JP7009807B2 - Hexoride particle-containing resin, hexaboride particle dispersion liquid and hexaboride particle dispersion powder - Google Patents

Description

The present invention comprises a hexaboride particle-containing resin mainly used to protect the eye from exposure to near-infrared light, a hexaboride particle dispersion liquid that can be used for producing the hexaboride particle-containing resin, and a hexaboride particle dispersion liquid. Hex Boride Particle dispersion powder.

Living tissues are affected by various wavelengths of ultraviolet light, visible light, and near-infrared light (electromagnetic waves). The effect depends on the part of the living tissue, but especially in the tissue of the eye, visible light and near infrared rays reach the retina. For this reason, it is known that when visible light and near-infrared rays act on the tissues of the eye for a long time or with strong intensity, they cause severe and persistent damage to the iris, retina, and the like. On the other hand, since ultraviolet rays are strongly absorbed by the cornea and the crystalline lens, it is known to cause disorders such as ophthalmitis and cataract when they act on eye tissues for a long time or with strong intensity.

For example, sunlight has a lot of light having wavelengths of ultraviolet light, visible light, and near-infrared light. For this reason, in general outdoor and indoor environments that are not sufficiently shielded, the sun's rays can cause the above-mentioned damage to the human eye. To avoid such obstacles, for example, car drivers, athletes, aircraft pilots, etc. who may be exposed to strong sunlight for a long time, to protect their eyes from the sun, ultraviolet to visible light -May wear eyewear with a layer that reduces light with each wavelength of near-infrared light.

Further, for example, a laser having each wavelength of ultraviolet-visible light-near-infrared light (may be referred to as "laser" in the present invention) is similar to or more seriously to the eye than the sun's rays due to its strong intensity. It is known to cause the disorder of.
In addition, for example, in gas welding work, gas fusing work, work using arc lamps or mercury lamps, work using infrared lamps or germicidal lamps, work such as blast furnaces, steel piece heating furnaces, ingots, etc., it is generated by the work. It is known that exposure to the eye by strong light can cause damage to the eye.
Those engaged in work exposed to such strong light also wear eyewear having a layer for reducing light having each wavelength of ultraviolet light, visible light, and near-infrared light. A protective surface or the like having a layer for reducing light as a window (working viewing window) may be used.

In the above-mentioned eyeglasses (eyewear), protective surfaces, etc., various members have been proposed as members for protecting the eyes from near-infrared light and the like.
For example, JIS T 8141: 2003 stipulates light-shielding protective equipment worn by each person to protect the eyes of workers in places that generate ultraviolet and near-infrared radiation that are harmful to the eyes and intense visible light. Has been done. JIS T 8143: 1994 also defines laser protection filters and laser protection goggles used to protect the operator's eyes from laser radiation with wavelengths from 180 nm to 1 mm.

Further, in Patent Document 1, as a more specific member, a multilayer film for spectacle lenses in which a dielectric film having a high refractive index and a dielectric film having a low refractive index are alternately laminated on both sides of a transparent resin substrate is provided. Infrared filters are disclosed.
Further, Patent Document 2 discloses an adapter for attaching various filters to binoculars, and discloses that a glass selected from at least one of yellow glass, heat ray absorbing glass and soda lime glass is used as the filter. There is.
Further, Patent Document 3 discloses a lens for protective eyeglasses in which a first lens element for light-shielding laser light and a second lens element for antiglare are superimposed. The first lens element for shading the laser light contains an absorber that selectively absorbs a laser beam having a specific wavelength in the ultraviolet wavelength range, the visible light wavelength range, or the infrared wavelength range, and also contains the visible light wavelength. It is disclosed that it is a transparent base material in the region.
Further, in Patent Document 4, a lens is prepared by polymerizing a predetermined acrylic resin, a copolymerizable polyfunctional monomer, an oil-soluble dye and / or a near-infrared absorber, and the lens is processed for laser protection. Lenses for spectacles are disclosed.

Japanese Unexamined Patent Publication No. 2015-161731 International Publication No. 1998/058290 Japanese Unexamined Patent Publication No. 2006-184596 Japanese Unexamined Patent Publication No. 4-353819

The present inventors have examined these prior arts.
Then, the prior art utilizes one of the principles of [1] light reflection by the multilayer film and [2] absorption by the organic dye regarding shading of near-infrared light, and each of them has a problem. there were.
Hereinafter, each principle and problem will be described.

[1] Reflection of light by a multilayer film In this principle, two types of layers having different refractive indexes (that is, a high refractive index layer and a low refractive index layer) are alternately laminated, and at this time, the thickness per layer is [1]. By setting [refractive index of light] ÷ 4, only light of a specific wavelength is selectively reflected by the interference effect of light. For example, among the above-mentioned prior art documents, Patent Documents 1 and 2 disclose the shielding of near-infrared light based on the principle of light reflection by such a multilayer film.

However, the reflection of light by the multilayer film has a problem that the laminated structure having one kind of layer thickness can reflect light only in a narrow region centered on a specific wavelength. Therefore, even if it has a high shielding performance for near-infrared light of a certain wavelength, it may have almost no shielding performance for light of a different wavelength. Here, it is possible to widen the reflected wavelength range by increasing the number of layers, but the process becomes complicated and the cost increases.

In addition, since the principle is light reflection by the multilayer film, the wavelength of the light reflected by the interference shifts to a wavelength different from the original design because the optical path length that causes interference changes when the incident angle of the light is different. It also had the problem of being lost. For example, when this principle is used for laser protective goggles, it is assumed that the scattered light of the laser is incident on the goggles not only from the front of the goggles but also from an unintended angle, which may cause a problem.

[2] Absorption by Organic Dye This principle is to selectively absorb only light of a specific wavelength by containing a high concentration of an organic dye having the property of absorbing near infrared light in the substrate. .. For example, among the above-mentioned prior art documents, Patent Documents 3 and 4 disclose the shielding of near-infrared light based on the principle of absorption by such an organic dye.

However, absorption by an organic dye has a problem that light can be absorbed only in a narrow region centered on a specific wavelength because the organic dye generally has absorption only in a very narrow wavelength range. rice field. Therefore, even if it has a high shielding performance for near-infrared light of a certain wavelength, it may have almost no shielding performance for light of a different wavelength. A configuration in which a plurality of organic dyes corresponding to various wavelengths are simultaneously contained to widen the wavelength range has been considered, but the process becomes complicated and the cost increases. Further, since the organic dye simultaneously absorbs visible light, there is a problem that the visible light transmittance is lowered. Moreover, the weather resistance of the organic dye is generally low, and depending on the environment and time of use, the deterioration of the organic dye may reduce the shielding performance against near-infrared light.

The present invention has been made under the above circumstances, and the problem to be solved is a high optical density (OD) for near-infrared light having a wavelength of 800 nm to 1150 nm while maintaining the visible light transmittance. A resin that exhibits excellent optical characteristics that can significantly reduce the effect on the eye even with strong near-infrared light such as a laser, a near-infrared shielding lens having a layer of the resin, near Infrared shielding optics, protective equipment, near-infrared shielding window material, near-infrared shielding equipment, and near-infrared shielding film and glass, hexaboroid particle dispersion liquid that can be used for producing the hexaboroid particle-containing resin, and six. It is to provide a borohydride particle dispersion powder.

As a result of diligent studies by the present inventors in order to solve the above-mentioned problems, by incorporating hexaboride particles in a medium such as a resin, a high optical density is exhibited with respect to near-infrared light. It was found that it is feasible to obtain a resin containing hexaboride particles, and the present invention was completed.

That is, the first invention for solving the above-mentioned problems is
The hexaboride particles are the hexaboride particle-containing resin dispersed in the resin.
It is a hexaboride particle-containing resin characterized by having an optical density (OD) value of 2.0 or more in the near infrared region having a wavelength of 800 nm to 1150 nm.
The second invention is
The hexaboride particles are the hexaboride particle-containing resin dispersed in the resin.
The hexaboride particle-containing resin is characterized in that the content of the hexaboride in the resin is 0.55 g / m ² or more and 2.00 g / m ² or less per projected area of the resin.
The third invention is
The hexaboride particle-containing resin according to the first or second invention, wherein the number average particle diameter of the hexaboride particles in the resin is 40 nm or less.
The fourth invention is
The particles of the hexaboride are from the general formula XB ₆ (X is from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. The hexaboride particle-containing resin according to any one of the first to third inventions, which is a hexaboroid particle represented by (1 or more elements selected). ..
The fifth invention is
The hexaboride particle-containing resin according to any one of the first to fourth inventions, wherein the hexaboride particles are hexaboride lanthanum particles.
The sixth invention is
The hexaboride particle-containing resin according to any one of the first to fifth inventions, wherein the resin layer contains any one or more selected from an acrylic resin, a polycarbonate resin, and a vinyl chloride resin. Is.
The seventh invention is
Further, the hexaboride particle-containing resin according to any one of the first to sixth inventions, which is characterized by containing an ultraviolet absorber.
The eighth invention is
Further, the hexaboride particle-containing resin according to any one of the first to seventh inventions, which is characterized by containing an antioxidant.
The ninth invention is
Further, one or more groups selected from an amine-containing group, a hydroxyl group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, a phosphoric acid ester, a sulfonic acid group, a sulfonic acid ester, a thiol group, or an epoxy group. The hexaboroid particle-containing resin according to any one of the first to eighth inventions, which comprises a dispersant having a functional group.
The tenth invention is
The hexaboride particle-containing resin according to any one of the first to ninth inventions, wherein the visible light transmittance calculated by JIS R 3106: 1998 is 2% or more.
The eleventh invention is
A near-infrared ray shielding lens characterized by having a resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions.
The twelfth invention is
The near-infrared shielding eyeglasses comprising the resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions or the near-infrared shielding lens according to the tenth invention.
The thirteenth invention is
A protective device comprising the resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions or the near-infrared ray shielding lens according to claim 10.
The fourteenth invention is
A near-infrared ray shielding window material having a resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions.
The fifteenth invention is
It is a near-infrared ray shielding device characterized by having the near-infrared ray shielding window material according to the fourteenth invention.
The sixteenth invention is
The near-infrared shielding film is characterized in that the resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions is provided on a film substrate.
The seventeenth invention is
The near-infrared shielding glass is characterized in that the resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions is provided on a glass substrate.
The eighteenth invention is
A hexaboride particle dispersion liquid used for producing the resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions.
A hexaboride particle containing one or more elements selected from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca , Dispersed in organic solvent,
It is a hexaboride particle dispersion liquid characterized in that the number average particle diameter of the hexaboride particles is 40 nm or less.
The nineteenth invention is
The particles of the hexaboride are from the general formula XB ₆ (X is from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. The hexaboride particle dispersion liquid according to the eighteenth invention, which comprises the hexaboride particles represented by (1 or more elements selected).
The twentieth invention is
Further, one or more groups selected from an amine-containing group, a hydroxyl group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, a phosphoric acid ester, a sulfonic acid group, a sulfonic acid ester, a thiol group, or an epoxy group. , The hexaborized particle dispersion liquid according to the eighteenth or nineteenth invention, which contains a dispersant having a functional group.
The 21st invention is
The hexaboride particle dispersion powder according to any one of the eighteenth to twenty-second inventions, wherein the organic solvent is removed from the hexaboride particle dispersion liquid.
The 22nd invention is
The hexaboride particle dispersion powder according to the 21st invention, wherein the number average particle diameter of the hexaboride particles is 40 nm or less.
The 23rd invention is
Further, one or more groups selected from an amine-containing group, a hydroxyl group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, a phosphoric acid ester, a sulfonic acid group, a sulfonic acid ester, a thiol group, or an epoxy group. The hexaboroid particle dispersion powder according to the 21st or 22nd invention, which comprises a dispersant having a functional group.

According to the present invention, it has a high optical density (OD) with respect to near-infrared light having a wavelength of 800 to 1150 nm while maintaining a high visible light transmittance, even if it is a powerful near-infrared light such as a laser. It is possible to provide a hexaboroid particle-containing resin that exhibits excellent optical properties such that the influence on the eye can be significantly reduced. Further, it is possible to provide a near-infrared shielding lens having the hexaboride particle-containing resin, near-infrared shielding glasses, protective equipment, a near-infrared shielding window material, a near-infrared shielding device, and a near-infrared shielding film or glass.

Hereinafter, embodiments for carrying out the present invention are described in [1] hexaborosin particle-containing resin and its constituent components, [2] hexaborosin particle-containing resin and a method for producing a resin layer using the resin, [3] 6. Products using the oleoresin-containing resin will be described in this order. However, the present invention is not limited to this embodiment. That is, various modifications and substitutions can be made to the embodiment without departing from the scope of the present invention.

[1] Hexoride particle-containing resin and its constituent components The hexaboride particle-containing resin according to the present invention contains hexaboride particles, a resin, and, if desired, other components.
Regarding the hexaboride particle-containing resin according to the present invention, (1) the hexaboride particle-containing resin according to the present invention, (2) hexaboride particles, (3) resin, (4) other components, (5) summary. , Will be explained in this order.

(1) Hexboride particle-containing resin according to the present invention The hexaboride particle-containing resin according to the present invention is a hexaboride particle of the general formula XB ₆ (provided that the element X is La, Ce, Pr, Nd, Gd. , Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca is preferably at least one selected from). ing.
The hexaboride particles have been conventionally used in a field of solar shading that is different from the field of eye protection from near-infrared light, such as a sun-shielding window film, a transparent substrate for sun-shielding, and a sun-shielding resin sheet.

In the above-mentioned field of solar radiation shielding, hexaboride particles have been used for the purpose of shielding near-infrared light while maintaining transparency. And, unlike the field of protecting the eye from near-infrared light, high optical density was not required in the field of solar radiation shielding. Specifically, in the near-infrared light region with a wavelength of 800 nm to 1150 nm, the transmittance is 40% (corresponding to an optical density of 0.4) or less, and even in an extreme case, 10% (corresponding to an optical density of 1.0). There was no example in which a high value of 3 or more was required for the optical density, which was a level that was lowered to the following level.

The reason why the hexaboride was used only in such a low optical density region is that it was thought that the transparency would be lost by increasing the amount of the hexaboride. That is, when hexaboride particles are used, the film has a strong green tint due to the absorption of the visible light region of the hexaboride even in the low optical density region as used in the field of solar shading. .. When the content is increased to achieve even higher optical densities, the absorption of the visible light region of the hexahoids further reduces the transparency of the visible light, and in addition, the scattering of light by the hexahoid particles ( Since Mie scattering and Rayleigh scattering also increase depending on the content of hexaboroid particles, it was naturally thought that the transparency of visible light would be lost.

That is, when the hexaboroid particles are used, the optical density corresponding to the level required in the solar shielding field can be realized while ensuring the transparency to visible light, but the high level of optics required in the laser shielding field is achieved. It was the conventional wisdom that the concentration could not be achieved.
However, as a result of diligent studies by the present inventors, the hexaboride particles have a content far exceeding the content of hexaboride particles per general projected area used in the field related to solar shading. It has been found that a resin layer having a high optical density with respect to near-infrared light can be realized by containing the particles in the resin.

Specifically, the amount of hexaboride particles added in the general field of solar shading is approximately 0.07 to 0.20 g / m ² per projected area. On the other hand, when the hexaboride is contained in the resin with a very high addition amount of 0.55 to 2.00 g / m ² per projected area, the optics in the near infrared region with a wavelength of 800 to 1150 nm. In the density (OD) profile, an optical density (OD) value of 2.0 or more at the minimum value and 8.0 or more at the maximum value (observed as the maximum value in the profile) can be realized. Was found.

Even more surprisingly, it was found that even when the content of hexaboride was increased enough to achieve such a high optical density, the transparency to visible light was ensured at a sufficiently high level. Specifically, it is possible to realize the above-mentioned high optical density (OD) while maintaining a high visible light transmittance such as 2 to 30% for the visible light transmittance calculated by JIS R 3106: 1998. It was found that there was.

It is said that the hexaborized particle-containing resin according to the present invention described above has a high optical density not only in the light of a specific wavelength but also in a wide range of wavelengths of 800 to 1150 nm among the light in the near infrared region. , Has a brilliant advantage over the laser shielding member according to the conventional technique.

This is because the laser shielding member according to the conventional technique is based on the principle of providing the shielding function only in a narrow wavelength range, such as interference by the multilayer film and absorption by the organic dye as described above. On the other hand, the hexaboride particles of the present invention are based on the principle of localized surface plasmon resonance due to free electrons in nanoparticles.

According to this principle of localized surface plasmon resonance, light absorption is realized over a wide photon energy range (that is, a wide light wavelength range) centered on a specific photon energy (that is, a specific light wavelength). Therefore, it is considered that a high optical density value could be realized in a wide wavelength range over a near-infrared light having a wavelength of 800 to 1150 nm.
In addition, since the hexaborized particles are far more transparent to visible light for absorption of near-infrared light than other particles having localized surface plasmon resonance, near-infrared light having a wavelength of 800 to 1150 nm is obtained. It is considered that high transmittance could be ensured in the visible light region, even though high optical density was realized in a wide range.

(2) Hex Boride Particles The hexaboride particles according to the present invention exhibit light absorption by plasmon absorption in the near infrared region. The component is represented by the general formula XB ₆ , and the shape has a non-spherical shape. Here, the element X is at least one selected from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. Is preferable.
Specifically, lanthanum hexaboride [LaB ₆ ], cerium hexaboride [CeB ₆ ], placeodim hexaboride [PrB ₆ ], neodym hexaboride [NdB ₆ ], gadrinium hexaboride [GdB ₆ ], Terbium hexaboride [TbB ₆ ], Disprosium hexaboride [DyB ₆ ], Hormium hexaboride [HoB ₆ ], Yttrium borides [YB ₆ ], Samarium hexaboride [SmB ₆ ], Hexaphorite Europium [EuB ₆ ], erbium hexaboride [ErB ₆ ], turium hexaboride [TmB ₆ ], itterbium borides [YbB ₆ ], lutetium hexaboride [LuB ₆ ], lanthanum hexaboride [(La) , Ce) B ₆ ], strontium hexaboride [SrB ₆ ], calcium hexaboride [CaB ₆ ] and the like can be mentioned as typical examples. Among them, it is preferable to use lanthanum hexaboride [LaB ₆ ] because the intensity of near-infrared absorption with respect to visible light absorption is high.

In the hexaboride particles according to the present invention, it is preferable that the surface thereof is not oxidized, but usually, it is often slightly oxidized. In addition, it is inevitable that surface oxidation will occur to some extent in the process of dispersing the hexaborosized fine particles. However, even in that case, there is no change in the effectiveness of exhibiting the near-infrared shielding effect. Therefore, for example, even a hexaboride particle whose surface is oxidized can be used as the hexaboride particle used in the present invention.

Further, the hexaboride particles according to the present invention can obtain a larger heat ray shielding effect as the integrity as a crystal is higher. However, even if the crystallinity is low and a broad diffraction peak is generated by X-ray diffraction, if the basic bond inside the particle is composed of the bond between each metal and boron, the heat ray shielding effect Therefore, it can be applied in the present invention. As a hexaboride, the ratio of metal to boron does not have to be exactly 6, and it may be in the range of 5.8 to 6.2.

The particle size of the hexaboride particles according to the present invention is not particularly limited and can be arbitrarily selected. For example, it can be selected based on the use of the resin layer, eyeglasses, windows, and multilayer film according to the present invention, the degree of light absorption in the near infrared region required by the purpose of use, productivity, and the like.
However, the hexaboride particles according to the present invention preferably have a finer particle diameter than those used for general heat ray shielding applications. For example, in a heat ray shielding application example different from the present invention, it is preferable that the volume average particle diameter of the hexaboride particles is 1 nm or more and 200 nm or less. This is because if the volume particle diameter is 200 nm or less, strong near-infrared absorption by the particles can be exhibited, and if the volume average particle diameter is 1 nm or more, industrial production is easy.

On the other hand, the amount of the hexaboride particles added per projected area according to the present invention is much larger than the amount used per projected area in the embodiment of the heat ray shielding application. Therefore, by making the particle size of the hexaboroid particles finer, the scattering of light due to Mie scattering and Rayleigh scattering caused by the hexaboride particles is suppressed. Then, the transparency to visible light is ensured by suppressing the scattering of the light, and the hexaboride particle-containing resin according to the present invention substantially exhibits transparency.

In order to avoid a situation in which this resin does not have substantially transparency, it is preferable that the hexaboride particles have a volume average particle diameter of 1 nm or more and 40 nm or less in the present invention. When the volume average particle diameter of the hexaboros particles is 40 nm or less, even if the content per projected area of the hexaboros particles is large as in the present invention, the light scattering due to the Mee scattering and Rayleigh scattering due to the particles is generated. This is because it is sufficiently suppressed, the visibility in the visible light wavelength region can be maintained, and at the same time, the transparency can be efficiently maintained.
When the resin is used for applications where transparency is particularly required, the volume average particle diameter of the hexaboride particles is more preferably 30 nm or less, and further preferably 20 nm or less in order to further suppress scattering. preferable.

The volume average particle size means the particle size at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method. In the present invention, the term "volume average particle size" is used with the same meaning in other parts as well.

As described above, from the viewpoint of avoiding light scattering, it is preferable that the volume average particle diameter of the hexaboride particles is small. However, from the viewpoint of ease of handling when producing a resin layer containing hexaboride particles and avoiding aggregation of hexaboride particles in the resin, the volume average particle diameter of the hexaboride particles is 1 nm or more. Is preferable.

The amount (content) of the hexaboroid particles contained in the resin is preferably, for example, the content per unit area in the projected area of the resin layer is 0.55 g / m ² or more and 2.00 g / m ² or less. More preferably, it is 0.55 g / m ² or more and 1.50 g / m ² or less. By setting it to 0.55 g / m ² or more, high optical density can be realized in the near infrared region. By setting the content to 2.00 g / m ² or less, it is possible to prevent the transmission of visible light from being lost due to the absorption and scattering of visible light contained in the hexaboride particles.

(3) Resin Any resin can be used as the resin used for the hexaboride particle-containing resin according to the present invention. However, considering the use of the hexaboride particle-containing resin according to the present invention, it is desirable that the resin has sufficient transparency. Further, in consideration of processability, a thermoplastic resin is preferable.
Specifically, polyethylene terephthalate resin, polycarbonate resin, acrylic resin, ionomer resin, styrene resin, polyamide resin, polyethylene resin, vinyl chloride resin, olefin resin, epoxy resin, polyimide resin, fluororesin, ethylene / vinyl acetate copolymer. , A preferred resin from one resin selected from the resin group, a mixture of two or more resins selected from the resin group, or a copolymer of two or more resins selected from the resin group. Can be selected.
Among them, one resin selected from polycarbonate resin, acrylic resin, vinyl chloride resin, or the resin group is selected in consideration of high transparency, rigidity, light weight, long-term durability, cost, and the like. It is preferable that it is a mixture of two or more kinds of resins, or a copolymer of two or more kinds of resins selected from the resin group.

As the polycarbonate resin used for the hexaboride particle-containing resin according to the present invention, those obtained by reacting divalent phenols with a carbonate-based precursor by a solution method or a melting method are preferable. Examples of the divalent phenol include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) cyclohexane. 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-) Typical examples include methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, and bis (4-hydroxyphenyl) sulfone.
Further, as the divalent phenol, there is an alkane type of bis (4-hydroxyphenyl), and a bisphenol A as a main component is particularly preferable.

(3) Other components In addition to the above-mentioned hexaboride and the resin component, any component can be further added to the resin layer of the present embodiment. Examples of components that can be arbitrarily added include (i) dispersants, (ii) ultraviolet absorbers, (iii) hindered amine-based light stabilizers, (iv) antioxidants, and (v) other additive components. These components will be described below.

(I) Dispersant A dispersant can be added to the resin layer according to the present invention in order to uniformly disperse the above-mentioned hexaboride particles in the ionomer resin.
The dispersant is not particularly limited, and can be arbitrarily selected depending on the resin production conditions and the like. For example, the thermal decomposition temperature measured using a differential thermal / thermogravimetric simultaneous measuring device (hereinafter, may be referred to as TG-DTA) is 250 ° C. or higher, and the urethane main chain, acrylic main chain, and styrene main chain are used. It is preferable that the dispersant has one main chain selected from the chains or a main chain in which two or more kinds of unit structures selected from urethane, acrylic and styrene are copolymerized. It is more preferable that the above-mentioned thermal decomposition temperature is 300 ° C. or higher. Here, the thermal decomposition temperature is a temperature at which weight loss due to thermal decomposition of the dispersant begins in a measurement based on JIS K 7120: 1987 using TG-DTA.

When the thermal decomposition temperature of the dispersant is 250 ° C. or higher, the dispersant can be suppressed from decomposing during kneading with the resin component, and the hexaborized particle-containing resin layer caused by the decomposition of the dispersant is colored brown and transmits visible light. This is because it is possible to suppress a decrease in the rate and more reliably avoid a situation in which the original optical characteristics cannot be obtained.
Further, the dispersant is one or more selected from an amine-containing group, a hydroxyl group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, a phosphoric acid ester, a sulfonic acid group, a sulfonic acid ester, a thiol group, or an epoxy group. It is preferable to have as a functional group. The dispersant having any of the above functional groups adsorbs on the surface of the hexaboride particles, prevents the hexaboride particles from aggregating, and disperses the hexaboride particles more uniformly in the hexaboride particle-containing resin. Therefore, it can be preferably used.
Further, the dispersant preferably has, as the main chain, a main chain composed of acrylic, styrene, urethane, polyethylene, ester, or polyethyleneimine, or a main chain composed of two or more types of copolymers selected from these structures. .. This is because the dispersant having any of the main chains described above prevents the hexaboride particles from aggregating due to steric damage and is compatible with the ink solvent and the resin to make the hexaboride particles more uniform in the resin. This is because it can be dispersed. Among them, when the main chain is polyester or polyethyleneimine, the main chain structure has a structure having an adsorptivity to hexaboride particles, so that aggregation of the hexaboride particles is prevented and the hexaboride particle-containing resin is used. It is more suitable because the hexaboride particles can be dispersed more uniformly.
Further, it is also preferable to use two or more kinds of the dispersant in combination as needed.

Specific examples of the dispersant having any of the above functional groups include an acrylic-styrene copolymer system dispersant having a carboxyl group as a functional group, an acrylic dispersant having an amine-containing group as a functional group, and the like. Can be mentioned. Further, an acrylic resin having a functional group such as a carboxyl group can also be used.
The dispersant having a group containing an amine as a functional group preferably has a molecular weight of Mw 2000 to 200,000 and an amine value of 5 to 100 mgKOH / g. Further, the dispersant having a carboxyl group preferably has a molecular weight of Mw 2000 to 200,000 and an acid value of 1 to 50 mgKOH / g.

The amount of the dispersant added is not particularly limited, but for example, it is preferable to add the dispersant so as to be 10 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the hexaboride particles, and 30 parts by mass or more and 400 parts by mass or less. It is more preferable to add as follows.
This is because if the amount of the dispersant added is within the above range, the hexaboride particles can be more reliably and uniformly dispersed in the ionomer resin, and the physical properties of the obtained resin layer are not adversely affected.

Specific examples of the above-mentioned dispersant in commercial products include ADEKA's Adecacol (registered trademark) TS-230E, CS-141E, CS-1361E, PS-984, PS-440E, PS-807, and Nichiyu's Polystar. (Registered Trademarks) OM, OMR, OMP, A-1060, SMX-1H, OMA, OMA-500, Marialim® AKM-0531, AKM-1511-60, AFB-1521, AAB-0851, AWS-0851 , HKM-50A, Nymeen® L-201, L-202, Marproof® G-0150M, G-0115S, G-0250S, G-0130S-P, G-1010S, Ajinomoto Ajisper (Registered Trademarks) PB-711, PB-821, PB-822, PB-881, PN-411, PA-111, Kusumoto Kasei Co., Ltd. Disparon (registered trademark) 1210, 2150, KS-860, KS-873N, 7004 , 1830, 1850, 1860, DA-1401, PW-36, DN-900, DA-1200, DA-550, DA-7301, DA-325, DA-375, DA-234, SOLSERSE manufactured by Lubrizol (registered). Trademarks) 3000, 5000, 9000, 11200, 12000, 13240, 13350, 13940, 16000, 17000, 18000, 20000, 21000, 22000, 24000SC, 24000GR, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 36000, 36600, 37500, 38500, 39000, 41000, 41090, 43000, 44000, 46000, 47000, 53095, 54000, 55000, 56000, 71000, 76500, Solplus® D510, D520 , D530, D540, L300, L400, K200, K210, K500, C800, C825, DP310, DP320, DP330, R700, Toa Synthetic Co., Ltd. Rezeda (registered trademark) GP-301, Alfon (registered trademark) UF-5022, UF. -5080, UC-3000, UC-3910, UC-3920, UG-4030, UG-4040, UG-4070, Big Chemie Disperbyk® 101, 108, 102, 103, 106, 109 , 110, 111, 112, 116, 130, 140, 142, 145, 160, 161, 162, 163, 164, 166, 167, 168, 170, 171, 171, 174, 180, 181, 182, 183, 184. , 185, 187, 190, 191, 192, 193, 194, 2000, 2010, 2020, 2025, 2050, 2070, 2090, 2091, 2095, 2096, 2150, 2155, 2163, 2164, BYK (registered trademark) P104, P104S, P105, 154, 9076, 9076, P9077, 220S, W980, W985, BASF EFKA (registered trademark) 2020, 2025, 2720, 3030, 3031, 3236, 4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4310, 4400, 4401, 4402, 4403, 4510, 4520, 4550, 4560, 4570, 4580, 4590, 6230, 7414, 8215, John Krill® J- 67, J-586, J-587, J-611, J-680, J-690, J-810, JDX-C3000, JDX-C3020 and the like can be mentioned.

(Ii) Ultraviolet absorber The hexaboride particle-containing resin according to the present invention may further contain an ultraviolet absorber.
As described above, the hexaborosin particle-containing resin according to the present invention and the resin layer using the resin (may be referred to as "resin or the like" in the present invention) are mainly for light in the near infrared region. It can suppress transmission and protect the eyes from such harmful light.
Further, by further adding an ultraviolet absorber to the hexaboride particle-containing resin according to the present invention, it is possible to further block the light in the ultraviolet region, and it is possible to particularly enhance the effect of suppressing harmful light.

Further, the polymer itself, which is a medium constituting the resin layer, may cause deterioration such as yellowing due to long-term exposure to ultraviolet rays. However, by further adding an ultraviolet absorber to the hexaboride particle-containing resin according to the present invention, deterioration such as yellowing of the polymer can be suppressed.

The ultraviolet absorber is not particularly limited, and can be arbitrarily selected depending on the influence on the visible light transmittance and the like of the resin layer, the ultraviolet absorption ability, the durability and the like. Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzophenone compounds, salicylic acid compounds, benzotriazole compounds, triazine compounds, benzotriazolyl compounds and benzoyl compounds, and inorganic ultraviolet absorbers such as zinc oxide, titanium oxide and cerium oxide. And so on. In particular, the ultraviolet absorber preferably contains at least one selected from a benzotriazole compound and a benzophenone compound. This is because the benzotriazole compound and the benzophenone compound can greatly increase the visible light transmittance of the resin layer even when a concentration sufficient to absorb ultraviolet rays is added, and are durable against long-term exposure to strong ultraviolet rays. This is because of its high sex.

The content of the ultraviolet absorber in the resin or the like of the hexaborized particle-containing resin according to the present invention is not particularly limited, and is arbitrary depending on the visible light transmittance required for the resin and the like, the ultraviolet shielding ability and the like. Can be selected for. The content of the ultraviolet absorber in the resin or the like is preferably, for example, 0.02% by mass or more and 5.0% by mass or less. This is because if the content of the ultraviolet absorber is 0.02% by mass or more, the ultraviolet light that cannot be completely absorbed by the hexaboride particles can be sufficiently absorbed. Further, when the content is 5.0% by mass or less, the ultraviolet absorber does not precipitate in the resin or the like, and the strength and penetration resistance of the film are not significantly affected.

(Iii) Hindered Amine-based Light Stabilizer The resin or the like of the hexaboride particle-containing resin according to the present invention further contains a hindered amine-based light stabilizer (may be referred to as “HALS” in the present invention). You can also.
As described above, the ultraviolet absorbing ability can be enhanced by adding the ultraviolet absorber to the hexaboride particle-containing resin or the like according to the present invention. However, depending on the environment in which the hexaboride particle-containing resin or the like according to the present invention is used, or the type of the ultraviolet absorber, the ultraviolet absorber deteriorates with the passage of a long period of time, and the ultraviolet absorbing ability deteriorates. It may end up. In such a case, the addition of HALS can prevent deterioration of the ultraviolet absorber and contribute to the maintenance of the ultraviolet absorption capacity of the hexaboride particle-containing resin or the like according to the present invention.

Further, as described above, there is a concern that the transmittance of the hexaboride particle-containing resin or the like according to the present invention may decrease due to long-term exposure to strong ultraviolet rays. However, when HALS is added to the hexaboride particle-containing resin or the like according to the present invention, it is possible to suppress such a decrease in transmittance as in the case of adding an ultraviolet absorber.
Furthermore, in HALS, there are compounds that have the ability to absorb ultraviolet rays by themselves. In this case, by adding the compound, the effect of adding the above-mentioned ultraviolet absorber and the effect of adding HALS can be combined.

The type of HALS to be added is not particularly limited, and can be arbitrarily selected depending on the influence on the visible light transmittance of the resin or the like, compatibility with the ultraviolet absorber, durability, and the like. For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacade, 1- [2- [3-( 3,5-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6 6-Tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [ 4,5] Decane-2,4-dione, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-Butylmalonate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6) -Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4 -Butane tetracarboxylate, Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β', β'-tetramethyl-3,9- [2,4,8,10- Tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2, 3,4-Butanetetracarboxylate, Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β', β'-tetramethyl-3,9- [2,4,8, 10-Tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidylmethacrylate, 1,2,2 6,6-Pentamethyl-4-piperidylmethacrylate, poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazin-2,4-diyl)] [(2, 2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol], dimethylsatinated polymer-with-4-hydroxy-2, 2, 6,6-Tetramethyl-1-piperidineethanol, N, N', N'', N'''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6) -Tetramethylpiperidin-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine-1,3,5-triazine-N, N'-bis (2) , 2,6,6-Tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethylpiperidyl) butylamine polycondensate, bisdecanthate (2, 2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like can be preferably used.

The content of HALS in the hexaboride particle-containing resin or the like according to the present invention is not particularly limited, and can be arbitrarily selected depending on the visible light transmittance, weather resistance and the like required for the resin and the like. .. The content of HALS in the resin or the like is preferably, for example, 0.05% by mass or more and 5.0% by mass or less. This is because if the content of HALS is 0.05% by mass or more, the effect of adding HALS can be sufficiently exerted in a resin or the like. Further, when the content is 5.0% by mass or less, HALS does not precipitate in the resin or the like, and the strength of the resin or the like and the penetration resistance of the resin or the like are not significantly affected.

(Iv) Antioxidant The hexaboride particle-containing resin or the like according to the present invention may further contain an antioxidant (antioxidant).
By adding an antioxidant to the hexaboride particle-containing resin or the like according to the present invention, it is possible to suppress oxidative deterioration of the resin or the like and further improve the weather resistance. In addition, other additives contained in the resin or the like, such as hexaborides, ultraviolet absorbers, HALS, dye compounds, pigment compounds, coupling agents, surfactants, antistatic agents, etc., which will be described later, are oxidatively deteriorated. It can be suppressed and weather resistance can be improved.

The antioxidant is not particularly limited, and can be arbitrarily selected depending on the influence on the visible light transmittance of the resin or the like, the desired durability, and the like. For example, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like can be preferably used.

Specifically, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisol, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-). t-Butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-butylphenol), 2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 4,4 '-Butylidene-bis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-t-butylphenyl) butane, tetrakis [methylene-3- (3) ', 5'-Butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydroxy-5-t-butylphenol) butane, 1,3,5-trimethyl-2 , 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,3'-t-butylphenol) butyric acid glycol ester, triphenylphosphine, bis- (diphenyl) Phosphinoetan), trinaphthylphosphine, tris (2,4-di-Tert-butylphenyl) phosphite and the like can be preferably used.

The content of the antioxidant in the hexaboride particle-containing resin or the like according to the present invention is not particularly limited, and may be arbitrarily selected according to the visible light transmittance, weather resistance and the like required for the resin and the like. Can be done. The content of the antioxidant in the resin or the like is preferably, for example, 0.05% by mass or more and 5.0% by mass or less. This is because if the content of the antioxidant is 0.05% by mass or more, the effect of adding the antioxidant can be sufficiently exerted in the resin or the like. Further, when the content is 5.0% by mass or less, the antioxidant does not precipitate in the resin or the like, and the strength and adhesive strength of the resin or the like and the penetration resistance of the resin or the like are not significantly affected. Because.

(V) Other Additive Components Although dispersants, ultraviolet absorbers, HALS, and antioxidants have been described above as optional additive components, various additives can also be blended.
For example, a dye compound or pigment compound that can be used for coloring a resin or the like, such as an azo dye, a cyanine dye, a quinoline dye, a perylene dye, or carbon black, is added to give an arbitrary color tone as desired. Is also good.
As other additives, for example, a coupling agent, a surfactant, an antistatic agent and the like can be added.

(5) Summary Resins and the like using the hexaboride particle-containing resin described above have high transparency of visible light and shielding property of near-infrared light.
However, the degree of transparency of visible light and shielding property of near-infrared light required for the resin or the like is not limited in advance, but is appropriately determined according to the application of the resin or the like. For example, when the resin or the like is used as a window material or the like, it is preferable that the visible light transmittance is high from the viewpoint of maintaining the light transmittance to the human eye. When the resin or the like is used for arc welding cutting work, gas welding / cutting work, laser experiment, etc. to reduce the incidence of near-infrared light, the optical density is high from the viewpoint of protecting the human eye from harmful rays. Is preferable.
The transparency of visible light and the shielding property of near-infrared light of the resin or the like can be evaluated by the visible light transmittance and the optical density, respectively.

[2] A hexaborosin particle-containing resin and a method for producing a resin or the like using the resin An example of a method for producing a hexaboride particle-containing resin according to the present invention and a resin or the like using the hexaborosin particle-containing resin. I will explain while citing. In the method for producing a resin or the like described below, the description of a known portion of the general method for producing a resin or the like is omitted.
The method for producing a hexaboride particle-containing resin or the like according to the present invention has, for example, the following steps.
(1) Dispersion liquid manufacturing step: A step of dispersing the hexaboride particles and the dispersant according to the present invention in an organic solvent to manufacture the hexaboride particle dispersion liquid according to the present invention.
(2) Dispersion powder manufacturing process: By removing the organic solvent from the hexaboride particle dispersion liquid according to the present invention produced in the dispersion liquid production step, the hexaboride particle dispersion powder according to the present invention (in the present invention, " It may be described as "dispersed powder").
(3) Resin kneading step: A step of kneading a hexaboride particle-dispersed powder according to the present invention with a predetermined resin to produce a hexaboride particle-containing resin according to the present invention.
(4) Resin molding step: A step of molding the hexaboride particle-containing resin according to the present invention into various predetermined resins or the like or a resin molded body.

In addition, without carrying out "(2) dispersion powder manufacturing process", the dispersion liquid produced in "(1) dispersion liquid manufacturing step" is subjected to "(3) resin kneading step", and in the resin kneading step. , The hexaboride particle dispersion liquid and the resin can also be kneaded. In this case, the kneading step allows the hexaboride particles to be uniformly dispersed in the resin or the like, and at the same time, the organic solvent can be removed. However, attention should be paid to the viewpoint of surely preventing a large amount of organic solvent and air bubbles from remaining in the resin and the like, and the safety viewpoint of preventing the large amount of organic solvent from being exposed to the high temperature of resin kneading exceeding 200 ° C. Is required.

Each of (1) dispersion liquid production process, (2) dispersion powder production process, (3) resin kneading process, and (4) resin molding process in the method for producing a resin or the like of a borohydride particle-containing resin according to the present invention. The process will be described.
(1) Dispersion liquid manufacturing step In the dispersion liquid manufacturing step, hexaboride particles and a dispersant are added and mixed with an organic solvent, and an organic solvent dispersion of hexaboride particles is obtained by using a general dispersion method. It is a process.
The dispersion method is not particularly limited, and for example, a dispersion method such as a bead mill, a ball mill, a sand mill, an ultrasonic dispersion, or a paint shaker can be used.
As the hexaboride particles and the dispersant that can be suitably used in the dispersion liquid manufacturing step, those described in the column of "(1) Resin layer according to the present invention" are used.

The type of organic solvent used in the dispersion liquid manufacturing process is not particularly limited, but for example, a solvent having a boiling point of 120 ° C. or lower can be preferably used. This is because if the boiling point is 120 ° C. or lower, the organic solvent can be easily removed in the dispersion powder manufacturing step, which is a subsequent step. By rapidly removing the organic solvent in the dispersed powder manufacturing process or the like, the productivity of the hexaboride particle dispersed powder can be improved. Further, since the dispersion powder production process proceeds easily and sufficiently, it is possible to prevent excess organic solvent from remaining in the hexaboride particle dispersion powder. As a result, it is possible to more reliably avoid the occurrence of problems such as the generation of air bubbles in the resin or the like in the molding process.

Specific examples of the organic solvent include, but are not limited to, toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, ethanol and the like. Anything having a boiling point of 120 ° C. or lower and capable of uniformly dispersing hexaboride particles can be preferably used.
The addition amount of the organic solvent is not particularly limited, and the addition amount thereof can be arbitrarily selected so that the dispersion liquid can be formed according to the addition amount of the hexaboride particles and the dispersant.

As described above, the amount of the dispersant added is not particularly limited. For example, it is preferable to add the hexaboride particles in an amount of 10 parts by mass or more and 1000 parts by mass or less, and more preferably 30 parts by mass or more and 400 parts by mass or less.
As for the method of adding the dispersant, it is not necessary to add the entire amount when producing the dispersion liquid in the dispersion liquid manufacturing process. For example, in consideration of the viscosity of the dispersion liquid, a part of the total amount of the dispersant added, hexaboride particles, and an organic solvent are mixed to form a dispersion liquid by the above-mentioned dispersion method, and then the balance. Dispersant may be added.

(2) Dispersion powder manufacturing process In the dispersion powder manufacturing step, the organic solvent is removed after adding an appropriate amount of the dispersant to the dispersion liquid in which the hexaboroid particles and the dispersant are dispersed in the organic solvent, if desired. Is used to produce hexaborized particle-dispersed powder.
The method for removing the organic solvent from the dispersion liquid in which the hexaboride particles and the dispersant are dispersed in the organic solvent is not particularly limited, but for example, vacuum drying can be preferably used. Specifically, the hexaboride particle dispersion powder and the organic solvent component can be separated by drying under reduced pressure while stirring the dispersion liquid in which the hexaboride particles and the dispersant are dispersed in an organic solvent. Examples of the apparatus used for vacuum drying include a vacuum stirring type dryer, but the apparatus is not particularly limited as long as it has the above-mentioned function. Further, the specific depressurizing pressure when removing the organic solvent is not limited and can be appropriately selected.

In the dispersed powder manufacturing process, the efficiency of removing the organic solvent is improved by using the vacuum drying method, and the hexaboride particle dispersed powder is not exposed to high temperature for a long time, so that the dispersed hexaboride is dispersed. It is preferable that the particle-dispersed powder does not aggregate. Furthermore, productivity is improved, it is easy to recover the evaporated organic solvent, and it is preferable from the viewpoint of environmental consideration.

(3) Resin kneading step In the kneading step, the hexaboride particle dispersion powder obtained in the dispersion powder manufacturing step and the resin are kneaded to obtain a hexaboride particle-containing resin.
In the kneading step, UV absorbers to be added to the resin layer as needed, and other additives such as HALS, antioxidants, and infrared-absorbing organic compounds are added and kneaded together to contain hexaboride particles. Resin can also be obtained. The timing of adding these additives and the like is not particularly limited, and they may be added in other steps such as a dispersion liquid manufacturing step. The kneading method is not particularly limited, and a known resin kneading method can be arbitrarily selected and used.

(4) Resin molding step The molding step is a step of molding the hexaboride particle-containing resin obtained in the kneading step to obtain various molded bodies.
The molding method is not particularly limited, and can be arbitrarily selected depending on the size and shape such as the thickness of the resin layer to be manufactured, the viscosity of the kneaded product, and the like. For example, a molding method such as an extrusion molding method or a calendar molding method can be adopted.
Further, the shape of the molded body is not particularly limited and can be selected according to the required shape, and can be molded into, for example, a sheet shape, a board shape, or a film shape. When the molded body is, for example, a lens of spectacles, a multilayer lens which is processed into a desired lens shape and bonded to another lens element by a known method can also be manufactured.

[3] Products Using Hex Boride Particle-Containing Resin The form of use of the hexaboride particle-containing resin according to the present invention is not particularly limited.
For example, it can be used for protective equipment such as a welding protective surface and light-shielding protective equipment for protecting from harmful light rays, protective eyeglasses for laser to protect from laser light, and eyeglasses such as general sunglasses. Here, protective goggles for lasers, general sunglasses, and the like include those with a degree for vision correction and those without a degree.
Here, the resin or the like of the hexaboride particle-containing resin according to the present invention can be molded into the above-mentioned protective equipment, eyeglasses, or the like. Further, a film or a resin film obtained by molding a resin or the like of the hexaboride particle-containing resin according to the present invention may be provided on the transparent base material to obtain the above-mentioned protective equipment, eyeglasses or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples.
The sample evaluation methods in Examples and Comparative Examples will be described in the order of (1) number average particle size, (2) visible light transmittance, and optical density.

(1) Number average particle size The number average particle size of the hexaborized particles in the fine particle dispersion is determined by dropping the dispersion on a sample table (mesh) for observation, drying the particles, and then using a transmission electron microscope (TEM, HF). -220, manufactured by Hitachi), and the TEM image was observed and measured. The number average particle size was determined as an average value obtained by measuring the particle size of 100 hexaboride particles in a TEM image having a magnification of 50,000 times.

(2) Visible light transmittance and optical density A spectrophotometer (Hitachi Co., Ltd. model: UH-4150) is used for the visible light transmittance of the hexaborized particle-containing resin resin and the like and the multilayer film according to the present invention. It was calculated based on JIS R 3106: 1998 from the transmittance measured in 380 nm to 780 nm.

ここでＯＤ（λ）は波長λでの光学濃度、Ｔ（λ）は波長λでの透過率（０～１００％）である。
尚、測定装置の限界により、この方法では８．０より大きい光学濃度を具体的に測定することが困難である。そこで本発明において、樹脂等および多層フィルムが８．０を超える光学濃度を持つと算出された場合、単に「８．０より大きい」あるいは「＞８．０」と記載する。 The optical density (OD) of the hexaborized particle-containing resin or the like and the multilayer film according to the present invention is as follows from the transmittance at a wavelength of 800 to 1300 nm measured using a spectrophotometer in the same manner as the visible light transmittance. It was calculated based on the formula of.

Here, OD (λ) is the optical density at the wavelength λ, and T (λ) is the transmittance (0 to 100%) at the wavelength λ.
Due to the limitation of the measuring device, it is difficult to specifically measure the optical density higher than 8.0 by this method. Therefore, in the present invention, when it is calculated that the resin or the like and the multilayer film have an optical density exceeding 8.0, it is simply described as "greater than 8.0" or ">8.0".

[Example 1]
LaB ₆ particles (may be referred to as "particle a" in the present invention) as hexaboride particles are 10 parts by mass, and a dispersant having an amine-containing group as a functional group and an acrylic main chain (amine value 48 mgKOH /). g, decomposition temperature 250 ° C.) (may be referred to as “dispersant a” in the present invention) to be 5 parts by mass, and methylisobutylketone (boiling point 116.2 ° C.) as an organic solvent to be 85 parts by mass. Weighed in. These raw materials are loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, pulverized and dispersed for 14 hours, and a dispersion liquid of particles a (may be referred to as “particle dispersion liquid a” in the present invention). Got
Here, when the number average particle diameter of the particles a in the particle dispersion liquid a was measured by the above method, it was 22 nm. In the subsequent steps, since the operation of changing the number average particle diameter of the particles a, such as pulverization treatment, is not performed, the particles in the hexaborized particle-containing resin or the like according to Example 1 with the number average particle diameter are used. The number average particle diameter of a was used.

Sufficiently after adding the dispersant a to the particle dispersion a so that the mass ratio of the dispersant to the hexaboride in the dispersion is [six boride] / [dispersant] = 100/300. The mixture was mixed to obtain a mixed solution. The mass of the dispersant in the above formula indicates the sum of the amount added when the particle dispersion a is manufactured, that is, in the dispersion manufacturing step, and the amount added after the particle dispersion a is manufactured.

Then, the obtained mixture was loaded into a stirring vacuum dryer.
Then, the mixture is dried under reduced pressure at room temperature with a stirring vacuum dryer to remove methyl isobutyl ketone from the mixed solution to obtain a dispersed powder of the particles a (may be referred to as “dispersed powder a” in the present invention). rice field. The content of methyl isobutyl ketone in the obtained dispersed powder a was 2.2% by mass.

Acrylic resin pellets, Acrypet VH000 (manufactured by Mitsubishi Rayon, which may be referred to as "acrylic resin A" in the present invention) and dispersed powder a were weighed and sufficiently mixed. The mixing ratio was adjusted so that the content of the hexaboride fine particles in the final acrylic resin layer sheet per projected area would be a value described later.
A mixture of the obtained acrylic resin pellets and the dispersed powder a is supplied to a twin-screw extruder set at 260 ° C., kneaded, and then extruded from a T-die by a calendar roll method to a thickness of 2.0 mm. It was molded into a shape. As a result, the resin layer according to Example 1 (may be referred to as "resin layer A" in the present invention) was obtained. The content of hexaboride particles per unit area in the projected area of the produced resin layer A is 0.57 g / m ² .
The above manufacturing conditions are shown in Table 1.

The visible light transmittance of the resin layer A was measured by the above method and found to be 28%. Further, the optical density (OD) in the near infrared region was measured in the same manner, and the profile of the optical density (OD) in the wavelength range of 800 nm to 1150 nm was observed. It may be described as "optical density". The same description may be used for other wavelengths.) Is 2.3, the optical density at 870 nm is 2.6, and the optical density at 975 nm is 3.0. The optical density at 1065 nm was 2.7, the optical density at 1150 nm was 2.1, and the optical density at 1300 nm was 1.1. Therefore, the minimum value of the optical density in the wavelength range of 800 nm to 1150 nm was 2.1, and the maximum value (observed as the maximum value in the profile) was 3.0.
The above measurement results are shown in Table 2.

[Examples 2 to 6]
When the acrylic resin A and the dispersed powder a are weighed and mixed, the resin layer according to Examples 2 to 6 (this) is the same as in Example 1 except that the mixing amount of the dispersed powder a with respect to the acrylic resin A is changed. In the present invention, "resin layer B", "resin layer C", "resin layer D", "resin layer E" and "resin layer F" may be described, respectively). The contents of the hexaboride particles per unit area in the projected area of the produced resin layers B to E are as shown in Table 1, respectively.
The visible light transmittance and the optical density in the near infrared region of the prepared resin layers B to E were measured in the same manner as in Example 1.
The measurement results are shown in Table 2.

[Example 7]
When weighing and mixing the acrylic resin A and the dispersed powder a, the mixing amount of the dispersed powder a with respect to the acrylic resin A was changed, and the ultraviolet absorber and the antioxidant were weighed and added in a predetermined amount. In the same manner as in Example 1, the resin layer according to Example 7 (in the present invention, each may be referred to as “resin layer G”) was produced.
Here, as the ultraviolet absorber, Tinuvin 326 (manufactured by BASF, a benzotriazole compound, which may be described as "ultraviolet absorber A" in the present invention) was used. As an antioxidant, Irganox 1010 (manufactured by BASF, represented by CAS No. 6683-19-8, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. In the present invention, each of them may be described as "antioxidant A"). The contents of the hexaboride particles per unit area and the concentrations of the ultraviolet absorber and the antioxidant in the projected area of the produced resin layer are as shown in Table 1.
The visible light transmittance of the resin layer G and the optical density in the near infrared region were measured in the same manner as in Example 1.
The measurement results are shown in Table 2.

[Example 8]
Dispersant having 10 parts by mass of particles a, a carboxyl group as a functional group, and an acrylic main chain (acid value 3.5 mgKOH / g, decomposition temperature 290 ° C.) (when described as "dispersant b" in the present invention. (There is)) was weighed to 10 parts by mass, and toluene (boiling point: 110.6 ° C.), which is an organic solvent, was weighed to 80 parts by mass. These raw materials may be loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, pulverized and dispersed for 18 hours, and described as a dispersion liquid of particles a (in the present invention, “particle dispersion liquid b”. ) Was obtained.
Here, the number average particle diameter of the hexaboride particles in the particle dispersion b was measured by the above method and found to be 26 nm. In the subsequent steps, since the operation of changing the number average particle diameter of the hexaboride particles such as pulverization treatment is not performed, the number average particle diameter is the same as the number average particle diameter of the hexaboride particles in the resin layer. Become.

After adding the dispersant b to the particle dispersion b, the dispersant b is sufficiently added so that the mass ratio of the dispersant to the hexaboride in the dispersion is [six-boride] / [dispersant] = 100/300. The mixture was mixed to obtain a mixed solution. The mass of the dispersant b in the above formula is the amount of the dispersant b added when the particle dispersion b is manufactured, that is, in the dispersion liquid manufacturing step, and the amount of the dispersant b added after the particle dispersion b is manufactured. Shows the sum of.

Then, the obtained mixture was loaded into a stirring vacuum dryer.
Then, toluene was removed from the mixture by vacuum drying at room temperature with a stirring type vacuum dryer to obtain a dispersed powder of particles a (may be referred to as "dispersed powder b" in the present invention). The toluene content in the obtained dispersed powder b was 3.0% by mass.

Panlite AD-5503 (manufactured by Teijin, which may be referred to as "polycarbonate resin A" in the present invention), which is a pellet of a polycarbonate resin, and the dispersed powder b were weighed and sufficiently mixed. The mixing ratio was adjusted so that the content of the hexaboride fine particles in the final polycarbonate resin layer sheet per projected area would be a value described later.
A mixture of the obtained polycarbonate resin pellets and the dispersed powder b was supplied to a twin-screw extruder set at 290 ° C., kneaded, and then extruded from a T-die by a calendar roll method to a thickness of 2.0 mm. It was molded into a shape. As a result, the resin layer according to Example 8 (may be referred to as "resin layer H" in the present invention) was obtained. The content of hexaboride particles per unit area in the projected area of the produced resin layer H is 1.21 g / m ² . This is shown in Table 1.
The visible light transmittance of the resin layer H and the optical density in the near infrared region were measured in the same manner as in Example 1.
The measurement results are shown in Table 2.

[Example 9]
As the hexaboride particles, ₆ CeB particles (hereinafter referred to as particles b) were weighed to 10 parts by mass, the dispersant a was weighed to 5 parts by mass, and the organic solvent methyl isobutyl ketone was weighed to 85 parts by mass. These raw materials may be loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, pulverized and dispersed for 14 hours, and described as a dispersion liquid of particles b (in the present invention, “particle dispersion liquid c”. ) Was obtained.
Here, the number average particle diameter of the hexaboride particles in the particle dispersion liquid c was measured by the above method and found to be 24 nm. In the subsequent steps, since the operation of changing the number average particle diameter of the hexaboride particles such as pulverization treatment is not performed, the number average particle diameter is the same as the number average particle diameter of the hexaboride particles in the resin layer. Become.

After adding the dispersant a to the particle dispersion c, the dispersant a is sufficiently added so that the mass ratio of the dispersant to the hexaboride in the dispersion is [six-boride] / [dispersant] = 100/300. Mixed. The mass of the dispersant in the above formula is the amount of the dispersant a added when the particle dispersion c is manufactured, that is, in the dispersion liquid manufacturing step, and the amount of the dispersant a added after the particle dispersion c is manufactured. Shows the sum.

Then, the obtained mixture was loaded into a stirring vacuum dryer.
Then, the mixture is dried under reduced pressure at room temperature with a stirring vacuum dryer to remove methyl isobutyl ketone from the mixed solution, and the dispersed powder of the particles b (may be referred to as “dispersed powder c” in the present invention). Obtained. The content of methyl isobutyl ketone in the obtained dispersion powder c was 2.3% by mass.
The pellet of acrylic resin A and the dispersed powder c were weighed and sufficiently mixed to obtain a mixture. The mixing ratio was adjusted so that the content of the hexaboride fine particles in the final acrylic resin layer sheet per projected area would be a value described later.

A mixture of the obtained acrylic resin pellets and dispersed powder c is supplied to a twin-screw extruder set at 260 ° C., kneaded, and then extruded from a T-die into a 2.0 mm thick sheet by a calendar roll method. Molded into. As a result, the resin layer according to Example 9 (may be referred to as "resin layer I" in the present invention) was obtained. The content of hexaboride particles per unit area in the projected area of the produced resin layer I is 1.01 g / m ² . This is shown in Table 1.
The visible light transmittance of the resin layer I and the optical density in the near infrared region were measured in the same manner as in Example 1.
The measurement results are shown in Table 2.

[Example 10]
The particle dispersion a obtained in Example 1 and Aronix UV-3701 (manufactured by Toagosei Co., Ltd., which may be referred to as "acrylic resin B" in the present invention), which is an acrylic ultraviolet curable resin, are used. Acrylic resin B was mixed in a proportion of 100 parts by weight with respect to 200 parts by mass of the particle dispersion liquid a, and the mixture was sufficiently stirred to prepare a mixed liquid.

The prepared coating liquid was applied on a polyethylene terephthalate (PET) film, Teijin Tetron Film HPE-50 (manufactured by Teijin DuPont Film Co., Ltd.) with a bar coater to form a coating film. At this time, the film thickness of the coating layer was adjusted so that the content of the hexaboride fine particles in the final multilayer film per projected area would be a value described later.

Then, the coating film was dried at 80 ° C. for 60 seconds to evaporate the solvent, and then cured with a high-pressure mercury lamp to form a resin layer (coating layer made of acrylic resin) containing hexaboride particles. By such an operation, a multilayer film composed of a resin layer containing hexaboride particles (may be referred to as "resin layer J" in the present invention) and a substrate layer of PET film (in the present invention, "multilayer". It may be described as "Film J"). The content of hexaboride particles per unit area in the projected area of the produced resin layer J is 1.39 g / m ² . Since the base material layer of the PET film does not contain hexaboride particles, the content of hexaboride particles per unit area in the projected area of the produced multilayer film J is also 1.39 g / m ² . .. This is shown in Table 1.
The visible light transmittance and the optical density in the near infrared region of the multilayer film J were measured in the same manner as in Example 1.
The measurement results are shown in Table 2.

[Comparative Example 1]
Only the pellets of acrylic resin A were supplied to a twin-screw extruder set at 260 ° C., kneaded, and then extruded from a T-die into a 2.0 mm thick sheet by a calender roll method. As a result, a resin layer according to Comparative Example 1 (may be referred to as "resin layer α" in the present invention) was obtained. The produced resin layer α does not contain hexaboride particles, and the content of hexaboride particles per unit area in the projected area of the resin layer α is 0.0 g / m ² . This is shown in Table 1.
The visible light transmittance of the resin layer α and the optical density in the near infrared region were measured in the same manner as in Example 1.
The measurement results are shown in Table 2.

[Comparative Example 2]
The resin layer according to Comparative Example 2 (in the present invention) in the same manner as in Example 1 except that the amount of the dispersed powder a with respect to the acrylic resin A was changed when the acrylic resin A and the dispersed powder a were weighed and mixed. , "Resin layer β" may be described.) Was prepared. The content of hexaboride particles per unit area in the projected area of the produced resin layer β is 0.35 g / m ² . This is shown in Table 1.
The visible light transmittance of the resin layer β and the optical density in the near infrared region were measured in the same manner as in Example 1.
The measurement results are shown in Table 2.

(Summary of Examples 1 to 10 and Comparative Examples 1 and 2)
According to the results of Examples shown above, the resin layers A to J and the multilayer film J according to Examples 1 to 10 have a wavelength of 800 to 1150 nm while maintaining a high visible light transmittance of 2 to 30%. In the profile of optical density (OD) in the near infrared region, the minimum value is 2.0 or more, and the maximum value (observed as the maximum value in the profile) is more than 8.0 (OD). The value of was realized.
Therefore, it has been found that the resin layers A to J and the multilayer film J exhibit excellent optical characteristics that can significantly reduce the influence of strong near-infrared light such as a laser on the eyes.

Since the resin layers A to J use a general acrylic resin as a medium, they can be processed into eyeglasses or windows by performing an appropriate known molding process. Then, a laser protective device having the window can be manufactured by a known method. On the other hand, the multilayer film J can be attached to an arbitrary transparent substrate by a known method to impart a laser protection function while maintaining the visible transparency of the transparent substrate.

On the other hand, since the resin layer α according to Comparative Example 1 does not contain hexaboride, it has a high visible light transmittance, but its optical density for light having a wavelength of 800 to 1150 nm is not sufficient, and it is a strong near-infrared light. It had little function to reduce the effect on the eyes.
Further, although the resin layer β according to Comparative Example 2 contains hexaboride, the content of hexaboride particles per unit area in the projected area is small, so that the optical density for light having a wavelength of 800 to 1150 nm is still sufficient. Instead, the ability to mitigate the effects of strong near-infrared light on the eyes remained low.

Claims (19)

The hexaboride particles are the hexaboride particle-containing resin dispersed in the resin.
The number average particle diameter of the hexaboride particles in the resin is 26 nm or less.
Further, one or more groups selected from an amine-containing group, a hydroxyl group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, a phosphoric acid ester, a sulfonic acid group, a sulfonic acid ester, a thiol group, or an epoxy group. , Contains a dispersant having as a functional group,
The dispersant is a dispersant having a thermal decomposition temperature of 250 ° C. or higher measured using a differential heat / thermogravimetric simultaneous measuring device (however, the thermal decomposition temperature is the differential heat / thermal weight simultaneous measuring device. In the measurement according to JIS K 7120: 1987, the temperature at which the weight loss due to thermal decomposition of the dispersant begins.),.
A hexaboride particle-containing resin characterized by having an optical density (OD) value of 2.0 or more in the near infrared region having a wavelength of 800 nm to 1150 nm. The hexaboride particles are the hexaboride particle-containing resin dispersed in the resin.
The number average particle diameter of the hexaboride particles in the resin is 26 nm or less.
Further, one or more groups selected from an amine-containing group, a hydroxyl group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, a phosphoric acid ester, a sulfonic acid group, a sulfonic acid ester, a thiol group, or an epoxy group. , Contains a dispersant having as a functional group,
The dispersant is a dispersant having a thermal decomposition temperature of 250 ° C. or higher measured using a differential heat / thermogravimetric simultaneous measuring device (however, the thermal decomposition temperature is the differential heat / thermal weight simultaneous measuring device. In the measurement according to JIS K 7120: 1987, the temperature at which the weight loss due to thermal decomposition of the dispersant begins.),.
A hexaboride particle-containing resin characterized in that the content of the hexaboride in the resin is 0.55 g / m ² or more and 2.00 g / m ² or less per projected area of the resin. The particles of the hexaboride are from the general formula XB ₆ (X is from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. The hexaboride particle-containing resin according to claim 1 or 2, wherein the hexaboride particles are represented by (1 or more elements selected). The hexaboride particle-containing resin according to any one of claims 1 to 3, wherein the hexaboride particles are particles of lanthanum hexaboride. The hexaboride particle-containing resin according to any one of claims 1 to 4, wherein the resin contains at least one selected from an acrylic resin, a polycarbonate resin, and a vinyl chloride resin. The hexaboride particle-containing resin according to any one of claims 1 to 5, further comprising an ultraviolet absorber. The hexaboride particle-containing resin according to any one of claims 1 to 6, further comprising an antioxidant. The hexaboride particle-containing resin according to any one of claims 1 to 7, wherein the visible light transmittance calculated by JIS R 3106: 1998 is 2% or more. A near-infrared ray shielding lens having a resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 8 . The near-infrared shielding eyeglasses comprising the resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 8 or the near-infrared shielding lens according to claim 9 . A protective device comprising the resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 8 or the near-infrared ray shielding lens according to claim 9 . A near-infrared ray shielding window material having a resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 8 . A near-infrared shielding device according to claim 12, wherein the near-infrared shielding window material is provided. A near-infrared shielding film, wherein the resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 8 is provided on a film substrate. A near-infrared ray shielding glass, wherein the resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 8 is provided on a glass substrate. A hexaboride particle dispersion liquid used for producing the resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 8 .
A hexaboride particle containing one or more elements selected from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca , Dispersed in organic solvent,
The number average particle diameter of the hexaboride particles is 26 nm or less .
Further, one or more groups selected from an amine-containing group, a hydroxyl group, a carboxyl group, a carboxylic acid ester, a phosphoric acid group, a phosphoric acid ester, a sulfonic acid group, a sulfonic acid ester, a thiol group, or an epoxy group. , Contains a dispersant having as a functional group,
The dispersant is a dispersant having a thermal decomposition temperature of 250 ° C. or higher measured using a differential heat / thermogravimetric simultaneous measuring device (however, the thermal decomposition temperature is the differential heat / thermal weight simultaneous measuring device. In the measurement according to JIS K 7120: 1987, the temperature at which the weight loss due to the thermal decomposition of the dispersant begins.), The hexaborized particle dispersion liquid. The particles of the hexaboride are derived from the general formula XB ₆ (X is from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. The hexaboride particle dispersion according to claim 16, wherein the hexaboride particles represented by (1 or more elements selected) are present. The hexaboride particle dispersion powder according to claim 16 or 17 , wherein the organic solvent is removed from the hexaboride particle dispersion liquid. The hexaboride particle dispersion powder according to claim 18, wherein the number average particle diameter of the hexaboride particles is 26 nm or less .