduced pressure drying method, the removal efficiency of the organic solvent from the boride particle dispersion liquid in which the organic solvent to which the plasticizer is added is a liquid medium can be improved, and therefore, the agglomeration of boride particles dispersed in the boride particle plasticizer dispersion liquid is preferably not caused. Furthermore, the boride particle plasticizer dispersion is also improved in productivity, and the vaporized organic solvent is also easily recovered, which is also preferable from the viewpoint of environment.
In order to obtain a uniform boride particle dispersion, various additives, the above-mentioned dispersing agents, or pH adjustment may be added.
In addition, although the description has been made here of the case where the plasticizer dispersion liquid of boride particles using the plasticizer as the dispersing agent is prepared, the present invention is not limited to this embodiment, and a dispersion liquid in which boride particles are dispersed in various dispersion media can be obtained by using other dispersion media (liquid media) such as water, an organic solvent, grease, and a liquid resin instead of the plasticizer.
The content, that is, the concentration of boride particles in the boride particle dispersion liquid is not particularly limited, and is preferably, for example, 0.01 mass% or more and 30 mass% or less.
This is because, when the content of boride particles is 0.01 mass% or more, a boride particle dispersion liquid having a sufficient infrared shielding function can be obtained.
Further, if the content of boride particles is 30 mass% or less, the viscosity of the boride particle dispersion liquid is not excessively high, and dispersion stability can be maintained, which is preferable. In particular, the content of boride particles in the boride particle dispersion liquid is more preferably 1 mass% or more and 30 mass% or less.
The boride particles in the boride particle dispersion liquid are preferably dispersed so that the average dispersion particle diameter measured by a dynamic light scattering method is 100nm or less, and more preferably dispersed so that the average dispersion particle diameter is 85nm or less. This is because, when the average dispersion particle diameter of the boride particles is 100nm or less, the occurrence of blue haze in the infrared shielding film produced by the boride particle dispersion liquid of the present embodiment can be suppressed, and the optical characteristics can be improved. In addition, when the average dispersion particle diameter is 85nm or less, occurrence of blue fog in the infrared shielding film can be suppressed particularly.
The inventors of the present invention have estimated the following reason that when a boride particle dispersion liquid is prepared using the above-described boride particles, the average dispersed particle diameter can be effectively reduced to 100nm or less, particularly to 85nm or less without causing problems such as gelation of the boride particle dispersion liquid (slurry).
Since boride particles are hard, when pulverized by a wet media mixer mill, fine powder worn out by media beads, fine bead pieces after the media beads are broken, and other wear debris are mixed into slurry. At this time, since the hardness of boride particles increases with an increase in carbon concentration, when boride particles having a carbon concentration higher than 0.2 mass% are used as a raw material, a large amount of abrasion slag of the medium beads is mixed into the slurry. The mixing of the abrasion slag of the media beads is a cause of increasing the slurry concentration.
The concentration ratio of the wear slag of the media beads to boride in the slurry can be used as an indicator of the amount of media bead wear. For example, when yttria-stabilized zirconia beads (also referred to simply as "zirconia beads") having high wear resistance are used as the medium beads, zr from the zirconia beads in the slurry can be combined with a zirconia bead represented by the general formula XB m The concentration ratio Zr/X of the weight concentration (mass%) of the metal element X in the boride shown is used as an index of the amount of wear of the medium beads.
When the carbon concentration of the boride particles is higher than 0.2 mass%, zirconium derived from zirconia beads in the obtained slurry is more excellent than that represented by the general formula XB m The concentration ratio Zr/X of the metal element X in the boride is more than 1.5. In other words, it is shown that the amount of wear of the media beads becomes very large. The abrasion slag mixing of the media beads is a cause of increasing the slurry viscosity.
In contrast, when yttrium-stabilized zirconia beads are used as the medium beads and pulverized to an average dispersion particle diameter of 100nm or less, particularly 85nm or less, the concentration ratio Zr/X in the resulting slurry can be made 1.5 or less by using boride particles having a carbon concentration of 0.2 mass% or less as the raw material. In other words, since the mixing amount of the abrasion slag of the media beads is greatly reduced, it is presumed that the pulverization can be effectively performed without deteriorating the viscosity of the slurry. However, the viscosity of the slurry is not increased in a part that is not explained, and the viscosity may also be other than the above-described operation, and thus the viscosity is not limited to the above-described operation.
When the dispersion treatment of the boride particle dispersion liquid is performed using zirconia beads as the medium beads, it is preferable that Zr derived from zirconia beads in the boride particle dispersion liquid and Zr represented by the general formula XB m The concentration ratio Zr/X of the metal element X in the boride is 1.5 or less. In other words, the boride particle dispersion may contain zirconia from the medium beads used at the time of pulverization, and the weight concentration of Zr is preferably the weight concentration of Zr with respect to the weight concentration of the metal element X in the boride particle dispersion1.5 times or less. This is because, when the concentration ratio Zr/X in the boride particle dispersion liquid obtained as described above is 1.5 or less, the increase in viscosity of the boride particles can be sufficiently suppressed.
The boride particle dispersion of the present embodiment described above can be used for various applications as an infrared shielding particle dispersion. The boride particle dispersion of the present embodiment contains the boride particles described above, and can easily have an average dispersion particle diameter of 100nm or less, particularly 85nm or less. Therefore, the occurrence of blue fog can be suppressed.
(Infrared shielding transparent substrate and infrared shielding optical Member)
An example of the structure of the infrared shielding transparent substrate according to the present embodiment will be described.
The infrared shielding transparent substrate of the present embodiment has a coating layer including infrared shielding particles and a binder on at least one surface of the transparent substrate.
Further, the infrared shielding particles may be represented by the general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, and m is a number indicating the boron content in the general formula), and the carbon content is 0.2% by mass or less as measured by the combustion infrared absorption method.
As described above, the infrared shielding transparent substrate of the present embodiment may have a transparent substrate and a coating layer disposed on at least one surface of the transparent substrate. And, the coating may include infrared shielding particles and a binder.
The components are described below.
(1) Infrared shielding particle and method for producing same
The boride particles can be used as the infrared shielding particles, and therefore, the description thereof is omitted here.
(2) Adhesive agent
Since the coating layer contains the binder as described above, the binder will be described below.
As the binder, for example, an Ultraviolet (UV) curable resin, a thermoplastic resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, or the like can be selected according to the purpose. In particular, the binder preferably includes at least one binder selected from Ultraviolet (UV) curable resins, thermoplastic resins, thermosetting resins, and room temperature curable resins.
Specifically, the binder may be a polyethylene resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polyvinyl alcohol resin, a polystyrene resin, a polypropylene resin, an ethylene vinyl acetate copolymer, a polyester resin, a polyethylene terephthalate resin, a fluorine resin, a polycarbonate resin, an acrylic resin, a polyvinyl butyral resin, or the like.
As the binder, for example, one or two or more kinds selected from the above resin groups may be used in combination. However, as the binder for coating, among the above resin groups, UV curable resins are particularly preferably used from the viewpoints of productivity, equipment cost, and the like.
In addition, an inorganic binder using a metal alkoxide may be used instead of the resin binder. As the metal alkoxide, an alkoxide such as Si, ti, al, zr is exemplified. The inorganic resin using these metal alkoxides is hydrolyzed by heating or the like and polycondensed, whereby a coating layer of an oxide film can be formed.
The resin binder and the inorganic binder may be mixed and used.
(3) Transparent substrate
The infrared shielding transparent substrate of the present embodiment may have a coating layer on at least one surface of the transparent substrate. Therefore, a configuration example of the transparent substrate will be described below.
As the transparent substrate, for example, a transparent film substrate or a transparent glass substrate can be preferably used.
The transparent film base material is not limited to the film shape, and may be, for example, a plate shape or a sheet shape. The material of the transparent film base is not particularly limited, and for example, one or more selected from polyester, acrylic, polyurethane, polycarbonate, polyethylene, ethylene-vinyl acetate copolymer, vinyl chloride, fluororesin, and the like can be used. The transparent film base material is preferably a polyester film, and more preferably a polyethylene terephthalate (PET) film.
The transparent glass substrate is not particularly limited, and a transparent glass substrate such as quartz glass or soda glass may be used.
In addition, the surface of the transparent substrate is preferably subjected to a surface treatment in order to improve the coating property of the infrared shielding particle dispersion liquid or the adhesion property to the coating layer. In order to improve the adhesion between the transparent substrate and the coating layer, an intermediate layer may be formed on the transparent substrate, and the coating layer may be formed on the intermediate layer. The intermediate layer is not particularly limited, and may be formed by, for example, a polymer film, a metal layer, an inorganic layer (for example, an inorganic oxide layer such as silica, titania, zirconia, or the like), an organic/inorganic composite layer, or the like.
As described above, the infrared shielding transparent substrate of the present embodiment has a coating layer including infrared shielding particles and a binder on at least one surface of the transparent substrate.
The coating layer may be composed of only infrared shielding particles and a binder, and may contain other components. For example, as described above, the coating layer can be produced using an infrared shielding particle dispersion liquid, and a solvent, a dispersant, a coupling agent, a surfactant, or the like can be added to the infrared shielding particle dispersion liquid. Therefore, the coating layer may contain an additive component added to the infrared shielding particle dispersion liquid or a component derived from the additive component.
In order to further impart an ultraviolet shielding function to the infrared shielding transparent substrate of the present embodiment, at least one or more ultraviolet shielding materials selected from particles of inorganic titanium oxide, zinc oxide, cerium oxide, and the like, organic benzophenone, benzotriazole, and the like may be added to the coating layer.
The ultraviolet shielding material is not limited to the form added to the coating layer, and a layer containing the ultraviolet shielding material may be formed separately. When the layer containing the ultraviolet shielding material is formed, the arrangement of the layer is not particularly limited, and for example, the layer may be formed on a coating layer.
In order to improve the visible light transmittance of the infrared shielding transparent substrate of the present embodiment, one or more particles selected from ATO, ITO, aluminum-added zinc oxide, and indium tin composite oxide may be further mixed into the coating layer. By adding these transparent particles to the coating layer, the transmittance around 750nm is increased, and the infrared light having a longer wavelength than 1200nm is shielded, so that a heat ray shielding body having high transmittance of near infrared light and high heat ray shielding characteristics can be obtained. The above-mentioned particles selected from one or more types of ATO and the like are not limited to the form added to the coating layer, and a layer containing the particles may be formed in addition to the coating layer.
The thickness of the coating layer on the transparent substrate is not particularly limited, but is preferably 20 μm or less, more preferably 6 μm or less in practical use. This is because, when the thickness of the coating layer is 20 μm or less, the coating layer exhibits sufficient pencil hardness and scratch resistance, and further, when the solvent in the coating layer volatilizes and the adhesive is cured, the occurrence of process abnormalities such as warpage of the substrate film can be avoided.
The lower limit of the thickness of the coating layer is not particularly limited, and is preferably 10nm or more, more preferably 50nm or more, for example.
The content of the infrared shielding particles contained in the coating layer is not particularly limited, and it is preferable that the content per unit projected area of the transparent substrate/coating layer is 0.01g/m 2 Above 1.0g/m 2 The following is given. This is because if the content is 0.01g/m 2 The above-mentioned heat ray shielding characteristics can be intentionally exhibited as compared with the case where the infrared shielding particles are not contained, and the content is 1.0g/m 2 The infrared shielding transparent substrate can sufficiently maintain the transmittance of visible light.
In the infrared shielding transparent substrate of the present embodiment, it is preferable that the maximum value of the diffuse transmission curve in the region of the wavelength of 360nm to 500nm when the visible light transmittance of the coating layer (wavelength of 400nm to 780 nm) is set to 45% to 55%.
When a transparent substrate having a sufficient visible light transmittance is used and the transparent substrate has little effect on the visible light transmittance of the infrared shielding transparent substrate, that is, when a transparent substrate having a visible light transmittance of 90% or more is used, for example, the visible light transmittance of the coating layer may be regarded as the visible light transmittance of the infrared shielding transparent substrate.
Here, a method of evaluating blue fog will be described.
No method for directly measuring blue fog is known. However, the applicant of the present invention has proposed a method of focusing on straight incident light and scattered light as components of transmitted light when light is irradiated to an infrared shielding particle dispersion or the like as a reagent, and evaluating "blue fog" by finding diffuse transmittance for each wavelength (see patent document 5). The principle of measuring the diffuse transmittance, that is, the diffuse transmittance curve for each wavelength will be described below with reference to fig. 1 and 2.
First, a measuring device for measuring a diffuse transmission curve will be described with reference to fig. 1 and 2.
As shown in fig. 1 and 2, the measuring device 10 includes an integrating sphere 14. The inner surface of the spherical body of the integrating sphere 14 has diffuse reflection, and the integrating sphere 14 has a first opening 141 to which the measurement reagent 12 (see fig. 2) is attached, a second opening 142 to which the standard reflection plate 15 or the optical trap member 16 is attached, and a third opening 143 to which the light receiver 13 is attached.
The light source 11 that emits the linear light to be incident into the spherical space through the first opening 141, an unillustrated beam splitter that is attached to the light receiver 13 and splits the received reflected light or scattered light, an unillustrated data storage section that is connected to the beam splitter and stores the split data of the split reflected light or scattered light, and an unillustrated calculation section that calculates the ratio of the diffuse transmission light intensity to each wavelength of the diffuse transmission light intensity from the stored respective split data of the blank (blank) transmission light intensity and the diffuse transmission light intensity, respectively, and obtains the diffuse transmission of each wavelength.
Here, the integrating sphere 14 is coated with barium sulfate, specfralon (registered trademark), or the like on the inner surface of the spherical body and has diffuse reflectivity, and the incident angle to the standard reflection plate 15 may be, for example, 10 ° on both the standard side and the contrast side. As the light receiver 13, for example, a photomultiplier tube (ultraviolet and visible light range) or a cooled lead sulfide (near infrared range) can be used. In addition, a wavelength measurement range and a photometry accuracy (±0.002 Abs) in the ultraviolet and visible light range are necessary for a not-shown spectroscope mounted on the photodetector 13.
As the light source 11 to be emitted into the spherical space, for example, a deuterium lamp may be used in the ultraviolet region, and a 50W halogen lamp may be used in the visible light and near infrared region.
For the standard reflection plate 15, for example, a white plate made of SPECTRALON may be used, and the function of capturing the incident linear light without reflection is necessary for the optical trap member 16, for example, a dark box that absorbs the incident linear light almost completely may be used.
The maximum value of the diffuse transmission curve of the infrared shielding transparent substrate or the like as the measurement reagent can be evaluated by the steps of the blank transmitted light intensity measurement step, the diffuse transmitted light intensity measurement step, and the diffuse transmission calculation step using the above diffuse transmission curve measurement device.
First, in the blank transmitted light intensity measurement step, as shown in fig. 1, the standard reflection plate 15 is attached to the second opening 142 of the integrating sphere 14, and the linear light from the light source 11 is injected into the spherical space through the first opening 141 in a state where the measurement reagent is not attached to the first opening 141. Then, the reflected light reflected by the standard reflection plate 15 is received by the light receiver 13, and the light is split by a not-shown splitter mounted on the light receiver 13 and the split data of the reflected light is obtained. The spectroscopic data at this time is the blank transmitted light intensity.
Next, in the diffuse transmission light intensity measurement step, as shown in fig. 2, the light trap member 16 is mounted on the second opening 142 of the integrating sphere 14. Next, with the measuring reagent attached to the first opening 141, the linear light from the light source 11 is made to enter the spherical space through the measuring reagent 12 and the first opening 141, and scattered light other than the light captured by the optical trap member 16 is received by the light receiver 13. At this time, the light is split by a not-shown light splitter mounted on the light receiver 13, and the split data of the scattered light is obtained. The spectroscopic data at this time is the diffuse transmission light intensity.
Next, in the diffuse transmittance calculation step, the diffuse transmittance of each wavelength may be calculated by a calculation unit (not shown) based on the respective data of the blank transmission light intensity and the diffuse transmission light intensity stored by a data storage unit (not shown), and the maximum value of the area of the wavelength 360nm to 500nm in the diffuse transmission curve of the measuring reagent 12 may be calculated from the obtained diffuse transmittance of each wavelength.
In the measuring device for measuring the diffuse transmission curve, an optical system for adjusting light may be provided between the light source 11 and the measuring reagent 12. In this optical system, for example, a plurality of lenses are combined to adjust parallel light, and an aperture is used to adjust the light amount. The removal of specific wavelengths may sometimes be performed using filters.
Further, as described above, in the infrared shielding transparent substrate of the present embodiment, it is preferable that the maximum value of the diffuse transmission curve in the region of 360nm to 500nm in wavelength when the visible light transmittance of the coating layer (wavelength 400nm to 780 nm) is set to 45% to 55% at any value is 1.5% or less. This is because it was confirmed that almost no blue fog was observed on the infrared shielding transparent substrate satisfying the above conditions.
The setting of the visible light transmittance of the coating layer to 45% or more and 55% or less is to limit the measurement conditions of diffuse transmittance (diffuse transmittance curve), and the range is set because the diffuse transmittance is proportional to the visible light transmittance. The diffuse transmittance (diffuse transmittance curve) in the region of 360nm to 500nm is measured because scattering in this region is the cause of blue haze. If the maximum value of diffuse transmittance in the above range is 1.5% or less, blue fog is experimentally not observed with the naked eye.
The infrared shielding transparent substrate according to the present embodiment can be used for various optical members, and may be an infrared shielding optical member including the infrared shielding transparent substrate according to the present embodiment.
Examples of the infrared shielding optical member include a window of a building, a window of an automobile, and the like.
According to the infrared shielding transparent substrate of the present embodiment and the infrared shielding optical member including the infrared shielding transparent substrate described above, an infrared shielding transparent substrate using boride particles that can be easily pulverized can be obtained. Therefore, the average dispersion particle diameter of the infrared shielding particles contained in the coating layer can be sufficiently reduced, and the occurrence of blue fog can be suppressed.
(method for producing an infrared-shielding transparent substrate)
The infrared shielding transparent substrate of the present embodiment can be produced using, for example, an infrared shielding particle dispersion. Therefore, the infrared shielding particle dispersion and the method for producing the same will be described first.
(1) Infrared shielding particle dispersion and method for producing same
As described above, the infrared shielding transparent substrate of the present embodiment can be produced using an infrared shielding particle dispersion liquid containing boride particles as infrared shielding particles described above. Therefore, a description will be given here of one configuration example of the infrared shielding particle dispersion liquid and the method for producing the same.
The infrared shielding particle dispersion liquid is a dispersion liquid in which the infrared shielding particles are dispersed in a solvent. The infrared shielding particle dispersion is obtained by adding the above-mentioned infrared shielding particles, a dispersant, a coupling agent, a surfactant, and the like as needed to a solvent, and performing dispersion treatment, and dispersing the infrared shielding particles in the solvent.
The solvent of the infrared shielding particle dispersion liquid is required to have a function for maintaining the dispersibility of the infrared shielding particles and a function for preventing coating defects when the dispersion liquid is coated.
Specifically, examples thereof include alcohol solvents such as Methanol (MA), ethanol (EA), 1-propanol (NPA), isopropanol (IPA), butanol, pentanol, benzyl alcohol, diacetone alcohol, ketone solvents such as acetone, methyl Ethyl Ketone (MEK), methyl propyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, isophorone, ester solvents such as 3-methyl-methoxy-propionate (MMP), ethylene glycol monomethyl ether (MCS), ethylene glycol monoether (ECS), ethylene glycol isopropyl ether (IPC), propylene glycol methyl ether (PGM), propylene glycol diethyl ether (PE), propylene Glycol Methyl Ether Acetate (PGMEA), glycol derivatives such as propylene glycol diethyl ether acetate (PE-AC), formamide (FA), amides such as N-methylformamide (DMF), dimethylacetamide, N-methyl-2-pyrrolidone (NMP), aromatic hydrocarbons such as toluene, xylene, chlorinated hydrocarbons such as chlorobenzene, and the like, and combinations of one or two or more selected from the above.
Among the above solvents, ketones such as MIBK and MEK, aromatic hydrocarbons such as toluene and xylene, and glycol ether acetates such as PGMEA and PE-AC are more preferable, and particularly high in hydrophobicity. Therefore, one or two or more selected from the above may be used in combination.
In order to form a coating layer on a transparent substrate such as a transparent film substrate or a transparent glass substrate, a low boiling point organic solvent is preferably selected as the solvent. This is because, if the solvent is a low-boiling organic solvent, the solvent can be easily removed in the drying step after the coating, and the properties of the coating layer such as hardness and transparency are not impaired.
Specifically, for example, one or more kinds of aromatic hydrocarbons selected from ketones such as methyl isobutyl ketone and methyl ethyl ketone, toluene and xylene are preferably used in combination.
The dispersant, the coupling agent, and the surfactant may be selected according to the purpose, and those having an amine group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group are preferable. These functional groups adsorb to the surface of the infrared shielding particles and prevent aggregation of the infrared shielding particles, so that when a coating layer is formed on a transparent substrate or an infrared shielding particle dispersion described below is formed, the effect of uniformly dispersing the infrared shielding particles in the coating layer or the infrared shielding particle dispersion is exhibited.
As the dispersant, coupling agent, and surfactant, for example, a phosphate compound, a polymer-based dispersant, a silane-based coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, and the like can be preferably used.
Examples of the polymer-based dispersant include an acrylic polymer-based dispersant, a polyurethane polymer-based dispersant, an acrylic-block copolymer polymer-based dispersant, a polyether-based dispersant, and a polyester-based polymer-based dispersant.
However, the dispersant, the coupling agent, and the surfactant are not limited thereto, and various dispersants, coupling agents, and surfactants may be used.
The amount of one or more materials selected from the group consisting of dispersants, coupling agents, and surfactants to be added to the infrared shielding particle dispersion is preferably in the range of 10 parts by weight to 1000 parts by weight, more preferably in the range of 20 parts by weight to 200 parts by weight, based on 100 parts by weight of boride particles as infrared shielding particles.
When the amount of the dispersant or the like is within the above range, aggregation of the infrared shielding particles in the dispersion can be suppressed, and dispersion stability can be maintained.
The method of dispersing boride particles as infrared shielding particles in a solvent (liquid medium) is not particularly limited. For example, a method of dispersing a raw material mixture of the infrared shielding particle dispersion liquid using a wet medium mill such as a bead mill, a ball mill, or a sand mill is mentioned. In particular, the infrared shielding particle dispersion liquid of the present embodiment preferably has a state in which infrared shielding particles having an average dispersion particle diameter of 100nm or less are dispersed in a solvent (liquid medium), and more preferably the infrared shielding particles have an average dispersion particle diameter of 85nm or less. Therefore, it is preferable to disperse boride particles by wet grinding using a medium stirring mill such as a bead mill to prepare a dispersion liquid.
In order to obtain a uniform infrared shielding particle dispersion, various additives or the above-mentioned dispersing agents may be added or pH adjustment may be performed.
The content of the infrared shielding particles in the infrared shielding particle dispersion is preferably 0.01 mass% or more and 30 mass% or less. This is because, when the content of the infrared shielding particles is 0.01 mass% or more, a coating layer having an infrared shielding function can be formed on the transparent substrate. Further, if the content of the infrared shielding particles is 30 mass% or less, the infrared shielding particles can be easily coated on the transparent substrate, and the productivity of the coating layer can be improved.
The infrared shielding particles in the infrared shielding particle dispersion are preferably dispersed so that the average dispersion particle diameter is 100nm or less, and more preferably dispersed so that the average dispersion particle diameter is 85nm or less. This is because, when the average dispersion particle diameter of the infrared shielding particles is 100nm or less, the occurrence of blue haze in the infrared shielding transparent substrate produced using the infrared shielding particle dispersion of the present embodiment can be suppressed, and the optical characteristics can be improved. In addition, when the average dispersion particle diameter is 85nm or less, occurrence of blue fog in the infrared shielding transparent substrate can be suppressed particularly.
The inventors of the present invention have estimated the following reason that the infrared shielding particle dispersion liquid can be effectively pulverized to an average dispersion particle diameter of 100nm or less, particularly 85nm or less without causing problems such as gelation of the infrared shielding particle dispersion liquid (slurry) when the infrared shielding particle dispersion liquid is produced using the boride particles.
Since boride particles are hard, when pulverized by a wet media mixer mill, fine powder worn out by media beads, fine bead pieces after the media beads are broken, and other wear debris are mixed into slurry. At this time, since the hardness of boride particles increases with an increase in carbon concentration, when boride particles having a carbon concentration higher than 0.2 mass% are used as a raw material, a large amount of abrasion slag of the medium beads is mixed into the slurry. The mixing of the abrasion slag of the media beads is a cause of increasing the slurry concentration.
In contrast, by using boride particles having a carbon concentration of 0.2 mass% or less as a raw material, when the particles are pulverized to an average dispersion particle diameter of 100nm or less, particularly 85nm or less, the mixing amount of abrasion slag of the medium beads can be greatly reduced, and therefore, it is presumed that the pulverization can be effectively performed without deteriorating the viscosity of the slurry. However, the viscosity of the slurry is not increased in a part that is not explained, and the viscosity may also be other than the above-described operation, and thus the viscosity is not limited to the above-described operation.
(2) Method for manufacturing infrared shielding transparent substrate
Next, a configuration example of a method for manufacturing an infrared shielding transparent substrate according to the present embodiment will be described.
The infrared shielding transparent substrate of the present embodiment is produced by using the above-described infrared shielding particle dispersion liquid and forming a coating layer containing infrared shielding particles on the transparent substrate. Examples of specific steps are described below.
The infrared shielding particle dispersion liquid is added with a binder to obtain a coating liquid.
After the obtained coating liquid is coated on the surface of the transparent substrate, the solvent is evaporated and the binder is cured by a predetermined method, whereby a coating layer in which the infrared shielding particles are dispersed in a medium can be formed.
The coating layer may be formed by preparing a coating liquid having a controlled concentration without adding a binder to the infrared shielding particle dispersion, coating the coating liquid on a transparent substrate, evaporating the solvent, and then coating the coating liquid containing the binder with a coating layer, and evaporating the solvent.
The adhesive and the transparent substrate which can be preferably used for the coating layer are already described, and therefore, the description thereof is omitted here.
The surface of the transparent substrate is preferably subjected to a surface treatment in order to improve the coatability of the infrared shielding particle dispersion or the adhesion to the coating layer. In order to improve the adhesion between the transparent substrate and the coating layer, an intermediate layer may be formed on the transparent substrate, and the coating layer may be formed on the intermediate layer. The intermediate layer may be formed, for example, by a polymer film, a metal layer, an inorganic layer (for example, an inorganic oxide layer such as silica, titania, zirconia, or the like), an organic/inorganic composite layer, or the like.
The method for providing the coating layer on the transparent substrate is not particularly limited as long as the method can uniformly apply the infrared shielding particle dispersion liquid to the surface of the transparent substrate. Examples thereof include bar coating (bar coat) method, gravure coating method, spray coating method, dip coating method, and the like.
For example, when a UV curable resin is used as a binder contained in the infrared shielding particles and a coating layer is formed by a bar coating method, it is preferable to appropriately adjust the liquid concentration and additives in advance for the infrared shielding particle dispersion liquid so as to have appropriate balance (leveling). Further, a bar (wire bar) of a bar number may be selected to form a coating film on the transparent substrate so that the thickness of the coating film and the content of the infrared shielding particles may be brought into the desired object of the obtained infrared shielding transparent substrate.
Then, the organic solvent contained in the coating film is removed by drying, and then the coating film is cured by irradiation with ultraviolet rays, whereby a coating layer can be formed on the transparent substrate. In this case, the drying conditions of the coating film may be varied depending on the respective components, the types of solvents, and the use ratios, and may be performed by heating at a temperature of 60 to 140℃for about 20 seconds to 10 minutes, for example. The method of irradiating ultraviolet rays is not particularly limited, and for example, a UV exposure machine such as an ultra-high pressure mercury lamp can be preferably used.
In addition, the steps before and after the formation of the coating layer may be used to handle adhesion between the transparent substrate and the coating layer, smoothness of the coating film at the time of coating, drying of the organic solvent, and the like. As the front and rear steps, for example, a surface treatment step of the transparent substrate, a pre-baking (pre-heating of the substrate), a post-baking (post-heating of the substrate), and the like can be appropriately selected. The heating temperature in the pre-baking step and/or the post-baking step is preferably 80 ℃ to 200 ℃ and the heating time is preferably 30 seconds to 240 seconds.
The preferred ranges of the thickness of the formed coating layer or the content of the infrared shielding particles in the coating layer have already been described, and therefore description thereof is omitted here.
In order to further impart an ultraviolet shielding function to the infrared shielding transparent substrate of the present embodiment, at least one or more ultraviolet shielding materials selected from the group consisting of particles of inorganic titanium oxide, zinc oxide, cerium oxide, and the like, organic benzophenone, benzotriazole, and the like may be added to the coating layer.
In order to improve the visible light transmittance of the infrared shielding transparent substrate of the present embodiment, one or more particles selected from ATO, ITO, aluminum-added zinc oxide, and indium tin composite oxide may be further mixed into the coating layer. By adding these transparent particles to the coating layer, the transmittance around 750nm is increased, and the infrared light having a longer wavelength than 1200nm is shielded, so that a heat ray shielding body having high transmittance of near infrared light and high heat ray shielding characteristics can be obtained.
According to the method for producing an infrared shielding transparent substrate of the present embodiment described above, an infrared shielding transparent substrate using boride particles that can be easily pulverized can be produced. According to the infrared shielding transparent substrate, the average dispersion particle diameter of the infrared shielding particles contained in the coating layer can be sufficiently reduced, and the occurrence of blue fog can be suppressed.
(Infrared shielding particle Dispersion)
An example of the constitution of the infrared shielding particle dispersion according to this embodiment will be described.
The infrared shielding particle dispersion of the present embodiment may include boride particles and a thermoplastic resin. Here, the boride particles may be represented by the general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula), and the carbon content is 0.2% by mass or less as measured by the infrared absorption by combustion method.
The components are described below.
(1) Boride particles (infrared shielding particles) and method for producing same
Since the boride particles described above can be used, the description thereof is omitted here.
(2) Thermoplastic resin
As described above, the infrared shielding particle dispersion of the present embodiment may have a thermoplastic resin. The thermoplastic resin is not particularly limited, and various thermoplastic resins can be used depending on the application and the like.
For example, when the infrared shielding particle dispersion of the present embodiment is used for various window materials, a thermoplastic resin having sufficient transparency is preferable.
Specifically, the thermoplastic resin is preferably one or more thermoplastic resins selected from the group consisting of: a resin selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, ethylene-vinyl acetate copolymer, ionomer resin, polyvinyl butyral resin, polyvinyl acetal resin; a mixture of two or more resins selected from the above resin group; or a copolymer of two or more resins selected from the group of resins.
In addition, for example, when the infrared shielding particle dispersion according to the present embodiment is used as a window material in a master plate shape, the thermoplastic resin is preferably a thermoplastic resin that satisfies high transparency and is required as general properties required for the window material, that is, requirements such as rigidity, light weight, long-term durability, and low cost. In this case, the thermoplastic resin is preferably at least one selected from polyethylene terephthalate resin, polycarbonate resin, ionomer resin, and acrylic resin, and more preferably a polycarbonate resin.
On the other hand, when the infrared shielding particle dispersion of the present embodiment is used as an intermediate layer of an infrared shielding interlayer transparent substrate to be described later, a polyvinyl acetal resin or an ethylene-vinyl acetate copolymer can be preferably used as the thermoplastic resin from the viewpoints of adhesion to the transparent substrate, weather resistance, penetration resistance, and the like. In particular, the thermoplastic resin at this time is more preferably a polyvinyl acetal resin.
In the case where the infrared shielding particle dispersion of the present embodiment is used as the intermediate layer, and the thermoplastic resin constituting the infrared shielding particle dispersion alone does not sufficiently have flexibility or adhesion to the transparent substrate, for example, in the case where the thermoplastic resin is polyvinyl acetal, it is preferable to further add a plasticizer.
The plasticizer is not particularly limited, and a material that functions as a plasticizer with respect to the thermoplastic resin used may be used. Examples of the plasticizer for the polyacetal resin include plasticizers which are compounds of monohydric alcohols and organic acid esters, plasticizers which are esters of polyhydric alcohol organic acid ester compounds and the like, and phosphoric plasticizers which are organic phosphoric plasticizers and the like. Each plasticizer is preferably liquid at room temperature. Among them, a plasticizer is preferable as an ester compound synthesized from a polyol and a fatty acid.
As described above, the infrared shielding particle dispersion of the present embodiment may contain boride particles and a thermoplastic resin, and may have a form in which the boride particles are dispersed in the thermoplastic resin, for example.
The infrared shielding particle dispersion of the present embodiment may contain any component as required in addition to boride particles and thermoplastic resin. For example, as described above, the infrared shielding particle dispersion may contain a plasticizer, an optional additive component added during the production of the infrared shielding particle dispersion, or a component derived from the additive component.
In order to further impart an ultraviolet shielding function to the infrared shielding particle dispersion of the present embodiment, at least one or more of particles of inorganic titanium oxide, zinc oxide, cerium oxide, or the like, organic benzophenone, benzotriazole, or the like may be added to the infrared shielding particle dispersion.
In order to improve the visible light transmittance of the infrared shielding particle dispersion of the present embodiment, one or more particles selected from ATO, ITO, aluminum-added zinc oxide, and indium tin composite oxide may be further mixed into the coating layer. By adding these transparent particles to the infrared shielding particle dispersion, the transmittance around 750nm is increased, and the infrared light having a wavelength longer than 1200nm is shielded, so that the infrared shielding particle dispersion having high transmittance of near infrared light and high heat ray shielding property can be obtained.
The content of boride particles as infrared shielding particles contained in the infrared shielding particle dispersion is not particularly limited, and the content of boride particles per unit projected area is preferably 0.01g/m 2 Above 1.0g/m 2 The following is given. This is because if the content is 0.01g/m 2 In the above, the heat ray shielding property is intentionally exhibited as compared with the case where boride particles as infrared shielding particles are not contained, and the content is 1.0g/m 2 Hereinafter, the infrared shielding particle dispersion can sufficiently maintain the transmittance of visible light.
The optical characteristics of the infrared shielding particle dispersion of the present embodiment are not particularly limited, and it is preferable that when the maximum transmittance in the visible light wavelength region is 70%, the transmittance of near infrared light having a wavelength of 850nm is 23% or more and 45% or less, and the minimum value of the transmittance of heat rays having a wavelength of 1200nm or more and 1800nm or less is 15% or less.
Here, as a method of adjusting the maximum transmittance in the visible light wavelength region to 70%, there is a method of adjusting the content of boride particles as infrared shielding particles of the infrared shielding particle dispersion, the thickness of the infrared shielding particle dispersion, or the like.
Specifically, the concentration of the infrared shielding particles contained in the infrared shielding particle dispersion powder, the infrared shielding particle plasticizer dispersion liquid, or the master batch, which will be described later, the addition amount of the infrared shielding particle dispersion powder, the infrared shielding particle plasticizer dispersion liquid, or the master batch, and the thickness of the film or sheet, etc. at the time of preparing the resin composition, can be easily adjusted.
The shape of the infrared shielding particle dispersion according to the present embodiment is not particularly limited, and may have a plate shape, for example, and specifically, may have a sheet shape, a plate shape, or a film shape. The infrared shielding particle dispersion according to the present embodiment may be referred to as, for example, an infrared shielding film or an infrared shielding sheet, depending on the shape thereof.
In the infrared shielding particle dispersion of the present embodiment, it is preferable that the maximum value of the diffuse transmission curve in the region of the wavelength of 360nm to 500nm is 1.5% or less when the visible light (wavelength of 400nm to 780 nm) transmittance is set to the range of 45% to 55%.
Since the evaluation method for blue fog has already been described, a description thereof is omitted here. Although the method of directly measuring blue fog is not known as described above, the applicant of the present invention has paid attention to the linear incident light and scattered light as components of transmitted light when the infrared shielding particle dispersion as a reagent is irradiated with light, and has proposed a method of evaluating "blue fog" by determining diffuse transmittance for each wavelength, and has been described in the present specification.
Further, in the infrared shielding particle dispersion of the present embodiment, it is preferable that the maximum value of the diffuse transmission curve in the region of the wavelength of 360nm to 500nm is 1.5% or less when the visible light transmittance (wavelength of 400nm to 780 nm) of the infrared shielding particle dispersion is set to any of 45% to 55% as described above. This is because it was confirmed that almost no blue fog was observed on the infrared shielding particle dispersion satisfying the above conditions.
The setting of the visible light transmittance of the infrared shielding particle dispersion to 45% to 55% is to limit the measurement conditions of diffuse transmittance (diffuse transmittance curve), and the range is set because the diffuse transmittance is proportional to the visible light transmittance. The diffuse transmittance (diffuse transmittance curve) in the region of 360nm to 500nm is measured because scattering in this region is the cause of blue haze. If the maximum value of diffuse transmittance in the above range is 1.5% or less, blue fog is experimentally not observed with the naked eye.
According to the infrared shielding particle dispersion of the present embodiment described above, an infrared shielding particle dispersion using boride particles that can be easily pulverized can be obtained. Therefore, the average dispersion particle diameter of boride particles contained as infrared shielding particles can be sufficiently reduced, and occurrence of blue fog can be suppressed.
(Infrared shielding particle-dispersed powder, masterbatch, and method for producing infrared shielding particle dispersion)
(1) Infrared shielding particle dispersion and method for producing same
The infrared shielding particle dispersion according to the present embodiment can be produced using the above-described infrared shielding particle dispersion liquid containing boride particles as the infrared shielding particles. Therefore, a description will be given here of one configuration example of the infrared shielding particle dispersion liquid and the method for producing the same.
The infrared shielding particle dispersion is a dispersion in which the boride particles are dispersed in a solvent. The infrared shielding particle dispersion is obtained by adding the boride particles as infrared shielding particles, and if necessary, a proper amount of a dispersant, a coupling agent, a surfactant, and the like to a solvent, and performing dispersion treatment, and dispersing the boride particles in the solvent.
The infrared shielding particle dispersion liquid can be the same as the dispersion liquid described in the method for producing an infrared shielding transparent substrate, and therefore, the description thereof will be omitted here.
The content of the infrared shielding particles in the infrared shielding particle dispersion is preferably 0.01 mass% or more and 30 mass% or less. This is because, when the content of the infrared shielding particles is 0.01 mass% or more, an infrared shielding particle dispersion having a sufficient infrared shielding function can be formed. Further, if the content of the infrared shielding particles is 30 mass% or less, the infrared shielding particle dispersion can be easily formed, and productivity of the infrared shielding particle dispersion can be improved.
The infrared shielding particles in the infrared shielding particle dispersion are preferably dispersed so that the average dispersion particle diameter is 100nm or less, and more preferably dispersed so that the average dispersion particle diameter is 85nm or less. This is because, when the average dispersion particle diameter of the infrared shielding particles is 100nm or less, the occurrence of blue haze in the infrared shielding particle dispersion produced using the infrared shielding particle dispersion liquid of the present embodiment can be suppressed, and the optical characteristics can be improved. In addition, when the average dispersion particle diameter is 85nm or less, occurrence of blue fog in the infrared shielding particle dispersion can be suppressed particularly.
(2) Infrared shielding particle dispersion powder, infrared shielding particle plasticizer dispersion liquid, master batch, and method for producing same
The boride particles as the infrared shielding particles may be dispersed in a solvent together with a dispersant, a coupling agent and/or a surfactant as needed to obtain an infrared shielding particle dispersion.
Further, by removing the solvent from the infrared shielding particle dispersion liquid, for example, the infrared shielding particle dispersion powder of the present embodiment in which the infrared shielding particles are dispersed in the dispersant can be obtained.
In this case, the infrared shielding particle dispersion powder may include boride particles of the general formula XB, and a dispersant m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula), and the carbon content is 0.2% by mass or less as measured by the infrared absorption by combustion method.
As a method for removing the solvent from the infrared shielding particle dispersion, drying under reduced pressure is preferable. Specifically, the infrared shielding particle-containing composition and the solvent component are separated by drying under reduced pressure while stirring the infrared shielding particle dispersion. The apparatus for the reduced pressure drying is not particularly limited, and may be any apparatus having the above-described functions. In addition, the pressure value at the time of depressurization in the drying step is appropriately selected.
By using the reduced pressure drying method, the efficiency of removing the solvent from the infrared shielding particle dispersion can be improved, and the infrared shielding particle dispersion of the present embodiment is not exposed to high temperature for a long period of time, so that aggregation of the infrared shielding particles dispersed in the dispersion powder or the plasticizer dispersion is not caused, which is preferable. Further, productivity of the infrared shielding particle dispersion powder is also improved, and the evaporated solvent is easily recovered, which is also preferable from the viewpoint of environment.
In the infrared shielding particle dispersion powder of the present embodiment obtained after the drying step, the residual organic solvent is preferably 5 mass% or less. When the amount of the organic solvent remaining is 5 mass% or less, no bubbles are generated during processing of the infrared shielding particle dispersion powder into an infrared shielding interlayer transparent substrate, and the appearance and optical characteristics are maintained well.
Further, the infrared shielding particles may be dispersed in a plasticizer together with a dispersant, a coupling agent and/or a surfactant to obtain an infrared shielding particle plasticizer dispersion.
The infrared shielding particle plasticizer dispersion is not limited to the above method, and may be obtained by adding a plasticizer to the infrared shielding particle dispersion and removing the solvent. The solvent is preferably removed by drying under reduced pressure in the same manner as in the process of producing the infrared shielding particle-dispersed powder.
As the infrared shielding particle plasticizer dispersion, there may be included boride particles and a plasticizer, the boride particles being represented by the general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula), and the carbon content is 0.2% by mass or less as measured by the infrared absorption by combustion method.
Further, boride particles or dispersion powder may be dispersed in a resin, and the resin may be pelletized (pellitizing), thereby obtaining a master batch of the present embodiment.
Further, a master batch can be obtained by uniformly mixing boride particles or infrared shielding particle-dispersed powder, powder particles or granules (pellet) of a thermoplastic resin, and other additives as needed, kneading the mixture by a vented single-or twin-rod extruder, and processing the melt-extruded filaments into a pellet shape by a cutting method.
The shape of the master batch is not particularly limited, and examples thereof include a cylindrical shape and a prismatic shape. In addition, a so-called thermal cutting method of directly cutting the molten extrudate may be employed. In this case, a nearly spherical shape is generally obtained.
The master batch of the present embodiment is an infrared shielding particle dispersion including boride particles and a thermoplastic resin, and has a particle shape, the boride particles being represented by the general formula XB m (wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula), and the carbon content is 0.2% by mass or less as measured by the infrared absorption by combustion method.
(3) Method for producing infrared shielding particle dispersion
The infrared shielding particle dispersion of the present embodiment can be produced by uniformly mixing the above-described infrared shielding particle dispersion powder, infrared shielding particle plasticizer dispersion, or master batch of the present embodiment into a thermoplastic resin that is a transparent resin.
According to the infrared shielding particle dispersion of the present embodiment, for example, the transmittance of near infrared light in the wavelength range of 700nm to 1200nm can be improved while ensuring the infrared shielding characteristics of the composite tungsten oxide of the related art.
Since the thermoplastic resin that can be preferably used for the infrared shielding particle dispersion of the present embodiment has already been described, a description thereof is omitted here.
Further, the infrared shielding particle dispersion can be produced by kneading the dispersion powder, the plasticizer dispersion liquid, the master batch, the thermoplastic resin, and other additives such as a plasticizer as needed, and then molding the kneaded product into a planar or curved sheet by a known method such as an extrusion molding method or an injection molding method.
As a method for forming the infrared shielding particle dispersion, a known method can be used. For example, a calender roll method, an extrusion method, a casting method, an inflation method, or the like can be used.
(Infrared shielding Sandwich transparent substrate)
The infrared shielding interlayer transparent substrate of the present embodiment may have a plurality of transparent substrates and the above-described infrared shielding particle dispersion. The infrared shielding particle dispersion may be provided between a plurality of transparent substrates.
The infrared shielding interlayer transparent substrate is a transparent substrate in which an infrared shielding particle dispersion as an intermediate layer is sandwiched from both sides using a transparent substrate.
As the transparent substrate, a glass plate transparent in the visible light range, a plate-like plastic, a film-like plastic, or the like can be used. In other words, a transparent glass substrate or a transparent plastic substrate may be used.
The material of the plastic is not particularly limited and may be selected according to the application, and for example, when used in a transportation device such as an automobile, a transparent resin such as a polycarbonate resin, an acrylic resin, or a polyethylene terephthalate resin is preferable from the viewpoint of securing the visibility of a driver or an occupant of the transportation device. In addition, polyamide resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, and the like can be used.
In the infrared shielding interlayer transparent substrate of the present embodiment, when the visible light transmittance (wavelength of 400nm to 780 nm) of the infrared shielding particle dispersion included is set to be 45% to 55%, the maximum value of the diffuse transmission curve in the region of 360nm to 500nm is preferably 1.5% or less. This is because, when the maximum value of the diffuse transmission curve is in the above range, blue fog can be reliably suppressed.
The infrared shielding interlayer transparent substrate of the present embodiment may be obtained by bonding and integrating a plurality of opposed inorganic glasses sandwiching the above-mentioned infrared shielding particle dispersion by a known method. The obtained infrared shielding laminated inorganic glass can be preferably used mainly as an inorganic glass for the front side of an automobile or a window of a building.
< embodiment >
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
The method for evaluating the reagent in the examples and comparative examples below will be described first.
(composition of boride particles)
Boride particles obtained in the following examples and comparative examples were analyzed by ICP (model: ICPE9000, manufactured by Shimadzu corporation) to calculate a boride represented by the general formula XB m The element ratio (molar ratio) of boron (B) to the metal element X in the representation, that is, the value of m as the element ratio (B/X) of boron (B) to the metal element X in the boride particles.
(carbon concentration in boride particles)
The carbon content (carbon concentration) in boride particles produced in each of examples and comparative examples below was measured by the infrared absorption by combustion.
(B in boride particles) 4 C concentration)
Among the boride particles obtained, B is 4 The reagents for measuring the concentration of C were divided into two, weighed in platinum crucibles, and 7N nitric acid was added thereto and heated to 50℃to dissolve boride particles. After cooling, pure water was added thereto, and undissolved residue (B) was removed by a membrane filter made of cellulose acetate having a pore size of 0.2. Mu.m 4 C) And (5) filtering and separating.
A part of the obtained undissolved residue was put in an original platinum crucible, wetted with a saturated aqueous solution of calcium hydroxide for the purpose of preventing volatilization of boron, and dried in a dryer at about 80 ℃. And adding sodium carbonate after drying, fully mixing, and heating for melting. After cooling, the molten salt in the crucible was dissolved in warm water and transferred to a Teflon (registered trademark) beaker. After adding nitric acid, the mixture was heated and boiled to remove carbonic acid gas, and then used as a reagent solution for ICP. The boron concentration of the obtained reagent solution was analyzed by ICP.
Further, XRD measurement was performed on the other part of the obtained undissolved residue to confirm whether or not the undissolved residue was B 4 C single phase. When B is 4 In the case of single phase C, B is calculated from the boron concentration analyzed by ICP 4 C concentration.
(average dispersed particle diameter)
The average dispersed particle diameter of boride particles in the infrared shielding particle dispersion (boride particle dispersion) prepared in the examples and comparative examples below was measured by a particle diameter measuring apparatus (manufactured by tsukamurella electronics (stock): model: ELS-8000) using a dynamic light scattering method. The refractive index of the particles was 1.81, and the particle shape was a non-spherical shape. The refractive index of the solvent was set to 1.50 as measured with toluene.
(weight concentration ratio of Zr to metallic element X in boride particle Dispersion (Zr/X))
The weight concentration ratio (Zr/X) of Zr to the metal element X in the boride particle dispersion was measured by ICP (model ICPE9000 manufactured by shimadzu corporation), and calculated from the measured value.
(visible light transmittance)
The visible light transmittance in the following examples and comparative examples is a ratio of a transmitted light beam to an incident light beam of a light beam of sunlight perpendicularly incident on the reagent. The sunlight herein means CIE sunlight specified by the international commission on illumination. For the CIE daylight, the spectral illuminance distribution of the daylight of the same color temperature as that of the blackbody radiation is expressed by a relative value with respect to a value of 560nm in wavelength based on the observation data. The light beam is a value obtained by integrating, for each wavelength, the value of the product of the radiation beam of each radiation wavelength and the value of the photosensitivity (sensitivity of human eyes to light). In other words, the visible light transmittance is a value indicating the brightness perceived by the human eye by using an integrated value of the transmitted light amount obtained by normalizing the light transmission amount of the region having a wavelength of 380nm to 780nm with the photosensitivity of the human eye.
For the measurement of visible light transmittance, a spectrophotometer (model: U-4100, manufactured by Hitachi Co., ltd.) was used, and the infrared shielding particle dispersion or the infrared shielding interlayer transparent substrate produced in the following examples and comparative examples was measured at 1nm intervals in the range of 300nm to 2600 nm.
(maximum value of diffuse transmission curve)
The boride particle dispersions produced in the following examples and comparative examples were adjusted so that the transmittance of visible light (wavelength: 400nm to 780 nm) was 50%, and a maximum value of a diffuse transmission curve in a region of 360nm to 500 nm was measured by using a method described with reference to FIGS. 1 and 2 using a spectrophotometer (model U-4100, manufactured by Hitachi Ltd.) as a spectroscope.
The boride particle dispersion prepared in each example and comparative example was diluted with the main solvent so as to have the above visible light transmittance, and placed in a 10mm rectangular glass tank for measurement.
When the maximum value of the measured diffuse transmission curve was 1.5% or less, it was confirmed that almost no blue haze was observed in the infrared shielding particle dispersion prepared using the boride particle dispersion liquid.
In the measurement, setting the visible light transmittance of the boride particle dispersion liquid to 50% or less is to limit the measurement conditions of diffuse transmittance (diffuse transmittance curve), and the range is set because the diffuse transmittance is proportional to the visible light transmittance. The diffuse transmittance (diffuse transmittance curve) in the region of 360nm to 500nm is measured because scattering in this region is the cause of blue haze.
The infrared shielding transparent substrates, infrared shielding particle dispersions, and infrared shielding sandwich transparent substrates produced in the following examples and comparative examples were measured for diffuse transmittance at 1nm intervals in a range of 300nm to 800nm using the method described with reference to FIGS. 1 and 2 using a spectrophotometer (model: U-4100, manufactured by Hitachi Ltd.) as a spectroscope. And, a maximum value is obtained from the obtained diffuse transmission curve.
When evaluating the maximum value of the diffuse transmission curve of the infrared shielding particle dispersion and the infrared shielding interlayer transparent substrate, an infrared shielding proportional dispersion and an infrared shielding interlayer transparent substrate for measuring the diffuse transmission curve were prepared and evaluated under the same conditions as those of each example and comparative example except that the thickness of the infrared shielding particle dispersion was adjusted so that the visible light transmittance was 50% in each example and comparative example.
(haze)
The haze value of the infrared shielding transparent substrate, the infrared shielding particle dispersion or the infrared shielding interlayer transparent substrate produced in the following examples and comparative examples was measured by using a haze meter (model: HM-150, manufactured by Country color technology Co., ltd.) based on JIS K7105-1981.
(blue fog)
The blue fog was confirmed by visual observation by irradiating an artificial solar light lamp (XC-100 manufactured by Seric corporation) to the infrared shielding transparent substrate, the infrared shielding particle dispersion, or the infrared shielding interlayer transparent substrate manufactured in the following examples and comparative examples.
The following describes the conditions for producing the reagents and the evaluation results in each example and comparative example.
Example 1
Boron carbide was used as a boron source and a reducing agent, lanthanum oxide was used as a lanthanum source, and the materials were weighed and mixed so that the element ratio of lanthanum to boron, B/La, was 5.90. Then, the mixture was fired at 1600.+ -. 50 ℃ for 6 hours in an argon atmosphere to obtain a powder containing lanthanum hexaboride particles.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.05 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were used as General formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 5.8.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was measured and found to be 0.2% by mass.
Next, the powder containing lanthanum hexaboride particles (infrared shielding material) thus prepared was weighed and mixed in a ratio of 10 parts by weight, 80 parts by weight of toluene, and 10 parts by weight of a dispersant (amino group-containing acrylic polymer dispersant), to prepare 3kg of a slurry. The slurry was put into a medium agitator mill together with the beads, and the slurry was circulated and subjected to pulverization and dispersion treatment for 20 hours.
The medium stirring mill used was a horizontal cylindrical type Annular-type (manufactured by Ashizawa Co., ltd.) and the material of the vessel interior and the rotor (rotary stirring section) was ZrO 2 . As the beads, beads made of YSZ (Yttria-Stabilized Zirconia: yttria-stabilized zirconia) having a diameter of 0.3mm were used. The rotation speed of the rotor was 13 m/sec, and the pulverization was performed at a slurry flow rate of 1 kg/min. The average particle diameter of the boride particles in the resulting boride particle dispersion was measured and found to be 70nm.
Further, regarding the dispersion liquid, the weight concentration ratio (Zr/La) of Zr to La in the boride particle dispersion liquid and the maximum value of the diffuse transmission curve were evaluated as described above.
The results are shown in Table 1.
In addition, the weight ratio of the dispersion liquid is as follows: ultraviolet curing resin: toluene=2: 1:1, the obtained dispersion, an ultraviolet curable resin, and toluene were mixed in the same ratio to prepare a coating liquid. It was coated on a transparent glass substrate with a bar coater to form a coating film. At this time, the bar used for coating was selected so that the visible light transmittance of the obtained coating layer was about 50%. The coating thickness of IMC-700 manufactured by wellsite fabrication was about 10 μm as a bar coater.
Then, the solvent was evaporated from the coating film by holding at 70 ℃ for 1 minute, and the coating film was cured by irradiation with ultraviolet rays. The optical characteristics of the obtained infrared shielding transparent substrate were measured. The measurement results are shown in table 1 below.
The obtained infrared shielding transparent substrate had a haze of 0.2% and was found to have extremely high transparency. The maximum value of the diffuse transmission curve in the region of the wavelength of 360nm to 500nm was 0.6%. In addition, blue fog upon irradiation with artificial sunlight was not observed.
Further, the same amount of dispersant (acrylic polymer dispersant having an amino group) was added to the obtained dispersion, and the obtained mixture was kept in a dryer to remove the solvent component and then pulverized, whereby an infrared shielding particle dispersant powder was obtained.
The obtained infrared shielding particle dispersion powder was mixed with a polycarbonate resin, and a masterbatch in the form of pellets was produced by using an extrusion processor.
The master batch was mixed with a polycarbonate resin, and an infrared shielding particle dispersion was formed by an extrusion processor. At this time, the mixing ratio of the polycarbonate resin and the master batch was adjusted so that the visible light transmittance of the obtained infrared shielding particle dispersion was about 70%. The measurement results of the optical properties of the obtained infrared shielding particle dispersion are shown in table 1 below.
The visible light transmittance was about 70%, and it was confirmed that light in the visible light region was sufficiently transmitted. Further, the haze was 0.3%, and it was confirmed that the transparency was extremely high. The maximum value of the diffuse transmission curve in the region of 360nm to 500nm was 0.8%, and blue fog (coloration) was not observed when artificial sunlight was irradiated.
When evaluating the maximum value of the diffuse transmission curve of the infrared shielding particle dispersion or the infrared shielding interlayer transparent substrate, the infrared shielding particle dispersion or the infrared shielding interlayer transparent substrate for measuring the diffuse transmission curve is prepared and evaluated. The same applies to the other examples and comparative examples described below.
Example 2
A powder containing lanthanum hexaboride particles was obtained in the same manner as in example 1, except that boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum to boron, B/La, was 5.95.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.1 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 5.9.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was measured and found to be 0.5% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used. Using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were prepared in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 1.
Example 3
A powder containing lanthanum hexaboride particles was obtained in the same manner as in example 1, except that boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum to boron, B/La, was 6.00.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.2 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 5.9.
The obtained powder containing lanthanum hexaboride particles was subjected to the above borideB in the particles 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was measured and found to be 0.9% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used. Using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were prepared in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 1.
Example 4
A powder containing lanthanum hexaboride particles was obtained in the same manner as in example 1, except that boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum to boron, B/La, was 6.10.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.2 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 6.0.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was measured and found to be 0.9% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used. Using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were prepared in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 1.
Example 5
A powder containing lanthanum hexaboride particles was obtained in the same manner as in example 1, except that boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum to boron, B/La, was 6.20, and the mixture was fired at a temperature of 1650±50 ℃.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.2 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 6.0.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was measured and found to be 0.9% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used. Using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were prepared in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 1.
Example 6
A powder containing lanthanum hexaboride particles was obtained in the same manner as in example 1, except that boron oxide was used as a boron source, lanthanum oxide was used as a lanthanum source, and carbon (graphite) was used as a reducing agent, and the ratio of B/La, which is an element ratio of lanthanum to boron, was 6.10. However, 60 parts by weight of carbon was weighed and mixed with 100 parts by weight of boron oxide.
The carbon content of the obtained powder containing lanthanum hexaboride particles was measured by the combustion infrared absorption method and found to be0.1 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 6.0.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was measured and found to be 0.4% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used. Using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were prepared in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 1.
Example 7
A powder containing cerium hexaboride particles was obtained in the same manner as in example 1, except that cerium oxide was used instead of lanthanum oxide so that the element ratio B/Ce of cerium to boron was 6.10.
The carbon concentration of the obtained powder containing cerium hexaboride particles was measured by the combustion infrared absorption method, and the carbon content was 0.2 mass%. Further, the obtained cerium hexaboride was confirmed to be represented by the general formula CeB by ICP m M of the element ratio (B/Ce) of boron (B) to cerium (Ce) is 6.0.
The powder containing cerium hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, and B for powder containing cerium hexaboride particles 4 The C concentration was measured and found to be 0.9% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing the cerium hexaboride particles was used. Using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were prepared in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 1.
Example 8
By weight ratio of 4:1:10 to obtain an infrared shielding particle plasticizer dispersion liquid by adding a dispersant (fatty acid amine dispersant) and a plasticizer to the infrared shielding particle dispersion liquid (boride particle dispersion liquid) prepared in example 1 and removing the solvent component in a reduced pressure dryer.
The obtained infrared shielding particle plasticizer dispersion was mixed with a polyvinyl butyral resin, and a sheet-shaped infrared shielding particle dispersion was obtained by an extrusion processor.
At this time, the mixing ratio was adjusted so that the visible light transmittance of the finally obtained infrared shielding interlayer transparent substrate was about 70%.
The obtained infrared shielding particle dispersion in a sheet shape was sandwiched between 2 glass substrates (thickness: 3 mm), and an infrared shielding laminated transparent substrate in the form of a laminated glass was produced by using a heated press.
The obtained line-shielding interlayer transparent substrate was evaluated in the same manner as in the case of the infrared shielding particle dispersion of example 1. The results are shown in Table 1.
Comparative example 1
Boron carbide was used as a boron source and a reducing agent, lanthanum oxide was used as a lanthanum source, and the above materials were weighed and mixed so that the elemental ratio B/La of lanthanum to boron was 6.10. Then, the mixture was fired at 1480.+ -. 50 ℃ for 6 hours in an argon atmosphere to obtain a powder containing lanthanum hexaboride particles.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.6 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 6.0.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was measured and found to be 2.6% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used.
The obtained dispersion was evaluated in the same manner as in example 1. The results are shown in Table 2.
In order to prepare the dispersion, it was determined that it was difficult to obtain a particle diameter of 100nm or less even if the above pulverization treatment was continued, because the average dispersion particle diameter was 105nm or more and the pulverization effect was significantly reduced due to the increase in the viscosity of the slurry at the time point when the pulverization treatment was performed for 20 hours.
In addition, zr/La in the obtained boride particle dispersion was 1.8, which was higher than in the cases of examples 1 to 8, and it was found that the medium beads were largely abraded and mixed into the slurry.
Further, the diffuse transmittance peak value of 1.8% was higher than in the cases of examples 1 to 8, and there was a concern that blue haze was strongly observed when the optical member was produced using the same.
The obtained dispersion was used to form a coating layer on a transparent glass substrate as an infrared shielding transparent substrate in the same manner as in example 1. The optical characteristics of the obtained infrared shielding transparent substrate were measured. The measurement results are shown in table 2 below.
The obtained infrared shielding transparent substrate had a haze of 1.6% and was found to have very low transparency. The maximum value of the diffuse transmission curve in the region of 360nm to 500nm inclusive was 1.9%, and blue fog was visually confirmed when artificial sunlight was irradiated.
Further, the same amount of dispersant (acrylic polymer dispersant having an amino group) was added to the obtained dispersion, and the obtained mixture was kept in a dryer to remove the solvent component and then pulverized, whereby an infrared shielding particle dispersant powder was obtained.
The obtained infrared shielding particle dispersion powder was mixed with a polycarbonate resin, and a masterbatch in the form of pellets was produced by using an extrusion processor.
The master batch was mixed with a polycarbonate resin, and an infrared shielding particle dispersion was formed by an extrusion processor. At this time, the mixing ratio of the polycarbonate resin and the master batch was adjusted so that the visible light transmittance of the obtained infrared shielding particle dispersion was about 70%. The measurement results of the optical properties of the obtained infrared shielding particle dispersion are shown in table 2 below.
The visible light transmittance was about 70%, and it was confirmed that light in the visible light region was sufficiently transmitted. However, the haze was 1.6%, and the transparency was confirmed to be very low. The maximum value of the diffuse transmission curve in the region of 360nm to 500nm was 2.0%, and blue fog was visually confirmed when artificial sunlight was irradiated.
Comparative example 2
A powder containing lanthanum hexaboride particles was obtained in the same manner as in comparative example 1, except that boron carbide and lanthanum oxide were weighed and mixed so that the element ratio of lanthanum to boron, B/La, was 6.20.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.8 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 6.1.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was 3.7 mass%.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used. Further, using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were produced in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 2.
In order to prepare the dispersion, it was determined that it was difficult to obtain a particle diameter of 100nm or less even if the above pulverization treatment was continued, because the average dispersion particle diameter was 111nm or more and the pulverization effect was significantly reduced due to the increase in the viscosity of the slurry at the time point when the pulverization treatment was performed for 20 hours.
In addition, zr/La in the obtained boride particle dispersion was 2.0, which was higher than in the cases of examples 1 to 8, and it was found that the medium beads were largely abraded and mixed into the slurry.
Further, the diffuse transmittance peak value of 2.4% was higher than in the cases of examples 1 to 8, and there was a concern that blue haze was strongly observed when the optical member was produced using the same.
In addition, a coating layer was formed on the transparent glass substrate using the obtained dispersion in the same manner as in example 1. The optical characteristics of the obtained infrared shielding transparent substrate were measured. The measurement results are shown in table 2 below.
The obtained infrared shielding transparent substrate had a haze of 1.8% and was found to have very low transparency. The maximum value of the diffuse transmission curve in the region of 360nm to 500nm inclusive was 2.4%, and blue fog was visually confirmed in the same manner as in comparative example 1 when artificial sunlight was irradiated.
Comparative example 3
A powder containing lanthanum hexaboride particles was obtained in the same manner as in comparative example 1, except that boron oxide was used as a boron source, lanthanum oxide was used as a lanthanum source, carbon (graphite) was used as a reducing agent, and the mixture was weighed and mixed so that the element ratio of lanthanum to boron, B/La, was 6.10. However, 60 parts by weight of carbon was weighed and mixed with 100 parts by weight of boron oxide.
The carbon concentration of the obtained powder containing lanthanum hexaboride particles was measured by a combustion infrared absorption method, and the carbon content was 0.7 mass%. Further, by evaluating the composition of the obtained lanthanum hexaboride-containing particles by ICP, it was confirmed that the particles were represented by the general formula LaB m M of the element ratio (B/La) of boron (B) to lanthanum (La) is 6.0.
The powder containing lanthanum hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, for B of powder containing lanthanum hexaboride particles 4 The C concentration was 3.4 mass%.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing lanthanum hexaboride particles was used. Further, using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were produced in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 2.
The obtained infrared shielding transparent substrate had a haze of 1.7% and was found to have very low transparency. The maximum value of the diffuse transmission curve in the region of 360nm to 500nm was 2.2%, and blue fog was visually confirmed in the same manner as in comparative example 1 when artificial sunlight was irradiated.
Comparative example 4
A powder containing cerium hexaboride particles was obtained in the same manner as in comparative example 1, except that cerium oxide was further used instead of lanthanum oxide so that the element ratio B/Ce of cerium to boron was 6.10.
The carbon concentration of the obtained powder containing cerium hexaboride particles was measured by the combustion infrared absorption method, and the carbon content was 0.9 mass%. Further, by evaluating the composition of the obtained cerium hexaboride-containing particles by ICP, it was confirmed that the cerium hexaboride-containing particles were represented by the general formula CeB m Elemental ratio (B/Ce) of boron (B) to lanthanum (Ce)m is 6.0.
The powder containing cerium hexaboride particles thus obtained was prepared by using B among the boride particles described above 4 Method for evaluating C concentration, and B for powder containing cerium hexaboride particles 4 The C concentration was measured and found to be 4.4% by mass.
Next, a boride particle dispersion was prepared in the same manner as in example 1, except that the powder containing the cerium hexaboride particles was used. Further, using the obtained dispersion, an infrared shielding transparent substrate, an infrared shielding particle dispersion powder, a master batch, and an infrared shielding particle dispersion were produced in the same manner as in example 1.
The obtained dispersion, the infrared shielding transparent substrate, and the infrared shielding particle dispersion were evaluated in the same manner as in example 1. The results are shown in Table 2.
The haze of the obtained infrared shielding transparent substrate was 1.9%, and it was confirmed that the transparency was very low. The maximum value of the diffuse transmission curve in the region of 360nm to 500nm was 2.5%, and blue fog was visually confirmed in the same manner as in comparative example 1 when artificial sunlight was irradiated.
TABLE 1
TABLE 2
In examples 1 to 8, it was confirmed that boride particles obtained by a solid phase reaction or the like were pulverized to have an average dispersed particle diameter of 100nm or less, particularly 85nm or less, easily and economically. In examples 1 to 8, the boride particles obtained had an average dispersion particle diameter of 100nm or less, particularly 85nm or less, and therefore, even when an infrared shielding film, an infrared shielding transparent substrate having a coating layer, or an infrared shielding particle dispersion prepared using the particles or the dispersion liquid was irradiated with artificial sunlight, the particles were not colored blue-white. In other words, it was confirmed that blue fog was suppressed.
Accordingly, it was confirmed that the infrared shielding films, the infrared shielding transparent substrates, the infrared shielding optical members having the infrared shielding transparent substrates, the infrared shielding particle dispersions, the infrared shielding interlayer transparent substrates, and the like, which were produced using the boride particle dispersions of examples 1 to 8, can be preferably used for window glass, and the like for building materials.
In each of examples 1 to 7, the thickness of the coating layer was about 10 μm and 20 μm or less.
On the other hand, in comparative examples 1 to 4, in which powders containing boride particles having a carbon concentration of more than 0.2 mass% were used as raw materials, it was confirmed that the average dispersion particle diameter was larger than 100nm in the case of the pulverization treatment for 20 hours, and that it was difficult to form particle diameters of 100nm or less even if the pulverization was further carried out due to the increase in viscosity. The maximum value of the diffuse transmission curve of the boride particle dispersion liquid was also higher than 1.5%. Therefore, it was confirmed that blue fog was likely to occur in an infrared shielding transparent substrate or the like produced using the boride particle dispersion liquid. In addition, there are problems with window glass, and the like used for building materials.
The boride particles, boride particle dispersion, infrared shielding transparent substrate, infrared shielding optical member, infrared shielding particle dispersion, infrared shielding interlayer transparent substrate, infrared shielding particle dispersion powder, and master batch are described above by way of embodiments and examples, but the present invention is not limited to the above embodiments and examples, and the like. Various modifications and changes may be made within the scope of the gist of the present invention described in the claims.
The present application uses, as a basis for priority, japanese patent application Nos. 2016-000298, 2016-000300, 2016-000301, 2016-254437, 2016-254440, 2016-000298, 2016-000301, 2016-254433, 2016-254437, and 2016-254440, respectively, of the application from 1 month 4 to the national franchise.
Claims (18)
1. An infrared shielding transparent substrate having a coating layer on at least one side of the transparent substrate,
the coating includes infrared shielding particles and a binder,
the infrared shielding particles are represented by the general formula XB m And a boride particle having a carbon content of more than 0.05 mass% and not more than 0.2 mass% as measured by a combustion infrared absorption method, wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula,
Wherein B contained in the boride particles 4 The amount of C is 0.2 to 1.0 mass%.
2. The infrared shielding transparent substrate of claim 1 wherein the general formula XB m M is 4.0 to 6.2 inclusive.
3. The infrared shielding transparent substrate according to claim 1 or 2, wherein the boride particles have an average dispersed particle diameter of 1nm to 100 nm.
4. The infrared shielding transparent substrate according to claim 1 or 2, wherein the adhesive comprises one or more selected from ultraviolet curable resins, thermoplastic resins, thermosetting resins, room temperature curable resins.
5. The infrared shielding transparent substrate according to claim 1 or 2, wherein the thickness of the coating layer is 20 μm or less.
6. The infrared shielding transparent substrate according to claim 1 or 2, wherein when the visible light transmittance of the coating layer is set to a range of 45% to 55%, the maximum value of the diffuse transmission curve at a region of a wavelength of 360nm to 500nm is 1.5% or less.
7. The infrared shielding transparent substrate according to claim 1 or 2, wherein the transparent substrate is a transparent film substrate or a transparent glass substrate.
8. An infrared shielding optical member comprising the infrared shielding transparent substrate according to any one of claims 1 to 7.
9. An infrared shielding particle dispersion comprising boride particles and a thermoplastic resin, the boride particles being represented by the general formula XB m And a carbon content of more than 0.05% by mass and not more than 0.2% by mass as measured by the infrared absorption by combustion method, wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula,
wherein B contained in the boride particles 4 The amount of C is 0.2 to 1.0 mass%.
10. The infrared shielding particle dispersion according to claim 9, wherein said general formula XB m M is 4.0 to 6.2 inclusive.
11. The infrared shielding particle dispersion according to claim 9 or 10, wherein the boride particles have an average dispersed particle diameter of 1nm to 100 nm.
12. The infrared shielding particle dispersion according to claim 9 or 10, wherein the thermoplastic resin is one or more selected from the group consisting of:
a resin selected from the group consisting of polyethylene terephthalate resin, polycarbonate resin, acrylic resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluorine resin, ethylene-vinyl acetate copolymer, ionomer resin, polyvinyl butyral resin, polyvinyl acetal resin;
A mixture of two or more resins selected from the group of resins; and
copolymers of two or more resins selected from the group of resins.
13. The infrared shielding particle dispersion according to claim 9 or 10, wherein the infrared shielding particle dispersion is in a sheet shape, a plate shape, or a film shape.
14. The infrared shielding particle dispersion according to claim 9 or 10, wherein the boride particles per unit projected area are contained in an amount of 0.01g/m 2 Above 1.0g/m 2 The following is given.
15. The infrared shielding particle dispersion according to claim 9 or 10, wherein when the visible light transmittance is set to a range of 45% to 55%, the maximum value of the diffuse transmission curve at a region of a wavelength of 360nm to 500nm is 1.5% or less.
16. An infrared shielding interlayer transparent substrate having:
a plurality of transparent substrates; and
the infrared shielding particle dispersion according to any one of claim 9 to 15,
wherein the infrared shielding particle dispersion is disposed between the plurality of transparent substrates.
17. An infrared shielding particle dispersion powder comprising boride particles of the general formula XB and a dispersant m And a carbon content of more than 0.05% by mass and not more than 0.2% by mass as measured by the infrared absorption by combustion method, wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula,
wherein B contained in the boride particles 4 The amount of C is 0.2 to 1.0 mass%.
18. A master batch is an infrared shielding particle dispersion including boride particles and a thermoplastic resin, and has a particle shape, the boride particles being represented by the general formula XB m And a carbon content of more than 0.05% by mass and not more than 0.2% by mass as measured by the infrared absorption by combustion method, wherein X is one or more metal elements selected from Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, sr, ca, m is a number indicating the boron content in the general formula,
wherein B contained in the boride particles 4 The amount of C is 0.2 to 1.0 mass%.
Applications Claiming Priority (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-000298 | 2016-01-04 | ||
| JP2016-000300 | 2016-01-04 | ||
| JP2016000301 | 2016-01-04 | ||
| JP2016000300 | 2016-01-04 | ||
| JP2016000298 | 2016-01-04 | ||
| JP2016-000301 | 2016-01-04 | ||
| JP2016-254437 | 2016-12-27 | ||
| JP2016-254440 | 2016-12-27 | ||
| JP2016254433A JP7272614B2 (en) | 2016-01-04 | 2016-12-27 | boride particle dispersion |
| JP2016254437A JP6838396B2 (en) | 2016-01-04 | 2016-12-27 | Infrared shielding transparent base material, infrared shielding optical member |
| JP2016254440A JP6859704B2 (en) | 2016-01-04 | 2016-12-27 | Infrared shielding particle dispersion, infrared shielding laminated transparent base material, infrared shielding particle dispersion powder, and masterbatch |
| JP2016-254433 | 2016-12-27 | ||
| PCT/JP2016/089095 WO2017119394A1 (en) | 2016-01-04 | 2016-12-28 | Boride particles, boride particle dispersed liquid, infrared light shielding transparent base, infrared light shielding optical member, infrared light shielding particle dispersed body, infrared light shielding laminated transparent base, infrared light shielding particle dispersed powder, and master batch |
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| CN108473324A CN108473324A (en) | 2018-08-31 |
| CN108473324B true CN108473324B (en) | 2023-06-02 |
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| KR (1) | KR102689813B1 (en) |
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| CN111285380B (en) * | 2020-02-04 | 2022-12-16 | 天津包钢稀土研究院有限责任公司 | Preparation method and application of multi-rare earth co-doped boride and nano heat insulation powder thereof |
| CN112408409B (en) * | 2020-10-29 | 2022-07-05 | 航天材料及工艺研究所 | High-temperature-resistant high-entropy wave-absorbing ceramic and preparation method and application thereof |
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| TW201739693A (en) | 2017-11-16 |
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| KR102689813B1 (en) | 2024-07-29 |
| CN108473324A (en) | 2018-08-31 |
| KR20180100123A (en) | 2018-09-07 |
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