JP2023018266A - Phosphor - Google Patents

Abstract

To provide a phosphor having enhanced emission intensity.SOLUTION: A phosphor has an elemental composition represented by the compositional formula (1): Sr(2-c)M4cMg(1-x-a)M1xM2aAl(22-b)M3bO36 [in the formula (1), M1 represents a metal element such as manganese, M2 represents a metal element that replaces Mg, M3 represents a metal element that replaces Al, M4 represents a metal element that replaces Sr, and a to c each represent the replacement ratio of each metal element].SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to phosphors, and more particularly to phosphors used in light emitting devices.

As a phosphor used for white LEDs, Non-Patent Document 1 discloses a phosphor represented by a composition formula: Sr ₂ MgAl ₂₂ O ₃₆ doped with Mn. Non-Patent Document 1 describes that the phosphor emits green light with a narrow half width and high color purity when irradiated with a blue LED.

Yingli Zhu et al., "Narrow-Band Green-Emitting Sr2MgAl22O36:Mn2+ Phosphors with Superior Thermal Stability and Wide Color Gamut for Backlighting Display Applications", Adv. Optical Mater., 2019, 7, 1801419, pp. 1-9

Phosphors used in light-emitting devices are required to have excellent emission intensity and high emission color purity. In this specification, the emission peak of the emission spectrum of the phosphor may be simply referred to as "the emission peak".

SUMMARY OF THE INVENTION The object of the present invention is to provide a phosphor with enhanced emission intensity, in particular a Mn-doped SrMgAlO compound phosphor with enhanced emission intensity. to provide.

The present invention has a composition formula Sr _(2-c) M4 _c Mg _(1-xa) M1 _x M2 _a Al _(22-b) M3 _b O ₃₆ (1)
[In formula (1), M1 represents at least one metal element selected from the group consisting of manganese, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium; Represents a divalent metal ion different from Mg and M1 having a coordination ionic radius of 0.30 or more and less than 1.00, and M3 represents M1 and Al having a 6-coordinate ionic radius of 0.30 or more and 0.91 or less represents a trivalent metal ion different from M4 represents a divalent metal ion different from Sr with a six-coordinate ionic radius of 1.00 or more and less than 1.17, or 1.18 or more and 1.35 or less, x is a value of 0.01≤x≤0.8, a is a value of 0≤a≤1-x, b is a value of 0≤b≤22, c is a value of 0≤c≤2, a and b The sum of c represents a value of 0<a+b+c≤25-x. ]
A phosphor having an elemental composition represented by is provided.

In one certain form, in Formula (1), M2 is Zn, M3 is Ga, M4 is Ca or Ba, and two of a, b, and c are zero.

In addition, the present invention has a composition formula SrMg _(1-xa) M1 _x M2 _a Al _(10-b) M3 _b O ₁₇ (2)
[In formula (2), M1 represents at least one metal element selected from the group consisting of manganese, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium; Represents a divalent metal ion different from Mg and M1 having a coordination ionic radius of 0.30 or more and less than 1.00, and M3 represents M1 and Al having a 6-coordinate ionic radius of 0.30 or more and 0.91 or less represents a trivalent metal ion different from, x is a value of 0.01 ≤ x ≤ 0.8, a is a value of 0 ≤ a ≤ 1-x, b is a value of 0 ≤ b ≤ 10, a and b represents a value of 0<a+b≦11−x. ]
A phosphor having an elemental composition represented by is provided.

In one certain form, M2 is Zn, M3 is Ga, and a or b is 0 in Formula (2).

In one certain form, M1 is manganese in Formula (1) or (2).

Moreover, this invention provides the film containing one of the said fluorescent substance.

Further, the present invention provides a light-emitting device containing any one of the phosphors described above.

The present invention also provides a light-emitting device including the light-emitting element.

Moreover, this invention provides the display provided with the said light emitting element.

The present invention also provides a sintered body containing any of the phosphors described above.

The present invention also provides a phosphor wheel containing any of the phosphors described above.

The present invention also provides a projector including the phosphor wheel.

According to the present invention there is provided a phosphor with enhanced emission intensity, in particular a Mn-doped SrMgAlO compound phosphor with enhanced emission intensity.

<Phosphor>
The phosphor of the present invention has a composition formula of Sr _y MgAl _z O _(1+y+1.5z) as a host crystal, where y represents a value of 1-2 and z represents a value of 10-22. ] and has an element M1 as an activating element. In the above formula, y preferably represents 1 or 2, more preferably 2, and z preferably represents 10 or 22, more preferably 22.

The phosphor of the present invention has a structure in which constituent elements other than the activating element M1 are further partially substituted with another element having a similar ionic radius and valence, based on the composition of the host crystal. This stabilizes the coordination environment of the activating element M1, which is the luminescence center, and improves the luminescence properties of the phosphor.

M2 is an element that substitutes for Mg in the host crystal. M2 is a divalent metal ion different from Mg and M1 having a six-coordinate ionic radius of 0.30 angstroms or more and less than 1.00 angstroms. Specific examples of M2 include Co (0.65 angstroms), Cu (0.73 angstroms), Fe (0.61 angstroms), Ni (0.690 angstroms), Ti (0.86 angstroms), V (0 .79 Angstroms), Zn (0.60 Angstroms), Ge (0.73 Angstroms). Numerical values in parentheses indicate the ionic radii. Said ionic radius of M2 is preferably between 0.55 and 0.7 angstroms, a preferred embodiment being Zn.

M3 is an element that substitutes for Al in the host crystal. M3 is a trivalent metal ion different from M1 and Al having an ionic radius of 0.30 angstroms to 0.91 angstroms for hexacoordination. Specific examples of M3 include Cr (0.615 angstroms), Ga (0.620 angstroms), In (0.800 angstroms), Ir (0.68 angstroms), Mo (0.69 angstroms), Nb (0 .72 Angstroms), Ta (0.72 Angstroms), Y (0.900 Angstroms). Numerical values in parentheses indicate the ionic radii. Said ionic radius of M3 is preferably between 0.6 and 0.7 angstroms, with Ga being a preferred embodiment.

M4 is an element that substitutes for Sr in the host crystal. M4 is a divalent metal ion different from Sr having a six-coordinate ionic radius of 1.00 angstroms or more and less than 1.17 angstroms, or 1.18 angstroms or more and 1.35 angstroms or less. Specific examples of M4 include Ba (1.35 angstroms), Ca (1.00 angstroms), and Pb (1.19 angstroms). Numerical values in parentheses indicate the ionic radii. Preferred examples of M4 are alkaline earth metals. Among them, Ca is preferable because it makes the crystal structure small and controls the distance between Mn--Mn so that the emission wavelength can be adjusted to the longer wavelength side. Moreover, Ba is preferable from the viewpoint of suppressing the oxidation of Mn and increasing the green/red emission intensity ratio of the emitted light.

If the ionic radii of M2 to M4 are too small or too large, the effect of stabilizing the crystal structure of the phosphor may not be obtained. The ionic radii described above are those of Shannon et al. , Acta A 32 (1976) 751. It is quoted from

Regarding the ratio of substitution of Mg by M2, referring to the above formulas (1) and (2), a is a value of 0≦a≦1−x, preferably 0<a≦0.1, and 0< More preferred is a≦0.07, and most preferred is 0.035≦a≦0.07. If a is larger than the upper limit of the above range, it may be difficult to obtain the effect of stabilizing the crystal structure of the phosphor, and the emission intensity may decrease.

Regarding the ratio of substitution of Al by M3, b is a value of 0≦b≦22, preferably 0<b≦10, and 0<b≦4. 4 is more preferred, and 1.1≦b≦4.4 is most preferred. If b is larger than the upper limit of the above range, it may be difficult to obtain the effect of stabilizing the crystal structure of the phosphor, and the emission intensity may decrease.

Regarding the ratio of substitution of Sr by M4, c is a value of 0≤c≤2, preferably 0<c≤0.4, and 0<c≤0. 2 is more preferred, and 0<c≦0.1 is most preferred. If c is larger than the upper limit of the above range, it may be difficult to obtain the effect of stabilizing the crystal structure of the phosphor, and the emission intensity may decrease.

Since M2, M3 or M4 must be present in the crystal structure of the phosphor of the present invention, a, b and c in formula (1) or a and b in formula (2) are simultaneously does not become 0. Moreover, as a preferred embodiment of the present invention, there is a phosphor in which only one of M2, M3 or M4 is present in the crystal structure. In such a phosphor, two of a, b and c in formula (1) are 0, and a or b in formula (2) is 0.

The activating element M1 is a metal element that changes the crystal size by partially substituting Mg in the semiconductor compound to produce fluorescence. Examples of the element M include at least one metal element selected from the group consisting of manganese, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium. In the phosphor of the present invention, when M is manganese, substantially divalent manganese ions serve as luminescence center ions and emit green light.

When the phosphor is irradiated with excitation light, the luminescence center ion contained in the phosphor absorbs the excitation light, and electrons at the ground level transition to the excitation level. When the excited electron returns from the excited level to the ground level, the energy corresponding to the energy level difference is emitted as fluorescence. The transition probability of electrons from the ground level to the excited level varies depending on the electronic configuration of the emission center ion, and if the transition probability is small, the forbidden transition has a low absorbance and an apparent weak emission intensity. On the other hand, if the transition probability is high, the absorbance is high and the emission intensity is apparently high.

Manganese (Mn ²⁺ ) has five electrons in the 3d orbital, and the transition to the excited level by light irradiation is a forbidden transition between the same kind of orbitals (dd). is weak. However, the emission intensity of the phosphor changes depending on the absorbance (number of absorbed photons) of the compound. Therefore, the luminescence ability of a phosphor can be objectively evaluated using the luminescence intensity per absorbance, that is, the quantum efficiency.

Definition: "Quantum efficiency (quantum yield) = luminescence intensity (number of fluorescence photons) / absorbance (number of absorption photons)"

As for the content of the activating element M1 in the host crystal, x in the formula (1) is 0.01≦x≦0.8, preferably 0.05≦x≦0.6, more preferably 0.1. ≤ x ≤ 0.5, more preferably 0.2 ≤ x ≤ 0.4, for example, 0.3. When x is less than 0.01, the amount of the element M serving as the emission center is small, and the emission intensity tends to decrease. Further, when x is greater than 0.8, the emission intensity tends to decrease due to an interference phenomenon between the elements M called concentration quenching.

In a preferred embodiment, the phosphor of the present invention has a hexagonal crystal structure. The hexagonal crystal structure protects the phosphor from external influences such as heat, ion bombardment, and vacuum ultraviolet irradiation, and at the same time improves the emission intensity of the phosphor. The phosphor of the present invention preferably has a crystal structure represented by ICSD #82105 in the XRD structure pattern when X-ray structure diffraction is measured using a CuKα ray source. In this specification, X-ray structural diffraction is sometimes referred to as "XRD".

In a more preferred embodiment, the phosphor of the present invention has a peak at 2θ = 15 to 25 ° on the 100 plane, or has a peak at 2θ = 5 to 15 on the 001 plane when subjected to XRD measurement using a CuKα ray source. It is preferable to have a peak at the position of °. A crystal structure having a peak at the position described above stabilizes the structure and protects it from external influences such as heat, ion bombardment, and vacuum ultraviolet irradiation, and at the same time increases the emission intensity of the phosphor.

The phosphor of the present invention preferably has a specific surface area of less than 2.1 m ² /g. When the specific surface area of the phosphor is small, the amount of luminescent centers present on the surface of the phosphor is reduced and oxidation is suppressed. improves the selectivity of When the specific surface area of the phosphor is 2.1 m ² /g or more, the oxidation of the luminescent center is accelerated, and the selectivity of green emission tends to decrease. An example of the emission peak present at a position other than the green emission is a red emission peak derived from a tetravalent manganese ion. The specific surface area of the phosphor of the present invention is more preferably 0.0891-0.256 m ² /g.

The specific surface area of the phosphor can be measured, for example, by the BET method. The BET method is one of methods for measuring the surface area of powder by a vapor phase adsorption method. From the adsorption isotherm, the total surface area per 1 g of sample, that is, the specific surface area can be obtained. Nitrogen gas is usually used as the adsorbed gas, and the amount of adsorption is measured from changes in the pressure or volume of the gas to be adsorbed. The amount of adsorption can be determined based on the BET formula, and the surface area can be obtained by multiplying the area occupied by one adsorbed molecule on the surface.

In a preferred embodiment, the phosphor of the present invention has an excitation wavelength in the vicinity of 450 nm, and when the emission wavelength is measured in the range of 470 nm to 800 nm, green light emission showing an emission peak having a maximum in the range of 510 nm to 550 nm. is preferably a phosphor of From the viewpoint of improving the color purity of the emitted light, the half width of this emission peak is preferably less than 27.7 nm, more preferably 26.4 to 27.3 nm, even more preferably 26.4 to 27.1 nm.

<Raw materials for phosphor>
Raw materials for producing the phosphor of the present invention include the M1 compound that is the raw material of the M1 element, the M2 compound that is the raw material of the M2 element, the M3 compound that is the raw material of the M3 element, and the M4 compound that is the raw material of the M4 element. , a Mg compound as a raw material for the Mg element, an Sr compound as a raw material for the Sr element, and an Al compound as a raw material for the Al element are used. These compounds are used in powder form.

Examples of M1 compounds that are raw materials of M1 elements include oxides containing M1, carbonates containing M1, nitrates containing M, acetates containing M, fluorides containing M, and chlorides containing M. Mg compounds that are raw materials of the Mg element include oxides containing Mg, carbonates containing Mg, nitrates containing Mg, acetates containing Mg, fluorides containing Mg, and chlorides containing Mg. Specific examples of these compounds include manganese oxide, manganese carbonate, manganese nitrate, manganese acetate, manganese fluoride and manganese chloride as M1 compounds. A preferred M1 compound among these is manganese carbonate. Examples of Mg compounds include magnesium oxide, magnesium carbonate, magnesium nitrate, magnesium acetate, magnesium fluoride and magnesium chloride. A preferred Mg compound among these is magnesium carbonate.

Examples of the M2-M4 compounds, which are raw materials of the M2-M4 elements, include oxides, hydroxides, carbonates, acetates, nitrates, chlorides and nitrides containing M2-M4. From the viewpoint of enhancing reactivity, carbonates, oxides, acetates and hydroxides are preferred, and carbonates and oxides are more preferred. Specific examples of M2 to M4 compounds include calcium carbonate, calcium oxide, calcium hydroxide, calcium acetate, barium carbonate, barium oxide, barium hydroxide, barium acetate, zinc carbonate, zinc oxide, zinc hydroxide, zinc acetate, carbonate. Gallium, gallium oxide, gallium hydroxide and gallium acetate are preferred, and barium carbonate, calcium carbonate, zinc oxide and gallium oxide are more preferred.

Sr compounds include strontium oxide, strontium carbonate and strontium nitrate. A preferred Sr compound among these is strontium carbonate. Al compounds include aluminum oxide, aluminum carbonate and aluminum nitrate. A preferable Al compound among these is aluminum oxide.

The aluminum oxide powder used as a raw material for the phosphor preferably has a specific surface area of less than 3.2 m ² /g, more preferably 0.01 to 1.5 m ² /g, still more preferably 0.08 to 0.8 m ² /g, particularly preferably 0.1 to 0.5 m ² /g. By using aluminum oxide with the above specific surface area, the emission intensity of the phosphor is enhanced.

The aluminum oxide powder used as a raw material preferably has a D50 value exceeding 0.58 μm, more preferably 1 to 50 μm, even more preferably 2 to 30 μm, and particularly preferably 3.5 to 20.3 μm. The use of D50 aluminum oxide as described above enhances the emission intensity of the phosphor.

<Manufacturing method of phosphor>
When producing the phosphor of the present invention, first, M1 to M4 compounds, Mg compounds, Al compounds, and Sr compounds are mixed so that M1 to M4, Mg, Al, Sr, and O have a predetermined ratio. Weigh, blend and mix to Mixing of the formulations can be performed using a mixing device such as a ball mill, sand mill, pico mill, or the like.

In order to promote crystallization of the raw material, a flux may be added to the raw material from the viewpoint of promoting grain growth of the phosphor of the present invention, increasing the grain size, and improving the crystallinity. A known flux such as barium fluoride can be used as the flux. The amount of flux used is preferably 1 to 20% by weight, more preferably 2 to 10% by weight, still more preferably 3 to 7% by weight, based on the total amount of raw materials.

The mixed raw materials are then fired. Firing is performed in the temperature range of 1250-1700°C. When the firing temperature is 1700° C. or lower, the desired crystal structure can be obtained without the host crystal of the phosphor collapsing. The firing temperature is preferably 1300°C to 1650°C, more preferably 1400°C to 1600°C, and still more preferably 1500°C to 1600°C. Firing in the above temperature range improves the reactivity of the solid solution, improves the crystallinity of the phosphor, and optimizes D90-D10 and D10.

The firing atmosphere is preferably a mixed atmosphere of hydrogen and nitrogen. The mixed atmosphere used for the firing atmosphere preferably has a hydrogen to nitrogen ratio of 1:99 to 100:0, more preferably a hydrogen to nitrogen ratio of 5:95 to 10:90.

When the firing temperature is within the above range, the firing time is 1 to 10 hours, preferably 3 to 7 hours. By setting the firing time within this range, a desired crystal structure can be obtained without collapsing the host crystal of the phosphor.

The phosphor of the present invention can be produced through a series of steps including the mixing and firing. The phosphor of the present invention may be produced using the solid-phase reaction method, or may be synthesized using other production methods such as a solution method and a melt synthesis method.

In a preferred embodiment, the phosphor of the present invention is obtained by firing a raw material mixture containing aluminum oxide powder having a specific surface area of less than 3.2 m ² /g at a temperature of 1250 to 1700°C. be.

Also, in one preferred embodiment, the aluminum oxide powder has a D50 greater than 0.58 μm.

<Composition>
The phosphor of the present invention can be used as a composition by dispersing it in a monomer, a resin, or a mixture of a monomer and a resin. The resin component of the composition may be a polymer obtained by polymerizing a monomer.

Examples of monomers used in the composition include methyl (meth) acrylate, ethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylates, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, Nonyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate , adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, nonylphenyl carbitol (meth)acrylate, 2-hydroxy- 3-phenoxypropyl (meth)acrylate, 2-ethylhexylcarbitol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di( meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, bis[(meth)acryloyloxyethyl]ether of bisphenol A, 3-ethylpentanediol di(meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta (meta ) acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, ethylene glycol-modified trimethylolpropane tri(meth)acrylate, propylene glycol-modified trimethylolpropane tri(meth)acrylate, ethylene glycol-modified pentaerythritol Tetra(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate , caprolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate succinic acid monoester, tris(2-(meth)acryloyloxyethyl)isocyanurate, dicyclopentanyl(meth)acrylate, etc. be done.

Preferred (meth)acrylates from the viewpoint of improving heat resistance, water resistance, light resistance and luminous intensity include isobornyl (meth)acrylate, stearyl (meth)acrylate, methyl (meth)acrylate, cyclohexyl (meth)acrylate, di Cyclopentanyl (meth)acrylate can be mentioned.

These monomers may be used alone or in combination of multiple types.

Resins used in the composition are not particularly limited, but include (meth)acrylic resins, styrene resins, epoxy resins, urethane resins and silicone resins.

The silicone resin is not particularly limited, but examples include addition-polymerizable silicones that polymerize by addition polymerization reaction of silyl groups and vinyl groups, and condensation-polymerizable silicones that polymerize by condensation polymerization of alkoxysilanes. Addition-polymerizable silicones are preferred from the viewpoint of improving the properties, light resistance, and luminescence intensity.

As the silicone resin, those in which an organic group is bonded to the Si element in silicone are preferable, and functional groups such as alkyl groups such as methyl groups, ethyl groups and propyl groups, phenyl groups and epoxy groups can be mentioned. A phenyl group is preferred from the viewpoint of improving water resistance, light resistance and luminous intensity.

Examples of silicone resins include KE-108 (manufactured by Shin-Etsu Chemical Co., Ltd.), KE-1031 (manufactured by Shin-Etsu Chemical Co., Ltd.), KE-109E (manufactured by Shin-Etsu Chemical Co., Ltd.), KE-255 (Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-112 (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-251 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KR-300 (manufactured by Shin-Etsu Chemical Co., Ltd.).

These silicones may be used alone or in combination of multiple types.

The ratio of the monomer component and/or the resin component contained in the composition is not particularly limited, but is 10 wt% or more and 99 wt% or less, preferably 20 wt% or more and 80 wt% or less, more preferably. is 30 wt % or more and 70 wt % or less.

The composition may contain a curing agent from the viewpoint of curing the monomer component and/or the resin component and improving heat resistance, water resistance, light resistance and luminescence intensity. Curing agents include curing agents having multiple functional groups. Curing agents having multiple functional groups include trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and mercapto compounds containing thiol groups.

The ratio of the curing agent contained in the composition is not particularly limited, but is 0.1 wt% or more and 20 wt% or less, preferably 1 wt% or more and 10 wt% or less, more preferably 2 wt%. % or more and 7 wt % or less.

The composition may contain an initiator from the viewpoint of improving heat resistance, water resistance, light resistance and luminous intensity by polymerizing the monomer component and/or the resin component. The initiator may be a photopolymerization initiator or a thermal polymerization initiator.

The thermal polymerization initiator used in the present invention is not particularly limited, but includes azo initiators, peroxides, persulfate acids, and redox initiators.

The azo initiator is not particularly limited, but 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-amidinopropane) dihydrochloride, 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis-2-methylbutyronitrile, 1,1-azobis (1- cyclohexanecarbonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), and 2,2'-azobis(methyl isobutyrate).

The peroxide initiator is not particularly limited, but benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicumyl peroxide, dicetylperoxydicarbonate, t-butylperoxyisopropylmonocarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate and the like.

Persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.

Redox initiators include, but are not limited to, combinations of the persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; organic peroxides and tertiary amines; based systems, such as those based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.

Other initiators include, but are not limited to, pinacols such as tetraphenyl 1,1,2,2-ethanediol.

As the thermal polymerization initiator, azo initiators and peroxide initiators are preferred, and 2,2'-azobis(methyl isobutyrate), t-butyl peroxypivalate and di(4- t-butyl cyclohexyl)peroxydicarbonate, t-butyl peroxyisopropyl monocarbonate, benzoyl peroxide.

Examples of the photopolymerization initiator include, but are not limited to, oxime compounds such as O-acyloxime compounds, alkylphenone compounds, acylphosphine oxide compounds, and the like.

O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1- On-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one -2-imine, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-[4-(1-methyl -2-methoxyethoxy)-2-methylphenyl]-1-(9-ethyl-6-nitro-9H-carbazol-3-yl)methan-1-imine and the like.

Commercially available products such as Irgacure (trade names) OXE01, OXE02, and OXE03 (manufactured by BASF), N-1919, NCI-930, and NCI-831 (manufactured by ADEKA) may also be used.

Alkylphenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1- one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- Oligomers of (4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, benzyl dimethyl ketal and the like can be mentioned.

Commercially available products such as Omnirad (trade name) 369, 907 and 379 (manufactured by IGM Resins B.V.) may also be used.

Examples of acylphosphine oxide compounds include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (for example, trade name "omnirad 819" (manufactured by IGM Resins B.V.)) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. etc. Further examples of photoinitiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- 4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di(N,N'-dimethyl benzophenone compounds such as amino)-benzophenone; xanthone compounds such as 2-isopropylthioxanthone and 2,4-diethylthioxanthone; 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene , 2-ethyl-9,10-diethoxyanthracene and other anthracene compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; benzyl, methyl phenylglyoxylate, titanocene compounds and the like. be done.

The composition may contain an antioxidant from the viewpoint of suppressing oxidation of the composition and improving heat resistance, water resistance, light resistance and luminescence intensity. Examples of antioxidants include amine-based antioxidants, sulfur-based antioxidants, phenol-based antioxidants, phosphorus-based antioxidants, phosphorus-phenol-based antioxidants, and metal compound-based antioxidants. , preferably contains at least one selected from the group consisting of amine-based antioxidants, sulfur-based antioxidants, phenol-based antioxidants and phosphorus-based antioxidants, more preferably sulfur-based antioxidants, phenolic antioxidants It contains at least one selected from the group consisting of antioxidants and phosphorus antioxidants.

An amine-based antioxidant is an antioxidant having an amino group in its molecule. Examples of amine antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, phenyl-2 - naphthylamine antioxidants such as naphthylamine; N,N'-diisopropyl-p-phenylenediamine, N,N'-diisobutyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N' -di-β-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N Phenylenediamine antioxidants such as '-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridylamine, diphenylamine, p,p'- di-n-butyldiphenylamine, p,p'-di-tert-butyldiphenylamine, p,p'-di-tert-pentyldiphenylamine, p,p'-dioctyldiphenylamine, p,p'-dinonyldiphenylamine, p, p'-didecyldiphenylamine, p,p'-didodecyldiphenylamine, p,p'-distyryldiphenylamine, p,p'-dimethoxydiphenylamine, 4,4'-bis(4-α,α-dimethylbenzoyl)diphenylamine , p-isopropoxydiphenylamine, dipyridylamine, and other diphenylamine antioxidants; Agent; bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (manufactured by BASF, trade name “Tinuvin 770”); [(4-methoxyphenyl)-methylene]-bis(1, 2,2,6,6-pentamethyl-4-piperidinyl) (manufactured by Clariant, trade name “Hostavin PR31”) and the like.

A sulfur-based antioxidant is an antioxidant having a sulfur atom in the molecule. Sulfur-based antioxidants include, for example, dilauryl thiodipropionate, dialkyl thiodipropionate compounds such as dimyristyl and distearyl (“Sumilizer TPM” (trade name, manufactured by Sumitomo Chemical Co., Ltd.), etc.), tetrakis[methylene (3-dodecylthio)propionate]methane, tetrakis[methylene(3-laurylthio)propionate]methane, β-alkylmercaptopropionate ester compounds of polyols, 2-mercaptobenzimidazole and the like.

A phenolic antioxidant is an antioxidant having a phenolic hydroxy group in the molecule. Phosphorus-phenolic antioxidants having both a phenolic hydroxy group and a phosphate or phosphite structure are classified as phenolic antioxidants herein. Phenolic antioxidants include, for example, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylidene-bis(3-methyl-6- tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-tert-butyl-6-(3-tert -butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, (tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (“Irganox 1076” (product name, manufactured by BASF)), 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6- triyl)tri-p-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-trione, 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H ,5H)-trione, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4 -hydroxy C7-C9 side chain alkyl ester, 4,6-bis(octylthiomethyl)-o-cresol, 2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di- tert-butylanilino)-1,3,5-triazine, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl )-2,4,8,10-tetraoxaspiro(5,5)undecane (manufactured by ADEKA Co., Ltd., trade name “ADEKA STAB AO-80”), triethylene glycol-bis[3-(3-tert-butyl- 5-methyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-tert- butyl-3-methylphenol), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl)-isocyanurate, 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3, 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene , 1,6-hexanediol-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 1,3,5-tris(4-hydroxybenzyl)benzene, 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol (manufactured by ADEKA Co., Ltd., trade name: ADEKA STAB AO-40) ), "Irganox 3125" (trade name, manufactured by BASF), "Sumilyzer BHT" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), "Sumilyzer GA-80" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), " Sumilizer GS" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), "Cyanox 1790" (trade name, manufactured by Cytec Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.), and the like.

Phosphorus-phenol antioxidants include, for example, 2,10-dimethyl-4,8-di-tert-butyl-6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propoxy ]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 2,4,8,10-tetra-tert-butyl-6-[3-(3,5-di-tert- Butyl-4-hydroxyphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepin, 2,4,8,10-tetra-tert-butyl-6-[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-dibenzo[d,f][1,3,2]dioxaphosphepine (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumilyzer GP”), etc. is mentioned.

A phosphorus antioxidant is an antioxidant having a phosphate ester structure or a phosphite ester structure. Phosphorus-based antioxidants include, for example, diphenylisooctylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, diphenylisodecylphosphite, diphenylisodecylphosphite, Triphenyl phosphate, tributyl phosphate, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl) phosphite, cyclic neopentane Tetraylbis(2,6-di-tert-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenyl)phosphite, 6-[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f][1,3,2]dioxaphosphepin, tris (Nonylphenyl) phosphite (manufactured by ADEKA Co., Ltd. under the trade name "ADEKA STAB 1178"), tris(mono-& dinonylphenyl mixed) phosphite, diphenyl mono(tridecyl) phosphite, 2,2'-ethylidene bis( 4,6-di-tert-butylphenol)fluorophosphite, phenyldiisodecylphosphite, tris(2-ethylhexyl)phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, tris(2,4-di- tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-di-phosphonite, 4,4'-isopropylidenediphenyltetraalkyl(C12-C15) Diphosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenyl)ditridecylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butyl Phenyl)pentaerythritol-di-phosphite, cyclic neopentanetetraylbis(2,6-di-tert-butyl-4-methylphenyl-phosphite), 1,1,3-tris(2-methyl-4 -ditridecylphosphite-5-tert-butylphenyl)butane, Trakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylenediphosphonite, tri-2-ethylhexylphosphite, triisodecylphosphite, tristearylphosphite, phenyldiisodecyl Phosphite, trilauryltrithiophosphite, distearylpentaerythritol diphosphite, tris(nonylatedophenyl)phosphite tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f ][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, bis(2,4-di- tert-butylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, triphenylphosphite, 4,4' -butylidene-bis(3-methyl-6-tert-butylphenylditridecyl)phosphite, octadecylphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3, 5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]- 4,4'-diylbisphosphonite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester, phosphonic acid, "ADEKA STAB 329K" (trade name, manufactured by ADEKA Corporation ), “ADEKA STAB PEP36” (trade name, manufactured by ADEKA Corporation), “ADEKA STAB PEP-8” (trade name, manufactured by ADEKA Corporation), “Sandstab P-EPQ” (trade name, manufactured by Clariant), “ Weston 618" (trade name, manufactured by GE), Weston 619G" (trade name, manufactured by GE), and "Ultranox 626" (trade name, manufactured by GE).

The proportion of the antioxidant contained in the composition is not particularly limited, but is 0.1 wt% or more and 20 wt% or less, preferably 1 wt% or more and 10 wt% or less, more preferably It is 2 wt % or more and 7 wt % or less.

The composition may contain a light scattering material from the viewpoint of scattering light passing through the composition to improve the amount of light absorbed by the composition and to improve the emission intensity. The light-scattering material is not particularly limited, but may be polymer fine particles or inorganic fine particles. Examples of polymers used for polymer fine particles include acrylic resins, epoxy resins, silicone resins, and urethane resins.

Inorganic fine particles used as light scattering materials include fine particles containing known inorganic compounds such as oxides, hydroxides, sulfides, nitrides, carbides, chlorides, bromides, iodides and fluorides.

In the light scattering material, oxides contained in the inorganic fine particles include silicon oxide, aluminum oxide, zinc oxide, niobium oxide, zirconium oxide, titanium oxide, magnesium oxide, cerium oxide, yttrium oxide, strontium oxide, barium oxide, oxide Known oxides such as calcium, tungsten oxide, indium oxide and gallium oxide, titanium oxide, or mixtures thereof, preferably aluminum oxide, zinc oxide and niobium oxide, more preferably aluminum oxide and niobium oxide, niobium oxide is most preferred.

In the light scattering material, examples of the aluminum oxide contained in the inorganic fine particles include known aluminum oxides such as α-alumina, γ-alumina, θ-alumina, δ-alumina, η-alumina, κ-alumina and χ-alumina. Alumina is preferred, and alpha alumina is more preferred.

In the light-scattering material, aluminum oxide may be a commercially available product, and alumina may be obtained by firing raw materials such as aluminum nitrate, aluminum chloride, and aluminum alkoxide. Examples of commercially available aluminum oxide include AKP-20 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-30 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-50 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-53 (manufactured by Sumitomo Chemical Co., Ltd.), AKP- 3000 (Sumitomo Chemical Co., Ltd.), AA-02 (Sumitomo Chemical Co., Ltd.), AA-03 (Sumitomo Chemical Co., Ltd.), AA-04 (Sumitomo Chemical Co., Ltd.), AA-05 (Sumitomo Chemical Co., Ltd.), AA- 07 (manufactured by Sumitomo Chemical Co., Ltd.), AA-1.5 (manufactured by Sumitomo Chemical Co., Ltd.), AA-3 (manufactured by Sumitomo Chemical Co., Ltd.), and AA-18 (manufactured by Sumitomo Chemical Co., Ltd.). -02 (manufactured by Sumitomo Chemical Co., Ltd.), AA-3 (manufactured by Sumitomo Chemical Co., Ltd.), AA-18 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-20 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-3000 (manufactured by Sumitomo Chemical Co., Ltd.), AKP -53 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-30 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-50 (manufactured by Sumitomo Chemical Co., Ltd.), AA-02 (manufactured by Sumitomo Chemical Co., Ltd.), AA-3 (manufactured by Sumitomo Chemical Co., Ltd.) ), AKP-53 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-3000 (manufactured by Sumitomo Chemical Co., Ltd.), AKP-30 (manufactured by Sumitomo Chemical Co., Ltd.), and AKP-50 (manufactured by Sumitomo Chemical Co., Ltd.) are more preferable.

In the light scattering material, the hydroxides contained in the inorganic fine particles include aluminum hydroxide, zinc hydroxide, magnesium hydroxide, cerium hydroxide, yttrium hydroxide, strontium hydroxide, barium hydroxide, calcium hydroxide, and water. Known oxides such as indium oxide and gallium hydroxide, or mixtures thereof may be mentioned, with aluminum hydroxide and zinc hydroxide being preferred.

In the light scattering material, the sulfides contained in the inorganic fine particles include silicon sulfide, aluminum sulfide, zinc sulfide, niobium sulfide, zirconium sulfide, titanium sulfide, magnesium sulfide, cerium sulfide, yttrium sulfide, strontium sulfide, barium sulfide, and sulfide. known sulfides such as calcium, tungsten sulfide, indium sulfide, and gallium sulfide, or mixtures thereof, with aluminum sulfide, zinc sulfide, and niobium sulfide being preferred, zinc sulfide and niobium sulfide being more preferred, and niobium sulfide being most preferred; preferable.

In the light scattering material, the nitrides contained in the inorganic fine particles include silicon nitride, aluminum nitride, zinc nitride, niobium nitride, zirconium nitride, titanium nitride, magnesium nitride, cerium nitride, yttrium nitride, strontium nitride, barium nitride, and nitride. Known nitrides such as calcium, tungsten nitride, indium nitride, and gallium nitride, or mixtures thereof, preferably aluminum nitride, zinc nitride, niobium nitride, more preferably aluminum nitride, niobium nitride, most preferably niobium nitride. preferable.

In the light scattering material, the carbides contained in the inorganic fine particles include silicon carbide, aluminum carbide, zinc carbide, niobium carbide, zirconium carbide, titanium carbide, magnesium carbide, cerium carbide, yttrium carbide, strontium carbide, barium carbide, and calcium carbide. , tungsten carbide, indium carbide, and gallium carbide, or mixtures thereof, preferably aluminum carbide, zinc carbide, niobium carbide, more preferably aluminum carbide, niobium carbide, most preferably niobium carbide. .

In the light scattering material, chlorides contained in the inorganic fine particles include silicon chloride, aluminum chloride, zinc chloride, niobium chloride, zirconium chloride, titanium chloride, magnesium chloride, cerium chloride, yttrium chloride, strontium chloride, barium chloride, and chloride. Known chlorides such as calcium, tungsten chloride, indium chloride and gallium chloride, or mixtures thereof, preferably aluminum chloride, zinc chloride, niobium chloride, more preferably aluminum chloride, niobium chloride, most preferably niobium chloride. .

In the light scattering material, the bromide contained in the inorganic fine particles includes silicon bromide, aluminum bromide, zinc bromide, niobium bromide, zirconium bromide, titanium bromide, magnesium bromide, cerium bromide, and yttrium bromide. , strontium bromide, barium bromide, calcium bromide, tungsten bromide, indium bromide and gallium bromide, or mixtures thereof; aluminum bromide, zinc bromide, niobium bromide; Preferred are aluminum bromide and niobium bromide, and most preferred is niobium bromide.

In the light scattering material, the iodides contained in the inorganic fine particles include silicon iodide, aluminum iodide, zinc iodide, niobium iodide, zirconium iodide, titanium iodide, magnesium iodide, gallium iodide, and iodide. Known iodides such as cerium iodide, yttrium iodide, strontium iodide, barium iodide, calcium iodide, tungsten iodide, indium iodide, or mixtures thereof, aluminum iodide, zinc iodide, iodide Niobium is preferred, aluminum iodide and niobium iodide are more preferred, and niobium iodide is most preferred.

In the light scattering material, the fluoride contained in the inorganic fine particles includes silicon fluoride, aluminum fluoride, zinc fluoride, niobium fluoride, zirconium fluoride, titanium fluoride, magnesium fluoride, cerium fluoride, and fluoride. known fluorides such as yttrium fluoride, strontium fluoride, barium fluoride, calcium fluoride, tungsten fluoride, indium fluoride, and gallium fluoride, or mixtures thereof; aluminum fluoride, zinc fluoride, fluoride; Niobium chloride is preferred, aluminum fluoride and niobium fluoride are more preferred, and niobium fluoride is most preferred.

As the light scattering material, aluminum oxide, silicon oxide, zinc oxide, titanium oxide, and niobium oxide are used from the viewpoint of scattering light that has passed through the composition to improve the amount of light absorbed by the composition and to improve the emission intensity. , zirconium oxide is preferred, and aluminum oxide is preferred.

The particle size of the light scattering material contained in the composition is not particularly limited, but is 0.1 μm or more and 50 μm or less, preferably 0.3 μm or more and 10 μm or less, more preferably 0 .5 μm or more and 5 μm or less.

The ratio of the light scattering material contained in the composition is not particularly limited, but is 0.1 wt% or more and 20 wt% or less, preferably 1 wt% or more and 10 wt% or less, more preferably It is 2 wt % or more and 7 wt % or less.

The composition may contain a light-emitting material other than the phosphor of the present invention, from the viewpoint of adjusting the emission color emitted by the composition and achieving a wide color gamut. Other luminescent materials other than the phosphor of the present invention contained in the composition include phosphors other than the phosphor of the present invention and quantum dots.

The quantum dots contained in the composition are not particularly limited as long as they are quantum dot particles capable of emitting fluorescence in the visible light wavelength region. - Group VI semiconductor compounds; Group IV elements or compounds containing them; and combinations thereof. These can be used alone or in combination of two or more.

The II-VI group semiconductor compound is a binary compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe , ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; , CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof.

The III-V group semiconductor compound is a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb and mixtures thereof; ternary compounds selected from the group consisting of GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof; It can be selected from the group consisting of quaternary compounds selected from the group consisting of GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb and mixtures thereof.

The group IV-VI semiconductor compound is a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe and mixtures thereof; ternary compounds selected from the group consisting of SnPbTe and mixtures thereof; and quaternary compounds selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe and mixtures thereof.

The group IV element or the compound containing it is selected from the group consisting of elemental compounds selected from the group consisting of Si, Ge and mixtures thereof; and binary compounds selected from the group consisting of SiC, SiGe and mixtures thereof. can

Quantum dots can be homogeneous single structures; dual structures such as core-shell, gradient structures, etc.; or mixed structures thereof.

In the core-shell dual structure, the materials constituting each core and shell may be composed of different semiconductor compounds mentioned above. For example, the core is one selected from the group consisting of CdSe, CdS, ZnS, ZnSe, ZnTe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs and ZnO. It can include, but is not limited to, one or more substances. For example, the shell may include, but is not limited to, one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe and HgSe.

From the viewpoint of obtaining white light, the quantum dots are preferably InP or CdSe.

The diameter of the quantum dots is not particularly limited, but the red, green, and blue quantum dot particles can be classified according to particle size, with the particle size decreasing in the order of red, green, and blue. Specifically, the red quantum dot particles have a particle size of 5 nm or more and 10 nm or less, the green quantum dot particles have a particle size of more than 3 nm and 5 nm or less, and the blue quantum dot particles have a particle size of 1 nm or more and 3 nm or less. can. Upon irradiation with light, red quantum dot particles emit red light, green quantum dot particles emit green light, and blue quantum dot particles emit blue light.

The phosphor other than the phosphor of the present invention contained in the composition is not particularly limited, but examples include sulfide phosphors, oxide phosphors, nitride phosphors, fluoride phosphors, etc. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the sulfide phosphor include CaS:Eu, SrS:Eu, _SrGa2S4 :Eu, _CaGa2S4 : _Eu , _Y2O2S : _Eu , _La2O2S : _Eu , _{Gd 2} O ₂ S:Eu, and the like.

Specific examples of the oxide-based phosphor include (Ba, Sr) ₃ SiO ₅ :Eu, (Ba, Sr) ₂ SiO ₄ :Eu, Tb ₃ Al ₅ O ₁₂ :Ce, and Ca ₃ Sc ₂ Si. ₃ O ₁₂ :Ce, and the like.

Specific examples of the nitride phosphor include _CaSi5N8 : _Eu , _Sr2Si5N8 : _Eu , _Ba2Si5N8 : _Eu , ₍ Ca, _Sr , Ba) _{2Si5N . 8} : Eu, Cax(Al, Si) _{12 (} O, _N ) ₁₆ : Eu ( ₀ < _x≤1.5 ), _CaSi2O2N2 : Eu, _SrSi2O2N2 : Eu, _{BaSi2O 2N2} :Eu, ₍ Ca,Sr,Ba) _Si2O2N2 :Eu, _CaAl2Si4N8 :Eu, _CaSiN2 : _{Eu , CaAlSiN3} :Eu, ₍ Sr _, Ca) _AlSiN3 :Eu , and so on.

Specific examples of the fluoride-based phosphors are not particularly limited, and include K ₂ TiF ₆ :Mn ⁴⁺ , Ba ₂ TiF ₆ :Mn ⁴⁺ , Na ₂ TiF ₆ :Mn ⁴⁺ , K ₃ ZrF ₇ :Mn ⁴⁺ . , K ₂ SiF ₆ :Mn ⁴⁺ , and the like.

_{Specific examples} of the other phosphors _are not particularly limited. Al) ₁₂ (O, N) ₁₆ : SiAlON-based phosphors such as Eu; perovskite phosphors also having a perovskite structure;

From the viewpoint of obtaining white light, the phosphor other than the phosphor of the present invention contained in the composition is preferably a red phosphor, and preferably K ₂ SiF ₆ :Mn ⁴⁺ .

The ratio of the luminescent material other than the phosphor of the present invention contained in the composition is not particularly limited, but is 0.1 wt% or more and 90 wt% or less, preferably 1 wt% or more and 80 wt% or less. Yes, more preferably 5 wt % or more and 60 wt % or less.

<Film>
The phosphor of the present invention can be used in the form of a film by processing the shape of the resin composition. The shape of the film is not particularly limited, and may be any shape such as sheet-like or bar-like. As used herein, the term “bar-shaped” means, for example, a band-shaped shape extending in one direction in plan view. Examples of the belt-like shape in a plan view include a plate-like shape in which each side has a different length. The thickness of the film may be from 0.01 μm to 1000 mm, from 0.1 μm to 10 mm, or from 1 μm to 1 mm.

In this specification, the thickness of the film refers to the distance between the front surface and the back surface in the thickness direction of the film when the side with the smallest value among the length, width, and height of the film is defined as the “thickness direction”. point to distance. Specifically, the thickness of the film is measured at three arbitrary points on the film using a micrometer, and the average value of the measured values at the three points is taken as the thickness of the film. Also, the film may be a single layer or multiple layers. In the case of multiple layers, each layer may be composed of the same type of embodiment composition, or may be composed of different types of embodiment compositions.

<Sintered body>
The phosphor of the present invention can be used as a sintered body containing the phosphor of the present invention by incorporating the phosphor of the present invention into an inorganic material and sintering and molding the inorganic material. The inorganic material used for the sintered body may be a glass molded body using a glass component, or a crystalline inorganic material component may be used.

<Glass molding>
The phosphor of the present invention can be dispersed in glass and used as a molded glass. Glass components used in the glass composition _are not particularly limited, but may be _SiO2 , _P2O5 , _GeO2 , _BeF2 , _As2S3 , _SiSe2 , _GeS2 , _TiO2 , _{TeO2 , Al2O3 .} , _Bi2O3 , _{V2O5 , Sb2O5} , PbO, CuO, _ZrF4 , _{AlF3 , InF3 , ZnCl2} , _ZnBr2 , _Li2O , _Na2O , _K2O , MgO, BaO , CaO, SrO, LiCl, BaCl, _BaF2 and _LaF3 . Among them, from the viewpoint of improving durability, heat resistance, and light resistance, it is preferable to include SiO ₂ or Bi ₂ O ₃ as a glass component. One type of glass component may be used, or two or more types may be used.

The proportion of the glass component contained in the molded glass is not particularly limited, but is 10 wt% or more and 99 wt% or less, preferably 20 wt% or more and 80 wt% or less, more preferably 30 wt% or more. , 70 wt % or less.

The glass molded body may contain a light scattering material from the viewpoint of scattering light that has passed through the molded body to improve the amount of light absorbed by the glass molded body and to improve the emission intensity. As the light scattering material, the same inorganic fine particles as the light scattering material used in the resin composition can be used.

The amount of the light-scattering material added to the molded glass body may be the same as that of the light-scattering material used in the resin composition.

The molded glass body may contain another light-emitting material in addition to the phosphor of the present invention from the viewpoint of adjusting the luminescent color emitted by the molded glass body and achieving a wide color gamut. As another luminescent material other than the phosphor of the present invention contained in the glass molding, the same luminescent material as used in the resin composition can be used.

The amount of the luminescent material to be added to the molded glass can be the same as that of the luminescent material used in the resin composition.

The shape of the molded glass body is not particularly limited, but examples thereof include plate-like, rod-like, columnar and wheel-like shapes.

<Light emitting element>
The phosphor of the present invention can constitute a light-emitting element together with a light source. As a light source an LED can be used which emits UV or visible light, in particular including wavelengths between 350 nm and 500 nm. When the phosphor of the present invention is irradiated with light having the above wavelength, the phosphor emits green light having a peak wavelength of 510 nm to 550 nm. For this reason, the phosphor of the present invention can constitute a white light emitting device by using, for example, an ultraviolet LED or a blue LED as a light source and combining it with another red phosphor.

<Light emitting device>
As described above, the phosphor of the present invention can constitute a white light-emitting element, and the white light-emitting element can be used as a member of a light-emitting device. In a light-emitting device, a light-emitting element is irradiated with light from a light source, the irradiated light-emitting element emits light, and the light is extracted.

<Display>
A light-emitting device containing the phosphor of the present invention and a light source can be used in a display. An example of such a display is a liquid crystal display in which the transmittance of light from light-emitting elements can be controlled by liquid crystal, and the transmitted light can be selectively extracted as red light, blue light, or green light using a color filter. be done.

<Phosphor wheel>
The phosphor of the present invention can be used to manufacture phosphor wheels. A phosphor wheel is a member having a disk-shaped substrate and a phosphor layer formed on the surface thereof. The phosphor wheel absorbs excitation light emitted from a light source, excites it, and emits converted light having a different wavelength. For example, the phosphor wheel absorbs blue excitation light, emits converted light different from the blue excitation light converted by the phosphor layer, and reflects the blue excitation light to combine with the converted light. , or only the converted light can be used to convert to different colors of light.

<Projector>
The phosphor of the present invention can be used as a member constituting a projector using the phosphor wheel. A projector is a display device that includes a light source, a phosphor wheel, a mirror device, and a projection optical system.

EXAMPLES The present invention will be described in more detail below with reference to examples. The invention is not limited to these examples.

<Example 1>
As raw materials for the phosphor, aluminum oxide powder (grade AA18, specific surface area 0.1 m ² /g, D50 20.3 μm, manufactured by Sumitomo Chemical Co., Ltd.), magnesium carbonate powder, manganese carbonate powder, strontium carbonate powder and gallium oxide powder. Considering that the carbonic acid of the carbonate is desorbed as carbon dioxide (CO ₂ ) after firing, the composition of the phosphor after firing is Mn:Mg:Al:Sr:Ga:O=0.3: The ingredients were weighed to give a molar ratio of 0.7:20.9:2:1.1:36 and dry mixed for 3 minutes. Next, the raw materials after mixing were filled in an alumina container. Subsequently, the alumina container was set in an electric furnace, and a mixed gas of hydrogen:nitrogen=10:90 was introduced. The temperature was raised to 1550° C., sintering was performed for 6 hours, and then the product was allowed to cool. The fired product was recovered from the container, and the phosphor of Example 1 was produced.

<Example 2>
Considering that the carbonic acid of the carbonate is desorbed as carbon dioxide (CO ₂ ) after firing, the composition of the phosphor after firing is Mn:Mg:Al:Sr:Ga:O=0. A phosphor was produced in the same manner as in Example 1, except that the molar ratio was changed to 3:0.7:17.6:2:4.4:36.

<Example 3>
Considering that the zinc oxide powder is used instead of the gallium oxide powder, and the amount of the raw materials mixed is adjusted so that the carbonic acid of the carbonate desorbs as carbon dioxide (CO ₂ ) after firing, the phosphor after firing is In the same manner as in Example 1 except that the composition was changed to a molar ratio of Mn:Mg:Al:Sr:Zn:O=0.3:0.665:22:2:0.035:36 , a phosphor was produced.

<Example 4>
Considering that the carbonic acid of the carbonate is desorbed as carbon dioxide (CO ₂ ) after firing, the composition of the phosphor after firing is Mn:Mg:Al:Sr:Zn:36=0. A phosphor was produced in the same manner as in Example 1, except that the molar ratio was changed to 3:0.63:22:2:0.07:36.

<Example 5>
Considering that the calcium carbonate powder is used instead of the gallium oxide powder, and the amount of the raw materials mixed is adjusted so that the carbonic acid of the carbonate desorbs as carbon dioxide (CO ₂ ) after firing, the phosphor after firing is Same as Example 1 except that the composition was changed to a molar ratio of Mn:Mg:Al:Sr:Ca:O=0.3:0.7:22:1.9:0.1:36 Then, a phosphor was produced. The emission wavelength of the obtained phosphor was 517 nm.
<Example 6>
Considering that the barium carbonate powder is used instead of the gallium oxide powder, and the amount of the raw materials mixed is adjusted so that the carbonic acid of the carbonate is desorbed as carbon dioxide (CO ₂ ) after firing, the phosphor after firing is Same as Example 1 except that the composition was changed to a molar ratio of Mn:Mg:Al:Sr:Ba:O=0.3:0.7:22:1.9:0.1:36 Then, a phosphor was produced. The selectivity value of green emission to red emission of the obtained phosphor was 104 as a relative value.

<Comparative Example 1>
Aluminum oxide powder (grade AA18, specific surface area of 0.1 m ² /g, D50 of 20.3 μm, manufactured by Sumitomo Chemical Co., Ltd.), magnesium carbonate powder, manganese carbonate powder, and strontium carbonate powder are used as raw materials for the phosphor, and fired. Considering that the carbonic acid of the carbonate is released later as carbon dioxide (CO ₂ ), the composition of the phosphor after firing is Mn:Mg:Al:Sr:O=0.3:0.7:22: Each ingredient was weighed to give a 2:36 molar ratio and dry mixed for 3 minutes. Next, the raw materials after mixing were filled in an alumina container. Subsequently, the alumina container was set in an electric furnace, and a mixed gas of hydrogen:nitrogen=10:90 was introduced. The temperature was raised to 1550° C., sintering was performed for 6 hours, and then the product was allowed to cool. A fired product was recovered from the container, and a phosphor of Comparative Example 1 was produced. The emission wavelength of the obtained phosphor was 516 nm. The selectivity value of green emission to red emission of the obtained phosphor was 100 as a relative value.

<Various measurements and evaluations>
The following items were measured for the phosphors produced in Examples and Comparative Examples.

(a) Crystal structure Powder X-ray diffraction using CuK _α rays was performed using an X-ray diffractometer ("X'Pert Pro" (trade name) manufactured by PANalytical). The obtained X-ray diffraction pattern has a hexagonal structure in all samples, and the 100 plane has a peak at 2θ = 15 to 25 °, and the 001 plane has a peak at 2θ = 5 to 15 °. was confirmed to be the crystal structure of ICSD #82105.

(b) Emission intensity of emission peak, wavelength measurement Absolute PL quantum yield measurement device (manufactured by Hamamatsu Photonics, trade name C9920-02, excitation light 450 nm, room temperature, in the atmosphere, 150 mg used) to measure the emission spectrum, The emission intensity of the emission peak was measured. The luminescence intensity of the green luminescence was in the range of 470 to 800, and the value of the luminescence intensity of the luminescence peak with the strongest luminescence was used. All of the phosphors were confirmed to be green-emitting phosphors exhibiting a maximum emission peak in the range of 510 nm to 550 nm when the emission at 470 to 800 nm was measured.

An emission peak was determined from the measured spectrum, and the emission peak intensity at the wavelength with the highest emission intensity in Comparative Example 1 was converted to 100 to calculate the relative emission intensities of Examples 1 to 6. From the measured spectrum, the wavelength at the position where the emission intensity was the highest was taken as the emission wavelength.

(c) Selectivity of Green Emission to Red Emission An emission spectrum was measured using a spectrofluorometer ("FP-6500" (trade name) manufactured by JASCO Corporation). For the measurement, a solid sample holder attached to the photometer was used, and an emission spectrum was measured at an excitation wavelength of 450 nm. The luminescence intensity of green luminescence is the luminescence intensity value of the most intense luminescence peak in the range of 485 to 627 nm, and the luminescence intensity of red luminescence is the luminescence intensity value of the most intense luminescence peak in the range of 650 to 733 nm. bottom. Evaluation of the selectivity of green emission to red emission was calculated according to the following formula.

Selectivity of green emission to red emission = emission peak intensity of green emission / emission peak intensity of red emission

The value of selectivity of green emission to red emission was calculated by converting the value of Comparative Example to 100 and calculating the relative value of Example 6.

Table 1 shows the characteristic values and evaluation results of the phosphors of Examples and Comparative Examples.

The phosphors of Examples 1 to 6 have structures in which constituent elements other than the emission center Mn are replaced with other elements based on the composition of the phosphor of the comparative example. As a result, it was confirmed that the phosphors of Examples 1 to 6 had improved emission intensity compared to the phosphor of Comparative Example 1.

<Reference example 1>
The phosphor described in Examples 1 to 6 is combined with a resin, placed in a glass tube or the like and sealed, and then placed between a blue light emitting diode as a light source and a light guide plate to emit blue light. To manufacture a backlight that can convert blue light of a diode into green light or red light.

<Reference example 2>
A resin composition can be obtained by combining the phosphors described in Examples 1 to 6 with a resin and forming a sheet, and a film obtained by sandwiching and sealing this between two barrier films is placed on a light guide plate. By installing the backlight, the blue light emitted from the blue light emitting diodes placed on the end face (side surface) of the light guide plate through the light guide plate to the sheet can be converted into green light or red light.

<Reference example 3>
A backlight capable of converting emitted blue light into green light or red light is manufactured by placing the phosphors described in Examples 1 to 6 in the vicinity of the light emitting portion of the blue light emitting diode.

<Reference example 4>
The wavelength conversion material can be obtained by mixing the phosphor and the resist described in Examples 1 to 6 and then removing the solvent. By arranging the obtained wavelength conversion material between a blue light emitting diode as a light source and a light guide plate or behind an OLED as a light source, a backlight capable of converting blue light from a light source into green light or red light is provided. manufacture.

<Reference example 5>
Conductive particles such as ZnS are mixed with the phosphors described in Examples 1 to 6 to form a film, an n-type transport layer is laminated on one side, and a p-type transport layer is laminated on the other side to obtain an LED. . When a current is applied, the charges of the holes of the p-type semiconductor and the electrons of the n-type semiconductor are canceled in the perovskite compound on the junction surface, so that light can be emitted.

<Reference example 6>
A titanium oxide dense layer is laminated on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer is laminated thereon, and the phosphors described in Examples 1 to 6 are laminated thereon. After removing the solvent, hole transport such as 2,2′,7,7′-tetrakis-(N,N′-di-p-methylphenylamine)-9,9′-spirobifluorene (Spiro-OMeTAD) Layers are laminated and a silver (Ag) layer is laminated thereon to create a solar cell.

<Reference example 7>
The composition of the present embodiment can be obtained by compounding and molding the phosphor and resin described in Examples 1 to 6, and by installing this after the blue light emitting diode, the composition from the blue light emitting diode To manufacture a laser diode illumination that emits white light by converting blue light irradiated to an object into green light or red light.

<Reference example 8>
The composition of the present embodiment can be obtained by forming a composite of the phosphors described in Examples 1 to 6 with a resin. By using the obtained composition as a part of a photoelectric conversion layer, a photoelectric conversion element (light detection element) material used in a detection portion that detects light is produced. Photoelectric conversion element materials are part of a living body such as an image detection part (image sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection part, a face detection part, a vein detection part and an iris detection part. Used in optical biosensors such as pulse oximeters and detectors that detect predetermined characteristics.

<Reference example 9>
The composition of the present embodiment can be obtained by forming a composite of the phosphors described in Examples 1 to 6 with a resin. The resulting composition can be used as a film that improves the light conversion efficiency of solar cells. Although the form of the conversion efficiency improving sheet is not particularly limited, it is used in the form of coating on a substrate. The substrate is not particularly limited as long as it has high transparency. For example, PET film and moth-eye film are desirable. The solar cell using the solar cell conversion efficiency improving sheet is not particularly limited, and the conversion efficiency improving sheet has a function of converting a wavelength region in which the solar cell has low sensitivity to a wavelength region in which it has high sensitivity.

<Reference Example 10>
The composition of the present embodiment can be obtained by forming a composite of the phosphors described in Examples 1 to 6 with a resin. The resulting composition can be used as a light source for single photon generation in quantum computers, quantum teleportation, quantum cryptographic communication, and the like.

Claims (12)

Composition formula Sr _(2-c) M4 _c Mg _(1-xa) M1 _x M2 _a Al _(22-b) M3 _b O ₃₆ (1)
[In formula (1), M1 represents at least one metal element selected from the group consisting of manganese, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium; Represents a divalent metal ion different from Mg and M1 having a coordination ionic radius of 0.30 or more and less than 1.00, and M3 represents M1 and Al having a 6-coordinate ionic radius of 0.30 or more and 0.91 or less represents a trivalent metal ion different from M4 represents a divalent metal ion different from Sr with a six-coordinate ionic radius of 1.00 or more and less than 1.17, or 1.18 or more and 1.35 or less, x is a value of 0.01≤x≤0.8, a is a value of 0≤a≤1-x, b is a value of 0≤b≤22, c is a value of 0≤c≤2, a and b The sum of c represents a value of 0<a+b+c≤25-x. ]
A phosphor having an elemental composition represented by 2. The phosphor of claim 1, wherein M2 is Zn, M3 is Ga, M4 is Ca or Ba, and two of a, b and c are zero. Composition formula SrMg _(1-xa) M1 _x M2 _a Al _(10-b) M3 _b O ₁₇ (2)
[In formula (2), M1 represents at least one metal element selected from the group consisting of manganese, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium; Represents a divalent metal ion different from Mg and M1 having a coordination ionic radius of 0.30 or more and less than 1.00, and M3 represents M1 and Al having a 6-coordinate ionic radius of 0.30 or more and 0.91 or less represents a trivalent metal ion different from, x is a value of 0.01 ≤ x ≤ 0.8, a is a value of 0 ≤ a ≤ 1-x, b is a value of 0 ≤ b ≤ 10, a and b represents a value of 0<a+b≦11−x. ]
A phosphor having an elemental composition represented by 4. The phosphor of claim 3, wherein M2 is Zn, M3 is Ga, and a or b is zero. The phosphor according to any one of claims 1 to 4, wherein M1 is manganese. A film comprising the phosphor according to any one of claims 1 to 5. A light-emitting device comprising the phosphor according to any one of claims 1 to 5. A light-emitting device comprising the light-emitting element according to claim 7 . A display comprising the light emitting device according to claim 7 . A sintered body comprising the phosphor according to any one of claims 1 to 5. A phosphor wheel comprising the phosphor according to any one of claims 1 to 5. A projector comprising the phosphor wheel of claim 11 .