TWI841690B - Compound, composition, film, laminated structure, light-emitting device, display and method for producing the compound - Google Patents

Abstract

The present invention is a (1) compound having a calcite-type crystal structure, wherein in an X-ray diffraction pattern, the half-value width of the peak of the Miller index (001) of the plane is greater than 0.10 and less than 0.60, and the compound has A as a monovalent cation, B as a metal ion, and X as at least one anion selected from the group consisting of halide ions and thiocyanate ions as constituent components.

Description

Compound, composition, film, laminated structure, light-emitting device, display and method for producing the compound

The present invention relates to a compound, a composition, a film, a laminate structure, a light-emitting device, a display and a method for producing the compound.

As a luminescent material, luminescent semiconductor compounds have attracted attention. In order to produce a luminescent material with higher color purity, as a luminescent semiconductor compound, it is required that the half-value width of the luminescent spectrum is narrower so as to form a steep luminescent peak. [Prior art literature] [Non-patent literature]

[Non-patent document 1] Advanced Materials 2016, 28, p.10088-10094

[The problem the invention is trying to solve]

As the above-mentioned semiconductor compound with light-emitting property, for example, a compound having a calcite-type crystal structure has been reported (Non-patent Document 1). However, the half-value width of the light-emitting spectrum of the compound having a calcite-type crystal structure described in Non-patent Document 1 is relatively wide, and it is not expected that the color purity will be improved.

The present invention was completed in view of the above-mentioned subject, and its purpose is to provide a compound having a calcite-type crystal structure with a narrow half-value width of the luminescence spectrum, a composition containing the above-mentioned compound, a film formed by the above-mentioned composition, a multilayer structure containing the above-mentioned film, a light-emitting device having the above-mentioned multilayer structure, a display and a method for manufacturing the compound. [Technical means for solving the problem]

In order to solve the above problems, the inventors and others conducted intensive research and completed the following invention.

The present invention includes the following [1] to [10]. [1] A compound having a tantalum-type crystal structure, wherein in an X-ray diffraction pattern, the half-value width of the peak of the Miller index (001) of the plane is greater than 0.10 and less than 0.60, and the compound has A, B and X as constituent components; (A is a component located at each vertex of a hexahedron with B as the center in the tantalum-type crystal structure, and is a monovalent cation; X is a component located at each vertex of an octahedron with B as the center in the tantalum-type crystal structure, and is at least one anion selected from the group consisting of halide ions and thiocyanate ions; B is a component located at the center of a hexahedron with A as the vertex and an octahedron with X as the vertex in a calcite-type crystal structure, and is a metal ion). [2] A composition comprising the compound of technical solution 1 and at least one compound selected from the group consisting of the following (2-1), the modified product of the following (2-1), the following (2-2), and the modified product of the following (2-2); (2-1) Silazane (2-2) A silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group, and an alkylthio group. [3] A composition comprising the compound of [1] and at least one selected from the group consisting of the following (3), the following (4), and the following (5); (3) Solvent (4) Polymerizable compound (5) Polymer. [4] A composition as described in [2], further comprising at least one selected from the group consisting of the following (3), the following (4) and the following (5); (3) a solvent (4) a polymerizable compound (5) a polymer. [5] A film comprising the compound as described in [1]. [6] A film formed from a composition as described in any one of [2] to [4]. [7] A layered structure comprising a film as described in [5] or [6]. [8] A light-emitting device having the layered structure as described in [7]. [9] A display having the layered structure as described in [7]. [10] A method for producing a semiconductor compound, comprising: mixing raw materials of either or both of a simple substance containing a metal element M and a compound containing a metal element M with water, and reacting the raw materials in the presence of the water, wherein the ratio of the mass W _W of the water to the mass W _M of the metal element M contained in the raw materials, i.e. (W _W /W _M ), is 0.05 to 100, and the half-value width of the peak of the Miller index (001) of the surface in the X-ray diffraction pattern is greater than 0.10 and less than 0.60. [Effects of the Invention]

According to the present invention, a compound having a narrow half-value width of a luminescence spectrum and a tantalum-type crystal structure, a composition containing the above compound, a film formed of the above composition, a multilayer structure containing the above film, a light-emitting device and a display having the above multilayer structure can be provided. In addition, according to the present invention, a method for producing a compound having a narrow half-value width of a luminescence spectrum can be provided.

The present invention is described in detail below with reference to the embodiments.

<Compounds having a calcite-type crystal structure> The compound of the present embodiment is a compound having a calcite-type crystal structure having A, B and X as constituent components (hereinafter also referred to as "(1) calcite-type compound" or simply "(1)"). A is a component located at each vertex of a hexahedron with B as the center in the calcite-type crystal structure, and is a monovalent cation. B is a component located at the center of a hexahedron with A as the vertex and an octahedron with X as the vertex in the calcite-type crystal structure, and is a metal ion. B is a metal cation that can be coordinated with the octahedron of X. X is a component at each vertex of an octahedron centered at B in a calcite-type crystal structure, and is at least one anion selected from the group consisting of halide ions and thiocyanate ions.

The structure of the calcium-titanium compound having A, B and X as constituent components may be any of a three-dimensional structure, a two-dimensional structure and a quasi-2D structure. In the case of a three-dimensional structure, the composition formula of the calcium-titanium compound is represented by ABX _(3+δ) . In the case of a two-dimensional structure, the composition formula of the calcium-titanium compound is represented by A ₂ BX _(4+δ) .

Here, δ is a number that can be appropriately changed according to the charge balance of B, and is between -0.7 and 0.7. For example, when A is a monovalent cation, B is a divalent cation, and X is a monovalent anion, δ can be selected so that the calcium-titanium compound becomes electrically neutral. The so-called electrically neutral calcium-titanium compound means that the charge of the calcium-titanium compound is 0.

The calcium-titanium compound contains an octahedron with B as the center and X as the vertex. The octahedron is represented by BX _6. When the calcium-titanium compound has a three-dimensional structure, BX ₆ contained in the calcium-titanium compound forms a three-dimensional network structure by making two adjacent octahedrons (BX ₆ ) in the crystal share one X located at the vertex of the octahedron (BX ₆ ).

In the case of a calcium-titanium compound having a two-dimensional structure, BX ₆ contained in the calcium-titanium compound forms a two-dimensionally connected layer by having two adjacent octahedrons (BX ₆ ) in the crystal share two Xs at the vertices of the octahedron (BX ₆ ) and share the edges of the octahedron. The calcium-titanium compound has a structure in which two-dimensionally connected layers containing BX ₆ and layers containing A are alternately stacked.

In this specification, the crystal structure of a calcium-titanium compound can be confirmed by X-ray diffraction pattern (hereinafter, also referred to as XRD). Furthermore, the crystal distribution of each calcium-titanium compound in an aggregate of calcium-titanium compounds including a plurality of calcium-titanium compounds can also be confirmed by XRD.

When the calcite-titano compound has a three-dimensional calcite-titano type crystal structure, the Miller index (hkl) of the surface of the calcite-titano compound usually confirms a peak derived from (hkl) = (001) at a position of 2θ = 12 to 18° in the X-ray diffraction pattern, or confirms a peak derived from (hkl) = (110) at a position of 2θ = 18 to 25°.

When the calcite-titanate compound has a three-dimensional calcite-titanate type crystal structure, it is usually preferred that the Miller index (hkl) of the surface of the calcite-titanate compound confirms a peak originating from (hkl) = (001) at a position of 2θ = 13 to 16°, or confirms a peak originating from (hkl) = (110) at a position of 2θ = 20 to 23° in an X-ray diffraction pattern.

When the calcite-titano compound has a two-dimensional calcite-titano type crystal structure, the Miller index (hkl) of the surface of the calcite-titano compound usually confirms a peak derived from (hkl) = (002) at a position of 2θ = 1 to 10° in the X-ray diffraction pattern. Preferably, a peak derived from (hkl) = (002) is confirmed at a position of 2θ = 2 to 8°.

The calcium-titanium compound preferably has a three-dimensional structure.

In the X-ray diffraction pattern measured by XRD, the half-value width of the peak of (hkl) = (001) of the calcium-titanium compound (1) of the present embodiment is 0.10 (deg) or more and less than 0.60 (deg). The above half-value width is preferably 0.15 (deg) or more and 0.50 (deg) or less, preferably 0.20 (deg) or more and 0.30 (deg) or less, preferably 0.15 (deg) or more and 0.28 (deg) or less, and preferably 0.20 (deg) or more and 0.25 (deg) or less. In other aspects of this embodiment, (1) the half-value width of the peak of (hkl) = (001) of the calcium-titanium compound is 0.10, 0.11, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55 (deg) or more. In other aspects of this embodiment, (1) the half width of the peak of (hkl) = (001) of the calcium-titanium compound is 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59 (deg) or less. If (1) the half-value width of the peak of (hkl) = (001) of the calcium-titanium compound is 0.15 or more, the crystal of the calcium-titanium compound is stably formed. Moreover, if the half-value width of the above peak is 0.20 or more, in addition to the above effect, the absorption rate of the excitation light is also improved. If (1) the half-value width of the peak of (hkl) = (001) of the calcium-titanium compound does not reach 0.60, the half-value width of the luminescence wavelength becomes narrower.

(1) The half width of (hkl) = (001) of the calcium-titanium compound can be calculated from the XRD pattern (CuKα ray) using the integrated powder X-ray analysis software PDXL (manufactured by Rigaku Corporation).

Specifically, the half-value width of (hkl) = (001) of the calcium-titanium compound of the present embodiment and the semiconductor compound produced by the following production method can be confirmed in the following manner. 0.05 mL of the dispersion composition containing the calcium-titanium compound of the present embodiment or the semiconductor compound produced by the following production method is dropped onto a clean non-reflective plate and allowed to dry naturally. Powder X-ray diffraction measurement is performed using CuKα as a radiation source and the measurement range of the diffraction angle 2θ is 5° to 60° to determine the peak corresponding to (hkl) = (001). Furthermore, the half-value width of the determined (hkl) = (001) is calculated using the above-mentioned analysis software.

(Component A) The component A constituting the calcium-titanium compound is a monovalent cation. Examples of A include: cesium ions, organic ammonium ions, or amidinium ions.

(Organic ammonium ions) Specific examples of organic ammonium ions as A include cations represented by the following formula (A3).

[Chemistry 1]

In formula (A3), R ⁶ to R ⁹ independently represent a hydrogen atom, an alkyl group or a cycloalkyl group, wherein at least one of R ⁶ to R ⁹ is an alkyl group or a cycloalkyl group, and all of R ⁶ to R ⁹ are not hydrogen atoms at the same time.

The alkyl groups represented by R ⁶ to R ⁹ may be linear or branched. Furthermore, the alkyl groups represented by R ⁶ to R ⁹ may each independently have an amino group as a substituent.

In one embodiment, the number of carbon atoms in the alkyl group represented by R ⁶ to R ⁹ is usually 1 to 20, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1. In one embodiment, the number of carbon atoms in the alkyl group represented by R ⁶ to R ⁹ is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or more. In another embodiment, the number of carbon atoms in the alkyl group represented by R ⁶ to R ⁹ is 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, or 2 or less.

The cycloalkyl groups represented by R ⁶ to R ⁹ may each independently have an amino group as a substituent.

In one embodiment, the number of carbon atoms in the cycloalkyl group represented by R ⁶ to R ⁹ is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms includes the number of carbon atoms in the substituent. In one embodiment, the number of carbon atoms in the cycloalkyl group represented by R ⁶ to R ⁹ is usually 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or more. In other embodiments, the number of carbon atoms in the cycloalkyl groups represented by R ⁶ to R ⁹ is independently 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, or 4 or less.

In a certain aspect, the groups represented by R ⁶ to R ⁹ are preferably independently a hydrogen atom or an alkyl group.

When the calcium-titanium compound contains the organic ammonium ion represented by the above formula (A3) as A, it is preferred that the number of alkyl and cycloalkyl groups that can be contained in the formula (A3) is small. In addition, it is preferred that the number of carbon atoms in the alkyl and cycloalkyl groups that can be contained in the formula (A3) is small. In this way, a calcium-titanium compound with a three-dimensional structure having a high luminescence intensity can be obtained.

In the organic ammonium ion represented by formula (A3), it is preferred that the total number of carbon atoms contained in the alkyl and cycloalkyl groups represented by R ⁶ to R ⁹ is 1 to 4. In the organic ammonium ion represented by formula (A3), it is more preferred that one of R ⁶ to R ⁹ is an alkyl group having 1 to 3 carbon atoms, and three of R ⁶ to R ⁹ are hydrogen atoms.

Examples of the alkyl group for R ⁶ to R ⁹ include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl.

As the cycloalkyl group for R ⁶ to R ⁹ , any of the alkyl groups having 3 or more carbon atoms listed as examples for the alkyl groups for R ⁶ to R ⁹ can be independently listed, and can include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, northiophene, isothiophene, 1-adamantyl, 2-adamantyl, tricyclodecyl, and the like, but the present invention is not limited thereto.

In one embodiment, the organic ammonium ion represented by A is preferably CH ₃ NH ₃ ⁺ (also called methylammonium ion), C ₂ H ₅ NH ₃ ⁺ (also called ethylammonium ion) or C ₃ H ₇ NH ₃ ⁺ (also called propylammonium ion), more preferably methylammonium ion or ethylammonium ion, and still more preferably methylammonium ion.

(Amidinium ion) In one embodiment, examples of the amidinium ion represented by A include amidinium ions represented by the following formula (A4). (R ¹⁰ R ¹¹ N=CH-NR ¹² R ¹³ ) ⁺ ... (A4)

In formula (A4), R ¹⁰ to R ¹³ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

The alkyl groups represented by R ¹⁰ to R ¹³ may be independently linear or branched. Furthermore, the alkyl groups represented by R ¹⁰ to R ¹³ may have an amino group as a substituent.

In one embodiment, the number of carbon atoms in the alkyl group represented by ^R10 to ^R13 is usually 1 to 20, preferably 1 to 4, and more preferably 1 to 3. In one embodiment, the number of carbon atoms in the alkyl group represented by ^R10 to ^R13 is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or more. In another embodiment, the number of carbon atoms in the alkyl group represented by R10 to R13 is 20, 19, 18, 17, 16, 15, 14, 13, ¹² , 11, ¹⁰ , 9, 8, 7, 6, 5, 4, 3, or 2 or less.

The cycloalkyl groups represented by R ¹⁰ to R ¹³ may each independently have an amino group as a substituent.

In one embodiment, the number of carbon atoms in the cycloalkyl group represented by ^R10 to ^R13 is usually 3 to 30, preferably 3 to 11, and more preferably 3 to 8. The number of carbon atoms includes the number of carbon atoms in the substituent. In one embodiment, the number of carbon atoms in the cycloalkyl group represented by ^R10 to ^R13 is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or more. In other embodiments, the number of carbon atoms in the cycloalkyl groups represented by ^R10 - ^R13 is independently 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, or 4 or less.

Specific examples of the alkyl group for R ¹⁰ to R ¹³ include the same groups as those exemplified for R ⁶ to R ^9. Specific examples of the cycloalkyl group for R ¹⁰ to R ¹³ include the same groups as those exemplified for R ⁶ to R ⁹ .

In a certain aspect, the groups represented by R ¹⁰ to R ¹³ are preferably independently a hydrogen atom or an alkyl group.

By reducing the number of alkyl and cycloalkyl groups contained in formula (A4) and reducing the number of carbon atoms in the alkyl and cycloalkyl groups, a three-dimensional calcium-titanium compound with a higher luminescence intensity can be obtained.

In one embodiment, in the amidinium ion, the total number of carbon atoms contained in the alkyl and cycloalkyl groups represented by R ¹⁰ to R ¹³ is preferably 1 to 4, and more preferably R ¹⁰ is an alkyl group having 1 carbon atom, and R ¹¹ to R ¹³ are hydrogen atoms.

In calcium-titanium compounds, when A is a cesium ion, an organic ammonium ion having 3 or less carbon atoms, or an amidinium ion having 3 or less carbon atoms, the calcium-titanium compound generally has a three-dimensional structure.

In the case where A is an organic ammonium ion with 4 or more carbon atoms or an amidinium ion with 4 or more carbon atoms, the calcite compound has either or both of a two-dimensional structure and a quasi-2D structure. In this case, the calcite compound may have a two-dimensional structure or a quasi-2D structure in a part or the whole of the crystal. If a two-dimensional calcite crystal structure is stacked multiple times, it is equivalent to a three-dimensional calcite crystal structure (reference: P. PBoix et al., J. Phys. Chem. Lett. 2015, 6, 898-907, etc.).

In one embodiment, A in the calcium-titanium compound is preferably a cesium ion or an amidinium ion, and more preferably an amidinium ion.

In (1) the calcium-titanium compound, only one type of A may be used, or two or more types may be used in combination.

(Component B) B constituting the calcium-titanium compound may be one or more metal ions selected from the group consisting of monovalent metal ions, divalent metal ions, and trivalent metal ions. In a certain embodiment, B preferably contains divalent metal ions, more preferably contains one or more metal ions selected from the group consisting of lead ions, tin ions, antimony ions, bismuth ions, and indium ions, further preferably is lead ions or tin ions, and particularly preferably is lead ions.

In (1) the calcium-titanium compound, only one type of B may be used, or two or more types may be used in combination.

(Component X) X constituting the calcium-titanium compound may be at least one anion selected from the group consisting of halide ions and thiocyanate ions.

Examples of the halide ion include chloride ion, bromide ion, fluoride ion, and iodide ion. X is preferably a bromide ion.

In (1) the calcium-titanium compound, only one type of X may be used, or two or more types may be used in combination.

When X contains two or more halogenide ions, the content ratio of the halogenide ions can be appropriately selected according to the emission wavelength. For example, it can be a combination of bromide ions and chloride ions, or a combination of bromide ions and iodide ions.

X can be appropriately selected according to the desired luminescence wavelength.

In one embodiment, the calcium-titanium compound in which X is a bromide ion can emit fluorescence with a peak intensity at a wavelength range of usually 480 nm or more, preferably 500 nm or more, and more preferably 520 nm or more. In other embodiments, the calcium-titanium compound in which X is a bromide ion can emit fluorescence with a peak intensity at a wavelength range of 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690 nm or more.

In one embodiment, the calcium-titanium compound in which X is a bromide ion can emit fluorescence with a peak intensity in a wavelength range of generally 700 nm or less, preferably 600 nm or less, and more preferably 580 nm or less. In other embodiments, the calcium-titanium compound in which X is a bromide ion can emit fluorescence with a peak intensity in a wavelength range of 700, 690, 680, 670, 660, 650, 640, 630, 620, 600, 590, 580, 570, 560, 550, 540, 530, 520, 510 nm or less. The upper and lower limits of the above wavelength ranges can be arbitrarily combined.

In one embodiment, when X in the calcium-titanium compound is a bromide ion, the peak wavelength of the emitted fluorescence is generally 480-700 nm, preferably 500-600 nm, and more preferably 520-580 nm.

In one embodiment, the calcium-titanium compound in which X is an iodide ion can emit fluorescence with a peak intensity at a wavelength range of usually 520 nm or more, preferably 530 nm or more, and more preferably 540 nm or more. In other embodiments, the calcium-titanium compound in which X is an iodide ion can emit fluorescence with a peak intensity at a wavelength range of 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790 nm or more.

In one embodiment, the calcium-titanium compound in which X is an iodide ion can emit fluorescence with a peak intensity in a wavelength range of generally below 800 nm, preferably below 750 nm, and more preferably below 730 nm. In other embodiments, the calcium-titanium compound in which X is an iodide ion can emit fluorescence with a peak intensity in a wavelength range of below 800, 790, 780, 770, 760, 750, 740, 730, 720, 710, 700, 690, 680, 670, 660, 650, 640, 630, 620, 600, 590, 580, 570, 560, 550, 540 nm. The upper and lower limits of the above wavelength ranges can be combined arbitrarily.

In one embodiment, when X in the calcium-titanium compound is an iodide ion, the peak wavelength of the emitted fluorescence is generally 520-800 nm, preferably 530-750 nm, and more preferably 540-730 nm.

In a certain embodiment, the calcium-titanium compound in which X is a chloride ion can emit fluorescence having an extremely high intensity peak in a wavelength range of usually above 300 nm, preferably above 310 nm, and more preferably above 330 nm. In other aspects, the calcium-titanium compound in which X is a chloride ion can emit fluorescence having an extremely high intensity peak in a wavelength range above 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590 nm.

In a certain embodiment, the calcium-titanium compound in which X is a chloride ion can emit fluorescence having an extremely high intensity peak in a wavelength range generally below 600 nm, preferably below 580 nm, and more preferably below 550 nm. In other aspects, the calcium-titanium compound in which X is a chloride ion can emit fluorescence having a peak with extremely high intensity in a wavelength range below 600, 590, 580, 570, 560, 550, 540, 530, 520, 510, 500, 490, 480, 470, 460, 450, 440, 430, 420, 410, 400, 390, 380, 370, 360, 350, 340, 330, 320, 310 nm. The upper and lower limits of the above wavelength range can be arbitrarily combined.

In one embodiment, when X in the calcium-titanium compound is a chloride ion, the peak wavelength of the emitted fluorescence is generally 300-600 nm, preferably 310-580 nm, and more preferably 330-550 nm.

(Examples of three-dimensional structured calcium titanite compounds) Preferred examples of three-dimensional structured calcium titanite compounds represented by ABX _(3+δ) include CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr _(3-y) I _y (0＜y＜3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0＜y＜3), (H ₂ N＝CH-NH ₂ )PbBr ₃ , (H ₂ N＝CH-NH ₂ )PbCl ₃ , and (H ₂ N＝CH-NH ₂ )PbI ₃ , but the present invention is not limited thereto.

Preferred examples of three-dimensional calcium-titanium compounds include: CH ₃ NH ₃ Pb _(1-a) Ca _a Br ₃ (0＜a≦0.7), CH ₃ NH ₃ Pb _(1-a) Sr _a Br ₃ (0＜a≦0.7), CH ₃ NH ₃ Pb _(1-a) La _a Br _(3+δ) (0＜a≦0.7, 0＜δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Ba _a Br ₃ (0＜a≦0.7), and CH ₃ NH ₃ Pb _(1-a) Dy _a Br _(3+δ) (0＜a≦0.7, 0＜δ≦0.7), but the present invention is not limited to these.

Preferred examples of three-dimensional calcium-titanium compounds include: CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ) (0＜a≦0.7, -0.7≦δ＜0), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ) (0＜a≦0.7, -0.7≦δ＜0), but the present invention is not limited thereto.

Preferred examples of three-dimensional calcium-titanium compounds include: CsPb _(1-a) Na _a Br _(3+δ) (0＜a≦0.7, -0.7≦δ＜0), CsPb _(1-a) Li _a Br _(3+δ) (0＜a≦0.7, -0.7≦δ＜0), but the present invention is not limited to these.

As good examples of three-dimensional calcium-titanium compounds, we can also cite: CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) I _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) I _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3), CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3), but not limited thereto.

As good examples of three-dimensional calcium-titanium compounds, we can also cite: (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ) (0＜a≦0.7, -0.7≦δ＜0), (H ₂ N=CH-NH ₂ )Pb _(1-a) Li _a Br _(3+δ) (0＜a≦0.7, -0.7≦δ＜0), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ-y) I _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜3), but not limited thereto.

Preferred examples of three-dimensional calcium-titanium compounds include, but are not limited to, CsPbBr ₃ , CsPbCl ₃ , CsPbI ₃ , CsPbBr _(3-y) I _y (0＜y＜3), and CsPbBr _(3-y) Cl _y (0＜y＜3).

Preferred examples of three-dimensional calcium-titanium compounds include: CH ₃ NH ₃ Pb _(1-a) Zn _a Br ₃ (0＜a≦0.7), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ) (0＜a≦0.7, 0≦δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Co _a Br ₃ (0＜a≦0.7), CH ₃ NH ₃ Pb _(1-a) Mn _a Br ₃ (0＜a≦0.7), and CH ₃ NH ₃ Pb _(1-a) Mg _a Br ₃ (0＜a≦0.7), but the present invention is not limited to these.

Preferred examples of three-dimensional calcium-titanium compounds include: CsPb _(1-a) Zn _a Br ₃ (0＜a≦0.7), CsPb _(1-a) Al _a Br _(3+δ) (0＜a≦0.7, 0＜δ≦0.7), CsPb _(1-a) Co _a Br ₃ (0＜a≦0.7), CsPb _(1-a) Mn _a Br ₃ (0＜a≦0.7), and CsPb _(1-a) Mg _a Br ₃ (0＜a≦0.7), but the present invention is not limited to these.

As preferred examples of three-dimensional calcium-titanium compounds, there are: CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3-y) I _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) I _y (0＜a≦0.7, 0＜δ≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3-y) I _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) I _y (0＜a≦0.7, 0＜y＜3), CH ₃ NH ₃ Pb _(1-a) Mg _a Br _(3-y) I _y y＜3）、CH ₃ NH ₃ Pb _(1-a) Zn _a Br _(3-y) Cl _y (0＜a ≦ 0.7, 0＜y＜3）、CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) Cl _y (0＜a ≦ 0.7, 0＜δ ≦ 0.7, 0＜y＜3）、CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3+δ-y) Cl _y (0＜a ≦ 0.7, 0＜δ ≦ 0.7, 0＜y＜3）、CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) Cl _y (0＜a ≦ 0.7, 0＜y＜3）、CH ₃ NH ₃ Pb _(1-a) Mg _a Br _(3-y) Cl _y (0＜a≦0.7, 0＜y＜3), but is not limited thereto.

Preferred examples of three-dimensional calcium-titanium compounds include: ( _H2N =CH- _NH2 )Zn _a Br ₃ (0＜a≦0.7), ( _H2N =CH- _NH2 )Mg _a Br ₃ (0＜a≦0.7), ( _H2N =CH- _NH2 )Pb _(1-a) Zn _a Br _(3-y) I _y (0＜a≦0.7, 0＜y＜3), and ( _H2N =CH- _NH2 )Pb _(1-a) Zn _a Br _(3-y) Cl _y (0＜a≦0.7, 0＜y＜3), but the present invention is not limited to these.

Among the three-dimensional calcium-titanium compounds, CsPbBr ₃ , CsPbBr _(3-y) I _y (0＜y＜3), (H ₂ N＝CH-NH ₂ )PbBr ₃ are more preferred, and (H ₂ N＝CH-NH ₂ )PbBr ₃ is even more preferred.

(Examples of two-dimensional calcium-titanium compounds) Preferred examples of two-dimensional calcium-titanium compounds include: (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbCl ₄ , (C ₄ H ₉ NH ₃ ) ₂ PbI ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbCl ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbI ₄ , (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0＜a≦0.7, -0.7≦δ＜0), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0＜a≦0.7, -0.7≦δ＜0), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) (0＜a≦0.7, -0.7≦δ＜0), but the present invention is not limited thereto.

Preferred examples of two-dimensional calcium-titanium compounds include: (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0＜a≦0.7, -0.7≦δ＜0), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0＜a≦0.7, -0.7≦δ＜0), and (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) (0＜a≦0.7, -0.7≦δ＜0), but the present invention is not limited to these.

Preferred examples of two-dimensional calcium-titanium compounds include: (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) I _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) I _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜4), and (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) I _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜4), but the present invention is not limited to these.

Preferred examples of two-dimensional calcium-titanium compounds include: (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜4), and (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) Cl _y (0＜a≦0.7, -0.7≦δ＜0, 0＜y＜4), but the present invention is not limited to these.

Preferred examples of two-dimensional calcium-titanium compounds include (C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ and (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ , but the present invention is not limited thereto.

Preferred examples of two-dimensional calcium-titanium compounds include (C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) Cl _y (0＜y＜4) and (C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) I _y (0＜y＜4), but the present invention is not limited thereto.

Preferred examples of two-dimensional calcium-titanium compounds include: (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0＜a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0＜a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0＜a≦0.7), and (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br ₄ (0＜a≦0.7), but the present invention is not limited to these.

Preferred examples of two-dimensional calcium-titanium compounds include: (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Zn _a Br ₄ (0＜a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0＜a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Co _a Br ₄ (0＜a≦0.7), and (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mn _a Br ₄ (0＜a≦0.7), but the present invention is not limited to these.

Preferred examples of two-dimensional calcium-titanium compounds include: (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) I _y (0＜a≦0.7, 0＜y＜4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) I _y (0＜a≦0.7, 0＜y＜4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4-y) I _y (0＜a≦0.7, 0＜y＜4), and (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) I _y (0＜a≦0.7, 0＜y＜4), but the present invention is not limited to these.

Preferred examples of two-dimensional calcium-titanium compounds include: (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zn _a Br _(4-y) Cl _y (0＜a≦0.7, 0＜y＜4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) Cl _y (0＜a≦0.7, 0＜y＜4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4-y) Cl _y (0＜a≦0.7, 0＜y＜4), and (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) Cl _y (0＜a≦0.7, 0＜y＜4), but the present invention is not limited to these.

<(1) Particle size of calcium-titanium compound> The average particle size of the (1) calcium-titanium compound is preferably 13.5 nm or more and 80.0 nm or less. In one embodiment, from the viewpoint that the (1) calcium-titanium compound can be stably dispersed in the dispersion, the average particle size of the (1) calcium-titanium compound is preferably 15.0 nm or more, more preferably 17.0 nm or more, and further preferably 18.0 nm or more. In other embodiments, from the viewpoint of obtaining a (1) calcium-titanium compound with a higher luminescence intensity, the average particle size of the (1) calcium-titanium compound is preferably 80.0 nm or less, more preferably 25.0 nm or less, and further preferably 22.0 nm or less. In other embodiments, the average particle size of the calcium-titanium compound is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79 nm or more. In other aspects, the average particle size of the calcium-titanium compound is 85, 84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13 nm or less.

In this specification, the average particle size of (1) calcium-titanium compound can be measured, for example, by transmission electron microscope (hereinafter, also referred to as TEM) or scanning electron microscope (hereinafter, also referred to as SEM). Specifically, the length of the longest side of 30 or more randomly selected cubic or rectangular particles of (1) calcium-titanium compound is measured by TEM or SEM, and the arithmetic mean of the measured values is calculated to obtain the average particle size.

As a method for observing the (1) calcium-titanium compound of the present embodiment, for example, there can be cited a method of observing a dispersion composition containing the (1) calcium-titanium compound using SEM or TEM. Furthermore, detailed element distribution can be analyzed by energy dispersive X-ray analysis (EDX) using SEM or TEM. From the perspective of higher spatial resolution, the method of observation using TEM is preferred.

As a method for observing (1) calcium-titanium compound by TEM, there can be cited a method in which a dispersion composition containing (1) calcium-titanium compound is cast on a grid with a support film for TEM and then naturally dried.

As a method for analyzing the average particle size of (1) calcium-titanium compounds, there is a method of importing TEM images into a computer and using image analysis software for analysis. First, the above TEM images are imported into a computer and binarized using image analysis software. An image is obtained after the binarization process is completed, in which (1) calcium-titanium compounds are converted to black and the rest are converted to white. At this time, by comparing with the element mapping image obtained by TEM-EDX measurement, it is confirmed that the components derived from (1) calcium-titanium compounds are partially converted to black. When a difference is visible, the threshold for binarization is adjusted. For the above binarized image, use image analysis software to measure (1) the average particle size of the calcium-titanium compound. The image analysis software may be Image J or Photoshop.

In other aspects of this embodiment, (1) the calcium-titanium compound is a calcium-titanium aggregate formed by a plurality of the above-mentioned compounds having a calcium-titanium crystal structure. The above-mentioned calcium-titanium aggregate includes one or more compounds having a calcium-titanium crystal structure. Therefore, the above-mentioned calcium-titanium aggregate includes one or more monovalent cations, metal ions or anions.

<Composition 1> Composition 1 of this embodiment contains the above-mentioned (1) calcium-titanium compound and at least one compound selected from the group consisting of the following (2-1), the modified product of the following (2-1), the following (2-2), and the modified product of the following (2-2). (2-1) Silazane (2-2) A silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group, and an alkylthio group

In this specification, at least one compound selected from the group consisting of the above (2-1), the modified product of the above (2-1), the above (2-2), and the modified product of the above (2-2) is sometimes collectively referred to as "(2) surface protective agent".

In one embodiment, the composition 1 of the present embodiment preferably contains the calcium-titanium compound (1) and at least one compound selected from the group consisting of the compound (2-1) and a modified form of the compound (2-1).

The composition 1 of this embodiment may further contain at least one selected from the group consisting of the following (3), the following (4) and the following (5). (3) Solvent (4) Polymerizable compound (5) Polymer

<Composition 2> Composition 2 of this embodiment contains the calcium-titanium compound (1) and at least one selected from the group consisting of (3), (4) and (5).

In the following description, (3) solvent, (4) polymerizable compound, and (5) polymer are sometimes collectively referred to as "dispersion medium." In the compositions 1 and 2 of the present embodiment, (1) calcium-titanium compound can be dispersed in the dispersion medium.

The term "dispersion" as used herein refers to a state in which (1) the calcium-titanium compound floats in a dispersion medium or a state in which (1) the calcium-titanium compound is suspended in a dispersion medium. In the case in which (1) the calcium-titanium compound is dispersed in a dispersion medium, a portion of (1) the calcium-titanium compound may precipitate.

Composition 1 and Composition 2 of this embodiment may further contain the following (6). The details of the following (6) are described below. (6) Surface modifier

The composition 1 and the composition 2 of this embodiment may contain other components besides the above (1) to (6). For example, the composition of this embodiment may further contain some impurities, a compound having an amorphous structure containing elements constituting the calcium-titanium compound (1), and a polymerization initiator.

Hereinafter, the above (2) to (6) contained in the composition of this embodiment will be described.

<(2) Surface Protectant> Composition 1 of the present embodiment contains at least one compound selected from the group consisting of (2-1) silazane, a modified form of (2-1), (2-2) a silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group and an alkylthio group, and a modified form of (2-2), as (2) a surface protectant for (1) a calcium-titanium compound.

The composition 1 of this embodiment can achieve the effect of improving the quantum yield and shortening the luminescent wavelength by coating the surface of the calcium-titanium compound (1) with the surface protective agent (2).

<(2-1) Silazane> (2-1) Silazane is a compound with Si-N-Si bonds. Silazane can be linear, branched, or cyclic.

The silazane may be a low molecular weight silazane or a high molecular weight silazane. In this specification, the high molecular weight silazane is sometimes described as a polysilazane.

In this specification, "low molecular weight" refers to a number average molecular weight of less than 600. In addition, "high molecular weight" in this specification refers to a number average molecular weight of more than 600 and less than 20,000.

The "number average molecular weight" referred to in this specification refers to the polystyrene conversion value measured by gel permeation chromatography (GPC).

(2-1-1. Low molecular weight silazane) As the low molecular weight silazane, for example, disilazane represented by the following formula (B1) is preferred.

[Chemistry 2]

In formula (B1), R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

R ¹⁴ and R ¹⁵ may have a substituent such as an amino group. A plurality of R ¹⁵ may be the same or different.

Examples of the low molecular weight silazane represented by formula (B1) include, but are not limited to, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, and 1,1,1,3,3,3-hexamethyldisilazane.

(2-1-2. Low molecular weight silazane) As the low molecular weight silazane, for example, the low molecular weight silazane represented by the following formula (B2) is also preferred.

[Chemistry 3]

In formula (B2), R ¹⁴ and R ¹⁵ are the same as R ¹⁴ and R ¹⁵ in the above formula (B1).

A plurality of R ^14s may be the same or different. A plurality of R ^15s may be the same or different.

In formula (B2), _n1 represents an integer greater than or equal to 1 and less than or equal to 20. _n1 may be an integer greater than or equal to 1 and less than or equal to 10, and may be 1 or 2.

Examples of the low molecular weight silazane represented by formula (B2) include octamethylcyclotetrasilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, but are not limited thereto.

In one embodiment, the low molecular weight silazane is preferably octamethylcyclotetrasilazane and 1,3-diphenyltetramethyldisilazane, and more preferably octamethylcyclotetrasilazane.

(2-1-3. Polymer silazane) As the polymer silazane, for example, a polymer silazane (polysilazane) represented by the following formula (B3) is preferred.

Polysilazane is a polymer compound having Si-N-Si bonds. The structural unit of the polysilazane represented by formula (B3) may be one or more.

[Chemistry 4]

In formula (B3), R ¹⁴ and R ¹⁵ are the same as R ¹⁴ and R ¹⁵ in the above formula (B1).

In formula (B3), * represents a bond. R ¹⁴ is bonded to the bond of the N atom at the end of the molecular chain. R ¹⁵ is bonded to the bond of the Si atom at the end of the molecular chain.

A plurality of R ^14s may be the same or different. A plurality of R ^15s may be the same or different.

m represents an integer greater than 2 and less than 10000.

The polysilazane represented by formula (B3) may be, for example, a perhydropolysilazane in which both R ¹⁴ and R ¹⁵ are hydrogen atoms.

The polysilazane represented by formula (B3) may be, for example, an organic polysilazane in which at least one R ¹⁵ is a group other than a hydrogen atom. Perhydropolysilazane and organic polysilazane may be appropriately selected according to the intended use, and may be used in combination.

In one aspect, from the viewpoint of improving the dispersibility of (1) and enhancing the effect of suppressing aggregation, the composition of this embodiment preferably contains an organic polysilazane represented by formula (B3).

The organic polysilazane represented by formula (B3) may be an organic polysilazane in which at least one of ^R14 and ^R15 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms.

In one embodiment, among the organic polysilazane, an organic polysilazane represented by formula (B3) in which at least one of R ¹⁴ and R ¹⁵ is a methyl group is preferred.

(2-1-4. Polymer silazane) As the polymer silazane, for example, polysilazane having a structure represented by the following formula (B4) is also preferred.

The polysilazane may have a ring structure at a part of the molecule, for example, it may have a structure represented by formula (B4).

[Chemistry 5]

In formula (B4), * represents a bond. The bond of formula (B4) can be bonded to a bond of the polysilazane represented by formula (B3) or a bond of a structural unit of the polysilazane represented by formula (B3).

Furthermore, when the polysilazane contains a plurality of structures represented by the formula (B4) in the molecule, a bond of the structure represented by the formula (B4) may directly bond with a bond of another structure represented by the formula (B4).

R ¹⁴ is bonded to a bond of a N atom that is not bonded to any of a bond of the polysilazane represented by the formula (B3), a bond of a structural unit of the polysilazane represented by the formula (B3), and a bond of another structure represented by the formula (B4).

R ¹⁵ is bonded to a bond of a Si atom that is not bonded to any of a bond of the polysilazane represented by the formula (B3), a bond of a structural unit of the polysilazane represented by the formula (B3), and a bond of another structure represented by the formula (B4).

In a certain aspect, n ₂ represents an integer greater than 1 and less than 10000. n ₂ may be an integer greater than 1 and less than 10, and may be 1 or 2.

From the viewpoint of improving the dispersibility of (1) and enhancing the effect of suppressing aggregation, the composition of this embodiment preferably contains an organic polysilazane having a structure represented by formula (B4).

The organic polysilazane having a structure represented by formula (B4) may be an organic polysilazane having at least one bond bonded to ^R14 or ^R15 , wherein at least one of ^R14 and ^R15 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylsilanyl group having 1 to 20 carbon atoms.

Among them, preferred is a polysilazane having a structure represented by formula (B4), at least one of which is bonded to R ¹⁴ or R ¹⁵ , and at least one of R ¹⁴ and R ¹⁵ is a methyl group.

Typical polysilazane has a structure having a linear structure and a 6-membered ring or an 8-membered ring, for example, that is, a structure represented by the above formula (B3) or the above formula (B4). The molecular weight of a typical polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and it can be a liquid or solid substance depending on the molecular weight.

As the polysilazane, commercially available products may be used. Examples of the commercially available products include NN120-10, NN120-20, NAX120-20, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, and NP140 (manufactured by AZ ELECTRONIC MATERIALS Co., Ltd.), 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.), but the present invention is not limited to these.

In one embodiment, the polysilazane is preferably AZNN-120-20, Durazane 1500 Slow Cure, Durazane 1500 Rapid Cure, and more preferably Durazane 1500 Slow Cure.

<(2-1) Modified silazane> In this specification, "modification" means hydrolysis of silicon compounds having Si-N bonds, Si-SR bonds (R is a hydrogen atom or an organic group) or Si-OR bonds (R is a hydrogen atom or an organic group) to generate silicon compounds having Si-O-Si bonds. Si-O-Si bonds can be generated by intermolecular condensation reactions or by intramolecular condensation reactions.

The term "modified product" used in this specification refers to a compound obtained by modifying a silicon compound having a Si-N bond, a Si-SR bond, or a Si-OR bond.

Preferred as the modified product of (2-1) are modified products of disilazane represented by the above formula (B1), modified products of low molecular weight silazane represented by the above formula (B2), modified products of polysilazane represented by the above formula (B3), and modified products of polysilazane having the structure represented by the above formula (B4) in the molecule.

In one embodiment, with respect to the modified low molecular weight silazane represented by formula (B2), the ratio of silicon atoms not bonded to nitrogen atoms relative to all silicon atoms contained in the modified low molecular weight silazane represented by formula (B2) is preferably 0.1 to 100%. In another embodiment, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, and further preferably 30 to 95%.

The "ratio of silicon atoms not bonded to nitrogen atoms" is obtained using the following measured value, ((Si (mole)) - (N (mole) in Si-N bond))/Si (mole) × 100. If the modification reaction is taken into account, the so-called "ratio of silicon atoms not bonded to nitrogen atoms" refers to the "ratio of silicon atoms contained in siloxane bonds generated during the modification process".

In one embodiment, with respect to the modified polysilazane represented by formula (B3), the ratio of silicon atoms not bonded to nitrogen atoms relative to all silicon atoms contained in the modified polysilazane represented by formula (B3) is preferably 0.1 to 100%. In another embodiment, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 98%, and further preferably 30 to 95%.

In one embodiment, with respect to the modified polysilazane having a structure represented by formula (B4), the ratio of silicon atoms not bonded to nitrogen atoms relative to all silicon atoms contained in the modified polysilazane having a structure represented by formula (B4) is preferably 0.1 to 99%. In another embodiment, the ratio of silicon atoms not bonded to nitrogen atoms is more preferably 10 to 97%, and further preferably 30 to 95%.

The number of Si atoms and Si-N bonds in the modified body can be determined by X-ray photoelectron spectroscopy (XPS).

In one embodiment, regarding the modified body, the “ratio of silicon atoms not bonded to nitrogen atoms” relative to all silicon atoms obtained using the measured value measured by the above method is preferably 0.1 to 99%, more preferably 10 to 99%, and even more preferably 30 to 95%.

<(2-2) Silicon compound having at least one group selected from the group consisting of amine groups, alkoxy groups and alkylthio groups> Composition 1 of the present embodiment may contain (2-2) silicon compound having at least one group selected from the group consisting of amine groups, alkoxy groups and alkylthio groups. Hereinafter, (2-2) silicon compound having at least one group selected from the group consisting of amine groups, alkoxy groups and alkylthio groups is sometimes collectively referred to as "(2-2) silicon compound".

Examples of the (2-2) silicon compound include, but are not limited to, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, dodecyltrimethoxysilane, trimethoxyphenylsilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, 3-butylpropyltrimethoxysilane, and 3-butylpropyltriethoxysilane.

In one embodiment, among the silicon compounds, from the viewpoint of durability of (1), 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and trimethoxyphenylsilane are preferred, and trimethoxyphenylsilane is more preferred.

<(2-2) Modified silicon compound> (2-2) Modified silicon compound is a compound obtained by modifying the above-mentioned (2-2) silicon compound. The "modification" is the same as that in (2-1) Modified silazane.

In the composition 1 of this embodiment, the above-mentioned (2) surface protecting agent may be present at least one type, or two or more types may be used in combination.

<(6) Surface modifier> The surface of the (1) calcium-titanium compound of this embodiment can be covered by a surface modifier layer. The surface modifier layer can be located between the (1) calcium-titanium compound and the (2) surface protective agent.

Furthermore, the so-called surface modifier layer covering the "surface" of (1) the calcium-titanium compound not only means that the surface modifier layer is directly in contact with the (1) calcium-titanium compound and covers it, but also includes the following meanings: the surface modifier layer is directly in contact with the surface of other layers formed on the surface of (1) the calcium-titanium compound and does not directly contact with the surface of (1) the calcium-titanium compound and covers it.

<Surface modifier layer> The surface modifier layer is formed of at least one ion or compound selected from the group consisting of ammonium ions, amines, primary to quaternary ammonium cations, ammonium salts, carboxylic acids, carboxylate ions, and carboxylate salts.

Among them, the surface modifier layer is preferably formed of at least one selected from the group consisting of amines and carboxylic acids. Hereinafter, the material forming the surface modifier layer is sometimes referred to as "(6) surface modifier".

The surface modifier is a compound that covers the surface of (1) the calcium-titanium compound when the composition of the present embodiment is produced by the following production method and has the function of stably dispersing the (1) calcium-titanium compound in the composition.

<Ammonium ions, primary to quaternary ammonium cations, and ammonium salts> Ammonium ions and primary to quaternary ammonium cations as (6) surface modifiers are represented by the following formula (A1). Ammonium salts as (6) surface modifiers are salts containing ions represented by the following formula (A1).

[Chemistry 6]

In the ion represented by formula (A1), R ¹ to R ⁴ represent a hydrogen atom or a monovalent hydrocarbon group.

The alkyl group represented by R ¹ to R ⁴ may be a saturated alkyl group or an unsaturated alkyl group. Examples of the saturated alkyl group include an alkyl group and a cycloalkyl group.

The alkyl group represented by R ¹ to R ⁴ may be linear or branched. In one embodiment, the alkyl group represented by R ¹ to R ⁴ generally has 1 to 20 carbon atoms, preferably 5 to 20, and more preferably 8 to 20 carbon atoms.

In a certain aspect, the number of carbon atoms in the cycloalkyl group is generally 3 to 30, preferably 3 to 20, and more preferably 3 to 11. The number of carbon atoms includes the number of carbon atoms in the substituent.

The unsaturated hydrocarbon groups of R ¹ to R ⁴ may be in the form of a straight chain or a branched chain.

In a certain aspect, the unsaturated alkyl group of R ¹ to R ⁴ generally has 2 to 20 carbon atoms, preferably 5 to 20, and more preferably 8 to 20 carbon atoms.

In one embodiment, R ¹ to R ⁴ are each independently preferably a hydrogen atom, an alkyl group or an unsaturated hydrocarbon group. In one embodiment, the unsaturated hydrocarbon group is preferably an alkenyl group. In one embodiment, R ¹ to R ⁴ are each independently preferably an alkenyl group having 8 to 20 carbon atoms.

Specific examples of the alkyl group for R ¹ to R ⁴ include the alkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the cycloalkyl group for R ¹ to R ⁴ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

Examples of the alkenyl group for R ¹ to R ⁴ include those in which a single bond (CC) between any carbon atoms in the linear or branched alkyl groups exemplified above for R ⁶ to R ⁹ is replaced by a double bond (C=C). The position of the double bond is not limited.

In one embodiment, preferred alkenyl groups for R ¹ to R ⁴ include, but are not limited to, ethenyl, propenyl, 3-butenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-nonenyl, 2-dodecenyl, and 9-octadecenyl.

When the ammonium cation represented by formula (A1) forms a salt, there is no particular limitation on the counter anion. Preferred counter anions are halogenide ions or carboxylate ions. Examples of halogenide ions include bromide ions, chloride ions, iodide ions, and fluoride ions.

As the ammonium salt having an ammonium cation and a counter anion represented by the formula (A1), n-octyl ammonium salt and oleyl ammonium salt can be cited as preferable examples.

<Amine> Amines used as surface modifiers can be represented by the following formula (A11).

[Chemistry 7]

In the above formula (A11), R ¹ to R ³ represent the same groups as R ¹ to R ³ in the above formula (A1). At least one of R ¹ to R ³ is a monovalent hydrocarbon group.

In a certain aspect, the amine used as the surface modifying agent may be any of primary to tertiary amines, preferably primary amines and secondary amines, and more preferably primary amines.

In one aspect, the amine used as the surface modifying agent is preferably oleylamine.

<Carboxylic acid, carboxylate ion, carboxylate salt> The carboxylate ion as a surface modifying agent is represented by the following formula (A2). The carboxylate salt as a surface modifying agent is a salt containing an ion represented by the following formula (A2). R ⁵ -CO ₂ ^-... (A2)

The carboxylic acid used as the surface modifying agent is a carboxylic acid formed by bonding a proton (H ⁺ ) to the carboxylate anion represented by (A2) above, but is not limited thereto.

In the ion represented by formula (A2), R ⁵ represents a monovalent hydrocarbon group. The hydrocarbon group represented by R ⁵ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the saturated hydrocarbon group include, but are not limited to, an alkyl group or a cycloalkyl group.

The alkyl group represented by R ⁵ may be a linear or branched chain.

In a certain aspect, the alkyl group represented by R ⁵ generally has 1 to 20 carbon atoms, preferably 5 to 20, and more preferably 8 to 20 carbon atoms.

The number of carbon atoms in the cycloalkyl group is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 11. The number of carbon atoms also includes the number of carbon atoms in the substituent.

The unsaturated hydrocarbon group represented by R ⁵ may be in the form of a straight chain or a branched chain.

In a certain aspect, the unsaturated alkyl group represented by R ⁵ generally has 2 to 20 carbon atoms, preferably 5 to 20, and more preferably 8 to 20 carbon atoms.

^R5 is preferably an alkyl group or an unsaturated hydrocarbon group. As the unsaturated hydrocarbon group, an alkenyl group is preferred.

Specific examples of the alkyl group for R ⁵ include the alkyl groups exemplified for R ⁶ to R ^9. Specific examples of the cycloalkyl group for R ⁵ include the cycloalkyl groups exemplified for R ⁶ to R ⁹ .

Specific examples of the alkenyl group for R ⁵ include the alkenyl groups exemplified for R ¹ to R ⁴ .

In one embodiment, the carboxylate anion represented by formula (A2) is preferably an oleate anion.

When the carboxylate anion forms a salt, the counter cation is not particularly limited, and alkali metal cations, alkaline earth metal cations, ammonium cations, etc. can be cited as preferred examples.

As for the carboxylic acid used as the surface modifying agent, oleic acid is preferred.

Among the above-mentioned surface modifying agents, ammonium salts, ammonium ions, primary to quaternary ammonium cations, carboxylate salts, and carboxylate ions are preferred.

Among the ammonium salts and ammonium ions, oleylamine salts and oleylammonium ions are more preferred.

Among the carboxylate salts and carboxylate ions, oleate salts and oleate anions are more preferred.

In the composition 1 and the composition 2 of this embodiment, only one kind of the above-mentioned (6) surface modifier may be present, or two or more kinds may be used in combination.

<(3) Solvent> The solvent contained in the composition of this embodiment is not particularly limited as long as it is a medium that can disperse the (1) calcium-titanium compound of this embodiment. The solvent contained in the composition of this embodiment is preferably a medium that is difficult to dissolve the (1) calcium-titanium compound of this embodiment. The "solvent" in this specification refers to a substance that is in a liquid state at one atmosphere and 25°C. The solvent does not include the following polymerizable compounds.

As the solvent, the following (a) to (k) can be listed, but it is not limited to them. (a) Ester (b) Ketone (c) Ether (d) Alcohol (e) Glycol ether (f) Organic solvent having an amide group (g) Organic solvent having a nitrile group (h) Organic solvent having a carbonate group (i) Halogenated hydrocarbon (j) Hydrocarbon (k) Dimethyl sulfoxide

Examples of the (a) ester include methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, and the like, but the ester is not limited thereto.

Examples of the ketone (b) include, but are not limited to, γ-butyrolactone, N-methyl-2-pyrrolidone, acetone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and the like.

Examples of the ether (c) include diethyl ether, methyl tert-butyl ether, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxacyclopentane, 4-methyldioxacyclopentane, tetrahydrofuran, methyltetrahydrofuran, anisole, and phenetole, but are not limited thereto.

(d) Alcohols include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, methoxypropanol, diacetone alcohol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, and 2,2,3,3-tetrafluoro-1-propanol.

(e) Glycol ethers include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, triethylene glycol dimethyl ether, and the like.

(f) Examples of the organic solvent having an amide group include, but are not limited to, N,N-dimethylformamide, acetamide, and N,N-dimethylacetamide.

(g) Examples of the organic solvent having a nitrile group include, but are not limited to, acetonitrile, isobutyronitrile, propionitrile, methoxyacetonitrile and the like.

(h) Examples of the organic solvent having a carbonate group include ethylene carbonate, propylene carbonate, and the like, but the present invention is not limited thereto.

(i) The halogenated hydrocarbon includes, but is not limited to, dichloromethane, chloroform, and the like.

Examples of the (j) hydrocarbon include, but are not limited to, n-pentane, cyclohexane, n-hexane, 1-octadecene, benzene, toluene, and xylene.

In one embodiment, among the above solvents, (a) esters, (b) ketones, (c) ethers, (g) organic solvents having a nitrile group, (h) organic solvents having a carbonate group, (i) halogenated hydrocarbons, and (j) hydrocarbons are considered to be preferred because they have low polarity and are difficult to dissolve the (1) calcium-titanium compound of the present embodiment.

Furthermore, the solvent used in the composition of this embodiment is more preferably (i) a halogenated hydrocarbon or (j) a hydrocarbon.

In the composition 1 and the composition 2 of the present embodiment, only one of the above solvents may be used, or two or more of them may be used in combination.

<(4) Polymerizable compound> The polymerizable compound of the composition of this embodiment is preferably one that is difficult to dissolve the (1) calcium-titanium compound of this embodiment at the temperature at which the composition of this embodiment is prepared.

In this specification, the term "polymerizable compound" refers to a monomer compound (monomer) having a polymerizable group. For example, a polymerizable compound can be a monomer that is in a liquid state at 1 atmospheric pressure and 25°C.

For example, when the polymerizable compound is produced at room temperature and pressure, there is no particular limitation. Examples of the polymerizable compound include well-known polymerizable compounds such as styrene, acrylate, methacrylate, and acrylonitrile. Among them, the polymerizable compound is preferably one or both of acrylate and methacrylate, which are monomers of acrylic resins.

In the composition 1 and the composition 2 of the present embodiment, only one kind of polymerizable compound may be used, or two or more kinds may be used in combination.

In the composition of this embodiment, the total amount of acrylate and methacrylate relative to the total amount of (4) polymerizable compounds may be 10 mol% or more. The ratio may be 30 mol% or more, 50 mol% or more, 80 mol% or more, or 100 mol%.

<(5) Polymer> The polymer contained in the composition of this embodiment is preferably a polymer having a lower solubility of the (1) calcium-titanium compound of this embodiment at the temperature at which the composition of this embodiment is prepared.

For example, when the polymer is produced at room temperature and pressure, there is no particular limitation on the polymer, and examples thereof include, but are not limited to, known polymers such as polystyrene, acrylic resins, and epoxy resins. Among them, acrylic resins are preferred as the polymer. Acrylic resins contain either or both of structural units derived from acrylates and structural units derived from methacrylates.

In the composition of this embodiment, the total amount of the structural units derived from acrylate and the structural units derived from methacrylate relative to all the structural units contained in the (5) polymer may be 10 mol% or more. The ratio may be 30 mol% or more, 50 mol% or more, 80 mol% or more, or 100 mol%.

(5) The weight average molecular weight of the polymer is preferably 100 to 1,200,000, more preferably 1,000 to 800,000, and even more preferably 5,000 to 150,000.

The "weight average molecular weight" referred to in this specification refers to the polystyrene conversion value measured by gel permeation chromatography (GPC).

In the composition 1 and the composition 2 of this embodiment, only one kind of the above-mentioned polymer (5) may be contained, or two or more kinds may be used in combination.

<Content of each component in the composition> In the composition 1 and the composition 2 of the present embodiment, (1) the content ratio of the calcium-titanium compound relative to the total mass of the composition is not particularly limited.

In a certain aspect, the content ratio is preferably 90 mass % or less, more preferably 40 mass % or less, further preferably 10 mass % or less, and particularly preferably 3 mass % or less from the viewpoint of preventing concentration quenching.

In other aspects, the content ratio is preferably 0.0002 mass % or more, more preferably 0.002 mass % or more, and further preferably 0.01 mass % or more from the viewpoint of obtaining a good quantum yield.

The above upper limit values and lower limit values may be combined arbitrarily.

(1) The content ratio of the calcium-titanium compound relative to the total mass of the composition is generally 0.0002 to 90 mass %.

In a certain embodiment, the content ratio of (1) the calcium-titanium compound relative to the total mass of the composition is preferably 0.001 to 40 mass%, more preferably 0.002 to 10 mass%, and further preferably 0.01 to 3 mass%. In a certain embodiment, the content ratio of (1) the calcium-titanium compound is 0.0002, 0.0005, 0.001, 0.002, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 10, 20, 30, 40, 50, 60, 70, 80 mass% or more. In other aspects, (1) the content ratio of the calcium-titanium compound is 90, 80, 70, 60, 50, 40, 30, 20, 10, 1, 0.5, 0.1, 0.05, 0.01, 0.005, 0.002, 0.001, 0.0005 mass % or less.

A composition in which the content ratio of the (1) calcium-titanium compound to the total mass of the composition is within the above range is preferable in that the (1) calcium-titanium compound is less likely to aggregate and that the luminescence property is well exhibited.

In the composition 1 of this embodiment, the content ratio of (2) the surface protecting agent relative to the total mass of the composition is not particularly limited.

In one embodiment, the content ratio is preferably 30% by mass or less, more preferably 10% by mass or less, and further preferably 7.5% by mass or less, from the viewpoint of improving (1) the dispersibility of the calcium-titanium compound and improving durability.

In addition, in a certain embodiment, the above content ratio is preferably 0.001 mass % or more, more preferably 0.01 mass % or more, and further preferably 0.1 mass % or more from the viewpoint of improving durability. In other embodiments, the above content ratio is 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 7.5, 10, 15, 20, 25 mass % or more. In other embodiments, the above content ratio is 30, 25, 20, 15, 10, 7.5, 5, 1, 0.5, 0.1, 0.05 mass % or less.

The above upper limit values and lower limit values may be combined arbitrarily.

In one embodiment, the content ratio of (2) the surface protective agent relative to the total mass of the composition is generally 0.001 to 30 mass %.

In one embodiment, the content ratio of (2) the surface protective agent relative to the total mass of the composition is preferably 0.001 to 30 mass%, more preferably 0.001 to 10 mass%, and further preferably 0.1 to 7.5 mass%. In other embodiments, the content ratio of (2) the surface protective agent is 0.001, 0.01, 0.05, 0.1, 0.5, 1, 5, 7.5, 10, 15, 20, 25 mass% or more. In other embodiments, the content ratio of (2) the surface protective agent is 30, 25, 20, 15, 10, 7.5, 5, 1, 0.5, 0.1, 0.05 mass% or less.

In the composition 1 and the composition 2 of the present embodiment, the content ratio of the dispersion medium relative to the total mass of the composition is not particularly limited.

In one embodiment, the content ratio is preferably 99.99 mass % or less, more preferably 99.9 mass % or less, and further preferably 99 mass % or less, from the viewpoint of improving (1) the dispersibility of the calcium-titanium compound and improving durability.

In a certain aspect, the content ratio is preferably 0.1 mass % or more, more preferably 1 mass % or more, further preferably 10 mass % or more, further preferably 50 mass % or more, further preferably 80 mass % or more, and most preferably 90 mass % or more from the viewpoint of improving durability.

The above upper limit values and lower limit values may be combined arbitrarily.

In one aspect, the content ratio of the dispersion medium relative to the total mass of the composition is usually 0.1 to 99.99 mass %.

In one embodiment, the content ratio of the dispersion medium relative to the total mass of the composition is preferably 1-99 mass%, more preferably 10-99 mass%, further preferably 20-99 mass%, particularly preferably 50-99 mass%, and most preferably 90-99 mass%. In other embodiments, the content ratio of the dispersion medium is 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95 mass% or more. In other embodiments, the content ratio of the dispersion medium is 99, 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5 mass% or less.

In a certain aspect, in the above composition, the total content ratio of (1) the calcium-titanium compound, (2) the surface protective agent and the dispersion medium relative to the total mass of the composition can be 90 mass % or more, 95 mass % or more, 99 mass % or more, or 100 mass %.

In Composition 1 and Composition 2 of this embodiment, the content ratio of (6) the surface modifying agent relative to the total mass of the composition is not particularly limited.

In a certain aspect, the content ratio is preferably 30 mass % or less, more preferably 1 mass % or less, and further preferably 0.1 mass % or less from the viewpoint of improving durability.

In addition, in a certain embodiment, the above content ratio is preferably 0.0001 mass % or more, more preferably 0.001 mass % or more, and further preferably 0.01 mass % or more from the viewpoint of improving thermal durability. In other embodiments, the above content ratio is 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, 25 mass % or more. In other embodiments, the above content ratio is 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.01, 0.005 mass % or less.

The above upper limit values and lower limit values may be combined arbitrarily.

In one embodiment, the content ratio of (6) the surface modifying agent relative to the total mass of the composition is generally 0.0001 to 30 mass %.

In one embodiment, the content ratio of (6) the surface modifier relative to the total mass of the composition is preferably 0.001-1 mass%, and more preferably 0.01-0.1 mass%. In other embodiments, the content ratio of (6) the surface modifier is 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 15, 20, 25 mass% or more. In other embodiments, the content ratio of (6) the surface modifier is 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.01, 0.005 mass% or less.

(6) The composition having the content ratio of the surface modifying agent relative to the total mass of the composition within the above range is better in terms of excellent thermal durability.

In a certain aspect, the total content ratio of the impurities, the amorphous compound containing the elements constituting the (1) calcium-titanium compound, and the polymerization initiator in the composition of the present embodiment is preferably 10 mass % or less, more preferably 5 mass % or less, and further preferably 1 mass % or less, relative to the total mass of the composition.

<Ratio of each component> In the compositions 1 and 2 of the present embodiment, the mass ratio of (1) the calcium-titanium compound to the dispersion medium [(1) calcium-titanium compound/dispersion medium] may be 0.00001 to 10, 0.0001 to 5, or 0.0005 to 3.

The composition having the mixing ratio of (1) the calcium-titanium compound to the dispersion medium within the above range is preferred in that (1) the calcium-titanium compound is less likely to aggregate and has good luminescence.

In the composition 1 of this embodiment, the mixing ratio of (1) the calcium-titanium compound and (2) the surface protecting agent can be appropriately determined according to the types of (1) and (2).

In the composition 1 of the present embodiment, the molar ratio [Si/B] of the metal ions as the B component of the (1) calcium-titanium compound and the Si element as the (2) surface protective agent can be 0.001 to 200, or 0.01 to 50.

In the composition 1 of the present embodiment, when the surface protective agent (2) is a modified form of silazane represented by formula (B1) or (B2), the molar ratio [Si/B] of the metal ion as the B component of the calcium-titanium compound (1) to Si of the modified form of silazane (2-1) may be 0.001 to 100, 0.001 to 50, or 1 to 20.

In the composition 1 of the present embodiment, when the (2) surface protective agent is a polysilazane having a structural unit represented by the formula (B3), the molar ratio [Si/B] of the metal ion as the B component of the (1) calcium-titanium compound to the Si element of the modified form of the (2-1) silazane can be 0.001 to 100, 0.01 to 100, 0.1 to 100, 1 to 50, or 1 to 20.

A composition in which the mixing ratio of (1) the calcium-titanium compound to (2) the surface protective agent is within the above range is preferred in that the effect of improving the durability against water vapor produced by the (2) surface protective agent is particularly good.

The molar ratio [Si/B] of the metal ion as the B component of the above-mentioned calcium-titanium compound to the Si element of the (2) surface protective agent can be obtained by the following method. The molar number (B) of the metal ion as the B component of the calcium-titanium compound is obtained by calculating the mass of the metal as the B component contained in the calcium-titanium compound by inductively coupled plasma mass spectrometry (ICP-MS) and converting it into moles. In addition, the molar number (Si) of the Si element of the (2) surface protective agent is obtained by converting the mass of the (2) surface protective agent used into moles. At this time, the ratio of the molar number of Si element in (2) the surface protective agent (Si) to the molar number of metal ions as the B component of the calcium-titanium compound (B) is [Si/B].

In a certain embodiment, in the composition of the present embodiment, from the viewpoint of sufficiently improving the quantum yield, the mass of (2) the surface protective agent is preferably 1.1 parts by mass or more, more preferably 1.5 parts by mass or more, and further preferably 1.8 parts by mass or more relative to the mass of (1) the calcium-titanium compound. In other embodiments, the mass of (2) the surface protective agent is preferably 10 parts by mass or less, more preferably 4.9 parts by mass or less, and further preferably 2.5 parts by mass or less relative to the mass of (1) the calcium-titanium compound. The above upper and lower limits may be arbitrarily combined.

By using the method for producing a semiconductor compound of the present embodiment, it is possible to produce (1) a calcium-titanium compound of the present embodiment and a semiconductor compound containing a metal element M having a peak half-value width of the Miller index (001) of a plane in an X-ray diffraction pattern of 0.10 or more and less than 0.60.

<Method for producing semiconductor compounds> The method for producing semiconductor compounds of this embodiment comprises: a step of mixing raw materials of either or both of a simple substance containing a metal element M and a compound containing a metal element M with water, and a step of reacting the raw materials in the presence of the water. The ratio of the mass W _W of the water to the mass W _M of the metal element M contained in the raw materials, i.e., (W _W /W _M ), is 0.05 to 100.

If water is present in the step of crystallizing the semiconductor compound generated by reacting either or both of the raw materials of a simple substance containing the metal element M and a compound containing the metal element M, a portion of the crystals of the generated semiconductor compound will dissolve, and then the semiconductor compound will recrystallize, thereby improving the crystallinity of the semiconductor compound.

<Metal element M> As the metal element M contained in the method for producing the semiconductor compound of the present embodiment, metal elements of Groups 2 to 14 of the periodic table can be cited as examples. The metal elements of Groups 2 to 14 of the periodic table are not particularly limited, and examples thereof include: Mg, Ca, Sr, Ba, Cu, Zn, Cd, Hg, Al, Ga, In, Sn, and Pb.

The semiconductor compound of this embodiment may contain non-metallic elements of Groups 13 to 17 of the periodic table in addition to the above-mentioned metal element M. The non-metallic elements of Groups 13 to 17 of the periodic table are not particularly limited, and examples thereof include: B, C, N, P, As, Sb, Se, Te, F, Cl, Br, I, and S.

As semiconductor compounds produced by the production method of this embodiment, there can be listed: (1) calcium titanium compound of this embodiment and the semiconductor compounds of (i) to (vii) below. (i) Semiconductor compound containing II-VI compound (ii) Semiconductor compound containing II-V compound (iii) Semiconductor compound containing III-V compound (iv) Semiconductor compound containing III-IV compound (v) Semiconductor compound containing III-VI compound (vi) Semiconductor compound containing IV-VI compound (vii) Semiconductor compound containing transition metal-p-zone compound

<(i) Semiconductor compounds containing Group II-VI compounds> As semiconductor compounds containing Group II-VI compounds, there can be listed: semiconductor compounds containing compounds containing Group 2 elements and Group 16 elements in the periodic table, and semiconductor compounds containing compounds containing Group 12 elements and Group 16 elements in the periodic table, but they are not limited to them. In addition, in this specification, the so-called "periodic table" refers to a long-periodic type periodic table.

In the following description, a semiconductor compound including a compound containing a Group 2 element and a Group 16 element is sometimes referred to as a "semiconductor compound (i-1)", and a semiconductor compound including a compound containing a Group 12 element and a Group 16 element is sometimes referred to as a "semiconductor compound (i-2)".

In one embodiment, the semiconductor compound (i-1) may be a binary semiconductor compound such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe or BaTe, but is not limited thereto.

In a certain embodiment, the semiconductor compound (i-1) may be: (i-1-1) a ternary semiconductor compound containing one Group 2 element and two Group 16 elements (i-1-2) a ternary semiconductor compound containing two Group 2 elements and one Group 16 element (i-1-3) a quaternary semiconductor compound containing two Group 2 elements and two Group 16 elements.

In one embodiment, the semiconductor compound (i-2) may be a binary semiconductor compound such as ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe or HgTe, but is not limited thereto.

In a certain embodiment, the semiconductor compound (i-2) may be: (i-2-1) a ternary semiconductor compound containing one element of Group 12 and two elements of Group 16 (i-2-2) a ternary semiconductor compound containing two elements of Group 12 and one element of Group 16 (i-2-3) a quaternary semiconductor compound containing two elements of Group 12 and two elements of Group 16.

The Group II-Group VI semiconductor compound may contain an element other than the Group 2 elements, the Group 12 elements, and the Group 16 elements as a doping element.

<(ii) Semiconductor compounds containing Group II-Group V compounds> Group II-Group V semiconductor compounds contain Group 12 elements and Group 15 elements.

Examples of binary semiconductor compounds in Group II to Group V semiconductor compounds include, but are not limited to, Zn ₃ P ₂ , Zn ₃ As ₂ , Cd ₃ P ₂ , Cd ₃ As ₂ , Cd ₃ N ₂ , and Zn ₃ N ₂ .

In a certain embodiment, the Group II-V semiconductor compound may be: (ii-1) a ternary semiconductor compound containing one Group 12 element and two Group 15 elements (ii-2) a ternary semiconductor compound containing two Group 12 elements and one Group 15 element (ii-3) a quaternary semiconductor compound containing two Group 12 elements and two Group 15 elements.

The Group II-V semiconductor compound may contain an element other than the Group 12 element and the Group 15 element as a doping element.

<(iii) Semiconductor compounds containing Group III-V compounds> Group III-V semiconductor compounds contain Group 13 elements and Group 15 elements.

Among the III-V semiconductor compounds, examples of binary semiconductor compounds include, but are not limited to, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, and AlN.

In a certain embodiment, the III-V semiconductor compound may be: (iii-1) a ternary semiconductor compound containing one element of the 13th group and two elements of the 15th group (iii-2) a ternary semiconductor compound containing two elements of the 13th group and one element of the 15th group (iii-3) a quaternary semiconductor compound containing two elements of the 13th group and two elements of the 15th group.

The Group III-V semiconductor compound may contain an element other than the Group 13 element and the Group 15 element as a doping element.

<(iv) Semiconductor compounds containing Group III-Group IV compounds> Group III-Group IV semiconductor compounds contain Group 13 elements and Group 14 elements.

Among the group III-group IV semiconductor compounds, examples of binary semiconductor compounds include Al ₄ C ₃ and Ga ₄ C ₃ .

In addition, as a group III-IV semiconductor compound, it can be (iv-1) a ternary semiconductor compound containing one group 13 element and two group 14 elements (iv-2) a ternary semiconductor compound containing two group 13 elements and one group 14 element (iv-3) a quaternary semiconductor compound containing two group 13 elements and two group 14 elements.

The Group III-IV semiconductor compound may contain an element other than the Group 13 element and the Group 14 element as a doping element.

<(v) Semiconductor compounds containing Group III-VI compounds> Group III-VI semiconductor compounds contain Group 13 elements and Group 16 elements.

Examples of binary semiconductor compounds of Group III _- VI semiconductor compounds include, but are not limited to, _{Al2S3 , Al2Se3 , Al2Te3 , Ga2S3 , Ga2Se3 , Ga2Te3 , GaTe, In2S3 , In2Se3 , In2Te3 ,} or InTe.

In a certain embodiment, the III-VI semiconductor compound may be: (v-1) a ternary semiconductor compound containing one element of the 13th group and two elements of the 16th group (v-2) a ternary semiconductor compound containing two elements of the 13th group and one element of the 16th group (v-3) a quaternary semiconductor compound containing two elements of the 13th group and two elements of the 16th group.

The Group III-VI semiconductor compound may contain an element other than the Group 13 elements and the Group 16 elements as a doping element.

<(vi) Semiconductor compounds containing Group IV-Group VI compounds> Group IV-Group VI semiconductor compounds contain Group 14 elements and Group 16 elements.

Among the Group IV-Group VI semiconductor compounds, examples of binary semiconductor compounds include PbS, PbSe, PbTe, SnS, SnSe, and SnTe, but are not limited thereto.

In a certain embodiment, the Group IV-Group VI semiconductor compound may be: (vi-1) a ternary semiconductor compound containing one Group 14 element and two Group 16 elements (vi-2) a ternary semiconductor compound containing two Group 14 elements and one Group 16 element (vi-3) a quaternary semiconductor compound containing two Group 14 elements and two Group 16 elements.

The Group IV-Group VI semiconductor compound may contain an element other than the Group 14 element and the Group 16 element as a doping element.

<(vii) Semiconductor compounds containing transition metal-p-block compounds> Transition metal-p-block semiconductor compounds contain transition metal elements and p-block elements. The so-called "p-block elements" refer to elements belonging to Groups 13 to 18 of the periodic table.

Among the transition metal-p-zone semiconductor compounds, examples of binary semiconductor compounds include NiS and CrS, but the present invention is not limited thereto.

Furthermore, in a certain embodiment, the transition metal-p-zone semiconductor compound may be: (vii-1) a ternary semiconductor compound containing one transition metal element and two p-zone elements (vii-2) a ternary semiconductor compound containing two transition metal elements and one p-zone element (vii-3) a quaternary semiconductor compound containing two transition metal elements and two p-zone elements.

The transition metal-p-zone semiconductor compound may contain elements other than the transition metal element and the p-zone element as doping elements.

Specific examples of the ternary semiconductor compound or quaternary semiconductor compound include: ZnCdS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, ZnCdSSe, CdZnSeS, CdZnS eTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, _CuInS2 or InAlPAs, etc., but not limited to them.

In one embodiment, the semiconductor compound of the present embodiment is preferably (1) a calcium-titanium compound, a semiconductor compound containing Cd as a Group 12 element, and a semiconductor compound containing In as a Group 13 element. In another embodiment, the compound of the present embodiment is more preferably (1) a calcium-titanium compound, a semiconductor compound containing Cd and Se, and a semiconductor compound containing In and P.

In one embodiment, the semiconductor compound containing Cd and Se is preferably any one of a binary semiconductor compound, a ternary semiconductor compound, and a quaternary semiconductor compound. In another embodiment, among the semiconductor compounds containing Cd and Se, CdSe, which is a binary semiconductor compound, is particularly preferred.

In one embodiment, the semiconductor compound containing In and P is preferably any one of a binary semiconductor compound, a ternary semiconductor compound, and a quaternary semiconductor compound. In another embodiment, among the semiconductor compounds containing In and P, InP, which is a binary semiconductor compound, is particularly preferred.

<Particle size of the semiconductor compound produced by the method for producing a semiconductor compound of this embodiment> The preferred average particle size of the semiconductor compound produced by the method for producing a semiconductor compound of this embodiment is the same as the average particle size of the calcium-titanium compound described in (1) above.

In this specification, the average particle size of the semiconductor compound produced by the method for producing a semiconductor compound of this embodiment can be measured by the same method as the measurement of the average particle size of the calcium-titanium compound in (1) above.

In the production of the semiconductor compound of the present embodiment, raw materials containing either or both of a simple substance containing a metal element M and a compound containing a metal element M are used (hereinafter, the raw materials containing either or both of a simple substance containing a metal element M and a compound containing a metal element M are sometimes referred to as "raw materials containing a metal element M"). When the semiconductor compound contains a non-metallic element, it is preferred to further use a compound containing a non-metallic element in the above raw materials (hereinafter, the compound containing a non-metallic element is sometimes referred to as "raw material compound containing a non-metallic element").

<Single substance of metal element M> The single substance of metal element M is not particularly limited, and the single substance of metal element M mentioned above can be cited.

<Compounds containing metal element M> The compounds containing metal element M are not particularly limited, and examples thereof include oxides, acetates, organometallic compounds, halides, nitrates, etc. containing the above-mentioned metal element M.

In the production of the semiconductor compound of this embodiment, only one kind of the metal element M may be used as a single substance, or two or more kinds may be used in combination.

In the production of the semiconductor compound of this embodiment, only one of the above-mentioned compounds containing the metal element M may be used, or two or more thereof may be used in combination.

<Compounds containing non-metallic elements> As raw material compounds containing non-metallic elements, there are no particular restrictions, and compounds containing non-metallic elements contained in semiconductor compounds can be used. In this embodiment, compounds containing non-metallic elements of Groups 13 to 17 of the above-mentioned periodic table can be used without restriction.

In the production of the semiconductor compound of this embodiment, only one of the above-mentioned raw material compounds containing non-metallic elements may be used, or two or more of them may be used in combination.

(Method for producing semiconductor compounds of (i) to (vii)) The semiconductor compounds of (i) to (vii) can be produced by heating a mixed solution containing a raw material containing a metal element M constituting the semiconductor compound and a fat-soluble solvent. It is also preferred to add a compound containing a non-metallic element constituting the semiconductor compound to the mixed solution as needed.

Examples of the fat-soluble solvent include nitrogen-containing compounds having a carbon number of 4 to 20 and oxygen-containing compounds having a carbon number of 4 to 20.

Examples of the alkyl group having 4 to 20 carbon atoms include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

Examples of the saturated aliphatic hydrocarbon group having 4 to 20 carbon atoms include n-butyl, isobutyl, n-pentyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl.

Examples of unsaturated aliphatic hydrocarbon groups having 4 to 20 carbon atoms include oleyl and oleyl.

Examples of the alicyclic alkyl group having 4 to 20 carbon atoms include cyclopentyl and cyclohexyl.

Examples of the aromatic hydrocarbon group having 4 to 20 carbon atoms include phenyl, benzyl, naphthyl, naphthylmethyl and the like.

As the alkyl group having 4 to 20 carbon atoms, a saturated aliphatic alkyl group and an unsaturated aliphatic alkyl group are preferred.

As nitrogen-containing compounds, amines or amides can be cited. As oxygen-containing compounds, fatty acids can be cited.

Among such fat-soluble solvents, nitrogen-containing compounds having a alkyl group having 4 to 20 carbon atoms are preferred. Examples of such nitrogen-containing compounds include alkylamines such as n-butylamine, isobutylamine, n-pentylamine, n-hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, and octadecylamine, and alkenylamines such as oleylamine.

Such a fat-soluble solvent can bond to the surface of the semiconductor compound produced by synthesis. When the fat-soluble solvent bonds to the surface of the semiconductor compound, for example, chemical bonds such as covalent bonds, ionic bonds, coordination bonds, hydrogen bonds, and Van der Waals bonds can be listed.

The heating temperature of the above-mentioned mixed solution can be appropriately set according to the type of raw materials (single substance or compound) used. The temperature of the mixed solution is usually room temperature to 300°C. For example, it is preferably 130-300°C, and more preferably 240-300°C. If the heating temperature is above the above lower limit, the crystal structure is easy to be unified, so it is better. If the heating temperature is below the above upper limit, the crystal structure of the produced semiconductor compound is not easy to collapse, and it is easy to obtain the target, so it is better. In a certain embodiment, the heating temperature is 0, 5, 10, 50, 75, 100, 130, 150, 175, 200, 250°C or above. In other aspects, the heating temperature is 300, 250, 200, 175, 150, 130, 100, 75, 50, 10, or less than 5°C.

The heating time of the mixed solution can be appropriately set according to the type of raw materials (single substance or compound) used and the heating temperature. The heating time of the mixed solution is preferably, for example, several seconds to several hours, more preferably 1 to 60 minutes.

In the above-mentioned method for producing a semiconductor compound, a precipitate containing the target semiconductor compound is obtained by cooling the heated mixed solution. The precipitate is separated and appropriately washed to obtain the target semiconductor compound.

A solvent in which the synthesized semiconductor compound is insoluble or poorly soluble may be added to the supernatant obtained by separating the precipitate, so that the solubility of the semiconductor compound in the supernatant is reduced, thereby generating a precipitate, and recovering the semiconductor compound contained in the supernatant. Examples of "solvent in which the semiconductor compound is insoluble or poorly soluble" include methanol, ethanol, acetone, acetonitrile, etc.

In the above-mentioned method for producing a semiconductor compound, the separated precipitate can be added to an organic solvent (such as chloroform, toluene, hexane, n-butanol, etc.) to prepare a solution containing the semiconductor compound.

The manufacturing method of the semiconductor compound of the present embodiment includes the step of mixing raw materials of either or both of a simple substance containing a metal element M and a compound containing a metal element M with water. This step can be performed by adding the solution before heating to water, or by adding water to either or both of the solution before heating and the solution being heated. Among them, it is preferred to add water to either or both of the solution before heating and the solution being heated. Furthermore, when water is added to the solution being heated, the temperature of the solution at the time of addition is preferably below 155°C, more preferably below 150°C, and further preferably below 140°C.

The amount of water added is set in such a way that the ratio of the mass W _W of the water added to the mass W _M of the metal element M contained in the raw material containing the metal element M, that is, (W _W /W _M ), becomes 0.05 to 100. The metal element M may be a metal element constituting B of (1) the calcium-titanium compound. (W _W /W _M ) is preferably 0.05 to 3.0, more preferably 0.50 to 3.0, more preferably 1.0 to 2.2, and more preferably 1.1 to 2.0. If (W _W /W _M ) is within the above range, the half width of the peak of (hkl) = (001) in the X-ray pattern of the obtained semiconductor compound can be made into a specific range. When a plurality of simple substances or compounds containing the metal element M are used in the raw material containing the metal element M, the W _M can be obtained by adding the sum of the masses of all simple substances of the metal element M used and the sum of the masses of the metal element M in all compounds containing the metal element M. Furthermore, when water is added multiple times, the mass of all water added can be used as the W _W.

In other aspects of the present embodiment, when the metal element M is a metal element constituting B of the (1) calcium-titanium compound, _WM may be the total mass of one or more metal elements selected from the group consisting of lead, tin, antimony, bismuth and indium contained in the (1) calcium-titanium compound.

In other aspects of this embodiment, the above (W _W /W _M ) is 0.05, 0.06, 0.07, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 or more, and the above (W _W /W _M ) is 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06 or less.

From the viewpoint of promoting the dissolution of water in an organic solvent, it is preferred that the solution to which water is added contain an ionic compound. As the ionic compound, an ammonium compound or a halide is preferred.

From the viewpoint of promoting the dissolution of water in the solvent, it is preferred that the preparation of the solution containing water be mixed at room temperature.

From the viewpoint of removing unnecessary water after the reaction and suppressing deterioration, it is preferred to conduct the reaction while flowing an inert gas.

In this specification, the water content in the solution can be measured using a trace water content measuring device (AQ-2000, manufactured by Hiranuma Sangyo Co., Ltd., ketone electrolyte Hydranal-Coulomat AK).

<(1) Method for producing calcium-titanium ore compounds> (1) The method for producing calcium-titanium ore compounds can be referred to known literature (Nano Lett. 2015, 15, 3692-3696, ACS Nano, 2015, 9, 4533-4542), and is produced by the method described below.

(First production method) As a production method of a calcium-titanium compound, there can be listed: a production method including the steps of dissolving component B, component X and component A constituting the calcium-titanium compound in the above-mentioned (3) solvent at a high temperature to obtain a solution, and the step of cooling the solution.

The first manufacturing method will be described in detail below.

First, a compound containing component B and component X and a compound containing component A are dissolved in a high-temperature (3) solvent to obtain a solution. The "compound containing component A" may contain component X. In this step, each compound may be added to a high-temperature (3) solvent to dissolve the compound and obtain a solution. In this step, each compound may be added to the (3) solvent and then heated to obtain a solution. In the first manufacturing method, the solution is preferably obtained by adding each compound to the (3) solvent and then heating to obtain a solution.

The solvent (3) is preferably a solvent that can dissolve the compound containing the B component and the X component and the compound containing the A component as the raw materials.

The so-called "high temperature" refers to any solvent having a temperature at which the raw materials can be dissolved. For example, the temperature of the high temperature (3) solvent is preferably 60 to 600°C, more preferably 80 to 400°C.

When the solution is obtained by heating the solution after adding each compound to the solvent (3), the temperature after heating is preferably 80 to 150°C, more preferably 120 to 140°C.

In the first production method, it is preferred that water is added to the solution before or during the heating.

When water is added to the solution being heated, the temperature of the solution at the time of addition is preferably 155° C. or lower, more preferably 150° C. or lower, and further preferably 140° C. or lower.

The amount of water added is set so that the ratio of the mass W _W of the water added to the mass W _M of the metal element M contained in the raw material containing the metal element M, that is, (W _W /W _M ), is 0.05 to 100. (W _W /W _M ) is preferably 0.05 to 3.0, more preferably 0.5 to 3.0, more preferably 1.0 to 2.2, and more preferably 1.1 to 2.0. If (W _{W /W M ) is within the above range, the half width of the peak of (hkl) = (001) in the X-ray pattern of the obtained (1) calcium-titanium compound can be made into a specific range. In a certain embodiment, (W W /W M )} is 0.5, 0.75, 1.0, 1.1, 1.5, 2.0, 2.2, 2.5 or more. In other aspects, (W _W /W _M ) is 3.0, 2.5, 2.2, 2.0, 1.5, 1.1, 1.0, or less than 0.75.

When a plurality of simple substances of the metal element M or compounds containing the metal element M are used in the raw material containing the metal element M, the W _M can be obtained by adding the sum of the masses of all simple substances of the metal element M used and the sum of the masses of the metal element M in all compounds containing the metal element M used. In addition, when water is added multiple times, the W _W can be the mass of all water added. In addition, in this embodiment, the B component is the metal element M.

From the viewpoint of promoting the dissolution of water in an organic solvent, it is preferred that the solution to which water is added contain an ionic compound. As the ionic compound, an ammonium compound or a halide is preferred.

From the viewpoint of promoting the dissolution of water in the solvent, it is preferred that the preparation of the solution containing water be mixed at room temperature.

From the viewpoint of removing unnecessary water after the reaction and suppressing deterioration, it is preferred to conduct the reaction while flowing an inert gas.

Then, the obtained solution is cooled. In one embodiment, the cooling temperature is preferably -20 to 50°C, and more preferably -10 to 30°C. In one embodiment, the cooling temperature is -20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45°C or more. In other embodiments, the cooling temperature is 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 0, -5, -10, -15°C or less. As the cooling rate, it is preferably 0.1 to 1500°C/min, and more preferably 10 to 150°C/min. In one embodiment, the cooling rate is 0.1, 0.5, 1, 5, 10, 25, 50, 75, 100, 150, 250, 500, 750, 1000, 1250°C/min or more. In other embodiments, the cooling rate is 1500, 1250, 1000, 750, 500, 250, 150, 100, 75, 50, 25, 10, 1, 0.5°C/min or less.

By cooling the high temperature solution, the calcium-titanium compound can be precipitated by utilizing the difference in solubility caused by the temperature difference of the solution. Thus, a dispersion containing the calcium-titanium compound is obtained.

The obtained dispersion containing calcium-titanium compounds is subjected to solid-liquid separation, thereby recovering the calcium-titanium compounds. As a method of solid-liquid separation, there can be cited: filtration, concentration by evaporation of solvent, etc. By performing solid-liquid separation, only calcium-titanium compounds can be recovered.

Furthermore, in the above-mentioned production method, in order to make the obtained calcium-titanium compound particles easily and stably dispersed in the dispersion liquid, it is preferred to include the step of adding the above-mentioned (6) surface modifier.

The step of adding (6) the surface modifying agent is preferably performed before the cooling step. Specifically, the surface modifying agent (6) can be added to the (3) solvent, or can be added to a solution containing the compound containing the B component and the X component and the compound containing the A component.

Furthermore, in the above production method, preferably, after the cooling step, a step of removing coarse particles by centrifugal separation, filtration, etc. is included. The size of the coarse particles removed by the removal step is preferably larger than 10 μm, more preferably larger than 1 μm, and further preferably larger than 500 nm.

(Second production method) As a production method of a calcium-titanium compound, there can be listed a production method including the following steps: a step of obtaining a first solution containing component A and component B constituting the calcium-titanium compound; a step of obtaining a second solution containing component X constituting the calcium-titanium compound; a step of mixing the first solution and the second solution to obtain a mixed solution, and a step of cooling the obtained mixed solution.

The second manufacturing method will be described in detail below.

First, a compound containing component A and a compound containing component B are dissolved in a high-temperature second solvent to obtain a first solution. In this step, each compound can be added to a high-temperature (3) solvent to dissolve them to obtain the first solution. In this step, each compound can be added to the (3) solvent and then heated to obtain the first solution. In the second manufacturing method, the first solution is preferably obtained by adding each compound to the (3) solvent and then heating.

The (3) solvent is preferably a solvent that can dissolve the compound containing the A component and the compound containing the B component.

The so-called "high temperature" may be any temperature at which the compound containing component A and the compound containing component B are dissolved. For example, the temperature of the high temperature (3) solvent is preferably 60 to 600°C, more preferably 80 to 400°C.

When the first solution is obtained by heating after adding each compound to the solvent (3), the holding temperature after heating is preferably 80 to 150°C, more preferably 120 to 140°C. In one embodiment, the holding temperature after heating is 80, 90, 100, 110, 120, 130, or 140°C or higher. In one embodiment, the holding temperature after heating is 150, 140, 130, 120, 110, 100, 90, 80, or 70°C or lower.

Furthermore, the compound containing component X is dissolved in the above-mentioned solvent (3) to obtain the second solution. Alternatively, the compound containing component X and the compound containing component B are dissolved in the solvent (3) to obtain the second solution.

Examples of (3) solvents include solvents that can dissolve a compound containing component X.

Then, the obtained first solution and the second solution are mixed to obtain a mixed solution. When the first solution and the second solution are mixed, one can be dropped into the other. Alternatively, the first solution and the second solution can be mixed while stirring.

In the second manufacturing method, water can be added to either or both of the first solution and the second solution before or during the heating, or can be added to a mixture of the first solution and the second solution. It is preferred to add water to either or both of the first solution and the second solution before or during the heating, and more preferably to the second solution.

In one embodiment, when water is added to the first solution during the heating process, the temperature of the solution during the addition is preferably 155° C. or lower, more preferably 150° C. or lower, and further preferably 140° C. or lower.

In one embodiment, when water is added to the second solution, the temperature of the first solution during mixing is preferably 155° C. or lower, more preferably 150° C. or lower, and further preferably 140° C. or lower.

In one embodiment, when water is added to the mixture of the first solution and the second solution, the temperature of the mixture during the addition is preferably 155° C. or lower, more preferably 150° C. or lower, and further preferably 140° C. or lower.

In one embodiment, the amount of water added is set in such a way that the ratio of the mass W _W of the water added to the mass W _M of the metal element M contained in the raw material containing the metal element M, that is, (W _W /W _M ), is 0.05 to 100. The metal element M may be a metal element B constituting the (1) calcium-titanium compound. (W _W /W _M ) is preferably 0.05 to 3.0, more preferably 0.5 to 3.0, more preferably 1.0 to 2.2, and more preferably 1.1 to 2.0. If (W _W /W _M ) is within the above range, the half-value width of the peak of (hkl) = (001) in the X-ray pattern of the obtained (1) calcium-titanium compound can be made into a specific range.

In other aspects, when a plurality of simple substances of the metal element M or compounds containing the metal element M are used in the raw material containing the metal element M, the above W _M can be obtained by adding the sum of the masses of all simple substances of the metal element M used and the sum of the masses of the metal element M in all compounds containing the metal element M used. Furthermore, when water is added multiple times, the above W _W can be the mass of all water added.

In other aspects of this embodiment, the W _M may be (1) the total mass of one or more metal elements selected from the group consisting of lead, tin, antimony, bismuth and indium contained in the calcium-titanium compound.

In other aspects of this embodiment, the above (W _W /W _M ) is 0.05, 0.06, 0.07, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 or more, and the above (W _W /W _M ) is 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06 or less.

From the viewpoint of promoting the dissolution of water in an organic solvent, it is preferred that the solution to which water is added contains an ionic compound. In one embodiment, the ionic compound is preferably an ammonium compound or a halide.

From the viewpoint of promoting the dissolution of water in the solvent, it is preferred that the preparation of the solution containing water be mixed at room temperature.

From the viewpoint of removing unnecessary water after the reaction and suppressing deterioration, it is preferred to conduct the reaction while flowing an inert gas.

Then, the obtained mixed liquid is cooled. In one embodiment, the cooling temperature is preferably -20 to 50°C, and more preferably -10 to 30°C. In one embodiment, the cooling temperature is above -20, -15, -10, -5, 0, 5, 10, 15, 20, 25°C. In other embodiments, the cooling temperature is below 30, 25, 20, 15, 10, 5, 0, -5, -10, -15°C. In one embodiment, the cooling rate is preferably 0.1 to 1500°C/min, and more preferably 10 to 150°C/min.

In one embodiment, by cooling the mixed solution, the calcium-titanium compound can be precipitated by utilizing the difference in solubility caused by the temperature difference of the mixed solution, thereby obtaining a dispersion containing the calcium-titanium compound.

In another embodiment, the obtained dispersion containing calcium-titanium compounds is subjected to solid-liquid separation to recover the calcium-titanium compounds. As a method for solid-liquid separation, the method shown in the first production method can be cited.

Furthermore, in other aspects, in the above-mentioned production method, in order to make the obtained calcium-titanium compound particles easy to be stably dispersed in the dispersion, it is preferred to include the step of adding the above-mentioned (6) surface modifier.

In one embodiment, the step of adding (6) the surface modifying agent is preferably performed before the cooling step. Specifically, the surface modifying agent (6) can be added to any one of the (3) solvent, the first solution, the second solution, and the mixed solution.

In one embodiment, the above production method preferably includes, after the cooling step, a step of removing coarse particles by centrifugal separation, filtration, etc. as described in the first production method.

<Production method 1 of composition 1> In order to facilitate understanding of the properties of the obtained composition, the composition obtained by the production method 1 of composition 1 is referred to as "composition 1-1". Composition 1-1 is a liquid composition.

In one embodiment, the composition 1-1 of the present embodiment can be prepared by further mixing one or both of (3) a solvent and (4) a polymerizable compound into (1) a calcium-titanium compound and (2) a surface protective agent.

In one embodiment, when (1) the calcium-titanium compound and (2) the surface protecting agent are mixed with (3) the solvent and (4) the polymerizable compound, or both, the mixture is preferably carried out while stirring.

When (1) the calcium-titanium compound and (2) the surface protective agent are mixed with either or both of (3) the solvent and (4) the polymerizable compound, the temperature during the mixing is not particularly limited. In order to facilitate uniform mixing of (1) the calcium-titanium compound and (2) the surface protective agent, the temperature during the mixing is preferably in the range of 0°C to 100°C, and more preferably in the range of 10°C to 80°C. In a certain embodiment, the temperature during the mixing of (1) the calcium-titanium compound and (2) the surface protective agent and either or both of (3) the solvent and (4) the polymerizable compound is 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95°C or above. In other embodiments, the temperature at which (1) the calcium-titanium compound and (2) the surface protecting agent are mixed with either or both of (3) the solvent and (4) the polymerizable compound is 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 25, 20, 15, 10, or 5° C. or less.

(Method for producing composition 1-1 containing (3) solvent) As a method for producing a composition containing (1) a calcium-titanium compound, (2) a surface protective agent, and (3) a solvent, for example, the following production method (a1) or the following production method (a2) may be used.

Production method (a1): A method for producing a composition comprising the steps of mixing (1) a calcium-titanium compound and (3) a solvent, and mixing the resulting mixture with (2) a surface protecting agent.

Production method (a2): A production method for a composition comprising the steps of mixing (1) a calcium-titanium compound and (2) a surface protective agent, and mixing the resulting mixture with (3) a solvent.

The solvent (3) used in the production methods (a1) and (a2) is preferably one that is difficult to dissolve the calcium-titanium compound (1). When such a solvent (3) is used, the mixture obtained in the production method (a1) and the composition obtained in the production methods (a1) and (a2) become a dispersion.

When the composition of the present embodiment contains either or both of the modified silazane (2-1) and the modified silicon compound (2-2) as (2) the surface protective agent, the composition may be produced by the following production method (a3) or the following production method (a4).

Preparation method (a3): A method for preparing a composition comprising the steps of mixing (1) a calcium-titanium compound and (3) a solvent, mixing the obtained mixture with either or both of the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound, and subjecting the obtained mixture to a modification treatment.

Production method (a4): A method for producing a composition comprising the steps of mixing (1) a calcium-titanium compound with either or both of the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound, mixing the obtained mixture with (3) a solvent, and subjecting the obtained mixture to a modification treatment.

(5) The polymer may be dissolved or dispersed in (3) the solvent.

In one embodiment, in the mixing step included in the above-mentioned production method, stirring is preferably performed from the viewpoint of improving dispersibility.

In the mixing step included in the above-mentioned manufacturing method, as long as mixing is possible, the temperature is not particularly limited. From the perspective of uniform mixing, it is preferably in the range of 0°C to 100°C, and more preferably in the range of 10°C to 80°C. In one embodiment, the temperature of the mixing step included in the above-mentioned manufacturing method is 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95°C or above. In other embodiments, the temperature of the mixing step included in the above-mentioned manufacturing method is 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5°C or below.

From the viewpoint of improving the dispersibility of the calcium-titanium compound (1), the method for producing the composition is preferably the method (a1) or the method (a3).

(Methods for implementing the modification treatment) The modification treatment methods include: a method of irradiating the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound with ultraviolet rays, and a method of reacting the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound with water vapor, and other well-known methods. In the following description, the treatment of reacting the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound with water vapor is sometimes referred to as "humidification treatment".

In a certain embodiment, the wavelength of the ultraviolet light used in the method of irradiating ultraviolet light is usually 10 to 400 nm, preferably 10 to 350 nm, and more preferably 100 to 180 nm. As a light source for generating ultraviolet light, for example, there can be listed: metal halogen lamp, high-pressure mercury lamp, low-pressure mercury lamp, xenon arc lamp, carbon arc lamp, excimer lamp, UV (ultraviolet) laser light, etc. In a certain embodiment, the wavelength of the ultraviolet light used in the method of irradiating ultraviolet light is 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350 nm or more. In other aspects, the wavelength of ultraviolet light used in the method of irradiating ultraviolet light is 400, 390, 380, 370, 360, 350, 340, 330, 320, 310, 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 150, or 100 nm or less.

Among them, from the viewpoint of (1) forming a stronger protective zone near the calcium-titanium compound, it is more preferable to apply wet treatment.

When the wet treatment is performed, for example, the composition may be left to stand for a certain period of time under the following temperature and humidity conditions, or may be stirred for a certain period of time under the same conditions.

The temperature of the moistening treatment can be any temperature at which the modification is sufficiently performed. The temperature of the moistening treatment is preferably 5 to 150°C, more preferably 10 to 100°C, and further preferably 15 to 80°C. In one embodiment, the temperature of the moistening treatment is 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140°C or more. In other embodiments, the temperature of the moistening treatment is 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10°C or less.

The humidity of the humidification treatment may be a humidity that can sufficiently supply water to the above (2-1) and the above (2-2) in the composition. The humidity of the humidification treatment is preferably 30% to 100%, more preferably 40% to 95%, and even more preferably 60% to 90%.

The time required for the wet treatment may be sufficient as long as the modification is performed. For example, the time required for the wet treatment is preferably 10 minutes to 1 week, more preferably 1 hour to 5 days, and further preferably 2 hours to 3 days.

From the viewpoint of improving the dispersibility of the above-mentioned (2-1) and (2-2) contained in the composition, stirring is preferably performed.

The water supply in the humidification treatment can be carried out by circulating a gas containing water vapor in the reaction container, or by stirring in an environment containing water vapor to supply water from the interface.

In a certain embodiment, when a gas containing water vapor is circulated in a reaction container, in order to improve the durability of the obtained composition, the flow rate of the gas containing water vapor is preferably 0.01 L/min to 100 L/min, more preferably 0.1 L/min to 10 L/min, and further preferably 0.15 L/min to 5 L/min. As the gas containing water vapor, for example, nitrogen containing saturated water vapor can be listed. In a certain embodiment, the flow rate of the gas containing water vapor is 0.01, 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 L/min or more. In other aspects, the flow rate of the gas containing water vapor is 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, or less than 0.5 L/min.

In the method for producing the composition of this embodiment, (2) the surface protective agent and (3) the solvent may be mixed in any step included in the method for producing the calcium-titanium compound (1) above. For example, the following production methods (a5) and (a6) may be used.

Production method (a5): comprising the steps of dissolving a compound containing component B constituting a calcium-titanium compound, a compound containing component X, a compound containing component A and (2) a surface protective agent in a high temperature (3) solvent to obtain a solution, and cooling the solution.

Production method (a6): comprising the steps of dissolving a compound containing component A constituting a calcium-titanium compound and a compound containing component B in a high temperature (3) solvent to obtain a first solution, dissolving a compound containing component X constituting a calcium-titanium compound in the (3) solvent to obtain a second solution, mixing the first solution and the second solution to obtain a mixed solution, and cooling the obtained mixed solution.

In the production method (a6), (2) the surface protecting agent is dissolved in either or both of the first solution and the second solution.

The conditions of each step included in these production methods are the same as the conditions of the first production method and the second production method in the above-mentioned (1) production method of calcium-titanium mineral compounds.

(Method for producing composition 1-2 containing (4) polymerizable compound) The method for producing a composition containing (1) a calcium-titanium compound, (2) a surface protective agent, and (4) a polymerizable compound may be exemplified by the following production methods (c1) to (c3).

Production method (c1): A production method comprising the steps of dispersing (1) a calcium-titanium compound in (4) a polymerizable compound to obtain a dispersion, and mixing the obtained dispersion with (2) a surface protective agent.

Production method (c2): A production method comprising the steps of dispersing (2) a surface protecting agent in (4) a polymerizable compound to obtain a dispersion, and mixing the obtained dispersion with (1) a calcium-titanium compound.

Production method (c3): A production method comprising the steps of dispersing a mixture of (1) a calcium-titanium compound and (2) a surface protective agent in (4) a polymerizable compound.

In one embodiment, among the production methods (c1) to (c3), the production method (c1) is preferred from the viewpoint of improving the dispersibility of the calcium-titanium compound (1).

In the manufacturing methods (c1) to (c3), in the step of obtaining each dispersion, the polymerizable compound (4) may be dripped into each material, or each material may be dripped into the polymerizable compound (4). In a certain embodiment, in order to facilitate uniform dispersion, it is preferred to drip at least one of the (1) calcium-titanium compound and the (2) surface protective agent into the (4) polymerizable compound.

In the manufacturing methods (c1) to (c3), in each mixing step, the dispersion can be dripped into each material, or each material can be dripped into the dispersion. In a certain embodiment, in order to facilitate uniform dispersion, it is preferred to drip at least one of (1) the calcium-titanium compound and (2) the surface protective agent into the dispersion.

At least one of (3) the solvent and (5) the polymer may be dissolved or dispersed in (4) the polymerizable compound.

The solvent for dissolving or dispersing the (5) polymer is not particularly limited. In a certain aspect, the solvent is preferably one that is difficult to dissolve the (1) calcium-titanium compound. As the solvent for dissolving the (5) polymer, for example, the above-mentioned (3) solvent can be cited.

In a certain aspect, among the (3) solvents, halogenated hydrocarbons and hydrocarbons are more preferred.

Furthermore, the method for producing the composition of this embodiment may be the following production method (c4) or the following production method (c5).

Production method (c4): A method for producing a composition comprising the steps of dispersing (1) a calcium-titanium compound in (3) a solvent to obtain a dispersion, mixing (4) a polymerizable compound and (5) a polymer in the obtained dispersion to obtain a mixed solution, and mixing the obtained mixed solution with (2) a surface protective agent.

Production method (c5): A method for producing a composition comprising the steps of dispersing (1) a calcium-titanium compound in (3) a solvent to obtain a dispersion, mixing the obtained dispersion with either or both of the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound to obtain a mixed solution, subjecting the obtained mixed solution to a modification treatment to obtain a mixed solution containing either or both of the modified product of the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound, and mixing the obtained mixed solution with (3) a solvent.

In the method 1 for producing the composition 1, when the (6) surface modifying agent is used, it can be added together with the (2) surface protecting agent.

<Production method 2 of composition 1> As a production method of the composition of this embodiment, there can be listed: a production method including the steps of mixing (1) a calcium-titanium compound, (2) a surface protective agent, and (4) a polymerizable compound, and polymerizing (4) the polymerizable compound.

The composition obtained in the production method 2 of the composition 1 is preferably a composition in which the total amount of (1) the calcium-titanium compound, (2) the surface protective agent, and (5) the polymer is at least 90% by weight of the entire composition.

In addition, as a method for producing the composition of the present embodiment, there can be listed: a method for producing the composition comprising the steps of mixing (1) a calcium-titanium compound, (2) a surface protective agent, and (5) a polymer dissolved in (3) a solvent, and removing (3) the solvent.

The mixing step included in the above-mentioned production method can use the same mixing method as the method shown in the production method 1 of the above-mentioned composition 1.

Examples of methods for producing the composition include the following production methods (d1) and (d2).

Production method (d1): A production method comprising the steps of dispersing (1) a calcium-titanium compound and (2) a surface protective agent in (4) a polymerizable compound, and polymerizing (4) the polymerizable compound.

In the step of adding (1) the calcium-titanium compound and (2) the surface protective agent to the (4) polymerizable compound, there is no restriction on the order. The (1) calcium-titanium compound may be added first, or the (2) surface protective agent may be added first, or the (1) calcium-titanium compound and (2) surface protective agent may be added simultaneously.

Production method (d2): A production method comprising the steps of dispersing (1) a calcium-titanium compound and (2) a surface protective agent in (3) a solvent in which (5) a polymer is dissolved, and removing the solvent.

There is no restriction on the order of adding (1) the calcium-titanium compound and (2) the surface protective agent to (3) the solvent in which (5) the polymer is dissolved in the separation step. (1) The calcium-titanium compound may be added first, or (2) the surface protective agent may be added first, or (1) the calcium-titanium compound and (2) the surface protective agent may be added simultaneously.

The step of removing the solvent (3) included in the production method (d2) may be a step of leaving the mixture to dry naturally at room temperature, a step of drying under reduced pressure using a vacuum dryer, or a step of evaporating the solvent (3) by heating.

In the step of removing the solvent (3), the solvent (3) can be removed by, for example, drying at a temperature of 0° C. to 300° C. for 1 minute to 7 days.

The step of polymerizing the polymerizable compound (4) included in the production method (d1) can be carried out by appropriately using a known polymerization reaction such as free radical polymerization.

For example, in the case of free radical polymerization, a free radical polymerization initiator is added to a mixture of (1) a calcium titanium compound, (2) a surface protective agent, and (4) a polymerizable compound to generate free radicals, thereby allowing the polymerization reaction to proceed.

The radical polymerization initiator is not particularly limited, and examples thereof include photoradical polymerization initiators and the like.

Examples of the photoradical polymerization initiator include bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and the like.

In the method 2 for producing the composition 1, when the surface modifying agent (6) is used, it can be added together with the surface protecting agent (2).

<Production method 3 of composition 1> In addition, the production method of the composition of this embodiment can also adopt the following production methods (d3) to (d6).

Production method (d3): A production method comprising the steps of melt-kneading (1) a calcium-titanium compound, (2) a surface protective agent and (5) a polymer.

Production method (d4): A production method comprising the steps of melt-kneading (1) a calcium-titanium compound, one or both of the above-mentioned (2-1) silazane and the above-mentioned (2-2) silicon compound, and (5) a polymer, and applying a wet treatment to the (5) polymer while it is molten.

Production method (d5): A production method comprising the steps of preparing a liquid composition containing (1) a calcium-titanium compound and (2) a surface protective agent, removing a solid component from the obtained liquid composition, and melt-kneading the obtained solid component with (5) a polymer.

Production method (d6): comprising the steps of preparing a liquid composition containing (1) a calcium-titanium compound but not containing (2) a surface protective agent, removing a solid component from the obtained liquid composition, and melt-kneading the obtained solid component, (2) a surface protective agent and (5) a polymer.

In the production methods (d3) to (d6), the method for melt-kneading the polymer (5) may be any known method for kneading a polymer. For example, extrusion using a single-screw extruder or a double-screw extruder may be used.

The step of applying the wet treatment in the manufacturing method (d4) may adopt the above-mentioned method.

The step of preparing the liquid composition in the preparation methods (d5) and (d6) may adopt the above-mentioned preparation method (a1) or (a2). In the step of preparing the liquid composition in the preparation method (d6), it is preferred that (2) the surface protective agent is not added in the above-mentioned preparation method (a1) or (a2).

The step of preparing the liquid composition in the preparation method (d5) may adopt the above-mentioned preparation method (a3) or (a4), for example.

The step of removing the solid components in the production methods (d5) and (d6) is carried out by removing (3) the solvent and (4) the polymerizable compound constituting the liquid composition from the liquid composition, for example, by heating, reducing pressure, blowing air, or a combination thereof.

In one embodiment, in the method 3 for producing the composition, when the surface modifying agent (6) is used, it can be added together with the surface protecting agent (2).

<Method for producing composition 2> In a certain aspect, composition 2 of this embodiment can be produced in the same manner as methods 1 to 3 for producing composition 1 above, except that (2) the addition and modification of the surface protective agent is not performed.

In one embodiment, in the method for producing the above-mentioned composition, if a solution containing halogen ions is added to the composition after the modification treatment, X in (1) the calcium-titanium compound and the above-mentioned halogen ions undergo an exchange reaction, thereby adjusting the value of the maximum emission wavelength of (1) the calcium-titanium compound.

In other aspects, after forming a surface protective layer including the above-mentioned (2) surface protective agent on the surface of (1) calcium-titanium compound, a layer of inorganic silicon compound having siloxane bonds can be further formed. In this specification, the so-called "inorganic silicon compound having siloxane bonds" refers to a modified form of a compound containing an organic group and a silicon element, wherein all of the above-mentioned organic groups are organic groups that are removed by modification treatment (hydrolysis), and a modified form of a compound containing a silicon element that does not have an organic group.

Examples of the inorganic silicon compound having a siloxane bond include a modified disilazane in which all of the plural R ¹⁵ 's in the above formula (B1) are hydrogen atoms, a modified low molecular weight silazane in which all of the plural R ¹⁵ 's in the above formula (B2) are hydrogen atoms, a modified high molecular weight silazane in which all of the plural R ¹⁵ 's in the above formula (B3) are hydrogen atoms, a modified high molecular weight silazane in which all of the plural R ¹⁵ 's in the polysilazane having the structure represented by the above formula (B4) are hydrogen atoms, and a modified sodium silicate (Na ₂ SiO ₃ ).

<Determination of the content of (1) calcium-titanium compound contained in the composition> The solid content concentration (mass %) of (1) calcium-titanium compound contained in the composition of this embodiment can be calculated by dry mass method. The details of dry mass method are described in the examples.

<Measurement of half-value width of luminescence spectrum, absorptivity, and luminescence wavelength> The half-value width, absorptivity, and luminescence wavelength of the luminescence spectrum of (1) the calcium-titanium compound of the present invention are measured using an absolute PL quantum yield measurement device (e.g., C9920-02 manufactured by Hamamatsu Photonics Co., Ltd.) at 450 nm of excitation light, room temperature, and atmosphere. The luminescence wavelength is the wavelength with the highest luminescence intensity.

In one embodiment, the absorptivity of the laser light emitted by the calcium-titanium compound (1) of the present embodiment is preferably 0.2 or more and less than 1, more preferably 0.3 or more and less than 0.9, and further preferably 0.6 or more and less than 0.9. In a certain embodiment, the absorptivity of the laser light emitted by the calcium-titanium compound (1) is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or more. In other embodiments, the absorptivity of the laser light emitted by the calcium-titanium compound (1) is 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3 or less.

<Membrane> The membrane of the present invention contains (1) a calcium-titanium compound of the present embodiment. The membrane of the present embodiment is formed by the above-mentioned composition. For example, the membrane of the present embodiment contains (1) a calcium-titanium compound and (5) a polymer, and the total amount of (1) a calcium-titanium compound and (5) a polymer is more than 90% by weight of the entire membrane.

The film shape is not particularly limited and may be in any shape such as a sheet or strip. In this specification, the term "strip shape" refers to, for example, a strip shape extending in one direction when viewed from above. As an example of a strip shape when viewed from above, a plate shape with different lengths of each side can be exemplified.

The thickness of the film can be 0.01 μm to 1000 mm, 0.1 μm to 10 mm, or 1 μm to 1 mm. In this specification, the thickness of the film refers to the distance between the front and back sides of the film in the thickness direction when the side with the smallest value among the longitudinal, transverse, and height of the film is regarded as the "thickness direction". Specifically, the thickness of the film is measured at any three points of 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. In one embodiment, the thickness of the film is 0.01 μm, 0.5 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 25 μm, 50 μm, 75 μm, 100 μm, 250 μm, 500 μm, 750 μm, 1 mm, 5 mm, 10 mm, 25 mm, 50 mm, 75 mm, 100 mm, 250 mm, 500 mm, 750 mm or more. In other aspects, the thickness of the film is 1000 mm, 750 mm, 500 mm, 250 mm, 100 mm, 75 mm, 50 mm, 25 mm, 10 mm, 5 mm, 1 mm, 750 μm, 500 μm, 250 μm, 100 μm, 75 μm, 50 μm, 25 μm, 10 μm, 5 μm, 1 μm, 0.5 μm, 0.1 μm, or less than 0.05 μm.

The film may be a single layer or a multi-layer film. In the case of a multi-layer film, each layer may use the same or different types of compositions.

The film can be obtained by, for example, forming a film on a substrate by the following method for producing a laminated structure. Alternatively, the film can be obtained by peeling off the substrate.

<Layered structure> The layered structure of this embodiment has a plurality of layers, at least one of which is the above-mentioned film.

Among the multiple layers possessed by the laminated structure, the layers other than the above-mentioned film may include any layer such as a substrate, a barrier layer, and a light scattering layer. The shape of the laminated film is not particularly limited and may be any shape such as a sheet or a strip.

(Substrate) The substrate is not particularly limited and may be a film. The substrate is preferably light-transmitting. In a laminated structure having a light-transmitting substrate, it is easier to extract the light emitted by (1) the calcium-titanium compound, so it is preferred.

As the forming material of the substrate, for example, a polymer such as polyethylene terephthalate or a known material such as glass can be used. For example, in a multilayer structure, the above-mentioned film can be set on a substrate.

1 is a cross-sectional view schematically showing the structure of a laminated structure of the present embodiment. A first laminated structure 1a has a film 10 of the present embodiment disposed between a first substrate 20 and a second substrate 21. The film 10 is sealed by a sealing layer 22.

One aspect of the present invention is a multilayer structure 1a, which is characterized in that it has a first substrate 20, a second substrate 21, a film 10 of the present embodiment located between the first substrate 20 and the second substrate 21, and a sealing layer 22, and the sealing layer 22 is arranged on the surface of the film 10 that is not in contact with the first substrate 20 and the second substrate 21.

(Barrier layer) The layer that the laminated structure of this embodiment may have is not particularly limited, and a barrier layer may be mentioned. From the perspective of protecting the above-mentioned composition from water vapor in the external atmosphere and air in the atmosphere, a barrier layer may be included.

The barrier layer is not particularly limited, but is preferably transparent from the viewpoint of extracting the luminescent light. As the barrier layer, for example, a polymer such as polyethylene terephthalate or a known barrier layer such as a glass film can be used.

(Light scattering layer) The layer that the layered structure of this embodiment may have is not particularly limited, and a light scattering layer can be listed. From the perspective of effectively utilizing incident light, a light scattering layer can be included. The light scattering layer is not particularly limited, and from the perspective of extracting emitted light, a transparent one is preferably used. As the light scattering layer, light scattering particles such as silica particles or known light scattering layers such as enhanced diffusion films can be used.

<Light-emitting device> The light-emitting device of the present invention can be obtained by combining the compound, composition or the above-mentioned multilayer structure of the embodiment of the present invention with a light source. The light-emitting device is a device that extracts light by irradiating the compound, composition or multilayer structure disposed in the back stage with light emitted from the light source so that the compound, composition or multilayer structure emits light. Among the multiple layers possessed by the multilayer structure in the above-mentioned light-emitting device, the layers other than the above-mentioned film, substrate, barrier layer and light scattering layer can be listed as any layer such as a light reflecting member, a brightness intensity part, a prism sheet, a light guide plate, and a dielectric material layer between components. One aspect of the present invention is a light emitting device 2 having a prism sheet 50, a light guide plate 60, the first laminated structure 1a and a light source 30 laminated in sequence.

(Light source) The light source constituting the light-emitting device of the present invention is not particularly limited. From the viewpoint of causing the above-mentioned compound, the above-mentioned composition or the (1) calcium-titanium compound in the layered structure to emit light, a light source having a light emission wavelength of 600 nm or less is preferred. As the light source, for example, a light-emitting diode (LED) such as a blue light-emitting diode, a laser, an electroluminescent body (EL), and other known light sources can be used.

(Light-reflecting component) The layer that the laminated structure constituting the light-emitting device of the present invention may have is not particularly limited, and a light-reflecting component may be listed. From the perspective of irradiating light from a light source toward the above-mentioned compound, composition or laminated structure, a light-reflecting component may be contained. The light-reflecting component is not particularly limited, and may be a reflective film. As the reflective film, for example, a known reflective film such as a reflective mirror, a film of reflective particles, a reflective metal film or a reflector may be used.

(Brightness enhancement part) The layer that the multilayer structure constituting the light-emitting device of the present invention may have is not particularly limited, and a brightness enhancement part may be listed. From the perspective of reflecting a part of the light back in the direction in which the light is transmitted, the brightness enhancement part may be included.

(Prism) There is no particular limitation on the layers that the multilayer structure constituting the light-emitting device of the present invention may have, and a prism may be cited. Typically, a prism has a substrate portion and a prism portion. Furthermore, the substrate portion may be omitted depending on the adjacent component. The prism may be bonded to the adjacent component via any suitable bonding layer (e.g., bonding agent layer, adhesive layer). The prism is formed by arranging a plurality of unit prisms that form a convex portion on the opposite side (back side) of the viewing side. By arranging the convex portion of the prism toward the back side, light passing through the prism is easily focused. Furthermore, if the convex portion of the prism sheet is arranged toward the back side, the amount of light that is not incident on the prism sheet but is reflected is less compared to the case where the convex portion is arranged toward the viewing side, and a high-brightness display can be obtained.

(Light guide plate) The layers that the multilayer structure constituting the light-emitting device of the present invention may have are not particularly limited, and a light guide plate may be cited. As the light guide plate, for example, any suitable light guide plate may be used, such as a light guide plate having a lens pattern formed on the back side so that light from the lateral direction is deflected in the thickness direction, a light guide plate having a prism shape formed on the back side and/or the viewing side, etc.

(Inter-element dielectric material layer) The layers that may be included in the multilayer structure constituting the light-emitting device of the present invention are not particularly limited, and examples thereof include: a layer containing one or more dielectric materials in the optical path between adjacent elements (layers) (inter-element dielectric material layer). There is no particular limitation on the one or more media contained in the dielectric material layer between the components, including: vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, curing material, optical bonding material, refractive index matching or refractive index mismatching material, refractive index gradient material, coating or anti-coating material, spacer, silicone, brightness enhancement material, scattering or diffusion material, reflective or anti-reflective material, wavelength selective material, wavelength selective anti-reflective material, color filter or better media known in the above technical field.

As specific examples of the light-emitting device of the present invention, for example, an electroluminescent (EL) display or a device having a wavelength conversion material for a liquid crystal display can be cited. Specifically, the following can be cited: (E1) The composition of the present invention is placed in a glass tube or the like and sealed, and it is arranged between a blue light emitting diode as a light source and a light guide plate along the end face (side face) of the light guide plate, and the blue light is converted into a backlight source of green or red light (backlight source of side tube packaging (On Edge) method); (E2) The composition of the present invention is made into a sheet, and it is sandwiched and sealed with two barrier films to obtain a film, and the film is set on the light guide plate, and the blue light irradiated from the blue light emitting diode placed on the end face (side face) of the light guide plate to the above-mentioned sheet is converted into a backlight source of green or red light (backlight source of surface packaging (On Edge) method). Surface) backlight source), (E3) dispersing the composition of the present invention in a resin or the like, setting it near the light-emitting portion of a blue light-emitting diode, and converting the irradiated blue light into a green or red backlight source (on-chip backlight source), and (E4) dispersing the composition of the present invention in a resist, setting it on a color filter, and converting the blue light irradiated from a light source into a green or red backlight source.

Furthermore, as a specific example of the light-emitting device of the present invention, the composition of the embodiment of the present invention is formed and arranged at the rear stage of a blue light-emitting diode as a light source, and the blue light is converted into green light or red light to emit white light.

<Display> As shown in FIG. 2, the display 3 of this embodiment has a liquid crystal panel 40 and the above-mentioned light-emitting device 2 in order from the viewing side. The light-emitting device 2 has a second multilayer structure 1b and a light source 30. The second multilayer structure 1b is the first multilayer structure 1a further having a prism sheet 50 and a light guide plate 60. The display may also further have any other suitable components. One aspect of the present invention is a liquid crystal display 3 having a liquid crystal panel 40, a prism sheet 50, a light guide plate 60, the above-mentioned first multilayer structure 1a and a light source 30 stacked in order.

(Liquid crystal panel) In one embodiment, the liquid crystal panel typically comprises: a liquid crystal unit, a viewing side polarizing plate disposed on the viewing side of the liquid crystal unit, and a back side polarizing plate disposed on the back side of the liquid crystal unit. The viewing side polarizing plate and the back side polarizing plate may be disposed in such a manner that their absorption axes are substantially orthogonal or parallel.

(Liquid crystal unit) In one embodiment, the liquid crystal unit has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the substrates. In other embodiments, in a conventional configuration, a color filter and a black matrix are provided on one substrate, and a switch element for controlling the electro-optical properties of the liquid crystal, a scanning line for providing a gate signal to the switch element and a signal line for providing a source signal, as well as a pixel electrode and a counter electrode are provided on the other substrate. The spacing (cell gap) between the substrates can be controlled by a spacer or the like. For example, an alignment film containing polyimide can be provided on the side of the substrate that is in contact with the liquid crystal layer.

(Polarizing plate) In one embodiment, the polarizing plate typically has a polarizing element and protective layers disposed on both sides of the polarizing element. The polarizing element is typically an absorption-type polarizing element. As the above-mentioned polarizing element, any suitable polarizing element can be used. For example, hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and partially saponified films of ethylene-vinyl acetate copolymers adsorb dichroic substances such as iodine or dichroic dyes and uniaxially stretch them, and polyene-based alignment films such as dehydrated polyvinyl alcohol films or dehydrochlorinated polyvinyl chloride films, etc. Among them, the polarizing element in which the polyvinyl alcohol film adsorbs dichroic substances such as iodine and is uniaxially stretched is particularly preferred because of its high polarization dichroism.

The compound or composition of the present embodiment can be used, for example, as a wavelength conversion material for a light-emitting diode (LED). <LED> The compound or composition of the present embodiment can be used, for example, as a material for a light-emitting layer of an LED. As an LED containing the compound or composition of the present embodiment, for example, the following method can be used: the compound or composition of the present embodiment is mixed with conductive particles such as ZnS and layered into a film, and a structure is prepared in which an n-type transport layer is layered on one side and a p-type transport layer is layered on the other side. By passing a current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel out the charges in the particles of the calcium-titanium compound (1) contained in the composition at the junction surface, thereby emitting light.

<Solar cell> The compound or composition of the present embodiment can be used as an electron transport material contained in the active layer of a solar cell. The composition of the above-mentioned solar cell is not particularly limited, and examples thereof include: a solar cell having, in order, a fluorine-doped tin oxide (FTO) substrate, a titanium oxide dense layer, a porous aluminum oxide layer, an active layer containing the compound or composition of the present embodiment, a hole transport layer such as 2,2',7,7'-tetrakis(N,N'-di-p-methoxyaniline)-9,9'-spirobifluorene (Spiro-MeOTAD), and a silver (Ag) electrode. The titanium oxide dense layer has the function of electron transport, the effect of suppressing the roughness of FTO, and the function of suppressing reverse electron transfer. The porous alumina layer has the function of improving light absorption efficiency. The compound or composition of the present embodiment contained in the active layer has the functions of charge separation and electron transport.

<Methods for producing membranes> Methods for producing membranes include, for example, the following methods (e1) to (e3).

Production method (e1): A method for producing a film comprising the steps of applying a liquid composition to obtain a coating film, and removing (3) the solvent from the coating film.

Production method (e2): A method for producing a film comprising the steps of applying a liquid composition containing (4) a polymerizable compound to obtain a coating film, and polymerizing the (4) polymerizable compound contained in the obtained coating film.

Production method (e3): A method for producing a film by molding the composition obtained by the above-mentioned production methods (d1) and (d2).

<Method for manufacturing a laminated structure> The method for manufacturing a laminated structure includes, for example, the following manufacturing methods (f1) to (f3).

Manufacturing method (f1): A method for manufacturing a layered structure, comprising the steps of preparing a liquid composition, coating the obtained liquid composition on a substrate, and removing (3) a solvent from the obtained coating film.

Manufacturing method (f2): A method for manufacturing a multilayer structure, comprising the step of bonding a film to a substrate.

Manufacturing method (f3): A manufacturing method comprising the steps of preparing a liquid composition containing a (4) polymerizable compound, coating the obtained liquid composition on a substrate, and polymerizing the (4) polymerizable compound contained in the obtained coating film.

The steps of preparing the liquid composition in the preparation methods (f1) and (f3) can adopt the above-mentioned preparation methods (c1) to (c4).

The step of coating the liquid composition on the substrate in the manufacturing methods (f1) and (f3) is not particularly limited, and known coating and application methods such as gravure coating, rod coating, printing, spraying, rotary coating, dipping, and die-nozzle coating can be used.

The step of removing the solvent (3) in the production method (f1) may be the same step as the step of removing the solvent (3) in the above-mentioned production method (d2).

The step of polymerizing the polymerizable compound (4) in the production method (f3) may be the same step as the step of polymerizing the polymerizable compound (4) included in the above-mentioned production method (d1).

In the step of bonding the film to the substrate in the manufacturing method (f2), any adhesive may be used.

The adhesive is not particularly limited as long as it does not dissolve (1) the calcium-titanium compound, and any known adhesive can be used.

The method for manufacturing a laminated structure may include a step of further bonding an arbitrary film to the obtained laminated structure.

Examples of the arbitrary film to be bonded include a reflective film and a diffusion film.

In the film lamination step, any adhesive may be used.

The above-mentioned bonding agent is not particularly limited as long as it does not dissolve the compound of the present embodiment, and a known bonding agent can be used.

<Method for manufacturing a light-emitting device> For example, the method may include the steps of providing the above-mentioned light source and providing the above-mentioned compound, the above-mentioned combination or the multilayer structure on the optical path at the rear section of the light source.

Furthermore, the technical scope of the present invention is not limited to the above-mentioned embodiments, and various modifications can be added without departing from the scope of the present invention.

<Sensor> The compound or composition of this embodiment can be used as an image detection unit (image sensor) for solid-state imaging devices such as X-ray imaging devices and CMOS (complementary metal oxide semiconductor) image sensors, a detection unit for detecting a specific feature of a part of a biological body such as a fingerprint detection unit, a face detection unit, a vein detection unit, and an iris detection unit, and a photoelectric conversion element (photodetection element) material contained in the detection unit of an optical biosensor such as a pulse oximeter. [Example]

Hereinafter, the present invention will be described in more detail based on embodiments and comparative examples, but the present invention is not limited to the following embodiments.

((1) Determination of solid content concentration of calcium-titanium compound) The solid content concentration of the calcium-titanium compound in the composition obtained in Example 5 was calculated by measuring the residual mass of the dispersion containing the calcium-titanium compound and the solvent obtained by redispersion at 105°C for 3 hours and applying it to the following formula 1. Solid content concentration (mass %) = mass after drying ÷ mass before drying × 100...Formula 1

(Measurement of the mass M _W of added water) The mass M _W of added water was measured using a trace water content measuring device (AQ-2000, manufactured by Hiranuma Sangyo Co., Ltd., ketone electrolyte Hydranal-Coulomat AK).

(Measurement of half-value width of luminescence spectrum, absorbance and luminescence wavelength) Using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., C9920-02), the half-value width of the luminescence spectrum and the luminescence wavelength of the compounds obtained in Examples 1 to 5 and Comparative Example 1 were measured at an excitation light of 450 nm, room temperature and atmosphere.

(Measurement of half-value width of (hkl) = (001)) After measuring the compounds obtained in Examples 1 to 5 and Comparative Example 1 by X-ray structure diffraction (XRD, CuKα ray = 1.5458λ, X'pert PRO MPD, manufactured by Spectris), the half-value width of the peak of (hkl) = (001) was measured. The half-value width of the peak of (hkl) = (001) was calculated using the integrated powder X-ray analysis software PDXL (manufactured by Rigaku).

(Average particle size measurement) The compounds obtained in Examples 1 to 5 and Comparative Example 1 were observed using a transmission electron microscope (manufactured by JEOL Ltd., JEM-2200FS). The compositions containing the compounds obtained in Examples 1 to 5 and Comparative Example 1 were cast on a grid with a support film for TEM, dried naturally, and observed at an accelerating voltage of 200 kV. In addition, energy dispersive X-ray analysis (manufactured by JEOL Ltd., JED-2300) was performed in the observation field to obtain elemental mapping images.

The average particle size of the calcium-titanium compound obtained in Examples 1 to 5 and Comparative Example 1 was calculated using the image analysis software Image J. A binary image was obtained in which the compounds obtained in Examples 1 to 5 and Comparative Example 1 in the TEM image of each composition were converted to black and the rest to white. At this time, by comparing with the element mapping image obtained by TEM-EDX measurement, it was confirmed that the positions of the components derived from the calcium-titanium compound obtained in Examples 1 to 5 and Comparative Example 1 could be detected and converted to black. The size of the calcium-titanium compound was measured for the above binary image. The average particle size is calculated from the average length of the longest side of 300 randomly selected particles of calcium-titanium compounds in the form of cubes or cuboids.

[Example 1] After mixing 25 mL of oleylamine and 200 mL of ethanol, the mixture was stirred while being cooled in an ice bath, and 17.12 mL of a hydrobromic acid solution (48%) was added, followed by drying under reduced pressure to obtain a precipitate. The precipitate was washed with diethyl ether, and then dried under reduced pressure to obtain oleylammonium bromide.

After mixing 21 g of oleylammonium bromide with 200 mL of toluene, water was added to the solution containing oleylammonium bromide in such a manner that the ratio of water (g) to lead (g) became 0.58 relative to the mass (g) of lead in the following lead acetate trihydrate (a raw material containing lead as the metal element M), thereby preparing 53.4 mL of a solution containing oleylammonium bromide. 1.52 g of lead acetate trihydrate, 1.56 g of formamidine acetate, 160 mL of a solvent of 1-octadecene, and 40 mL of oleic acid were mixed. After stirring, the mixture was heated to 130°C while nitrogen was flowing, and then 53.4 mL of the solution containing oleylammonium bromide and water was added. After the addition, the solution was cooled to room temperature to obtain a dispersion 1 containing (1) a calcium-titanium compound.

If the luminescence characteristics of a solution obtained by mixing 1.50 μL of the dispersion with 3.95 mL of toluene are evaluated, the half-value width of the luminescence spectrum is 20.93 nm, the absorptivity of the excitation light is 0.65, and the luminescence wavelength is 541 nm.

200 mL of the above dispersion 1 was mixed with 100 mL of toluene and 50 mL of acetonitrile to obtain a solution to separate solid from liquid by filtration. Thereafter, the solid component on the filter was washed twice with a mixed solution of 100 mL of toluene and 50 mL of acetonitrile and filtered. Thus, (1) a calcium-titanium compound was obtained.

The obtained (1) calcium titanite compound was dispersed in 100 mL of toluene to obtain dispersion 2. Dispersion 2 was cast on a 50 μL non-reflective plate, dried, and then subjected to XRD measurement. The result showed that the XRD spectrum had a peak originating from (hkl) = (001) at 2θ = 14-15°. The half-value width of (hkl) = (001) was measured to be 0.272. Based on the measurement results, it was confirmed that the recovered (1) calcium titanite compound was a compound having a three-dimensional calcium titanite crystal structure. The average particle size measured by TEM was 14.6 nm.

[Example 2] Except that the water content of the solution containing oleylammonium bromide in the production step of the calcium-titanium compound was set to 1.13 relative to the mass (g) of lead in lead acetate trihydrate (a raw material containing lead as the metal element M), a dispersion was obtained in the same manner as in Example 1. The half-value width of (hkl) = (001) was 0.232. In addition, the half-value width of the luminescence spectrum was 20.68 nm, the absorptivity of the excitation light was 0.72, and the luminescence wavelength was 541 nm. The average particle size measured by TEM was 21.6 nm.

[Example 3] Except that the water content of the solution containing oleylammonium bromide in the production step of the calcium-titanium compound was set to 1.69 relative to the mass (g) of lead in lead acetate trihydrate (a raw material containing lead as the metal element M), a dispersion was obtained in the same manner as in Example 1. The half-value width of (hkl) = (001) was 0.213. In addition, the half-value width of the luminescence spectrum was 20.15 nm, the absorptivity of the excitation light was 0.65, and the luminescence wavelength was 542 nm. The average particle size measured by TEM was 18.4 nm.

[Example 4] A dispersion was obtained in the same manner as in Example 1 except that the water content of the solution containing oleylammonium bromide in the step of producing the calcium-titanium compound was set to 2.25 relative to the mass (g) of lead in lead acetate trihydrate (a raw material containing lead as the metal element M). The half-value width of (hkl) = (001) was 0.150. In addition, the half-value width of the luminescence spectrum was 20.16 nm, the absorptivity of the excitation light was 0.29, and the luminescence wavelength was 539 nm. The average particle size measured by TEM was 26.6 nm.

[Example 5] After mixing 25 mL of oleylamine and 200 mL of ethanol, add 17.12 mL of hydrobromic acid solution (48%) while stirring in an ice bath, and then dry under reduced pressure to obtain a precipitate. The precipitate is washed with diethyl ether and dried under reduced pressure to obtain oleylammonium bromide.

After mixing 21 g of oleylammonium bromide with 200 mL of toluene, water was added to the solution containing oleylammonium bromide in such a manner that the ratio of water (g) to lead (g) became 1.69 relative to the mass (g) of lead in the following lead acetate trihydrate (a raw material containing lead as the metal element M), thereby preparing a solution containing oleylammonium bromide. 1.52 g of lead acetate trihydrate, 1.56 g of formamidine acetate, 160 mL of a solvent of 1-octadecene, and 40 mL of oleic acid were mixed. After stirring, the mixture was heated to 130°C while nitrogen was flowing, and then 53.4 mL of the solution containing oleylammonium bromide and water was added. After the addition, the solution was cooled to room temperature to obtain a dispersion 3 containing (1) a calcium-titanium compound. The average particle size measured by TEM was 18.4 nm.

200 mL of the above dispersion 3 was mixed with 100 mL of toluene and 50 mL of acetonitrile to obtain a solution to separate solid from liquid by filtration. Thereafter, the solid component on the filter was washed twice with a mixed solution of 100 mL of toluene and 50 mL of acetonitrile and filtered. Thus, (1) a calcium-titanium compound was obtained.

The obtained (1) calcium titanite compound was dispersed in 100 mL of toluene to obtain dispersion 4. Dispersion 4 was cast on a 50 μL non-reflective plate, dried, and then subjected to XRD measurement. The result showed that the XRD spectrum had a peak originating from (hkl) = (001) at the position of 2θ = 14-15°. The half-value width of (hkl) = (001) was measured to be 0.213. Based on the measurement results, it was confirmed that the recovered (1) calcium titanite compound was a compound having a three-dimensional calcium titanite crystal structure.

The above calcium-titanium compound was mixed with xylene to prepare 185 mL of dispersion 5 in a manner such that the solid content concentration was 0.9 mass %. Two mass parts of organic polysilazane (1500 Slow Cure, Durazane, manufactured by Merck Performance Materials Co., Ltd.) were added thereto relative to one mass part of the calcium-titanium compound in dispersion 5. When the half-value width of the luminescence spectrum was measured by the above method, it was 20.60 nm, and the luminescence wavelength was 538 nm.

[Comparative Example 1] The dispersion was obtained in the same manner as in Example 1 except that the water content of the solution containing oleylammonium bromide in the step of producing the calcium-titanium compound was set to 0.046 relative to the mass (g) of lead in lead acetate trihydrate (a raw material containing lead as the metal element M). Furthermore, the water was not intentionally added but was derived from the water contained in the raw material. If the half-value width of (hkl) = (001) is calculated by the above method, it is 0.600. If the half-value width of the luminescence spectrum is measured by the above method, it is 24.30 nm, the absorptivity of the excitation light is 0.64, and the luminescence wavelength is 535 nm. The average particle size measured by TEM is 13.1 nm.

The results of Examples 1 to 5 and Comparative Example 1 are shown in Table 1.

[Table 1] Half value width [(hkl) = (001)] Half-value width of luminescence spectrum (nm) Embodiment 1 0.272 20.93 Embodiment 2 0.232 20.68 Embodiment 3 0.213 20.15 Embodiment 4 0.150 20.16 Embodiment 5 0.213 20.60 Comparison Example 1 0.600 24.30

From the above results, it can be confirmed that the calcium-titanium compounds of Examples 1 to 5 of the present invention have narrower half-widths of luminescence spectra than the calcium-titanium compound of Comparative Example 1 to which the present invention is not applied.

[Reference Example 1] The following backlight source is manufactured: the compound or composition described in Examples 1 to 5 is placed in a glass tube or the like and sealed, and then arranged between a blue light emitting diode as a light source and a light guide plate, thereby converting the blue light of the blue light emitting diode into green light or red light.

[Reference Example 2] The following backlight source is manufactured: a resin composition can be obtained by forming a sheet of the compound or composition described in Examples 1 to 5, and the resin composition is sandwiched and sealed with two barrier films to obtain a film, and the film is placed on a light guide plate, thereby converting the blue light from the blue light-emitting diode placed on the end face (side face) of the light guide plate through the light guide plate and irradiating the above-mentioned sheet into green light or red light.

[Reference Example 3] The following backlight source is manufactured: the compound or composition described in Examples 1 to 5 is placed near the light-emitting portion of a blue light-emitting diode, thereby converting the irradiated blue light into green light or red light.

[Reference Example 4] After mixing the compound or composition described in Examples 1 to 5 with a resist, the solvent is removed to obtain a wavelength conversion material. The following backlight source is manufactured: the obtained wavelength conversion material can be arranged between a blue light-emitting diode as a light source and a light guide plate or in the rear section of an OLED (Organic Light-Emitting Diode) as a light source to convert the blue light of the light source into green light or red light.

[Reference Example 5] The compounds or compositions described in Examples 1 to 5 are mixed with conductive particles such as ZnS and formed into films, with an n-type transmission layer on one surface and a p-type transmission layer on another surface, thereby obtaining an LED. By flowing current, the holes of the p-type semiconductor and the electrons of the n-type semiconductor cancel out the charges in the calcium-titanium compound at the junction, thereby emitting light.

[Reference Example 6] A titanium oxide dense layer is deposited on the surface of a fluorine-doped tin oxide (FTO) substrate, a porous aluminum oxide layer is deposited thereon, a compound or composition described in Examples 1 to 5 is deposited thereon, after removing the solvent, a hole transport layer such as 2,2',7,7'-tetrakis(N,N'-di-p-methoxyaniline)-9,9'-spirobiphenylene (Spiro-OMeTAD) is deposited thereon, and a silver (Ag) layer is deposited thereon to prepare a solar cell.

[Reference Example 7] Manufacture the following laser diode lighting: By removing the solvent of the compound or composition described in Examples 1 to 5 and forming it, the composition of this embodiment can be obtained, and it is set in the rear section of the blue light emitting diode, thereby converting the blue light irradiated from the blue light emitting diode to the composition into green light or red light to emit white light.

[Reference Example 8] The composition of this embodiment can be obtained by removing the solvent of the compound or composition described in Examples 1 to 5 and forming it. By using the obtained composition as a part of the photoelectric conversion layer, a photoelectric conversion element (photodetection element) material used in a detection unit for detecting light is manufactured. The photoelectric conversion element material is used in image detection units (image sensors) for solid-state imaging devices such as X-ray imaging devices and CMOS image sensors, fingerprint detection units, face detection units, vein detection units, iris detection units, etc., which detect specific features of a part of a biological body, and optical biosensors such as pulse oximeters. [Industrial Applicability]

According to the present invention, a compound having a calcite-tantalum crystal structure with a narrow half-value width of the luminescence spectrum, a composition containing the above compound, a film formed by the above composition, a laminated structure containing the above film, a luminescent device and a display having the above laminated structure can be provided. Therefore, the compound having a calcite-tantalum crystal structure, the composition containing the above compound, the film formed by the above composition, the laminated structure containing the above film, and the luminescent device and display having the above laminated structure of the present invention can be preferably used for luminescence purposes.

The present invention also includes the following [1] to [28]. [1] A calcite aggregate, wherein in an X-ray diffraction pattern, the half-value width of the peak of the Miller index (001) of the plane is greater than 0.10 and less than 0.60, and the aggregate is composed of a plurality of compounds having a calcite type crystal structure and having A, B and X as constituent components. (A is a component located at each vertex of a hexahedron with B as the center in the calcite-titanoic crystal structure, and is a monovalent cation; X is a component located at each vertex of an octahedron with B as the center in the calcite-titanoic crystal structure, and is at least one anion selected from the group consisting of halide ions and thiocyanate ions; B is a component located at the center of a hexahedron with A as the vertex and an octahedron with X as the vertex in the calcite-titanoic crystal structure, and is a metal ion) [2] A calcite-titanoic aggregate as in [1], wherein the half-value width of the peak of the above-mentioned Miller index (001) is greater than 0.15 and less than 0.60. [3] The calcium-titanium aggregate of [1], wherein the half-value width of the peak of the Miller index (001) is not less than 0.15 and not more than 0.28. [4] The calcium-titanium aggregate of any one of [1] to [3], wherein the B is a divalent metal ion. [5] The calcium-titanium aggregate of any one of [1] to [4], wherein the B is a metal ion selected from the group consisting of lead ions, tin ions, antimony ions, bismuth ions and indium ions. [6] The calcium-titanium aggregate of any one of [1] to [5], comprising one or more metal ions selected from the group consisting of lead ions, tin ions, antimony ions, bismuth ions and indium ions. [7] The calcium-titanium aggregate of any one of [1] to [6], wherein B is a lead ion. [8] The calcium-titanium aggregate of any one of [1] to [7], wherein the compound comprises one or more valence cations selected from the group consisting of cesium ions, organic ammonium ions and amidinium ions. [9] The calcium-titanium ore aggregate of any one of [1] to [8], wherein the above X is one or more halide ions selected from the group consisting of chloride ions, bromide ions, fluoride ions and iodide ions. [10] The calcium-titanium ore aggregate of any one of [1] to [8], wherein the above X is one or more thiocyanate ions. [11] The calcium-titanium ore aggregate of [9], wherein the above X is a bromide ion. [12] A composition comprising the calcium-titanium ore aggregate of any one of [1] to [11] and at least one compound selected from the group consisting of the following (2-1), the following modified product of (2-1), the following (2-2) and the following modified product of (2-2). (2-1) Silazane (2-2) A silicon compound [13] having at least one group selected from the group consisting of an amino group, an alkoxy group and an alkylthio group, which comprises a calcium-titanium aggregate as described in any one of [1] to [11] and at least one selected from the group consisting of the following (3), the following (4) and the following (5). (3) Solvent (4) Polymerizable compound (5) Polymer [14] A composition as described in [12], which further comprises at least one selected from the group consisting of the following (3), the following (4) and the following (5). (3) Solvent (4) Polymerizable compound (5) Polymer [15] A membrane comprising a calcium-titanium aggregate as described in any one of [1] to [11]. [16] A film formed of a composition as described in any one of [12] to [14]. [17] A laminated structure comprising a film as described in [15] or [16]. [18] A light-emitting device having a laminated structure as described in [17]. [19] A display having a laminated structure as described in [17]. [20] A method for producing an aggregate, comprising the steps of mixing raw materials of either or both of a simple substance containing a metal element M and a compound containing a metal element M with water, and reacting the raw materials in the presence of the water, wherein the aggregate is composed of a plurality of aggregates of semiconductor compounds containing the metal element M, wherein the ratio of the mass W _W of the water to the mass W _M of the metal element M contained in the raw materials, i.e. (W _W /W _M ), is 0.05 to 100, and in the X-ray diffraction pattern, the half-value width of the peak of the Miller index (001) of the plane is greater than 0.10 and less than 0.60. [21] The method of [20], wherein the aggregate is a calcium-titanium ore aggregate as described in any one of [1] to [11]. [22] The method of production as described in [20] or [21], comprising the step of mixing at least one compound selected from the group consisting of (2-1), a modified product of (2-1), (2-2), and a modified product of (2-2). (2-1) Silazane (2-2) A silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group, and an alkylthio group. [23] The method of production as described in [20] or [21], comprising the step of mixing a polysilazane. [24] The method of production as described in [20] or [24], further comprising the step of mixing at least one compound selected from the group consisting of (3), (4), and (5). (3) Solvent (4) Polymerizable compound (5) Polymer [25] The method of any one of [20] to [24], wherein the aggregate is a film-forming material. [26] The method of [25], wherein the film is contained in a multilayer structure. [27] The method of [26], wherein the multilayer structure is used in a light-emitting device. [28] The method of [26], wherein the multilayer structure is used in a display.

1a: 1st layer structure 1b: 2nd layer structure 2: Light-emitting device 3: Display 10: Film 20: 1st substrate 21: 2nd substrate 22: Sealing layer 30: Light source 40: Liquid crystal panel 50: Prism 60: Light guide plate

FIG1 is a cross-sectional view showing one embodiment of the multilayer structure of the present invention. FIG2 is a cross-sectional view showing one embodiment of the display of the present invention.

1b: Second layer structure

2: Light-emitting device

3: Display

10: Membrane

20: 1st substrate

21: Second substrate

22: Sealing layer

30: Light source

40: LCD panel

50: Prism

60: Light guide plate

Claims (11)

A compound having a calcite-type crystal structure, wherein in an X-ray diffraction pattern, the half-value width of the peak of the Miller index (001) of the plane is greater than 0.10 and less than 0.60, and the compound has A, B and X as constituent components; (A is a component located at each vertex of a hexahedron with B as the center in the calcite-type crystal structure, and is a monovalent cation; X is a component located at each vertex of an octahedron with B as the center in the calcite-titanoic crystal structure, and is at least one anion selected from the group consisting of halide ions and thiocyanate ions; B is a component located at the center of a hexahedron with A as the vertex and an octahedron with X as the vertex in the calcite-titanoic crystal structure, and is a metal ion). The compound of claim 1 has a three-dimensional structure. A composition comprising a compound as claimed in claim 1 or 2, and at least one compound selected from the group consisting of (2-1), a modified form of (2-1), (2-2), and a modified form of (2-2); (2-1) silazane (2-2) a silicon compound having at least one group selected from the group consisting of an amino group, an alkoxy group, and an alkylthio group. A composition comprising a compound as claimed in claim 1 or 2, and at least one selected from the group consisting of the following (3), the following (4) and the following (5); (3) solvent (4) polymerizable compound (5) polymer. The composition of claim 3 further contains at least one selected from the group consisting of the following (3), the following (4) and the following (5); (3) solvent (4) polymerizable compound (5) polymer. A film containing the compound as claimed in claim 1 or 2. A film formed from a composition as described in any one of claims 3 to 5. A layered structure comprising a membrane as claimed in claim 6 or 7. A light-emitting device having a layered structure as claimed in claim 8. A display having a layered structure as claimed in claim 8. A method for producing a semiconductor compound comprises: mixing raw materials of either or both of a simple substance containing a metal element M and a compound containing a metal element M with water, and reacting the raw materials in the presence of the water, wherein the ratio of the mass W _W of the water to the mass W _M of the metal element M contained in the raw materials (W _W /W _M ) is 0.05-100, and in an X-ray diffraction pattern, the half-value width of the peak of the Miller index (001) of the plane containing the metal element M is greater than 0.10 and less than 0.60.