JP2023019650A - Resin composition containing phosphor - Google Patents

Abstract

To provide a resin composition having excellent emission intensity, containing a phosphor that does not show increased light absorption in the visible region even when dispersed in the resin composition and maintains its emission properties.SOLUTION: A resin composition comprises: a phosphor having a core-shell structure which includes a core part composed of a crystal phase of an inorganic compound having an elemental composition represented by formula (A) MxMgaAlyOzNw [in formula (A), M represents a metal element such as manganese, x satisfies 0.001≤x≤0.3, a satisfies 0≤a≤1.0-x, and y satisfies 1.2≤y≤11.3, z satisfies 2.8≤z≤18, and w satisfies 0≤w≤1.0], and a shell part formed on at least a portion of the surface of the core part and containing boron or silicon; a modifier of a silane coupling agent containing no halogen atoms and present on the surface of the shell part; and a matrix resin.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a phosphor-containing resin composition for use in light-emitting devices and the like.

Some white-emitting LED devices have a structure in which a blue LED that emits blue light is used as a light source, and the light source is covered with a phosphor that emits green or red light mixed with a transparent resin material. . In such a light emitting device, blue light emitted from the blue LED is mixed with red and green light emitted from the phosphor to generate white light. Therefore, in order to improve the emission intensity of the white light emitting LED device, it is necessary to improve the emission intensity of the resin layer containing the phosphor.

Patent Document 1 describes a Mn-doped MgAl ₂ O ₄ -based spinel-type oxide fluorescent emitter. The phosphor of Patent Document 1 contains an excessive amount of Mg. MgAl ₂ O ₄ -based oxide fluorescent emitters with a doping amount of Mn within a specific range and an excess amount of Mg can emit bright red light.

In Patent Document 2, a rare earth-activated alkaline earth metal fluorohalide-based stimulable phosphor is surface-treated with a silane coupling agent in the presence of at least one or more metal oxide particles. A method of forming phosphor particles is described.

In the method of Patent Document 2, after the phosphor particles are coated with the metal oxide particles, surface treatment is performed with a silane coupling agent. A silicon-containing coating formed by surface treatment using a silane coupling agent fills the periphery of the metal oxide particles dispersed on the phosphor particles to form a continuous phase. In other words, a silicon-containing film is directly formed on the surface of the stimulable phosphor particles by the silane coupling agent. Here, it is described that as a result, the moisture resistance of the stimulable phosphor, which was inferior in moisture resistance, is improved.

JP 2016-17125 A JP-A-2001-81457

Regarding phosphors that emit red to green light, which are used in white light emitting LED devices, when dispersed in a resin composition, light absorption in the visible region, particularly around 630 nm, increases, resulting in a decrease in light emission characteristics. It was found that there is something to do.

The object of the present invention is to solve the above-mentioned problems, and to provide a phosphor that does not increase light absorption in the visible region at 630 nm and that does not reduce light emission characteristics even when dispersed in a resin composition. It is an object of the present invention to provide a resin composition containing an excellent luminescence intensity.

The present invention is based on the formula
MxMgaAlyOzNw (A)
[In formula (A), M represents at least one metal element selected from the group consisting of manganese, strontium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium, and x represents 0.001≦x≦0.3, a is 0≦a≦1.0−x, y is 1.2≦y≦11.3, and z is 2.8≦z≦18 Yes, and w is 0≤w≤1.0. ]
A core portion made of a crystal phase of an inorganic compound having an elemental composition represented by
A phosphor having a core-shell structure, comprising a shell portion formed on at least a portion of the surface of the core portion and containing at least one element selected from the group consisting of boron and silicon;
a modified silane coupling agent containing no halogen atoms present on the surface of the shell portion; and a matrix resin;
Provide a resin composition comprising

In one embodiment, the silane coupling agent has the formula

[In the formula,
R ¹ is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a (meth)acryloyloxy group, an amino group, an alkylamino group having 1 to 20 carbon atoms or a mercapto group; ,
R ² is a hydrogen atom or a saturated or unsaturated C 1-20 optionally substituted by a (meth)acryloyloxy group, an amino group, an alkylamino group having 1 to 20 carbons or a mercapto group. is a hydrocarbon group,
R ¹ or R ² may be different groups when there are more than one,
a is an integer from 1 to 3; ]
It is a compound represented by

In one embodiment, the Hansen solubility parameter distance between the silane coupling agent and the matrix resin is less than 7.06.

In one certain form, the matrix resin is a silicone resin or an acrylic resin.

In one embodiment, R ¹ includes an alkyl group having 8 to 12 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, or a vinyl group.

In one embodiment, M represents at least one metal element selected from the group consisting of manganese, strontium, europium and terbium.

In one embodiment, x is 0.05≦x≦0.15, a is 0≦a≦0.95, y is 1.5≦y≦2.5, and z is 3 .5≤z≤4.5 and w is 0≤w≤1.0.

In one form, the crystalline phase includes crystallites, and the crystallites have a spinel crystal structure.

Further, the present invention provides a film comprising any one of the resin compositions described above.

Further, the present invention provides a light-emitting device comprising any one of the resin compositions 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.

ADVANTAGE OF THE INVENTION According to the present invention, a resin composition having excellent luminescence intensity is provided, which contains a phosphor that does not increase light absorption in the visible range, particularly around 630 nm, and does not reduce luminescence characteristics even when dispersed in a resin composition. be done. When the resin composition of the present invention is used in a white light LED device in combination with a phosphor that emits red light (630 nm light emission), it is possible to suppress a decrease in the emission intensity of the red component.

<Phosphor>
The phosphor used in the present invention is a phosphor having a core portion made of a crystalline phase and a shell portion formed on at least part of the surface of the core portion. The shell is generally an oxide containing at least one element selected from the group consisting of boron and silicon.

It has been confirmed that phosphors having a core-shell structure have a problem that when they are dispersed in a resin composition, light absorption in the visible region increases and light emission characteristics deteriorate. The reason for this is that the coating with the shell reduces the affinity of the surface of the phosphor for the resin, creating a large number of voids at the interface between the phosphor and the resin, and increasing the absorption of stray light in the visible region. Conceivable.

The core part is the formula
MxMgaAlyOzNw (A)
[In the formula (A), M represents a metal element constituting the emission center ion, and x, a, y, z and w represent the composition ratio of the elements. ]
It contains a crystal phase of an inorganic compound having an elemental composition represented by.

Examples of the metal element M include at least one metal element selected from the group consisting of manganese, strontium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium, manganese, strontium , europium and terbium, preferably at least one metal element selected from the group consisting of manganese and strontium, more preferably manganese.

When the metal element M is manganese, manganese constitutes the luminescence center ion, and a green-emitting phosphor that emits green light can be obtained.

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 arrangement of the emission center ion, and if the transition probability is small, the forbidden transition has a low absorbance and an apparent low emission intensity. On the other hand, if the transition probability is high, the absorbance is high and the emission intensity is apparently high.

Divalent manganese (Mn ²⁺ ) has five electrons in the 3d orbital, and the transition to the excited level by light irradiation is a forbidden transition because it is between homogeneous orbitals (dd), and the absorbance is small and the emission intensity is low. small. On the other hand, for example, divalent europium (Eu ²⁺ ) has seven electrons in the 4f orbital, and the transition to the excited level by light irradiation is an allowable transition because it is between heterogeneous orbitals (f−d), and the absorbance is It is large and has a high emission intensity.

The emission intensity of a compound changes depending on the absorbance (number of absorbed photons) of the compound. As in the case of comparing a compound in which the metal element M is manganese and a compound in which europium is used, when comparing the emission intensity between compounds having different absorbances, it is impossible to compare the emission intensities to determine the superiority or inferiority of the emission characteristics. Appropriate. The luminescence properties of compounds having different absorbances can be appropriately compared by using, for example, the luminescence intensity corrected for the difference in absorbance, that is, the quantum efficiency.

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

The phosphor used in the present invention exhibits an excitation wavelength near 450 nm in a preferred embodiment. By exciting the phosphor with an excitation wavelength of 450 nm, a green emission spectrum having an emission peak in the wavelength range of 510 nm to 550 nm can be obtained. From the viewpoint of improving the color purity of light emission, the half width of the emission peak is preferably less than 50 nm, more preferably 45 nm or less, and even more preferably 40 nm or less.

The composition ratio x of the metal element M is 0.001≤x≤0.3, for example 0.005≤x≤0.3, preferably 0.01≤x≤0.2, more preferably 0.05≤x. ≤0.15, more preferably 0.05≤x≤0.1, and particularly preferably 0.05≤x≤0.08. When x is less than 0.001, the amount of the metal element M constituting the luminescence center ion is small, and the luminescence intensity tends to decrease. Further, when x is greater than 0.3, the emission intensity tends to decrease due to an interference phenomenon between the metal elements M called concentration quenching. The composition ratio a of Mg is 0≤a≤1.0-x, for example, 0≤a≤0.95.

The Al composition ratio y is 1.2≦y≦11.3, for example 1.3≦y≦8.5, preferably 1.4≦y≦5.5, more preferably 1.5≦y≦2. .5, particularly preferably 1.5≤y≤2.3. The composition ratio z of O is 2.8≦z≦18, for example 3.0≦z≦13.0, preferably 3.3≦z≦8.5, more preferably 3.5≦z≦4.5. , particularly preferably 3.5≤z≤4.0. The composition ratio w of N satisfies 0≦w≦1.0. If the composition ratios y, z, and w are not within these ranges, the host crystal of the phosphor will have an unstable structure, and the quenching process will increase, resulting in a decrease in emission intensity.

In one embodiment, the composition ratio a of Mg is 0.1≦a≦0.98, for example 0.3≦a≦0.95, preferably 0.5≦a≦0.94, more preferably 0.5≦a≦0.94. 7≤a≤0.93, more preferably 0.8≤a≤0.93, particularly preferably 0.85≤a≤0.93, and the Al composition ratio y is 1.25≤y≤10 .3, for example 1.35≤y≤7.0, preferably 1.45≤y≤3.5, more preferably 1.65≤y≤2.4, even more preferably 1.85≤y≤2. 2. Particularly preferably, 1.95≤y≤2.1, and the O composition ratio z is 2.9≤z≤15.0, for example, 3.15≤z≤10.5, preferably 3.4. ≤z≤6.5, more preferably 3.6≤z≤4.0, still more preferably 3.7≤z≤4.0.

The upper and lower limits of the numerical values of x, a, y and z can be appropriately selected from the above range in order to obtain a desired phosphor.

The core preferably has the formula
MxMg(1-x)AlyOz (B)
[In the formula, M, x, y and z have the same meanings as defined above. ]
It contains a crystal phase of an inorganic compound having an elemental composition represented by.

The phosphor used in the present invention is sintered particles obtained by heating raw materials. The sintered particles contain a crystal phase. A crystalline phase is a solid phase in which atoms are regularly arranged. On the other hand, a phase that is not a crystalline phase is an amorphous state in which atoms are not regularly arranged. By analyzing the phosphor by X-ray structure diffraction and detecting the regular arrangement of atoms, it can be confirmed that the phosphor contains a crystalline phase.

The crystalline phase includes crystallites consisting of single crystals. Phosphors that are sintered particles are generally polycrystalline. In such a case, the crystal phase of the phosphor contains a plurality of crystallites, and the crystal phase is composed of, for example, a collection of a plurality of crystallites.

It was found that the emission intensity of the phosphor is improved by increasing the crystallite size. When increasing the size of the crystallites, the area of the interface between the crystallites decreases. As a result, the reflection and/or scattering of light at the grain boundaries of the crystallites is suppressed, and the emission intensity is considered to be improved.

The effect of improving the emission intensity of the phosphor by increasing the size of the crystallite is due to the mechanism of improving the efficiency with which the generated light exits the crystallite. This mechanism does not increase the amount of light produced by optimizing the elemental composition of the crystalline phase. Therefore, it is considered that the effects of the present invention are achieved regardless of the elemental composition of the crystal phase.

The average size of crystallites contained in the phosphor is, for example, 2 μm to 100 μm, preferably 3 μm to 80 μm, more preferably 4 μm to 50 μm, still more preferably 5 μm to 30 μm. If the average crystallite size is less than 2 μm, the improvement in luminescence intensity is insufficient, and if the average crystallite size is greater than 100 μm, it becomes difficult to use it as a raw material for members such as films and devices.

The average crystallite size can be determined by observing a cross-section of the phosphor. In other words, the size of the crystallites is determined by observing the cross section of the phosphor and analyzing the image of the crystallites observed there. The size here means an equivalent circle diameter.

First, the phosphor is processed to obtain a cross section of the phosphor. Examples of methods for obtaining a cross section of the phosphor include a method of processing with a focused ion beam (FIB) processing device, a method of processing with an ion milling device, and a method of processing by polishing. The method of processing with an FIB processing apparatus is preferable from the viewpoint of easily obtaining a highly accurate image because the processing position can be accurately determined in addition to less damage to the sample.

A cross section of the phosphor obtained by the processing is observed with an electron microscope. Examples of electron microscopes include a transmission electron microscope (TEM), a scanning electron microscope (SEM), and a scanning transmission electron microscope (STEM). Since the spatial resolution is high, the method of observing with a TEM is preferable from the viewpoint of easily obtaining a highly accurate image.

When a cross section of the phosphor obtained by the processing is irradiated with an electron beam, the degree of scattering of electrons changes depending on the arrangement of atoms, so the contrast of the acquired TEM image changes for each crystallite. In this way, each crystallite is recognized. When the contrast of the TEM image is weak, an electron diffraction (ED) pattern is acquired in order to recognize crystallites more accurately. Electron diffraction patterns represent information about the arrangement of atoms, and if the patterns are the same, it is recognized that the arrangement of atoms is the same, that is, the crystallites are the same.

The obtained TEM image is loaded into a computer, and the equivalent circle diameter of one crystallite is calculated. The equivalent circle diameter is calculated by the area-weighted average of one crystallite defined by the method described above. Note that the equivalent circle diameter refers to the diameter of a perfect circle corresponding to the area of the corresponding region. Image analysis software may be used to calculate the equivalent circle diameter. Image analysis software such as Image J and Photoshop can be selected as appropriate.

In the calculation of the average size of crystallites using this method, it is preferable to analyze 50 or more crystallites and use the average equivalent circle diameter using the average value from the viewpoint of improving accuracy.

In a preferred embodiment, the crystallites of the phosphor used in the present invention have a spinel crystal structure. A spinel-type crystal structure is a crystal structure belonging to a cubic system, and is represented by the chemical formula: AB ₂ X ₄ . The A-site in the spinel crystal structure is surrounded by four X-site anions, forming an isolated tetrahedron. The B-site in the spinel crystal structure is surrounded by six X-site anions to form an edge-sharing octahedron. It is found in oxides in which A is a divalent metal element, B is a trivalent metal element, and X is oxygen. Since the crystallites contained in the phosphor have a spinel crystal structure, they are protected from external influences such as heat, ion bombardment, and vacuum ultraviolet irradiation, and at the same time, the emission intensity of the phosphor can be enhanced.

The shell portion is preferably an oxide containing boron, more preferably containing boron oxide B ₂ O ₃ . In a preferred embodiment of the phosphor used in the present invention, the shell portion contains the metal element M.

The amount of the shell part is 30% by weight or less, preferably 0.01-20% by weight, more preferably 0.05-10% by weight, based on the core part. When the amount of the shell portion is more than 30% by weight based on the core portion, the ratio of the core portion to the total weight of the phosphor decreases, and the luminous intensity of the phosphor tends to decrease.

Since the crystal structure of the crystalline phase surface is likely to collapse, defects that do not have luminescence are formed. For example, when the metal element M constitutes the emission center ion, the metal element M on the surface of the crystal phase is thought to form defects and reduce the emission intensity. On the other hand, when the crystal phase surface is covered with the shell portion, the metal element M forming the defect portion on the crystal layer surface migrates to the shell portion, thereby reducing the defect portion of the crystal phase and increasing the emission intensity. be done.

The effect of improving the emission intensity of the phosphor by forming the shell on the surface of the crystal phase is due to the mechanism of improving the efficiency with which the generated light exits the crystallite. This mechanism does not increase the amount of light produced by optimizing the elemental composition of the crystalline phase. Therefore, it is considered that the effects of the present invention are achieved regardless of the elemental composition of the crystal phase.

The shell portion present on the surface of the crystal phase contained in the phosphor used in the present invention is analyzed by X-ray photoelectron spectroscopy (XPS) or energy dispersive X-ray spectroscopy (EDX). , by composition analysis such as inductively coupled plasma atomic emission spectroscopy (ICP-AES), by detecting boron and/or silicon constituting the shell portion.

The core-shell structure of the phosphor used in the present invention can be confirmed by performing EDX measurement on the cross section of the phosphor and obtaining an elemental mapping image. In the elemental mapping image, the region where the metal element M and boron and/or silicon coexist is the shell portion. From the results of the EDX measurement, the ratio Y/X of the peak area value Y of boron or silicon to the peak area value X of the metal element M present in the shell can be calculated. When the shell portion contains both boron and silicon, the ratio Y (B)/X or the ratio Y (Si )/X is used as the ratio Y/X.

A method for calculating the peak area value of each element from the results of EDX measurement will be described. The peak with the highest characteristic X-ray intensity in the element of interest, that is, the peak detected with the highest intensity among the peaks derived from the element of interest is selected. In the peak, the point where the peak rises is determined on each of the high energy side and the low energy side. The point at which the peak rises refers to the point at which it continues to monotonically increase toward the top of the peak. A point with a low intensity is selected from these two starting points, and the intensity at that point is set as the background, ie, 0, and the peaks are accumulated between the two points where the peak rises with reference to the background. The calculated integrated value is taken as the peak area value of the element. In particular, for manganese, two points of 5.66 keV and 6.15 keV are used as the points where the peak rises, and the point with the lowest intensity among these two points is set to 0, and the peaks are integrated between the two points. Let this integrated value be the peak area value of manganese. For boron, two points of 0.14 keV and 0.23 keV are set as points where the peak rises, and the point with the lowest intensity among these two points is set to 0, and peaks are integrated between the two points. This integrated value is taken as the boron peak area value. For silicon, two points of 1.60 keV and 1.95 keV are set as points where the peak rises, and the point with the lowest intensity among these two points is set to 0, and the peaks are integrated between the two points. This integrated value is taken as the silicon peak area value.

Y/X in the phosphor used in the present invention is, for example, 0<Y/X≤0.095, preferably 0<Y/X≤0.06, more preferably 0<Y/X≤0.05. When Y/X is 0, the metal element M on the surface of the crystal phase forms defects, and the emission intensity tends to decrease. Moreover, when Y/X is larger than 0.095, the metal element M is excessively transferred to the shell portion, so that the metal element in the core portion decreases, and the emission intensity tends to decrease.

In the phosphor used in the present invention, the metal element M forms an intermediate with the element forming the shell when the raw material of the shell is liquefied. Therefore, the metal element M exists in the shell portion of the core-shell structure, and X does not become zero. That is, in the phosphor used in the present invention, the metal element M is never detected from the shell portion. Y/X=0 is defined when both boron and silicon are not detected.

For EDX measurement, a suitable measurement method can be selected according to the thickness of the sample to be measured. Examples of measurement methods include SEM-EDX, TEM-EDX, and STEM-EDX. In order to accurately detect boron by EDX measurement, it is preferable to use windowless EDX.

From the viewpoint of high spatial resolution and being able to observe the cross section of many phosphors at once, the phosphor is processed with an ion milling device to obtain a cross section of the phosphor, and then the cross section of the obtained phosphor is subjected to SEM. - A method of EDX measurement is preferred. In calculating Y/X using this method, it is preferable to analyze 20 or more shell portions and use the average value from the viewpoint of improving accuracy. Moreover, from the viewpoint of improving the shape of the spectrum, it is preferable to set the acceleration voltage of the SEM to 20 kV.

The phosphor used in the present invention has a median particle size of the particle size distribution, that is, D50, is usually 0.1 μm or more, may be 1 to 500 μm, may be 1 to 200 μm, may be 1 to 100 μm may be When the D50 of the particle size distribution is less than 0.1 μm, the emission intensity tends to decrease due to an increase in reflection on the outermost surface of the phosphor, and when the D50 of the particle size distribution is greater than 500 μm, the film And it becomes difficult to use it as a raw material for members such as elements.

The particle size distribution of the phosphor can be measured by, for example, a laser diffraction particle size analyzer. The D50 of the particle size distribution is the particle size corresponding to 50% of the cumulative under-sieve distribution on a volume basis.

<Silane coupling agent>
The phosphor used in the present invention has a modified silane coupling agent containing no halogen atoms on the surface of the shell. A silane coupling agent is an organosilicon compound having a functional group that reacts and bonds with an organic material and a functional group that reacts and bonds with an inorganic material in its molecule. The silane coupling agent reacts with hydroxyl groups and the like present on the surface of the shell portion at the stage of mixing the phosphor and the silane coupling agent, bonds with them, and is modified. As a result, the phosphor surface is modified by the modified silane coupling agent. Some silane coupling agents exist as modifiers in which functional groups are siloxane-bonded on the surface of the shell portion, and others exist as unreacted compounds. The term "silane coupling agent" as used herein includes modified silane coupling agents.

As used herein, the term “modified silane coupling agent” refers to Si—O—Si bonds generated by hydrolysis of the silane coupling agent, or Si—O— bonded to boron oxide on the surface of the phosphor. A silicon compound having a B bond. The modified silane coupling agent can be prepared by known methods such as a method of irradiating the silane coupling agent with ultraviolet rays and a method of reacting the silane coupling agent with water vapor.

By modifying the surface of the phosphor shell with a modified silane coupling agent that has a high affinity with the resin, the compatibility with the matrix resin is improved, and the dispersibility of the phosphor in the matrix resin is improved. do. As a result, the number of voids in the resin composition is reduced, the absorptivity of light at 630 nm is lowered, and the effect of improving the emission intensity is obtained. In addition, since the modified silane coupling agent does not contain halogen atoms, the adhesiveness between the resin, the phosphor, and the phosphor shell portion is improved, and voids in the resin composition are reduced.

(Silane compound)
Specific examples of the silane coupling agent used in the present invention include the formula

[In the formula,
R ¹ is a saturated or unsaturated hydrocarbon group which may have a substituent,
R ² is a hydrogen atom or a saturated or unsaturated hydrocarbon group which may have a substituent,
a is an integer from 1 to 3; ]
A silane compound represented by is mentioned.

Commercially available silane compounds are, for example, those in which the hydrocarbon group has 1 to 20 carbon atoms. Substituents of the hydrocarbon group can be appropriately changed in consideration of the polarity of the bonding target and the like. Generally, it is appropriately selected from a (meth)acryloyloxy group, an amino group, an alkylamino group having 1 to 20 carbon atoms, a mercapto group, and the like. Specific examples of alkylamino groups having 1 to 20 carbon atoms include methylamino, ethylamino, propylamino and butylamino groups.

In one embodiment, the saturated or unsaturated hydrocarbon group is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group , 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group , hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl groups.

Preferred alkyl groups are those having 1 to 12 carbon atoms, more preferably 8 to 12 carbon atoms.

In one embodiment, the saturated or unsaturated hydrocarbon group is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, -adamantyl group, 2-adamantyl group, tricyclodecyl group and other cycloalkyl groups.

Among the preferred cycloalkyl groups are those having 4 to 6 carbon atoms, more preferably 6 carbon atoms.

In one embodiment, the saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms includes unsaturated alkyl groups such as vinyl groups and allyl groups.

In one aspect, the saturated or unsaturated hydrocarbon group includes an aryl group such as a phenyl group, a benzyl group, a tolyl group and an o-xylyl group.

In a preferred embodiment, R ¹ contains an alkyl group having 8 to 12 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, or a vinyl group.

Specific examples of the silane compound used in the present invention include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxyphenylsilane, ethoxytriethylsilane, methoxytrimethylsilane, methoxydimethyl(phenyl)silane, and pentafluoro. Phenylethoxydimethylsilane, trimethylethoxysilane, diethoxydimethylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, dimethoxymethylvinylsilane, diethoxy(methyl)phenylsilane, allyltriethoxysilane, allyltri methoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, triethoxyethylsilane, decyltrimethoxysilane, ethyltrimethoxysilane, hexyltriethoxysilane, hexyltrimethoxysilane, hexadecyltrimethoxysilane, trimethoxy(methyl)silane, triethoxymethylsilane, n-octyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, (3-mercaptopropyl)triethoxysilane and vinyltrimethoxysilane.

Preferred silane compounds among these are dimethoxydiphenylsilane, dodecyltrimethoxysilane, trimethoxyphenylsilane, n-octyltriethoxysilane, and vinyltrimethoxysilane, and more preferred are dodecyltrimethoxysilane, vinyltrimethoxysilane, trimethoxyphenylsilane, more preferably trimethoxyphenylsilane. By using such a silane compound, the compatibility of the phosphor with the resin is likely to be improved, and effects such as reduction of light absorption in the visible range by the resin composition containing the phosphor are likely to be obtained.

(silazane compound)
Another example of the silane coupling agent used in the present invention is a silazane compound having a Si—N—Si bond. The silazane compound may be linear, branched, or cyclic. The silazane compound may be a low-molecular-weight silazane or a high-molecular-weight silazane.

The type of silazane compound is not particularly limited as long as it is a type commonly used for modifying the surface of inorganic substances such as phosphors. Specific examples of such silazane compounds are described, for example, in paragraphs 0148 to 0197 of JP-A-2020-66725, and the description of this part is incorporated herein by reference. However, for the same reason as the silane compound, the silazane compound is also halogen-free.

Specific examples of the low-molecular-weight silazane compound used in the present invention include 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,1,1,3 ,3,3-hexamethyldisilazane octamethylcyclotetrasilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclo and trisilazane.

As the polymer silazane compound, commercially available products may be used, such as NN120-10, NN120-20, NAX120-20, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (manufactured by AZ Electronic Materials Co., Ltd.). and AZNN-120-20, Durazane (registered trademark) 1500 Slow Cure, Durazane 1500 Rapid Cure, Durazane 1800, and Durazane 1033 (manufactured by Merck Performance Materials Co., Ltd.).

<Raw material of phosphor>
As a raw material for producing the phosphor used in the present invention, a compound or simple substance containing at least a metal element or aluminum constituting the luminescence center ion is used as a raw material for the crystalline phase. In one embodiment, a compound or simple substance containing M element, Al, Mg, oxygen or nitrogen is used as the raw material of the crystal phase. Such raw material compounds include oxides, hydroxides, carbonates, acetates, nitrates, fluorides, chlorides or nitrides containing element M, Al or Mg. For example, raw material compounds containing the M element include manganese oxide, manganese carbonate, manganese acetate, manganese nitrate, manganese fluoride, manganese chloride, and manganese nitride; raw material compounds containing Mg include magnesium oxide, magnesium hydroxide, magnesium carbonate, and acetic acid. magnesium, magnesium nitrate, magnesium fluoride, magnesium chloride, magnesium nitride; mentioned.

The raw material compound containing aluminum is not particularly limited, but from the viewpoint of increasing the crystallite size of the phosphor, the specific surface area should be 0.01 to 15 m ² /g, preferably 0.1 to 10 m ² /g, or more. Preferably 0.6 to 6 m ² /g, more preferably 4 to 6 m ² /g is used.

The specific surface area of the raw material compound containing aluminum can be measured 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 addition, from the viewpoint of increasing the crystallite size of the phosphor, the raw material compound containing aluminum has a particle size distribution D50 of 0.2 μm to 90 μm, preferably 0.2 to 21 μm, more preferably 0.2 to 10 μm. More preferably, it is 0.2 to 1 μm.

When the phosphor used in the present invention has a core-shell structure having a core portion made of a crystalline phase and a shell portion covering at least a portion of the surface of the core portion, the raw material for the shell portion is the group consisting of boron and silicon. A compound containing at least one element selected from can be used. During heating, the crystallite size of the phosphor is increased by using the raw material of the crystalline phase and the raw material of the shell portion. Examples of raw materials for the shell include boron oxide, boron nitride, boric acid, and glass frit.

Glass frit is powdered glass obtained by pulverizing glass. The main component is silicon dioxide, but it may contain aluminum oxide, bismuth oxide, calcium oxide, boron oxide, barium oxide, strontium oxide, calcium oxide, sodium oxide, zinc oxide, lithium oxide, potassium oxide, zirconium oxide, and the like.

When producing the phosphor used in the present invention, lithium fluoride may be added as a raw material other than the raw material compounds described above from the viewpoint of improving crystallinity.

<Manufacturing method of phosphor>
The phosphor used in the present invention can be produced, for example, by the following method. That is, first, raw materials for the crystalline phase are weighed and mixed so that the M element, Mg, Al, O and N have a predetermined molar ratio defined by the formula (A) or (B). At this time, the raw material for the shell portion may be weighed in a predetermined ratio with respect to the total amount and mixed with the raw material for the crystal phase. Mixing can be performed using a mixing device such as a ball mill, sand mill, pico mill, or the like.

Next, the prepared raw material mixture is heated. The heating is carried out at a temperature at which the raw material of the shell portion is liquefied but the host crystals of the resulting phosphor can be maintained. For example, when the heating temperature is 1700° C. or less, the desired crystal structure can be obtained without the host crystal of the phosphor collapsing. The heating temperature is, for example, 1250 to 1700°C, preferably 1300 to 1650°C, more preferably 1350 to 1600°C, still more preferably 1400 to 1600°C. In the production method of the present invention, the host crystal is a crystal having the crystal structure of the core portion of the resulting phosphor.

The heating atmosphere is preferably a mixed atmosphere of hydrogen and nitrogen. The mixed atmosphere used for the heating 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.

As for the heating time, there is no problem as long as it is an industrially realistic time. For example, when the heating temperature is within the above range, it is 1 to 10 hours, preferably 2 to 8 hours. By setting the heating time within this range, a desired crystal structure can be obtained without collapsing the host crystal of the phosphor. The phosphor used in 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.

Next, the obtained phosphor having a core-shell structure is surface-treated with a silane coupling agent.

The phosphor surface treatment is performed by mixing phosphor particles with a silane coupling agent. The atmosphere at the time of mixing may be air or an inert atmosphere such as nitrogen, but the reaction in air is preferable from the viewpoint of promoting the surface treatment by reacting with oxygen and moisture in the air. From the viewpoint of allowing the phosphor particles to react with the silane coupling agent and promoting the surface treatment, water or water vapor may be added after the phosphor particles and the silane coupling agent are mixed. Mixing of the phosphor and the silane coupling agent may be performed in the presence of a coexistent solvent. The amount of the silane coupling agent used is 0.1-50% by weight, preferably 1-30% by weight, more preferably 5-20% by weight, based on the phosphor.

<Composition>
The phosphor surface-treated with a silane coupling agent used in the present invention can be used as a composition by dispersing it in a resin, a monomer, or a mixture of a monomer and a resin. Hereinafter, the term "phosphor" means a phosphor surface-treated with a silane coupling agent. When the phosphor is dispersed in a resin, the phosphor forms the domains and the resin forms the matrix in the composition. Such compositions are referred to herein as resin compositions.

The concentration of phosphor in the composition varies depending on the use of the composition. Generally, the concentration of phosphor in the composition is 5-90%, preferably 15-85%, more preferably 25-70% by weight based on the composition. If the concentration of the phosphor in the composition is too low, the emission intensity of the composition tends to be insufficient.

Acrylic resins, styrene resins, epoxy resins, urethane resins, silicone resins, and the like can be used as the resin. Among them, acrylic resins and silicone resins are preferable, and acrylic resins are more preferable, from the viewpoint of improving the emission intensity and suppressing the absorption of light of 630 nm.

Examples of silicone resins 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. From the viewpoint of improving strength, addition-polymerizable silicone is preferred.

As the silicone resin, those in which an organic group is bonded to the Si element in silicone are preferable, and examples thereof include functional groups such as alkyl groups such as methyl group, ethyl group and propyl group, phenyl group and epoxy group. 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.

Acrylic resins are, for example, homopolymers or copolymers of two or more of (meth)acrylic monomers such as (meth)acrylic acid esters and (meth)acrylonitrile, or copolymers of acrylic monomers and other monomers. A polymer etc. are mentioned. In this specification, the term "(meth)acryl" means "acryl" or "methacryl".

(Meth)acrylic resin is a polymer obtained by polymerizing a monomer mainly composed of (meth)acrylic acid ester (alkyl (meth)acrylate). Copolymers of (polyalkyl methacrylate) and (meth)acrylic esters, copolymers of 50% by weight or more of (meth)acrylic esters and 50% by weight or less of monomers other than (meth)acrylic esters Amalgamation etc. are mentioned. In the case of a copolymer of a (meth)acrylic acid ester and a monomer other than the (meth)acrylic acid ester, the (meth)acrylic acid ester is preferably 70% by weight or more based on the total amount of the monomers, and the other The content of monomers is 30% by weight or less, and more preferably 90% by weight or more of (meth)acrylic acid ester and 10% by weight or less of other monomers.

Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n (meth)acrylate. -butyl, isobutyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate , isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid benzyl, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, 2-naphthyl (meth)acrylate, phenoxymethyl (meth)acrylate, etc. mentioned. Among these, alkyl (meth)acrylates having 1 to 8 carbon atoms in the alkyl group portion are preferred, and methyl (meth)acrylate is more preferred.

Monomers other than (meth)acrylate include acrylic ester (alkyl acrylate) monomers, aromatic vinyl monomers, unsaturated nitrile monomers, ethylenically unsaturated ether monomers, halogen vinyl chloride-based monomers, aliphatic conjugated diene-based monomers, etc., among which acrylic acid esters are preferably used. Monomers other than the (meth)acrylic acid ester may be used alone, or two or more of them may be used in combination.

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, o-chlorostyrene, p-chlorostyrene, p- methoxystyrene, p-acetoxystyrene, α-vinylnaphthalene, 2-vinylfluorene and the like. Among these, styrene is more preferable.

Examples of unsaturated nitrile monomers include acrylonitrile, α-chloroacrylonitrile, α-methoxyacrylonitrile, methacrylonitrile, vinylidene cyanide and the like.

Ethylenically unsaturated ether monomers include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether, ethyl allyl ether and the like.

Examples of vinyl halide monomers include vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl bromide, vinylidene bromide, 1,2-dibromoethylene and the like.

Aliphatic conjugated diene-based monomers include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene , 2-chloro-1,3-butadiene, 1,2-dichloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2-bromo-1,3-butadiene, 2-cyano-1, 3-butadiene, substituted linear conjugated pentadienes, linear and side chain conjugated hexadienes, and the like.

The acrylic resin is obtained by subjecting the above-described monomers to polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and injection polymerization (cast polymerization). Polymerization is carried out using light irradiation or a polymerization initiator, and azo initiators (e.g., 2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc. ), peroxide-based initiators (lauroyl peroxide, benzoyl peroxide, etc.), and redox-based initiators combining organic peroxides and amines. The polymerization initiator is usually used in a proportion of 0.01 to 1 part by mass, preferably 0.01 to 0.5 part by mass, per 100 parts by mass of monomers constituting the acrylic resin. Furthermore, a chain transfer agent (linear or branched alkyl mercaptan compounds such as methyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, etc.), a cross-linking agent, etc. may be added for molecular weight control.

The acrylic resin preferably has a viscosity average molecular weight of 50,000 to 300,000, more preferably 70,000 to 2,000,000.

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.

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 name) OXE01, OXE02, OXE03 (manufactured by BASF), N-1919, NCI-930, NCI-831 (manufactured by ADEKA) may 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- (4-isopropenylphenyl)propan-1-one oligomers, α,α-diethoxyacetophenone, benzyl dimethyl ketal and the like.

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 (eg, trade name “omnirad 819” (manufactured by IGM Resins B.V.)), 2,4,6-trimethylbenzoyl diphenylphosphine oxide and the like. 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 antioxidants, sulfur antioxidants, phenol antioxidants and phosphorus antioxidants, more preferably sulfur antioxidants, phenol at least one selected from the group consisting of antioxidants and phosphorus antioxidants.

An amine antioxidant is an antioxidant having an amino group in its molecule. Amine antioxidants include, for example, 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, phenyl-2 - naphthylamine-based 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-te rt-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 “Sumilizer 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′-ethylidenebis ( 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 , tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylenediphosphonite, tri-2-ethylhexylphosphite, triisodecylphosphite, tristearylphosphite, phenyl diisodecylphosphite, 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, Co., Ltd. ) ADEKA), “ADEKA STAB PEP36” (trade name, manufactured by ADEKA Co., Ltd.), “ADEKA STAB PEP-8” (trade name, manufactured by ADEKA Co., Ltd.), “Sandstab P-EPQ” (trade name, manufactured by Clariant ), “Weston 618” (trade name, manufactured by GE) , “Weston 619G” (trade name, manufactured by GE), “Ultranox 626” (trade name, manufactured by GE), and the like.

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, the aluminum oxide contained in the inorganic fine particles includes 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 preferred.

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. Examples include known oxides such as indium oxide and gallium hydroxide, and mixtures thereof, 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, preferably aluminum sulfide, zinc sulfide, and niobium sulfide, more preferably zinc sulfide and niobium sulfide, most preferably niobium sulfide. 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, with aluminum nitride, zinc nitride, and niobium nitride being preferred, aluminum nitride and niobium nitride being more preferred, and niobium nitride being most preferred; 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. , known sulfides such as tungsten carbide, indium carbide, and gallium carbide, or mixtures thereof, preferably aluminum carbide, zinc carbide, and niobium carbide, more preferably aluminum carbide and niobium carbide, and 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 and niobium chloride, more preferably aluminum chloride and 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; and 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; 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 used in 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 used in the present invention contained in the composition include phosphors other than the phosphor used in 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, for example, II-VI group semiconductor compounds; III-V group semiconductor compounds; IV - 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.

II-VI semiconductor compounds are binary compounds 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, 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 used in the present invention contained in the composition is not particularly limited, but examples include sulfide phosphors, oxide phosphors, nitride phosphors, and 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 , etc.

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 used in 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 used in 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. and more preferably 5 wt % or more and 60 wt % or less.

<Hansen Solubility Parameter>
The Hansen Solubility Parameter (HSP) is based on the idea that two substances with similar intermolecular interactions are more likely to dissolve in each other. HSP consists of the following three parameters.

δd: Energy due to intermolecular dispersion force δp: Energy due to intermolecular dipole interaction δh: Energy due to intermolecular hydrogen bonding

These three parameters can be regarded as coordinates in a three-dimensional space (Hansen space). And when the HSPs of two substances are placed in the Hansen space, the closer the distance between the two points, the easier it is to dissolve each other.

The distance between the two points of the Hansen solubility parameter between the silane coupling agent and the matrix resin is calculated using Hansen solubility parameter software (HSPiP ver5.3.05, Charles M. Hansen, Y-MB method). After calculating the energy δd derived from the force, the energy δp derived from the intermolecular polar force, and the energy δh derived from the intermolecular hydrogen bonding force, it can be calculated by applying the following formula (D). .

The distance between two points of the Hansen solubility parameter between the silane coupling agent and the matrix resin is
(δd of matrix resin-δd of silane coupling agent) ² ,
(δp of matrix resin-δp of silane coupling agent) ² ;
(δh of the matrix resin-δh of the silane coupling agent) ² ,
is the square root of the sum (D).

The distance between the two points of the Hansen solubility parameter between the silane coupling agent and the matrix resin is preferably less than 7.06 from the viewpoint of improving the emission intensity of the composition of the present invention and reducing the absorptance of light at 630 nm. , is more preferably 6.00 or less, more preferably 0 to 4.97, and most preferably 3.24 to 4.97.

When the distance between the two points of the Hansen solubility parameter between the silane coupling agent and the matrix resin is within the above range, the compatibility of the phosphor with the resin is easily improved, and the visible range of the resin composition containing the phosphor is improved. Effects such as reduction in light absorption can be easily obtained.

<Film>
The composition of the invention can be used in film form. 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.

The composition of the present invention may be formed into a film on a substrate to form a laminate. The substrate may be a resin substrate such as PET or PEN, or may be a metal substrate such as aluminum foil.

<Light emitting element>
The composition of the present invention can constitute a light-emitting device in combination 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 comprising the composition of the present invention and a light source can be used in displays. 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.

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

<Production Example 1>
(Production of phosphor having core-shell structure)
Aluminum oxide powder (grade: AA18 (purity: 99.99%, D50: 20.3 μm, specific surface area: 0.2 m ² /g), manufactured by Sumitomo Chemical Co., Ltd.), magnesium oxide as raw materials for the crystal phase of the phosphor Using powder (MgO (purity: 4N), manufactured by Kanto Chemical Co., Ltd.) and manganese carbonate powder ( _MnCO (purity: 99.9%), manufactured by Sigma-Aldrich Japan LLC), the carbonic acid of the carbonate is converted to carbon dioxide after firing. (CO ₂ ), each raw material is weighed so that the composition after firing has a molar ratio of Mn:Mg:Al:O = 0.07:0.93:2:4. Next, boron oxide (B ₂ O ₃ (purity: 99.995%), manufactured by Kojundo Chemical Laboratory Co., Ltd.) was weighed so as to be 1% by weight of the total weight of the raw materials, and added to the raw materials. dry mixed for 3 minutes. The mixture was then filled into containers. Subsequently, the container was set in an electric furnace, and a mixed gas of hydrogen:nitrogen=10:90 was introduced. The electric furnace was heated to 1550° C., heated for 4 hours, and then allowed to cool. The heated product was collected from the container and pulverized to obtain a powdery phosphor.

(Confirmation of core-shell structure of phosphor)
The resulting phosphor powder, an epoxy resin obtained by mixing a main agent (“EpoxiCure 2 Resin” (trade name) manufactured by Buehler) and a curing agent (“EpoxiCure 2 Hardener” (trade name) manufactured by Buehler) at a ratio of 4:1. were mixed at a weight ratio of 1:10 and dried in the atmosphere for one day to obtain a molded body. The obtained molded body was processed with an ion milling device ("IM4000" (trade name) manufactured by Hitachi High-Tech Co., Ltd.) to obtain a cross section of the phosphor. Using a scanning electron microscope (SEM) ("S-4800" (trade name) manufactured by Hitachi High-Tech Co., Ltd.), the cross section of the obtained phosphor was observed at an acceleration voltage of 20 kV. Elemental mapping images were obtained by windowless EDX ("X-max 80" (trade name) manufactured by Oxford Instruments Co., Ltd.) by appropriately adjusting the field of view and magnification. From the elemental mapping image obtained by the above technique, it was confirmed that the phosphor had a core portion composed of a crystal phase and a shell portion in which boron was present.

<Production Example 2>
(Production of Phosphor Not Having Core-Shell Structure)
A phosphor having no core-shell structure was obtained in the same manner as in Production Example 1, except that boron oxide was not used as a raw material for the crystal phase.

<Measurement of Emission Intensity of Phosphor of Production Example>
Emission intensities of the phosphors of Production Examples 1 and 2 were measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics, “C9920-02” (trade name)). The measurement conditions were a powder sample of 150 mg, an excitation wavelength of 450 nm, room temperature, and the atmosphere.

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. The phosphor was confirmed to be a green-emitting phosphor 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 Production Example 2 was converted to 100 to calculate the relative emission intensity of Production Example 1. Table 1 shows the results.

<Example 1>

A methacrylic resin (“Sumipex” (trade name) manufactured by Sumitomo Chemical Co., Ltd., grade: MH, molecular weight of about 120,000, specific gravity of 1.2 g/ml) was mixed with toluene in an amount to give a concentration of 20% by mass, and heated at 60°C for 3 hours. After heating for hours, a resin solution was obtained.

After 0.5 g of the phosphor obtained in Production Example 1 and 0.05 g of vinyltrimethoxysilane as a silane coupling agent were mixed, 2 g of the resin solution was added and mixed uniformly. After that, the toluene was air-dried to obtain a resin composition having a phosphor concentration of 52.6% by weight. A resin composition containing a phosphor was molded into a plate-like body having a length of 2 cm, a width of 2 cm, and a width of 300 μm to prepare a measurement sample.

<Example 2>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 1, except that trimethoxyphenylsilane was used instead of vinyltrimethoxysilane.

<Example 3>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 1, except that dodecyltrimethoxysilane was used instead of vinyltrimethoxysilane.

<Comparative Example 1>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 1, except that trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane was used instead of vinyltrimethoxysilane. bottom.

<Comparative Example 2>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 1, except that vinyltrimethoxysilane was not used.

<Reference example 1>
A phosphor-containing resin composition and a sample for measurement were prepared in the same manner as in Example 1, except that boron oxide was not used as a raw material for the crystal phase.

<Reference example 2>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 1, except that neither boron oxide nor vinyltrimethoxysilane was used as the starting material for the crystal phase.

<Distance between two points of Hansen solubility parameter>
According to the method described in the specification, the distance of the Hansen solubility parameter was calculated between the methacrylic resin and the silane coupling agent used in Examples and Comparative Examples. Table 2 shows the results.

<Measurement of luminescence intensity of resin compositions of Examples and Comparative Examples>
Emission intensities of the resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were measured using a spectrofluorophotometer (“FP-6500” (trade name) manufactured by JASCO Corporation). The measurement conditions were set with the main surface of the measurement sample facing the light source, an excitation wavelength of 450 nm, room temperature, and the atmosphere.

The emission intensity of green emission was in the range of 485 to 627 nm, and the emission intensity value of the emission peak with the strongest emission 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 2 was converted to 100 to calculate the relative emission intensity of Examples 1 to 3 and Comparative Example 1. The evaluation criteria for the relative emission intensity were as follows.

A: 150 or more (good)
B: 116 or more (acceptable)
C: 115 or less (impossible)

<Measurement of Visible Light Absorbance of Resin Compositions of Examples and Comparative Examples>
Visible light absorption of the resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 was measured using an ultraviolet-visible-near-infrared spectrophotometer (“V-670” (trade name, integrating sphere unit) manufactured by JASCO Corporation). That is, the main surface of the measurement sample was placed facing the light source, and the reflectance (%R) of light at 630 nm was measured at an irradiation wavelength of 630 nm, at room temperature, in the atmosphere, in a reflection spectrum measurement mode.

The absorptivity was calculated using the following formula using the reflectance (%R) value measured above.
630 nm light absorption = 100 - 630 nm light reflectance (%R)

The absorbance of 630 nm light of Comparative Example 2 was converted to 100, and the relative absorbances of Examples 1 to 3 and Comparative Example 1 were calculated. The evaluation criteria for the relative absorbance were as follows.

A: less than 48 (good)
B: less than 100 (acceptable)
C: 100 or more (impossible)

<Evaluation of Resin Composition of Reference Example>
In the same manner as described above, the Hansen solubility parameter distance between the methacrylic resin used in Reference Example and the silane coupling agent was calculated, and the emission intensity and visible light absorptance were measured. Table 3 shows the results.

<Example 4>
After mixing 0.5 g of the phosphor obtained in Production Example 1 and 0.05 g of dodecyltrimethoxysilane as a silane coupling agent, 1 g of silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd. "KE-109E-A" (trade name): 0.5 g and the same "KE-109E-B" (trade name): 0.5 g) were added and mixed uniformly. By reacting the mixture at 100° C. for 1 hour, a resin composition having a phosphor concentration of 32.3% by weight was obtained. A resin composition containing a phosphor was molded into a plate-like body having a length of 2 cm, a width of 2 cm, and a width of 300 μm to prepare a measurement sample.

<Example 5>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 4, except that trimethoxyphenylsilane was used instead of dodecyltrimethoxysilane.
<Comparative Example 3>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 4, except that trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane was used instead of dodecyltrimethoxysilane. .

<Comparative Example 4>
A phosphor-containing resin composition and a measurement sample were prepared in the same manner as in Example 4, except that dodecyltrimethoxysilane was not used.

<Measurement of luminescence intensity of resin compositions of Examples and Comparative Examples>
Emission intensities of the resin compositions of Examples 4 and 5 and Comparative Examples 3 and 4 were measured using a spectrofluorophotometer (“FP-6500” (trade name) manufactured by JASCO Corporation). The measurement conditions were set with the main surface of the measurement sample facing the light source, with an excitation wavelength of 450 nm, at room temperature, and in the atmosphere.

The emission intensity of green emission was in the range of 485 to 627 nm, and the emission intensity value of the emission peak with the strongest emission 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 4 was converted to 100 to calculate the relative emission intensity of Examples 4 and 5 and Comparative Example 3. The evaluation criteria for the relative emission intensity were as follows.

A: 150 or more (good)
B: 101 or more (acceptable)
C: 100 or less (impossible)

<Measurement of Visible Light Absorbance of Resin Compositions of Examples and Comparative Examples>
Visible light absorption of the resin compositions of Examples 4 and 5 and Comparative Examples 3 and 4 was measured using an ultraviolet-visible-near-infrared spectrophotometer (“V-670” (trade name, integrating sphere unit) manufactured by JASCO Corporation). That is, the main surface of the measurement sample was placed facing the light source, and the reflectance (%R) of light at 630 nm was measured at an irradiation wavelength of 630 nm, at room temperature, in the atmosphere, in a reflection spectrum measurement mode.

The absorptivity was calculated using the following formula using the reflectance (%R) value measured above.
630 nm light absorption = 100 - 630 nm light reflectance (%R)

The relative absorbance of Examples 4 and 5 and Comparative Example 3 was calculated by converting the absorbance of 630 nm light of Comparative Example 4 to 100. The evaluation criteria for the relative absorbance were as follows.

A: less than 90 (good)
B: less than 100 (acceptable)
C: 100 or more (impossible)

Claims (12)

formula
MxMgaAlyOzNw (A)
[In formula (A), M represents at least one metal element selected from the group consisting of manganese, strontium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, thulium and ytterbium, and x represents 0.001≦x≦0.3, a is 0≦a≦1.0−x, y is 1.2≦y≦11.3, and z is 2.8≦z≦18 Yes, and w is 0≤w≤1.0. ]
A core portion made of a crystal phase of an inorganic compound having an elemental composition represented by
A phosphor having a core-shell structure, comprising a shell portion formed on at least a portion of the surface of the core portion and containing at least one element selected from the group consisting of boron and silicon;
a modified silane coupling agent containing no halogen atoms present on the surface of the shell portion; and a matrix resin;
A resin composition comprising: The silane coupling agent has the formula

[In the formula,
R ¹ is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a (meth)acryloyloxy group, an amino group, an alkylamino group having 1 to 20 carbon atoms or a mercapto group; ,
R ² is a hydrogen atom or a saturated or unsaturated C 1-20 optionally substituted by a (meth)acryloyloxy group, an amino group, an alkylamino group having 1 to 20 carbons or a mercapto group. is a hydrocarbon group,
R ¹ or R ² may be different groups when there are more than one,
a is an integer from 1 to 3; ]
The resin composition according to claim 1, which is a compound represented by: 3. The resin composition according to claim 1, wherein the distance in Hansen solubility parameters between the silane coupling agent and the matrix resin is less than 7.06. 4. The resin composition according to any one of claims 1 to 3, wherein the matrix resin is a silicone resin or an acrylic resin. 5. The resin composition according to any one of claims 2 to 4, wherein R ¹ comprises an alkyl group having 8 to 12 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms or a vinyl group. The resin composition according to any one of claims 1 to 5, wherein said M represents at least one metal element selected from the group consisting of manganese, strontium, europium and terbium. x is 0.05≤x≤0.15, a is 0≤a≤0.95, y is 1.5≤y≤2.5, and z is 3.5≤z≤4 .5 and w satisfies 0≦w≦1.0. The resin composition according to any one of claims 1 to 7, wherein the crystal phase contains crystallites, and the crystallites have a spinel-type crystal structure. A film comprising the resin composition according to any one of claims 1 to 8. A light emitting device comprising the resin composition according to any one of claims 1 to 8. A light-emitting device comprising the light-emitting element according to claim 10 . A display comprising the light emitting device according to claim 10 .