JP2019020603A - Resin containing hexaboride particle, dispersion liquid of hexaboride particle and dispersion powder of hexaboride particle - Google Patents

Abstract

To provide a resin containing hexaboride particles exhibiting excellent optical characteristics such that the resin has a high optical density (OD) with respect to near-infrared light at a wavelength of 800 nm to 1150 nm while maintaining a visible light transmittance and that influences on eyes even by intense near-infrared light such as laser light can be reduced, a near-infrared ray-shielding lens, near-infrared ray-shielding spectacles, a protection tool, a near-infrared ray-shielding window material, near-infrared ray-shielding fixtures and a near-infrared ray-shielding film or glass having a layer of the above resin, a dispersion liquid of hexaboride particles that can be used for the production of the resin containing hexaboride particles, and a dispersion powder of hexaboride particles.SOLUTION: The resin containing hexaboride particles contains hexaboride particles dispersed in a resin, and the resin containing hexaboride particles has a value of optical density (OD) of 2.0 or more in a near-infrared ray region at a wavelength from 800 nm to 1150 nm.SELECTED DRAWING: None

Description

  The present invention mainly uses a hexaboride particle-containing resin used for protecting eyes from exposure to near infrared light, a hexaboride particle dispersion liquid that can be used in the production of the hexaboride particle-containing resin, and It relates to a hexaboride particle-dispersed powder.

  Living tissue is affected variously by light (electromagnetic waves) having wavelengths of ultraviolet light, visible light, and near infrared light. Although the influence varies depending on the part of the living tissue, visible light and near infrared rays reach the retina, especially in the eye tissue. For this reason, it is known that when visible light and near-infrared rays act on eye tissues for a long time or with high intensity, they cause heavy 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 acting on the eye tissue for a long time or with high 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, sunlight may cause the above-described obstacles to human eyes. In order to avoid such obstacles, for example, car drivers, athletes, aircraft pilots, and others who may be exposed to strong sunlight for a long time, ultraviolet light to visible light can be used to protect the eyes from sunlight. ~ Glasses (eyewear) having a layer that reduces light having each wavelength of near infrared light may be worn.

Further, for example, a laser having each wavelength of ultraviolet light, visible light, and near infrared light (in the present invention, sometimes referred to as “laser”) is similar to sunlight or more seriously to the eye due to its strong intensity. Is known to cause disability.
In addition, for example, gas welding work, gas fusing work, work using an arc lamp or mercury lamp, work using an infrared lamp or sterilization lamp, work such as blast furnace, billet furnace, ingot, etc. are generated by this work. It is known that exposure to the eye with intense light can cause damage to the eye.
Persons involved in work exposed to such powerful light also wear eyeglasses (eyewear) having a layer that reduces light having wavelengths of ultraviolet light, visible light, and near infrared light, A protective surface or the like having a light reducing layer as a window (working viewing window) may be used.

Various members have been proposed as members for protecting eyes from near-infrared light or the like in the above-described glasses (eyewear), protective surface, and the like.
For example, JIS T 8141: 2003 stipulates light-shielding protective equipment worn by each person in order to protect the eyes of workers in places where ultraviolet radiation and near-infrared radiation harmful to the eyes and intense visible light are generated. Has been. JIS T 8143: 1994 defines a laser protective filter and laser protective glasses used to protect an operator's eyes from laser radiation having a wavelength of 180 nm to 1 mm.

Further, in Patent Document 1, as a more specific member, a multilayer film near eyeglass lens in which a high-refractive index dielectric film and a low-refractive index dielectric film are alternately laminated on both surfaces of a transparent resin substrate. An infrared filter is 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. Yes.
Patent Document 3 discloses a protective eyeglass lens in which a first lens element for shielding laser light and a second lens element for antiglare are superimposed. The first lens element for shielding laser light contains an absorber that selectively absorbs a laser beam having a specific wavelength in the ultraviolet wavelength region, the visible light wavelength region, or the infrared wavelength region, and has a visible light wavelength. It is disclosed that the substrate is transparent in the region.
In Patent Document 4, a lens is produced by polymerizing a predetermined acrylic resin, a copolymerizable polyfunctional monomer, an oil-soluble dye and / or a near-infrared absorber, and laser protection obtained by processing the lens. An eyeglass lens is disclosed.

Japanese Patent Laying-Open No. 2015-161731 International Publication No. 1998/058290 JP 2006-184596 A JP-A-4-353819

The present inventors examined these prior arts.
Then, the prior art uses one of the principles of [1] reflection of light by a multilayer film and [2] absorption by an organic dye with respect to light shielding of near infrared light, and each has a problem. there were.
Hereinafter, each principle and problem will be described.

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

  However, the reflection of light by the multilayer film has a problem that light can be reflected only in a narrow region centered on a specific wavelength in a laminated structure having a single layer thickness. For this reason, even if it has high shielding performance for near-infrared light of a certain wavelength, it may have little shielding performance for light of different wavelengths. Here, the wavelength range to be reflected can be widened by increasing the number of layers, but the process becomes complicated and the cost increases.

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

[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 a property of absorbing near infrared light in a base material. . For example, among the above-described prior art documents, Patent Documents 3 and 4 disclose shielding of near infrared light based on the principle of absorption by such an organic dye.

  However, the absorption by organic dyes has a problem that light can be absorbed only in a narrow region centered on a specific wavelength because the organic dyes generally absorb only in a very narrow wavelength range. It was. For this reason, even if it has high shielding performance for near-infrared light of a certain wavelength, it may have little shielding performance for light of different wavelengths. Although a configuration in which the wavelength range is widened by simultaneously containing a plurality of organic dyes corresponding to various wavelengths has been considered, the process becomes complicated and the cost increases. Further, since the organic dye absorbs visible light at the same time, there is a problem that the visible light transmittance is lowered. In addition, the weather resistance of organic dyes is generally low, and depending on the environment and time used, the shielding performance against near-infrared light may deteriorate due to deterioration of the organic dye.

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

  As a result of intensive studies by the present inventors to solve the above-described problems, a high value optical density with respect to near-infrared light is exhibited by including hexaboride particles in a medium such as a resin. The present invention was completed by discovering that it is feasible to obtain a resin containing hexaboride particles.

That is, the first invention for solving the above-described problem is
The hexaboride particles are a hexaboride particle-containing resin dispersed in a resin,
A hexaboride particle-containing resin having an optical density (OD) value of 2.0 or more in the near-infrared region of wavelengths from 800 nm to 1150 nm.
The second invention is
The hexaboride particles are a hexaboride particle-containing resin dispersed in a 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 hexaboride particles are represented by the general formula XB ₆ (X is 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, wherein the resin is a hexaboride particle represented by at least one selected element. .
The fifth invention is:
The hexaboride particle-containing resin according to any one of the first to fourth inventions, wherein the hexaboride particles are lanthanum hexaboride 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 at least one selected from an acrylic resin, a polycarbonate resin, and a vinyl chloride resin. It is.
The seventh invention
Furthermore, the hexaboride particle-containing resin according to any one of the first to sixth inventions, further comprising an ultraviolet absorber.
The eighth invention
Furthermore, the hexaboride particle-containing resin according to any one of the first to seventh inventions, further comprising an antioxidant.
The ninth invention
Furthermore, 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 hexaboride particle-containing resin according to any one of the first to eighth inventions, further comprising a dispersant having a functional group.
The tenth invention is
The visible light transmittance calculated according to JIS R 3106: 1998 is 2% or more. The hexaboride particle-containing resin according to any one of the first to ninth inventions.
The eleventh invention is
A near-infrared shielding lens comprising the resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions.
The twelfth invention
A near-infrared shielding eyeglass 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
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 shielding lens according to claim 10.
The fourteenth invention is
A near-infrared shielding window material comprising the resin layer of the hexaboride particle-containing resin according to any one of the first to tenth inventions.
The fifteenth invention
It is a near-infrared shielding instrument characterized by having the near-infrared shielding window material as described in 14th invention.
The sixteenth invention is
A near-infrared shielding film, wherein 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
A near-infrared shielding glass, wherein 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
A hexaboride particle dispersion used for producing a 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 an organic solvent,
The hexaboride particle dispersion is characterized in that the number average particle diameter of the hexaboride particles is 40 nm or less.
The nineteenth invention
The hexaboride particles are represented by the general formula XB ₆ (X is 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 aspect of the invention, wherein the hexaboride particles are represented by at least one selected element.
The twentieth invention is
Furthermore, 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 hexaboride particle dispersion according to the eighteenth or nineteenth invention, characterized by containing a dispersant having a functional group.
The twenty-first invention
A hexaboride particle-dispersed powder obtained by removing the organic solvent from the hexaboride particle dispersion according to any one of the eighteenth to twentieth inventions.
The twenty-second invention
The hexaboride particle-dispersed powder according to the twenty-first aspect, wherein the number average particle diameter of the hexaboride particles is 40 nm or less.
The twenty-third invention
Furthermore, 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 hexaboride particle-dispersed powder according to the twenty-first or twenty-second invention, characterized by containing a dispersant having a functional group.

  According to the present invention, while maintaining a high visible light transmittance, it has a high optical density (OD) with respect to near infrared light with a wavelength of 800 to 1150 nm, It is possible to provide a hexaboride particle-containing resin that exhibits excellent optical properties that can significantly reduce the influence on the eye. Moreover, the near-infrared shielding lens, near-infrared shielding glasses, protective equipment, near-infrared shielding window material, near-infrared shielding instrument, near-infrared shielding film, and glass which have the said hexaboride particle containing resin can be provided.

  Hereinafter, about a form for carrying out the present invention, [1] hexaboride particle-containing resin and its constituent components, [2] hexaboride particle-containing resin and resin layer production method using the resin, [3] six The products using the boride particle-containing resin will be described in this order. However, the present invention is not limited to the embodiment. That is, various modifications and substitutions can be made to the embodiment without departing from the scope of the present invention.

[1] Hexboride particle-containing resin and its constituent components The hexaboride particle-containing resin according to the present invention contains hexaboride particles, a resin, and optionally other components.
About the hexaboride particle-containing resin according to the present invention, (1) hexaboride particle-containing resin according to the present invention, (2) hexaboride particles, (3) resin, (4) other components, (5) Summary Will be described in the order.

(1) Hexaboride particle-containing resin according to the present invention The hexaboride particle-containing resin according to the present invention is represented by the general formula XB ₆ (wherein element X is La, Ce, Pr, Nd, Gd). At least one selected from Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. ing.
The hexaboride particles have heretofore been used in solar radiation shielding fields different from the field of eye protection from near infrared light, such as solar radiation shielding window films, solar radiation shielding laminated transparent base materials, and solar radiation shielding resin sheets.

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

  The reason why hexaboride was used only in such a low optical density region was that it was thought that transparency was lost by increasing the amount of hexaboride. That is, when hexaboride particles are used, the film has a strong green tint due to absorption of the visible light region of hexaboride, even in the low optical density region used in the solar shading field. . When the content is increased to achieve higher optical density, the transparency of visible light is further lost due to absorption of the visible light region of hexaboride, and in addition, light scattering by hexaboride particles ( Naturally, the transparency of visible light was thought to be lost because the Mie scattering and Rayleigh scattering) also increased with the content of hexaboride particles.

That is, when hexaboride particles are used, an optical density corresponding to the level required for the solar radiation shielding field can be realized while ensuring transparency to visible light, but the high level of opticalness required for the laser shielding field is achieved. The conventional common sense is that the concentration cannot be realized.
However, as a result of intensive studies by the present inventors, the hexaboride particles having a content far exceeding the general content of hexaboride particles per projected area used in the field related to solar radiation shielding are obtained. It has been found that a resin layer having a high optical density with respect to near-infrared light can be realized by being contained in a resin.

Specifically, the amount of hexaboride particles used in the general solar shading field is approximately 0.07 to 0.20 g / m ² per projected area. On the other hand, when 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 is used. In the density (OD) profile, it is possible to realize an optical density (OD) value of 2.0 or more at the minimum value and 8.0 (maximum value is observed in the profile) at the maximum value of 8.0. I found out.

  Surprisingly, it has been found that even when the hexaboride content is increased to achieve such a high optical density, the transparency to visible light is ensured at a sufficiently high level. Specifically, the above-described high optical density (OD) can be achieved while maintaining a high visible light transmittance of, for example, 2 to 30%, as calculated by JIS R 3106: 1998. It was found that there was.

  The hexaboride particle-containing resin according to the present invention described above is said to have a high optical density over a wide range of wavelengths from 800 to 1150 nm as well as light of a specific wavelength in the light in the near infrared region. Compared with the laser shielding member according to the prior art, it has a remarkable advantage.

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

According to the principle of localized surface plasmon resonance, light absorption is realized over a wide range of photon energy (ie, a wide range of light wavelength) centered on a specific photon energy (ie, a specific light wavelength). Therefore, it is considered that a high optical density value could be realized in a wide wavelength range covering near infrared light having a wavelength of 800 to 1150 nm.
In addition, the hexaboride particles have a far higher transparency of visible light with respect to absorption of near infrared light than other particles having localized surface plasmon resonance, so that near infrared light having a wavelength of 800 to 1150 nm is used. In spite of realizing high optical density in a wide range of regions, it is considered that high transmittance was secured in the visible light region.

(2) Hexaboride Particles The hexaboride particles according to the present invention express light absorption by plasmon absorption in the near infrared region. Its components are those represented by the general formula XB _6, the shape is one having a shape of non-spherical. 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. It is preferable.
Specifically, lanthanum hexaboride [LaB ₆ ], cerium hexaboride [CeB ₆ ], praseodymium hexaboride [PrB ₆ ], neodymium hexaboride [NdB ₆ ], gadolinium hexaboride [GdB ₆ ], hexaboride terbium _[TbB 6], hexaboride dysprosium _[DyB 6], hexaboride holmium _[HoB 6], hexaboride yttrium _[YB 6], hexaboride samarium _[SmB 6], hexaboride Europium [EuB ₆ ], erbium hexaboride [ErB ₆ ], thulium hexaboride [TmB ₆ ], ytterbium hexaboride [YbB ₆ ], lutetium hexaboride [LuB ₆ ], lanthanum cerium hexaboride [(La , _{Ce) B} 6], hexaboride strontium _[SrB 6], the hexaboride calcium [CaB _6] or the like, as a typical It can gel. Among these, lanthanum hexaboride [LaB ₆ ] is preferably used because the intensity of near-infrared absorption with respect to visible light absorption is high.

  In the hexaboride particles according to the present invention, the surface is preferably not oxidized, but is usually slightly oxidized in many cases. In addition, it is inevitable that the surface is oxidized in the step of dispersing the hexaboride fine particles. However, even in that case, there is no change in the effectiveness of developing the near-infrared shielding effect. Therefore, for example, even hexaboride particles having an oxidized surface can be used as the hexaboride particles used in the present invention.

  Further, the hexaboride particles according to the present invention have a greater heat ray shielding effect as the crystal completeness 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 a bond between each metal and boron, the heat ray shielding effect Can be applied in the present invention. In addition, as a hexaboride, the ratio of a metal and boron does not need to be strictly 6, and may be in a range of 5.8 to 6.2.

The particle diameter 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, glasses, windows, 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, it is preferable that the hexaboride particles according to the present invention have a finer particle diameter than that used in general heat ray shielding applications. For example, in a heat ray shielding application example different from the present invention, the volume average particle diameter of hexaboride particles is preferably 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 addition amount per projected area of the hexaboride particles according to the present invention is much larger than the usage amount per projected area in the embodiment of the heat ray shielding application. Therefore, by reducing the particle diameter of the hexaboride particles, light scattering due to Mie scattering and Rayleigh scattering caused by the hexaboride particles is suppressed. And the transparency with respect to visible light is ensured by suppression of the said scattering of light, and the hexaboride particle | grain containing resin which concerns on this invention exhibits transparency substantially.

In order to avoid a situation in which this resin is not substantially transparent, the hexaboride particles in the present invention preferably have a volume average particle diameter of 1 nm or more and 40 nm or less. When the volume average particle diameter of hexaboride particles is 40 nm or less, even when the content of hexaboride particles per projected area is large as in the present invention, light scattering due to Mie scattering and Rayleigh scattering caused by the particles is caused. This is because it is sufficiently suppressed and visibility in the visible light wavelength region can be maintained, and at the same time, transparency can be efficiently maintained.
When the resin is used for applications requiring transparency, 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 diameter” is used with the same meaning in other parts.

  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, the volume average particle diameter of hexaboride particles is 1 nm or more from the viewpoint of easy handling when producing a resin layer containing hexaboride particles and avoiding aggregation of hexaboride particles in the resin. It is preferable.

The amount (content) of hexaboride particles contained in the resin is preferably such that 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, and more preferably 0.55 g / ^{m 2} or more 1.50 g / ^{m 2} or less. By setting it to 0.55 g / m ² or more, a high optical density can be realized in the near infrared region. By setting it to 2.00 g / m ² or less, it is possible to prevent loss of visible light permeability due to absorption and scattering of visible light possessed by hexaboride particles.

(3) Resin As the resin used for the hexaboride particle-containing resin according to the present invention, any resin can be used. However, in view of the use of the hexaboride particle-containing resin according to the present invention, a resin having sufficient transparency is desirable. 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, fluorine resin, ethylene / vinyl acetate copolymer Preferred resin from one resin selected from the group of resins, 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, it is selected from one resin selected from polycarbonate resin, acrylic resin, vinyl chloride resin, or the resin group in consideration of high transparency, rigidity, light weight, long-term durability, and cost. 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.

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

(3) Other components In addition to the hexaboride and the resin component described above, an optional component can be further added to the resin layer of the present embodiment. Examples of components that can be optionally added include (i) a dispersant, (ii) an ultraviolet absorber, (iii) a hindered amine light stabilizer, (iv) an antioxidant, and (v) other additive components. These components are described below.

(I) Dispersant A dispersant may be added to the resin layer according to the present invention in order to uniformly disperse the above-described hexaboride particles in the ionomer resin.
The dispersant is not particularly limited, and can be arbitrarily selected according to the resin production conditions. For example, the thermal decomposition temperature measured using a differential heat / thermogravimetric simultaneous measurement device (hereinafter sometimes referred to as TG-DTA) is 250 ° C. or more, and the urethane main chain, acrylic main chain, styrene main It is preferable that the dispersant has a main chain selected from any chain, or a main chain obtained by copolymerization of two or more unit structures selected from urethane, acrylic, and styrene. The aforementioned pyrolysis temperature is more preferably 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 the 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 prevented from being decomposed during kneading with the resin component, and the hexaboride particle-containing resin layer is colored brown and visible light is transmitted due to the decomposition of the dispersant. This is because it is possible to more reliably avoid a situation in which the original optical characteristics cannot be obtained by suppressing the decrease in the rate.
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 one of the functional groups described above is adsorbed on the surface of the hexaboride particles, prevents aggregation of the hexaboride particles, and more uniformly disperses the hexaboride particles in the resin containing hexaboride particles. Therefore, it can be preferably used.
Further, the dispersant preferably has a main chain composed of acrylic, styrene, urethane, polyethylene, ester, polyethyleneimine, or a main chain composed of two or more kinds of copolymers selected from these structures as the main chain. . This is because the dispersant having any of the above-mentioned main chains prevents aggregation of hexaboride particles due to steric hindrance and is compatible with the ink solvent or 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 and polyethyleneimine, the main chain structure has a structure having adsorptivity to hexaboride particles, so that aggregation of hexaboride particles is prevented, and in the hexaboride particle-containing resin. Since hexaboride particles can be more uniformly dispersed, it is more preferable.
Moreover, it is also preferable that two or more kinds of the dispersants are used in combination as necessary.

Specific examples of the dispersant having any of the functional groups described above include, for example, an acrylic-styrene copolymer dispersant having a carboxyl group as a functional group, an acrylic dispersant having an amine-containing group as a functional group, and the like. Is mentioned. An acrylic resin having a functional group such as a carboxyl group can also be used.
The dispersant having a functional group containing an amine is preferably one having a molecular weight Mw of 2,000 to 200,000 and an amine value of 5 to 100 mgKOH / g. Moreover, in the dispersing agent which has a carboxyl group, the thing of molecular weight Mw2000-200000 and an acid value of 1-50 mgKOH / g is preferable.

The addition amount of the dispersant is not particularly limited, but for example, it is preferably added 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 hexaboride particles, and 30 parts by mass or more and 400 parts by mass It is more preferable to add so that it may become the following.
This is because if the added amount of the dispersant is within the above range, the hexaboride particles can be more uniformly dispersed in the ionomer resin, and the physical properties of the resulting resin layer will not be adversely affected.

  Specific examples of the above-mentioned commercially available dispersants include ADEKA COAL (registered trademark) TS-230E, CS-141E, CS-1361E, PS-984, PS-440E, PS-807 manufactured by ADEKA, and NOF polystar. (Registered trademark) OM, OMR, OMP, A-1060, SMX-1H, OMA, OMA-500, Mariarim (registered trademark) AKM-0531, AKM-1511-60, AFB-1521, AAB-0851, AWS-0851 , HKM-50A, Naimene (registered trademark) L-201, L-202, Marproof (registered trademark) G-0150M, G-0115S, G-0250S, G-0130S-P, G-1010S, Ajinomoto Co., Ltd. (Registered trademark) PB-711, PB-821, PB-822, PB-881, PN-4 1, PA-111, Disparon (registered trademark) 1210, 2150, KS-860, KS-873N, 7004, 1830, 1850, 1860, DA-1401, PW-36, DN-900, DA-1200 manufactured by Enomoto Kasei Co., Ltd. DA-550, DA-7301, DA-325, DA-375, DA-234, SOLPERSE (registered trademark) 3000, 5000, 9000, 11200, 12000, 13240, 13350, 13940, 16000, 17000, manufactured by Lubrizol. 18000, 20000, 21000, 22000, 24000SC, 24000GR, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 36 00, 36600, 37500, 38500, 39000, 41000, 41090, 43000, 44000, 46000, 47000, 53955, 54000, 55000, 56000, 71000, 76500, Solplus (registered trademark) D510, D520, D530, D540, L300, L400 K200, K210, K500, C800, C825, DP310, DP320, DP330, R700, Reseda (registered trademark) GP-301 manufactured by Toagosei Co., Ltd., Alfon (registered trademark) UF-5022, UF-5080, UC-3000, UC -3910, UC-3920, UG-4030, UG-4040, UG-4070, Disperbyk (registered trademark) 101, 108, 102, 103, 106, 109 manufactured by Big Chemie 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, EFKA (registered trademark) 2020, 2025, 2720, 3030, 3031, 3236, 4008, 4009, 4010, 4015, 4020, 404 manufactured by BASF 4047, 4050, 4055, 4060, 4080, 4300, 4310, 4400, 4401, 4402, 4403, 4510, 4520, 4550, 4560, 4570, 4580, 4590, 6230, 7414, 8215, Jonkrill (registered trademark) J -67, J-586, J-587, J-611, J-680, J-690, J-810, JDX-C3000, JDX-C3020 and the like.

(Ii) Ultraviolet Absorber The hexaboride particle-containing resin according to the present invention may further contain an ultraviolet absorber.
As described above, the hexaboride particle-containing resin according to the present invention and the resin layer using the resin (may be described as “resin etc.” in the present invention) are mainly used for light in the near infrared region. Transmission can be suppressed and eyes can be protected 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 cut off light in the ultraviolet region, and to particularly enhance the harmful light suppression effect.

  Furthermore, the polymer itself that 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 according to the influence on the visible light transmittance of the resin layer, the ultraviolet absorbing ability, durability, and the like. Examples of ultraviolet absorbers 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. Etc. In particular, the ultraviolet absorber preferably contains one or more selected from benzotriazole compounds and benzophenone compounds. This is because the benzotriazole compound and benzophenone compound can increase the visible light transmittance of the resin layer even when a concentration sufficient to absorb ultraviolet rays is added, and is durable against long-term exposure to strong ultraviolet rays. This is because the nature is high.

  The content of the ultraviolet absorber in the resin or the like of the hexaboride 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, the ultraviolet shielding ability, etc. Can be selected. It is preferable that the content rate of the ultraviolet absorber in resin etc. is 0.02 mass% or more and 5.0 mass% or less, for example. This is because if the content of the ultraviolet absorber is 0.02% by mass or more, ultraviolet light that cannot be absorbed by the hexaboride particles can be sufficiently absorbed. In addition, when the content is 5.0% by mass or less, the ultraviolet absorber does not precipitate in the resin or the like, and does not significantly affect the strength and penetration resistance of the film.

(Iii) Hindered amine light stabilizer The resin of the hexaboride particle-containing resin according to the present invention further contains a hindered amine light stabilizer (may be described as “HALS” in the present invention). You can also.
As described above, the ultraviolet absorbing ability can be increased by adding an ultraviolet absorber to the hexaboride particle-containing resin according to the present invention. However, depending on the environment in which the hexaboride particle-containing resin according to the present invention is used, or depending on the type of the ultraviolet absorber, the ultraviolet absorber is deteriorated with the passage of a long time, and the ultraviolet absorbing ability is reduced. May end up. In such a case, the addition of HALS can prevent the UV absorber from deteriorating and contribute to the maintenance of the UV absorbing ability of the hexaboride particle-containing resin according to the present invention.

Further, as described above, the hexaboride particle-containing resin according to the present invention has a concern that the transmittance decreases 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, a decrease in the transmittance can be suppressed as in the case where an ultraviolet absorber is added.
Furthermore, in HALS, there are compounds that themselves have the ability to absorb ultraviolet rays. In this case, the addition of the compound can combine the effects of adding the ultraviolet absorber and the effects of adding HALS.

  The type of HALS to be added is not particularly limited, and can be arbitrarily selected according to the influence on the visible light transmittance of a 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) sebacate, 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-butylma , 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-butanetetracarboxylate, 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-butante Lacarboxylate, 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-piperidyl methacrylate, 1,2,2,6,6-pentamethyl -4-piperidyl methacrylate, poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl)] [(2,2,6,6 -Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol], dimethyl succinate polymer-with-4-hydroxy-2,2,6,6 -Te Lamethyl-1-piperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N′-bis (2,2,6,6) A polycondensate of 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethylpiperidyl) butylamine, bis (2,2,6,6) decanedioate -Tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like can be suitably 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 according to the visible light transmittance, weather resistance, etc. required for the resin or the like. . For example, the HALS content in the resin or the like is preferably 0.05% by mass or more and 5.0% by mass or less. This is because if the HALS content is 0.05% by mass or more, the effect of the addition of the HALS can be sufficiently exhibited in a resin or the like. If the content is 5.0% by mass or less, HALS does not precipitate in the resin or the like, and does not significantly affect the strength of the resin or the penetration resistance of the resin or the like.

(Iv) Antioxidant The hexaboride particle-containing resin 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, such as hexaboride, UV absorber, HALS, dye compounds, pigment compounds, coupling agents, surfactants, antistatic agents, etc. described later are oxidatively deteriorated. It can suppress and can improve a weather resistance.

  The antioxidant is not particularly limited, and can be arbitrarily selected according to the influence on the visible light transmittance of a 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 suitably used.

  Specifically, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 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-tert-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenol) butane, , 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,3'-tert-butylphenol) butyric acid glycol ester, Triphenylphosphine, bis- (diphenylphosphinoethane), trinaphthylphosphine, tris (2,4-di-tert-butylphenyl) phosphite and the like can be suitably used.

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

(V) Other additive components As described above, the dispersant, the ultraviolet absorber, the HALS, and the antioxidant have been described as optional additive components, but various other additives can be blended.
For example, an azo dye, a cyanine dye, a quinoline dye, a perylene dye, a carbon black, or the like, which can be used for coloring a resin or the like to add an arbitrary color tone if desired, is added. Also good.
As other additives, for example, a coupling agent, a surfactant, an antistatic agent, and the like can be added.

(5) Summary Resins using the hexaboride particle-containing resin described above have high visible light transparency and near-infrared light shielding properties.
However, the degree of visible light transparency and near-infrared light shielding required for the resin and the like are not limited in advance, and are appropriately determined according to the use of the resin and the like. For example, when the resin or the like is used for 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. Also, when the resin is used for applications that reduce near-infrared light incidence by arc welding cutting work, gas welding / cutting work, laser experiments, etc., the optical density is high from the viewpoint of protecting human eyes from harmful rays. It is preferable.
And the transparency of visible light, such as the said resin, and the shielding property of near-infrared light can be evaluated by visible light transmittance and optical density, respectively.

[2] Method for producing a hexaboride particle-containing resin and a resin using the resin, etc. 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 hexaboride particle-containing resin I will explain it. In addition, in the manufacturing method of resin etc. demonstrated below, it is a manufacturing method of general resin etc., and is abbreviate | omitting description about a well-known part.
The method for producing a hexaboride particle-containing resin or the like according to the present invention includes, for example, the following steps.
(1) Dispersion production process: This is a process for producing the hexaboride particle dispersion according to the present invention by dispersing the hexaboride particles and the dispersant according to the present invention in an organic solvent.
(2) Dispersed powder manufacturing process: By removing the organic solvent from the hexaboride particle dispersion according to the present invention manufactured in the dispersion manufacturing process, the hexaboride particle dispersed powder according to the present invention (in the present invention, “ It may be described as “dispersed powder”.).
(3) Kneading step of resin: A step of producing a hexaboride particle-containing resin according to the present invention by kneading the hexaboride particle-dispersed powder according to the present invention and a predetermined resin.
(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) Dispersed powder manufacturing process", the dispersion manufactured in "(1) Dispersion manufacturing process" is subjected to "(3) Resin kneading process". The hexaboride particle dispersion and the resin can be kneaded. In this case, the organic solvent can be removed at the same time as the hexaboride particles are uniformly dispersed in the resin or the like by the kneading step. However, pay attention to the viewpoint of reliably preventing a large amount of organic solvent and bubbles from remaining in the resin and the safety aspect of preventing a large amount of organic solvent from being exposed to the high temperature of resin kneading exceeding 200 ° C. Is required.

(1) Dispersion production process, (2) Dispersion powder production process, (3) Resin kneading process, (4) Resin molding process in the method for producing a resin of boride particle-containing resin according to the present invention The process will be described.
(1) Dispersion production process In the dispersion production process, hexaboride particles and a dispersant are added to and mixed with an organic solvent to obtain an organic solvent dispersion of hexaboride particles using a general dispersion method. It is a process.
Although it does not specifically limit as a dispersion method, For example, dispersion methods, such as a bead mill, a ball mill, a sand mill, ultrasonic dispersion, a paint shaker, can be used.
As the hexaboride particles and the dispersant that can be suitably used in the dispersion manufacturing process, those described in the column of “(1) Resin layer according to the present invention” are used.

  Moreover, the kind of the organic solvent used in the dispersion manufacturing process is not particularly limited, but, for example, a solvent having a boiling point of 120 ° C. or less can be preferably used. This is because if the boiling point is 120 ° C. or lower, the organic solvent can be easily removed in a dispersion powder manufacturing process, which is a subsequent process. The productivity of the hexaboride particle dispersed powder can be improved by the rapid removal of the organic solvent in the dispersed powder production process and the like. Furthermore, since the dispersion powder manufacturing process proceeds easily and sufficiently, it is possible to avoid the excess organic solvent remaining in the hexaboride particle dispersion powder. As a result, it is possible to more reliably avoid the occurrence of defects such as bubbles in the resin or the like in the molding process.

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

In addition, the addition amount of a dispersing agent is not specifically limited as mentioned above. For example, it is preferably added so as to be 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 with respect to 100 parts by mass of the hexaboride particles.
With respect to the method of adding the dispersant, it is not necessary to add the entire amount when the dispersion is produced in the dispersion production process. For example, considering the viscosity of the dispersion, etc., a part of the total amount of dispersant added, hexaboride particles, and an organic solvent are mixed, and after the dispersion is formed by the dispersion method described above, the remainder A dispersant may be added.

(2) Dispersed powder manufacturing process In the dispersed powder manufacturing process, an appropriate amount of a dispersant is added to the dispersion obtained by dispersing hexaboride particles and a dispersant in an organic solvent, and then the organic solvent is removed. To produce hexaboride particle dispersion powder.
The method for removing the organic solvent from the dispersion 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-dispersed powder and the organic solvent component can be separated by drying under reduced pressure while stirring a dispersion obtained by dispersing hexaboride particles and a dispersant in an organic solvent. As an apparatus used for drying under reduced pressure, for example, a vacuum agitation type dryer may be mentioned. Moreover, the specific pressure of the reduced pressure when the organic solvent is removed is not limited and can be appropriately selected.

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

(3) Resin Kneading Step In the kneading step, the hexaboride particle-dispersed powder obtained in the dispersed powder production step and the resin are kneaded to obtain a hexaboride particle-containing resin.
In the kneading step, UV absorbers added to the resin layer as needed, HALS, antioxidants, other additives such as infrared absorbing organic compounds are added, and kneaded together, containing hexaboride particles A resin can also be obtained. In addition, the timing which adds these additives etc. is not specifically limited, For example, it can also add in other processes, such as a dispersion manufacturing process. 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 according to the size and shape such as the thickness of the resin layer to be produced, the viscosity of the kneaded material, and the like. For example, a molding method such as an extrusion molding method or a calendar molding method can be employed.
Moreover, the shape of a molded object is not specifically limited, It can select according to the shape requested | required, For example, it can shape | mold in a sheet form, board shape, and a film form. When the molded body is a spectacle lens, for example, it can be processed into a desired lens shape, and a multilayer lens bonded to other lens elements can be manufactured by a known method.

[3] Product using hexaboride particle-containing resin The usage form of the resin or the like 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 protective surface for welding and a light-shielding protective device for protecting from harmful rays, protective glasses for laser for protecting from laser light, and glasses such as general sunglasses. Here, the protective glasses for laser, general sunglasses, and the like include those with and without eyesight correction.
Here, the above-described protective equipment, glasses, and the like can be formed by molding the resin of the hexaboride particle-containing resin according to the present invention. In addition, a protective film, glasses, and the like described above can be provided by providing a film or resin film obtained by molding a resin or the like of the hexaboride particle-containing resin according to the present invention on a transparent substrate.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
About the evaluation method of the sample in an Example and a comparative example, it demonstrates in order of (1) number average particle diameter, (2) visible light transmittance | permeability, and optical density.

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

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

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 resin and the like of the hexaboride particle-containing resin according to the present invention and the multilayer film are as follows from the transmittance at a wavelength of 800 to 1300 nm measured using a spectrophotometer similarly to the visible light transmittance. Based on the formula of

Here, OD (λ) is the optical density at wavelength λ, and T (λ) is the transmittance (0 to 100%) at wavelength λ.
It should be noted that due to the limitations of the measuring apparatus, it is difficult to specifically measure an optical density greater than 8.0 by this method. Therefore, in the present invention, when the resin or the like and the multilayer film are calculated to have an optical density exceeding 8.0, they are simply described as “greater than 8.0” or “> 8.0”.

[Example 1]
6 parts by mass of LaB ₆ particles (sometimes referred to as “particle a” in the present invention) as hexaboride particles, a dispersant having an amine group as a functional group and an acrylic main chain (amine value 48 mgKOH / g, decomposition temperature 250 ° C.) (may be described as “dispersant a” in the present invention) 5 parts by mass, and methyl isobutyl ketone (boiling point 116.2 ° C.) as an organic solvent 85 parts by mass. Weighed out. These raw materials are loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, pulverized and dispersed for 14 hours, and a dispersion of particles a (sometimes referred to as “particle dispersion a” in the present invention). Got.
Here, when the number average particle diameter of the particles a in the particle dispersion a was measured by the above-described method, it was 22 nm. In addition, since the operation which changes the number average particle diameter of particle | grains a, such as a grinding | pulverization process, is not performed in subsequent processes, the particle | grains in resin etc. of the hexaboride particle | grain containing resin which concerns on Example 1 with the said number average particle diameter. It was set as the number average particle diameter of a.

  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 [hexaboride] / [dispersant] = 100/300, Mixed to obtain a mixed solution. The mass of the dispersant in the above formula represents the sum of the amount added in the step of producing the particle dispersion a, that is, the amount added after the production of the particle dispersion a.

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

Acrypet VH000 (manufactured by Mitsubishi Rayon Co., Ltd .; may be described as “acrylic resin A” in the present invention) and the dispersed powder a were weighed and mixed thoroughly. The mixing ratio was adjusted so that the content per projected area of the hexaboride fine particles in the final acrylic resin layer sheet became a value described later.
The mixture of the obtained acrylic resin pellets and the dispersed powder a is fed to a twin-screw extruder set at 260 ° C., kneaded, and then extruded from a T-die and a 2.0 mm thick sheet by a calender roll method. Formed into a shape. This obtained the resin layer concerning Example 1 (it may describe as "resin layer A" in this invention). In addition, content of the hexaboride particle | grains per unit area in the projection area of the produced resin layer A is 0.57 g / m < ² >.
The above production conditions are shown in Table 1.

It was 28% when the visible light transmittance | permeability of the resin layer A was measured by the above-mentioned method. Further, when 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, the optical density with respect to light having a wavelength of 805 nm (in the present invention, simply “805 nm”). May be described as the same description at other wavelengths.) Is 2.3, the optical density at 870 nm is 2.6, 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. Accordingly, 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 a maximum value in the profile) was 3.0.
The above measurement results are shown in Table 2.

[Examples 2 to 6]
Resin layers (Examples) according to Examples 2 to 6 were the same as Example 1 except that the amount of dispersion powder a mixed with acrylic resin A was changed when the acrylic resin A and the dispersion powder a were weighed and mixed. In the invention, “resin layer B”, “resin layer C”, “resin layer D”, “resin layer E”, and “resin layer F” may be described respectively). The contents of hexaboride particles per unit area in the projected areas of the produced resin layers B to E are as shown in Table 1, respectively.
The visible light transmittance and optical density in the near-infrared region of the produced 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 the acrylic resin A and the dispersed powder a are weighed and mixed, the mixing amount of the dispersed powder a with respect to the acrylic resin A is changed, and the ultraviolet absorber and the antioxidant are weighed and added in predetermined amounts. In the same manner as in Example 1, resin layers according to Example 7 (in the present invention, each may be described as “resin layer G”) were produced.
Here, Tinuvin 326 (manufactured by BASF, a benzotriazole compound. In the present invention, sometimes referred to as “ultraviolet absorber A”) was used as the ultraviolet absorber. As an antioxidant, Irganox 1010 (manufactured by BASF, CAS No. 6683-19-8, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] In the present invention, each may be referred to as “antioxidant A”). The content of hexaboride particles per unit area in the projected area of the produced resin layer, and the concentrations of the ultraviolet absorber and the antioxidant 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]
Dispersing agent having 10 parts by mass of particle a and a carboxyl group as a functional group and an acrylic main chain (acid value 3.5 mgKOH / g, decomposition temperature 290 ° C.) (in the present invention, “dispersing agent b” is described) 10 parts by weight, and toluene (boiling point 110.6 ° C.) as an organic solvent was weighed to 80 parts by weight. These raw materials are loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, pulverized and dispersed for 18 hours, and a dispersion of particles a (in the present invention, sometimes referred to as “particle dispersion b”). )
Here, when the number average particle diameter of the hexaboride particles in the particle dispersion b was measured by the above-mentioned method, it was 26 nm. In addition, in the subsequent steps, since the operation of changing the number average particle size of the hexaboride particles such as pulverization is not performed, the number average particle size is the number average particle size of the hexaboride particles in the resin layer. Become.

  After adding the dispersant b to the particle dispersion b so that the mass ratio of the dispersant to the hexaboride in the dispersion is [hexaboride] / [dispersant] = 100/300, Mixing was performed to obtain a mixed solution. In addition, the mass of the dispersant b in the above formula is the amount of the dispersant b added in the step of manufacturing the particle dispersion b, that is, the amount of the dispersant b added after manufacturing the particle dispersion b. Indicates the sum of

Subsequently, the obtained mixed liquid was loaded into a stirring type vacuum dryer.
Then, the mixture was dried under reduced pressure at room temperature with a stirring type vacuum dryer to remove toluene from the mixed solution 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 dispersion 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 polycarbonate resin, and dispersed powder b were weighed and mixed thoroughly. The mixing ratio was adjusted so that the content per projected area of the hexaboride fine particles in the final polycarbonate resin layer sheet became a value described later.
The mixture of the obtained polycarbonate resin pellets and the dispersion powder b was supplied to a twin-screw extruder set at 290 ° C., kneaded, and then extruded from a T die and a sheet 2.0 mm thick by a calender roll method. Formed into a shape. This obtained the resin layer concerning Example 8 (in this invention, it may describe as "the resin layer H"). In addition, 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 hexaboride particles, CeB ₆ particles (hereinafter referred to as particle b) were weighed so as to be 10 parts by mass, dispersant a was 5 parts by mass, and methyl isobutyl ketone as an organic solvent was 85 parts by mass. These raw materials are loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, pulverized and dispersed for 14 hours, and a dispersion of particles b (in the present invention, sometimes referred to as “particle dispersion c”). )
Here, when the number average particle diameter of the hexaboride particles in the particle dispersion c was measured by the above-mentioned method, it was 24 nm. In addition, in the subsequent steps, since the operation of changing the number average particle size of the hexaboride particles such as pulverization is not performed, the number average particle size is the number average particle size of the hexaboride particles in the resin layer. Become.

  After adding the dispersant a to the particle dispersion c, the mass ratio of the dispersant to the hexaboride in the dispersion is [hexaboride] / [dispersant] = 100/300. Mixed. In addition, the mass of the dispersant in the above formula is the amount of the dispersant a added in the step of manufacturing the particle dispersion c, that is, the amount of the dispersant a added after the particle dispersion c is manufactured. Shows the sum.

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

The resulting mixture of acrylic resin pellets and dispersed powder c was fed to a twin-screw extruder set at 260 ° C., kneaded, and then extruded from a T-die by a calender roll method to form a 2.0 mm thick sheet. Molded into. This obtained the resin layer concerning Example 9 (it may describe as "resin layer I" in this invention.). In addition, 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. The acrylic resin B was mixed at a ratio of 100 parts by weight with respect to 200 parts by mass of the particle dispersion a, and sufficiently mixed to prepare a mixed solution.

  The prepared coating solution was coated on a Teijin Tetron film HPE-50 (manufactured by Teijin DuPont Films), which is a polyethylene terephthalate (PET) film, with a bar coater to form a coating film. At this time, the film thickness of the coating layer was adjusted such that the content of the hexaboride fine particles in the final multilayer film per projection area became a value described later.

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 (acrylic resin coating layer) containing hexaboride particles. By such an operation, a multilayer film (in the present invention, “multilayer” comprising a resin layer containing hexaboride particles (may be referred to as “resin layer J” in the present invention) and a PET film base layer. May be described as “film J”). In addition, content of the hexaboride particle | grains per unit area in the projection area of the produced resin layer J is 1.39 g / m < ² >. And since the base 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 of the multilayer film J 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 1]
After feeding only the acrylic resin A pellets to a twin screw extruder set at 260 ° C. and kneading, the pellets were extruded from a T die and formed into a 2.0 mm thick sheet by the calender roll method. Thus, a resin layer according to Comparative Example 1 (in the present invention, sometimes referred to as “resin layer α”) 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]
Resin layer according to Comparative Example 2 (in the present invention), except that the amount of the dispersion powder a relative to the acrylic resin A was changed when the acrylic resin A and the dispersion powder a were weighed and mixed. , Sometimes referred to as “resin layer β”). In addition, 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 1-10 and Comparative Examples 1-2)
According to the results of the 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 optical density (OD) profile in the near-infrared region, the minimum value is 2.0 or more, and the maximum value (observed as a maximum value in the profile) exceeds 8.0. The value of was realized.
Accordingly, it has been found that the resin layers A to J and the multilayer film J exhibit excellent optical characteristics that can greatly reduce the influence of powerful near infrared light such as laser on the eyes.

  Since the resin layers A to J use a general acrylic resin as a medium, the resin layers A to J can be processed into glasses or windows by performing an appropriate known molding process. And the laser protection instrument which has the said window can be produced by a well-known method. On the other hand, the multilayer film J can be imparted with a laser protection function while maintaining the visible transparency of the transparent base material by being attached to an arbitrary transparent base material by a known method.

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

Claims (23)

The hexaboride particles are a hexaboride particle-containing resin dispersed in a resin,
A hexaboride particle-containing resin having an optical density (OD) value of 2.0 or more in a near infrared region having a wavelength of 800 nm to 1150 nm. The hexaboride particles are a hexaboride particle-containing resin dispersed in a resin,
The hexaboride particle-containing resin, wherein 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 hexaboride particle-containing resin according to claim 1 or 2, wherein the number average particle diameter of the hexaboride particles in the resin is 40 nm or less. The hexaboride particles are represented by the general formula XB ₆ (X is 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 claims 1 to 3, wherein the hexaboride particle is a particle of hexaboride expressed by at least one selected element.   The hexaboride particle-containing resin according to any one of claims 1 to 4, wherein the hexaboride particles are lanthanum hexaboride particles.   The hexaboride particle-containing resin according to any one of claims 1 to 5, wherein the resin layer contains at least one selected from an acrylic resin, a polycarbonate resin, and a vinyl chloride resin.   The hexaboride particle-containing resin according to claim 1, further comprising an ultraviolet absorber.   The hexaboride particle-containing resin according to any one of claims 1 to 7, further comprising an antioxidant.   Furthermore, 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 hexaboride particle-containing resin according to claim 1, further comprising a dispersant having a functional group.   The hexaboride particle-containing resin according to any one of claims 1 to 9, wherein the visible light transmittance calculated by JIS R 3106: 1998 is 2% or more.   A near-infrared shielding lens comprising the resin layer of the hexaboride particle-containing resin according to claim 1.   11. Near-infrared shielding glasses comprising the resin layer of the hexaboride particle-containing resin according to claim 1 or the near-infrared shielding lens according to claim 10.   A protective device comprising the resin layer of the hexaboride particle-containing resin according to claim 1 or the near-infrared shielding lens according to claim 10.   A near-infrared shielding window material comprising the resin layer of the hexaboride particle-containing resin according to claim 1.   A near-infrared shielding instrument comprising the near-infrared shielding window material according to claim 14.   A near-infrared shielding film, wherein the resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 10 is provided on a film substrate.   A near-infrared shielding glass, wherein the resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 10 is provided on a glass substrate. A hexaboride particle dispersion used for producing a resin layer of the hexaboride particle-containing resin according to any one of claims 1 to 10,
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 an organic solvent,
The hexaboride particle dispersion liquid, wherein the number average particle diameter of the hexaboride particles is 40 nm or less. The hexaboride particles are represented by the general formula XB ₆ (X is 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 18, wherein the hexaboride particle dispersion is represented by at least one selected element.   Furthermore, one or more groups selected from an amine-containing group, hydroxyl group, carboxyl group, carboxylic acid ester, phosphoric acid group, phosphoric acid ester, sulfonic acid group, sulfonic acid ester, thiol group, or epoxy group The hexaboride particle dispersion according to claim 18 or 19, further comprising a dispersant having a functional group.   21. A hexaboride particle-dispersed powder obtained by removing the organic solvent from the hexaboride particle dispersion according to claim 18.   The hexaboride particle-dispersed powder according to claim 21, wherein the number average particle diameter of the hexaboride particles is 40 nm or less.   Furthermore, 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 hexaboride particle-dispersed powder according to claim 21 or 22, further comprising a dispersant having a functional group.