JP6158905B2 - Light emitting device or phosphor-containing sheet for light emitting device - Google Patents

Description

  The present invention relates to phosphor-containing particles, a light-emitting device using the same, and a phosphor-containing sheet.

  Semiconductor nanoparticle phosphors (also called quantum dots) are of commercial interest due to their size-tunable electronic properties due to quantum size effects. The variable size electronic properties can be used in a variety of applications such as biomarkers, solar power generation, catalysis, bioimaging, LEDs, general spatial illumination, and electroluminescent displays.

  For example, in Japanese translations of PCT publication No. 2013-505347 (Patent Document 1), each primary particle is composed of a primary matrix material and includes a group of semiconductor nanoparticles, and each primary particle is a surface coating material. A plurality of coated primary particles are disclosed, wherein the layers are provided separately, the primary particles are provided in the form of microbeads, and the surface coating material comprises a polymeric material. By producing a plurality of primary particles coated in this way, the reactivity with respect to the surrounding environment and the processing steps after the production of the primary particles can be reduced.

  However, in the prior art disclosed in Patent Document 1, a resin such as epoxy, silicone, (meth) acrylate, silica, or the like is used as the primary matrix material. When semiconductor nanoparticle phosphors are blended directly into an encapsulant such as silicone or acrylate, the nanoparticles will aggregate and degrade optical properties, and oxygen will migrate to the surface of the nanoparticle through the encapsulant after encapsulation. As a result, photo-oxidation occurs, resulting in a decrease in quantum yield.

  In Patent Document 1, in order to solve such a problem, a plurality of semiconductor nanoparticles are held in advance in a matrix material such as a polymer or glass, and primary particles coated on the surface thereof are prepared. A method of embedding in a host LED material such as acrylate has been proposed (see FIG. 8 of Patent Document 1). However, in this method, since the matrix material of the primary particles is the same as that of the host LED material, there still remains a problem that the nanoparticles are agglomerated at the time of producing the primary particles and the optical properties are lowered.

Special table 2013-505347 gazette

  The present invention has been made to solve the above-described problems, and the object of the present invention is to use phosphor-containing particles that can be produced while preventing deterioration due to aggregation of semiconductor nanoparticle phosphors, and using the same A light-emitting device and a phosphor-containing sheet are provided.

  In the technique described in Patent Document 1, the present inventors use epoxy, silicone, resin such as (meth) acrylate, silica, and the like as a light-transmitting medium. In view of the deterioration of the semiconductor nanoparticle phosphor when incorporated, the translucent medium for dispersing the semiconductor nanoparticle phosphor includes a structural unit derived from an ionic liquid having a polymerizable functional group By using the resin, it was found that the semiconductor nanoparticle phosphor was not deteriorated at the time of particle production, and it was possible to show excellent stability against photooxidation thereafter, and the present invention was completed. That is, the present invention is as follows.

  The phosphor-containing particles of the present invention include a semiconductor nanoparticle phosphor and a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group, and the semiconductor nanoparticle phosphor is dispersed in the resin. It is characterized by that.

  The phosphor-containing particles of the present invention preferably have a particle diameter in the range of 100 nm to 30 μm.

  The phosphor-containing particles of the present invention may include one kind of semiconductor nanoparticle phosphor, and include a semiconductor nanoparticle phosphor that emits red fluorescence and a semiconductor nanoparticle phosphor that emits green fluorescence. May be.

  In the phosphor-containing particles of the present invention, the resin is preferably cross-linked.

  It is preferable that the phosphor-containing particles of the present invention have a translucent coating layer on the outermost surface. In this case, the material forming the coating layer is more preferably an inorganic material having a band gap of 3.0 eV or more.

  The present invention also provides a light-emitting device including a light source and a wavelength conversion unit in which the phosphor-containing particles of the present invention described above are dispersed in a light-transmitting medium.

  In the light emitting device of the present invention, phosphor-containing particles in which a semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group, and green fluorescence The emitted semiconductor nanoparticle phosphor may contain phosphor-containing particles dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group.

  In the light emitting device of the present invention, in addition to the phosphor-containing particles, a phosphor other than the semiconductor nanoparticle phosphor may be further dispersed in the medium.

  The present invention also provides a phosphor-containing sheet in which the phosphor-containing particles of the present invention described above are dispersed in a sheet-like medium having translucency.

  In the phosphor-containing sheet of the present invention, phosphor-containing particles in which a semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group; The semiconductor nanoparticle phosphor that emits fluorescence may include phosphor-containing particles dispersed in a resin including a structural unit derived from an ionic liquid having a polymerizable functional group.

  In the phosphor-containing sheet of the present invention, a phosphor other than the semiconductor nanoparticle phosphor may be further dispersed in the medium.

  According to the present invention, a semiconductor nanoparticle phosphor is produced by making particles (phosphor-containing particles) dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. The aggregation of the semiconductor nanoparticle phosphor at the time can be prevented, high optical characteristics can be maintained, and deterioration of the semiconductor nanoparticle phosphor due to moisture and oxygen can be reduced after the particles are produced. Thereby, it is possible to provide phosphor-containing particles having high luminous efficiency, excellent chemical stability, and excellent handleability. In addition, the phosphor-containing particles obtained in this way are used in the same form as phosphors currently used commercially by making them to the same size as phosphors currently used. It is possible to provide a light emitting device, a phosphor-containing sheet, and the like using the same.

It is a figure which shows typically the fluorescent substance containing particle 1 of the 1st embodiment of this invention. It is a figure which shows typically the fluorescent substance containing particle | grains 11 of the 2nd embodiment of this invention. It is a figure which shows typically the fluorescent substance containing particle | grains 21 of the 3rd embodiment of this invention. It is a figure which shows typically the fluorescent substance containing particle 31 of the 4th embodiment of this invention. It is a figure which shows typically the light-emitting device 41 of the 5th embodiment of this invention. It is a figure which shows typically the light-emitting device 51 of the 6th embodiment of this invention. It is a figure which shows typically the light-emitting device 61 of the 7th embodiment of this invention. It is a figure which shows typically the fluorescent substance containing sheet | seat 71 of the 8th embodiment of this invention. It is a figure which shows typically the fluorescent substance containing sheet | seat 81 of the 9th embodiment of this invention. It is a figure which shows typically the fluorescent substance containing sheet | seat 91 of the 10th embodiment of this invention.

<Phosphor-containing particles>
(Fluorescent substance-containing particles of the first embodiment)
FIG. 1 is a diagram schematically showing phosphor-containing particles (microbeads) 1 according to the first embodiment of the present invention. The phosphor-containing particle 1 of the present invention includes a semiconductor nanoparticle phosphor 2 and a resin 3 containing a structural unit derived from an ionic liquid having a polymerizable functional group, and the semiconductor nanoparticle phosphor 2 is the resin. 3 is dispersed.

The “ionic liquid” used in the present invention is a salt in a molten state (room temperature molten salt) even at room temperature (for example, 25 ° C.), and has the following general formula (I)
X ⁺ Y ⁻ (I)
Is preferred.

In the general formula (I), X ⁺ is a cation selected from an imidazolium ion, a pyridinium ion, a phosphonium ion, an aliphatic quaternary ammonium ion, pyrrolidinium, and sulfonium. Among these, aliphatic quaternary ammonium ions are particularly preferable cations because they are excellent in stability to air and moisture in the atmosphere.

In the general formula (I), Y ⁻ represents tetrafluoroborate ion, hexafluorophosphate ion, bistrifluoromethylsulfonylimido ion, perchlorate ion, tris (trifluoromethylsulfonyl) carbonate ion, trifluoro. An anion selected from lomethanesulfonate ion, trifluoroacetate ion, carboxylate ion, and halogen ion. Among these, bistrifluoromethylsulfonylimido ion is mentioned as a particularly preferable anion because it has excellent stability to air and moisture in the atmosphere.

  The ionic liquid used in the phosphor-containing particles 1 of the present invention has a polymerizable functional group. By using an ionic liquid having a polymerizable functional group, the ionic liquid that functions as a dispersion liquid of the semiconductor nanoparticle phosphor can be polymerized as it is with the polymerizable functional group. Thus, in a state where the semiconductor nanoparticle phosphor is dispersed, an ionic liquid having a polymerizable functional group is polymerized to form a resin including a structural unit derived from the ionic liquid having a polymerizable functional group. Thus, aggregation or the like that has occurred when the resin in which the semiconductor nanoparticle phosphor is dispersed is solidified can be suppressed. Further, as described above, the semiconductor nanoparticle phosphor is electrostatically dispersed by dispersing it in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. The surface of the semiconductor nanoparticle phosphor can be protected from air and moisture, and a light emitting device with high luminous efficiency can be realized. .

  The polymerizable functional group possessed by the ionic liquid is not particularly limited, but it can be polymerized by heating or catalytic reaction, so that the semiconductor nanoparticle phosphor is dispersed as it is from the liquid state in which it is stably dispersed. Since it can be solidified while maintaining the state, a (meth) acrylic acid ester group ((meth) acryloyloxy group) is preferable.

  As a suitable example of the ionic liquid having such a (meth) acrylic acid ester group, for example, the following formula can be used because of its excellent stability to air and moisture in the atmosphere.

2- (methacryloyloxy) -ethyltrimethylammonium bis (trifluoromethanesulfonyl) imide represented by the following formula

In indicated by 1- (3-acryloyloxy-propyl) - 3-methylimidazolium Liu Mubi scan (trifluoromethanesulfonyl) imide and the like.

  The ionic liquid having a polymerizable functional group as described above can be obtained by introducing a polymerizable functional group into a conventionally known appropriate ionic liquid by a conventionally known appropriate technique. Of course, it may be used.

In addition, the temperature, time, and other conditions for polymerizing the ionic liquid having a polymerizable functional group in a state where the semiconductor nanoparticle phosphor is dispersed are the type and amount of the ionic liquid having the polymerizable functional group to be used. Suitable conditions are appropriately selected depending on the above, and are not particularly limited. For example, when 2- (methacryloyloxy) -ethyltrimethylammonium bis (trifluoromethanesulfonyl) imide is used as the ionic liquid having a polymerizable functional group, for example, at a temperature of 60 to 100 ° C. for 1 to 10 hours. Polymerization can be suitably performed. Further, for example polymerizable functional group ionic liquids as 1 having a (3-acryloyloxy - propyl) -3 in the case of using a methylimidazo Liu Mubi scan (trifluoromethanesulfonyl) imide, for example at a temperature of 60 to 150 ° C. It can superpose | polymerize suitably on the conditions of 1 to 10 hours.

In the case of using the catalyst in the polymerization, the catalyst is not particularly limited, conventionally known for example azobisisobutyronitrile, dimethyl 2,2'-azobis (2-methylpropionate) the like to be used be able to. Among these, azobisisobutyronitrile is preferably used as a catalyst because the polymerization proceeds rapidly.

  The semiconductor nanoparticle phosphor 2 in the phosphor-containing particle 1 of the present invention is a single phosphor particle that does not scatter visible light, and any conventionally known appropriate semiconductor nanoparticle phosphor can be used without particular limitation. . By using the semiconductor nanoparticle phosphor, there is an advantage that the emission wavelength can be precisely controlled by controlling the particle diameter and composition.

  The raw material of the semiconductor nanoparticle phosphor is not particularly limited, and CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InN, InP, InAs, InSb, AlP, conventionally used as the semiconductor nanoparticle phosphor. It may be at least one selected from AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, Ge, MgS, MgSe, and MgTe. In addition, semiconductor nanoparticle phosphors are known to those skilled in the art two-component core, three-component core, four-component core, core-shell or core multi-shell, doped semiconductor nanoparticle phosphor or tilted It may be a semiconductor nanoparticle phosphor. FIG. 1 shows a case where one kind of semiconductor nanoparticle phosphor is dispersed in a resin containing a plurality of structural units derived from an ionic liquid having a polymerizable functional group.

  The shape of the semiconductor nanoparticle phosphor is not particularly limited, but a semiconductor nanoparticle phosphor having a conventionally known appropriate shape such as a spherical shape, a rod shape, or a wire shape can be used without any particular limitation. In particular, from the viewpoint of easy control of light emission characteristics by shape control, it is preferable to use a spherical semiconductor nanoparticle phosphor.

  The particle diameter of the semiconductor nanoparticle phosphor can be appropriately selected according to the raw material and the desired emission wavelength, and is not particularly limited, but is preferably in the range of 1 to 20 nm, and in the range of 2 to 5 nm. More preferably. This is because when the particle diameter of the semiconductor nanoparticle phosphor is less than 1 nm, the ratio of the surface area to the volume increases, so that surface defects tend to be dominant and the effect tends to decrease. This is because when the particle diameter of the body exceeds 20 nm, the dispersed state tends to decrease and aggregation / sedimentation tends to occur. Here, when the shape of the semiconductor nanoparticle phosphor is spherical, the particle diameter refers to, for example, an average particle diameter measured by a particle size distribution measuring apparatus or a particle size observed by an electron microscope. When the semiconductor nanoparticle phosphor is rod-shaped, the particle diameter refers to the size of the short axis and the long axis measured by, for example, an electron microscope. Furthermore, when the shape of the semiconductor nanoparticle phosphor is a wire shape, the particle diameter refers to the size of the short axis and the long axis measured by, for example, an electron microscope.

  The content of the semiconductor nanoparticle phosphor (the total amount when two or more semiconductor nanoparticle phosphors are used as described later) is not particularly limited, but is 0 with respect to 100 weight of the ionic liquid having a polymerizable functional group. It is preferably in the range of 0.001 to 50 parts by weight, and more preferably in the range of 0.01 to 20 parts by weight. When the content of the semiconductor nanoparticle phosphor is less than 0.001 part by weight with respect to 100 parts by weight of the ionic liquid having a polymerizable functional group, the light emission from the semiconductor nanoparticle phosphor tends to be too weak. In addition, when the content of the semiconductor nanoparticle phosphor exceeds 50 parts by weight with respect to 100 parts by weight of the ionic liquid having a polymerizable functional group, in the ionic liquid having a polymerizable functional group. This is because it tends to be difficult to uniformly disperse.

  There is no particular limitation on the method of forming a particle in which a semiconductor nanoparticle phosphor is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group (polymer matrix). It can manufacture suitably by grind | pulverizing physically and making it a desired size.

  In the phosphor-containing particles of the present invention, ions constituting the ionic liquid are coordinated on the surface of the semiconductor nanoparticle phosphor, thereby stabilizing the nanoparticles and thereby imparting high luminous efficiency. In addition, the semiconductor nanoparticle phosphor is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group having a low oxygen and moisture permeability, thereby producing a semiconductor for producing particles. Aggregation of the nanoparticle phosphor can be prevented, high optical characteristics can be maintained, and deterioration of the semiconductor nanoparticle phosphor due to moisture and oxygen can be reduced after the particles are produced. Accordingly, when the semiconductor nanoparticle phosphor is excited to emit light, photooxidation hardly occurs, and thus has excellent chemical stability.

  The shape of the phosphor-containing particles of the present invention may be a conventionally known appropriate shape such as a spherical shape, a rod shape, or a wire shape. However, from the viewpoint of easy control of light emission characteristics by shape control, A true spherical shape is preferred.

  The particle diameter of the phosphor-containing particles of the present invention is not particularly limited, but is preferably in the range of 100 nm to 30 μm, and more preferably in the range of 1 μm to 20 μm. This is because when the particle size of the phosphor-containing particles is less than 100 nm, the surface area / volume ratio per one phosphor-containing particle is increased, and thus the loss due to scattering of excitation light tends to increase. This is because when the particle diameter of the phosphor-containing particles exceeds 30 μm, it tends to be difficult to disperse the phosphor-containing particles in a light-transmitting medium by the same process as that of the conventional phosphor. Since the particle diameter of the phosphor-containing particles is within the above-mentioned range, the handling property (handling property) is good, and it is currently used commercially by making it to the same size as the phosphor currently used. The present invention can be used in the same form as the existing phosphor without changing it, and a light-emitting device, a phosphor-containing sheet, and the like using this can be provided. The particle diameter of the phosphor-containing particles refers to the size of particles observed with an optical microscope or a scanning microscope (SEM) or a value measured with a particle size distribution measuring device.

(Fluorescent substance-containing particles of the second embodiment)
FIG. 2 is a diagram schematically showing phosphor-containing particles (microbeads) 11 according to the second embodiment of the present invention. In FIG. 2, parts having the same configuration as the phosphor-containing particles 1 of the first embodiment shown in FIG.

  In the phosphor-containing particle 11 of the second embodiment shown in FIG. 2, the semiconductor nanoparticle phosphor includes a semiconductor nanoparticle phosphor 12 that emits red fluorescence and a semiconductor nanoparticle phosphor 13 that emits green fluorescence. Including. In the phosphor-containing particle 1 of the first embodiment shown in FIG. 1, the semiconductor nanoparticle phosphor 2 has only one type and has a single fluorescence wavelength, whereas the first embodiment shown in FIG. The phosphor-containing particles 11 of the second embodiment each include a plurality of semiconductor nanoparticle phosphors having two different fluorescence wavelengths. When such a phosphor-containing particle is used to produce a light-emitting device in combination with a light-emitting element as will be described later, individual differences among the light-emitting devices can be reduced. Moreover, the phosphor containing particle which can improve the uniformity of luminescent color over the whole area | region can be obtained. FIG. 2 shows a case where a plurality of semiconductor nanoparticle phosphors, ie, a semiconductor nanoparticle phosphor that emits red fluorescence and a semiconductor nanoparticle phosphor that emits green fluorescence, are used. Three or more types of semiconductor nanoparticle phosphors including the above-mentioned types of semiconductor nanoparticle phosphors may be included.

  The content of the semiconductor nanoparticle phosphor (the total amount when two or more semiconductor nanoparticle phosphors are used as described later) is not particularly limited, but is 0 with respect to 100 weight of the ionic liquid having a polymerizable functional group. It is preferably in the range of 0.001 to 50 parts by weight, and more preferably in the range of 0.01 to 20 parts by weight. When the content of the semiconductor nanoparticle phosphor is less than 0.001 part by weight with respect to 100 parts by weight of the ionic liquid having a polymerizable functional group, the light emission from the semiconductor nanoparticle phosphor tends to be too weak. In addition, when the content of the semiconductor nanoparticle phosphor exceeds 50 parts by weight with respect to 100 parts by weight of the ionic liquid having a polymerizable functional group, in the ionic liquid having a polymerizable functional group. This is because it tends to be difficult to uniformly disperse.

  In addition, in the phosphor-containing particles 11 of the second embodiment shown in FIG. 2, the mixing ratio of the semiconductor nanoparticle phosphor emitting red fluorescence and the semiconductor nanoparticle phosphor emitting green fluorescence is particularly limited. Although not intended, the semiconductor nanoparticle phosphor emitting green fluorescence is preferably in the range of 10 to 1000 when the semiconductor nanoparticle phosphor emitting red fluorescence is 100 by weight ratio, and 20 More preferably, it is in the range of ˜500. When the number of semiconductor nanoparticle phosphors emitting green fluorescence is less than 10 when the number of semiconductor nanoparticle phosphors emitting red fluorescence is 100, there is a large deviation from white due to the difference in emission intensity between red and green. If the semiconductor nanoparticle phosphor emitting green fluorescence is more than 1000 when the semiconductor nanoparticle phosphor emitting red fluorescence is 100, This is because there is a tendency that the emission color deviates greatly from white due to the difference in emission intensity between red and green, and the emission color is biased to green.

(Phosphor-containing particles of the third embodiment)
FIG. 3 is a diagram schematically showing phosphor-containing particles (microbeads) 21 according to the third embodiment of the present invention. In FIG. 3, parts having the same configuration as the phosphor-containing particles 1 of the first embodiment shown in FIG. The phosphor-containing particle 21 of the third embodiment shown in FIG. 3 is different from the phosphor-containing particle 1 of the first embodiment shown in FIG. 1 in that the resin 22 is crosslinked (FIG. 1). The resin in the phosphor-containing particles 1 of the first embodiment shown in FIG. That is, the resin in the phosphor-containing particles of the third embodiment shown in FIG. 3 is derived from an ionic liquid having a polymerizable functional group to which a crosslinkable material is added. By using the resin 22 derived from an ionic liquid having a polymerizable functional group, to which a crosslinkable material is added in this way, when the ionic liquid having a polymerizable functional group is polymerized, it is more solid. This has the advantage that the stability of the wavelength converter is improved. In addition, it can confirm that the resin 22 is bridge | crosslinked by the measurement by X-ray photoelectron spectroscopy (XPS).

  The crosslinkable material may be any appropriate conventionally known crosslinking agent, and is not particularly limited. Examples thereof include diethylene glycol dimethacrylate and 1,1,1-trimethylolpropane triacrylate. Among them, it is preferable to use 1,1,1-trimethylolpropane triacrylate as a crosslinkable material because it has a large number of cross-linking sites and polymerizes strongly.

  When the crosslinkable material is added, the addition amount is not particularly limited, but is preferably in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the ionic liquid having a polymerizable functional group, and 1 to 30 parts by weight. More preferably within the range of parts. When the addition amount of the crosslinkable material is less than 1 part by weight based on 100 parts by weight of the ionic liquid having a polymerizable functional group, the crosslink structure does not progress and the strength of the resin tends to be weak. This is because when the amount of the material added exceeds 50 parts by weight with respect to 100 parts by weight of the ionic liquid having a polymerizable functional group, the semiconductor nanoparticle phosphor tends to be not stably dispersed.

  FIG. 3 shows a case where a plurality of one kind of semiconductor nanoparticle phosphors are used as in FIG. 1, but instead of this, semiconductor nanoparticles emitting red fluorescence as shown in FIG. Two or more types of phosphors and semiconductor nanoparticle phosphors emitting green fluorescence may be used, and three or more types of semiconductor nanoparticle phosphors including other types of semiconductor nanoparticle phosphors are included. Also good.

(Phosphor-containing particles of the fourth embodiment)
FIG. 4 is a diagram schematically showing phosphor-containing particles (microbeads) 31 according to the fourth embodiment of the present invention. In FIG. 4, parts having the same configuration as the phosphor-containing particles 1 of the first embodiment shown in FIG. The phosphor-containing particles 31 of the fourth embodiment shown in FIG. 4 are the same as the phosphor-containing particles 1 of the first embodiment shown in FIG. 1 in that the outermost surface includes a coating layer 32 having translucency. Different. By providing the translucent coating layer 32 on the outermost surface, it is possible to reduce the transmittance of oxygen and moisture, and as a result, it is possible to suppress deterioration due to photo-oxidation of the semiconductor nanoparticle phosphor, and thus the semiconductor nanoparticle. The chemical stability of the particle phosphor can be further improved.

The material for forming the coating layer 32 is not particularly limited as long as it is a light-transmitting material, but a light-transmitting inorganic material such as a metal oxide or a silica-based material is preferable. The covering layer 32 is preferably an inorganic material having a band gap of preferably 3.0 eV or more among any of these materials. Examples of the metal oxide inorganic material having a band gap of 3.0 eV or more and absorbing ultraviolet rays include SiO ₂ , ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ , Al ₂ O ₃ , and ZnO: Mg. Illustrated. Among these, ZnO, TiO ₂ , Al ₂ O ₃ , CeO ₂ , and SnO ₂ can absorb a wide range of ultraviolet rays (up to a range close to visible light among ultraviolet rays) because the band gap is close to 3.0 eV. . Since SiO ₂ , ZrO ₂ , and ZnO: Mg have a band gap that is considerably larger than 3.0 eV, they absorb only ultraviolet rays having a considerably short wavelength and transmit ultraviolet rays in a range close to visible light. By providing a coating layer 32 formed of an inorganic material having a band gap of 3.0 eV or more on the outermost surface, an ultraviolet ray of a resin including a structural unit derived from an ionic liquid having a semiconductor nanoparticle phosphor and a polymerizable functional group There is an advantage that deterioration due to can be suppressed, and as a result, chemical stability can be improved. In the present invention, it is more preferable if the inorganic material is an inorganic crystal.

<Light emitting device>
(Light Emitting Device of Fifth Embodiment)
FIG. 5 is a diagram schematically showing a light emitting device 41 according to a fifth embodiment of the present invention. As shown in FIG. 5, the present invention is a light emitting device (LED package) including a light source 42 and a wavelength conversion unit in which the phosphor-containing particles 1 of the present invention described above are dispersed in a translucent medium 43. 41 is also provided. As described above, the phosphor-containing particles of the present invention have good handleability (handling properties), and are manufactured in the same size as the phosphors currently used, so that The same process can be used without changing the current process. In the light-emitting device shown in FIG. 5, as the light source 42 other than the phosphor-containing particles 1, the translucent medium 43, the frame body 44, the lead wire 45, and the like, conventionally known appropriate ones can be used without particular limitation. .

  FIG. 5 shows the case where the phosphor-containing particles 1 of the first embodiment shown in FIG. 1 are used. However, the present invention is not limited to this, and the first embodiment shown in FIGS. The phosphor-containing particles 11, 21, 31 of the second to fourth embodiments may be used, or three or more kinds of semiconductor nanoparticle phosphors may be included.

  In the light emitting device of the present invention, the light source is not particularly limited, and a light emitting diode (LED), a laser diode (LD), or the like can be used.

  In the light emitting device 41 of the present invention, the light-transmitting medium for encapsulating the light source and the phosphor-containing particles is not particularly limited, and epoxy, silicone and (meth) acrylate, silica glass, silica gel, siloxane, sol-gel , Hydrogel, agarose, cellulose, epoxy, polyether, polyethylene, polyvinyl, polydiacetylene, polyphenylene vinylene, polystyrene, polypyrrole, polyimide, polyimidazole, polysulfone, polythiophene, polyphosphate, poly (meth) acrylate, polyacrylamide, polypeptide, Examples include polysaccharides. A plurality of these may be used as a light-transmitting medium.

(Light Emitting Device of Sixth Embodiment)
FIG. 6 is a diagram schematically showing a light emitting device 51 according to a sixth embodiment of the present invention. In FIG. 6, parts having the same configuration as the light emitting device 41 of the fifth embodiment shown in FIG. The light emitting device 51 of the sixth embodiment shown in FIG. 6 is a phosphor in which a semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. In that it contains contained particles 52 and phosphor-containing particles 53 dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group, the semiconductor nanoparticle phosphor emitting green fluorescence. 5 is different from the light emitting device 41 of the fifth embodiment shown in FIG.

  As described above, the phosphor-containing particles of the present invention have good handleability (handling properties), and are manufactured in the same size as the phosphors currently used, so that the phosphors currently used commercially. Can be used without changing the current process. According to the light-emitting device 51 of the sixth embodiment, a light-emitting device is manufactured by the same process as that of a conventional phosphor, and further desired by using phosphor-containing particles including semiconductor nanoparticle phosphors having different wavelengths. A light-emitting device that emits light can be manufactured. In addition, like the light emitting device 51 of the sixth embodiment, a phosphor in which a semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin including a structural unit derived from an ionic liquid having a polymerizable functional group When the contained particles 52 are used in combination with the phosphor-containing particles 53 dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group, the semiconductor nanoparticle phosphor emitting green fluorescence is used. Since a light emitting device that emits white light with high color reproducibility can be obtained, a light emitting diode (LED) that emits blue light, a laser diode (LD) that emits blue light, and the like can be preferably used.

  In the light-emitting device 51 shown in FIG. 6, phosphor-containing particles 52 in which a semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. And the mixing ratio of the phosphor-containing particles 53 dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group in which the semiconductor nanoparticle phosphor emitting green fluorescence is not particularly limited, When the phosphor-containing particles 52 are 100 in terms of weight ratio, the phosphor-containing particles 53 are preferably in the range of 10 to 1000, and more preferably in the range of 20 to 500. If the phosphor-containing particles 53 are less than 10 when the phosphor-containing particles 52 are set to 100, the phosphor-containing particles 53 tend to deviate greatly from white due to the difference in emission intensity between red and green, and the emission color tends to be red. For this reason, when the phosphor-containing particle 53 exceeds 100 when the phosphor-containing particle 52 is 100, the emission color deviates greatly from white due to the difference in emission intensity between red and green, and is biased to green. This is because it tends to become.

(Light Emitting Device of Seventh Embodiment)
FIG. 7 is a diagram schematically showing a light emitting device 61 according to a seventh embodiment of the present invention. In FIG. 7, parts having the same configuration as the light emitting device 41 of the fifth embodiment shown in FIG. In the light emitting device 61 of the seventh embodiment shown in FIG. 7, a phosphor (conventional phosphor) 62 other than the semiconductor nanoparticle phosphor is dispersed in the medium 43 in addition to the phosphor-containing particles 1 of the present invention. This is different from the light emitting device 41 of the fifth embodiment shown in FIG. Thus, in this invention, you may make it provide the light-emitting device which has a desired luminescent color combining the fluorescent substance containing particle | grains of this invention, and the conventional fluorescent substance.

As such a conventional phosphor 62, for example, α-sialon phosphor, β-sialon phosphor, JEM blue phosphor (LaAl (Si _6-z Al _z ) N _10-z O _z , γ-AlON phosphor) Rare earth activated oxynitride phosphors, oxide phosphors such as YAG: Ce phosphors, inorganic phosphors such as nitride phosphors such as CASN phosphors (CaAlSiN ₃ ), soluble azo pigments, insoluble azo pigments , Benzimidazolone pigments, β-naphthol pigments, naphthol AS pigments, condensed azo pigments and other azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments , Polycyclic pigments such as quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, dyes There are no particular restrictions on organic pigments such as ink pigments, etc. In particular, in order to achieve high chemical stability and high color rendering, an inorganic phosphor should be used as the conventional phosphor 62. Is preferred.

  In the light emitting device 61 of the seventh embodiment, the mixing ratio of the phosphor-containing particles 1 and the conventional phosphor is not particularly limited, and depends on the type of semiconductor nanoparticle phosphor and conventional phosphor used. However, when the semiconductor nanoparticle phosphor contained in the phosphor-containing particles is CdSe and the conventional phosphor is a β-sialon phosphor, when the phosphor-containing particles are 100 by weight ratio, The phosphor is preferably in the range of 10 to 1000, more preferably in the range of 20 to 500.

  FIG. 7 shows the case where the phosphor-containing particles 1 of the first embodiment shown in FIG. 1 are used. However, the present invention is not limited to this, and the first embodiment shown in FIGS. The phosphor-containing particles 11, 21, 31 of the second to fourth embodiments may be used, or three or more kinds of semiconductor nanoparticle phosphors may be included.

<Phosphor-containing sheet>
(The phosphor-containing sheet of the eighth embodiment)
FIG. 8 is a diagram schematically showing a phosphor-containing sheet 71 according to the eighth embodiment of the present invention. As shown in FIG. 8, the present invention also provides a phosphor-containing sheet 71 in which the phosphor-containing particles 1 of the present invention are dispersed in a sheet-like medium 72 having translucency. As described above, the phosphor-containing particles of the present invention have good handleability (handling properties), and are manufactured in the same size as the phosphors currently used, so that the phosphors currently used commercially. Can be used without changing the current process. Therefore, like the phosphor-containing sheet 71 of the eighth embodiment shown in FIG. 8, the phosphor-containing sheet can be manufactured by the same manufacturing process as that of the conventional phosphor. Such a phosphor-containing sheet of the present invention can be suitably used for applications such as a liquid crystal backlight and a white LED device, as in the prior art.

  Furthermore, according to the phosphor-containing sheet using the phosphor-containing particles of the present invention, due to the following reasons (1) and (2), restrictions on the material of the medium in which the phosphor-containing particles are dispersed are alleviated. There is an advantage that the degree of freedom of selection of the material is improved.

  (1) Compared to the conventional case where the semiconductor nanoparticle phosphor is resinated in an exposed state, the resin may be resinized in a state protected and contained in the phosphor-containing particles. You don't have to worry about deterioration.

  (2) Compared to the conventional case where the medium contains a semiconductor nanoparticle phosphor in an exposed state, it is used in a state protected by the phosphor-containing particles, so there is no concern about deterioration of the semiconductor nanoparticle phosphor due to use. It's okay.

  Moreover, since it is not necessary to worry about deterioration of the nanoparticle phosphor due to use as described above, there is an advantage that a portion for protecting the sheet is unnecessary and space saving is possible. That is, the sheet can be made thin by eliminating the protective portion that has been essential in the past in order to prevent moisture and oxygen, which are degradation factors of the exposed semiconductor nanoparticle phosphor. More specifically, since it is not necessary (or less) to provide an edge portion, it is possible to save space in the surface direction, and it is not necessary (or less) to provide a protective layer for protection. Space can be saved in the thickness direction.

As the translucent medium 72 used for the phosphor-containing sheet of the present invention, the same medium as the translucent medium 43 described above in the light emitting device of the present invention can be suitably used. In addition, as a method for forming a light-transmitting medium in which the phosphor-containing particles of the present invention are dispersed into a sheet shape, for example, as in the case of manufacturing a conventional phosphor-containing sheet, first, for example, a phosphor sheet As a forming coating solution, a solution in which phosphor-containing particles are dispersed in a resin (hereinafter referred to as “phosphor-containing particle-dispersed silicone resin for sheet production”) is prepared. The phosphor-containing particle-dispersed silicone resin for sheet production is obtained by mixing phosphor-containing particles and a resin. When an addition reaction type silicone resin is used, when a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom are mixed, the curing reaction may start even at room temperature. It is also possible to extend the pot life by adding a hydrosilylation reaction retarder such as a compound to the phosphor-containing particle-dispersed silicone resin for sheet production. In addition, a dispersing agent and leveling agent for stabilizing the coating film as an additive , and an adhesion aid such as a silane coupling agent as a sheet surface modifier are mixed with the phosphor-containing particle-dispersed silicone resin for sheet production. Is also possible. Moreover, it is also possible to mix alumina fine particles, silica fine particles, silicone fine particles and the like as the phosphor sedimentation inhibitor with the phosphor-containing particle-dispersed silicone resin for sheet production.

  If necessary to make fluidity appropriate, a solvent can be added to form a solution. A solvent will not be specifically limited if the viscosity of resin of a fluid state can be adjusted. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, terpineol and the like can be mentioned.

  After preparing these components to a predetermined composition, they are mixed and dispersed homogeneously in a homogenizer, a revolving stirrer, a three-roller, a ball mill, a planetary ball mill, a bead mill, etc. A phosphor-containing particle-dispersed silicone resin is obtained. Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing or dispersing.

Next, the phosphor-containing particle-dispersed silicone resin for sheet production is applied on the substrate and dried. Coating, reverse roll coater, a blade coater, a slit die coater, direct gravure coater, offset gravure coater over, key Sukota, natural roll coater, air knife coater, a roll blade coater, burrs bar roll blade coater, Two streams coater, a rod coater , Wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater and the like. The phosphor sheet of the present invention can also be produced by using a printing method such as screen printing, gravure printing, or lithographic printing. When using a printing method, screen printing is particularly preferably used.

  The sheet can be dried using a general heating device such as a hot air dryer or an infrared dryer. For heating and curing the sheet, a general heating device such as a hot air dryer or an infrared dryer is used. In this case, the heat curing conditions are usually 40 to 250 ° C. for 1 minute to 5 hours, preferably 100 ° C. to 200 ° C. for 2 minutes to 3 hours.

  FIG. 8 shows the case where the phosphor-containing particles 1 of the first embodiment shown in FIG. 1 are used. However, the present invention is not limited to this, and the first embodiment shown in FIGS. The phosphor-containing particles 11, 21, 31 of the second to fourth embodiments may be used, or three or more kinds of semiconductor nanoparticle phosphors may be included.

(The phosphor-containing sheet of the ninth embodiment)
FIG. 9 is a diagram schematically showing a phosphor-containing sheet 81 according to the ninth embodiment of the present invention. In FIG. 9, parts having the same configuration as the phosphor-containing sheet 71 of the eighth embodiment shown in FIG. The phosphor-containing sheet 81 of the ninth embodiment shown in FIG. 9 is dispersed in a resin in which a semiconductor nanoparticle phosphor that emits red fluorescence contains a structural unit derived from an ionic liquid having a polymerizable functional group. In terms of including phosphor-containing particles 52 and phosphor-containing particles 53 in which a semiconductor nanoparticle phosphor emitting green fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. , Different from the phosphor-containing sheet 71 of the eighth embodiment shown in FIG.

  As described above, the phosphor-containing particles of the present invention have good handleability (handling properties), and are manufactured in the same size as the phosphors currently used, so that the phosphors currently used commercially. Can be used without changing the current process. According to the phosphor-containing sheet 81 of the ninth embodiment, a phosphor-containing sheet is produced by the same process as that of a conventional phosphor, and further, phosphor-containing particles including semiconductor nanoparticle phosphors having different wavelengths are used. Thus, a phosphor-containing sheet exhibiting a desired emission color can be produced by combining with an appropriate light source. In addition, like the phosphor-containing sheet 81 of the ninth embodiment, the semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin including a structural unit derived from an ionic liquid having a polymerizable functional group. The phosphor-containing particles 52 are used in combination with the phosphor-containing particles 53 in which the semiconductor nanoparticle phosphor emitting green fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. In this case, since a light emitting device that emits white light with high color reproducibility can be obtained, a light emitting diode (LED) that emits blue light, a laser diode (LD) that emits blue light, or the like is preferably used in combination as a light source. it can.

  In addition, in the phosphor-containing sheet 81 shown in FIG. 9, the phosphor containing a phosphor dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group is emitted from a semiconductor nanoparticle phosphor emitting red fluorescence. The mixing ratio of the particles 52 and the phosphor-containing particles 53 dispersed in a resin containing a structural unit derived from an ionic liquid in which the semiconductor nanoparticle phosphor emitting green fluorescence has a polymerizable functional group is not particularly limited. However, when the phosphor-containing particles 52 are 100 in terms of weight ratio, the phosphor-containing particles 53 are preferably in the range of 10 to 1000, and more preferably in the range of 20 to 500. If the phosphor-containing particles 53 are less than 10 when the phosphor-containing particles 52 are set to 100, the phosphor-containing particles 53 tend to deviate greatly from white due to the difference in emission intensity between red and green, and the emission color tends to be red. For this reason, when the phosphor-containing particle 53 exceeds 100 when the phosphor-containing particle 52 is 100, the emission color deviates greatly from white due to the difference in emission intensity between red and green, and is biased to green. This is because it tends to become.

(Phosphor-containing sheet of tenth embodiment)
FIG. 10 is a diagram schematically showing a phosphor-containing sheet 91 according to the tenth embodiment of the present invention. In FIG. 10, parts having the same configuration as the phosphor-containing sheet 71 of the eighth embodiment shown in FIG. In the phosphor-containing sheet 91 of the tenth embodiment shown in FIG. 10, a phosphor (conventional phosphor) 62 other than the semiconductor nanoparticle phosphor is included in the medium 72 in addition to the phosphor-containing particles 1 of the present invention. It differs from the phosphor-containing sheet 71 of the eighth embodiment shown in FIG. 8 in that it is dispersed. As described above, the present invention provides a light-emitting device having a desired emission color by combining the phosphor-containing particles of the present invention with a conventional phosphor and further combining with an appropriate light source. Also good.

  As such a conventional phosphor 62, a phosphor similar to that described above for the light emitting device 61 of the seventh embodiment can be suitably used. Further, the mixing ratio of the phosphor-containing particles 1 and the conventional phosphor is not particularly limited, and is as described above as a suitable example.

  FIG. 10 shows the case where the phosphor-containing particles 1 of the first embodiment shown in FIG. 1 are used. However, the present invention is not limited to this, and the first embodiment shown in FIGS. The phosphor-containing particles 11, 21, 31 of the second to fourth embodiments may be used, or three or more kinds of semiconductor nanoparticle phosphors may be included.

  DESCRIPTION OF SYMBOLS 1 Phosphor containing particle | grains, 2 Semiconductor nanoparticle fluorescent substance, 3 Resin containing the structural unit derived from the ionic liquid which has a polymeric functional group, 11 Phosphor containing particle | grains, 12 Semiconductor nanoparticle fluorescent substance which emits red fluorescence, 13 Semiconductor nanoparticle phosphor emitting green fluorescence, 21 phosphor-containing particle, 22 resin containing a structural unit derived from an ionic liquid having a polymerizable functional group and a component derived from a crosslinkable material, 31 phosphor-containing particle , 32 coating layer, 41 light emitting device, 42 light source, 43 translucent medium, 44 frame, 45 lead wire, 51 light emitting device, 52 phosphor-containing particles including semiconductor nanoparticle phosphor emitting red fluorescence, 53 phosphor-containing particles including a semiconductor nanoparticle phosphor emitting green fluorescence, 61 light-emitting device, 62 conventional phosphor, 71 phosphor-containing sheet, 72 Medium having light resistance, 81 phosphor-containing sheet, 91 phosphor-containing sheet.

Claims (18)

A light-emitting device comprising a light source and a wavelength conversion unit in which phosphor-containing particles are dispersed in a light-transmitting medium,
The phosphor-containing particles are:
A semiconductor nanoparticle phosphor;
A resin containing a structural unit derived from an ionic liquid having a polymerizable functional group,
A light-emitting device, wherein the semiconductor nanoparticle phosphor is dispersed in the resin . The light emitting device according to claim 1, wherein a particle diameter of the phosphor-containing particles is in a range of 100 nm to 30 μm. The light-emitting device according to claim 1, wherein the semiconductor nanoparticle phosphor contained in the phosphor-containing particles is one kind. The light-emitting device according to claim 1, wherein the phosphor-containing particles include a semiconductor nanoparticle phosphor that emits red fluorescence and a semiconductor nanoparticle phosphor that emits green fluorescence. The light emitting device according to claim 1, wherein the resin is crosslinked. The light emitting device according to any one of claims 1 to 5, wherein the phosphor-containing particles include a translucent coating layer on an outermost surface. The light emitting device according to claim 6, wherein the material forming the covering layer is an inorganic material having a band gap of 3.0 eV or more. A phosphor-containing particle in which a semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group, and a semiconductor nanoparticle phosphor that emits green fluorescence The light emitting device according to claim 1 , comprising phosphor-containing particles dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. During the medium, phosphor other than the semiconductor nanoparticle phosphor was further dispersed, the light emitting device according to claim 1 or 8. A phosphor-containing sheet for use in a light-emitting device, in which phosphor-containing particles are dispersed in a sheet-like medium having translucency,
The phosphor-containing particles are:
A semiconductor nanoparticle phosphor;
A resin containing a structural unit derived from an ionic liquid having a polymerizable functional group,
A phosphor-containing sheet for a light-emitting device, wherein the semiconductor nanoparticle phosphor is dispersed in the resin . The phosphor-containing sheet for a light-emitting device according to claim 10, wherein a particle diameter of the phosphor-containing particles is in a range of 100 nm to 30 μm . The phosphor-containing sheet for a light-emitting device according to claim 10 or 11, wherein the semiconductor nanoparticle phosphor contained in the phosphor-containing particles is one kind . The phosphor-containing sheet for a light-emitting device according to claim 10 or 11, wherein the phosphor-containing particles include a semiconductor nanoparticle phosphor that emits red fluorescence and a semiconductor nanoparticle phosphor that emits green fluorescence . The phosphor-containing sheet for a light-emitting device according to claim 10, wherein the resin is cross-linked . The phosphor-containing sheet for a light-emitting device according to any one of claims 10 to 14, wherein the phosphor-containing particle includes a translucent coating layer on an outermost surface . The phosphor-containing sheet for a light-emitting device according to claim 15, wherein the material forming the coating layer is an inorganic material having a band gap of 3.0 eV or more . A phosphor-containing particle in which a semiconductor nanoparticle phosphor that emits red fluorescence is dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group, and a semiconductor nanoparticle phosphor that emits green fluorescence The phosphor-containing sheet for a light-emitting device according to claim 10 , comprising phosphor-containing particles dispersed in a resin containing a structural unit derived from an ionic liquid having a polymerizable functional group. The phosphor-containing sheet for a light-emitting device according to claim 10 or 17 , wherein a phosphor other than the semiconductor nanoparticle phosphor is further dispersed in the medium.

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